CN109390481A - A kind of nano-electrode, preparation method and application - Google Patents
A kind of nano-electrode, preparation method and application Download PDFInfo
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Abstract
The present invention provides at least one of a kind of nano-electrode, including CNTs, AgNWs and functional graphene oxides, and the functional graphene oxide is the graphene oxide containing active function groups.Contain functional graphene oxide in the nano-electrode, the functional graphene oxide contains active function groups, therefore, it can effectively improve the adhesion of electrode material and the planarization of electrode layer, it enhances product performance, and electric leakage is reduced, increase luminous efficiency, is conducive to CNTs, AgNWs as electrode material application.
Description
Technical field
The invention belongs to technical field of flat panel display more particularly to a kind of nano-electrodes, preparation method and application.
Background technique
The optico-electronic properties that semiconductor-quantum-point has size adjustable humorous, are widely used in light emitting diode, solar energy
Battery and biological fluorescent labelling field.By development in more than 20 years, quantum dot synthetic technology achieved significant achievement, can be with
Synthesis obtains the CdS quantum dots of various high quality, and photoluminescence efficiency can achieve 85% or more.Due to quantum dot
Have the characteristics that the luminous of dimension adjustable, the line width that shines, photoluminescence efficiency height and thermal stability, is luminous with quantum dot
The light emitting diode with quantum dots (QLED) of layer becomes next-generation display and the solid-state lighting light source of great potential.Quantum dot light emitting two
Pole pipe is obtained in illumination and display field in recent years because having many advantages, such as high brightness, low-power consumption, wide colour gamut, easy processing
Extensive concern and research.By the development of many years, QLED technology obtains huge development.From the documents and materials of open report
From the point of view of, red and green QLED external quantum efficiency highest at present alreadys exceed or close to 20%, shows red green QLED's
The limit of the internal quantum efficiency actually already close to 100%.However, the blue indispensable as the full-color display of high-performance
QLED is far below red green QLED, to limit at present whether in electro-optical efficiency or on service life
Application of the QLED in terms of full-color display.
In conventional transparent conductive electrode ITO, containing microelement In, the content of In on earth is few, so facing money
Source anxiety problem, therefore replace ITO and studying increasingly by the favor of researcher as transparent conductive electrode, such as: carbon is received
Mitron (CNTs) or silver nanowires (AgNWs).Due to having very greatly with good conductive characteristic and translucency, CNTs or AgNWs
Potentiality be applied to transparent conductive electrode.But since the adhesive force of CNTs or AgNWs on the glass substrate is poor, shadow significantly
Its electric conductivity and planarization are rung.
Summary of the invention
The purpose of the present invention is to provide a kind of nano-electrodes and preparation method thereof, it is intended to solve the prior art using CNTs
Or AgNWs as electrode material when poor adhesive force, lead to electrode conductivuty and the bad problem of planarization.
Another object of the present invention is to provide a kind of QLED device containing above-mentioned nano-electrode.
The invention is realized in this way at least one of a kind of nano-electrode, including CNTs, AgNWs and functionalization oxygen
Graphite alkene, and the functional graphene oxide is the graphene oxide containing active function groups.
Correspondingly, a kind of preparation method of nano-electrode, comprising the following steps:
Modification agent material and graphene oxide are provided, by the modification agent material and the graphene oxide in acidic environment
Middle heating hybrid reaction prepares functional graphene oxide；
By at least one of the functional graphene oxide and CNTs, AgNWs mixed processing, it is multiple to obtain nano-electrode
Condensation material；
The nano-electrode composite material is deposited on substrate, nano-electrode is prepared.
A kind of preparation method of nano-electrode, comprising the following steps:
Modification agent material and graphene oxide are provided, by the modification agent material and the graphene oxide in acidic environment
Middle heating hybrid reaction prepares functional graphene oxide；
Substrate is provided, deposits functional graphene oxide on the substrate, prepares functional graphene oxide layer；
Nano-electrode material layer is deposited on the functional graphene oxide layer, wherein the nano-electrode material layer
For one of mixed material layer made of CNTs layers, AgNWs layers, CNTs and AgNWs.
And a kind of QLED device, including the anode, quantum dot light emitting layer and cathode successively combined, the anode and/or
The cathode is above-mentioned nano-electrode.
Nano-electrode provided by the invention is used as electrode material using at least one of CNTs, AgNWs, has preferable
Conductive characteristic and translucency.Contain functional graphene oxide in the nano-electrode, the graphene oxide has a large amount of
Negatively charged functional group can be combined together with CNTs, AgNWs by Coulomb force；Meanwhile the functional graphene oxide contains
Therefore active functional group can effectively improve the adhesion of electrode material and the planarization of electrode layer, enhance product performance,
And electric leakage is reduced, increase luminous efficiency, is conducive to CNTs, AgNWs as electrode material application.
The preparation method of two kinds of nano-electrodes provided by the invention, method is simple, mild condition, and industry metaplasia may be implemented
It produces.
