CN109326729A - A kind of QLED device and preparation method thereof - Google Patents
A kind of QLED device and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of display devicees, provide QLED device and preparation method thereof.QLED device provided by the invention, its luminescent layer introduces carbon material layer of the surface with functional group and hole is filled with the porous silicon film layer of quantum dot, on the one hand, quantum dot is filled in the hole of porous silicon film layer, the arrangement tightness degree and thickness of quantum dot can easily be regulated and controled by changing voidage, pore size and the film thickness etc. of porous silicon film layer, to improve the uniformity of luminance and stability of device；On the other hand, the introducing of carbon material layer of the surface with functional group not only serves as the platform of quantum dot sequence, and the transmission and injection of carrier can be improved in its excellent electric conductivity, to improve the luminous efficiency of device.
Description
Technical field
The invention belongs to the field of display devicees more particularly to a kind of QLED device and preparation method thereof.
Background technique
Quantum dot (Quantum dot, QD) is a kind of quasi-zero dimension nano material, similar superlattices and Quantum Well, particle
Size is about 1nm-100nm, has the performances such as quantum confined effect, skin effect, quantum size effect and quantum tunneling effect,
And outstanding advantages of monochromaticjty is good, excitation purity is high, luminescent spectrum is narrow, it is a kind of very promising nano material.Based on amount
Son point light emitting diode be referred to as light emitting diode with quantum dots (Quantum dots light-emitting diode,
It QLED), is a kind of novel display skill device.The advantage that quantum dot is shown be that colour gamut covering is wide, color is easy to control and
The advantages that excitation purity is high, it is considered to be the nova of display technology, while being also considered as the revolutionary of display technology and representing.
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 the particle size of quantum dot is larger compared with conventional ion or small organic molecule, and quantum
Surface organic ligand rich in is put, the connection after film forming between quantum dot particle is not close, film layer relative loose, simultaneously
Tightness is low between hole transmission layer below, and post-depositional quantum dot still has very big chance in subsequent other function layer
It is re-dissolved in solwution method film forming procedure and takes away or directly wash away, cause quantum dot film layer uneven and device luminance nonuniformity
It is even.Even if using the solvent of indissoluble solution quantum dot, it is also difficult to avoid the generation of the process, and because of this, follow-up function
The selection of layer material also will receive the limitation of its optional solvent.
Therefore, existing QLED device exists due to uneven, the loosely organized, group of being easy to appear of quantum dot light emitting layer film forming
The problems such as poly- and uniform device of device luminance nonuniformity caused by covering is not congruent is unstable.
Summary of the invention
The purpose of the present invention is to provide a kind of QLED devices and preparation method thereof, it is intended to solve existing QLED device and deposit
As quantum dot light emitting layer form a film it is uneven, loosely organized, be easy to appear reunion and covering it is not congruent caused by device shine
The problems such as uneven and device is unstable.
The present invention provides a kind of QLED device, the device includes the substrate set gradually, hearth electrode, the first function
Layer, luminescent layer, the second functional layer and top electrode, the luminescent layer include
Carbon material layer of the surface with functional group in first functional layer is set；
Porous silicon film layer on the carbon material layer is set, and the hole of the porous silicon film layer is filled with quantum dot.
The present invention also provides a kind of preparation method of QLED device, the preparation method includes the following steps:
It is sequentially depositing hearth electrode and the first functional layer on substrate；
Carbon material layer of the deposition surface with functional group, the deposited porous on the carbon material layer in first functional layer
Silicon film and in depositing quantum dot in the porous silicon film layer, obtains luminescent layer；Or carbon material layer of the surface with functional group is provided,
Deposited porous silicon film forms composite layer on the carbon material layer, and the composite layer is deposited in first functional layer,
In depositing quantum dot in the porous silicon film layer of the composite layer, luminescent layer is obtained；
It is sequentially depositing the second functional layer and top electrode on the light-emitting layer.
