CN106549111B - Exchange electrically driven (operated) light emitting diode with quantum dots, preparation method and application - Google Patents
Exchange electrically driven (operated) light emitting diode with quantum dots, preparation method and application Download PDFInfo
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- CN106549111B CN106549111B CN201611116039.5A CN201611116039A CN106549111B CN 106549111 B CN106549111 B CN 106549111B CN 201611116039 A CN201611116039 A CN 201611116039A CN 106549111 B CN106549111 B CN 106549111B
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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Abstract
The present invention provides a kind of electrically driven (operated) light emitting diode with quantum dots of exchange, including substrate, hearth electrode, quantum dot light emitting layer, the top electrode being cascading, it further include the first ionic liquid layer being arranged between the top electrode and the quantum dot light emitting layer, first ionic liquid layer is made of the first ionic liquid for containing only anion and cation, first ionic liquid is in a liquid state at -10~200 DEG C, and in the case where exchanging electric drive, first ionic liquid layer forms interfacial electric double layer at the interface of the quantum dot light emitting layer and the top electrode.
Description
Technical field
The invention belongs to light emitting diode with quantum dots field more particularly to a kind of electrically driven (operated) two poles of quantum dot light emitting of exchange
Pipe, preparation method and application.
Background technique
Quantum dot (Quantum dot, QD) is a kind of nano material of quasi-zero dimension (Quasi-zero-dimensional),
It is made of a small number of atoms, with fluorescence efficiency height, that luminescent spectrum is narrow, emission wavelength is adjustable, spectral purity is high etc. is special
Advantage, the potential core for replacing traditional organic or inorganic illuminator to become next-generation luminescent device.Based on quantum dot
Light emitting diode be referred to as light emitting diode with quantum dots (Quantum dot light-emitting diode, QLED),
There is outstanding advantages of luminescent properties are good, long service life, preparation process is simple, excitation purity is high, colour temperature is good, gradually take
Become new " green " illuminating source for traditional lighting material.
The QLED device studied at present, the overwhelming majority belong to dc electroluminescence device, and working principle mainly will
Direct current load on two electrodes of the QLED device with typical sandwich structure, under forward bias (anode connect anode,
Cathode connects cathode), electrons and holes are injected into electron transfer layer and hole transmission layer from cathode and anode respectively, subsequently into
To quantum dot light emitting layer, exciton, exciton recombination luminescence are formed.Although at present using the QLED device of dc electroluminescence form
Study it is more mature, and in terms of achieve quick development, but this device needs stable DC
Supply could work normally, and the electricity consumption in living or producing at present is mainly alternating current, in order to guarantee dc electroluminescence
The normal work of QLED device, on the one hand can additionally increase exchanges-current/direct-current conversion device to luminescent system, but in this way can be big
Increase the expense of adding system, and the system integration is complicated, energy loss is big, is unfavorable for the popularization of QLED device.It on the other hand, can be with
From the structure of QLED device, one or more layers dielectric layer, dielectric layer material are set between electrode and carrier blocking layers
It is the insulating metal oxide with high dielectric constant, such as silica, aluminium oxide, hafnium oxide, tantalum oxide, plays and stop both ends electricity
The effect of pole charge injection, making the carrier in QLED device for recombination luminescence is no longer the carrier of external circuit injection.Though
Right dielectric layer structure can obtain the electrically driven (operated) QLED device of exchange, and but its structure is complex, and preparation process is cumbersome, and QLED device
Luminous efficiency can greatly reduce, and be unfavorable for large-scale industrialization promotion.Therefore, the prior art needs to be further studied
And development.
Summary of the invention
The purpose of the present invention is to provide a kind of electrically driven (operated) light emitting diode with quantum dots of exchange and preparation method thereof, it is intended to
The existing electrically driven (operated) light emitting diode with quantum dots of exchange is solved to need multiple dielectric layers, lead to labyrinth；Or existing alternating current
The light emitting diode with quantum dots of driving needs to be unfavorable for industrialization promotion using complex devices such as AC-DC conversion equipments
Problem.
Another object of the present invention is to provide the applications that kind exchanges electrically driven (operated) light emitting diode with quantum dots.
The invention is realized in this way a kind of electrically driven (operated) light emitting diode with quantum dots of exchange, including be cascading
Substrate, hearth electrode, quantum dot light emitting layer, top electrode, further include setting the top electrode and the quantum dot light emitting layer it
Between the first ionic liquid layer, first ionic liquid layer by contain only anion and cation the first ionic liquid be made,
First ionic liquid is in a liquid state at -10~200 DEG C, and in the case where exchanging electric drive, first ionic liquid layer is in institute
The interface for stating quantum dot light emitting layer and the top electrode forms interfacial electric double layer.
And a kind of preparation method for exchanging electrically driven (operated) light emitting diode with quantum dots, comprising the following steps:
Depositions of bottom electrode on substrate deposits quantum dot light emitting layer on the hearth electrode；
The first ionic liquid layer is deposited on the quantum dot light emitting layer；
Top electrode is deposited in first ionic liquid layer.
And a kind of illuminating module, including the above-mentioned electrically driven (operated) light emitting diode with quantum dots of exchange.
And a kind of display device, including the above-mentioned electrically driven (operated) light emitting diode with quantum dots of exchange.
