CN109285947A - Printing LED film LED substrate, LED film LED device and preparation method thereof - Google Patents
Printing LED film LED substrate, LED film LED device and preparation method thereof Download PDFInfo
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- CN109285947A CN109285947A CN201710597158.5A CN201710597158A CN109285947A CN 109285947 A CN109285947 A CN 109285947A CN 201710597158 A CN201710597158 A CN 201710597158A CN 109285947 A CN109285947 A CN 109285947A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
- H10K77/10—Substrates, e.g. flexible substrates
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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- H—ELECTRICITY
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Abstract
The present invention provides a kind of film for printing LED substrates, the film for printing LED substrate is grooved substrate, including substrate, and the patterning composite layer being arranged on the substrate, the patterning composite layer is enclosed pixel array groove, wherein, the patterning composite layer includes the patterned Graphene layer of setting on the substrate, and it is incorporated in the hydrophobic layer of the patterned Graphene layer surface, and the patterned Graphene layer is in the active functional group of surface modification back to the substrate.
Description
Technical field
The invention belongs to LED technology field more particularly to a kind of film for printing LED substrates, film LED device
Part and preparation method thereof.
Background technique
In recent years, with the development of science and technology display technology achieves quick development.Modern display technology is aobvious according to information
The major way shown is divided into cathode-ray tube (Cathode Ray Tube, CRT) and FPD (Flat Panel
Display,FPD).Currently on the market, traditional CRT technology is faded out on the display technology arena of history substantially, and various new
The flat panel display of type gradually rises.In flat panel display, led display technology (Light Emitting
Diode, LED) compared to LCD technology (Liquid Crystal Display, LCD), in color representation, energy saving
Etc. have advantage outstanding, become the novel display technology with great potential, wherein most study and hair at present
The maximum LED component of exhibition prospect mainly includes Organic Light Emitting Diode (Organic Light Emitting Diode, OLED)
With light emitting diode with quantum dots (Quantum Dot Light Emitting Diode, QLED).
For film LED device, especially OLED and QLED device, most it is hopeful to realize the life of extensive industrialization at present
Production. art is ink printed method.Traditional printed form film LED device, usually by luminescent layer ink or other function layer ink
It prints on the strip groove substrate with array, is deposited into film after solvent volatilization.However, in print procedure, luminescent layer
The formula of ink or functional layer ink, the quality of printing substrate, accuracy of printing device etc. all have the uniformity of film layer
Vital influence, phenomena such as easily causing film forming such as " coffee rings " uneven.In addition to this, printing film LED device at present
The complexity of substrat structure used in part, complex manufacturing technology cause serious pollution to the environment and its planform is not fully conducive to film layer
Deposition, meanwhile, the factors such as height of substrate material, substrate thickness and recess edge can make product thickness larger, and be unfavorable for doing
At flexible device.
Summary of the invention
The purpose of the present invention is to provide a kind of film for printing LED substrates and preparation method thereof, it is intended to solve existing print
Structure is complicated for brush grooved substrate, preparation process is cumbersome and the problem of being unfavorable for film LED functional layer ink printed.
Another object of the present invention is to provide a kind of film LED device containing above-mentioned film for printing LED substrate and
Preparation method.
The invention is realized in this way a kind of film for printing LED substrate, the film for printing LED substrate is groove
Substrate, including substrate, and the patterning composite layer being arranged on the substrate, the patterning composite layer are enclosed pixel
Array groove,
Wherein, the patterning composite layer includes the patterned Graphene layer of setting on the substrate, and is incorporated in
The hydrophobic layer of the patterned Graphene layer surface, and the patterned Graphene layer has in the surface modification back to the substrate
Active function groups, the hydrophobic material in the hydrophobic layer are bonded connection with the active function groups.
Correspondingly, a kind of preparation method of film for printing LED substrate, comprising the following steps:
Graphene layer is deposited on substrate；
Patterned process is carried out to the graphene layer and obtains patterned Graphene layer, the patterned Graphene layer is carried on the back
Surface from the substrate carries out moditied processing, obtains the patterned Graphene layer of the active functional group of surface modification；
In the patterned Graphene layer surface depositing hydrophobic material, hydrophobic layer is obtained.