The luminescent layer of QLED device provided by the invention introduces carbon material layer of the surface with functional group and hole is filled with
The porous silicon film layer of quantum dot, on the one hand, quantum dot is filled in the hole of porous silicon film layer, the arrangement tightness degree of quantum dot
And thickness can easily be regulated and controled by changing voidage, pore size and the film thickness etc. of porous silicon film layer, to improve
The uniformity of luminance and stability of device；On the other hand, the introducing of carbon material layer of the surface with functional group not only serves as quantum
The platform of point sequence has anchoring effect to quantum dot, so that solwution method film forming procedure of the quantum dot in subsequent other function layer
In be not easy to be re-dissolved and take away or directly wash away, and transmission and the note of carrier can be improved in its excellent electric conductivity
Enter, to improve the luminous efficiency of device.The preparation method of QLED device provided by the invention, preparation process is simple, at low cost,
Large-scale production can be achieved.
Detailed description of the invention
Fig. 1 is the structural schematic diagram for the QLED device that the embodiment of the present invention provides；
Fig. 2 is the flow diagram of the preparation method for the QLED device that the embodiment of the present invention provides；
Fig. 3 is the flow diagram of the preparation method for the QLED device that another embodiment of the present invention provides.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
In the description of the present invention, it is to be understood that, term " first ", " second " are used for description purposes only, and cannot
It is interpreted as indication or suggestion relative importance or implicitly indicates the quantity of indicated technical characteristic.Define as a result, " the
One ", the feature of " second " can explicitly or implicitly include one or more of the features.In the description of the present invention,
The meaning of " plurality " is two or more, unless otherwise specifically defined.
Referring to Fig. 1, Fig. 1 is the structural schematic diagram of QLED device provided in an embodiment of the present invention.The QLED device includes
Substrate 1, hearth electrode 2, the first functional layer 3, luminescent layer 4, the second functional layer 5 and the top electrode 6 set gradually, luminescent layer 4 wrap
The porous silicon film layer for including carbon material layer of the surface with functional group being arranged in the first functional layer 3 and being arranged on carbon material layer,
The hole of porous silicon film layer is filled with quantum dot.
In embodiments of the present invention, the selection of substrate 1 is unrestricted, can use rigid substrates, can also be using flexibility
Substrate.Wherein, rigid substrates include but is not limited to one of glass, metal foil or a variety of；Flexible base board includes but unlimited
In polyethylene terephthalate (PET), polyethylene terephthalate (PEN), polyether-ether-ketone (PEEK), polystyrene
(PS), polyether sulfone (PES), polycarbonate (PC), poly- aryl acid esters (PAT), polyarylate (PAR), polyimides (PI), polychlorostyrene second
One of alkene (PV), polyethylene (PE), polyvinylpyrrolidone (PVP), textile fabric are a variety of.
In embodiments of the present invention, QLED device is not limited by device architecture, can be autologous device, can also
With the device of reciprocal form structure.When the structure of QLED device is eurymeric structure, then hearth electrode 2 is anode, and the first functional layer 3 is sky
Acupoints layer, the second functional layer 5 are electronic work ergosphere, and top electrode 6 is cathode；When the structure of QLED device is reciprocal form structure,
Then hearth electrode 2 is cathode, and the first functional layer 3 is electronic work ergosphere, and the second functional layer 5 is hole functional layer, and top electrode 6 is sun
Pole.
The present embodiment is explained device by eurymeric structure of the structure of QLED device, it should be noted that this
Embodiment is not only limited in autologous description, together the description of anode, hole functional layer, electronic work ergosphere and cathode
Sample is suitable for the description to the QLED device anode, hole functional layer, electronic work ergosphere and cathode of reciprocal form structure.
In embodiments of the present invention, hearth electrode 2 is anode, is deposited on substrate 1, the selection of 2 material of hearth electrode is unrestricted
System, can be selected from blended metal oxide, including but not limited to indium doping tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony is mixed
Miscellaneous tin oxide (ATO), aluminium-doped zinc oxide (AZO), Ga-doped zinc oxide (GZO), indium doping zinc oxide (IZO), magnesium adulterate oxygen
Change one of zinc (MZO), aluminium doping magnesia (AMO) or a variety of, doped or non-doped transparent metal oxygen can also be selected from
The combination electrode of metal, including but not limited to AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/ are clipped between compound
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 a variety of.
