CN105315792A - Quantum dot printing ink and preparation method thereof and quantum dot light-emitting diode - Google Patents
Quantum dot printing ink and preparation method thereof and quantum dot light-emitting diode Download PDFInfo
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Abstract
The invention relates to the technical field of quantum dot light emitting, and provides quantum dot printing ink and a preparation method thereof and a quantum dot light-emitting diode. The quantum dot printing ink is prepared from, by weight, 0.1%-20.0% of quantum dots, 0.1%-15.0% of charge transfer agents, 40.0%-90.0% of solvent, 0.1%-15.0% of viscosity modifier and 0-15.0% of dispersing agent, wherein the charge transfer agents comprise a positive charge transfer agent and a negative charge transfer agent, and the solvent comprises main solvent and cosolvent.
Description
Technical field
The invention belongs to quantum dot light emitting technical field, particularly relate to quantum dot ink and preparation method thereof, light emitting diode with quantum dots.
Background technology
Quantum dot (quantumdot, QD) is the nano material of accurate zero dimension (quasi-zero-dimensional), is made up of a small amount of atom.Roughly, the size of quantum dot three dimensions all in 100 nanometers (nm) below, all limited to by the motion of its internal electron in all directions, so quantum confined effect (quantumconfinementeffect) is remarkable especially.Therefore quantum dot just can utilizing emitted light under the stimulation being subject to light or electricity, and utilizing emitted light has following character: transmitting frequency changes with the change of quantum dot nano-particles size, emission peak is narrow, the light stability of the relatively high and superelevation of luminous quantum efficiency, quantum dot can by regulating part thus being dispersed in different solvents simultaneously, therefore, quantum dot has the characteristic of solution-treated, namely can by simple solution processing mode film forming, wherein particularly meet film forming properties requirement in spray ink Printing mode, and it is simple to have technique, controlled and the accurately image technology of resolving power.By being placed between positive and negative electrode by the quantum dot film of spray ink Printing, thus be electrically excited lower luminescence, the quantum dot organic luminescent device (quantumdotlightemittingdiodes, QLED) of the novel texture namely obtained.Light emitting diode with quantum dots displaying appliance has the advantages such as colour gamut is high, luminous, makes its application prospect allow very much people rouse oneself, and is the direction, forward position that countries in the world display technology falls over each other to research and develop.
But due to quantum spot semiconductor nanoparticle poorly conductive in quantum dot light emitting layer, and be subject to the impact of quantum dot long alkane segment part, transferring charge character is poor, makes QLED efficiency not high.InkJet printing processes has certain requirement to quantum dot ink to viscosity and surface tension simultaneously, and it is low with the quantum dot ink solution viscosity of quantum dot-solvent composition, surface tension is also little, a lot of film forming problem can be there is after cannot printing or print, the problems such as uneven in film surfaces such as coffee ring, cracks, defect, affect the performance of quantum dot light emitting layer.
Summary of the invention
The object of the present invention is to provide a kind of quantum dot ink, be intended to solve the poor and quantum dot ink solution of existing quantum dot light emitting layer transferring charge validity because viscosity is low, surface tension is little, after causing printing or to print, the problem that coffee ring, crack etc. affect quantum dot light emitting layer performance can be there is.
Another object of the present invention is to the preparation method that a kind of quantum dot ink is provided.
Another object of the present invention is to provide a kind of light emitting diode with quantum dots.
The present invention is achieved in that a kind of quantum dot ink, in the weight percentage of described quantum dot ink for 100%, comprises the following component of following weight percentage:
Wherein, described transferring charge agent comprises positive charge transport agent and negative charge transport agent, and described solvent comprises main solvent and cosolvent.
And a kind of preparation method of quantum dot ink, comprises the following steps:
Take the recipe ingredient of above-mentioned quantum dot ink;
Quantum dot, transferring charge agent, dispersion agent and viscosity modifier are dissolved in solvent, form blend;
Described blend is carried out combination treatment.
And a kind of light emitting diode with quantum dots, it comprises quantum dot light emitting layer, and described quantum dot light emitting layer is printed by above-mentioned quantum dot ink to form.
In quantum dot ink composite provided by the invention, containing positive and negative two kinds of transferring charge agent, the transferring charge validity of the quantum dot light emitting layer printing preparation can be made to improve; Simultaneously by regulating ratio, the distribution of positive and negative two kinds of transferring charge agent, can make the hole/electron pair transmission balance of quantum dot, thus make quantum dot light emitting layer produce more excitons, and then radiative recombination is luminous, thus reduce and open bright voltage, improve QLED efficiency.In addition, the quantum dot ink containing positive and negative two kinds of transferring charge agent, can have specific viscosity and surface tension, realizes the spray ink Printing mode of quantum dot light emitting layer, obtains the quantum dot light emitting layer with pixel-matrix, high resolving power, electroexcitation.
The preparation method of quantum dot ink provided by the invention, only need be dissolved in each component in solvent and carry out combination treatment, simple to operate controlled, is easy to realize industrialization.
Light emitting diode with quantum dots provided by the invention, it contains the quantum dot light emitting layer printed by described quantum dot ink.Owing to containing transferring charge agent in described quantum dot ink, thus described quantum dot light emitting layer charge transfer efficiency is improved, reach the effect reducing and open bright voltage, improve efficiency afterwards.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiments provide a kind of quantum dot ink, in the weight percentage of described quantum dot ink for 100%, comprise the following component of following weight percentage:
Wherein, described transferring charge agent comprises positive charge transport agent and negative charge transport agent, and described solvent comprises main solvent and cosolvent.
Concrete, in the embodiment of the present invention, described quantum dot, as the matrix component of described quantum dot ink, can be II-IV compound semiconductor, includes but not limited to CdS or CdSe or CdS/ZnS or CdSe/ZnS or CdSe/CdS/ZnS; Can also be III-V or group IV-VI compound semiconductor, include but not limited to GaAs or InP and PbS/ZnS or PbSe/ZnS, and I-III-VI
2the semiconductor nanos such as race.
The composition form of described quantum dot is unrestricted, can be the quantum dot of doping or undoped.Doping refers to quantum dot inside and also has other ions such as Mn, Cu.The part of described quantum dot is at least one in sour part, mercaptan part, amine ligand, (oxygen) Phosphine ligands, phosphatide, soft phosphatide, polyvinylpyridine etc.As specific embodiment, described sour part is at least one in ten acid, undecylenic acid, TETRADECONIC ACID, oleic acid and stearic acid; Described mercaptan part is one or more in eight alkyl sulfhydryls, lauryl mercaptan and Stearyl mercaptan; Described amine ligand comprises at least one in oleyl amine, stearylamine and eight amine; Described (oxygen) Phosphine ligands is at least one of tri octyl phosphine, trioctylphosphine oxide (TOPO).
In the embodiment of the present invention, the structure type of described quantum dot is unrestricted, can adopt homogeneous mixed type, gradient mixed type, core-shell structure copolymer type or union type.
Because described quantum dot ink is used for spray ink Printing quantum dot light emitting layer, therefore, when water-content is higher in described quantum dot ink, because shipwreck is in volatilization or removal, therefore, easily residual in described quantum dot ink, and then the performance of the described quantum dot light emitting layer of impact formation.In view of this, quantum dot described in the embodiment of the present invention is preferably oil soluble quantum dot.
As specific embodiment, the mean sizes of described quantum dot is 2 ~ 10nm.
In the gross weight of described quantum dot ink for 100%, the consumption of described quantum dot is 0.1-20.0%, as specific embodiment, the consumption of described quantum dot can be the concrete numerical value content such as 0.1%, 0.2%, 0.5%, 0.8%, 1.0%, 2.0%, 4.0%, 5.0%, 8.0%, 10.0%, 12.0%, 15.0%, 18.0%, 20.0%.Further, as preferred embodiment, the consumption of described quantum dot is 2-10%.