And a kind of film LED device stacks gradually including hearth electrode on substrate is laminated and is incorporated in the bottom electricity
The first functional layer, luminescent layer, the second functional layer and top electrode on extremely, wherein the substrate is above-mentioned film for printing LED
Substrate, and the hearth electrode is arranged in the pixel array groove that patterning composite layer is enclosed.
Correspondingly, a kind of preparation method of film LED device, comprising the following steps:
Above-mentioned film for printing LED substrate is provided, the patterning composite layer in the film for printing LED substrate encloses shape
Pixel arrays groove；
The depositions of bottom electrode in the pixel array groove is sequentially depositing the first functional layer on the hearth electrode, shines
Layer, the second functional layer and top electrode,
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.
And a kind of display panel including above-mentioned film for printing LED substrate.
A kind of display device including above-mentioned film for printing LED substrate.
The figure for containing active function groups in surface is arranged in film for printing LED substrate provided by the invention on the substrate
Hydrophobic layer, and the hydrophobic material in the hydrophobic layer and the active official are arranged on patterned Graphene layer for case graphite alkene layer
Bonding connection can be rolled into a ball, to be firmly bonded to the patterned Graphene layer, forming patterned hydrophobic region, (i.e. patterning is multiple
Close layer), meanwhile, the region that the patterning composite layer encloses forms pixel array groove.Film for printing provided by the invention
LED substrate does not carry out hydrophobic treatment, therefore, has to marking ink for depositing the pixel array groove of printing ink
There is compatibility, is conducive to the deposition of each functional layer.And it is used to be isolated the patterning composite layer of pixel array, due to having carried out surface
Hydrophobic treatment, ink cannot effectively infiltrate, form a film in printing process, to can prevent colour contamination, and have in printing functionality layer
Effect improves the printing performance of film LED device, and then improves the uniformity of luminance and device stability of device.In addition, using
Film for printing LED substrate provided by the invention is able to satisfy the requirement of various ultra-thin rigidity or flexible device, and it is multiple to simplify technique
Miscellaneous degree improves the plasticity of film LED device architecture.
The preparation method of film for printing LED substrate provided by the invention, in the premise not handled conventional substrate
Under, hydrophobic patterning composite layer is formed on substrate, not only simplifies complex process degree, and flexible design degree is high, it can
To be adjusted flexibly according to the design of pixel array.In addition, being served as a contrast by the film for printing LED that this method prepares
Bottom can be improved printing effect during printing functionality layer, and uniformity of luminance, luminous efficiency, the device for improving device are steady
It is qualitative.
Film LED device provided by the invention, can be in printing functionality layer using above-mentioned film for printing LED substrate
Colour contamination is prevented, and effectively increases the printing performance of film LED device, and then the uniformity of luminance of raising device and device are stablized
Property.In addition, the requirement of various ultra-thin rigidity or flexible device is able to satisfy using film for printing LED substrate provided by the invention,
Complex process degree is simplified, the plasticity of film LED device architecture is improved.
The preparation method of film LED device provided by the invention, the film for printing LED substrate use above method system
It is standby, process flow is not only simplified, and be conducive to improve the uniformity of luminance of device, luminous efficiency, device stability and set
Count flexibility.
Detailed description of the invention
Fig. 1 is the preparation flow schematic diagram of film for printing LED substrate provided in an embodiment of the present invention；
Fig. 2 is the preparation flow schematic diagram of film LED 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 film for printing LED substrate, the film for printing LED substrate is groove lining
Bottom, including substrate, and the patterning composite layer being arranged on the substrate, the patterning composite layer are enclosed pixel battle array
Column groove,
Wherein, the patterning composite layer includes the patterned Graphene layer of setting on the substrate, and is incorporated in
The hydrophobic layer of the patterned Graphene layer surface, and the patterned Graphene layer has in the surface modification back to the substrate
Active function groups, the hydrophobic material in the hydrophobic layer are bonded connection with the active function groups.