In embodiments of the present invention, the first functional layer 3 is hole functional layer, for injection and transporting holes, including but not
It is limited to be successively set at least one layer of hole injection layer and at least one layer of hole transmission layer on hearth electrode；In order to further increase
The injection efficiency in hole, the first functional layer 3 can also include the electronic barrier layer of setting on the hole transport layer.
Specifically, hole injection layer includes but is not limited to organic hole injection material, doped or non-doped transition metal
One of oxide, doped or non-doped metal chalcogenide are a variety of.Wherein, organic hole injection material include but
It is fluoro- to be not limited to poly- (3,4- ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), CuPc (CuPc), 2,3,5,6- tetra-
7,7', 8,8'- tetra- cyanogen quinones-bismethane (F4-TCNQ), six cyano -1,4,5,8,9,12- of 2,3,6,7,10,11-, six azepine benzo
It is one of luxuriant and rich with fragrance (HATCN) or a variety of；Transition metal oxide includes but is not limited to MoO3、VO2、WO3、CrO3, in CuO one
Kind is a variety of；Metal chalcogenide includes but is not limited to MoS2、MoSe2、WS2、WSe2, one of CuS or a variety of.
Specifically, hole transmission layer can be selected from the organic material with cavity transmission ability and/or have hole transport energy
The inorganic material of power.Wherein, with including but not limited to poly- (9, the 9- dioctyl fluorene-CO-N- of organic material of cavity transmission ability
(4- butyl phenyl) diphenylamines) (TFB), polyvinylcarbazole (PVK), poly- (N, N' bis- (4- butyl phenyl)-N, N'- are bis- (phenyl)
Benzidine) (poly-TPD), poly- (double-N of 9,9- dioctyl fluorene -co-, N- phenyl -1,4- phenylenediamine) (PFB), 4,4 ', 4 "-three
(carbazole -9- base) triphenylamine (TCTA), 4,4'- bis- (9- carbazole) biphenyl (CBP), N, N '-diphenyl-N, N '-two (3- methylbenzene
Base) -1,1 '-biphenyl -4,4 '-diamines (TPD), N, N '-diphenyl-N, N '-(1- naphthalene) -1,1 '-biphenyl -4,4 '-diamines
One of (NPB) or it is a variety of；Inorganic material with cavity transmission ability includes but is not limited to doped graphene, undoped stone
Black alkene, C60, doped or non-doped MoO3、VO2、WO3、CrO3、CuO、MoS2、MoSe2、WS2、WSe2, one of CuS or more
Kind.
In embodiments of the present invention, luminescent layer 4 is by carbon material layer of the surface with functional group that is arranged in the first functional layer
With the porous silicon film layer complex group that is arranged on carbon material layer at the hole of porous silicon film layer is filled with quantum dot.Specifically, more
Hole silicon film is deposited on carbon material layer of the surface with functional group of single-layer or multi-layer, composite layer is consequently formed, then porous
One or more layers quantum dot is deposited on silicon film, quantum dot is filled in the hole of porous silicon film layer, and quantum dot is by porous
The hole of silicon film leaves and is anchored in the functional group of carbon material layer simultaneously, to form the regular sequence of quantum dot and anchoring
In the luminescent layer 4 of carbon material layer, solve that existing quantum dot light emitting layer film forming is uneven, loosely organized, is easy to appear reunion
The infull problem with covering, so that luminescent device shines uniformly and stablizes.
In embodiments of the present invention, the material in carbon material layer of the surface with functional group includes doped or non-doped carbon materials
Material, specifically includes graphene, graphene oxide, carbon nanotube, mesoporous carbon, carbon fiber, carbon nano-particle, fullerene, carbon quantum
At least one of point, graphite, carbon aerogels；Functional group therein include carbon-carbon double bond, carbon-carbon triple bond, halogen atom, hydroxyl,
Ether, sulfydryl, thioether group, aldehyde radical, carbonyl, carboxyl, ester group, nitro, nitroso, amino, imido grpup, sulfo group, acyl group, nitryl
At least one of base, sulfonyl, cyano, isocyano group, hydrazone group, phosphino-, oximido, epoxy group, azo group, fragrant ring group.Quantum
Point is compounded in carbon material layer in the functional group of carbon material by the regular sequence of porous silicon film layer, and carbon material layer not only serves as
The platform of quantum dot sequence has anchoring effect to quantum dot, so that quantum dot is not easy to be weighed in the preparation process of device
New dissolution is taken away or is directly washed away, and the transmission and injection of carrier can be improved in its excellent electric conductivity, to improve
The luminous efficiency of device.
