CN109216566A - Composite luminescence layer, QLED device and preparation method thereof - Google Patents
Composite luminescence layer, QLED device and preparation method thereof Download PDFInfo
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- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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Abstract
Composite luminescence layer, QLED device and preparation method thereof.The present invention provides a kind of composite luminescence layers, the composite luminescence layer is the fixed quantum dot light emitting layer of three-dimensional grapheme, including porous three-dimensional Web materials and the quantum dot being fixed on the porous three-dimensional Web materials, wherein, three-dimensional grapheme and/or three-dimensional graphene oxide are contained in the porous three-dimensional Web materials.
Description
Technical field
The invention belongs to light emitting diode with quantum dots technical field more particularly to a kind of composite luminescence layer, QLED device and
Preparation method.
Background technique
Light emitting diode with quantum dots (Quantum dot light-emitting diode, QLED), due to spontaneous
The advantages that light, low energy consumption, high excitation purity, becomes next-generation display and lighting engineering that people pay close attention to the most.
It is the most frequently used and be most hopeful to realize the production and processing side of extensive industrialization currently, in the technology of preparing of QLED
Method is solution film formation, the quantum dot light emitting layer and various functions layers in addition to electrode especially in device.For example, for amount
The deposition method of son point luminescent layer, current most of solution phase film-forming process are to be dissolved in the quantum dot of surface ligand functionalization to have
In solvent, it is configured to quantum dot solution or quantum dot ink, then passes through spin coating or mode of printing deposition substrate or bottom function
On layer, electron transfer layer (such as ZnO) is then deposited on quantum dot light emitting layer using same film build method, finally vapor deposition electricity
Pole obtains QLED device.But since the particle size of quantum dot is larger compared with conventional ion or small organic molecule, and
Quantum dot surface organic ligand rich in, the connection after film forming between quantum dot particle is not close, film layer relative loose,
Post-depositional quantum dot still has very big chance to re-dissolve in the solwution method film forming procedure of subsequent other function layer to take away or directly
It connects and washes away, lead to that quantum dot film layer is uneven, boundary defect is larger, and then lead to device non-uniform light.Especially with ZnO
The electron transfer layer of preparation, interface between quantum dot light emitting layer and ZnO electron transfer layer to the stability of QLED device and
Uniformity of luminance has a major impact.Even if using the solvent of indissoluble solution quantum dot, it is also difficult to the generation of the process is avoided, and
Because of this, the selection of follow-up function layer material also will receive the limitation of its optional solvent.
Summary of the invention
The purpose of the present invention is to provide a kind of composite luminescence layers, it is intended in the preparation method for solving existing QLED device,
Quantum dot in quantum dot light emitting layer is easy preparing solution dissolution or wash away by other function layer, leads to device non-uniform light
The problem of.
Another object of the present invention is to provide a kind of QLED device and preparation method thereof containing above-mentioned composite luminescence layer.
The invention is realized in this way a kind of composite luminescence layer, the composite luminescence layer is the fixed amount of three-dimensional grapheme
Son point luminescent layer, including porous three-dimensional Web materials and the quantum dot being fixed on the porous three-dimensional Web materials, wherein institute
It states in porous three-dimensional Web materials containing three-dimensional grapheme and/or three-dimensional graphene oxide.
And a kind of QLED device, including stack gradually the substrate of combination, anode, hole injection layer, hole transmission layer,
Luminescent layer, electron transfer layer and cathode, the luminescent layer are above-mentioned composite luminescence layer.
Correspondingly, a kind of preparation method of QLED device, comprising the following steps:
Substrate is provided, is sequentially depositing anode, hole injection layer, hole transmission layer over the substrate；
The three-dimensional netted material of deposited porous on the hole transport layer, the deposition on the porous three-dimensional Web materials
Son point layer, the porous three-dimensional Web materials form composite luminescence layer in conjunction with the quantum dot layer, wherein the porous three-dimensional
Contain three-dimensional grapheme and/or three-dimensional graphene oxide in Web materials；
Electron transfer layer and cathode are sequentially depositing in the composite luminescence layer.
