CN106549111A - Exchange electrically driven (operated) light emitting diode with quantum dots, its preparation method and application - Google Patents
Exchange electrically driven (operated) light emitting diode with quantum dots, its preparation method and application Download PDFInfo
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- CN106549111A CN106549111A CN201611116039.5A CN201611116039A CN106549111A CN 106549111 A CN106549111 A CN 106549111A CN 201611116039 A CN201611116039 A CN 201611116039A CN 106549111 A CN106549111 A CN 106549111A
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Abstract
The invention provides a kind of exchange electrically driven (operated) light emitting diode with quantum dots, including the substrate, hearth electrode, quantum dot light emitting layer, top electrode that are cascading, also 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 up of the first ionic liquid for only containing anion and cation, first ionic liquid is in a liquid state at 10～200 DEG C, and under exchange 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 pole of quantum dot light emitting of exchange
Pipe, its preparation method and application.
Background technology
Quantum dot (Quantum dot, QD) is a kind of nano material of quasi-zero dimension (Quasi-zero-dimensional),
It is made up of the atom of minority, it is special which has that fluorescence efficiency is high, luminescent spectrum is narrow, emission wavelength is adjustable, spectral purity is high etc.
Advantage, the traditional organic or inorganic illuminator of potential replacement become the core of luminescent device of future generation.Based on quantum dot
Light emitting diode be referred to as light emitting diode with quantum dots (Quantum dot light-emitting diode, QLED), its
With luminescent properties are good, the outstanding advantages such as long service life, preparation process is simple, excitation are high, colour temperature is good, progressively take
Become new " green " illuminating source for traditional lighting material.
The QLED devices studied at present, the overwhelming majority belong to dc electroluminescence device, and its operation principle mainly will
Direct current is carried on two electrodes of the QLED devices with typical sandwich structure, under forward bias (positive pole connect anode,
Negative pole connects negative electrode), electronics and hole are injected in electron transfer layer and hole transmission layer from negative electrode and anode respectively, subsequently into
To quantum dot light emitting layer, exciton, exciton recombination luminescence are formed.Although adopting the QLED devices of dc electroluminescence form at present
Research is more ripe, and achieves quickly development at aspects such as luminous efficiencies, but this device needs galvanic current
Supply ability normal work, and the electricity consumption in living at present or producing is mainly alternating current, in order to ensure dc electroluminescence
The normal work of QLED devices ,-current/direct-current conversion device of on the one hand can additionally increasing exchanges to luminescent system, but so 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 devices.On the other hand, can be with
From the structure of QLED devices, 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-k, such as silica, aluminum oxide, hafnium oxide, tantalum oxide play stop two ends electricity
The effect of pole electric charge injection, make in QLED devices for recombination luminescence carrier be no longer external circuit injection carrier.Though
So dielectric layer structure can obtain the electrically driven (operated) QLED devices of exchange, but its complex structure, and preparation technology is loaded down with trivial details, and QLED devices
Luminous efficiency can be greatly reduced, and be unfavorable for large-scale Industry Promotion.Therefore, prior art need further research
And development.
The content of the invention
It is an object of the invention to provide a kind of exchange electrically driven (operated) light emitting diode with quantum dots and preparation method thereof, it is intended to
Solving the electrically driven (operated) light emitting diode with quantum dots of existing exchange needs multiple dielectric layers, causes labyrinth；Or existing alternating current
The light emitting diode with quantum dots of driving is needed using complex devices such as AC-DC conversion equipments, is unfavorable for Industry Promotion
Problem.
Another object of the present invention is to provide kind of an application for the electrically driven (operated) light emitting diode with quantum dots of exchange.
The present invention is achieved in that a kind of electrically driven (operated) light emitting diode with quantum dots of exchange, including being cascading
Substrate, hearth electrode, quantum dot light emitting layer, top electrode, also including be arranged on the top electrode and the quantum dot light emitting layer it
Between the first ionic liquid layer, first ionic liquid layer is made up of the first ionic liquid for only containing anion and cation,
First ionic liquid is in a liquid state at -10～200 DEG C, and under exchange 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 is comprised the following steps：
The 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 electrically driven (operated) light emitting diode with quantum dots of above-mentioned exchange.