In embodiments of the present invention, porous silicon film layer has regular and regulatable hole and regulatable thicknesses of layers,
Wherein, pore diameter 4nm-200nm, thicknesses of layers 5nm-200nm, it is preferable that thicknesses of layers 5nm-100nm, it is more excellent
Selection of land, thicknesses of layers 5nm-30nm.It is filled in the arrangement tightness degree and thickness energy of the quantum dot in porous silicon film layer hole
It is enough easily to be regulated and controled by changing porosity, pore size, the film thickness etc. of porous silicon film layer during the preparation process, to mention
The uniformity of luminance and stability of high device.
In embodiments of the present invention, porous silicon film layer can be by silane coupling agent, block copolymer, strong acid promoter, organic
Solvent is made.Wherein, silane coupling agent, block copolymer, strong acid promoter, organic solvent mass ratio be 1:(0.0001-
0.01):(0.0001-0.01):(0.5-50):(0.5-100).Different mass ratioes is thick to the hole and film layer of porous silicon film layer
Degree distribution has an impact, and can pass through and adjust mass ratio and regulate and control porous silicon film layer hole and thicknesses of layers, it is preferable that mass ratio can be with
It is 1:(0.0001-0.008): (0.001-0.01): (2-20): (4-50).
Further, block polymer specifically refers to the different polymer segment of two or more property being connected in one
Act a kind of particular polymer being prepared.Block contained by block polymer includes polyethylene glycol, polyoxyethylene, polyoxy third
Alkene, polyethylene oxide, polypropylene oxide, polyethylene pyrrole alkanone, long-chain perfluoroalkyl, polysiloxane group, polylactic acid, lactic acid-
Co-glycolic acid, poly-epsilon-caprolactone, poly- benzyl asparatate, poly- benzyl glutamate, polystyrene, poly- isopropyl propylene
At least one of amide.Particularly, this case technical effect is realized to be more preferable, block polymer preferably comprises ethyoxyl-the third
The block polymer that oxygroup is formed.
Further, organic solvent can be polar solvent or nonpolar solvent.The organic solvent includes saturated hydrocarbons, insatiable hunger
At least one of with hydrocarbon, aromatic hydrocarbon, alcohol, ketone, ether, ester and their derivative.More specifically, the organic solvent includes
Hexane, hexamethylene, heptane, normal octane, isooctane, pentane, methylpentane, ethylpentane, pentamethylene, methyl cyclopentane, ethyl
Pentamethylene, benzene,toluene,xylene, ethylbenzene, methylene chloride, chloroform, carbon tetrachloride, dichloroethanes, trichloroethanes, chlorine third
Alkane, dichloropropane, trichloropropane, chlorobutane, methylene bromide, bromoform, bromoethane, N-Propyl Bromide, iodomethane, chlorobenzene, bromobenzene,
Benzyl chloride, benzyl bromide, benzotrifluoride, methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, amylalcohol,
Isoamyl alcohol, tert-pentyl alcohol, cyclohexanol, octanol, benzylalcohol, ethylene glycol, phenol, o-cresol, ether, methyl phenyl ethers anisole, phenetole, diphenyl ether,
Tetrahydrofuran, glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol diethyl ether, ethoxy ether, propylene glycol monopropyl ether, the third two
Alcohol single-butyl ether, acetaldehyde, benzaldehyde, acetone, butanone, cyclohexanone, acetophenone, formic acid, acetic acid, ethyl acetate, diethy-aceto oxalate,
Diethyl malonate, propyl acetate, methyl propyl ester, butyl acetate, methyl amyl acetate, nitrobenzene, acetonitrile, diethylamine, three second
Amine, aniline, pyridine, picoline, ethylenediamine, N,N-dimethylformamide, carbon disulfide, methyl sulfide, ethyl sulfide, diformazan are sub-
At least one of sulfone, mercaptan, ethyl mercaptan, methoxyl group tetrahydrofuran.