QLED device provided by the invention is used as anode and/or cathode material using at least one of CNTs, AgNWs,
Meanwhile containing functional graphene oxide in nano-electrode.Due to containing active function groups in the functional graphene oxide,
Therefore, the adhesion of anode and/or cathode and the planarization of electrode layer with the hydroxy combining on substrate, can be improved, product is improved
Performance, and electric leakage is reduced, increase the luminous efficiency of QLED device.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of eurymeric QLED device provided in an embodiment of the present invention；
Fig. 2 is the structural schematic diagram of transoid QLED device provided in an embodiment of the present invention；
Fig. 3 is the structural schematic diagram of preferred QLED device provided in an embodiment of the present invention.
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
The embodiment of the invention provides at least one of a kind of nano-electrodes, including CNTs, AgNWs and functionalization to aoxidize
Graphene (FGO), and the functional graphene oxide is the graphene oxide containing active function groups.
Nano-electrode provided in an embodiment of the present invention is used as electrode material, tool using at least one of CNTs, AgNWs
There are preferable conductive characteristic and translucency.Contain functional graphene oxide, the graphene oxide tool in the nano-electrode
There are a large amount of negatively charged functional groups, can be combined together with CNTs, AgNWs by Coulomb force；Meanwhile the functionalization aoxidizes stone
Black alkene contains active function groups, therefore, can effectively improve the adhesion of electrode material and the planarization of electrode layer, improves product
Performance, and electric leakage is reduced, increase luminous efficiency, is conducive to CNTs, AgNWs as electrode material application.
Specifically, the active function groups can be by being bonded or electrostatic side with the hydroxyl on substrate or other function layer
The form of formula combines, so that nano-electrode material is adhered on substrate or other layer of structure.Preferably, the active function groups
For-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.Preferred functional group, with hydroxyl
With preferable reactivity, can be anchored on substrate or other function layer, assist the CNTs as electrode material,
At least one of AgNWs film forming, and the adhesion of electrode material and the planarization of electrode layer are improved, it enhances product performance.
As particular preferred embodiment, the functional graphene oxide is Dopamine graphene oxide, benzene second
Alkene sulfonic acid funtionalized graphene oxide, cetyl Trimethylamine functional graphene oxide, the oxidation of mercaptoethylmaine functionalization
Graphene, chloroacetic chloride functional graphene oxide, butanone functional graphene oxide, aldehyde functionalized graphene oxide, acetic acid
At least one of ethyl ester functional graphene oxide.Preferred functional graphene oxide, the not only work good containing reactivity
Property functional group, and translucency is preferable, can be used for producing light lateral electrode.Specifically, aoxidizing stone with the Dopamineization
For black alkene, on the one hand, on the catechol group and substrate (such as glass substrate) on Dopamine graphene oxide
Hydroxyl group can be dehydrated bonding, on the other hand, the amino group-NH on functional graphene oxide surface3+With hydroxyl group-OH
Electrostatic interaction connection, can be such that it is attached on substrate well.
In the embodiment of the present invention, it is preferred that gross mass and the functionalization graphene of the CNTs, the AgNWs
Mass ratio is 3:1~6:1.If the content of the functionalization graphene is excessive, obtained nano-electrode translucency is poor；If institute
The content for stating functionalization graphene is very few, then limited to the improvement of CNTs, AgNWs adhesion property, or even cannot play and stick work
With.
In nano-electrode provided in an embodiment of the present invention, at least one of functional graphene oxide and CNTs, AgNWs
Combination there are two types of form.
As a kind of implementation situation, the nano-electrode is composite electrode layers, including the function for being fixed on substrate surface
Graphene oxide layer can be changed, and stacking is incorporated in the nano-electrode material layer of the functional graphene oxide layer surface, wherein
The nano-electrode material layer is CNTs layers, AgNWs layers, one of mixed material layer made of CNTs and AgNWs.It should manage
Solution, the substrate of meaning of the embodiment of the present invention, either the substrate as substrate, is also possible to the base containing functional layer
Plate.In the embodiment of the present invention, by the way that a layer function graphene oxide layer is arranged between substrate and electrode material, it can increase
The adhesive force of mixed material layer and substrate made of CNTs layers, AgNWs layers or CNTs and AgNWs, thus improve CNTs layers,
The planarization of mixed material layer made of AgNWs layers or CNTs and AgNWs reduces electric leakage, increases efficiency.
As another implementation situation, the nano-electrode aoxidizes stone by least one of CNTs, AgNWs and functionalization
The mixing material of black alkene composition is made.In the embodiment of the present invention, the graphene oxide has a large amount of negatively charged functional groups, can
It is combined together with CNTs, AgNWs by Coulomb force.And the functionalization oxygen being blended at least one of described CNTs, AgNWs
Graphite alkene reduces electric leakage with the hydroxy combining on substrate so as to increase the planarization of composite layer, increases efficiency.
Nano-electrode 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 nano-electrode, comprising the following steps:
S01. modification agent material and graphene oxide are provided, by the modification agent material and the graphene oxide in acidity
Hybrid reaction is heated in environment, prepares functional graphene oxide；
S02. by least one of the functional graphene oxide and CNTs, AgNWs mixed processing, nanometer electricity is obtained
Pole composite material；
S03. the nano-electrode composite material is deposited on substrate, nano-electrode is prepared.