The electrically driven (operated) light emitting diode with quantum dots of exchange provided by the invention, in the quantum dot light emitting layer and top electricity
The first ionic liquid layer is introduced between pole.When light emitting diode with quantum dots connects alternating current, first ionic liquid layer exists
The interface of the quantum dot light emitting layer and the top electrode forms interfacial electric double layer, and generates respectively not at interfacial electric double layer both ends
The carrier (electronics or hole) of same type, electronics or hole migrate to quantum dot light emitting layer under electric field action, are finally measuring
Recombination luminescence at son point luminescent layer.Specifically, in the case where exchanging electro ultrafiltration, interfacial electric double layer both ends when applying positive pressure and applying negative pressure
Carrier type and effect on the contrary, to realize light emitting diode with quantum dots exchange electric drive shine.With prior art phase
Than the alternating current of Ionic Liquid Modified provided by the invention drives light emitting diode with quantum dots, on the one hand, it is more both not need setting
A dielectric layer does not need the complex devices such as AC-DC conversion equipment yet, and therefore, device architecture is simple, mature preparation process is simple
Just, it is conducive to industrialization promotion；On the other hand, the introducing of first ionic liquid layer, can effectively realize QLED device
It exchanges electric drive to shine, and device light emitting efficiency is high, performance is stablized.
The preparation method of the electrically driven (operated) light emitting diode with quantum dots of exchange provided by the invention, it is only necessary in conventional QLED
In the structure basis of device, the first ionic liquid layer, the mature letter of method are introduced between quantum dot light emitting layer and top electrode
It is single, it is easy to accomplish industrialization.
Illuminating module and display device provided by the invention, due to containing electrically driven (operated) two pole of quantum dot light emitting of above-mentioned exchange
Pipe, therefore, is conducive to large-scale industrialization promotion application.
Detailed description of the invention
Fig. 1 is the structural schematic diagram for the electrically driven (operated) light emitting diode with quantum dots of exchange that the embodiment of the present invention 1 provides；
Fig. 2 is the level structure effect picture for the electrically driven (operated) light emitting diode with quantum dots of exchange that the embodiment of the present invention 1 provides；
Fig. 3 is the structural schematic diagram for the electrically driven (operated) light emitting diode with quantum dots of exchange that the embodiment of the present invention 2 provides；
Fig. 4 is the structural schematic diagram for the electrically driven (operated) light emitting diode with quantum dots of exchange that the embodiment of the present invention 3 provides.
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
The embodiment of the invention provides a kind of electrically driven (operated) light emitting diode with quantum dots of exchange, including what is be cascading
Substrate, hearth electrode, quantum dot light emitting layer, top electrode further include being arranged between the top electrode and the quantum dot light emitting layer
The first ionic liquid layer, first ionic liquid layer by contain only anion and cation the first ionic liquid be made, institute
It states the first ionic liquid to be in a liquid state at -10~200 DEG C, and in the case where exchanging electric drive, first ionic liquid layer is described
The interface of quantum dot light emitting layer and the top electrode forms interfacial electric double layer.
Specifically, the selection of the substrate does not limit strictly, rigid substrate can be selected, flexible liner can also be selected
Bottom.Wherein, the rigid substrate includes but is not limited to glass, metal foil；The flexible substrate includes but is not limited to poly- to benzene
Naphthalate (PET), ethylene glycol terephthalate (PEN), polyether-ether-ketone (PEEK), polyether sulfone (PES), poly- carbonic acid
Ester (PC), poly- aryl acid esters (PAT), polyarylate (PAR), polyimides (PI), textile fabric.
The hearth electrode can be prepared using this field conventional material, including metal material, conductive carbon material, conductive metal
One of oxide material is a variety of.Wherein, the metal material include but is not limited to Al, Ag, Cu, Mo, Au or they
Alloy, physical form include but is not limited to dense film, nano wire, nanosphere, nanometer rods, nanocone, nano-hollow ball or
Their mixture；The conductive carbon material includes but is not limited to doped or non-doped carbon nanotube, graphene, graphite oxide
Alkene, C60, graphite, carbon fiber, more empty carbon or their mixture；The conductive metal oxide material includes but is not limited to indium
One of doped stannum oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), aluminium-doped zinc oxide (AZO)
Or it is a variety of.