Composite luminescence layer provided by the invention, including porous three-dimensional Web materials and it is fixed on the netted material of the porous three-dimensional
Quantum dot on material, wherein contain three-dimensional grapheme and/or three-dimensional graphene oxide in the porous three-dimensional Web materials.One
Aspect, the three-dimensional grapheme, three-dimensional graphene oxide can play the effect of bracket in film forming procedure, assist quantum dot
Film forming effectively avoids quantum dot because device non-uniform light, luminescent properties are low caused by reuniting, covering not congruent reason and device
The problems such as stability is poor.On the other hand, the three-dimensional porous reticular structure energy that the three-dimensional grapheme, three-dimensional graphene oxide provide
A large amount of gap is enough provided, quantum dot is embedded in tridimensional network, to tightly hold quantum dot, quantum dot is avoided to exist
In the film forming procedure of follow-up function layer by other solution wash away or film forming procedure in fall, to significantly improve the film forming of quantum dot
Quality, and then it is effectively improved the uniformity of luminance and luminous efficiency of device.Further, since the quantum dot is combined closely porous
In three-dimensional netted material, solvent selection when depositing to follow-up function layer requires to reduce, that is, improves follow-up function layer and its molten
The alternative of agent improves the structure flexible design degree of QLED device.
QLED device provided by the invention, contains above-mentioned composite luminescence layer.Due to quantum solid point in the composite luminescence layer
It is scheduled on porous three-dimensional Web materials, therefore, effectively quantum dot can not only be avoided to reunite, and in the composite luminescence layer
When depositing other function layer using solwution method, it is possible to prevente effectively from preparing erosion of the solvent to quantum dot layer, prevent quantum dot molten
It solves or is flushed away.To sum up, QLED device provided by the invention, uniformity of luminance, membranous layer stability, luminous efficiency and service life
It is improved.
The preparation method of QLED device provided by the invention, before depositing quantum dot layer, the first three-dimensional netted material of deposited porous
Material.By the fixed quantum dot of the porous three-dimensional Web materials, prevent from being produced solvent in the preparation process of follow-up function layer
Dissolve or be flushed away, improve quantum dot at film uniformity, and then improve the uniformity of luminance of QLED device, membranous layer stability,
Luminous efficiency and service life.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of QLED device provided in an embodiment of the present invention.
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 composite luminescence layer, the composite luminescence layer is the fixed quantum of three-dimensional grapheme
Point luminescent layer, including porous three-dimensional Web materials and the quantum dot being fixed on the porous three-dimensional Web materials, wherein described
Contain three-dimensional grapheme and/or three-dimensional graphene oxide in porous three-dimensional Web materials.
Specifically, the porous three-dimensional Web materials include three-dimensional grapheme and/or three-dimensional graphene oxide.Herein, institute
Stating porous three-dimensional Web materials can be individual three-dimensional grapheme or three-dimensional graphene oxide, be also possible to three-dimensional grapheme and
The mixing material that three-dimensional graphene oxide is formed.It is understood, however, that the composition of the porous three-dimensional Web materials is not limited to
Three-dimensional grapheme and/or three-dimensional graphene oxide can also include in addition to three-dimensional grapheme and/or three-dimensional graphene oxide
Other carbon materials.Preferably, in the porous three-dimensional Web materials also containing in carbon nanotube, fullerene, carbon fiber at least
It is a kind of.The i.e. described porous three-dimensional Web materials can be three-dimensional grapheme and at least one in carbon nanotube, fullerene, carbon fiber
The composite material of kind composition, is also possible to three-dimensional graphene oxide and at least one of carbon nanotube, fullerene, carbon fiber group
At composite material.Due in the porous three-dimensional Web materials three-dimensional grapheme and/or three-dimensional graphene oxide can mention
For a large amount of hole, the quantum dot can be embedded in gap structure, be fixed on the porous three-dimensional Web materials, thus real
The anchoring of existing quantum dot.When the porous three-dimensional Web materials include three-dimensional graphene oxide, due to three-dimensional graphene oxide
A large amount of electron rich group is contained on surface, these electron riches groups on the one hand with the quantum dot by Electrostatic Absorption in conjunction with；Separately
On the one hand, the electron rich group is formed with the quantum dot by the dipole effect in the metal cation vacancy of quantum dot surface
Chemical bonds.When the porous three-dimensional Web materials include three-dimensional grapheme-carbon nano tube compound material, carbon nanotube
It is interspersed in three-dimensional grapheme, so as to preferably fix quantum dot in the composite.
