CN109285954A - 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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- CN109285954A CN109285954A CN201710600114.3A CN201710600114A CN109285954A CN 109285954 A CN109285954 A CN 109285954A CN 201710600114 A CN201710600114 A CN 201710600114A CN 109285954 A CN109285954 A CN 109285954A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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- H—ELECTRICITY
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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Abstract
The present invention provides a kind of composite luminescence layer, the composite luminescence layer is the fixed quantum dot light emitting layer of grapheme foam skeleton, including grapheme foam skeleton and the quantum dot being fixed in the grapheme foam skeleton.Composite luminescence layer provided by the invention, including grapheme foam skeleton and quantum dot.Wherein, the grapheme foam skeleton is loose porous, quantum dot can effectively be fixed, prevent quantum dot in the film forming procedure of follow-up function layer by other solution wash away or film forming procedure in fall, assist the film forming of quantum dot, the composite luminescence layer made has the performances such as uniform stabilization that shine, so as to improve the luminous efficiency of device, uniformity of luminance and stability.
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
Semiconductor-quantum-point (Quantum dot, QDs) has that fluorescence quantum efficiency is high, visible light wave range shines adjustable, color
The special characteristics such as domain coverage broadness.It is referred to as light emitting diode with quantum dots by the light emitting diode of luminescent material of quantum dot
(Quantum dot light-emitting diode, QLED), have color saturation, efficiency is higher, colour temperature more preferably, the service life it is long
The advantages that, it is expected to become the mainstream technology of next-generation solid-state lighting and FPD.
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 is then deposited on quantum dot light emitting layer using same film build method, last electrode evaporation obtains
QLED device.But since the particle size of quantum dot is larger compared with conventional ion or small organic molecule, and quantum dot table
Face organic ligand rich in, the connection after film forming between quantum dot particle is not close, and film layer relative loose is 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 wash away, lead
Cause quantum dot film layer is uneven, boundary defect is larger, and then leads to device non-uniform light.Even if using indissoluble solution quantum dot
Solvent, it is also difficult to avoid the generation of the process, and because of this, the selection of follow-up function layer material also to will receive its optional
The limitation of 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 that grapheme foam skeleton is fixed
Quantum dot light emitting layer, including grapheme foam skeleton and the quantum dot that is fixed in the grapheme foam skeleton.
And a kind of QLED device, including stack gradually in conjunction on substrate hearth electrode, the first functional layer, luminescent layer,
Second functional layer and top electrode, wherein the luminescent layer is above-mentioned composite luminescence layer.
Correspondingly, a kind of preparation method of QLED device, comprising the following steps:
Metal foam form cage is provided, the apposition growth graphene on the metal foam form cage obtains graphite
Alkene/metal foam skeleton；
The graphene/metal foam skeleton is immersed in etching liquid, etching removal metal foam template obtains graphite
Alkene foam framework；
Substrate is provided, hearth electrode, the first functional layer is sequentially depositing over the substrate, is deposited in first functional layer
The grapheme foam skeleton deposits quantum dot at composite luminescence layer, described compound on the grapheme foam skeleton
The second functional layer and top electrode are sequentially depositing on luminescent layer,
Wherein, the hearth electrode is anode, and the top electrode is cathode, and first functional layer is to stack gradually to be incorporated in
Hole injection layer and hole transmission layer on the anode, second functional layer are the electricity of stacking combination on the light-emitting layer
Sub- injection/transport layer；Or
The hearth electrode is cathode, and the top electrode is anode, and first functional layer is that stacking is incorporated in the cathode
On electron injection/transport layer, second functional layer be the hole transmission layer that stacks gradually Jie Hes on the light-emitting layer and
Hole injection layer.