In the embodiment of the present invention, hydrophobic patterning composite layer is formed on substrate, the patterning composite layer encloses
Form pixel array groove.Since the compound layer region of patterning has high hydrophobicity, marking ink cannot be made effectively to infiltrate
And film forming；And in the region i.e. pixel array recess region for not being patterned composite layer covering, do not have hydrophobic performance, so as to
Enough effectively improve the printing effect of ink.
Specifically, the active function of the surface modification of patterned Graphene layer back to the substrate described in the embodiment of the present invention
Group.The active function groups can be bonded combination with the hydrophobic material, so that the hydrophobic layer is firmly bonded to the figure
Case graphite alkene layer；And other regions other than the patterned Graphene layer, due to not having containing surface-active functional group
Graphene, cannot in conjunction with hydrophobic material without having hydrophobicity, it is ensured that the smooth printing of each functional layer.It improves as a result,
The print performance of film for printing LED substrate.In the embodiment of the present invention, the graphene in the patterned Graphene layer does not have
Considered critical can be single-layer graphene or multi-layer graphene.
Preferably, the active function groups are-OH ,-COOH ,-NH2、-NH-、-SH、-CN、-SO3H、-SOOH、-NO2、-
CONH2,-CONH- ,-COCl ,-CO- ,-CHO ,-Cl, at least one of-Br, but not limited to this.The preferred functional group,
With preferable reactivity, be conducive to and the combination of the hydrophobic material.
In the embodiment of the present invention, the hydrophobic material is organic high molecular compound.Preferably, the organic polymer
Conjunction object be polymethyl methacrylate, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polybutylene terephthalate (PBT),
Polyethylene terephthalate, nitrile rubber, chlorobenzene rubber, polyvinyl alcohol, polycarbonate, polyether-ether-ketone, gathers polyimides
At least one in ether sulfone, poly- aryl acid esters, polyarylate, polyvinylpyrrolidone, polytetrafluoroethylene (PTFE), organosilicon and its derivative
Kind.The preferred organic high molecular compound, not only has preferable hydrophobic performance, is capable of forming patterned hydrophobic region
Domain, moreover, above-mentioned organic high molecular compound and the active function groups, particularly preferred active function groups have preferably
Reactivity is conducive to the fixation of hydrophobic material and the formation of hydrophobic region.
Substrate for the embodiment of the present invention can be rigid substrates or flexible base board.Specifically, the rigid substrates packet
Include but be not limited to glass, metal foil；The flexible substrate includes but is not limited to polyethylene terephthalate, poly- naphthalene diformazan
Sour glycol ester, polyether-ether-ketone, polystyrene, polyether sulfone, polycarbonate, poly- aryl acid esters, polyarylate, polyimides, polychlorostyrene
Ethylene, polyethylene, polyvinylpyrrolidone, textile fabric.
Surface is arranged on the substrate and contains active function for film for printing LED substrate provided in an embodiment of the present invention
The patterned Graphene layer of group, is arranged hydrophobic layer on patterned Graphene layer, and the hydrophobic material in the hydrophobic layer with it is described
Active function groups bonding connection, to be firmly bonded to the patterned Graphene layer, forms patterned hydrophobic region and (schemes
Case composite layer), meanwhile, the region that the patterning composite layer encloses forms pixel array groove.The embodiment of the present invention provides
Film for printing LED substrate do not carry out hydrophobic treatment for depositing the pixel array groove of printing ink, therefore,
It is affinity to marking ink, be conducive to the deposition of each functional layer.And it is used to be isolated the patterning composite layer of pixel array, by
In having carried out surface hydrophobicity processing, ink cannot effectively infiltrate, form a film in printing process, can be with thus in printing functionality layer
Colour contamination is prevented, and effectively increases the printing performance of film LED device, and then the uniformity of luminance of raising device and device are stablized
Property.In addition, being able to satisfy various ultra-thin rigidity or flexible device using film for printing LED substrate provided in an embodiment of the present invention
Requirement, simplify complex process degree, improve the plasticity of film LED device architecture.