In the embodiment of the present invention, containing transferring charge agent component in described quantum dot ink, described transferring charge agent is conduction micromolecular compound or conductive polymers.Should be appreciated that in the embodiment of the present invention, indication polymkeric substance includes oligopolymer.
Described transferring charge agent comprises the positive charge transport agent of at least one and the negative charge transport agent of at least one.In the embodiment of the present invention, described positive charge transport agent is the material with hole transport function, and described negative charge transport agent is the material with electric transmission function.The ratio of described positive charge transport agent and described negative charge transport agent does not have strict restriction, and as preferred embodiment, the weight ratio of described positive charge transport agent and described negative charge transport agent is 1:9-9:1.
In the embodiment of the present invention, the molecular weight of described positive charge transport agent, described negative charge transport agent is respectively 10
2-10
5g/mol.
As a preferred embodiment, described positive charge transport agent comprises at least one in micromolecular compound containing following structural unit or polymkeric substance: amine, aromatic amine, biphenyl class triaryl amine, fluorenes, two fluorenes, spiral shell two fluorenes, pyrroles, aniline, carbazole, indolocarbazole, phthalocyanine, porphyrin, organosilicon, organometallic complex, fluorohydrocarbon, and derivative.
As another preferred embodiment, described negative charge transport agent is at least one in polysubstituted paraffinic hydrocarbons, heterogeneous ring compound, wherein, the replacement atom of described polysubstituted paraffinic hydrocarbons comprises at least one in F, O, N, S, and the heteroatoms of described heterogeneous ring compound comprises at least one in F, O, N, S.
Further, described negative charge transport agent comprises at least one in micromolecular compound containing following structural unit or polymkeric substance: three (oxine) aluminium, anthracene, luxuriant and rich with fragrance, to phenylacetylene, triazine, pyrene, perylene, azophenlyene, phenanthroline, anti-indenofluorene, dibenzo-indenofluorene, indeno naphthalene, benzanthrene, oxadiazole, Ben bis-oxazole, imidazoles, oxazole, triazole, benzodiazole, benzene sulphur diazole, benzo dithiazole, thiadiazoles, pyridine, pyrimidine, pyrazine, quinoline, quinoxaline, phenanthroline, anthracene azoles, triazine, thiophene, two thienothiophenes, thiophthene, oxidation of thiophene, for cyano-containing and the imines organic compounds of electronic material, organic boron, organosilicon, organometallic complex, and derivative.
As concrete preferred embodiment, the structural unit of described positive charge transport agent or the said structure unit of described negative charge transport agent all can comprise at least one can chemical combination/polymer-based group, describedly can comprise vinyl by chemical combination/polymer-based group, acrylate-based, perfluoro-ethylene ether, alkene bisphosphate ester group, allyl amido, allyl alcohol radical, allyl mercaptan base, acrylic, (methyl) acrylate hydroxy ester containing hydroxy functional group, primary amine, secondary amine, epoxy compounds base, α, β beta-unsaturated carbonyl compounds base, alcohol hydroxy compound base, carboxylic acid group, acid chloride group, anhydride group, propylene oxide compound base, annular lactone base, aldehyde compound base, more preferably vinyl.
Further, described positive charge transport agent is described structural unit by can the side chain type positive charge transport polymkeric substance that formed of chemical combination/polymer-based group generation polyaddition reaction.Described negative charge transport agent is described structural unit by can the side chain type electric charge negative charge transport polymkeric substance that formed of chemical combination/polymer-based group generation polyaddition reaction.Wherein, describedly vinyl, acrylate-based, perfluoro-ethylene ether, alkene bisphosphate ester group, allyl amido, allyl alcohol radical, allyl mercaptan base, acrylic, the acrylate hydroxy ester containing hydroxy functional group, the methacrylic ester hydroxy ester containing hydroxy functional group can be comprised by chemical combination/polymer-based group.
Preferably, described polyaddition reaction is the double bond polyaddition reaction occurred under heating or ultraviolet light conditions.Concrete, when obtaining addition polymer by thermofixation crosslinked (i.e. type of heating), radical initiator is free radical thermal initiator, and described free radical thermal initiator can be one or more in azo, superoxide, persulphate, redox initiator, when carrying out UV-crosslinked (i.e. ultraviolet light conditions) and obtaining addition polymer, radical initiator is free radical photo-initiation, described free radical photo-initiation can be 2-hydroxy-2-methyl-1-phenyl-1 acetone, 2, 2-dimethoxy-2-phenyl acetophenone, 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl-1-acetone, 1-hydroxycyclohexyl phenyl ketone, 2, 2-dimethoxy-phenylf ketone, phenyl two (2, 4, 6-trimethylbenzoyl) phosphine oxide, 2-phenyl benzyl-2-dimethyl amine-1-(4-morpholine benzyl phenyl) butanone, 2, 4-dimethyl thioxanthone or 2, one or more in 4-diethyl thioxanthone.
As further concrete preferred embodiment, described positive charge transport agent be containing can the described structural unit of chemical combination/polymer-based group occurred by least one in the Michael reaction of the addition reaction of primary amine and/or secondary amine and epoxy compounds, primary amine and/or secondary amine and α, β beta-unsaturated carbonyl compounds, alcoholic extract hydroxyl group compound and carboxylic acid, acyl chlorides, acid anhydrides condensation reaction, propylene oxide based compound, the ring-opening polymerization of annular lactone, primary amine and aldehyde compound the backbone chain type positive charge transport polymkeric substance that obtains of schiff alkali reaction; Described negative charge transport agent be containing can the described structural unit of chemical combination/polymer-based group occurred by least one in the Michael reaction of the addition reaction of primary amine and/or secondary amine and epoxy compounds, primary amine and/or secondary amine and α, β beta-unsaturated carbonyl compounds, alcoholic extract hydroxyl group compound and carboxylic acid, acyl chlorides, acid anhydrides condensation reaction, propylene oxide based compound, the ring-opening polymerization of annular lactone, primary amine and aldehyde compound the backbone chain type electric charge negative charge transport polymkeric substance that obtains of schiff alkali reaction.
As another concrete preferred embodiment, the structural unit of described positive charge transport agent or described negative charge transport agent contains at least one substituted radical, and described substituted radical comprises halogen, alkyl, thiazolinyl, alkynyl, haloalkyl, haloalkenyl group, assorted alkyl, cycloalkyl, cycloalkenyl group, Heterocyclylalkyl, heterocycloalkenyl, aryl, heteroaryl, cycloalkyl, Heterocyclylalkyl, arylalkyl, heteroarylalkyl, aryl alkenyl, cycloalkylheteroalkyl, Heterocyclylalkyl is mixed alkyl, heteroaryl heteroalkyl, Arylheteroalkyl, hydroxyl, hydroxyalkyl, alkoxyl group, alkoxyalkyl, alkoxy aryl, alkene oxygen base, alkynyloxy group, cycloalkyl oxy, Heterocyclylalkyl oxygen base, aryloxy, alkoxy aryl, phenoxy group, benzyloxy, heteroaryl oxygen base, amino, alkylamino, aminoalkyl group, acyl amino, arylamino, sulfuryl amino, sulfinylamino,-COOH,-COR,-COOR,-CONHR,-NHCOR,-NHCOOR,-NHCONHR, alkoxy carbonyl, alkyl amino-carbonyl, alkylsulfonyl, alkyl sulphonyl, alkyl sulphinyl, aryl sulfonyl, aryl sulfonyl kia, amino-sulfonyl-SR, R1S (O) R3-, R1C (O) N (R2) (R3)-, R1S (O) N (R2) (R3)-, R1N (R2) C (O) R3-, R1N (R2) SOR3-, R1N (R2) C (O) N (R2) (R3)-and acyl group, and the replacement site of described substituted radical is any, wherein, described R, R1, R2, R3 is selected from H independently of one another, alkyl, thiazolinyl, alkynyl, haloalkyl, assorted alkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, cycloalkyl, Heterocyclylalkyl, arylalkyl, one in heteroarylalkyl and acyl group.