Composite luminescence layer provided by the invention, including grapheme foam skeleton and quantum dot.Wherein, the grapheme foam
Skeleton is loose porous, can effectively fix quantum dot, prevents quantum dot in the film forming procedure of follow-up function layer by other solution
Wash away or film forming procedure in fall, assist the film forming of quantum dot, the composite luminescence layer made has the uniform stabilization etc. of shining
Performance, so as to improve the luminous efficiency of device, uniformity of luminance and stability.
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, therefore, when using solwution method deposition other function layer in the composite luminescence layer, it is possible to prevente effectively from preparing molten
Erosion of the agent to quantum dot layer prevents quantum dot from dissolving or being flushed away.To sum up, QLED device provided by the invention shines uniform
Property, membranous layer stability, luminous efficiency and service life are improved.
The preparation method of QLED device provided by the invention first deposits grapheme foam skeleton before depositing quantum dot layer.
The grapheme foam skeleton is obtained by template growth of the metal foam, therefore, has foam corresponding with metal foam
Skeleton structure is conducive to the fixation of quantum dot, prevents from being produced solvent dissolution in the preparation process of follow-up function layer or be rushed
Walk, 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 composite luminescence layer provided in an embodiment of the present invention；
Fig. 2 is the structural schematic diagram of eurymeric 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.
In conjunction with Fig. 1, the embodiment of the invention provides a kind of composite luminescence layer, the composite luminescence layer is grapheme foam bone
The fixed quantum dot light emitting layer of frame, including grapheme foam skeleton and the quantum dot being fixed in the grapheme foam skeleton.
In the embodiment of the present invention, the grapheme foam skeleton is loose porous, quantum dot can be effectively fixed, to prevent
Quantum dot in the film forming procedure of follow-up function layer by other solution wash away or film forming procedure in fall, improve quantum dot light emitting layer
Filming performance.In addition, the grapheme foam skeleton can play the effect of bracket in film forming procedure, quantum is effectively avoided
Point because device non-uniform light caused by reuniting, covering not congruent reason, luminescent properties are low and device stability is poor the problems such as, into
One step improves device performance.
Preferably, the grapheme foam skeleton specific surface area is 10~300m2/g.The preferred grapheme foam skeleton
With loose and porous structure, specific surface is larger, on the one hand, the template of a physics can be provided to quantum dot, so that quantum dot
It preferably fills and forms a film, and prevent that quantum dot is washed away or re-dissolved in follow-up function layer deposition process.
It is further preferred that active function groups are contained on grapheme foam skeleton surface, so as to further be anchored
The filling and film forming of above-mentioned quantum dot is better achieved in quantum dot.It is specific preferred, the active function groups be-OH ,-
COOH、-NH2、-NH-、-NHCONH-、-SH、-CN、-SO3H、-SOOH、-NO2、-CONH2、-CONH-、-COCl、-CO-、-
O- ,-COS- ,-CH=N-, O=P (R)2,-CHO ,-Cl, at least one of-Br.
Composite luminescence layer provided in an embodiment of the present invention, including grapheme foam skeleton and quantum dot.Wherein, the graphite
Alkene foam framework is loose porous, can effectively fix quantum dot, prevents quantum dot in the film forming procedure of follow-up function layer by it
He solution wash away or film forming procedure in fall, assist the film forming of quantum dot, the composite luminescence layer made have shine it is uniform
The performances such as stable, so as to improve the luminous efficiency of device, uniformity of luminance and stability.
And the embodiment of the invention provides a kind of QLED device, including stack gradually in conjunction on substrate hearth electrode,
First functional layer, luminescent layer, the second functional layer and top electrode, wherein the luminescent layer is above-mentioned composite luminescence layer.
Specifically, QLED device can be eurymeric QLED device, or transoid QLED device in the present invention.
As a kind of implementation situation, as shown in Fig. 2, the QLED device can be eurymeric LED component, including stack gradually
Hearth electrode 2, the first functional layer (3 and 4), luminescent layer 5, the second functional layer (6) and the top electrode 7 being incorporated on substrate 1, wherein
The hearth electrode 2 is anode, and the top electrode is cathode, and first functional layer is to stack gradually to be incorporated on the anode 2
Hole injection layer 3 and hole transmission layer 4, second functional layer be stacking combine electron injection on the light-emitting layer/
Transport layer 6.