Conventional quanta point material preparation can be used in the quantum dot light emitting layer, and the quanta point material can be selected from doping
Or undoped II-V compound semiconductor, Group III-V compound semiconductor, group IV-VI compound semiconductor and its nucleocapsid
One of structure is a variety of.The quanta point material further include doped or non-doped inorganic Ca-Ti ore type semiconductor, and/or
Hybrid inorganic-organic Ca-Ti ore type semiconductor.Specifically, the inorganic Ca-Ti ore type semiconductor structure general formula is AMX3,
Middle A is Cs+Ion, M are divalent metal, including but not limited to Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、
Fe2+、Ge2+、Yb2+、Eu2+, X is halide anion, including but not limited to Cl-、Br-、I-.The hybrid inorganic-organic perovskite
Type semiconductor structure general formula is BMX3, wherein B is organic amine cation, including but not limited to CH3(CH2)n-2NH3 +(n >=2) or
NH3(CH2)nNH3 2+(n≥2).As n=2, inorganic metal hal ide octahedron MX6 4-It is connected by way of total top, metal sun
Ion M is located at the octahedral body-centered of halogen, and organic amine cation B is filled in the gap between octahedron, what formation infinitely extended
Three-dimensional structure；As n > 2, the inorganic metal hal ide octahedron MX that is connected in a manner of total top6 4-Extend shape in two-dimensional directional
Layered structure, Intercalation reaction organic amine cation bilayer (protonation monoamine) or organic amine cation monolayer (matter
Sonization diamine), organic layer and inorganic layer mutually overlap and form stable two-dimensional layered structure；M is divalent metal, including
But it is not limited to Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+；X is halide anion, packet
It includes but is not limited to Cl-、Br-、I-。
In the embodiment of the present invention, the first ionic liquid is provided between the top electrode and the quantum dot light emitting layer
Layer, first ionic liquid layer are made of ionic liquid, and the ionic liquid is by organic cation and inorganic anion group
At salt (without containing other molecules or reagent).Since ionic liquid has certain viscosity, in nanometer grade thickness model
In enclosing, it can adhere to form functional layer.Specifically, first ionic liquid layer by contain only anion and cation first from
Sub- liquid is made, and first ionic liquid is in a liquid state at -10~200 DEG C.Thus obtained light emitting diode with quantum dots exists
It exchanges under electric drive, first ionic liquid layer forms interface pair at the interface of the quantum dot light emitting layer and the top electrode
Electric layer, and different types of carrier (electronics or hole) is generated respectively at interfacial electric double layer both ends, electronics or hole are in electric field
It is migrated under effect to quantum dot light emitting layer, finally the recombination luminescence at quantum dot light emitting layer.Particularly, in the case where exchanging electro ultrafiltration,
The carrier type at interfacial electric double layer both ends and effect are on the contrary, to realize quantum dot light emitting two when applying positive pressure and applying negative pressure
The exchange electric drive of pole pipe shines.Specifically, the cation in ionic liquid is close when applying negative voltage to the top electrode
Top electrode, makes the interface accumulation electronics of first ionic liquid layer and the top electrode, and the quantum dot light emitting layer and institute
The interface for belonging to the first ionic liquid layer generates hole；Anion when applying positive voltage to the top electrode, in ionic liquid
Close to the top electrode, make the interface of first ionic liquid layer and top electrode accumulation hole, and the quantum dot is sent out
The interface of photosphere and first ionic liquid layer generates electronics, and answers with the hole for being gathered in the quantum dot light emitting bed boundary
It closes, goes out recombination luminescence in the quantum dot light emitting layer.
Preferably, first ionic liquid layer is made of inorganic anion and organic cation, to guarantee to be consequently formed
Ionic liquid keep liquid condition under the conditions of -10~200 DEG C.It is further preferred that the organic cation includes alkyl
Quaternary ammonium ion [NRxH4-x]+, alkyl quaternary phosphonium ion [PRxH4-x]+, alkyl-substituted imidazol ion [R1R3im]+, it is alkyl-substituted
Pyridinium ion [RPy]+；And/or the inorganic anion is halide ion or inorganic acid ion.Preferred anion or cation
Type, can be mobile rapidly in the case where exchanging electric drive, and forms boundary at the interface of the quantum dot light emitting layer and the top electrode
Face electric double layer.It is furthermore preferred that the organic cation be alkyl quaternary ammonium ion, alkyl-substituted imidazol ion, specifically include but
It is not limited to 1- butyl -3- methyl imidazolium cation, N, N- diethyl-N- methyl-N- (n- propyl) ammonium cation, N, N- diethyl
At least one of base-N- methyl-(2- methoxyethyl) ammonium cation.The halide ion includes but is not limited to F-、Cl-、Br-、
I-At least one of；The inorganic acid ion includes BF4 -、PF6 -、CF3SO3 -、CF3COO-、(CF3SO2)3C-、(C2F5SO2)3C-、(CF3SO2)2N-、C3F7COO-、C4F9SO3 -、(C2F5SO2)2N-、SbF6 -、AsF6 -、CB11H12 -、NO2 -、NO3 -、ClO4 -In
At least one, more preferably CF3SO3 -、BF4 -At least one of.
The embodiment of the present invention can be selected from above-mentioned inorganic negative particle and organic cation, form ionic liquid.As
Preferred embodiment, first ionic liquid layer is by N, three ammonium fluoroborate of N- diethyl-N- methyl-N- (n- propyl) trifluoromethyl
(Et2PrNMe-CF3BF3), 1- butyl -3- methylimidazole fluoroform sulphonate (BMIM-OTF), N, N- diethyl-N- methyl-N-
Bis- (trimethyl fluoride sulfonyl) acid imides (DEME-TFSI) of (2- methoxy ethyl) ammonium, N, N- diethyl-N- methyl-N- (2- first
Oxygroup ethyl) tetrafluoroborate (DEME-BF4) at least one of be made.The first ionic liquid layer being consequently formed, energy
Enough in the case where exchanging electric drive, zwitterion can be rapidly separated and displacement, thus in the quantum dot light emitting layer and the top
The interface of electrode forms interfacial electric double layer, so interfacial electric double layer both ends generate respectively different types of carrier (electronics or
Hole), electronics or hole are migrated under electric field action to quantum dot light emitting layer, finally the recombination luminescence at quantum dot light emitting layer.
The ionic liquid type of i.e. preferred first ionic liquid layer can mention under the premise of guaranteeing that exchange electric drive shines
High-luminous-efficiency and optical purity.
Further, first ionic liquid layer is the laminated construction formed by different ionic liquid, according to being constituted
Ionic liquid variety classes and heterogeneity, photism of the adjustable light emitting diode with quantum dots in the case where exchanging electric drive
Energy.