Film for printing LED substrate described in the embodiment of the present invention can be prepared by following methods.
Correspondingly, the embodiment of the invention provides a kind of preparation methods of film for printing LED substrate in conjunction with Fig. 1, including
Following steps:
S01. graphene layer 2 ' is deposited on substrate 1；
S02. patterned process is carried out to the graphene layer 2 ' and obtains patterned Graphene layer 2, to the pattern fossil
Black alkene layer 2 carries out moditied processing away from the surface of the substrate 1, obtains the patterned Graphene of the active functional group of surface modification
Layer 2；
S03. in the 2 surface depositing hydrophobic material of patterned Graphene layer, hydrophobic layer 3 is obtained.
Specifically, in above-mentioned steps S01, the method for depositing graphene layer on substrate 1, not stringent restriction can be with
By the way of Direct precipitation or transfer deposition.The not stringent restriction of selection of graphene described in the embodiment of the present invention, can be with
Using single-layer graphene or multi-layer graphene.
In above-mentioned steps S02, patterned process is carried out to the graphene layer 2 ', can be realized using physical method, it is excellent
Choosing is realized using lithographic method.Specifically, the graphene layer of stating can be carved with using plasma etching or photoengraving approach
The pattern of predetermined pattern or pixel array is provided in erosion.Groove structure is formed by etching, the region etched away is correspondingly formed
Pixel array region.
Further, moditied processing is carried out away from the surface of the substrate 1 to the patterned Graphene layer 2.Using change
It learns processing and/or physical treatment and moditied processing is carried out away from the surface of the substrate 1 to the patterned Graphene layer 2, make institute
State the active functional group of 2 surface modification of patterned Graphene layer.Specifically, the chemical treatment is sour processing, alkali process, electrification
At least one of processing, photochemical treatment；The physical treatment is corona treatment, UV ozone is handled, at laser
At least one of reason, heat treatment.As a particular preferred embodiment, the graphene surface that will be patterned into using strong acid is living
Change, introduces functional group abundant, obtain patterned graphene oxide.The active function groups of moditied processing formation are carried out,
It is selected as it was noted above, details are not described herein again in order to save length.
In above-mentioned steps S03, in the 2 surface depositing hydrophobic material of patterned Graphene layer, the hydrophobic material passes through
The active function groups are bonded, 2 surface of patterned Graphene layer is close-coupled at and forms hydrophobic layer 3, so that pattern
Changing region has hydrophobicity, and printing ink effectively cannot be infiltrated and be formed a film, and is thus also formed the picture that can effectively print film forming
Pixel array groove.
The preparation method of film for printing LED substrate provided in an embodiment of the present invention is not being handled conventional substrate
Under the premise of, hydrophobic patterning composite layer is formed on substrate, not only simplifies complex process degree, and flexible design degree
Height can be adjusted flexibly according to the design of pixel array.In addition, the film for printing prepared by this method
LED substrate can be improved printing effect during printing functionality layer, improve the uniformity of luminance of device, luminous efficiency,
Device stability.
And the embodiment of the invention also provides a kind of film LED devices, including hearth electrode on substrate is laminated, according to
It is secondary that the first functional layer, luminescent layer, the second functional layer and the top electrode being incorporated on the hearth electrode is laminated, wherein the substrate
For above-mentioned film for printing LED substrate, and that the pixel array that patterning composite layer is enclosed is arranged in is recessed for the hearth electrode
In slot.
In the film LED device, due to containing film for printing LED substrate, each functional layer of film LED device can be with
It is limited in pixel array groove and effectively forms a film, improve the filming performance of device.
In the present invention, film LED device can be eurymeric film LED device, or transoid film LED device.Make
For a kind of implementation situation, the film LED device can be eurymeric film LED device, i.e., the described hearth electrode is anode, the top
Electrode is cathode, and first functional layer is the hole injection layer and hole transmission layer stacked gradually Jie Hes on the anode,
Second functional layer is the electron injection/transport layer of stacking combination on the light-emitting layer.