As another implementation situation, the QLED device can be transoid QLED device, and the QLED device can be
Eurymeric LED component, including stacking gradually in conjunction with hearth electrode, the first functional layer, luminescent layer, the second functional layer and top on substrate
Electrode, wherein the hearth electrode is cathode, and the top electrode is anode, and first functional layer is that stacking is incorporated in the yin
Electron injection/transport layer on extremely, second functional layer are the hole transmission layer stacked gradually Jie Hes on the light-emitting layer
And hole injection layer.
In above-mentioned implementation situation, specifically, the composite luminescence layer is the fixed quantum dot light emitting of grapheme foam skeleton
Layer, including grapheme foam skeleton and the quantum dot being fixed in the grapheme foam skeleton.Pass through the grapheme foam
Fixation of the skeleton to the quantum dot, prevents quantum dot from being washed away or being formed a film by other solution in the film forming procedure of follow-up function layer
It falls in the process, improves the filming performance of quantum dot light emitting layer.
Preferably, the grapheme foam skeleton specific surface area is 10~300m2/g.The preferred grapheme foam skeleton
With loose and porous structure, specific surface is larger, on the one hand, the template of a physics can be provided to quantum dot, so that quantum dot
It preferably fills and forms a film, and prevent that quantum dot is washed away or re-dissolved in follow-up function layer deposition process.
It is further preferred that active function groups are contained on grapheme foam skeleton surface, so as to further be anchored
The filling and film forming of above-mentioned quantum dot is better achieved in quantum dot.It is specific preferred, the active function groups be-OH ,-
COOH、-NH2、-NH-、-NHCONH-、-SH、-CN、-SO3H、-SOOH、-NO2、-CONH2、-CONH-、-COCl、-CO-、-
O- ,-COS- ,-CH=N-, O=P (R)2,-CHO ,-Cl, at least one of-Br.
It is further preferred that the grapheme foam skeleton has skeleton structure corresponding with metal foam, so as to more
The fixed quantum dot well.Specific preferred, the metal foam includes but is not limited to Ni foam, Co foam, Cu foam, Fe
At least one of foam, Sn foam, Zn foam, Mg foam, Ti foam.Preferred metal foam can be grapheme foam bone
Frame provides better form cage, so that there is obtained grapheme foam skeleton higher porosity and more suitable aperture to tie
Structure, can preferably improve quantum dot at film uniformity.
In the embodiment of the present invention, the substrate is rigid substrate or flexible substrate, and the rigid substrate includes but is not limited to
Glass, metal foil；The flexible substrate includes but is not limited to polyethylene terephthalate, polyethylene terephthalate
Ester, polyether-ether-ketone, polystyrene, polyether sulfone, polycarbonate, poly- aryl acid esters, polyarylate, polyimides, polyvinyl chloride, poly- second
Alkene, polyvinylpyrrolidone, textile fabric.
The anode can choose the anode material of the field QLED routine.As a kind of implementation situation, the anode is to mix
Miscellaneous 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.
The hole injection layer is selected from the organic material with Hole injection capacity.Prepare the hole of the hole injection layer
Including but not limited to poly- (3,4- the ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS) of injection material, CuPc
(CuPc), tetra- cyanogen quinone of 2,3,5,6- tetra- fluoro- 7,7', 8,8'--bismethane (F4-TCNQ), six cyano -1 2,3,6,7,10,11-,
Six azepine benzophenanthrene (HATCN) of 4,5,8,9,12-, doped or non-doped transition metal oxide, doped or non-doped metal sulphur
One of based compound is a variety of.Wherein, the transition metal oxide includes but is not limited to MoOx、VOx、WOx、CrOx、
At least one of CuO；The metal chalcogenide includes but is not limited to MoS2、MoSe2、WS2、WSe2, in CuS at least
It is a kind of.