Preferably, first ionic liquid layer with a thickness of 10-500nm.If the thickness of first ionic liquid layer
It is excessively thin, then it is difficult to effectively cover the quantum dot light emitting layer, to cause defect, influences illumination effect；If first ion
The thickness of liquid level is blocked up, then possibly can not effectively be adhered to the quantum dot light emitting layer surface and form fixed layer structure, and
And the carrier number at interfacial electric double layer both ends may be will affect, to influence photism of the QLED device in the case where exchanging electric drive
Energy.
The top electrode can be prepared using this field conventional material, including metal material, conductive carbon material, conductive metal
One of oxide material is a variety of.Wherein, the metal material include but is not limited to Al, Ag, Cu, Mo, Au or they
Alloy, physical form include but is not limited to dense film, nano wire, nanosphere, nanometer rods, nanocone, nano-hollow ball or
Their mixture；The conductive carbon material includes but is not limited to doped or non-doped carbon nanotube, graphene, graphite oxide
Alkene, C60, graphite, carbon fiber, more empty carbon or their mixture；The conductive metal oxide material includes but is not limited to indium
One of doped stannum oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), aluminium-doped zinc oxide (AZO)
Or it is a variety of.
In above embodiment, as a kind of preferred situation, set between the quantum dot light emitting layer and the hearth electrode
It is equipped with the second ionic liquid layer.Quantum dot hair at the same time with first ionic liquid layer and second ionic liquid layer
In optical diode, different types of carrier can be orientated simultaneously in the ionic liquid layer at the quantum dot light emitting layer both ends, thus
Improve the luminous efficiency of device.Wherein, second ionic liquid layer is made of ionic liquid, and the ionic liquid is by organic
The salt of cation and inorganic anion composition.Since ionic liquid has certain viscosity, in nanometer grade thickness range
It is interior, it can adhere to form functional layer.Specifically, second ionic liquid layer is by containing only anion and the second cationic ion
Liquid is made, and second ionic liquid is in a liquid state at -10~200 DEG C.Thus obtained light emitting diode with quantum dots is being handed over
Under galvanic electricity driving, second ionic liquid layer forms the double electricity in interface at the interface of the quantum dot light emitting layer and the hearth electrode
Layer, and generate different types of carrier (electronics or hole), electronics or hole respectively at interfacial electric double layer both ends and make in electric field
It is migrated under to quantum dot light emitting layer, finally the recombination luminescence at quantum dot light emitting layer.Particularly, it in the case where exchanging electro ultrafiltration, applies
The carrier type at interfacial electric double layer both ends and effect are on the contrary, to realize two pole of quantum dot light emitting when adding positive pressure and applying negative pressure
The exchange electric drive of pipe shines.
Preferably, second ionic liquid layer is made of inorganic anion and organic cation, to guarantee to be consequently formed
Ionic liquid keep liquid condition under the conditions of -10~200 DEG C.It is further preferred that the organic cation includes alkyl
Quaternary ammonium ion [NRxH4-x]+, alkyl quaternary phosphonium ion [PRxH4-x]+, alkyl-substituted imidazol ion [R1R3im]+, it is alkyl-substituted
Pyridinium ion [RPy]+；And/or the inorganic anion is halide ion or inorganic acid ion.Preferred anion or cation
Type, can be mobile rapidly in the case where exchanging electric drive, and forms boundary at the interface of the quantum dot light emitting layer and the hearth electrode
Face electric double layer.It is furthermore preferred that the organic cation be alkyl quaternary ammonium ion, alkyl-substituted imidazol ion, specifically include but
It is not limited to 1- butyl -3- methyl imidazolium cation, N, N- diethyl-N- methyl-N- (n- propyl) ammonium cation, N, N- diethyl
At least one of base-N- methyl-(2- methoxyethyl) ammonium cation.The halide ion includes but is not limited to F-、Cl-、Br-、
I-At least one of；The inorganic acid ion includes BF4 -、PF6 -、CF3SO3 -、CF3COO-、(CF3SO2)3C-、(C2F5SO2)3C-、(CF3SO2)2N-、C3F7COO-、C4F9SO3 -、(C2F5SO2)2N-、SbF6 -、AsF6 -、CB11H12 -、NO2 -、NO3 -、ClO4 -In
At least one, more preferably CF3SO3 -、BF4 -At least one of.
The embodiment of the present invention can be selected from above-mentioned inorganic negative particle and organic cation, form ionic liquid.As
Preferred embodiment, second ionic liquid layer is by N, three ammonium fluoroborate of N- diethyl-N- methyl-N- (n- propyl) trifluoromethyl
(Et2PrNMe-CF3BF3), 1- butyl -3- methylimidazole fluoroform sulphonate (BMIM-OTF), N, N- diethyl-N- methyl-N-
Bis- (trimethyl fluoride sulfonyl) acid imides (DEME-TFSI) of (2- methoxy ethyl) ammonium, N, N- diethyl-N- methyl-N- (2- first
Oxygroup ethyl) tetrafluoroborate (DEME-BF4) at least one of be made.The second ionic liquid layer being consequently formed, energy
Enough in the case where exchanging electric drive, zwitterion can be rapidly separated and displacement, thus in the quantum dot light emitting layer and the bottom
The interface of electrode forms interfacial electric double layer, so interfacial electric double layer both ends generate respectively different types of carrier (electronics or
Hole), electronics or hole are migrated under electric field action to quantum dot light emitting layer, finally the recombination luminescence at quantum dot light emitting layer.
The ionic liquid type of i.e. preferred second ionic liquid layer can mention under the premise of guaranteeing that exchange electric drive shines
High-luminous-efficiency and optical purity.