And, a kind of display device, including the electrically driven (operated) light emitting diode with quantum dots of above-mentioned exchange.
The electrically driven (operated) light emitting diode with quantum dots of exchange that the present invention is provided, in the quantum dot light emitting layer and the 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 quantum dot light emitting layer forms interfacial electric double layer with the interface of the top electrode, and produces respectively not at interfacial electric double layer two ends
The carrier (electronics or hole) of same type, electronics or hole are migrated to quantum dot light emitting layer, finally in amount under electric field action
Recombination luminescence at son point luminescent layer.Specifically, under exchange electro ultrafiltration, apply malleation and interfacial electric double layer two ends when applying negative pressure
Carrier type and effect conversely, so as to realize light emitting diode with quantum dots exchange electric drive light.With prior art phase
Than the alternating current of the Ionic Liquid Modified that the present invention is provided drives light emitting diode with quantum dots, on the one hand, need not both arrange many
Individual dielectric layer, it is not required that the complex device such as AC-DC conversion equipment, therefore, device architecture is simple, mature preparation process is simple
Just, beneficial to Industry Promotion；On the other hand, the introducing of first ionic liquid layer, can be effectively realized QLED devices
Exchange electric drive lights, and device light emitting efficiency is high, stable performance.
The preparation method of the electrically driven (operated) light emitting diode with quantum dots of exchange that the present invention is provided, it is only necessary in conventional QLED
On the architecture basics of device, the first ionic liquid layer, the ripe 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 that the present invention is provided, due to containing electrically driven (operated) two pole of quantum dot light emitting of above-mentioned exchange
Pipe, therefore, be conducive to large-scale Industry Promotion application.
Description of the drawings
Fig. 1 is the structural representation of the electrically driven (operated) light emitting diode with quantum dots of exchange that the embodiment of the present invention 1 is provided；
Fig. 2 is the level structure design sketch of the electrically driven (operated) light emitting diode with quantum dots of exchange that the embodiment of the present invention 1 is provided；
Fig. 3 is the structural representation of the electrically driven (operated) light emitting diode with quantum dots of exchange that the embodiment of the present invention 2 is provided；
Fig. 4 is the structural representation of the electrically driven (operated) light emitting diode with quantum dots of exchange that the embodiment of the present invention 3 is provided.
Specific embodiment
In order that the technical problem to be solved in the present invention, technical scheme and beneficial effect become more apparent, 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 to explain
The present invention, is not intended to limit the present invention.
A kind of electrically driven (operated) light emitting diode with quantum dots of exchange is embodiments provided, including what is be cascading
Substrate, hearth electrode, quantum dot light emitting layer, top electrode, also including being arranged between the top electrode and the quantum dot light emitting layer
The first ionic liquid layer, first ionic liquid layer is made up of the first ionic liquid for only containing anion and cation, institute
State the first ionic liquid to be in a liquid state at -10～200 DEG C, and under exchange 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 is not strictly limited, and can select rigid substrate, it is also possible to select flexible liner
Bottom.Wherein, the rigid substrate includes but is not limited to glass, tinsel；The flexible substrate is including but 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 area conventional material, including metal material, conductive carbon material, conducting metal
One or more in oxide material.Wherein, the metal material include but is not limited to Al, Ag, Cu, Mo, Au or they
Alloy, its 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 CNT, Graphene, graphite oxide
Alkene, C60, graphite, carbon fiber, many sky carbon or their mixture；The conducting metal oxide material includes but is not limited to indium
One kind in doped stannum oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), aluminium-doped zinc oxide (AZO)
Or it is various.