The hole transmission layer is selected from the organic material with cavity transmission ability, and including but not limited to poly- (9,9- bis- is pungent
Base fluorenes-CO-N- (4- butyl phenyl) diphenylamines) (TFB), polyvinylcarbazole (PVK), it is poly- (bis- (4- the butyl phenyl)-N of N, N',
Bis- (phenyl) benzidine of N'-) (poly-TPD), 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, N '-(1- naphthalene) -1,1 '-biphenyl -
At least one of 4,4 '-diamines (NPB), doped graphene, undoped graphene, C60.It is described as another embodiment
Hole transmission layer 4 is selected from the inorganic material with cavity transmission ability, including but not limited to doped or non-doped MoOx、VOx、
WOx、CrOx、CuO、MoS2、MoSe2、WS2、WSe2, at least one of CuS.
Quantum dot in the luminescent layer can be conventional quantum dot.The quantum dot can for II-VI group it is nanocrystalline,
Iii-v is nanocrystalline, II-V race is nanocrystalline, III-VI race is nanocrystalline, group IV-VI is nanocrystalline, I-III-VI race is nanocrystalline, II-
Group IV-VI is nanocrystalline or one of IV race simple substance or a variety of.Specifically, the II-VI it is nanocrystalline include CdS, CdSe,
CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, PbS, PbSe, PbTe, but not limited to this, it can also be other binary, three
Member, the II-VI of quaternary are nanocrystalline；It includes GaP, GaAs, InP, InAs that the iii-v is nanocrystalline, but not limited to this, it can be with
For other binary, ternary, the III-V compound of quaternary.
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 injection/transport layer is selected from the material with electronic transmission performance, including but not
It is limited to ZnO, TiO2、SnO2、Ta2O3、AlZnO、ZnSnO、InSnO、Alq3、Ca、Ba、CsF、LiF、CsCO3At least one of.
In the embodiment of the present invention, the cathode is various conductive carbon materials, in conductive metal oxide material, metal material
It is one or more.Wherein, the conductive carbon material include but is not limited to doped or non-doped carbon nanotube, it is doped or non-doped
Graphene, doped or non-doped graphene oxide, C60, graphite, carbon fiber, more empty carbon or their mixture；The conduction
Metal oxide materials include but is not limited to ITO, FTO, ATO, AZO or their mixture；The metal material includes but not
It is limited to Al, Ag, Cu, Mo, Au or their alloy.Wherein, in the metal material, form include but is not limited to nanosphere,
Nano wire, nanometer rods, nanocone, nano-hollow ball or their mixture.Particularly preferably, the cathode is 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.
The packaged type of the QLED device can be partial encapsulation, full encapsulation or not encapsulate that the embodiment of the present invention does not have
Stringent limitation.
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 be fixed on, therefore, in the composite luminescence layer use solwution method deposition other function layer when, it is possible to prevente effectively from
Erosion of the solvent to quantum dot layer is prepared, prevents quantum dot from dissolving or being flushed away.To sum up, QLED device provided by the invention, hair
Optical uniformity, membranous layer stability, luminous efficiency and service life are improved.
QLED device provided in an embodiment of the present invention can be prepared by following methods.
Correspondingly, the embodiment of the invention also provides a kind of preparation methods of QLED device, comprising the following steps:
S01. metal foam form cage is provided, the apposition growth graphene on the metal foam form cage obtains
Graphene/metal foam skeleton；
S02. the graphene/metal foam skeleton is immersed in etching liquid, etching removal metal foam template obtains
Grapheme foam skeleton；
S03., substrate is provided, is sequentially depositing hearth electrode, the first functional layer over the substrate, in first functional layer
The grapheme foam skeleton is deposited, quantum dot is deposited on the grapheme foam skeleton at composite luminescence layer, described
The second functional layer and top electrode are sequentially depositing in composite luminescence layer,
Wherein, the hearth electrode is anode, and the top electrode is cathode, and first functional layer is to stack gradually to be incorporated in
Hole injection layer and hole transmission layer on the anode, second functional layer are the electricity of stacking combination on the light-emitting layer
Sub- injection/transport layer；Or
The hearth electrode is cathode, and the top electrode is anode, and first functional layer is that stacking is incorporated in the cathode
On electron injection/transport layer, second functional layer be the hole transmission layer that stacks gradually Jie Hes on the light-emitting layer and
Hole injection layer.