Further, second ionic liquid layer is the laminated construction formed by different ionic liquid, according to being constituted
Ionic liquid variety classes and heterogeneity, photism of the adjustable light emitting diode with quantum dots in the case where exchanging electric drive
Energy.
Preferably, second ionic liquid layer with a thickness of 10-500nm.If the thickness of second ionic liquid layer
It is excessively thin, then it is difficult to effectively cover the quantum dot light emitting layer, to cause defect, influences illumination effect；If second ion
The thickness of liquid level is blocked up, then possibly can not effectively be adhered to the quantum dot light emitting layer surface and form fixed layer structure, and
And the carrier number at interfacial electric double layer both ends may be will affect, to influence photism of the QLED device in the case where exchanging electric drive
Energy.
In the embodiment of the present invention, first ionic liquid layer, second ionic liquid layer ionic type can be complete
It is exactly the same, can also be entirely different, can also part it is identical, as anionic type is identical, cationic difference；Or cationic phase
Same, anion difference.
In above embodiment, as another preferred situation, between the quantum dot light emitting layer and the hearth electrode
It is provided with insulating layer.The effect of the insulating layer is to obstruct the contact between the quantum dot light emitting layer and the hearth electrode,
Make the injection of different carriers pass through ionic liquid layer one end completely to generate, while preventing the current-carrying in the quantum dot light emitting layer
It is sub to be captured with the defects of bottom electrode interface state, to improve QLED device light emitting efficiency.The material of the insulating layer selects
From inorganic insulating material, and/or organic insulating material, wherein the inorganic insulating material includes but is not limited to adulterate or non-mix
Miscellaneous Al2O3、SiO2、ZrO2、HfO2、Ta2O5、LiF、BaF2、SiC、SnO2、MgO、WO3、BaTiO3、BaZrO3、Y2O3、
ZrSiO4、Si3N4, TiN or their mixture；The organic insulating material include but is not limited to epoxy resin, phenolic resin,
Fatty acid mono polymer, polyester or their mixture.It is further preferred that the thickness of insulating layer is 10-1000nm.
Particularly, if the insulating layer is too thin, insulation effect is unobvious, and electronics is likely to occur tunnel；And if described exhausted
Edge layer is too thick, then will increase the thickness of device, and device more difficult higher luminous efficiency of acquisition in low bias.
In above embodiment, as another preferred situation, between the quantum dot light emitting layer and the hearth electrode
It is provided with the second ionic liquid layer and insulating layer simultaneously, and second ionic liquid layer is arranged in the insulating layer and the amount
Between son point luminescent layer.In the case of this embodiment, the material and thickness of second ionic liquid layer and the insulating layer are such as
It is described above.The structure can be simultaneously or partially with the beneficial effect of QLED device architecture as described above.
In the above embodiment of the present invention, in order to preferably improve carrier mobility, it is preferred that the exchange is electrically driven (operated)
Light emitting diode with quantum dots further includes interfactial work ergosphere or interface-modifying layer, the interfactial work ergosphere or interface-modifying layer include but
It is not limited to electronic barrier layer, hole blocking layer, electrode modification layer, at least one layer in isolated protective layer.
Further, in the above embodiment of the present invention, the electrically driven (operated) light emitting diode with quantum dots of exchange further includes envelope
Assembling structure, the encapsulating structure can be local encapsulating structure, that is, partial encapsulation or full encapsulating structure.
In the above embodiment of the present invention, the electrically driven (operated) light emitting diode with quantum dots of exchange can be top emission type quantum
Point luminescent diode, or bottom emitting type light emitting diode with quantum dots.
The electrically driven (operated) light emitting diode with quantum dots of exchange provided in an embodiment of the present invention, in the quantum dot light emitting layer and institute
It states and introduces the first ionic liquid layer between top electrode.When light emitting diode with quantum dots connects alternating current, first ionic liquid
Body layer forms interfacial electric double layer at the interface of the quantum dot light emitting layer and the second electrode lay, and at interfacial electric double layer both ends
Different types of carrier (electronics or hole) is generated respectively, and electronics or hole are migrated under electric field action to quantum dot light emitting
Layer, the finally recombination luminescence at quantum dot light emitting layer.Specifically, applying positive pressure in the case where exchanging electro ultrafiltration and applying negative pressure when circle
Carrier type and the effect at face electric double layer both ends are on the contrary, to realize that the exchange electric drive of light emitting diode with quantum dots shines.
Compared with prior art, the alternating current driving light emitting diode with quantum dots of Ionic Liquid Modified provided in an embodiment of the present invention, one
Aspect does not both need that multiple dielectric layers are arranged, does not need the complex devices such as AC-DC conversion equipment, therefore, device architecture yet
Simply, mature preparation process is easy, is conducive to industrialization promotion；On the other hand, the introducing of first ionic liquid layer, Neng Gouyou
Effect ground realizes that the exchange electric drive of QLED device shines, and device light emitting efficiency is high, and performance is stablized.
The electrically driven (operated) light emitting diode with quantum dots of exchange provided in an embodiment of the present invention can be prepared by following methods to be obtained
?.
Correspondingly, the embodiment of the invention also provides a kind of preparation sides for exchanging electrically driven (operated) light emitting diode with quantum dots
Method, comprising the following steps:
S01. depositions of bottom electrode on substrate, deposits quantum dot light emitting layer on the hearth electrode；
S02. the first ionic liquid layer is deposited on the quantum dot light emitting layer；
S03. top electrode is deposited in first ionic liquid layer.