Wherein, the general formula of described alkyl is C
nh
2n+1, wherein, n is the positive integer of 1-25, and described alkyl comprises side chain or straight chain saturated fatty alkyl, cyclic alkyl, described aryl comprises following structure and derivative thereof: benzene, biphenyl, triphen, naphthalene, En, Fu, phenanthrene, fluorenes, pyrene, Qu, perylene, Azulene, described heteroaryl comprises following structure and derivative thereof: dibenzothiophene, diphenylene-oxide, furans, thiophene, cumarone, thionaphthene, carbazole, pyrazoles, imidazoles, triazole, isoxzzole, thiazole, oxadiazole, dislike triazole, dioxazole, thiadiazoles, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazines, oxathiazine, oxadiazine, indoles, benzoglyoxaline, indazole, indoxazine, benzoxazoles, benzisoxazole, benzothiazole, quinoline, isoquinoline 99.9, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, azophenlyene, thiodiphenylamine, Phenazoxine, dibenzoselenophene, benzoselenophene, benzofuropyridine, indolocarbazole, pyridylindole, pyrrolodipyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine.
As specific embodiment, above-mentioned aryl comprises the aryl compound structure shown in following formula 1-10:
Wherein, n is the integer of 1-20, and X1 to X8 is independently selected from CH or N, and Ar1 is aromatic yl group.
As there being a specific embodiment, described positive charge transport agent is formed by identical or different described structural unit direct reaction; Or described positive charge transport agent is connected to form by least one heteroatoms or linking group by identical or different described structural unit.Described negative charge transport agent is formed by identical or different described structural unit direct reaction; Or described negative charge transport agent is connected to form by least one heteroatoms or linking group by identical or different described structural unit; Wherein, described heteroatoms is at least one in Sauerstoffatom, nitrogen-atoms, sulphur atom, Siliciumatom, phosphorus atom, boron atom, and described linking group is at least one in methylene radical, aliphatic cyclic group, aryl and heteroaryl.Described structural unit direct reaction in the embodiment of the present invention refers to that reactant is only structural unit, does not introduce other reactants.
Concrete, described aliphatic cyclic group, aryl and heteroaryl are independently containing at least one substituent aliphatic cyclic group, aryl and heteroaryl, described substituting group comprises halogen, alkyl, thiazolinyl, alkynyl, haloalkyl, haloalkenyl group, assorted alkyl, cycloalkyl, cycloalkenyl group, Heterocyclylalkyl, heterocycloalkenyl, aryl, heteroaryl, cycloalkyl, Heterocyclylalkyl, arylalkyl, heteroarylalkyl, aryl alkenyl, cycloalkylheteroalkyl, Heterocyclylalkyl is mixed alkyl, heteroaryl heteroalkyl, Arylheteroalkyl, hydroxyl, hydroxyalkyl, alkoxyl group, alkoxyalkyl, alkoxy aryl, alkene oxygen base, alkynyloxy group, cycloalkyl oxy, Heterocyclylalkyl oxygen base, aryloxy, alkoxy aryl, phenoxy group, benzyloxy, heteroaryl oxygen base, amino, alkylamino, aminoalkyl group, acyl amino, arylamino, sulfuryl amino, sulfinylamino,-COOH,-COR,-COOR,-CONHR,-NHCOR,-NHCOOR,-NHCONHR, alkoxy carbonyl, alkyl amino-carbonyl, alkylsulfonyl, alkyl sulphonyl, alkyl sulphinyl, aryl sulfonyl, aryl sulfonyl kia, amino-sulfonyl-SR, R1S (O) R3-, R1C (O) N (R2) (R3)-, R1S (O) N (R2) (R3)-, R1N (R2) C (O) R3-, R1N (R2) SOR3-, R1N (R2) C (O) N (R2) (R3)-and acyl group, and the replacement site of described substituted radical is any, wherein, described R, R1, R2, R3 is selected from H independently of one another, alkyl, thiazolinyl, alkynyl, haloalkyl, assorted alkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, cycloalkyl, Heterocyclylalkyl, arylalkyl, one in heteroarylalkyl and acyl group.
Wherein, the general formula of described alkyl is C
nh
2n+1, wherein, n is the positive integer of 1-25, and described alkyl comprises side chain or straight chain saturated fatty alkyl, cyclic alkyl, described aryl comprises the substituting group containing following structure: comprise benzene, biphenyl, triphen, naphthalene, En, Fu, phenanthrene, fluorenes, pyrene, Qu, perylene, Azulene, described heteroaryl comprises the substituting group containing following structure: dibenzothiophene, diphenylene-oxide, furans, thiophene, cumarone, thionaphthene, carbazole, pyrazoles, imidazoles, triazole, isoxzzole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazoles, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazines, oxathiazine, oxadiazine, indoles, benzoglyoxaline, indazole, indoxazine, benzoxazoles, benzisoxazole, benzothiazole, quinoline, isoquinoline 99.9, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, azophenlyene, thiodiphenylamine, Phenazoxine, dibenzoselenophene, benzoselenophene, benzofuropyridine, indolocarbazole, pyridylindole, pyrrolodipyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine.
As preferred embodiment, the structural unit of described positive charge transport agent is arylamines derivative compound.Concrete, the structural unit of described positive charge transport agent includes but not limited to the structure shown in following formula 11-18:
Wherein, described Ar1, Ar2 to Ar13 are independently selected from the one in aryl compound, heteroaryl compound, and wherein, described aryl compound comprises benzene, biphenyl, triphenyl, naphthalene, anthracene, phenalene, phenanthrene, fluorenes, pyrene, Qu, perylene, Azulene, and derivative, described heteroaryl compound comprises dibenzothiophene, diphenylene-oxide, furans, thiophene, cumarone, thionaphthene, carbazole, pyrazoles, imidazoles, triazole, isoxzzole, thiazole, oxadiazoles, oxatriazole, dioxazole, thiadiazoles, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazines, oxathiazine, oxadiazine, indoles, benzoglyoxaline, indazole, indoxazine, benzoxazoles, benzisoxazole, benzothiazole, quinoline, isoquinoline 99.9, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, azophenlyene, thiodiphenylamine, Phenazoxine, dibenzoselenophene, benzoselenophene, benzofuropyridine, indolocarbazole, pyridylindole, pyrrolodipyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine, and derivative.
As another preferred embodiment, the structural unit of described positive charge transport agent is the group comprising 2-10 ring structure, and described ring structure is aromatic yl group or the heteroaryl groups of identical or different type, and described ring structure is directly connected to each other; Or described ring structure is connected by least one following heteroatoms or linking group, wherein, described heteroatoms is at least one in Sauerstoffatom, nitrogen-atoms, sulphur atom, Siliciumatom, phosphorus atom, boron atom, and described linking group is at least one in methylene radical, aliphatic cyclic group.
As concrete preferred embodiment, the structural unit of described positive charge transport agent can be the arylamine derivatives structure shown in following formula 19-24:
Described positive charge transport agent can be the arylamine derivatives polymer architecture of structure shown in following formula 25-28:
In the embodiment of the present invention, the structural unit of described positive charge transport agent can also be metal complex.Concrete, the structure of described metal complex can as shown in the formula shown in 29, wherein, m, n are the maximum coordination number of integer, its 1≤m≤M, the maximum coordination number of m+n=M, M is the metallic element of nucleidic mass > 40, and L is assistant ligand, and (Y1-Y2) is two tooth parts, or (Y1-Y2) is the aromatic heterocycle containing at least one in C, N, O, P, S
When described (Y1-Y2) is two tooth parts, Y1, Y2 are independently selected from the one in C, N, O, P, S.When described (Y1-Y2) is for aromatic heterocycle, described aromatic heterocycle comprises dibenzothiophene, diphenylene-oxide, furans, thiophene, cumarone, thionaphthene, carbazole, pyrazoles, imidazoles, triazole, isoxzzole, thiazole, oxadiazoles, oxatriazole, dioxazole, thiadiazoles, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazines, oxathiazine, oxadiazine, indoles, benzoglyoxaline, indazole, indoxazine, benzoxazoles, benzisoxazole, benzothiazole, quinoline, isoquinoline 99.9, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, azophenlyene, thiodiphenylamine, Phenazoxine, dibenzoselenophene, benzoselenophene, benzofuropyridine, indolocarbazole, pyridylindole, pyrrolodipyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, selenophenodipyridine, and derivative.