The quantum dot light emitting layer can adopt conventional quanta point material to prepare, and the quanta point material can be selected from doping
Or the II-V compound semiconductors of undoped, Group III-V compound semiconductor, group IV-VI compound semiconductor and its nucleocapsid
One or more in structure.The quanta point material also 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 formula is AMX3, its
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 formula is BMX3, wherein B be 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-Connected by way of common top, metal sun
Ion M is located at the octahedral body-centered of halogen, and organic amine cation B is filled in the space between octahedron, forms unlimited extension
Three-dimensional structure；As n ＞ 2, the inorganic metal hal ide octahedron MX connected in the way of common 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 is mutually overlapped with inorganic layer and forms 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, bag
Include but be 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 up of ionic liquid, and the ionic liquid is by organic cation and inorganic anion group
Into salt (not containing other molecules or reagent).As ionic liquid has certain viscosity, therefore, in nanometer grade thickness model
In enclosing, can adhere to form functional layer.Specifically, first ionic liquid layer by only contain the first of anion and cation 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
Under exchange electric drive, it is double that first ionic liquid layer forms interface 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 produced respectively at interfacial electric double layer two ends, electronics or hole are in electric field
Migrate under effect to quantum dot light emitting layer, finally the recombination luminescence at the quantum dot light emitting layer.Especially, under exchange electro ultrafiltration,
The carrier type and effect for applying malleation with interfacial electric double layer two ends during applying negative pressure is conversely, so as to realize quantum dot light emitting two
The exchange electric drive of pole pipe lights.Specifically, when negative voltage is applied to the top electrode, the cation in ionic liquid is close
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 produces hole；When positive voltage is applied to the top electrode, the anion in ionic liquid
Near the top electrode, the interface accumulation hole of first ionic liquid layer and the top electrode is made, and the quantum dot is sent out
Photosphere produces electronics with the interface of first ionic liquid layer, and multiple with the hole for being gathered in the quantum dot light emitting bed boundary
Close, go out recombination luminescence in the quantum dot light emitting layer.
Preferably, first ionic liquid layer is made up of inorganic anion and organic cation, to ensure 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 rapid mobile under exchange 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 cations, N, N- diethyl-N- methyl-N- (n- propyl group) ammonium cations, N, N- diethyls
At least one in base-N- methyl-(2- methoxyethyls) ammonium cation.The halide ion includes but is not limited to F-、Cl-、Br-、
I-In at least one；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 -In at least one.
The embodiment of the present invention can be selected from above-mentioned inorganic cloudy particle and organic cation, constitute ionic liquid.As
Preferred embodiment, first ionic liquid layer is by N, N- diethyl-N- methyl-N- (n- propyl group) three ammonium fluoroborates of trifluoromethyl
(Et2PrNMe-CF3BF3), 1- butyl -3- methylimidazole fluoroform sulphonates (BMIM-OTF), N, N- diethyl-N- methyl-N-
(2- methoxy ethyls) ammonium double (trimethyl fluoride sulfonyl) acid imide (DEME-TFSI), N, N- diethyl-N- methyl-N- (2- first
Epoxide ethyl) tetrafluoroborate (DEME-BF4) at least one make.The first ionic liquid layer being consequently formed, energy
Enough under exchange electric drive, zwitterion can be rapidly separated and displacement, so as on the quantum dot light emitting layer and the top
The interface of electrode forms interfacial electric double layer, so interfacial electric double layer two ends produce respectively different types of carrier (electronics or
Hole), electronics or hole are migrated to quantum dot light emitting layer under electric field action, finally the recombination luminescence at the quantum dot light emitting layer.
The ionic liquid type of i.e. preferred first ionic liquid layer, can carry on the premise of ensureing that exchange electric drive is luminous
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, can with quantum point luminescent diode exchange electric drive under photism
Energy.
Preferably, the thickness of first ionic liquid layer is 10-500nm.If the thickness of first ionic liquid layer
Cross thin, be then difficult to effectively cover the quantum dot light emitting layer, so as to cause defect, affect illumination effect；If first ion
The thickness of liquid level is blocked up, then possibly cannot effectively stick to the quantum dot light emitting layer surface and form fixed Rotating fields, and
And the carrier number at interfacial electric double layer two ends may be affected, so as to affect photism of the QLED devices under exchange electric drive
Energy.
The top electrode can be prepared using this area conventional material, including metal material, conductive carbon material, conducting metal
One or more in oxide material.Wherein, the metal material include but is not limited to Al, Ag, Cu, Mo, Au or they
Alloy, its 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 CNT, Graphene, graphite oxide
Alkene, C60, graphite, carbon fiber, many sky carbon or their mixture；The conducting metal oxide material includes but is not limited to indium
One kind in doped stannum oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), aluminium-doped zinc oxide (AZO)
Or it is various.