In embodiments of the present invention, quantum dot include nanocrystalline inorganic semiconductor, inorganic Ca-Ti ore type semiconductor, it is organic-
At least one of inorganic hybridization Ca-Ti ore type semiconductor.Wherein, it includes doped or non-doped II- that inorganic semiconductor is nanocrystalline
In V compound semiconductor, Group III-V compound semiconductor, group IV-VI compound semiconductor and its core-shell structure semiconductor
It is one or more.Inorganic Ca-Ti ore type semiconductor can be it is doped or non-doped, specifically, inorganic Ca-Ti ore type semiconductor
General structure is AMX3, wherein 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-.Organic-
Inorganic hybridization Ca-Ti 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-By altogether
The mode on top connects, and metal cation M is located at the octahedral body-centered of halogen, and organic amine cation B is filled in the sky between octahedron
In gap, the three-dimensional structure infinitely extended is formed；As n > 2, the inorganic metal hal ide connected in a manner of total top is octahedra
MX6 4-Layer structure, Intercalation reaction organic amine cation bilayer (protonation monoamine) or organic are extended to form in two-dimensional directional
Amine cation monolayer (protonation diamine), organic layer and inorganic layer mutually overlap and form stable two-dimensional layered structure；M is
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-。
In embodiments of the present invention, the second functional layer 5 is electronic work ergosphere, is used for transmission electronics, includes but is not limited to set
Set electron transfer layer on the light-emitting layer；In order to further increase the efficiency of transmission of electronics, the second functional layer 5 can also include setting
Set the hole blocking layer between luminescent layer 4 and electron transfer layer；In order to further increase the efficiency of transmission of electronics, the second function
Layer 5 can also include the electrode modification layer of setting on the electron transport layer.Wherein, electron transfer layer is N-shaped ZnO, TiO2、SnO、
Ta2O3、AlZnO、ZnSnO、InSnO、Alq3、Ca、Ba、CsF、LiF、CsCO3One of or it is a variety of.
In embodiments of the present invention, top electrode 6 is cathode, and material is various conductive carbon materials, conductive metal oxide
One of material, metal material are a variety of；Wherein conductive carbon material includes but is not limited to doped or non-doped carbon nanotube, mixes
Miscellaneous or undoped graphene, doped or non-doped graphene oxide, C60, graphite, carbon fiber, more empty carbon or their mixing
Object；Conductive metal oxide material includes but is not limited to ITO, FTO, ATO, AZO or their mixture；Metal material includes
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 cause
Close film, nano wire, nanosphere, nanometer rods, nanocone, nano-hollow ball or their mixture；Preferably, the yin
Extremely Ag, Al.
It in embodiments of the present invention, can also be in top electricity in order to protect device not by extraneous oxidation or other infringements
One layer of isolated protective layer of outside deposition of pole.
In embodiments of the present invention, the packaged type of device is unrestricted, can be partial encapsulation, full encapsulation, does not encapsulate
One of.
QLED device provided in an embodiment of the present invention, luminescent layer 4 introduce carbon material layer of the surface with functional group and hole
Gap is filled with the porous silicon film layer of quantum dot, on the one hand, quantum dot is filled in porous silicon film layer, and the arrangement of quantum dot is close
Degree and thickness can easily be regulated and controled by changing voidage, pore size and the film thickness etc. of porous silicon film layer, thus
Improve the uniformity of luminance and stability of device；On the other hand, the introducing of carbon material layer of the surface with functional group not only serves as
The platform of quantum dot sequence, and the transmission and injection of carrier can be improved in its excellent electric conductivity, to improve device
Luminous efficiency.
QLED device provided in an embodiment of the present invention can be prepared by the preparation method for the QLED device that following embodiment provides
It obtains.
Referring to Fig. 2, Fig. 2 is the flow diagram of the preparation method of QLED device provided in an embodiment of the present invention.This hair
Bright embodiment provides a kind of preparation method of QLED device, the preparation method the following steps are included:
Step S101: it is sequentially depositing hearth electrode and the first functional layer on substrate.