Specifically, the embodiment of the present invention is handled by surface modification in the surface of graphene oxide in above-mentioned steps S01
Introduce active function groups.Preferably, the mass ratio of the modification agent material and graphene oxide is 1:2~1:4.If the modification
Agent material is very few, then the lazy weight of the active function groups introduced is anode electrode to be fixed on substrate；The dressing agent material
When expecting excessive, graphene oxide can be taken by abundant functionalization, improve adhesion strength, while can reduce finally obtained nanometer
The translucency of electrode.
The graphene oxide of poly-dopamine functionalization and AgNWs are mixed, concussion mixing 12-36h keeps its full and uniform mixed
It closes.Concretely for 24 hours, but not limited to this.
The modification agent material and the graphene oxide are placed in acidic environment, acidic environment can promote reaction into
Row.Preferably, the hydrogen ion concentration in acidic environment is 1-5mol/L (pH is about between 3 and 6).If the hydrogen ion concentration is dense
Degree is very low, then reacts progress not exclusively, or very slow；If the hydrogen ion concentration concentration is very big, it is understood that there may be security risk, and
Also it is unfavorable for the progress of reaction.Specifically optional dilute hydrochloric acid or dilution heat of sulfuric acid.By heating hybrid reaction, the graphite oxide
Alkene is functionalized, and forms functionalization graphene.Preferably, the temperature of heat treatment is 80-200 DEG C.If the temperature of heat treatment
Too low, reaction efficiency is lower, or even is unable to normal reaction；If the temperature of heat treatment is excessively high, a large amount of heat of reaction process release
Amount, there will be certain risk, it is possible to explode.Preferably, the hybrid reaction can be shaken by stirring after ultrasound
Realization is swung, but not limited to this.As a specific embodiment, the hybrid reaction are as follows: after ultrasonic treatment 30-60min, stirring shake
It swings for 24 hours, obtains functional graphene oxide.
In above-mentioned steps S02, by least one of the functional graphene oxide and CNTs, AgNWs mixed processing,
Its mixed proportion is as it was noted above, in order to save length, and details are not described herein again.The mixed processing is preferably using concussion mixing side
Formula, but not limited to this.
In above-mentioned steps S03, the nano-electrode composite material is deposited on substrate, it is preferably real by solution processing method
It is existing, so as to preferably meet the industrialization production requirement of LED thin-film device.
The embodiment of the invention also provides a kind of preparation methods of nano-electrode, comprising the following steps:
E01. modification agent material and graphene oxide are provided, by the modification agent material and the graphene oxide in acidity
Hybrid reaction is heated in environment, prepares functional graphene oxide；
E02., substrate is provided, deposits functional graphene oxide on the substrate, prepares functional graphene oxide layer；
E03. nano-electrode material layer is deposited on the functional graphene oxide layer, wherein the nano-electrode material
The bed of material is CNTs layers, AgNWs layers, one of mixed material layer made of CNTs and AgNWs.
Specifically, the method for functional graphene oxide is prepared as described in above step S01 in above-mentioned steps E01, in order to
Length is saved, details are not described herein again.
In above-mentioned steps E02, the substrate can be substrate, or be deposited with the substrate of functional layer.In the base
Deposition functional graphene oxide preferably passes through solution processing method and realizes on plate, so as to preferably meet LED thin-film device
Industrialization production requirement.The functional graphene oxide of deposition in conjunction with the substrate, is fixedly secured by active function groups
In substrate surface.
In above-mentioned steps E03, deposition nano-electrode material layer preferably passes through molten on the functional graphene oxide layer
Liquid processing method is realized, so as to preferably meet the industrialization production requirement of LED thin-film device.
The preparation method of two kinds of nano-electrodes provided in an embodiment of the present invention, method is simple, mild condition, may be implemented to produce
Industry metaplasia produces.
And the embodiment of the invention provides a kind of QLED device, including successively combine anode, quantum dot light emitting layer and
Cathode, the anode and/or cathode are above-mentioned nano-electrode.
QLED device described in the embodiment of the present invention can be eurymeric QLED device, or transoid QLED device.Work as institute
State QLED device be eurymeric QLED device when, the anodic deposition is on substrate.Specifically, as shown in Figure 1, the QLED device
Including substrate 1, anode 2, quantum dot light emitting layer 5 and the cathode 7 successively combined.When the QLED device is transoid QLED device
When, the anodic deposition is on hole injection layer.Specifically, as shown in Fig. 2, the QLED device includes the substrate successively combined
1, cathode 7, quantum dot light emitting layer 5 and anode 2.
Preferably, the QLED device further includes hole functional layer, at least one layer in electronic work ergosphere, wherein described
Hole functional layer includes but is not limited at least one of hole injection layer, hole transmission layer, the electronic work ergosphere include but
It is not limited at least one of electron injecting layer, electron transfer layer.It is specific preferred, as shown in figure 3, the QLED device includes
Anode 2, hole injection layer 3, hole transmission layer 4, quantum dot light emitting layer 5, electron transfer layer 6 and the cathode 7 successively combined.