In above-mentioned 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.There is first ionic liquid layer and the quantum dot of second ionic liquid layer to send out at the same time
In optical diode, different types of carrier can be orientated simultaneously in the ionic liquid layer at the quantum dot light emitting layer two ends, so as to
Improve the luminous efficiency of device.Wherein, second ionic liquid layer is made up of ionic liquid, and the ionic liquid is by organic
The salt of cation and inorganic anion composition.As ionic liquid has certain viscosity, therefore, in nanometer grade thickness scope
It is interior, can adhere to form functional layer.Specifically, second ionic liquid layer is by the second ion for only containing anion and cation
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 stream electric drive, 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 different types of carrier (electronics or hole) is produced respectively at interfacial electric double layer two ends, electronics or hole are made in electric field
Migrate with to quantum dot light emitting layer, finally the recombination luminescence at the quantum dot light emitting layer.Especially, under exchange electro ultrafiltration, apply
Plus malleation with apply negative pressure when interfacial electric double layer two ends carrier type and effect conversely, so as to realize two pole of quantum dot light emitting
The exchange electric drive of pipe lights.
Preferably, second ionic liquid layer is made up of inorganic anion and organic cation, to ensure 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 rapid mobile under exchange 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 cations, N, N- diethyl-N- methyl-N- (n- propyl group) ammonium cations, N, N- diethyls
At least one in base-N- methyl-(2- methoxyethyls) ammonium cation.The halide ion includes but is not limited to F-、Cl-、Br-、
I-In at least one；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 -In at least one.
The embodiment of the present invention can be selected from above-mentioned inorganic cloudy particle and organic cation, constitute ionic liquid.As
Preferred embodiment, second ionic liquid layer is by N, N- diethyl-N- methyl-N- (n- propyl group) three ammonium fluoroborates of trifluoromethyl
(Et2PrNMe-CF3BF3), 1- butyl -3- methylimidazole fluoroform sulphonates (BMIM-OTF), N, N- diethyl-N- methyl-N-
(2- methoxy ethyls) ammonium double (trimethyl fluoride sulfonyl) acid imide (DEME-TFSI), N, N- diethyl-N- methyl-N- (2- first
Epoxide ethyl) tetrafluoroborate (DEME-BF4) at least one make.The second ionic liquid layer being consequently formed, energy
Enough under exchange electric drive, zwitterion can be rapidly separated and displacement, so as at the quantum dot light emitting layer and the bottom
The interface of electrode forms interfacial electric double layer, so interfacial electric double layer two ends produce respectively different types of carrier (electronics or
Hole), electronics or hole are migrated to quantum dot light emitting layer under electric field action, finally the recombination luminescence at the quantum dot light emitting layer.
The ionic liquid type of i.e. preferred second ionic liquid layer, can carry on the premise of ensureing that exchange electric drive is luminous
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, can with quantum point luminescent diode exchange electric drive under photism
Energy.
Preferably, the thickness of second ionic liquid layer is 10-500nm.If the thickness of second ionic liquid layer
Cross thin, be then difficult to effectively cover the quantum dot light emitting layer, so as to cause defect, affect illumination effect；If second ion
The thickness of liquid level is blocked up, then possibly cannot effectively stick to the quantum dot light emitting layer surface and form fixed Rotating fields, and
And the carrier number at interfacial electric double layer two ends may be affected, so as to affect photism of the QLED devices under exchange electric drive
Energy.
In the embodiment of the present invention, first ionic liquid layer, second ionic liquid layer ionic type can be with complete
Exactly the same, it is also possible to entirely different, acceptable part is identical, as anionic type is identical, cation is different；Or cation phase
Same, anion is different.
In above-mentioned embodiment, as another kind of preferred situation, between the quantum dot light emitting layer and the hearth electrode
It is provided with insulating barrier.The effect of the insulating barrier is to intercept the contact between the quantum dot light emitting layer and the hearth electrode,
The injection of different carriers is made to produce by ionic liquid layer one end completely, while preventing the current-carrying in the quantum dot light emitting layer
The sub defect state with the bottom electrode interface is captured, so as to improve QLED device light emitting efficiencies.The material choosing of the insulating barrier
From inorganic insulating material, and/or organic insulation, wherein, the inorganic insulating material including but not limited to adulterates or non-mixes
Miscellaneous Al2O3、SiO2、ZrO2、HfO2、Ta2O5、LiF、BaF2、SiC、SnO2、MgO、WO3、BaTiO3、BaZrO3、Y2O3、
ZrSiO4、Si3N4, TiN or their mixture；The organic insulation 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.