As preferred embodiment, the structural unit of described negative charge transport agent is the structure shown in following formula 30-59:
Wherein, n is the integer of 1-20, X1 to X1 is independently selected from CH or N, Ar1 to Ar5 is independently selected from the one in aryl compound, heteroaryl compound, R1 is selected from the one in hydrogen, alkyl, alkoxyl group, amino, thiazolinyl, alkynyl, aralkyl, assorted alkyl, aryl and heteroaryl, or R1 is selected from containing can the alkyl of substituting group group of chemical combination/polymerization, alkoxyl group, amino, thiazolinyl, alkynyl, aralkyl, the one of mixing in alkyl, aryl and heteroaryl;
Wherein, described aryl compound comprises benzene, biphenyl, triphenyl, naphthalene, anthracene, phenalene, phenanthrene, fluorenes, pyrene, Qu, perylene, Azulene and derivative thereof, described heteroaryl compound, as dibenzothiophene, diphenylene-oxide, furans, thiophene, cumarone, thionaphthene, carbazole, pyrazoles, imidazoles, triazole, isoxzzole, thiazole, oxadiazoles, oxatriazole, dioxazole, thiadiazoles, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazines, oxathiazine, oxadiazine, indoles, benzoglyoxaline, indazole, indoxazine, benzoxazoles, benzisoxazole, benzothiazole, quinoline, isoquinoline 99.9, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, azophenlyene, thiodiphenylamine, Phenazoxine, dibenzoselenophene, benzoselenophene, benzofuropyridine, indolocarbazole, pyridylindole, pyrrolodipyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine, and derivative.
Described negative charge transport agent can be the polymer architecture shown in following formula 59-62:
In the embodiment of the present invention, the structural unit of described negative charge transport agent can also be metal complex.Concrete, the structure of described metal complex can as shown in the formula shown in 63-66, wherein, z is the maximum coordination number of integer, its 1≤z≤metal, and L is assistant ligand, (O-N) or (N-N) be two tooth parts, metal and (O-N) or (N-N) coordination
In quantum dot ink described in the embodiment of the present invention, according to the difference of described positive charge transport agent and described negative charge transport agent type (micromolecular compound or polymkeric substance), described positive charge transport agent and the distribution of described negative charge transport agent in quantum dot light emitting layer can be variant.
As a specific embodiment, described positive charge transport agent is micromolecular compound, and described negative charge transport agent is polymkeric substance.Now, described positive charge transport agent and described negative charge transport agent dispersed each other.
As another specific embodiment, described positive charge transport agent is polymkeric substance, and described negative charge transport agent is micromolecular compound.Now, described positive charge transport agent and described negative charge transport agent dispersed each other.
As another specific embodiment, described positive charge transport agent and described negative charge transport agent are micromolecular compound.Now, described positive charge transport agent and described negative charge transport agent dispersed each other.
As another specific embodiment, described positive charge transport agent and described negative charge transport agent are polymkeric substance, and described positive charge transport agent and described negative charge transport agent form interpenetrating polymer.Interpenetrating polymer comprises interpenetrating net polymer (IPN) or semi-interpenetrating network polymer.
Wherein, described interpenetrating net polymer is that the network be cross-linked to form separately by the cross-linked polymer of described positive charge transport agent and the cross-linked polymer of negative charge transport agent interts continuously mutually.According to the difference of its crosslinked character, described interpenetrating net polymer can be divided into chemical interpenetrating net polymer and physics interpenetrating net polymer.
Concrete, described interpenetrating net polymer can be positive charge transport substance polymeric with negative charge transport agent cross-linked polymer together with respective linking agent (and catalyzer), after mixing with described quantum dot, in film process, form chemical interpenetrating net polymer.Described interpenetrating net polymer also can be by the small molecule structure unit of positive charge transport agent, the small molecule structure unit of negative charge transport agent, together with respective linking agent (and catalyzer) and initiator (or activator), after mixing with quantum dot, in film process, there is the chemical interpenetrating net polymer that crosslinking polymerization is formed with cross-linking set.Described interpenetrating net polymer can also be together with linking agent and initiator (or activator) by the small molecule structure unit of just (or negative) transferring charge agent, with negative (or just) transferring charge agent polymkeric substance and linking agent (and catalyzer) mixing after, mix with quantum dot again, make the small molecule structure unit polymerization in situ of just (or negative) transferring charge agent in film process and be cross-linked to form polymkeric substance, the polymkeric substance of negative (or just) transferring charge agent is also cross-linked, and forms chemically crosslinked interpenetrating net polymer.Described interpenetrating net polymer can also be that the small molecule structure unit of positive charge transport agent and the small molecule structure unit of negative charge transport agent first aggregate into positive charge transport substance polymeric and negative charge transport substance polymeric together with respective initiator (or activator), mix with quantum dot again, in film process, form physics interpenetrating net polymer.
Describedly partly wear network polymer, be have a kind of polymkeric substance to be uncrosslinked thread-like molecule in the network of two kinds of polymkeric substance compositions, it is interspersed in crosslinked another kind of polymkeric substance, is called and partly wears network.Wherein cross-linked polymer I/simple linear polymer II is called semi-I; Simple linear polymer I/cross-linked polymer II is called semi-II.
Concrete, describedly partly wear the small molecule structure unit that network polymer can be small molecule structure unit by positive charge transport agent and negative charge transport agent, together with respective initiator (or activator), wherein a kind of linking agent (and catalyzer) of polymkeric substance of micromolecular compound formation, after mixing with quantum dot, there is crosslinking polymerization in film process and be formed with chemically crosslinked semi-interpenetrating network polymer.It is described that partly to wear network polymer also can be the polymkeric substance of positive charge transport agent and the linking agent (and catalyzer) of the polymkeric substance of negative charge transport agent together with wherein a kind of polymkeric substance, after mixing with quantum dot, in film process, form chemically crosslinked semi-interpenetrating network polymer.Described network polymer of partly wearing can also be together with initiator (or activator) by the small molecule structure unit of just (or negative) transferring charge agent, together with the polymkeric substance of negative (or just) transferring charge agent and linking agent (with catalyzer) thereof, after mixing with quantum dot, make the small molecule structure unit polymerization in situ of just (or negative) transferring charge agent in film process and form the polymkeric substance of just (or negative) transferring charge agent, polymkeric substance occurs crosslinked, the polymkeric substance of negative (or just) transferring charge agent is interspersed in crosslinked just (or negative) transferring charge agent polymkeric substance, form chemically crosslinked semi-interpenetrating network polymer.Described network polymer of partly wearing also can be also together with linking agent and initiator (or activator) by the small molecule structure unit of just (or negative) transferring charge agent, together with the polymkeric substance of negative (or just) transferring charge agent, after mixing with quantum dot, make the small molecule structure unit polymerization in situ of just (or negative) transferring charge agent in film process and be cross-linked to form the polymkeric substance of just (or negative) transferring charge agent, the polymkeric substance of negative (or just) transferring charge agent is interspersed in crosslinked just (or negative) transferring charge agent polymkeric substance, form chemically crosslinked semi-interpenetrating network polymer.
In described quantum dot ink, the interpolation of described transferring charge agent should have suitable ratio.Its content is too low, is difficult to play the effect improving transferring charge validity, reduce threshold voltage, improve efficiency; Its too high levels, then charge transport properties is excessively strong, and described transferring charge agent itself forms conductive path, thus causes electron-hole to transmit without quantum dot transmission charge, and then causes described quantum dot not luminous, loses its effect.Therefore, in the embodiment of the present invention, in the gross weight of described quantum dot ink for 100%, the consumption of described transferring charge agent is 0.1-15.0%, as specific embodiment, the consumption of described transferring charge agent can be 0.1%, 0.2%, 0.5%, 0.8%, 1.0%, 2.0%, 3.0%, 4.0%, 5.0%, 6.0%, 7.0%, 8.0%, 9.0%, 10.0%, 15% etc. concrete containing numerical quantity.
