CN105315792B - Quantum dot printing ink, preparation method thereof and quantum dot light-emitting diode - Google Patents
Quantum dot printing ink, preparation method thereof and quantum dot light-emitting diode Download PDFInfo
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Abstract
The invention is applicable to the technical field of quantum dot light emitting, and provides quantum dot ink, a preparation method thereof and a quantum dot light emitting diode. The quantum dot ink comprises the following components in percentage by weight, based on 100% of the quantum dot ink in percentage by weight: 0.1-20.0% of quantum dots; 0.1-15.0% of charge transport agent; 40.0-90.0% of solvent; 0.1 to 15.0 percent of viscosity regulator; 0 to 15.0 percent of dispersant; wherein the charge transport agent comprises a positive charge transport agent and a negative charge transport agent, and the solvent comprises a main solvent and a co-solvent.
Description
Technical Field
The invention belongs to the technical field of quantum dot light emitting, and particularly relates to quantum dot ink, a preparation method of the quantum dot ink and a quantum dot light emitting diode.
Background
Quantum Dots (QDs) are quasi-zero-dimensional nanomaterials, consisting of a small number of atoms. Roughly speaking, the quantum dots have three dimensions of less than 100 nanometers (nm), and the movement of electrons in the quantum dots is limited in all directions, so that the quantum confinement effect (quantum confinement effect) is particularly significant. Therefore, the quantum dots can emit light under the stimulation of light or electricity, and the emitted light has the following properties: the emission frequency is changed along with the change of the size of the quantum dot nano particles, the emission peak is narrow, the luminous quantum efficiency is relatively high, the light stability is ultrahigh, and meanwhile, the quantum dots can be dispersed in different solvents by adjusting ligands, so that the quantum dots have the characteristic of solution treatment, namely, the quantum dots can be formed into films in a simple solution processing mode, wherein the film forming performance requirements are particularly met in an ink-jet printing mode, and the method has the advantages of simple process, controllable resolution and accurate imaging technology. The quantum dot organic light emitting device (QLED) with a novel structure is obtained by placing the quantum dot film printed by ink jet printing between a positive electrode and a negative electrode so as to emit light under electric excitation. The quantum dot light emitting diode display has the advantages of high color gamut, self-luminescence and the like, so that the application prospect of the quantum dot light emitting diode display is very exciting, and the quantum dot light emitting diode display is a leading direction of disputed and researched display technologies of all countries in the world.
However, the quantum dot semiconductor nanoparticles in the quantum dot light emitting layer have poor conductivity and are affected by the long alkane chain segment ligands of the quantum dots, so that the charge transmission property is poor, and the QLED has low energy efficiency. Meanwhile, the ink-jet printing process has certain requirements on the viscosity and the surface tension of the quantum dot ink, and a quantum dot ink solution consisting of the quantum dot and the solvent has low viscosity and small surface tension, so that the quantum dot ink cannot be printed or has a plurality of film forming problems after printing, such as uneven film surfaces, defects and the like of coffee rings, cracks and the like, and the performance of a quantum dot light-emitting layer is influenced.
Disclosure of Invention
The invention aims to provide quantum dot ink, and aims to solve the problems that the charge transmission effectiveness of an existing quantum dot light-emitting layer is poor, and the performance of the quantum dot light-emitting layer can not be printed or can be influenced by coffee rings, cracks and the like due to low viscosity and small surface tension of a quantum dot ink aqueous solution.
The invention also aims to provide a preparation method of the quantum dot ink.
Another object of the present invention is to provide a quantum dot light emitting diode.
The invention is realized in such a way that the quantum dot ink comprises the following components in percentage by weight, based on 100% of the quantum dot ink in percentage by weight:
wherein the charge transport agent comprises a positive charge transport agent and a negative charge transport agent, and the solvent comprises a main solvent and a co-solvent.
And, a method for preparing the quantum dot ink, comprising the steps of:
weighing the components of the formula of the quantum dot ink;
dissolving quantum dots, a charge transport agent, a dispersing agent and a viscosity regulator in a solvent to form a blend;
and (3) mixing the blend.
And the quantum dot light-emitting diode comprises a quantum dot light-emitting layer, wherein the quantum dot light-emitting layer is formed by printing the quantum dot printing ink.