It is further preferred that contain electron rich functional group in the three-dimensional graphene oxide, the electron rich functional group packet
It includes but is not limited to-OH ,-COOH ,-NH2、-NH-、-SH、-CN、-SO3H、-SOOH、-NO2、-CONH2、-CONH-、-COCl、-
At least one of CO- ,-CHO ,-Cl ,-Br.Above-mentioned electron rich functional group can provide electronics, pass through the gold of quantum dot surface
Belong to and forms chemical bonding between the dipole effect and quantum dot of cation vacancy.
In composite luminescence layer described in the embodiment of the present invention, the three-dimensional grapheme, three-dimensional graphene oxide total amount with
The mass ratio of the quantum dot is 0.5~120:1, to keep the composite luminescence layer simultaneous while effectively anchoring quantum dot
Care for preferable luminous efficiency.If the content of the three-dimensional grapheme, three-dimensional graphene oxide is higher, composite luminescence layer is blocked up, leads
The compound difficulty of exciton is caused, device light emitting efficiency is reduced；If the content of the three-dimensional grapheme, three-dimensional graphene oxide is relatively low,
Quantum dot cannot be sufficiently anchored in porous network structure.
Composite luminescence layer provided in an embodiment of the present invention, including porous three-dimensional Web materials and it is fixed on the porous three-dimensional
Quantum dot on Web materials, wherein contain three-dimensional grapheme and/or three-dimensional graphite oxide in the porous three-dimensional Web materials
Alkene.On the one hand, the three-dimensional grapheme, three-dimensional graphene oxide can play the effect of bracket, auxiliary quantity in film forming procedure
Son point film forming, effectively avoid quantum dot because caused by reuniting, covering not congruent reason device non-uniform light, luminescent properties it is low
The problems such as poor with device stability.On the other hand, the three-dimensional grapheme, three-dimensional graphene oxide provide three-dimensional porous netted
Structure is capable of providing a large amount of gap, quantum dot is embedded in tridimensional network, to tightly hold quantum dot, the amount of avoiding
Son point in the film forming procedure of follow-up function layer by other solution wash away or film forming procedure in fall, to significantly improve quantum dot
Quality of forming film, and then be effectively improved the uniformity of luminance and luminous efficiency of device.Further, since the quantum dot is combined closely
In porous three-dimensional Web materials, solvent selection when depositing to follow-up function layer requires to reduce, that is, improves follow-up function layer
And its alternative of solvent, improve the structure flexible design degree of QLED device.
And in conjunction with Fig. 1, the embodiment of the invention provides a kind of QLED device, including stack gradually combination substrate 1,
Anode 2, hole injection layer 3, hole transmission layer 4, luminescent layer 5, electron transfer layer 6 and cathode 7, the luminescent layer are above-mentioned answer
Close luminescent layer.
Specifically, the limitation that the selection of the substrate 1 is not stringent, can be rigid substrate or flexible substrate.Wherein, institute
Stating rigid substrate includes but is not limited to one of glass, metal foil or a variety of；The flexible substrate includes but is not limited to poly-
Ethylene glycol terephthalate (PET), ethylene glycol terephthalate (PEN), polyether-ether-ketone (PEEK), polystyrene (PS),
Polyether sulfone (PES), polycarbonate (PC), poly- aryl acid esters (PAT), polyarylate (PAR), polyimides (PI), polyvinyl chloride
(PV), one of polyethylene (PE), polyvinylpyrrolidone (PVP), textile fabric or a variety of.
The anode 2 can choose the anode material of the field QLED routine.As a kind of implementation situation, the anode 2 is
Blended metal oxide, the blended metal oxide include but is not limited to indium doping tin oxide (ITO), fluorine-doped tin oxide
(FTO), antimony-doped tin oxide (ATO), aluminium-doped zinc oxide (AZO), Ga-doped zinc oxide (GZO), indium doping zinc oxide
(IZO), one of magnesium doping zinc-oxide (MZO), aluminium doping magnesia (AMO) or a variety of.As another implementation situation, institute
Stating anode 2 is the combination electrode containing metal sandwich in transparent metal oxide, wherein the transparent metal oxide can be
Doping transparent metal oxide, or undoped transparent metal oxide.The combination electrode includes but is not limited to
AZO/Ag/AZO、AZO/Al/AZO、ITO/Ag/ITO、ITO/Al/ITO、ZnO/Ag/ZnO、ZnO/Al/ZnO、TiO2/Ag/
TiO2、TiO2/Al/TiO2、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO2/Ag/TiO2、TiO2/Al/TiO2One of or it is more
Kind.