Specifically, the anode can be conventional anodes electrode, more preferably nano-electrode, including in CNTs, AgNWs extremely
A kind of few and functional graphene oxide, and the functional graphene oxide is the graphene oxide containing active function groups.
Anode used in the embodiment of the present invention can be firmly bonded on substrate, improve nano-electrode material (in CNTs, AgNWs extremely
Few one kind) film forming (material adhesion and film layer planarization), to improve device performance.The preferred feelings of the nano-electrode
Shaped like described above, in order to save length, details are not described herein again.
Preferably, the anode with a thickness of 50-200nm.If the anode is too thin, electric conductivity is poor, hole injection fluence
It is few, cause device efficiency to reduce；If the anode is too thick, translucency is poor, and the light that electron-hole recombinations issue cannot be through electricity
Pole and be received by a detector, cause test device low efficiency.
Preferably, the hole functional layer such as hole injection layer is made of p-type dipole material, and the dipole material contains
There is electron rich functional group.Dipole material due to contain electron rich functional group and cation group, with electron rich group and
The weaker group of electronic capability is drawn, is formed in material internal a part of positively charged, a part of electronegative have effectively transmission electricity
Son or the dipole in hole.
Preferably, the electron rich functional group includes phenyl ,-O-、-COO-、-CO-、-S-、-N-、-P-、-NH-、-SO3 -、-
At least one of CN.Preferred p-type dipole material has low lumo energy, close with the fermi level of anode, and
The electron affinity energy power of lumo energy is very strong, and the electronics of the HOMO energy level of adjacent hole mobile material is easy to pass through dipole
The lumo energy of material and be fetched into anode, to promote the injection in hole, be conducive to improve luminous efficiency.Specifically, institute
Stating p-type dipole material includes but is not limited to HAT-CN (six cyano -1,4,5,8,9,12- of 2,3,6,7,10,11-, six pyridine
And it is luxuriant and rich with fragrance), o-chloronitrobenzene, 2- nitro-chlorobenzene, 1- cyanoethyl -2-ethyl-4-methylimidazole, (S)-Boc-4- cyano-β-phenylpropyl alcohol
Propylhomoserin.Preferably, the dipole material is HAT-CN.Preferably, the hole functional layer made of p-type dipole material
With a thickness of 5-20nm, to assign the hole functional layer excellent hole injection, transmission performance and electric conductivity.
In the embodiment of the present invention, the hole injection layer is also an option that conventional hole-injecting material.The hole passes
Defeated layer also can choose conventional hole mobile material, including but not limited to poly- (9,9- dioctyl fluorene-CO-N- (4- butyl benzenes
Base) diphenylamines), polyvinylcarbazole, poly- (bis- bis- (phenyl) benzidine of (4- butyl phenyl)-N, N'- of N, N'), poly- (9,9- bis- is pungent
Double-the N of base fluorenes -co-, N- phenyl -1,4- phenylenediamine), 4,4 ', 4 "-three (carbazole -9- base) triphenylamines, 4,4'- bis- (9- carbazole) connection
Benzene.The hole transmission layer with a thickness of 0-100nm.When the thickness of the hole transmission layer is excessively thin, hole-injection rate is fast,
So that electron hole imbalance influences luminous efficiency and luminance purity；If the thickness of the hole transmission layer is blocked up, and is easy shadow
Pilot is electrical.It is preferred, therefore, that the hole transmission layer with a thickness of 40-50nm.
The quantum dot light emitting layer can be using conventional quantum dot light emitting material, such as II-VI group compound, iii-v
Compound, II-V compounds of group, III-VI compound, group IV-VI compound, I-III-VI group compound, II-IV-VI race
Close one of object or IV race simple substance or a variety of.The quantum dot light emitting layer with a thickness of 10-100nm.
The electronic work ergosphere such as electron injecting layer is made of N-type dipole material, and the dipole material contains rich electricity
Sub- functional group.Dipole material is due to containing electron rich functional group and cation group, group and drawing electronics with electron rich
The weaker group of ability, forms a part of positively charged in material internal, and a part of electronegative have effectively transmission electronics or sky
The dipole in cave.
Preferably, the electron rich functional group includes phenyl ,-O-、-COO-、-CO-、-S-、-N-、-P-、-NH-、-SO3 -、-
At least one of CN.The energy level of preferred N-type dipole material and the fermi level of cathode are close, and electron affinity energy power is very
By force, the injection transmission for being conducive to electronics, is conducive to improve luminous efficiency.Specifically, the N-type dipole material includes but unlimited
In Liq, Alq3, NDN1 (ethylenediamine tetra-acetic acid is every disodium salt hydrate), CsF, LiF.Preferably, the dipole material is
NDN1。
The material of the electron transfer layer can choose the metals such as Ca, Ba of low work function, also can choose CsF, LiF,
CsCO3Equal compounds, it is also an option that other Electrolyte type electron transport layer materials.Preferably, the electron transfer layer is tool
There is the N-shaped zinc oxide of high electronic transmission performance, preferably with a thickness of 30-60nm.