As another implementation situation, the film LED device can be transoid film LED device, i.e., the described hearth electrode
For cathode, the top electrode is anode, and first functional layer is the electron injection/transmission of stacking combination on the cathode
Layer, second functional layer is the hole transmission layer and hole injection layer stacked gradually Jie Hes on the light-emitting layer.
In above-mentioned implementation situation, specifically, the film for printing LED substrate is grooved substrate, including substrate, Yi Ji
The patterning composite layer being arranged on the substrate, the patterning composite layer are enclosed pixel array groove, wherein the figure
Case composite layer includes the patterned Graphene layer of setting on the substrate, and is incorporated in the patterned Graphene layer table
The hydrophobic layer in face, and the patterned Graphene layer is in the active functional group of surface modification back to the substrate, it is described hydrophobic
Hydrophobic material in layer is bonded connection with the active function groups.
Wherein, the substrate is rigid substrates or flexible base board, and the rigid substrates include but is not limited to glass, metal foil
Piece；The flexible substrate include but is not limited to polyethylene terephthalate, polyethylene naphthalate, polyether-ether-ketone,
Polystyrene, polyether sulfone, polycarbonate, poly- aryl acid esters, polyarylate, polyimides, polyvinyl chloride, polyethylene, polyethylene pyrrole
Pyrrolidone, textile fabric.
Graphene in the patterned Graphene layer is single-layer graphene or multi-layer graphene.Preferably, the activity
Functional group is-OH ,-COOH ,-NH2、-NH-、-SH、-CN、-SO3H、-SOOH、-NO2、-CONH2、-CONH-、-COCl、-
At least one of CO- ,-CHO ,-Cl ,-Br.
The hydrophobic material is organic high molecular compound.Specifically, the organic high molecular compound is poly- methyl-prop
E pioic acid methyl ester, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polybutylene terephthalate (PBT), poly terephthalic acid second
Diol ester, polyimides, nitrile rubber, chlorobenzene rubber, polyvinyl alcohol, polycarbonate, polyether-ether-ketone, polyether sulfone, poly- aryl acid
At least one of ester, polyarylate, polyvinylpyrrolidone, polytetrafluoroethylene (PTFE), organosilicon and its derivative.
In the embodiment of the present invention, the anode can choose the anode material of film LED field routine.As a kind of implementation
Situation, the anode are blended metal oxide, and the blended metal oxide includes 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), one of indium doping zinc oxide (IZO), magnesium doping zinc-oxide (MZO), aluminium doping magnesia (AMO) or a variety of.Make
For another implementation situation, the anode is the combination electrode containing metal sandwich in transparent metal oxide, wherein described
Bright metal oxide can be doping transparent metal oxide, or undoped transparent metal oxide.It is described compound
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/TiO2
One of or it is a variety of.
Preferably, the hole injection layer is selected from the organic material with Hole injection capacity.Prepare the hole injection
Including but not limited to poly- (3,4- the ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS) of hole-injecting material, the phthalocyanine of layer
Copper (CuPc), 2,3,5,6- tetra- fluoro- 7,7', 8,8'- tetra- cyanogen quinones-bismethane (F4-TCNQ), six cyano of 2,3,6,7,10,11--
Six azepine benzophenanthrene (HATCN) of 1,4,5,8,9,12-, doped or non-doped transition metal oxide, doped or non-doped metal
One of chalcogenide compound 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, in CuS at least
It is a kind of.
Preferably, the hole transmission layer be selected from cavity transmission ability organic material, it is including but not limited to poly- (9,
9- dioctyl fluorene-CO-N- (4- butyl phenyl) diphenylamines) (TFB), polyvinylcarbazole (PVK), poly- (bis- (the 4- butyl benzenes of N, N'
Base)-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 ' -
At least one of biphenyl -4,4 '-diamines (NPB), doped graphene, undoped graphene, C60.As another embodiment,
The hole transmission layer 4 is selected from the inorganic material with cavity transmission ability, including but not limited to doped or non-doped MoO3、
VO2、WO3、CrO3、CuO、MoS2、MoSe2、WS2、WSe2, at least one of CuS.