Step S102: carbon material layer of the deposition surface with functional group in the first functional layer deposits more on carbon material layer
Hole silicon film and in depositing quantum dot in porous silicon film layer, obtains luminescent layer.Wherein, quantum dot is filled into more during the deposition process
In the hole of hole silicon film.
Step S103: it is sequentially depositing the second functional layer and top electrode on the light-emitting layer.
Wherein, porous silicon film layer can be prepared by the following steps acquisition:
Step S01: silane coupling agent, block copolymer, strong acid promoter and organic solvent are provided by preset ratio.
Step S02: silane coupling agent, block copolymer, strong acid promoter and organic solvent are mixed, and it is molten to form mixing
Liquid.
Step S03: mixed solution is deposited on carbon material layer and is heating and curing.
In embodiments of the present invention, the hole and film of different preset ratios and different solidification temperatures to porous silicon film layer
Layer thickness profile has an impact, can be by adjusting preset quality ratio and solidification temperature to regulate and control porous silicon film layer hole and film layer
Thickness.Specifically, in order to make solution mixing more evenly and prepare hole and thicknesses of layers is evenly distributed, preferably 1:
(0.0001-0.01): (0.0001-0.01): (0.5-50): the mass ratio of (0.5-100), it is highly preferred that can be 1:
(0.0001-0.008): (0.001-0.01): (2-20): the mass ratio of (4-50)；In order to make the hole and film of porous silicon film layer
Thickness degree more easy-regulating, the temperature being heating and curing are preferably 60 DEG C -500 DEG C, it is highly preferred that be heating and curing temperature be 100 DEG C -
400℃。
In embodiments of the present invention, step S101, substrate, hearth electrode involved in step S102 and step S103,
One functional layer, luminescent layer, the second functional layer and top electrode the associated description substrate 1 being related to corresponding with previous embodiment,
Hearth electrode 2, the first functional layer 3, luminescent layer 4, the description of the second functional layer 5 and top electrode 6 are consistent, no longer describe herein.
Illustratively, with autologous QLED device and the first functional layer include be successively set on anode hole note
Enter layer and for hole transmission layer, the second functional layer include setting electron transfer layer on the light-emitting layer, then step S101, step
The combination of S102 and step S103 specifically may is that
Step S1011: depositing one layer of anode on substrate, at least one layer of hole injection layer is deposited on anode, in hole
At least one layer of hole transmission layer is deposited on implanted layer.
Step S1021: carbon material layer of the deposition surface with functional group on the hole transport layer deposits more on carbon material layer
Hole silicon film and in depositing quantum dot in porous silicon film layer, quantum dot is filled into the hole of porous silicon film layer during the deposition process
In, obtain luminescent layer.
Step S1031: depositing one layer of electron transfer layer on the light-emitting layer, deposits one layer of cathode on the electron transport layer, obtains
To light emitting diode with quantum dots.
In embodiments of the present invention, step S101, the method for deposition involved in step S102 and step S103 can be with
Chemical method or physical method, wherein chemical method include but is not limited to chemical vapour deposition technique, successive ionic layer adsorption and reaction method,
One of anodizing, strike, coprecipitation are a variety of；Physical method includes but is not limited to physical coating method or molten
Liquid method, wherein solwution method includes but is not limited to spin-coating method, transfer printing, print process, knife coating, dip-coating method, infusion method, spraying
Method, roll coating process, casting method, slit coating method, strip rubbing method；Physical coating method include but is not limited to 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.
The preparation method of QLED device provided in an embodiment of the present invention, can prepare shine it is uniform, stable and luminous
High-efficient QLED device, and technology difficulty is low, operation is simple, at low cost, it can be achieved that large-scale production.
Referring to Fig. 3, Fig. 3 be another embodiment of the present invention provides QLED device preparation method flow diagram.
The embodiment of the invention provides a kind of preparation method of QLED device, the preparation method the following steps are included:
Step S201: it is sequentially depositing hearth electrode and the first functional layer on substrate.
Step S202: providing carbon material layer of the surface with functional group, and deposited porous silicon film forms multiple on carbon material layer
Layer is closed, composite layer is deposited in the first functional layer, in depositing quantum dot in the porous silicon film layer of composite layer, obtains luminescent layer.