The quantum dot ink composition provided by the invention contains a positive charge transport agent and a negative charge transport agent, so that the charge transport effectiveness of the printed and prepared quantum dot light-emitting layer is improved; meanwhile, by adjusting the proportion and the distribution state of the positive charge transport agent and the negative charge transport agent, the hole/electron pair transport of the quantum dot can be balanced, so that the quantum dot light emitting layer generates more excitons, and then the radiation recombination light emitting is realized, the starting voltage is reduced, and the QLED energy efficiency is improved. In addition, the quantum dot ink containing the positive charge transport agent and the negative charge transport agent has specific viscosity and surface tension, realizes an ink-jet printing mode of the quantum dot light-emitting layer, and obtains the quantum dot light-emitting layer with pixel lattice, high resolution and electro-excitation.
The preparation method of the quantum dot ink provided by the invention only needs to dissolve all the components in the solvent for mixing treatment, is simple and controllable to operate, and is easy to realize industrialization.
The quantum dot light-emitting diode provided by the invention comprises a quantum dot light-emitting layer printed by the quantum dot ink. The quantum dot ink contains the charge transport agent, so that the charge transport efficiency of the quantum dot light-emitting layer is improved, and the effects of reducing the starting voltage and improving the energy efficiency are achieved.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides quantum dot ink, which comprises the following components in percentage by weight based on 100 percent of the quantum dot ink:
wherein the charge transport agent comprises a positive charge transport agent and a negative charge transport agent, and the solvent comprises a main solvent and a co-solvent.
Specifically, in the embodiment of the present invention, the quantum dots as the matrix component of the quantum dot ink may be II-IV compound semiconductors including but not limited to CdS or CdSe or CdS/ZnS or CdSe/CdS/ZnS; and may also be a group III-V or IV-VI compound semiconductor including, but not limited to, GaAs or InP and PbS/ZnS or PbSe/ZnS, and I-III-VI2Group and the like semiconductor nanocrystals.
The composition form of the quantum dots is not limited, and the quantum dots can be doped or undoped quantum dots. Doping means that other ions such as Mn, Cu and the like exist in the quantum dots. The ligand of the quantum dot is at least one of acid ligand, thiol ligand, amine ligand, (oxy) phosphine ligand, phospholipid, soft phospholipid, polyvinyl pyridine and the like. As a specific example, the acid ligand is at least one of deca acid, undecenoic acid, tetradecanoic acid, oleic acid, and stearic acid; the mercaptan ligand is one or more of octaalkylmercaptan, dodecyl mercaptan and octadecyl mercaptan; the amine ligand comprises at least one of oleylamine, octadecylamine and octamine; the (oxy) phosphine ligand is at least one of trioctylphosphine and trioctylphosphine.
In the embodiment of the present invention, the structure type of the quantum dot is not limited, and a uniform mixing type, a gradient mixing type, a core-shell type, or a combination type may be used.
Because the quantum dot ink is used for ink-jet printing of the quantum dot light-emitting layer, when the water content in the quantum dot ink is high, the water is difficult to volatilize or remove, so that the water is easy to remain in the quantum dot ink, and the performance of the formed quantum dot light-emitting layer is influenced. In view of this, the quantum dots according to the embodiments of the present invention are preferably oil-soluble quantum dots.
As a specific embodiment, the average size of the quantum dots is 2-10 nm.
The quantum dots are used in an amount of 0.1 to 20.0% based on 100% of the total weight of the quantum dot ink, and as a specific example, the quantum dots may be used in an amount of 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%, and other specific numerical values. Further, as a preferred embodiment, the quantum dots are used in an amount of 2 to 10%.
In the embodiment of the invention, the quantum dot ink contains a charge transport agent component, and the charge transport agent is a conductive small molecular compound or a conductive polymer. It should be understood that the polymers referred to in the examples of the present invention all include oligomers.
The charge transport agent comprises at least one positive charge transport agent and at least one negative charge transport agent. In the embodiment of the invention, the positive charge transport agent is a substance with a hole transport function, and the negative charge transport agent is a substance with an electron transport function. The ratio of the positive charge transport agent to the negative charge transport agent is not critical, and as a preferred embodiment, the weight ratio of the positive charge transport agent to the negative charge transport agent is 1:9 to 9: 1.