The cathode can be using conventional cathode material, such as metallic aluminium, silver.
QLED device provided in an embodiment of the present invention is used as anode and/or yin using at least one of CNTs, AgNWs
Pole material, meanwhile, functional graphene oxide is contained in nano-electrode.It is active due to containing in the functional graphene oxide
Therefore functional group with the hydroxy combining on substrate, can improve the adhesion of anode and/or cathode and the planarization of electrode layer, mention
High product performance, and electric leakage is reduced, increase the luminous efficiency of QLED device.
Correspondingly, type of the embodiment of the present invention according to QLED device, provides the preparation method of QLED device.As one
Kind embodiment situation, the preparation method of QLED device, comprising the following steps:
Q01., substrate is provided, deposits nano-electrode on the substrate, obtains anode, the anode is above-mentioned nanometer sun
Pole；
Q02. quantum dot light emitting layer and cathode are sequentially prepared in the anode surface.
Specifically, carrying out cleaning treatment before depositing nano-electrode, including to the substrate, specifically in above-mentioned steps Q01
, the cleaning treatment includes: to be placed in substrate in order in acetone, washing lotion, deionized water and isopropanol to carry out ultrasound clearly
It washes, each ultrasound 10-20 minutes.It is dried for standby after which substrate is placed in cleaning oven after the completion of ultrasound.
The method for depositing nano-electrode on the substrate can be with are as follows: modification agent material and graphene oxide is provided, by institute
It states modification agent material and the graphene oxide heats hybrid reaction in acidic environment, prepare functional graphene oxide；It will
At least one of the functional graphene oxide and CNTs, AgNWs mixed processing, obtain nano-electrode composite material,
10-20min is heated under the conditions of 100-200 DEG C；The nano-electrode composite material is deposited on substrate, nanometer electricity is prepared
Pole.
The method for depositing nano-electrode on the substrate may be: modification agent material and graphene oxide are provided, it will
The modification agent material and the graphene oxide heat hybrid reaction in acidic environment, prepare functional graphene oxide；
Substrate is provided, deposits functional graphene oxide on the substrate, prepares functional graphene oxide layer；In the functionalization
Nano-electrode material layer is deposited in graphene oxide layer, heats 10-20min under the conditions of 100-200 DEG C, wherein the nanometer
Electrode material layer is CNTs layers, AgNWs layers, one of mixed material layer made of CNTs and AgNWs.
In above-mentioned steps Q02, quantum dot light emitting layer is sequentially prepared in the anode surface and cathode can be by conventional side
Method preparation.It preferably, further include preparing hole injection layer, hole transmission layer, electron injecting layer, at least one in electron transfer layer
Layer.Specifically, deposition of hole implanted layer on the anode, 100-200 DEG C of annealing 10-30min, then on hole injection layer
Deposition of hole transport layer, thickness 50-100nm, 100-200 DEG C of annealing 10-30min.After piece is cooling, deposition on it
Son point luminescent layer is not required to heat with a thickness of 20-40nm.Electron transfer layer is deposited on the quantum dot light emitting layer, with a thickness of
10-100nm.Piece is placed on 60-100 DEG C of warm table after the completion of deposition and heats 20-40min, removes remaining solvent.
Finally, piece for having deposited each functional layer is placed in vapor deposition storehouse through the metallic silver of one layer of 50-150nm of mask plate hot evaporation or
Person's aluminium is as cathode.Further, processing can be packaged.
Situation as another embodiment, the preparation method of QLED device, comprising the following steps:
W01., substrate is provided, is sequentially depositing cathode, quantum dot light emitting layer on the substrate；
W02. anode is prepared on the hole injection layer, the anode is above-mentioned nanometer anode.
Specifically, cleaning treatment is carried out before depositing cathode, including to the substrate in above-mentioned steps W01, specifically,
The cleaning treatment includes: that substrate is placed in order in acetone, washing lotion, deionized water and isopropanol to be cleaned by ultrasonic,
Each ultrasound 10-20 minutes.It is dried for standby after which substrate is placed in cleaning oven after the completion of ultrasound.
Preferably, further include prepare hole injection layer, hole transmission layer, electron injecting layer, in electron transfer layer at least
One layer.Cathode, electron transfer layer, quantum dot light emitting layer, hole transmission layer and hole injection layer are deposited, it can be by conventional method
It realizes, be specifically shown in described above, details are not described herein again.
In above-mentioned steps W02, the method that anode is prepared on the hole injection layer can be with are as follows: provide modification agent material and
The modification agent material and the graphene oxide are heated in acidic environment hybrid reaction, prepare function by graphene oxide
Change graphene oxide；By at least one of the functional graphene oxide and CNTs, AgNWs mixed processing, nanometer is obtained
Electrode composite material heats 10-20min under the conditions of 100-200 DEG C；The nano-electrode composite material is deposited on hole note
Enter on layer, nano-electrode is prepared.