The luminescent layer is different according to the type of film LED device, can be quantum dot light emitting layer, or You Jifa
Photosphere.The i.e. described film LED device can be QLED device, or OLED device.
When the luminescent layer is quantum dot light emitting layer, the quantum dot light emitting layer can be made of conventional quantum dot.Institute
Stating quantum dot can be for II-VI group is nanocrystalline, iii-v is nanocrystalline, II-V race is nanocrystalline, III-VI race is nanocrystalline, group IV-VI
It is nanocrystalline, I-III-VI race is nanocrystalline, II-IV-VI race is nanocrystalline or one of IV race simple substance or a variety of.Specifically, described
II-VI nanocrystalline includes CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, PbS, PbSe, PbTe, but unlimited
It, can also be nanocrystalline for other binary, ternary, the II-VI of quaternary in this；The iii-v it is nanocrystalline include GaP, GaAs,
InP, InAs, but not limited to this, it can also be 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-。
When the luminescent layer is organic luminous layer, the organic luminous layer can have using OLED device field is conventional
Machine luminescent material is made.
In the embodiment of the present invention, the electron injection/transport layer is selected from the material with electronic transmission performance, preferably has
There is the metal oxide of electronic transmission performance, the metal oxide includes but is not limited to N-shaped 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 film LED device described in the embodiment of the present invention further includes interface-modifying layer, the modifying interface
Layer is electronic barrier layer, hole blocking layer, electrode modification layer, at least one layer in isolated protective layer.
The packaged type of the film LED device can be partial encapsulation, full encapsulation or not encapsulate, the embodiment of the present invention
Do not limit strictly.
Film LED device provided in an embodiment of the present invention, using above-mentioned film for printing LED substrate, in printing functionality layer
When, colour contamination can be prevented, and effectively increase the printing performance of film LED device, and then improve device uniformity of luminance and
Device stability.In addition, being able to satisfy various ultra-thin rigidity or flexible device using film for printing LED substrate provided by the invention
The requirement of part simplifies complex process degree, improves the plasticity of film LED device architecture.
Film LED device provided in an embodiment of the present invention can be prepared by following methods.
Correspondingly, the embodiment of the invention provides a kind of preparation methods of film LED device, including following step in conjunction with Fig. 2
It is rapid:
E01. above-mentioned film for printing LED substrate is provided, the patterning composite layer in the film for printing LED substrate encloses
Conjunction forms pixel array groove；
E02. the depositions of bottom electrode 4 in the pixel array groove, is sequentially depositing the first functional layer on the hearth electrode 4
5, luminescent layer 6, the second functional layer 7 and top electrode 8,
Wherein, the hearth electrode 4 is anode, and the top electrode 8 is cathode, and first functional layer 5 is to stack gradually knot
Hole injection layer and hole transmission layer on the anode is closed, second functional layer 7 is that stacking is incorporated in the luminescent layer 6
On electron injection/transport layer；Or
The hearth electrode 4 is cathode, and the top electrode 8 is anode, and first functional layer 5 is that stacking is incorporated in the yin
Electron injection/transport layer on extremely, second functional layer 7 are to stack gradually the hole transport being incorporated on the luminescent layer 6
Layer and hole injection layer.
Specifically, film for printing LED substrate described in the embodiment of the present invention is grooved substrate, packet in above-mentioned steps E01
Substrate 1, and the patterning composite layer being arranged on the substrate 1 are included, the patterning composite layer is enclosed pixel array
Groove, wherein the patterning composite layer includes the patterned Graphene layer 2 being arranged on the substrate 1, and is incorporated in institute
The hydrophobic layer 3 on 2 surface of patterned Graphene layer is stated, and the patterned Graphene layer 2 is in the surface modification back to the substrate 1
Active functional group, the hydrophobic material in the hydrophobic layer 3 are bonded connection with the active function groups.Specifically, the printing
As described above with the structure of film LED substrate, layers of material and its preferred situation, in order to save length, details are not described herein again.