Specifically, the deposition of the hearth electrode, quantum dot light emitting layer, top electrode, can pass through conventional method in that art reality
It is existing.First ionic liquid layer preferably uses solution processing method to prepare.
It preferably, further include that the second ionic liquid layer is deposited on the hearth electrode before depositing quantum dot light emitting layer
And/or insulating layer.Two ionic liquid layer preferably uses solution processing method to prepare.
In the embodiment of the present invention, the deposition method of each layer can be chemical method, be also possible to physical method, wherein describedization
Method include but is not limited to chemical vapour deposition technique, successive ionic layer adsorption and reaction method, anodizing, strike,
One of coprecipitation is a variety of；The physical method include but is not limited to spin-coating method, print process, knife coating, dip-coating method,
Infusion method, spray coating method, roll coating process, casting method, slit coating method, strip rubbing method, thermal evaporation coating method, electron beam evaporation plating
Embrane method, magnetron sputtering method, multi-arc ion coating embrane method, physical vaporous deposition, atomic layer deposition method, pulsed laser deposition.
The preparation method of the electrically driven (operated) light emitting diode with quantum dots of exchange provided in an embodiment of the present invention, it is only necessary in routine
QLED device structure basis on, the first ionic liquid layer, method are introduced between quantum dot light emitting layer and top electrode
It is mature simple, it is easy to accomplish industrialization.
And the embodiment of the invention also provides the applications of the above-mentioned electrically driven (operated) light emitting diode with quantum dots of exchange.
Specifically, a kind of illuminating module, including the above-mentioned electrically driven (operated) light emitting diode with quantum dots of exchange.
And a kind of display device, including the above-mentioned electrically driven (operated) light emitting diode with quantum dots of exchange.
Illuminating module and display device provided in an embodiment of the present invention, due to containing the electrically driven (operated) quantum dot hair of above-mentioned exchange
Therefore optical diode is conducive to large-scale industrialization promotion application.
It is illustrated combined with specific embodiments below.
Embodiment 1
A kind of electrically driven (operated) light emitting diode with quantum dots of exchange, as shown in Figure 1, including the substrate 1 being cascading, bottom
Electrode 2, quantum dot light emitting layer 5, the first ionic liquid layer 6 and top electrode 7, wherein the substrate 1 is glass substrate, the bottom
Electrode 2 is ITO, and the quantum dot light emitting layer 5 is CdSe/ZnS quantum dot light emitting layer, and first ionic liquid layer 6 is N, N-
Three ammonium fluoroborate (Et of diethyl-N- methyl-N- (n- propyl) trifluoromethyl2PrNMe-CF3BF3) ionic liquid layer, with a thickness of
10nm, the top electrode 7 are Al.
The preparation method of the above-mentioned electrically driven (operated) light emitting diode with quantum dots of exchange, comprising the following steps:
S11. one layer of CdSe/ZnS quantum dot light emitting layer of spin coating on ITO electro-conductive glass；
S12. one layer of N of spin coating on CdSe/ZnS quantum dot light emitting layer, N- diethyl-N- methyl-N- (n- propyl) trifluoro
Methyl trifluoro ammonium borate (Et2PrNMe-CF3BF3) the first ionic liquid layer is formed, with a thickness of 10nm；
S13. one layer of Al is deposited in the first ionic liquid layer, obtains exchanging electrically driven (operated) light emitting diode with quantum dots.
The level structure figure for the electrically driven (operated) light emitting diode with quantum dots of exchange that embodiment 1 provides is as shown in Figure 2.
Embodiment 2
A kind of electrically driven (operated) light emitting diode with quantum dots of exchange, as shown in figure 3, including the substrate 1 being cascading, bottom
Electrode 2, the second ionic liquid layer 3, quantum dot light emitting layer 5, the first ionic liquid layer 6 and top electrode 7, wherein the substrate 1 is
Glass substrate, the hearth electrode 2 are ITO, and second ionic liquid layer 3 is 1- butyl -3- methylimidazole fluoroform sulphonate
(BMIM-OTF) ionic liquid layer, with a thickness of 20nm, the quantum dot light emitting layer 5 is CdSe/ZnS quantum dot light emitting layer, described
First ionic liquid layer 6 is N, three ammonium fluoroborate (Et of N- diethyl-N- methyl-N- (n- propyl) trifluoromethyl2PrNMe-
CF3BF3) ionic liquid layer, with a thickness of 10nm, the top electrode 7 is Al.
The preparation method of the above-mentioned electrically driven (operated) light emitting diode with quantum dots of exchange, comprising the following steps:
S21. one layer of 1- butyl -3- methylimidazole fluoroform sulphonate (BMIM-OTF) shape of spin coating on ITO electro-conductive glass
At the second ionic liquid layer, with a thickness of 20nm；
S22. one layer of CdSe/ZnS quantum dot light emitting layer of spin coating in the second ionic liquid layer；
S23. one layer of N of spin coating on CdSe/ZnS quantum dot light emitting layer, N- diethyl-N- methyl-N- (n- propyl) trifluoro
Methyl trifluoro ammonium borate (Et2PrNMe-CF3BF3) the first ionic liquid layer is formed, with a thickness of 10nm；
S24. one layer of Al is deposited in the first ionic liquid layer, obtains exchanging electrically driven (operated) light emitting diode with quantum dots.