Wherein, quantum dot is filled into during the deposition process in the hole of porous silicon film layer.
Step S203: it is sequentially depositing the second functional layer and top electrode on the light-emitting layer.
In embodiments of the present invention, step S201 and step S202, which can be, first carries out step S201 and executes step again
S202 is also possible to the two while intersecting progress.For example, it may be being sequentially depositing hearth electrode and the first functional layer on substrate
Carry out the preparation of composite layer together simultaneously.
In embodiments of the present invention, step S201, substrate, hearth electrode involved in step S202 and step S203,
The associated description and aforementioned reality of one functional layer, luminescent layer (preparation including porous silicon film layer), the second functional layer and top electrode
It is (including more to apply substrate involved in a step S101, step S102 and step S103, hearth electrode, the first functional layer, luminescent layer
The preparation of hole silicon film), the description of the second functional layer and top electrode it is consistent, no longer describe herein.
Illustratively, with autologous QLED device and the first functional layer include be successively set on anode hole note
Enter layer and for hole transmission layer, the second functional layer include setting electron transfer layer on the light-emitting layer, then step S201, step
The combination of S202 and step S203 specifically may is that
Step S2011: depositing one layer of anode on substrate, at least one layer of hole injection layer is deposited on anode, in hole
At least one layer of hole transmission layer is deposited on implanted layer.
Step S2021: deposited porous silicon film is compounded to form composite layer on carbon material layer of the surface with functional group, will before
It states composite layer to be transferred on hole transmission layer, and in depositing quantum dot in the porous silicon film layer of composite layer, quantum dot was being deposited
It is filled into journey in the hole of porous silicon film layer, obtains luminescent layer.
Step S2031: depositing one layer of electron transfer layer on the light-emitting layer, deposits one layer of cathode on the electron transport layer, obtains
To light emitting diode with quantum dots.
In embodiments of the present invention, step S201, the method for deposition involved in step S202 and step S203 can be with
Chemical method or physical method, wherein chemical method include but is not limited to chemical vapour deposition technique, successive ionic layer adsorption and reaction method,
One of anodizing, strike, coprecipitation are a variety of；Physical method includes but is not limited to physical coating method or molten
Liquid method, wherein solwution method includes but is not limited to spin-coating method, transfer printing, print process, knife coating, dip-coating method, infusion method, spraying
Method, roll coating process, casting method, slit coating method, strip rubbing method；Physical coating method include but is not limited to 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.
Illustratively illustrate preparation method below:
(1) one layer of PEDOT:PSS film of spin coating is as hole injection layer on ITO electro-conductive glass, on PEDOT:PSS layer
One layer TFB layers of spin coating.
(2) tetraethoxysilane, polyoxyethylene poly-oxygen propylene aether block copolymer, hydrochloric acid, dehydrated alcohol are pressed 1:
The mass ratio of 0.006:0.008:10:30 is uniformly mixed, and is configured to mixed solution；Then the mixed solution is spin-coated on graphene
On, it is heating and curing to form porous silicon film layer then at 350 DEG C, thus obtains the composite layer of graphene and porous silicon film layer.It is wherein more
The pore diameter of hole silicon film is 30nm；Thicknesses of layers is 20nm.One layer of foregoing composite layer is transferred on TFB layer,
One layer of CdSe/ZnS quantum dot light emitting layer of spin coating in the porous silicon film layer of composite layer.
(3) one layer of Al cathode layer is deposited in ZnO layer, obtains for the spin coating layer of ZnO layer on CdSe/ZnS quantum dot light emitting layer
To light emitting diode with quantum dots.
The preparation method of QLED device provided in an embodiment of the present invention, can prepare shine it is uniform, stable and luminous
High-efficient QLED device, and technology difficulty is low, operation is simple, at low cost, it can be achieved that large-scale production.
The above is merely preferred embodiments of the present invention, be not intended to limit the invention, it is all in spirit of the invention and
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within principle.
Claims (14)
1. a kind of QLED device, the device includes the substrate set gradually, hearth electrode, the first functional layer, luminescent layer, the second function
Ergosphere and top electrode, which is characterized in that the luminescent layer includes
Carbon material layer of the surface with functional group in first functional layer is set；
Porous silicon film layer on the carbon material layer is set, and the hole of the porous silicon film layer is filled with quantum dot.