The embodiment of the present invention can voluntarily prepare film for printing LED according to the preparation method of above-mentioned film for printing LED substrate
Substrate.In the film for printing LED substrate, region (being not covered with the region of graphene) shape of patterning composite layer enclosing
Pixel arrays groove.
In above-mentioned steps E02, the depositions of bottom electrode 4 in the pixel array groove is sequentially depositing on the hearth electrode 4
First functional layer 5, luminescent layer 6, the second functional layer 7 and top electrode 8, can be realized by conventional method in that art.
It there are eurymeric film LED device and transoid film LED device based on film LED device, as a kind of implementation feelings
Shape, the hearth electrode 4 are anode, and the top electrode 8 is cathode, and first functional layer 5 is to stack gradually to be incorporated in the sun
Hole injection layer and hole transmission layer on extremely, second functional layer 7 are the electronics note that stacking is incorporated on the luminescent layer 6
Enter/transport layer.As another implementation situation, the hearth electrode 4 is cathode, and the top electrode 8 is anode, first function
Layer 5 is the electron injection/transport layer of stacking combination on the cathode, and second functional layer 7 is incorporated in institute to stack gradually
State the hole transmission layer and hole injection layer on luminescent layer 6.
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 film LED device provided in an embodiment of the present invention, the film for printing LED substrate is using above-mentioned
Method preparation, not only simplifies process flow, and the uniformity of luminance, luminous efficiency, the device that are conducive to improve device are stablized
Property and design flexibility.
And the embodiment of the invention also provides a kind of display panels and one including above-mentioned film for printing LED substrate
Kind includes the display device of above-mentioned film for printing LED substrate.
It is illustrated combined with specific embodiments below.
Embodiment 1
A kind of preparation method of printed form QLED device, comprising the following steps:
E11. printing QLED substrate is prepared, including
E111. one layer of graphene layer is deposited on a glass substrate, and graphene layer is etched into shape using plasma etching method
At patterning, make the region being etched away with the groove of regular pixel array；
E112. it is activated using the graphene surface that the concentrated sulfuric acid will be patterned into, introduces active function groups, obtain patterned oxygen
Graphite alkene；Polymethyl methacrylate layers are formed in the patterned surface of graphene oxide, obtain printing QLED substrate.
Wherein, the region for not covering graphene forms pixel array groove.
E12. ito anode, the injection of the printing hole PEDOT are sequentially depositing with the recess region in QLED substrate in the printing
Layer, TFB hole transmission layer, CdSe/ZnS quantum dot light emitting layer, ZnO electron transfer layer, evaporating Al cathode obtain printing quantum dot
Light emitting diode.
Embodiment 2
A kind of preparation method of printed form OLED device, comprising the following steps:
E21. printing OLED substrate is prepared, including
E211. one layer of graphene layer is deposited on a glass substrate, and graphene layer is etched into shape using plasma etching method
At patterning, make the region being etched away with the groove of regular pixel array；
E212. it is activated using the graphene surface that the concentrated sulfuric acid will be patterned into, introduces active function groups, obtain patterned oxygen
Graphite alkene；Polymethyl methacrylate layers are formed in the patterned surface of graphene oxide, obtain printing OLED substrate.
Wherein, the region for not covering graphene forms pixel array groove.
E22. it is sequentially depositing ito anode with the recess region in OLED substrate in the printing, prints the hole PEDOT:PSS
Implanted layer, NPB hole transmission layer, Alq3 luminescent layer/electron transfer layer, evaporating Al cathode obtain printing OLED.
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 film for printing LED substrate, which is characterized in that the film for printing LED substrate is grooved substrate, including base
Plate, and the patterning composite layer being arranged on the substrate, the patterning composite layer are enclosed pixel array groove,
Wherein, the patterning composite layer includes the patterned Graphene layer of setting on the substrate, and is incorporated in described
The hydrophobic layer of patterned Graphene layer surface, and the patterned Graphene layer is active in the surface modification back to the substrate
Functional group, the hydrophobic material in the hydrophobic layer are bonded connection with the active function groups.