In the embodiment of the invention, the molecular weights of the positive charge transport agent and the negative charge transport agent are respectively 102-105g/mol。
As a preferred embodiment, the positive charge transport agent comprises at least one of a small molecule compound or a polymer comprising the following structural units: amines, aromatic amines, biphenyl triarylamines, fluorenes, bifluorenes, spirobifluorenes, pyrroles, anilines, carbazoles, benzazoles, phthalocyanines, porphyrins, silicones, organometallic complexes, fluorocarbons, and derivatives thereof.
As another preferred embodiment, the negative charge transport agent is at least one of a polysubstituted alkane, wherein the substituent atom of the polysubstituted alkane comprises at least one of F, O, N, S, and a heterocyclic compound wherein the heteroatom comprises at least one of F, O, N, S.
Further, the negative charge transport agent comprises at least one of a small molecule compound or a polymer comprising the following structural units: tris (8-hydroxyquinoline) aluminum, anthracene, phenanthrene, paraphenylacetylene, triazine, pyrene, perylene, phenazine, phenanthroline, anti-indenofluorene, dibenzo-indenofluorene, indenonaphthalene, benzanthracene, oxadiazole, benzodioxazole, imidazole, oxazole, triazole, benzodiazole, thiophenadiazole, benzodithiazole, thiadiazole, pyridine, pyrimidine, pyrazine, quinoline, quinoxaline, orthophenanthroline, anthraceneazole, triazine, thiophene, dithienothiophene, bithiophene, oxythiophene, cyano-containing and imine organic compounds for electronic materials, organoboron, organosilicon, organometallic complexes, and derivatives thereof.
As a particularly preferred embodiment, each of the structural units of the positive charge transport agent or the negative charge transport agent may include at least one combinable/polymerizable group including a vinyl group, an acrylate group, a perfluorovinyl ether group, an enediphosphate group, an allylamine group, an allylthiol group, an acrylic group, a (meth) acrylate hydroxyl ester having a hydroxyl functional group, a primary amine, a secondary amine, an epoxy group, an α, β unsaturated carbonyl compound group, an alcoholic hydroxyl compound group, a carboxylic acid group, an acid chloride group, an acid anhydride group, a propylene oxide compound group, a cyclic lactone group, an aldehyde compound group, and more preferably a vinyl group.
Further, the positive charge transport agent is a side chain type positive charge transport polymer formed by addition polymerization of the structural units through a combinable/polymerizable group. The negative charge transport agent is a side chain type charge negative charge transport polymer formed by addition polymerization reaction of the structural units through a combinable/polymerizable group. Wherein the chemically combinable/polymerizable group comprises a vinyl group, an acrylate group, a perfluorovinyl ether group, an enediphosphate group, an allylamine group, an allylalcohol group, an allylthiol group, an acrylic acid group, an acrylate hydroxyl ester containing a hydroxyl functional group, a methacrylate hydroxyl ester containing a hydroxyl functional group.
Preferably, the addition polymerization reaction is a double bond addition polymerization reaction under a heating or ultraviolet light condition. Specifically, when the addition polymer is obtained by thermal curing crosslinking (i.e., heating), the radical initiator is a radical thermal initiator, which may be one or more of azo, peroxide, persulfate, redox initiator; when the addition polymer is obtained by UV crosslinking (i.e., UV light conditions), the radical initiator is a radical photoinitiator, which may be 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-dimethoxy-2-phenylacetophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2-dimethoxy-phenyl ketone, phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinyl benzyl) butanone, 2, 4-dimethylthioxanthone or 2, one or more of 4-diethylthioxanthone.