In the embodiment of the present invention, the hole injection layer 3 is selected from the organic material with Hole injection capacity.Described in preparation
Including but not limited to poly- (3,4- the ethene dioxythiophene)-polystyrolsulfon acid of the hole-injecting material of hole injection layer 3 (PEDOT:
PSS), CuPc (CuPc), tetra- cyanogen quinone of 2,3,5,6- tetra- fluoro- 7,7', 8,8'--bismethane (F4-TCNQ), 2,3,6,7,10,
Six cyano -1,4,5,8,9,12- of 11-, six azepine benzophenanthrene (HATCN), doped or non-doped transition metal oxide, doping or
One of undoped metal chalcogenide is a variety of.Wherein, the transition metal oxide includes but is not limited to MoO3、
VO2、WO3、CrO3, at least one of CuO；The metal chalcogenide includes but is not limited to MoS2、MoSe2、WS2、WSe2、
At least one of CuS.
In the present invention, as one embodiment, the hole transmission layer 4 is selected from organic material with cavity transmission ability
Material, including but not limited to poly- (9,9- dioctyl fluorene-CO-N- (4- butyl phenyl) diphenylamines) (TFB), polyvinylcarbazole (PVK),
Poly- (bis- bis- (phenyl) benzidine of (4- butyl phenyl)-N, N'- of N, N') (poly-TPD), it is poly- (double-N of 9,9- dioctyl fluorene -co-,
N- phenyl -1,4- phenylenediamine) (PFB), 4,4 ', 4 "-three (carbazole -9- base) triphenylamines (TCTA), 4,4'- bis- (9- carbazole) biphenyl
(CBP), N, N '-diphenyl-N, N '-two (3- aminomethyl phenyl) -1,1 '-biphenyl -4,4 '-diamines (TPD), N, N '-diphenyl-N,
At least one of N '-(1- naphthalene) -1,1 '-biphenyl -4,4 '-diamines (NPB), doped graphene, undoped graphene, C60.
As another embodiment, it includes but is not limited to mix that the hole transmission layer 4, which is selected from the inorganic material with cavity transmission ability,
Miscellaneous or undoped MoO3、VO2、WO3、CrO3、CuO、MoS2、MoSe2、WS2、WSe2, at least one of CuS.
In the embodiment of the present invention, the luminescent layer 5 is above-mentioned composite luminescence layer.Specifically, the composite luminescence layer is
The fixed quantum dot light emitting layer of three-dimensional grapheme, including porous three-dimensional Web materials and it is fixed on the porous three-dimensional Web materials
On quantum dot, wherein contain three-dimensional grapheme and/or three-dimensional graphene oxide in the porous three-dimensional Web materials.It is described
Porous three-dimensional Web materials include three-dimensional grapheme and/or three-dimensional graphene oxide, are capable of providing a large amount of hole, the quantum
Point can be embedded in gap structure, be fixed on the porous three-dimensional Web materials, so that the quantum dot be enable to combine closely
It is not easily to fall off on porous three-dimensional Web materials, to improve the quality of forming film of luminescent layer 5, improve shining for QLED device
Uniformity and luminous efficiency.
Specifically, the porous three-dimensional Web materials are three-dimensional grapheme, three-dimensional graphene oxide, three-dimensional grapheme-carbon
At least one of nanometer tube composite materials.Further, contain electron rich functional group in the three-dimensional graphene oxide, it is described
Electron rich functional group includes but is not limited to-OH ,-COOH ,-NH2、-NH-、-SH、-CN、-SO3H、-SOOH、-NO2、-CONH2、-
At least one of CONH- ,-COCl ,-CO- ,-CHO ,-Cl ,-Br.
Quantum dot in the quantum dot layer can for II-VI group compound, III-V compound, II-V compounds of group,
One in III-VI compound, group IV-VI compound, I-III-VI group compound, II-IV-VI compounds of group or IV race simple substance
Kind is a variety of.