Especially, if the insulating barrier is too thin, its insulation effect is not obvious, and electronics is likely to occur tunnel；And if described exhausted
Edge layer is too thick, then can increase the thickness of device, and device higher luminous efficiency of more difficult acquisition in low bias.
In above-mentioned 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 barrier simultaneously, and second ionic liquid layer is arranged on the insulating barrier 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 barrier are such as
It is mentioned above.The structure can simultaneously or partially have the beneficial effect of QLED device architectures 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 also include interfactial work ergosphere or interface-modifying layer, the interfactial work ergosphere or interface-modifying layer include but
At least one of which being not limited in electronic barrier layer, hole blocking layer, electrode modification layer, isolated protective layer.
Further, it is in the above embodiment of the present invention, described to exchange electrically driven (operated) light emitting diode with quantum dots also including envelope
Assembling structure, the encapsulating structure can be partial encapsulation or full encapsulating structure for local encapsulating structure.
In the above embodiment of the present invention, the electrically driven (operated) light emitting diode with quantum dots of the exchange can be top emission type quantum
Point luminescent diode, or bottom emitting type light emitting diode with quantum dots.
It is provided in an embodiment of the present invention to exchange electrically driven (operated) light emitting diode with quantum dots, in the quantum dot light emitting layer and institute
State.When light emitting diode with quantum dots connects alternating current, first ionic liquid
Body layer forms interfacial electric double layer with the interface of the second electrode lay in the quantum dot light emitting layer, and at interfacial electric double layer two ends
Different types of carrier (electronics or hole) is produced respectively, and electronics or hole are migrated to quantum dot light emitting under electric field action
Layer, the finally recombination luminescence at the quantum dot light emitting layer.Specifically, under exchange electro ultrafiltration, apply malleation and apply negative pressure when circle
The carrier type and effect at face electric double layer two ends is conversely, so as to the exchange electric drive for realizing light emitting diode with quantum dots lights.
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, need not both arrange multiple dielectric layers, it is not required that the complex device such as AC-DC conversion equipment, therefore, device architecture
Simply, mature preparation process is easy, beneficial to Industry Promotion；On the other hand, the introducing of first ionic liquid layer, Neng Gouyou
Realize to effect that the exchange electric drive of QLED devices lights, and device light emitting efficiency is high, stable performance.
The electrically driven (operated) light emitting diode with quantum dots of exchange provided in an embodiment of the present invention can be obtained by the preparation of following methods
.
Accordingly, the embodiment of the present invention additionally provides a kind of preparation side of the electrically driven (operated) light emitting diode with quantum dots of exchange
Method, comprises the following steps：
S01. the 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 this area conventional method reality
It is existing.First ionic liquid layer is preferably prepared using solution processing method.
Preferably, before deposition quantum dot light emitting layer, it is additionally included on the hearth electrode and deposits the second ionic liquid layer
And/or insulating barrier.Two ionic liquid layer is preferably prepared using solution processing method.
In the embodiment of the present invention, the deposition process of each layer can be chemical method, or Physical, wherein, describedization
Method include but is not limited to chemical vapour deposition technique, successive ionic layer adsorption and reaction method, anodizing, strike,
One or more in coprecipitation；The Physical include but is not limited to spin-coating method, print process, knife coating, dip-coating method,
Infusion method, spraying process, 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 for exchanging electrically driven (operated) light emitting diode with quantum dots provided in an embodiment of the present invention, it is only necessary in routine
QLED devices architecture basics on, the first ionic liquid layer, method are introduced between quantum dot light emitting layer and top electrode
It is ripe simple, it is easy to accomplish industrialization.
And, the embodiment of the present invention additionally provides the application of the above-mentioned electrically driven (operated) light emitting diode with quantum dots of exchange.