Described solvent is as the host component of quantum dot ink described in the embodiment of the present invention, and in order to fully realize the abundant dissolving dispersion of each component in described quantum dot ink, described solvent is divided into main solvent and cosolvent.Main solvent described in the embodiment of the present invention is non-polar solvent, and described cosolvent is polar solvent.
As specific embodiment, described main solvent is the mixed solvent that single non-polar solvent or two or more non-polar solvent are formed.As preferred embodiment, described main solvent uses boiling point to be 60-250 DEG C, the one of the long chain alkane at least containing 6 carbon atoms, alcohol, ester and ether, or the mixture that two or more described long chain alkane, alcohol, ester and ether are formed.This preferred described main solvent, can prevent described quantum dot ink in the process of spray ink Printing quantum dot light emitting layer, and the performance of volatilization to the quantum dot light emitting layer obtained of solvent impacts; Meanwhile, because described main solvent boiling point can not be too high, therefore, do not need high temperature to remove solvent, thus ensure that described quantum dot fluorescent quenching can not occur.Concrete, described main solvent is preferably straight or branched alkane, such as the alkane of 6-10 carbon atom.Further, described main solvent is chlorobenzene, orthodichlorobenzene, tetrahydrofuran (THF), methyl-phenoxide, morpholine, toluene, o-Xylol, m-xylene, p-Xylol, normal hexane, methylene dichloride, trichloromethane, 1,4-dioxane, 1,2 ethylene dichloride, 1,1,1-trichloroethane, 1,1, at least one in 2,2-tetrachloroethane, naphthane, naphthalane.In order to fully realize in described quantum dot ink, the abundant dissolving of the abundant dispersion of quantum dot and the more weak composition of polarity, the weight of described main solvent accounts for more than 50% of described solvent gross weight.
Described cosolvent is the double solvents that alcohol or alcohol and other polar solvents are formed.Wherein, described alcohol includes but not limited to methyl alcohol, ethanol, Virahol, butanols, amylalcohol, 2-methyl cellosolve, other polar solvents described include but not limited to various ester, ether, acid amides, specifically include but not limited to acetone, methyl ethyl ketone, vinyl acetic monomer, N-BUTYL ACETATE, dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), or the monoalky lether of ethylene glycol, propylene glycol and polyoxyethylene glycol, e.g., one or more in ethylene glycol monobutyl ether, dipropylene glycol monomethyl ether.Further, other polar solvents described preferably use described ether.As preferred embodiment, in order to fully realize in described quantum dot ink, the abundant dissolving of polar component, the weight of described cosolvent accounts for the 1.0-20.0% of solvent gross weight, and further, the weight of preferred described cosolvent accounts for the 1.0-10% of solvent gross weight.
The described quantum dot ink that the embodiment of the present invention provides, during for spray ink Printing quantum dot light emitting layer, the quality of mobility has considerable influence to printing effect.As preferred embodiment, in order to ensure suitable solid content, and then make described quantum dot ink have suitable mobility, in the gross weight of described quantum dot ink for 100%, the consumption of described solvent is 40.0-90.0%.Further, described solvent load is preferably 40.0-70wt%; Further, described solvent load is preferably 40.0-65%.
In the embodiment of the present invention, described solvent can select heating and pressurizing mode to remove in last handling process.
In described quantum dot ink, optionally can add dispersion agent according to actual needs.Described dispersion agent effectively can make described quantum dot be dispersed in described solvent and make this dispersion system keep stable.Concrete, described dispersion agent can be one or more tensio-active agents.Described tensio-active agent can be anionic, cationic, non-ionic type or amphoterics.
As specific embodiment, described nonionogenic tenside includes but not limited at least one in straight chain or secondary alcohol ethoxylate, alkylphenol polyoxyethylene, fluorochemical surfactant, polyoxyethylene carboxylate, aliphatic amine polyoxyethylene ether, polyoxyethylene block copolymer and propoxylated block copolymers, polyoxyethylene and propyl group silica resin based surfactants, APG and acetylenic polyethylene oxides tensio-active agent.Described anion surfactant includes but not limited to that carboxylate salt (such as; ether carboxylate and sulfosuccinate), vitriol (such as; sodium lauryl sulphate), sulfonate (such as; dodecylbenzene sulfonate, α olefin sulfonate, p alkylphenylaceticacid, fatty acid taurides, sulfonated alkyl naphathalene), at least one in phosphoric acid salt (such as, alkyl and aryl alcohol phosphate), phosphonate and amine oxide surfactant and anion fluorinated surfactants.Described amphoterics includes but not limited at least one in Trimethylamine 99 second lactones, sultaine and alanine fat.Described cats product includes but not limited at least one in quaternary ammonium compound, cationic amine oxide compound, ethoxy fatty amine and imidazoline surfactant.
In the gross weight of described quantum dot ink for 100%, the consumption of described dispersion agent is 0-15%.As specific embodiment, the consumption of described dispersion agent can be 0,0.1%, 0.2%, 0.5%, 0.8%, 1.0%, 2.0%, 3.0%, 4.0%, 5.0%, 10%, 15% etc. concrete containing numerical quantity.
Described viscosity modifier is the important component regulating described quantum dot ink viscosity.In order to obtain the quantum dot ink with proper viscosity, in embodiments of the present invention, described viscosity modifier is preferably at least one in polyhydroxy-alcohol, alkyl glycol ether or TriMethylolPropane(TMP), trimethylolethane, casein, carboxymethyl cellulose.Concrete, described polyhydroxy-alcohol is ethylene glycol, glycol ether, Diethylene Glycol, triethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1,3-butyleneglycol, 1,4-butyleneglycol, 1,5-pentanediol, 2-butylene-1, at least one in 4-glycol and 2-methyl-2-pentanediol, 1,2,6-hexanetriol, glycerol, polyoxyethylene glycol and dipropylene glycol, polyvinyl alcohol.Described alkyl glycol ether is at least one in polyoxyethylene glycol monobutyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether and Propylene glycol n-propyl ether.
As specific embodiment, in the gross weight of described quantum dot ink for 100%, the consumption of described viscosity modifier is 0.1-15.0%, as specific embodiment, the consumption of described viscosity modifier can be 0.1%, 0.2%, 0.5%, 0.8%, 1.0%, 2.0%, 3.0%, 4.0%, 5.0%, 6.0%, 7.0%, 8.0%, 9.0%, 10.0%, 11.0%, 12.0%, 13.0%, 14.0%, 15.0% etc. concrete containing numerical quantity.
When carrying out spray ink Printing for making described quantum dot ink, ink suitably discharges from the nozzle of ink jet-print head and does not block, and have good film forming characteristics, viscosity and the surface tension of described quantum dot ink need meet some requirements simultaneously.As preferred embodiment, under room temperature, the viscosity of (25 DEG C) described quantum dot ink is preferably 0.1-50.0mPa.s, specifically can be 0.1mPa.s, 0.5mPa.s, 1mPa.s, 5mPa.s, 10mPa.s, 15mPa.s, 20mPa.s, 25mPa.s, 30mPa.s, 35mPa.s, 40mPa.s, 45mPa.s, 50mPa.s; Further, the viscosity of described quantum dot ink is preferably 0.5-20.0mPa.s.As another preferred embodiment, described quantum dot ink surface tension is 15.0-50.0mN/m, specifically can be 15.0mN/m, 20.0mN/m, 25.0mN/m, 30.0mN/m, 35.0mN/m, 40.0mN/m, 55.0mN/m, 50.0mN/m.Further, described quantum dot ink surface tension is preferably 20.0-40.0mN/m.