As a kind of preferred implementation situation, the quantum dot be 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,
Wherein, A 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 calcium
Titanium ore 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 cation M is located at the octahedral body-centered of halogen, and organic amine cation B is filled in the gap between octahedron, and it is unlimited to be formed
The three-dimensional structure of extension；As n > 2, the inorganic metal hal ide octahedron MX that is connected in a manner of total top6 4-In two-dimensional directional
Extend to form layer structure, Intercalation reaction organic amine cation bilayer (protonation monoamine) or organic amine cation unimolecule
Layer (protonation diamine), organic layer and inorganic layer mutually overlap and form stable two-dimensional layered structure；M be divalent metal sun from
Son, including but not limited to Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+, X is halogen yin
Ion, including but not limited to Cl-、Br-、I-。
In the embodiment of the present invention, the electron transfer layer 6 is selected from the material with electronic transmission performance, it is however preferred to have electricity
The metal oxide of sub- transmission performance, the metal oxide include but is not limited to N-shaped ZnO, TiO2、SnO、Ta2O3、AlZnO、
ZnSnO、InSnO、Alq3、Ca、Ba、CsF、LiF、CsCO3At least one of.
In the embodiment of the present invention, the cathode 7 is various conductive carbon materials, conductive metal oxide material, metal material
One of or it is a variety of.Wherein, the conductive carbon material includes but is not limited to doped or non-doped carbon nanotube, doping or non-mixes
Miscellaneous graphene, doped or non-doped graphene oxide, C60, graphite, carbon fiber, more empty carbon or their mixture；It is described to lead
Metal oxide material includes but is not limited to ITO, FTO, ATO, AZO or their mixture；The metal material include but
It is not limited to Al, Ag, Cu, Mo, Au or their alloy.Wherein, in the metal material, form includes but is not limited to nanometer
Ball, nano wire, nanometer rods, nanocone, nano-hollow ball or their mixture.Particularly preferably, the cathode 7 be Ag,
Al。
It is further preferred that QLED device described in the embodiment of the present invention further includes interface-modifying layer, the interface-modifying layer
For at least one layer in electronic barrier layer, hole blocking layer, electrode modification layer, isolated protective layer.
Of course it is to be understood that the QLED device of the embodiment of the present invention, can be eurymeric QLED device, or transoid
QLED device.The packaged type of the QLED device can be partial encapsulation, full encapsulation or not encapsulate, the embodiment of the present invention
Do not limit strictly.
QLED device provided in an embodiment of the present invention, contains above-mentioned composite luminescence layer.Due to being measured in the composite luminescence layer
Son point is fixed on porous three-dimensional Web materials, therefore, can not only effectively avoid quantum dot from reuniting, and in the compound hair
When on photosphere using solwution method deposition other function layer, it is possible to prevente effectively from preparing erosion of the solvent to quantum dot layer, the amount of preventing
Son point dissolution is flushed away.To sum up, QLED device provided in an embodiment of the present invention, uniformity of luminance, membranous layer stability, shine effect
Rate and service life are improved.
Correspondingly, the embodiment of the invention also provides a kind of preparation methods of QLED device, comprising the following steps:
S01., substrate is provided, is sequentially depositing anode, hole injection layer, hole transmission layer over the substrate；
S02. the three-dimensional netted material of deposited porous on the hole transport layer sinks on the porous three-dimensional Web materials
Product quantum dot layer, the porous three-dimensional Web materials form composite luminescence layer in conjunction with the quantum dot layer, wherein described porous
Contain three-dimensional grapheme and/or three-dimensional graphene oxide in three-dimensional netted material；
S03. electron transfer layer and cathode are sequentially depositing in the composite luminescence layer.
Specifically, in above-mentioned steps S01, it is for example above for the selection of substrate, anode, hole injection layer, hole transmission layer
Described, in order to save length, details are not described herein again.The deposition method of each layer can realize using conventional method, such as chemical method or
Physical method.Wherein, chemical method includes but is not limited to chemical vapour deposition technique, successive ionic layer adsorption and reaction method, anodic oxidation
One of method, strike, coprecipitation are a variety of；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 deposition method, magnetron sputtering method, multi-arc ion coating embrane method, physical vaporous deposition, atomic layer deposition method, pulse swash
One of Photodeposition is a variety of.Preferably, anode is deposited over the substrate, uses solution processing method on the anode
It is sequentially depositing hole injection layer, hole transmission layer.
In above-mentioned steps S02, the three-dimensional netted material of deposited porous on the hole transport layer, because three-dimensional netted material has
Multiple choices, depositional mode also there are many.Specifically, the porous three-dimensional Web materials can be for by graphene and/or oxidation
The porous three-dimensional Web materials of graphene composition may be to be made of graphene and/or graphene oxide and other carbon materials
Composite material.