Embodiment 3
A kind of electrically driven (operated) light emitting diode with quantum dots of exchange, as shown in figure 4, including the substrate 1 being cascading, bottom
Electrode 2, insulating layer 4, quantum dot light emitting layer 5, the first ionic liquid layer 6 and top electrode 7, wherein the substrate 1 is glass lined
Bottom, the hearth electrode 2 are ITO, and the insulating layer 4 is Al2O3, with a thickness of 50nm, the quantum dot light emitting layer 5 is CdSe/ZnS
Quantum dot light emitting layer, first ionic liquid layer 6 are N, N- diethyl-N- methyl-N- (2- methoxy ethyl) tetrafluoro boric acid
Quaternary ammonium salt (DEME-BF4) ionic liquid layer, with a thickness of 10nm, the top electrode 7 is Al.
The preparation method of the above-mentioned electrically driven (operated) light emitting diode with quantum dots of exchange, comprising the following steps:
S31. one layer of Al of spin coating on ITO electro-conductive glass2O3Insulating layer is formed, with a thickness of 50nm；
S32. one layer of CdSe/ZnS quantum dot light emitting layer of spin coating on the insulating layer；
S33. one layer of N of spin coating on CdSe/ZnS quantum dot light emitting layer, N- diethyl-N- methyl-N- (2- methoxyl group second
Base) tetrafluoroborate (DEME-BF4) the first ionic liquid layer is formed, with a thickness of 10nm；
S34. one layer of Al is deposited in the first ionic liquid layer, obtains exchanging electrically driven (operated) light emitting diode with quantum dots.
It should be appreciated that above-mentioned 3 embodiments are only used to illustrate electrically driven (operated) two pole of quantum dot light emitting of three kinds of different exchanges
The structure composition of pipe is not intended to limit the material, thickness and deposition method of its specific functional layer.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (13)
1. a kind of electrically driven (operated) light emitting diode with quantum dots of exchange, including substrate, hearth electrode, the quantum dot hair being cascading
Photosphere, top electrode, which is characterized in that further include the first ion being arranged between the top electrode and the quantum dot light emitting layer
Liquid level, first ionic liquid layer are made of the first ionic liquid for containing only anion and cation, first ion
Liquid is in a liquid state at -10~200 DEG C, and in the case where exchanging electric drive, first ionic liquid layer is in the quantum dot light emitting
The interface of layer and the top electrode forms interfacial electric double layer.
2. exchanging electrically driven (operated) light emitting diode with quantum dots as described in claim 1, which is characterized in that sent out in the quantum dot
The second ionic liquid layer and/or insulating layer are provided between photosphere and the hearth electrode, wherein second ionic liquid layer by
The second ionic liquid for containing only anion and cation is made, and second ionic liquid is in a liquid state at -10~200 DEG C,
When only the second ionic liquid layer of setting between the quantum dot light emitting layer and the hearth electrode, in the case where exchanging electric drive,
Second ionic liquid layer forms interfacial electric double layer at the interface of the quantum dot light emitting layer and the hearth electrode；
When second ionic liquid layer and the insulating layer exist simultaneously, the second ionic liquid layer setting is described exhausted
Between edge layer and the quantum dot light emitting layer.
3. exchanging electrically driven (operated) light emitting diode with quantum dots as claimed in claim 2, which is characterized in that first ionic liquid
Body layer, second ionic liquid layer are made of inorganic anion and organic cation, and first ionic liquid layer, described
The ionic type of second ionic liquid layer is identical or different.
4. exchanging electrically driven (operated) light emitting diode with quantum dots as claimed in claim 3, which is characterized in that the organic cation
Including alkyl quaternary ammonium ion, alkyl quaternary phosphonium ion, alkyl-substituted imidazol ion, alkyl-substituted pyridinium ion；And/or
The inorganic anion is halide ion or inorganic acid ion.
5. exchanging electrically driven (operated) light emitting diode with quantum dots as claimed in claim 4, which is characterized in that the organic cation
For alkyl quaternary ammonium ion, alkyl-substituted imidazol ion, including 1- butyl -3- methyl imidazolium cation, N, N- diethyl-N- first
Base-N- (n- propyl) ammonium cation, N, at least one of N- diethyl-N- methyl-(2- methoxyethyl) ammonium cation.
6. exchanging electrically driven (operated) light emitting diode with quantum dots as claimed in claim 4, which is characterized in that the halide ion packet
Include F-、Cl-、Br-、I-At least one of；The inorganic acid ion includes BF4 -、PF6 -、CF3SO3 -、CF3COO-、(CF3SO2)3C-、(C2F5SO2)3C-、(CF3SO2)2N-、C3F7COO-、C4F9SO3 -、(C2F5SO2)2N-、SbF6 -、AsF6 -、CB11H12 -、NO2 -、
NO3 -、ClO4 -At least one of.
7. the electrically driven (operated) light emitting diode with quantum dots of exchange as described in claim 4-6 is any, which is characterized in that described first
Ionic liquid layer is by N, three ammonium fluoroborate of N- diethyl-N- methyl-N- (n- propyl) trifluoromethyl, 1- butyl -3- methylimidazole
Fluoroform sulphonate, N, bis- (trimethyl fluoride sulfonyl) acid imides of N- diethyl-N- methyl-N- (2- methoxy ethyl) ammonium, N,
At least one of N- diethyl-N- methyl-N- (2- methoxy ethyl) tetrafluoroborate is made；And/or
Second ionic liquid layer is by N, three ammonium fluoroborate of N- diethyl-N- methyl-N- (n- propyl) trifluoromethyl, 1- fourth
Base -3- methylimidazole fluoroform sulphonate, N, bis- (the trifluoromethyl sulphurs of N- diethyl-N- methyl-N- (2- methoxy ethyl) ammonium
Acyl) acid imide, N, at least one of N- diethyl-N- methyl-N- (2- methoxy ethyl) tetrafluoroborate is made.