Specifically, a kind of illuminating module, including the electrically driven (operated) light emitting diode with quantum dots of above-mentioned exchange.
And, a kind of display device, including the electrically driven (operated) light emitting diode with quantum dots of above-mentioned exchange.
Illuminating module provided in an embodiment of the present invention and display device, due to sending out containing the electrically driven (operated) quantum dot of above-mentioned exchange
Optical diode, therefore, be conducive to large-scale Industry Promotion application.
Illustrate with reference to specific embodiment.
Embodiment 1
It is a kind of to exchange electrically driven (operated) light emitting diode with quantum dots, as shown in figure 1, including the substrate 1, bottom being cascading
Electrode 2, quantum dot light emitting layer 5, the first ionic liquid layer 6 and top electrode 7, wherein, the substrate 1 be glass substrate, the bottom
Electrode 2 is ITO, and the quantum dot light emitting layer 5 is CdSe/ZnS quantum dot light emitting layers, and first ionic liquid layer 6 is N, N-
Three ammonium fluoroborate (Et of diethyl-N- methyl-N- (n- propyl group) trifluoromethyl2PrNMe-CF3BF3) ionic liquid layer, thickness is
10nm, the top electrode 7 are Al.
The preparation method of the electrically driven (operated) light emitting diode with quantum dots of above-mentioned exchange, comprises 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 layers, N- diethyl-N- methyl-N- (n- propyl group) trifluoros
Methyl trifluoro ammonium borate (Et2PrNMe-CF3BF3) the first ionic liquid layer is formed, its thickness is 10nm；
S13. one layer of Al is deposited with the first ionic liquid layer, obtain exchanging electrically driven (operated) light emitting diode with quantum dots.
The level structure figure of the electrically driven (operated) light emitting diode with quantum dots of exchange that embodiment 1 is provided is as shown in Figure 2.
Embodiment 2
It is a kind of to exchange electrically driven (operated) light emitting diode with quantum dots, as shown in figure 3, including the substrate 1, bottom being cascading
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 sulphonates
(BMIM-OTF) ionic liquid layer, thickness are 20nm, and the quantum dot light emitting layer 5 is CdSe/ZnS quantum dot light emitting layers, described
First ionic liquid layer 6 is N, three ammonium fluoroborate (Et of N- diethyl-N- methyl-N- (n- propyl group) trifluoromethyl2PrNMe-
CF3BF3) ionic liquid layer, thickness is 10nm, and the top electrode 7 is Al.
The preparation method of the electrically driven (operated) light emitting diode with quantum dots of above-mentioned exchange, comprises the following steps：
S21. one layer of 1- butyl -3- methylimidazole fluoroform sulphonate (BMIM-OTF) shape of spin coating on ITO electro-conductive glass
Into the second ionic liquid layer, its thickness is 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 layers, N- diethyl-N- methyl-N- (n- propyl group) trifluoros
Methyl trifluoro ammonium borate (Et2PrNMe-CF3BF3) the first ionic liquid layer is formed, its thickness is 10nm；
S24. one layer of Al is deposited with the first ionic liquid layer, obtain exchanging electrically driven (operated) light emitting diode with quantum dots.
Embodiment 3
It is a kind of to exchange electrically driven (operated) light emitting diode with quantum dots, as shown in figure 4, including the substrate 1, bottom being cascading
Electrode 2, insulating barrier 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 barrier 4 is Al2O3, thickness is 50nm, and the quantum dot light emitting layer 5 is CdSe/ZnS
Quantum dot light emitting layer, first ionic liquid layer 6 be N, N- diethyl-N- methyl-N- (2- methoxy ethyls) tetrafluoro boric acids
Quaternary ammonium salt (DEME-BF4) ionic liquid layer, thickness is 10nm, and the top electrode 7 is Al.
The preparation method of the electrically driven (operated) light emitting diode with quantum dots of above-mentioned exchange, comprises the following steps：
S31. one layer of Al of spin coating on ITO electro-conductive glass2O3Insulating barrier is formed, its thickness is 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 layers, N- diethyl-N- methyl-N- (2- methoxyl group second
Base) tetrafluoroborate (DEME-BF4) the first ionic liquid layer is formed, its thickness is 10nm；
S34. one layer of Al is deposited with the first ionic liquid layer, obtain exchanging electrically driven (operated) light emitting diode with quantum dots.