As a specific embodiment, the porous three-dimensional Web materials are three-dimensional grapheme and/or three-dimensional graphite oxide
Alkene, the on the hole transport layer method of the three-dimensional netted material of deposited porous are as follows:
Three-dimensional grapheme and/or three-dimensional graphene oxide dispersion in a solvent, are configured to porous three-dimensional Web materials solution；
Then by solution processing method by the porous three-dimensional Web materials liquid deposition on the hole transport layer.
As another specific embodiment, the porous three-dimensional Web materials are three-dimensional grapheme, three-dimensional graphene oxide
At least one of at least one of carbon nanotube, fullerene, carbon fiber formed three-dimensional porous composite material, described
The method of the three-dimensional netted material of deposited porous on hole transmission layer are as follows:
In a solvent by the dispersion of at least one of three-dimensional grapheme, three-dimensional graphene oxide, it is configured to the first solution, is led to
It crosses solution processing method deposition and forms three-dimensional grapheme and/or three-dimensional graphene oxide layer on the hole transport layer；Then lead to
Cross solution processing method deposition of carbon nanotubes, fullerene, carbon fiber on the three-dimensional grapheme and/or three-dimensional graphene oxide layer
At least one of, form three-dimensional porous composite construction layer.
As another specific embodiment, the porous three-dimensional Web materials are three-dimensional grapheme, three-dimensional graphene oxide
At least one of at least one of carbon nanotube, fullerene, carbon fiber formed three-dimensional porous composite material, described
The method of the three-dimensional netted material of deposited porous on hole transmission layer are as follows:
By at least one of three-dimensional grapheme, three-dimensional graphene oxide and carbon nanotube, fullerene, carbon fiber extremely
A kind of few dispersion in a solvent, is configured to mixed solution；Then the mixed solution is deposited on by solution processing method described
On hole transmission layer, three-dimensional porous composite construction layer is formed.
In above-mentioned specific embodiment, the solution processing method includes but is not limited to spin-coating method, print process, knife coating, dipping
Czochralski method, infusion method, spray coating method, roll coating process, casting method, slit coating method, strip rubbing method.
Quantum dot layer is deposited on the porous three-dimensional Web materials, quantum dot passes through three-dimensional porous insertion porous three-dimensional net
Shape material, realizes the fixation of quantum dot, and the quantum dot layer of deposition forms recombination luminescence in conjunction with the porous three-dimensional Web materials
Layer improves the film forming of luminescent layer, and then improves the uniformity of luminance and device stability of QLED device.
In above-mentioned steps S03, the method that electron transfer layer and cathode are sequentially depositing in the composite luminescence layer can join
Examine the deposition method of each layer in step S02.Preferably, electron-transport is deposited in the composite luminescence layer using solution processing method
Layer, then evaporation cathode, obtains QLED device.
Further, can be according to device performance requirements, deposition interface decorative layer, the interface-modifying layer is electronic blocking
Layer, hole blocking layer, electrode modification layer, at least one layer in isolated protective layer.
The preparation method of QLED device provided in an embodiment of the present invention, before depositing quantum dot layer, first deposited porous is three-dimensional
Web materials.By the fixed quantum dot of the porous three-dimensional Web materials, prevent from being made in the preparation process of follow-up function layer
Standby solvent is dissolved or is flushed away, improve quantum dot at film uniformity, and then it is steady to improve the uniformity of luminance of QLED device, film layer
Qualitative, luminous efficiency and service life.
It is illustrated combined with specific embodiments below.
Embodiment 1
A kind of preparation method of QLED device, which comprises the following steps:
S11. ITO electro-conductive glass is provided, spin coating PEDOT:PSS film is injected as hole on the ITO electro-conductive glass
Layer is used as hole transmission layer for one layer TFB layers of spin coating on hole injection layer；
S12. spin coating graphene dispersing solution on the hole transport layer forms one layer of three-dimensional porous graphene layer；Institute
Spin coating CdSe/ZnS quantum dot light emitting layer on three-dimensional porous graphene layer is stated, composite luminescence layer is formed；
S13. spin coating ZnO is as electron transfer layer in the composite luminescence layer, evaporating Al cathode on the electron transport layer
Layer, obtains light emitting diode with quantum dots.
It should be appreciated that the embodiment of the present invention 1 is illustrated as just one, the practical guarantor of technical solution of the present invention is not represented
Protect range.Selection, structure and its preferred situation of layers of material of the embodiment of the present invention can be selected under situation shown in the text
It selects.