The method that anode is prepared on the hole injection layer may be: modification agent material and graphene oxide are provided,
The modification agent material and the graphene oxide are heated into hybrid reaction in acidic environment, prepare functionalization graphite oxide
Alkene；Functional graphene oxide is deposited on the hole injection layer, prepares functional graphene oxide layer；In the functionalization
Nano-electrode material layer is deposited in graphene oxide layer, heats 10-20min under the conditions of 100-200 DEG C, wherein the nanometer
Electrode material layer is CNTs layers, AgNWs layers, one of mixed material layer made of CNTs and AgNWs.
It is illustrated combined with specific embodiments below.
Embodiment 1
A kind of preparation method of eurymeric QLED device, comprising the following steps:
Glass substrate is provided, glass substrate is placed in order in acetone, washing lotion, deionized water and isopropanol and is surpassed
Sound cleaning, it is 15 minutes ultrasonic every time.It is dried for standby after which substrate is placed in cleaning oven after the completion of ultrasound.It is dry to substrate
Afterwards, one layer of FGO-AgNWs mixed liquor is deposited on it, this is placed on 80 DEG C of warm table and heats with a thickness of 80nm by this layer
15min obtains anode.
After above-mentioned substrate is cooling, QD is deposited on anode, this layer with a thickness of 20-40nm, be not required to heat.Later, will
Piece is placed in metallic silver or aluminium in vapor deposition storehouse by one layer of 100nm of mask plate hot evaporation as cathode.
Embodiment 2
A kind of preparation method of eurymeric QLED device, comprising the following steps:
Glass substrate is provided, glass substrate is placed in order in acetone, washing lotion, deionized water and isopropanol and is surpassed
Sound cleaning, it is 15 minutes ultrasonic every time.It is dried for standby after which substrate is placed in cleaning oven after the completion of ultrasound.It is dry to substrate
Afterwards, one layer of FGO-AgNWs mixed liquor is deposited on it, this is placed on 80 DEG C of warm table and heats with a thickness of 80nm by this layer
15min obtains anode.
After above-mentioned substrate is cooling, one layer of dipole material HAT-CN is deposited on anode, with a thickness of 20nm, 100 DEG C add
Hot 30min.After above-mentioned substrate is cooling, one layer of hole transmission layer TFB is deposited in dipole material layer, and this is placed in 150
DEG C warm table on heat 15min.After upper sheet is cooling, deposit QD on the hole transport layer, this layer with a thickness of 20-
40nm is not required to heat.Later, electron transfer layer ZnO is deposited, with a thickness of between 10-100nm.Piece is put after the completion of deposition
It sets and heats 30min on 80 DEG C of warm table, remove remaining solvent.Finally, piece for having deposited each functional layer is placed in steaming
It plates in storehouse through the metallic silver of one layer of 100nm of mask plate hot evaporation or aluminium as cathode.
Embodiment 3
A kind of preparation method of eurymeric QLED device, comprising the following steps:
Glass substrate is provided, glass substrate is placed in order in acetone, washing lotion, deionized water and isopropanol and is surpassed
Sound cleaning, it is 15 minutes ultrasonic every time.It is dried for standby after which substrate is placed in cleaning oven after the completion of ultrasound.It is dry to substrate
Afterwards, one layer of FGO-AgNWs mixed liquor is deposited on it, this is placed on 80 DEG C of warm table and heats in 80nm by this thickness degree
15min obtains anode.
After above-mentioned substrate is cooling, one layer of hole mobile material TFB is deposited on it, with a thickness of 40nm, 150 DEG C of heating
15min.After upper sheet is cooling, QD is deposited on hole transport material, this layer with a thickness of 40nm, be not required to heat.It
Afterwards, electron transfer layer ZnO is deposited, removes remaining solvent with a thickness of 50nm, 80 DEG C of heating 30min.Finally, will deposit
Piece of each functional layer is placed in metallic silver or aluminium in vapor deposition storehouse by one layer of 100nm of mask plate hot evaporation as cathode.
Embodiment 4
A kind of preparation method of eurymeric QLED device, comprising the following steps:
Glass substrate is provided, glass substrate is placed in order in acetone, washing lotion, deionized water and isopropanol and is surpassed
Sound cleaning, it is 15 minutes ultrasonic every time.It is dried for standby after which substrate is placed in cleaning oven after the completion of ultrasound.It is dry to substrate
Afterwards, one layer of FGO-AgNWs mixed liquor is deposited on it, this is placed on 80 DEG C of warm table and heats in 80nm by this thickness degree
15min obtains anode.
After above-mentioned substrate is cooling, one layer of p-type dipole material HAT-CN is deposited on it, with a thickness of 10nm, at 80 DEG C
Lower annealing 30min.After cooling, one layer of hole transmission layer TFB is deposited on it, and in 150 DEG C of heating 15min.To upper sheet
After cooling, deposit QD on it, this layer with a thickness of 40nm, be not required to heat.Later, electron transfer layer ZnO is deposited, with a thickness of
50nm removes remaining solvent in 80 DEG C of heating 30min.Lead to finally, piece for having deposited each functional layer is placed in vapor deposition storehouse
Mask plate hot evaporation one layer of N-type electron injection material Liq, 10nm are crossed, heat treatment is not had to.Then, the metallic silver of 100nm is deposited
Or aluminium is as cathode.