8. exchanging electrically driven (operated) light emitting diode with quantum dots as claimed in claim 1 or 2, which is characterized in that described first from
Sub- liquid level with a thickness of 10-500nm.
9. exchanging electrically driven (operated) light emitting diode with quantum dots as claimed in claim 2, which is characterized in that second ionic liquid
Body layer with a thickness of 10-500nm；And/or
The insulating layer with a thickness of 10-1000nm.
10. a kind of preparation method for exchanging electrically driven (operated) light emitting diode with quantum dots, comprising the following steps:
Depositions of bottom electrode on substrate deposits quantum dot light emitting layer on the hearth electrode；
The first ionic liquid layer is deposited on the quantum dot light emitting layer, first ionic liquid layer is by containing only anion and sun
First ionic liquid of ion is made, and first ionic liquid is in a liquid state at -10~200 DEG C；
Top electrode is deposited in first ionic liquid layer, in the case where exchanging electric drive, first ionic liquid layer is described
The interface of quantum dot light emitting layer and the top electrode forms interfacial electric double layer.
11. exchanging the preparation method of electrically driven (operated) light emitting diode with quantum dots as claimed in claim 10, which is characterized in that also
Including depositing the second ionic liquid layer and/or insulating layer on the hearth electrode, wherein second ionic liquid layer is by containing only
Second ionic liquid of anion and cation is made, and second ionic liquid is in a liquid state at -10~200 DEG C,
When only the second ionic liquid layer of setting between the quantum dot light emitting layer and the hearth electrode, in the case where exchanging electric drive,
Second ionic liquid layer forms interfacial electric double layer at the interface of the quantum dot light emitting layer and the hearth electrode；
When second ionic liquid layer and the insulating layer exist simultaneously, the second ionic liquid layer setting is described exhausted
Between edge layer and the quantum dot light emitting layer.
12. a kind of illuminating module, which is characterized in that including the electrically driven (operated) quantum dot hair of any exchange of claim 1-9
Optical diode.
13. a kind of display device, which is characterized in that including the electrically driven (operated) quantum dot hair of any exchange of claim 1-9
Optical diode.
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| CN108932926A (en) * | 2017-05-23 | 2018-12-04 | Tcl集团股份有限公司 | A kind of QLED device and its reversed driven mode |
| CN109064968A (en) * | 2017-05-23 | 2018-12-21 | Tcl集团股份有限公司 | A kind of driving method of active driving quantum dot display panel |
| CN108932927A (en) * | 2017-05-23 | 2018-12-04 | Tcl集团股份有限公司 | A kind of driving method of quantum dot display panel |
| CN108932928A (en) * | 2017-05-23 | 2018-12-04 | Tcl集团股份有限公司 | A kind of driving method of passive type driving quantum dot display panel |
| CN108962129A (en) * | 2017-05-23 | 2018-12-07 | Tcl集团股份有限公司 | A kind of QLED device and its backward voltage drive mode |
| CN108962133A (en) * | 2017-05-23 | 2018-12-07 | Tcl集团股份有限公司 | A kind of QLED device and its reverse current drive mode |
| CN108962130A (en) | 2017-05-23 | 2018-12-07 | Tcl集团股份有限公司 | It is a kind of to be driven in the reverse direction method applied to default in video display process |
| CN108962127A (en) * | 2017-05-23 | 2018-12-07 | Tcl集团股份有限公司 | A kind of QLED device and its reverse drive mode |
| CN108832010A (en) * | 2018-05-29 | 2018-11-16 | 合肥工业大学 | A kind of perovskite light emitting diode and preparation method thereof of ionic liquid as electric charge injection layer |
| CN111244308B (en) * | 2018-11-29 | 2021-09-10 | Tcl科技集团股份有限公司 | Quantum dot light emitting layer and quantum dot light emitting diode |
| CN111244302B (en) * | 2018-11-29 | 2021-09-10 | Tcl科技集团股份有限公司 | Quantum dot light-emitting diode and preparation method thereof |
| CN111244301A (en) * | 2018-11-29 | 2020-06-05 | Tcl集团股份有限公司 | Quantum dot light emitting diode |
| CN111244300A (en) * | 2018-11-29 | 2020-06-05 | Tcl集团股份有限公司 | Quantum dot light-emitting diode and preparation method thereof |
| CN111354856A (en) * | 2018-12-24 | 2020-06-30 | Tcl集团股份有限公司 | Quantum dot light-emitting diode |
| CN111384269B (en) * | 2018-12-29 | 2021-08-03 | Tcl科技集团股份有限公司 | Quantum dot light-emitting diode and preparation method thereof |
| CN110137359B (en) * | 2019-04-09 | 2021-05-18 | 华中科技大学 | Method and device for inhibiting current drift of perovskite photoelectric detector by using alternating current |
| CN110729411A (en) * | 2019-11-29 | 2020-01-24 | 福州大学 | Alternating current driven flexible QLED device |
| US11377723B2 (en) | 2020-03-30 | 2022-07-05 | Tcl China Star Optoelectronics Technology Co., Ltd. | Method of patterning quantum dots, device using same, and system thereof |
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