Specifically, the metal foam in the metal foam form cage is to contain foam stomata in above-mentioned steps S01
Special metal material, containing very high porosity, including but not limited to Ni foam, Co foam, Cu foam, Fe foam, Sn foam,
At least one of Zn foam, Mg foam, Ti foam.Preferred metal foam form cage is the grapheme foam skeleton
Foam framework formation, provide good duplication template so that obtained grapheme foam skeleton have higher hole
Degree and more suitable aperture structure, can preferably improve quantum dot at film uniformity.
The method of apposition growth graphene includes CVD method, epitaxial growth method, change on the metal foam form cage
Method etc..The embodiment of the present invention preferably uses CVD method, can not only improve the proximity of graphene, improves film layer electric conductivity,
And be conducive to obtain growth uniformly and the comprehensive grapheme foam skeleton of covering by vapor deposition, consequently facilitating being subsequently formed
Uniformly, the comprehensive luminous composite layer of covering.
In above-mentioned steps S02, the graphene/metal foam skeleton immersion is performed etching into processing in an acidic solution,
The metal foam template is removed.The etching liquid can be aqueous slkali or acid solution, more preferably acid solution.Specifically,
The acid solution includes but is not limited to the mixed solution of acid solution, metal salt solution, acid solution and metal salt solution composition,
In, the metal salt in the metal salt solution is after hydrolyzing in acid metal salt.Preferably, the acid solution is hydrochloric acid, sulphur
At least one of acid, nitric acid, phosphoric acid, perchloric acid, hydrofluoric acid, acetic acid, carbonic acid, benzoic acid.Preferably, the metal salt is chlorine
Change at least one of iron, ferrous sulfate, copper nitrate, copper sulphate, aluminum sulfate.It is further preferred that the acid solution and metal
In the mixed solution of salting liquid composition, the molar ratio of hydrogen ion and the metal salt in the acid solution is 1:0.001~10.
If the hydrogen ion concentration in the acid solution is too low, may cause incomplete to the etching of virgin metal foam；If the acid is molten
Hydrogen ion concentration in liquid is too low, then may cause over etching, the performance of the grapheme foam skeleton influenced.It is general to use
The solution of lower ph realizes better etching effect.Therefore, it is furthermore preferred that hydrogen ion and the gold in the acid solution
The molar ratio for belonging to salt is 1:0.1~2.
Preferably, etching remove metal foam template during or etching obtain grapheme foam skeleton after, also wrap
It includes and introduces active function groups on grapheme foam skeleton surface.As an embodiment, acidification exists in etching process
Grapheme foam skeleton surface introduces active function groups.As another embodiment, after etching to grapheme foam
Skeleton carries out acidification and introduces active function groups.
In above-mentioned steps S03, grapheme foam skeleton described in the embodiment of the present invention replicates the skeleton of the metal foam
Structure.The grapheme foam skeleton is deposited in first functional layer, it is preferred to use transfer method is realized.
It is sequentially depositing hearth electrode, the first functional layer over the substrate, deposits quantum on the grapheme foam skeleton
Point forms composite luminescence layer, and the second functional layer and top electrode are sequentially depositing in the composite luminescence layer, can pass through ability
Domain conventional method is realized.