The quantum dot ink that the embodiment of the present invention provides, has suitable viscosity and surface tension, and can pass through inkjet printing methods, formation of deposits has the quantum dot light emitting layer of pixel-matrix, high resolving power, electroexcitation; Simultaneously, owing to containing the positive and negative transferring charge agent can being convenient to transferring charge in described quantum dot ink, make the transferring charge of the quantum dot light emitting layer using described quantum dot ink to prepare more effectively smooth and easy, reduce threshold voltage, thus make electronics, hole can carry out recombination radiation luminescence.In addition, can by controlling the described positive and negative transferring charge agent ratio added, and the dispersion state of described positive and negative transferring charge agent is made by regulation and control, as dispersed or form network interpenetrating or semi-interpenetrating polymer, make balanced charge transport in quantum dot light emitting layer, reduce and open bright voltage, thus make electronics, hole can carry out radiative recombination luminescence.
Quantum dot ink described in the embodiment of the present invention can prepare through but not limited to following method.
Correspondingly, the embodiment of the present invention additionally provides a kind of preparation method of quantum dot ink, comprises the following steps:
S01. the recipe ingredient of described quantum dot ink is taken;
S02. quantum dot, transferring charge agent, dispersion agent and viscosity modifier are dissolved in solvent, form blend;
S03. described blend is carried out combination treatment.
Concrete, in above-mentioned steps S01, the formula of described quantum dot ink and preferred ingredient thereof, content are stated hereinbefore all, in order to save length, repeat no more herein.
In above-mentioned steps S02, quantum dot, transferring charge agent, dispersion agent and viscosity modifier are dissolved in solvent, and its mode is unrestricted.As preferred embodiment, first quantum dot is dissolved in after in solvent, then adds other components.As another preferred embodiment, can respectively by polar compound as described in quantum dot etc., first be dissolved in described main solvent and form nonpolar mixed solution, by polar phase to strong component as described in transferring charge agent etc. be dissolved in as described in form polarity mixed solution in cosolvent, and then described nonpolar mixed solution and polarity mixed solution are mixed, form blend.This preferred method, can realize the abundant dissolving dispersion of each component, and then improve the overall performance of described quantum dot ink.
In above-mentioned steps S03, by unrestricted for the mode that described blend carries out combination treatment, as long as can realize fully mixing.As preferred embodiment, described combination treatment adopts the mode stirred to realize, and described churning time is 25-35min, more preferably 30min.
Correspondingly, the embodiment of the present invention additionally provides a kind of light emitting diode with quantum dots, and it comprises quantum dot light emitting layer, and described quantum dot light emitting layer is that the printing of described quantum dot ink forms.
Concrete, the method using described quantum dot ink to prepare the quantum dot light emitting layer in light emitting diode with quantum dots preferably adopts piezoelectricity or thermal inkjet-printing mode to realize.The dry film that described spray ink Printing is formed, thickness is preferably 10-100nm; Further, the build that described spray ink Printing is formed is 20-50nm.
The light emitting diode with quantum dots that the embodiment of the present invention provides, it contains the quantum dot light emitting layer printed by described quantum dot ink.Owing to containing transferring charge agent in described quantum dot ink, thus described quantum dot light emitting layer charge transfer efficiency is improved, reach the effect reducing threshold voltage, improve efficiency afterwards.
Be described below in conjunction with specific embodiment.
Embodiment 1
A kind of quantum dot ink, in the weight percentage of described quantum dot ink for 100%, comprise the component of weight percentage as shown in following table 1 embodiment 1, wherein, described quantum dot is the stable red CdSe/ZnS quantum dot of oleyl amine, described positive charge transport agent is Polyvinyl carbazole PVK, its structure is as shown in following structural formula 67, described negative charge transport Ji Wei oxadiazole acrylic ester polymer, its structure is as shown in following structural formula 68, described main solvent is high purity chlorobenzene, described cosolvent is dimethyl formamide, described dispersion agent is Trimethylamine 99 second lactones tensio-active agent, described viscosity modifier is glycerol.
The preparation method of described quantum dot ink, comprises the following steps:
S11. the recipe ingredient of above-mentioned quantum dot ink is taken;
S12. under agitation, each component is added in the 500mL high-density polyethylene bottle containing solvent, form blend;
S13. described blend is uniformly mixed 30 minutes, obtains the quantum dot ink that physics is gone here and there mutually.
Further, by described quantum dot ink by ink-jet printer, 70 × 200um is printed as, the quantum dot layer of resolving power 80 × 80ppi.Hot plate is heated to 100 DEG C, volatile dry 30min under nitrogen gas stream, obtain monochromatic quantum dot luminescent layer.
Embodiment 2
Three kinds of quantum dot ink, in the weight percentage of described quantum dot ink for 100%, comprise the component of weight percentage as shown in following table 1 embodiment 2, wherein, described quantum dot is that oleyl amine stablizes quantum dot, described positive charge transport agent is methacrylic acid triphenylamine ester and a small amount of azo-bis-isobutyl cyanide and the acid of ditrimethylolpropane tetrapropylene, its structure is as shown in following structural formula 69, described negative charge transport agent is polypyridine-alkoxyl phenyl, its structure is as shown in following structural formula 70, described main solvent is high purity toluene, described cosolvent is dimethyl sulfoxide (DMSO), described dispersion agent is ethoxy fatty amine tensio-active agent, described viscosity modifier is Propylene glycol n-propyl ether,
Wherein, in the first quantum dot ink, quantum dot is blue CdS/CdZnS quantum dot, and in the second quantum dot ink, quantum dot is green CdZnSe/CdZnS quantum dot, and in the third quantum dot ink, quantum dot is red CdSe/ZnS quantum dot.
The preparation method of described quantum dot ink, comprises the following steps:
S11. the recipe ingredient of above-mentioned quantum dot ink is taken;
S12. under agitation, each component is added in the 500mL high-density polyethylene bottle containing solvent by following order successively: quantum dot, transferring charge agent, dispersion agent and viscosity modifier, form blend;
S13. described blend is uniformly mixed 30 minutes, obtains quantum dot ink.
Prepare the quantum dot ink of three kinds of different colours according to the method described above respectively.
Further, by described three kinds of quantum dot ink by ink-jet printer, 50 × 150um is printed as, the indigo plant of resolving power 80 × 80ppi, green, red side-by-side three primary colours quantum dot layer.Hot plate is heated to 100 DEG C, volatile dry 30min under nitrogen gas stream, obtain three primary colours quantum dot light emitting layer.
Table 1
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (17)
1. a quantum dot ink, is characterized in that, in the weight percentage of described quantum dot ink for 100%, comprises the following component of following weight percentage:
Wherein, described transferring charge agent comprises positive charge transport agent and negative charge transport agent, and described solvent comprises main solvent and cosolvent.
2. quantum dot ink as claimed in claim 1, is characterized in that, described transferring charge agent is conduction micromolecular compound or conductive polymers.
3. quantum dot ink as claimed in claim 2, it is characterized in that, described negative charge transport agent is at least one in polysubstituted paraffinic hydrocarbons, heterogeneous ring compound, wherein, replacement atom in described polysubstituted paraffinic hydrocarbons comprises at least one in F, O, N, S, and the heteroatoms in described heterogeneous ring compound comprises at least one in F, O, N, S.
4. quantum dot ink as claimed in claim 3, it is characterized in that, described positive charge transport agent is at least one in micromolecular compound containing following structural unit or polymkeric substance: amine, aromatic amine, biphenyl class triaryl amine, fluorenes, two fluorenes, spiral shell two fluorenes, pyrroles, aniline, carbazole, indolocarbazole, phthalocyanine, porphyrin, organosilicon, organometallic complex, fluorohydrocarbon, and derivative; And/or
Described negative charge transport agent is at least one in micromolecular compound containing following structural unit or polymkeric substance: three (oxine) aluminium, anthracene, luxuriant and rich with fragrance, to phenylacetylene, triazine, pyrene, perylene, azophenlyene, phenanthroline, anti-indenofluorene, dibenzo-indenofluorene, indeno naphthalene, benzanthrene, oxadiazole, Ben bis-oxazole, imidazoles, oxazole, triazole, benzodiazole, benzene sulphur diazole, benzo dithiazole, thiadiazoles, pyridine, pyrimidine, pyrazine, quinoline, quinoxaline, phenanthroline, anthracene azoles, triazine, thiophene, two thienothiophenes, thiophthene, oxidation of thiophene, organic boron, organosilicon, organometallic complex, and derivative.