2. film for printing LED substrate as described in claim 1, which is characterized in that the hydrophobic material is organic polymer
Compound.
3. film for printing LED substrate as claimed in claim 2, which is characterized in that the organic high molecular compound is poly-
Methyl methacrylate, polypropylene, polystyrene, polyvinyl chloride, polybutylene terephthalate (PBT), gathers to benzene two polyethylene
Formic acid glycol ester, nitrile rubber, chlorobenzene rubber, polyvinyl alcohol, polycarbonate, polyether-ether-ketone, polyether sulfone, gathers polyimides
At least one of aryl acid esters, polyarylate, polyvinylpyrrolidone, polytetrafluoroethylene (PTFE), organosilicon and its derivative.
4. film for printing LED substrate as described in claim 1, which is characterized in that the active function groups be-OH ,-
COOH、-NH2、-NH-、-SH、-CN、-SO3H、-SOOH、-NO2、-CONH2、-CONH-、-COCl、-CO-、-CHO、-Cl、-Br
At least one of.
5. film for printing LED substrate according to any one of claims 1-4, which is characterized in that the patterned Graphene
Graphene in layer is single-layer graphene or multi-layer graphene.
6. film for printing LED substrate according to any one of claims 1-4, which is characterized in that the substrate is rigid base
Plate or flexible base board, wherein the rigid substrates include glass, metal foil；The flexible substrate includes poly terephthalic acid
Glycol ester, polyethylene naphthalate, polyether-ether-ketone, polystyrene, polyether sulfone, polycarbonate, poly- aryl acid esters, poly- virtue
Ester, polyimides, polyvinyl chloride, polyethylene, polyvinylpyrrolidone, textile fabric.
7. a kind of preparation method of film for printing LED substrate, which comprises the following steps:
Graphene layer is deposited on substrate；
Patterned process is carried out to the graphene layer and obtains patterned Graphene layer, institute is deviated to the patterned Graphene layer
The surface for stating substrate carries out moditied processing, obtains the patterned Graphene layer of the active functional group of surface modification；
In the patterned Graphene layer surface depositing hydrophobic material, hydrophobic layer is obtained.
8. the preparation method of film for printing LED substrate as claimed in claim 7, which is characterized in that using chemical treatment and/
Or physical treatment carries out moditied processing away from the surface of the substrate to the patterned Graphene layer, makes the pattern graphite
Alkene layer surface is modified with active function groups.
9. the preparation method of film for printing LED substrate as claimed in claim 8, which is characterized in that the chemical treatment is
At least one of sour processing, alkali process, electrochemical treatments, photochemical treatment；And/or
The physical treatment is at least one of corona treatment, UV ozone processing, laser treatment, heat treatment.
10. a kind of film LED device, which is characterized in that including hearth electrode on substrate is laminated, stack gradually described in being incorporated in
The first functional layer, luminescent layer, the second functional layer and top electrode on hearth electrode, wherein the substrate is that claim 1-6 is any
Film for printing LED substrate described in, and that the pixel array that is enclosed of patterning composite layer is arranged in is recessed for the hearth electrode
In slot.
11. film LED device as claimed in claim 10, which is characterized in that the hearth electrode is anode, and the top electrode is
Cathode, first functional layer are the hole injection layer and hole transmission layer stacked gradually Jie Hes on the anode, described
Two functional layers are the electron injection/transport layer of stacking combination on the light-emitting 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.
12. a kind of preparation method of film LED device, which comprises the following steps:
The film for printing LED substrate as described in claim any one of 1-6, the figure in the film for printing LED substrate are provided
Case composite layer is enclosed pixel array groove；
The depositions of bottom electrode in the pixel array groove is sequentially depositing the first functional layer, luminescent layer, on the hearth electrode
Two functional layers and top electrode,
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.
13. a kind of display panel, which is characterized in that the display panel includes printing as claimed in any one of claims 1 to 6
With film LED substrate.
14. a kind of display device, which is characterized in that the display device includes printing as claimed in any one of claims 1 to 6
With film LED substrate.
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