Specifically, the hole injection layer, hole transmission layer, luminescent layer, electron injection/transport layer deposition method are excellent
It is selected as print process, is specifically including but not limited to ink-jet printing, roll coating process, transfer printing, knife coating, slit coating method, strip
Rubbing method, it is further preferred that the deposition method is ink-jet printing.The anode, cathode deposition can using chemistry
Method or physical method are realized, wherein the chemical method includes but is not limited to chemical vapour deposition technique, successive ionic layer adsorption and reaction
One of method, anodizing, strike, coprecipitation are a variety of；The physical method includes but is not limited to physics plating
Embrane method or solution processing method, wherein solution processing 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；Physical coating method includes but is not limited to heat
Evaporation coating method, electron beam evaporation deposition method, magnetron sputtering method, multi-arc ion coating embrane method, physical vaporous deposition, atomic layer deposition
One of area method, pulsed laser deposition are a variety of.
The preparation method of QLED device provided in an embodiment of the present invention first deposits graphene bubble before depositing quantum dot layer
Foam skeleton.The grapheme foam skeleton is obtained by template growth of the metal foam, therefore, is had corresponding with metal foam
Foam framework structure, be conducive to the fixation of quantum dot, prevent from being produced solvent dissolution in the preparation process of follow-up function layer
Or be flushed away, improve quantum dot at film uniformity, and then improve the uniformity of luminance of QLED device, membranous layer stability, shine
Efficiency and service life.
It is illustrated combined with specific embodiments below.
Embodiment 1
A kind of preparation method of QLED device, comprising the following steps:
S11., Ni foam formwork skeleton is provided, CVD method apposition growth graphene is used on the Ni foam formwork skeleton,
Obtain graphene/metal foam skeleton；
S12. the graphene/metal foam skeleton is immersed in FeCl3In/HCl etching liquid, etching removal metal foam
Template obtains grapheme foam skeleton, wherein the FeCl3HCl and FeCl in/HCl etching liquid3Molar ratio be 1:0.6；
S13., glass substrate is provided, ito anode, PEDOT layers and TFB layers are sequentially depositing in the glass substrate, in institute
It states and deposits the grapheme foam skeleton on TFB layers, CdSe/ZnS quantum dot is deposited on the grapheme foam skeleton and is formed
Composite luminescence layer is sequentially depositing ZnO layer and Al cathode in the composite luminescence layer.
Embodiment 2
A kind of preparation method of QLED device, comprising the following steps:
S11., Co foam formwork skeleton is provided, CVD method apposition growth graphene is used on the Co foam formwork skeleton,
Obtain graphene/metal foam skeleton；
S12. the graphene/metal foam skeleton is immersed in FeCl3In/HCl etching liquid, etching removal metal foam
Template obtains grapheme foam skeleton, wherein the FeCl3HCl and FeCl in/HCl etching liquid3Molar ratio be 1:0.3；
S13., glass substrate is provided, ito anode, PEDOT layers and TFB layers are sequentially depositing in the glass substrate, in institute
It states and deposits the grapheme foam skeleton on TFB layers, CdSe/ZnS quantum dot is deposited on the grapheme foam skeleton and is formed
Composite luminescence layer is sequentially depositing ZnO layer and Al cathode in the composite luminescence 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 (14)
1. a kind of composite luminescence layer, which is characterized in that the composite luminescence layer is the fixed quantum dot hair of grapheme foam skeleton
Photosphere, including grapheme foam skeleton and the quantum dot being fixed in the grapheme foam skeleton.
2. composite luminescence layer as described in claim 1, which is characterized in that the specific surface area of the grapheme foam skeleton is 10
~300m2/g。
3. composite luminescence layer as claimed in claim 1 or 2, which is characterized in that contain work in grapheme foam skeleton surface
Property functional group.
4. composite luminescence layer as claimed in claim 3, which is characterized in that the active function groups are-OH ,-COOH ,-NH2、-
NH-、-NHCONH-、-SH、-CN、-SO3H、-SOOH、-NO2、-CONH2,-CONH- ,-COCl ,-CO- ,-O- ,-COS- ,-CH=
N-, O=P (R)2,-CHO ,-Cl, at least one of-Br.