5. quantum dot ink as claimed in claim 4, it is characterized in that, the structural unit of described positive charge transport agent or the structural unit of described negative charge transport agent comprise at least one can chemical combination/polymer-based group, describedly can comprise vinyl by chemical combination/polymer-based group, acrylate-based, perfluoro-ethylene ether, alkene bisphosphate ester group, allyl amido, allyl alcohol radical, allyl mercaptan base, acrylic, acrylate hydroxy ester containing hydroxy functional group, methacrylic ester hydroxy ester, primary amine, secondary amine, epoxy compounds base, α, β beta-unsaturated carbonyl compounds base, alcohol hydroxy compound base, carboxylic acid group, acid chloride group, anhydride group, propylene oxide compound base, annular lactone base, aldehyde compound base.
6. quantum dot ink as claimed in claim 5, is characterized in that, described positive charge transport agent is described structural unit by can the side chain type positive charge transport polymkeric substance that formed of chemical combination/polymer-based group generation polyaddition reaction; And/or
Described negative charge transport agent is described structural unit by can the side chain type negative charge transport polymkeric substance that formed of chemical combination/polymer-based group generation polyaddition reaction,
Wherein, describedly vinyl, acrylate-based, perfluoro-ethylene ether, alkene bisphosphate ester group, allyl amido, allyl alcohol radical, allyl mercaptan base, acrylic, (methyl) acrylate hydroxy ester containing hydroxy functional group can be comprised by chemical combination/polymer-based group.
7. quantum dot ink as claimed in claim 5, it is characterized in that, described positive charge transport agent and/or described negative charge transport agent be containing can the described structural unit of chemical combination/polymer-based group by the addition reaction of primary amine and/or secondary amine and epoxy compounds, primary amine and/or secondary amine and α, the Michael reaction of β beta-unsaturated carbonyl compounds, alcoholic extract hydroxyl group compound and carboxylic acid, acyl chlorides, the condensation reaction that at least one in acid anhydrides occurs, propylene oxide based compound, the ring-opening polymerization of annular lactone, at least one in the backbone chain type charge transfer polymer that the schiff alkali reaction of primary amine and aldehyde compound obtains.
8. quantum dot ink as claimed in claim 4, it is characterized in that, the structural unit of described positive charge transport agent or the structural unit of described negative charge transport agent contain at least one substituted radical, and described substituted radical comprises halogen, alkyl, thiazolinyl, alkynyl, haloalkyl, haloalkenyl group, assorted alkyl, cycloalkyl, cycloalkenyl group, Heterocyclylalkyl, heterocycloalkenyl, aryl, heteroaryl, cycloalkyl, Heterocyclylalkyl, arylalkyl, heteroarylalkyl, aryl alkenyl, cycloalkylheteroalkyl, Heterocyclylalkyl is mixed alkyl, heteroaryl heteroalkyl, Arylheteroalkyl, hydroxyl, hydroxyalkyl, alkoxyl group, alkoxyalkyl, alkoxy aryl, alkene oxygen base, alkynyloxy group, cycloalkyl oxy, Heterocyclylalkyl oxygen base, aryloxy, alkoxy aryl, phenoxy group, benzyloxy, heteroaryl oxygen base, amino, alkylamino, aminoalkyl group, acyl amino, arylamino, sulfuryl amino, sulfinylamino,-COOH,-COR,-COOR,-CONHR,-NHCOR,-NHCOOR,-NHCONHR, alkoxy carbonyl, alkyl amino-carbonyl, alkylsulfonyl, alkyl sulphonyl, alkyl sulphinyl, aryl sulfonyl, aryl sulfonyl kia, amino-sulfonyl-SR, R1S (O) R3-, R1C (O) N (R2) (R3)-, R1S (O) N (R2) (R3)-, R1N (R2) C (O) R3-, R1N (R2) SOR3-, R1N (R2) C (O) N (R2) (R3)-and acyl group, and the replacement site of described substituted radical is any, wherein, described R, R1, R2, R3 is selected from H independently of one another, alkyl, thiazolinyl, alkynyl, haloalkyl, assorted alkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, cycloalkyl, Heterocyclylalkyl, arylalkyl, one in heteroarylalkyl and acyl group.
9. quantum dot ink as claimed in claim 4, it is characterized in that, described positive charge transport agent is formed by identical or different described structural unit direct reaction; Or described positive charge transport agent is connected to form by least one heteroatoms or linking group by identical or different described structural unit; And/or
Described negative charge transport agent is formed by identical or different described structural unit direct reaction; Or described negative charge transport agent is connected to form by least one heteroatoms or linking group by identical or different described structural unit;
Wherein, described heteroatoms is at least one in Sauerstoffatom, nitrogen-atoms, sulphur atom, Siliciumatom, phosphorus atom, boron atom, and described linking group is at least one in methylene radical, aliphatic cyclic group, aryl and heteroaryl.
10. quantum dot ink as claimed in claim 9, is characterized in that, described aliphatic cyclic group, aryl and heteroaryl are independently containing at least one substituent aliphatic cyclic group, aryl and heteroaryl, described substituting group comprises halogen, alkyl, thiazolinyl, alkynyl, haloalkyl, haloalkenyl group, assorted alkyl, cycloalkyl, cycloalkenyl group, Heterocyclylalkyl, heterocycloalkenyl, aryl, heteroaryl, cycloalkyl, Heterocyclylalkyl, arylalkyl, heteroarylalkyl, aryl alkenyl, cycloalkylheteroalkyl, Heterocyclylalkyl is mixed alkyl, heteroaryl heteroalkyl, Arylheteroalkyl, hydroxyl, hydroxyalkyl, alkoxyl group, alkoxyalkyl, alkoxy aryl, alkene oxygen base, alkynyloxy group, cycloalkyl oxy, Heterocyclylalkyl oxygen base, aryloxy, alkoxy aryl, phenoxy group, benzyloxy, heteroaryl oxygen base, amino, alkylamino, aminoalkyl group, acyl amino, arylamino, sulfuryl amino, sulfinylamino,-COOH,-COR,-COOR,-CONHR,-NHCOR,-NHCOOR,-NHCONHR, alkoxy carbonyl, alkyl amino-carbonyl, alkylsulfonyl, alkyl sulphonyl, alkyl sulphinyl, aryl sulfonyl, aryl sulfonyl kia, amino-sulfonyl-SR, R1S (O) R3-, R1C (O) N (R2) (R3)-, R1S (O) N (R2) (R3)-, R1N (R2) C (O) R3-, R1N (R2) SOR3-, R1N (R2) C (O) N (R2) (R3)-and acyl group, and the replacement site of described substituted radical is any, wherein, described R, R1, R2, R3 is selected from H independently of one another, alkyl, thiazolinyl, alkynyl, haloalkyl, assorted alkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, cycloalkyl, Heterocyclylalkyl, arylalkyl, one in heteroarylalkyl and acyl group.
11. quantum dot ink as claimed in claim 3, is characterized in that, the structural unit of described positive charge transport agent and/or the structural unit of described positive charge transport agent are at least one in arylamines derivative compound, metal complex.
12. as arbitrary in claim 1-4 as described in quantum dot ink, it is characterized in that, the weight ratio of described positive charge transport agent and described negative charge transport agent is 1:9-9:1.
13. as arbitrary in claim 1-4 as described in quantum dot ink, it is characterized in that, the molecular weight of described positive charge transport agent, described negative charge transport agent is respectively 10
2-10
5g/mol.