Embodiment 5
A kind of preparation method of eurymeric QLED device, comprising the following steps:
Glass substrate is provided, glass substrate is placed in order in acetone, washing lotion, deionized water and isopropanol and is surpassed
Sound cleaning, each ultrasound 15min.It is dried for standby after which substrate is placed in cleaning oven after the completion of ultrasound.After substrate is dry,
One layer of FGO-AgNWs mixed liquor is deposited on it, this is placed on 80 DEG C of warm table and heats in 80nm by this thickness degree
15min obtains anode.
After cooling, one layer of hole transmission layer TFB, 150 DEG C of heating 15min are deposited on it.After upper sheet is cooling,
Deposit QD thereon, this layer with a thickness of 40nm, be not required to heat.Later, electron transfer layer ZnO, with a thickness of 50nm, 80 DEG C are deposited
30min is heated, remaining solvent is removed.Finally, piece for having deposited each functional layer is placed in vapor deposition storehouse through mask plate heat
One layer of N-type electron injection material Liq, 10nm is deposited, does not have to heat treatment.Then, metallic silver or the aluminium conduct of 100nm is deposited
Cathode.
Embodiment 6
A kind of preparation method of transoid QLED device, comprising the following steps:
Glass substrate is provided, glass substrate is placed in order in acetone, washing lotion, deionized water and isopropanol and is surpassed
Sound cleaning, it is 15 minutes ultrasonic every time.It is dried for standby after which substrate is placed in cleaning oven after the completion of ultrasound.It is dry to substrate
Afterwards, one layer of FGO-AgNWs mixed liquor is deposited on it, this is placed on 80 DEG C of warm table and heats in 80nm by this thickness degree
15min obtains cathode.
After cooling, deposit QD, this layer with a thickness of 40nm, be not required to heat.Later, piece is placed in vapor deposition storehouse by covering
The metallic silver of one layer of 100nm of diaphragm plate hot evaporation is as anode.
Embodiment 7
A kind of preparation method of transoid QLED device, comprising the following steps:
Glass substrate is provided, glass substrate is placed in order in acetone, washing lotion, deionized water and isopropanol and is surpassed
Sound cleaning, it is 15 minutes ultrasonic every time.It is dried for standby after which substrate is placed in cleaning oven after the completion of ultrasound.It is dry to substrate
Afterwards, one layer of FGO-AgNWs mixed liquor is deposited on it, this is placed on 80 DEG C of warm table and heats in 80nm by this thickness degree
15min obtains cathode.
After cooling, electron transfer layer ZnO is deposited, removes remaining solvent with a thickness of 50nm, 80 DEG C of heating 30min.To
After upper sheet is cooling, deposit QD on it, this layer with a thickness of 40nm, be not required to heat.Later, one layer of hole is deposited on it
Transport layer TFB, and in 150 DEG C of heating 15min.Pass through exposure mask finally, piece for having deposited each functional layer is placed in vapor deposition storehouse
The metallic silver of one layer of 100nm of plate hot evaporation is as anode.
Embodiment 8
A kind of preparation method of transoid QLED device, comprising the following steps:
Glass substrate is provided, glass substrate is placed in order in acetone, washing lotion, deionized water and isopropanol and is surpassed
Sound cleaning, it is 15 minutes ultrasonic every time.It is dried for standby after which substrate is placed in cleaning oven after the completion of ultrasound.It is dry to substrate
Afterwards, one layer of FGO-AgNWs mixed liquor is deposited on it, this is placed on 80 DEG C of warm table and heats in 80nm by this thickness degree
15min。
Piece for having deposited each functional layer is placed in vapor deposition storehouse through one layer of N-type electron injection material of mask plate hot evaporation
Liq, 10nm do not have to heat treatment.Later, electron transfer layer ZnO is deposited, with a thickness of 50nm, 80 DEG C of heating 30min, is removed
Remaining solvent.After upper sheet is cooling, deposit QD on it, this layer with a thickness of 40nm, be not required to heat.Later, it deposits
One layer of hole transmission layer TFB, and in 150 DEG C of heating 15min.Finally, piece for having deposited each functional layer is placed in vapor deposition storehouse
By the metallic silver of one layer of 100nm of mask plate hot evaporation as anode.
Embodiment 9
A kind of preparation method of transoid QLED device, comprising the following steps:
Glass substrate is provided, glass substrate is placed in order in acetone, washing lotion, deionized water and isopropanol and is surpassed
Sound cleaning, it is 15 minutes ultrasonic every time.It is dried for standby after which substrate is placed in cleaning oven after the completion of ultrasound.It is dry to substrate
Afterwards, one layer of FGO-AgNWs mixed liquor is deposited on it, this is placed on 80 DEG C of warm table and heats in 80nm by this thickness degree
15min。
Piece for having deposited each functional layer is placed in vapor deposition storehouse through one layer of N-type electron injection material of mask plate hot evaporation
Liq, 10nm do not have to heat treatment.Later, electron transfer layer ZnO is deposited, is removed with a thickness of 50nm in 80 DEG C of heating 30min
Remove remaining solvent.After upper sheet is cooling, deposit QD on it, this layer with a thickness of 40nm, be not required to heat.Later, it sinks
One layer of hole transmission layer TFB of product, and this is placed in 150 DEG C of heating 15min.After above-mentioned substrate is cooling, one layer of P is deposited on it
Type dipole material HAT-CN, 10nm, anneal 30min at 80 DEG C.Finally, piece for having deposited each functional layer is placed in vapor deposition
Metallic silver in storehouse by one layer of 100nm of mask plate hot evaporation is as anode.