5. a kind of QLED device, which is characterized in that including stacking gradually in conjunction with hearth electrode, the first functional layer, hair on substrate
Photosphere, the second functional layer and top electrode, wherein the luminescent layer is the described in any item composite luminescence layers of claim 1-4.
6. QLED device as claimed in claim 5, which is characterized in that the hearth electrode is anode, and the top electrode is cathode,
First functional layer is the hole injection layer and hole transmission layer stacked gradually Jie Hes on the anode, second function
Layer combines electron injection/transport layer on the light-emitting layer for stacking.
7. QLED device as claimed in claim 5, which is characterized in that the hearth electrode is cathode, and the top electrode is anode,
First functional layer is the electron injection/transport layer of stacking combination on the cathode, and second functional layer is successively layer
The hole transmission layer and hole injection layer of folded combination on the light-emitting layer.
8. a kind of preparation method of QLED device, which comprises the following steps:
Metal foam form cage is provided, the apposition growth graphene on the metal foam form cage obtains graphene/gold
Belong to foam framework；
The graphene/metal foam skeleton is immersed in etching liquid, etching removal metal foam template obtains graphene bubble
Foam skeleton；
Substrate is provided, is sequentially depositing hearth electrode, the first functional layer over the substrate, in first functional layer described in deposition
Grapheme foam skeleton deposits quantum dot at composite luminescence layer, in the recombination luminescence on the grapheme foam skeleton
It is sequentially depositing the second functional layer and top electrode on layer,
Wherein, the hearth electrode is anode, and the top electrode is cathode, first functional layer be stack gradually be incorporated in it is described
Hole injection layer and hole transmission layer on anode, second functional layer are that stacking combines electronics on the light-emitting layer to infuse
Enter/transport layer；Or
The hearth electrode is cathode, and the top electrode is anode, and first functional layer is that stacking combines on the cathode
Electron injection/transport layer, second functional layer are the hole transmission layer stacked gradually Jie Hes on the light-emitting layer and hole
Implanted layer.
9. the preparation method of QLED device as claimed in claim 8, which is characterized in that in etching removal metal foam template
Simultaneously during or etching obtain grapheme foam skeleton after, further include grapheme foam skeleton surface introduce activity
Functional group.
10. the preparation method of QLED device as claimed in claim 9, which is characterized in that the active function groups be-OH ,-
COOH、-NH2、-NH-、-NHCONH-、-SH、-CN、-SO3H、-SOOH、-NO2、-CONH2、-CONH-、-COCl、-CO-、-
O- ,-COS- ,-CH=N-, O=P (R)2,-CHO ,-Cl, at least one of-Br.
11. the preparation method of QLED device as claimed in claim 8, which is characterized in that the etching liquid is acid solution, packet
Include the mixed solution of acid solution, metal salt solution, acid solution and metal salt solution composition, wherein in the metal salt solution
Metal salt is after hydrolyzing in acid metal salt.
12. the preparation method of QLED device as claimed in claim 11, which is characterized in that the acid solution be hydrochloric acid, sulfuric acid,
At least one of nitric acid, phosphoric acid, perchloric acid, hydrofluoric acid, acetic acid, carbonic acid, benzoic acid；And/or
The metal salt is at least one of iron chloride, ferrous sulfate, copper nitrate, copper sulphate, aluminum sulfate.
13. the preparation method of QLED device as claimed in claim 11, which is characterized in that the acid solution and metal salt solution
In the mixed solution of composition, the molar ratio of hydrogen ion and the metal salt in the acid solution is 1:0.001~10.
14. such as the preparation method of the described in any item QLED devices of claim 8-13, which is characterized in that the metal foam mould
Metal foam in framework is Ni foam, in Co foam, Cu foam, Fe foam, Sn foam, Zn foam, Mg foam, Ti foam
At least one.
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