14. as arbitrary in claim 1-4 as described in quantum dot ink, it is characterized in that, described positive charge transport agent and described negative charge transport agent are micromolecular compound; And/or
Described positive charge transport agent and described negative charge transport agent are polymkeric substance, and described positive charge transport agent and described negative charge transport agent form interpenetrating polymer.
15. as arbitrary in claim 1-4 as described in quantum dot ink, it is characterized in that, described positive charge transport agent is micromolecular compound, and described negative charge transport agent is polymkeric substance; And/or
Described positive charge transport agent is polymkeric substance, and described negative charge transport agent is micromolecular compound.
The preparation method of 16. 1 kinds of quantum dot ink, comprises the following steps:
Take the recipe ingredient of quantum dot ink as described in claim as arbitrary in claim 1-15;
Quantum dot, transferring charge agent, dispersion agent and viscosity modifier are dissolved in solvent, form blend;
Described blend is carried out combination treatment.
17. 1 kinds of light emitting diode with quantum dots, it comprises quantum dot light emitting layer, and described quantum dot light emitting layer is printed by quantum dot ink described in any one of claim 1-15 to form.
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| CN109932285A (en) * | 2017-12-15 | 2019-06-25 | Tcl集团股份有限公司 | The measuring method and quantum dot ink formulation method of quantum dot surface ligand content |
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| CN113122226A (en) * | 2019-12-30 | 2021-07-16 | Tcl集团股份有限公司 | Preparation method of quantum dot, quantum dot composite material and quantum dot light-emitting diode |
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| CN113122070A (en) * | 2019-12-31 | 2021-07-16 | Tcl集团股份有限公司 | Composition, preparation method thereof and light-emitting diode |
| CN113671614A (en) * | 2021-08-17 | 2021-11-19 | 深圳市华星光电半导体显示技术有限公司 | Color filter manufacturing method and color filter |
| US11492547B2 (en) | 2020-06-04 | 2022-11-08 | UbiQD, Inc. | Low-PH nanoparticles and ligands |
| CN115537072A (en) * | 2021-06-29 | 2022-12-30 | 广东聚华印刷显示技术有限公司 | Quantum dot ink, quantum dot light-emitting diode, preparation method of quantum dot light-emitting diode and display device |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1826393A (en) * | 2003-06-17 | 2006-08-30 | 伊利诺斯大学理事会 | Polyelectrolyte ink |
| CN101712808A (en) * | 2008-09-29 | 2010-05-26 | 气体产品与化学公司 | electrically conductive films formed from dispersions comprising polythiophenes and ether containing polymers |
| CN101903345A (en) * | 2007-11-06 | 2010-12-01 | Hcf合伙人股份两合公司 | Be used in the hole transport polymer in the electron device |
| CN102255019A (en) * | 2010-05-20 | 2011-11-23 | 乐金显示有限公司 | Quantum dot light emitting element and method for manufacturing the same |
| CN103081133A (en) * | 2010-09-03 | 2013-05-01 | 宝洁公司 | Light emitting device |
| CN103228980A (en) * | 2010-09-01 | 2013-07-31 | 无限科技全球公司 | Diodes, printable compositions of a liquid or gel suspension of diodes or other two-terminal integrated circuits, and methods of making same |
| CN103345884A (en) * | 2013-06-26 | 2013-10-09 | 京东方科技集团股份有限公司 | Double-face display device and preparation method thereof |
| CN103427049A (en) * | 2013-08-21 | 2013-12-04 | 京东方科技集团股份有限公司 | Manufacturing method of quantum dot light-emitting component and quantum dot displaying device |
| CN103555048A (en) * | 2013-10-18 | 2014-02-05 | 上海交通大学 | Preparation method of monomolecular-layer titanium oxide quantum dot semiconductor ink |
| JP2014077046A (en) * | 2012-10-10 | 2014-05-01 | Konica Minolta Inc | Ink composition for forming light-emitting layer, method for preparing light-emitting device and electroluminescence device |
| CN103872250A (en) * | 2012-12-11 | 2014-06-18 | 潘才法 | Electroluminescent device |
| CN104756273A (en) * | 2012-11-20 | 2015-07-01 | 默克专利有限公司 | Formulation in high-purity solvent for producing electronic devices |
| CN105038408A (en) * | 2015-08-14 | 2015-11-11 | 广州华睿光电材料有限公司 | Printing ink and electronic device printed by applying printing ink |
-
2015
- 2015-11-18 CN CN201510801193.5A patent/CN105315792B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1826393A (en) * | 2003-06-17 | 2006-08-30 | 伊利诺斯大学理事会 | Polyelectrolyte ink |
| CN101903345A (en) * | 2007-11-06 | 2010-12-01 | Hcf合伙人股份两合公司 | Be used in the hole transport polymer in the electron device |
| CN101712808A (en) * | 2008-09-29 | 2010-05-26 | 气体产品与化学公司 | electrically conductive films formed from dispersions comprising polythiophenes and ether containing polymers |
| CN102255019A (en) * | 2010-05-20 | 2011-11-23 | 乐金显示有限公司 | Quantum dot light emitting element and method for manufacturing the same |
| CN103228980A (en) * | 2010-09-01 | 2013-07-31 | 无限科技全球公司 | Diodes, printable compositions of a liquid or gel suspension of diodes or other two-terminal integrated circuits, and methods of making same |
| CN103081133A (en) * | 2010-09-03 | 2013-05-01 | 宝洁公司 | Light emitting device |
| JP2014077046A (en) * | 2012-10-10 | 2014-05-01 | Konica Minolta Inc | Ink composition for forming light-emitting layer, method for preparing light-emitting device and electroluminescence device |
| CN104756273A (en) * | 2012-11-20 | 2015-07-01 | 默克专利有限公司 | Formulation in high-purity solvent for producing electronic devices |
| CN103872250A (en) * | 2012-12-11 | 2014-06-18 | 潘才法 | Electroluminescent device |
| CN103345884A (en) * | 2013-06-26 | 2013-10-09 | 京东方科技集团股份有限公司 | Double-face display device and preparation method thereof |
| CN103427049A (en) * | 2013-08-21 | 2013-12-04 | 京东方科技集团股份有限公司 | Manufacturing method of quantum dot light-emitting component and quantum dot displaying device |
| CN103555048A (en) * | 2013-10-18 | 2014-02-05 | 上海交通大学 | Preparation method of monomolecular-layer titanium oxide quantum dot semiconductor ink |
| CN105038408A (en) * | 2015-08-14 | 2015-11-11 | 广州华睿光电材料有限公司 | Printing ink and electronic device printed by applying printing ink |
Non-Patent Citations (1)
| Title |
|---|
| 孙加振等: ""功能喷墨墨水的图案化与应用"", 《高分子通报》 * |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017190378A1 (en) * | 2016-05-03 | 2017-11-09 | 深圳市华星光电技术有限公司 | Manufacturing method for quantum dot light-emitting diode display and quantum dot light-emitting diode display |
| CN105907180A (en) * | 2016-05-04 | 2016-08-31 | Tcl集团股份有限公司 | Quantum dot ink and preparation method thereof |
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| CN106519800A (en) * | 2016-11-04 | 2017-03-22 | 苏州星烁纳米科技有限公司 | Quantum dot ink and electroluminescent device |
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| CN113122053A (en) * | 2019-12-30 | 2021-07-16 | Tcl集团股份有限公司 | Quantum dot ink and preparation method of quantum dot film |
| CN113122226B (en) * | 2019-12-30 | 2023-04-18 | Tcl科技集团股份有限公司 | Preparation method of quantum dot, quantum dot composite material and quantum dot light-emitting diode |
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| US11492547B2 (en) | 2020-06-04 | 2022-11-08 | UbiQD, Inc. | Low-PH nanoparticles and ligands |
| CN115537072A (en) * | 2021-06-29 | 2022-12-30 | 广东聚华印刷显示技术有限公司 | Quantum dot ink, quantum dot light-emitting diode, preparation method of quantum dot light-emitting diode and display device |
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