It should be appreciated that above-mentioned 3 embodiments are only used for illustrating 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 material, thickness and the deposition process of its specific functional layer.
Presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all essences in the present invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (13)
1. a kind of electrically driven (operated) light emitting diode with quantum dots of exchange, sends out including the substrate, hearth electrode, quantum dot being cascading
Photosphere, top electrode, it is characterised in that also including the first ion being arranged between the top electrode and the quantum dot light emitting layer
Liquid level, first ionic liquid layer are made up of the first ionic liquid for only containing anion and cation, first ion
Liquid is in a liquid state at -10～200 DEG C, and under exchange 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. electrically driven (operated) light emitting diode with quantum dots is exchanged as claimed in claim 1, it is characterised in that sent out in the quantum dot
The second ionic liquid layer and/or insulating barrier are provided between photosphere and the hearth electrode, wherein, second ionic liquid layer by
Only contain anion and the second ionic liquid of cation is made, second ionic liquid is in a liquid state at -10～200 DEG C, and
Under exchange electric drive, second ionic liquid layer forms interface at the interface of the quantum dot light emitting layer and the hearth electrode
Electric double layer,
When second ionic liquid layer and the insulating barrier simultaneously in the presence of, second ionic liquid layer be arranged on it is described absolutely
Between edge layer and the quantum dot light emitting layer.
3. exchange electrically driven (operated) light emitting diode with quantum dots as claimed in claim 1 or 2, it is characterised in that described first from
Sub- liquid level, second ionic liquid layer are made up of inorganic anion and organic cation, and first ionic liquid layer,
The ionic type of second ionic liquid layer is identical or different.
4. electrically driven (operated) light emitting diode with quantum dots is exchanged as claimed in claim 3, it is characterised 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. electrically driven (operated) light emitting diode with quantum dots is exchanged as claimed in claim 4, it is characterised in that the organic cation
For alkyl quaternary ammonium ion, alkyl-substituted imidazol ion, including 1- butyl -3- methyl imidazolium cations, N, N- diethyl-N- first
Base-N- (n- propyl group) ammonium cation, N, at least one in N- diethyl-N- methyl-(2- methoxyethyls) ammonium cation.
6. electrically driven (operated) light emitting diode with quantum dots is exchanged as claimed in claim 4, it is characterised in that the halide ion bag
Include but be not limited to F-、Cl-、Br-、I-In at least one；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.
7. the electrically driven (operated) light emitting diode with quantum dots of exchange as described in claim 4-6 is arbitrary, it is characterised in that the ion
Liquid level is by N, N- diethyl-N- methyl-N- (n- propyl group) three ammonium fluoroborates of trifluoromethyl, 1- butyl -3- methylimidazole trifluoros
Mesylate, N, N- diethyl-N- methyl-N- (2- methoxy ethyls) ammonium double (trimethyl fluoride sulfonyl) acid imide, N, N- bis-
At least one in ethyl-N-methyl-N- (2- methoxy ethyls) tetrafluoroborate is made.
8. exchange electrically driven (operated) light emitting diode with quantum dots as claimed in claim 1 or 2, it is characterised in that described first from
The thickness of sub- liquid level is 10-500nm.
9. electrically driven (operated) light emitting diode with quantum dots is exchanged as claimed in claim 2, it is characterised in that second ionic liquid
The thickness of body layer is 10-500nm；And/or
The thickness of the insulating barrier is 10-1000nm.
10. a kind of preparation method of the electrically driven (operated) light emitting diode with quantum dots of exchange, comprises the following steps：
The 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.
11. preparation methods for exchanging electrically driven (operated) light emitting diode with quantum dots as claimed in claim 10, it is characterised in that also
It is included on the hearth electrode and deposits the second ionic liquid layer and/or insulating barrier.
12. a kind of illuminating modules, it is characterised in that send out including the electrically driven (operated) quantum dot of the arbitrary described exchange of claim 1-9
Optical diode.
13. a kind of display devices, it is characterised in that send out including the electrically driven (operated) quantum dot of the arbitrary described exchange of claim 1-9
Optical diode.
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