2. QLED device as described in claim 1, which is characterized in that the diameter of the hole is 4nm-200nm.
3. QLED device as described in claim 1, which is characterized in that the thicknesses of layers of the porous silicon film layer is 5nm-
200nm。
4. QLED device as described in any one of claims 1-3, which is characterized in that the porous silicon film layer is by silane coupled
Agent, block copolymer, strong acid promoter and organic solvent are made.
5. QLED device as claimed in claim 4, which is characterized in that the porous silicon film layer is total by silane coupling agent, block
The mass ratio of polymers, strong acid promoter and organic solvent is 1:(0.0001-0.01): (0.0001-0.01): (0.5-50):
(0.5-100)。
6. QLED device as claimed in claim 4, which is characterized in that block contained by the block copolymer includes poly- second two
Alcohol, polyoxyethylene, polyoxypropylene, polyethylene oxide, polypropylene oxide, polyethylene pyrrole alkanone, long-chain perfluoroalkyl, poly- silicon oxygen
Alkyl, polylactic acid, poly lactic coglycolic acid, poly-epsilon-caprolactone, poly- benzyl asparatate, poly- benzyl glutamate, polyphenyl
At least one of ethylene, polyisopropyl acrylamide.
7. QLED device as claimed in claim 4, which is characterized in that the organic solvent includes saturated hydrocarbons, unsaturated hydrocarbons, virtue
At least one of fragrant hydrocarbon, alcohol, ketone, ether, ester and their derivative.
8. QLED device as described in any one of claims 1-3, which is characterized in that the material of the carbon material layer includes graphite
Alkene, graphene oxide, carbon nanotube, mesoporous carbon, carbon fiber, carbon nano-particle, fullerene, carbon quantum dot, graphite, carbon aerogels
At least one of.
9. QLED device as described in any one of claims 1-3, which is characterized in that the functional group includes carbon-carbon double bond, carbon
Three key of carbon, halogen atom, hydroxyl, ether, sulfydryl, thioether group, aldehyde radical, carbonyl, carboxyl, ester group, nitro, nitroso, amino, Asia
Amido, sulfo group, acyl group, nitroxyl, sulfonyl, cyano, isocyano group, hydrazone group, phosphino-, oximido, epoxy group, azo group, aromatic rings
At least one of base.
10. QLED device as described in any one of claims 1-3, which is characterized in that the quantum dot includes inorganic semiconductor
At least one of nanocrystalline, inorganic Ca-Ti ore type semiconductor, hybrid inorganic-organic Ca-Ti ore type semiconductor.
11. a kind of preparation method of QLED device, which is characterized in that the preparation method includes the following steps:
It is sequentially depositing hearth electrode and the first functional layer on substrate；
Carbon material layer of the deposition surface with functional group in first functional layer, the deposited porous silicon fiml on the carbon material layer
Layer and in depositing quantum dot in the porous silicon film layer, obtain luminescent layer；Or carbon material layer of the surface with functional group is provided, in institute
It states deposited porous silicon film on carbon material layer and forms composite layer, the composite layer is deposited in first functional layer, in institute
It states and deposits quantum dot in the porous silicon film layer of composite layer, obtain luminescent layer；
It is sequentially depositing the second functional layer and top electrode on the light-emitting layer.
12. preparation method as claimed in claim 11, which is characterized in that the preparation step of the porous silicon film layer includes:
Silane coupling agent, block copolymer, strong acid promoter and organic solvent are provided by preset ratio；
The silane coupling agent, the block copolymer, the strong acid promoter and the organic solvent are mixed, formed mixed
Close solution；
The mixed solution is deposited on the carbon material layer and is heating and curing.
13. preparation method as claimed in claim 12, which is characterized in that the silane coupling agent, the block copolymer, institute
The mixing mass ratio for stating strong acid promoter and the organic solvent is 1:(0.0001-0.01): (0.0001-0.01): (0.5-
50):(0.5-100)。
14. preparation method as described in claim 12 or 13, which is characterized in that the temperature being heating and curing is 60 DEG C -500
℃。
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Application publication date: 20190212 |