Embodiment 10
A kind of preparation method of transoid QLED device, comprising the following steps:
Glass substrate is provided, glass substrate is placed in order in acetone, washing lotion, deionized water and isopropanol and is surpassed
Sound cleaning, it is 15 minutes ultrasonic every time.It is dried for standby after which substrate is placed in cleaning oven after the completion of ultrasound.It is dry to substrate
Afterwards, one layer of FGO-AgNWs mixed liquor is deposited on it, this is placed on 80 DEG C of warm table and heats in 80nm by this thickness degree
15min。
Later, electron transfer layer ZnO is deposited, removes remaining solvent in 80 DEG C of heating 30min with a thickness of 50nm.To
After upper sheet is cooling, deposit QD on it, this layer with a thickness of 40nm, be not required to heat.Later, one layer of hole transmission layer is deposited
TFB, and in 150 DEG C of heating 15min.After above-mentioned substrate is cooling, one layer of p-type dipole material HAT-CN is deposited on it,
10nm, anneal 30min at 80 DEG C.It is steamed finally, piece for having deposited each functional layer is placed in vapor deposition storehouse by mask plate heat
The metallic silver of one layer of 100nm is plated as anode.
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 (12)
1. a kind of nano-electrode, which is characterized in that including at least one of CNTs, AgNWs and functional graphene oxide, and
The functional graphene oxide is the graphene oxide containing active function groups.
2. nano-electrode as described in claim 1, 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.
3. nano-electrode as described in claim 1, which is characterized in that the CNTs, the gross mass of the AgNWs and the function
The mass ratio of energy graphite alkene is 3:1~6:1.
4. nano-electrode as described in any one of claims 1-3, which is characterized in that the functional graphene oxide is DOPA
Amino-functionalization graphene oxide, styrene sulfonic acid functional graphene oxide, cetyl Trimethylamine functionalization aoxidize stone
Black alkene, mercaptoethylmaine functional graphene oxide, chloroacetic chloride functional graphene oxide, butanone functional graphene oxide, second
At least one of aldehyde functional graphene oxide, ethyl acetate functional graphene oxide.
5. nano-electrode as described in any one of claims 1-3, which is characterized in that the nano-electrode is composite electrode layers,
Including for being fixed on substrate surface functional graphene oxide layer and stacking be incorporated in the functional graphene oxide layer
The nano-electrode material layer on surface, wherein the nano-electrode material layer is made of CNTs layers, AgNWs layers, CNTs and AgNWs
One of mixed material layer.
6. nano-electrode as described in any one of claims 1-3, which is characterized in that the nano-electrode is by CNTs, AgNWs
The mixing material of at least one and functional graphene oxide composition be made.
7. a kind of preparation method of any one of such as claim 1-4,6 nano-electrodes, which comprises the following steps:
Modification agent material and graphene oxide are provided, the modification agent material and the graphene oxide are added in acidic environment
Hot mixing reaction, prepares functional graphene oxide；
By at least one of the functional graphene oxide and CNTs, AgNWs mixed processing, nano-electrode composite wood is obtained
Material；
The nano-electrode composite material is deposited on substrate, nano-electrode is prepared.
8. a kind of preparation method of any one of such as claim 1-5 nano-electrode, which comprises the following steps:
Modification agent material and graphene oxide are provided, the modification agent material and the graphene oxide are added in acidic environment
Hot mixing reaction, prepares functional graphene oxide；
Substrate is provided, deposits functional graphene oxide on the substrate, prepares functional graphene oxide layer；
Nano-electrode material layer is deposited on the functional graphene oxide layer, wherein the nano-electrode material layer is
One of mixed material layer made of CNTs layers, AgNWs layers, CNTs and AgNWs.
9. a kind of QLED device, including the anode, quantum dot light emitting layer and cathode successively combined, which is characterized in that the anode
And/or the cathode is nano-electrode described in any one of claims 1-6.
10. QLED device as claimed in claim 9, which is characterized in that the QLED device further includes hole functional layer, electronics
At least one layer in functional layer.
11. QLED device as claimed in claim 10, which is characterized in that the hole functional layer is by p-type dipole material system
At the dipole material contains electron rich functional group；And/or
The electronic work ergosphere is made of N-type dipole material, and the dipole material contains electron rich functional group.
12. QLED device as claimed in claim 11, which is characterized in that the electron rich functional group includes phenyl ,-O-、-
COO-、-CO-、-S-、-N-、-P-、-NH-、-SO3 -, at least one of-CN.
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Application publication date: 20190226 |