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 (10)
1. a kind of composite luminescence layer, which is characterized in that the composite luminescence layer is the fixed quantum dot light emitting layer of three-dimensional grapheme,
Including porous three-dimensional Web materials and the quantum dot being fixed on the porous three-dimensional Web materials, wherein the porous three-dimensional
Contain three-dimensional grapheme and/or three-dimensional graphene oxide in Web materials.
2. composite luminescence layer as described in claim 1, which is characterized in that also received containing carbon in the porous three-dimensional Web materials
At least one of mitron, fullerene, carbon fiber.
3. composite luminescence layer as claimed in claim 2, which is characterized in that contain electron rich official in the three-dimensional graphene oxide
It can roll into a ball, the electron rich functional group includes-OH ,-COOH ,-NH2、-NH-、-SH、-CN、-SO3H、-SOOH、-NO2、-CONH2、-
At least one of CONH- ,-COCl ,-CO- ,-CHO ,-Cl ,-Br.
4. composite luminescence layer a method according to any one of claims 1-3, which is characterized in that in the composite luminescence layer, the three-dimensional
The mass ratio of graphene, the gross mass of three-dimensional graphene oxide and the quantum dot is 0.5~120:1.
5. a kind of QLED device, including stack gradually the substrate of combination, anode, hole injection layer, hole transmission layer, luminescent layer,
Electron transfer layer and cathode, which is characterized in that the luminescent layer is any composite luminescence layer of claim 1-4.
6. QLED device as claimed in claim 5, which is characterized in that further include interface-modifying layer, the interface-modifying layer is
Electronic barrier layer, hole blocking layer, electrode modification layer, at least one layer in isolated protective layer.
7. a kind of preparation method of QLED device, which comprises the following steps:
Substrate is provided, is sequentially depositing anode, hole injection layer, hole transmission layer over the substrate；
The three-dimensional netted material of deposited porous on the hole transport layer deposits quantum dot on the porous three-dimensional Web materials
Layer, the porous three-dimensional Web materials form composite luminescence layer in conjunction with the quantum dot layer, wherein the porous three-dimensional is netted
Contain three-dimensional grapheme and/or three-dimensional graphene oxide in material；
Electron transfer layer and cathode are sequentially depositing in the composite luminescence layer.
8. the preparation method of QLED device as claimed in claim 7, which is characterized in that the porous three-dimensional Web materials are three
Graphene and/or three-dimensional graphene oxide are tieed up, on the hole transport layer the method for the three-dimensional netted material of deposited porous are as follows:
In a solvent by three-dimensional grapheme and/or three-dimensional graphene oxide dispersion, it is configured to porous three-dimensional Web materials solution；So
Afterwards by solution processing method by the porous three-dimensional Web materials liquid deposition on the hole transport layer.
9. the preparation method of QLED device as claimed in claim 7, which is characterized in that the porous three-dimensional Web materials are three
Tie up what at least one of graphene, three-dimensional graphene oxide were formed at least one of carbon nanotube, fullerene, carbon fiber
Three-dimensional porous composite material, the on the hole transport layer method of the three-dimensional netted material of deposited porous are as follows:
In a solvent by the dispersion of at least one of three-dimensional grapheme, three-dimensional graphene oxide, it is configured to the first solution, by molten
Liquid processing method deposition forms three-dimensional grapheme and/or three-dimensional graphene oxide layer on the hole transport layer；Then by molten
Liquid processing method on the three-dimensional grapheme and/or three-dimensional graphene oxide layer deposition of carbon nanotubes, fullerene, in carbon fiber
At least one forms three-dimensional porous composite construction layer.
10. the preparation method of QLED device as claimed in claim 7, which is characterized in that the porous three-dimensional Web materials are
At least one of three-dimensional grapheme, three-dimensional graphene oxide and the formation of at least one of carbon nanotube, fullerene, carbon fiber
Three-dimensional porous composite material, the method for the three-dimensional netted material of deposited porous on the hole transport layer are as follows:
By at least one at least one of three-dimensional grapheme, three-dimensional graphene oxide and carbon nanotube, fullerene, carbon fiber
Kind dispersion in a solvent, is configured to mixed solution；Then the mixed solution is deposited on by the hole by solution processing method
In transport layer, three-dimensional porous composite construction layer is formed.
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