As a further specific preferred embodiment, the positive charge transport agent is a main chain type positive charge transport polymer obtained by an addition reaction of a primary amine and/or a secondary amine with an epoxy compound, a michael addition reaction of a primary amine and/or a secondary amine with an α, β unsaturated carbonyl compound, a condensation reaction of an alcoholic hydroxyl compound with at least one of a carboxylic acid, an acid chloride, an acid anhydride, a ring-opening polymerization reaction of a glycidyl compound, a cyclic lactone, a schiff base reaction of a primary amine with an aldehyde compound, of the structural unit having a combinable/polymerizable group; the negative charge transport agent is a main chain type charge negative charge transport polymer which is obtained by the addition reaction of a primary amine and/or a secondary amine with an epoxy compound, the Michael addition reaction of the primary amine and/or the secondary amine with an alpha, beta unsaturated carbonyl compound, the condensation reaction of an alcoholic hydroxyl compound with at least one of carboxylic acid, acyl chloride and acid anhydride, the ring-opening polymerization reaction of a glycidyl compound and a cyclic lactone, and the schiff base reaction of the primary amine with an aldehyde compound, wherein the structural unit containing a combinable/polymerizable group.
As another particularly preferred embodiment, the structural element of the positive charge transport agent or the negative charge transport agent contains at least one substituent group including halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, heteroalkyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, heterocycloalkenyl, aryl, heteroaryl, cycloalkyl, heterocycloalkyl, arylalkyl, heteroarylalkyl, arylalkenyl, cycloalkylheteroalkyl, heterocycloalkylheteroalkyl, heteroarylheteroalkyl, arylheteroalkyl, hydroxy, hydroxyalkyl, alkoxy, alkoxyalkyl, alkoxyaryl, alkenyloxy, alkynyloxy, cycloalkyloxy, heterocycloalkyloxy, aryloxy, arylalkoxy, phenoxy, benzyloxy, heteroaryloxy, amino, alkylamino, aminoalkyl, acylamino, arylamino, sulfonylamino, sulfinylamino, di-or tri-alkyl, and mixtures thereof, -COOH, -COR, -COOR, -CONHR, -NHCOR, -NHCOOR, -NHCONHR, alkoxycarbonyl, alkylaminocarbonyl, sulfonyl, alkylsulfonyl, alkylsulfinyl, arylsulfonyl, arylsulfinyl, aminosulfonyl-R, 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, and the substitution site of said substituent is arbitrary, wherein R, R1, R2, R3 are each independently selected from one of H, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, cycloalkyl, heterocycloalkyl, arylalkyl, heteroarylalkyl, and acyl.
Wherein the alkyl group has the general formula CnH2n+1Wherein n is a positive integer of 1 to 25, and the alkyl group includes a branched or straight chain saturated aliphatic hydrocarbon group, a cyclic alkyl group; the aryl group includes the following structures and derivatives thereof: benzene, biphenyl, triphenyl, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; the heteroaryl group includes the following structures and derivatives thereof: dibenzothiophene, dibenzofuran, furan, thiophene, benzofuran, benzothiophene, carbazole, pyrazole, imidazole, triazole, isoxazole, oxathiazine, oxadiazole, oxatriazole, bisoxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, thiazine, oxadiazine, indole, benzimidazole, indazole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, o-dinitrogen (hetero) naphthalene, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, dibenzoselenophene, benzoselenophene, benzofuropyridine, indolocarbazole, pyridylindole, pyrrolobipyridine, furanbipyridine, benzothienopyridine, thienopyridine, thienodipyridinePyridine, benzoselenophenepyridine and selenophenedipyridine.
As specific examples, the above aryl group includes aryl compound structures represented by the following formulas 1 to 10:
wherein N is an integer of 1-20, X1 to X8 are independently selected from CH or N, and Ar1 is an aryl group.
As a specific example, the positive charge transport agent is formed by direct reaction of the same or different structural units; or the positive charge transport agents are formed by the same or different structural units being linked through at least one heteroatom or linking group. The negative charge transport agent is formed by direct reaction of the same or different structural units; or said negative charge transport agent is formed by the same or different of said building blocks being linked via at least one heteroatom or linking group; wherein the heteroatom is at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom and boron atom, and the connecting group is at least one of methylene, aliphatic ring group, aryl and heteroaryl. The structural unit is directly reacted in the embodiment of the invention, namely that reactants are only structural units and other reactants are not introduced.
Specifically, the alicyclic group, aryl group and heteroaryl group are alicyclic group, aryl group and heteroaryl group independently having at least one substituent group including halogen, alkyl group, alkenyl group, alkynyl group, haloalkyl group, haloalkenyl group, heteroalkyl group, cycloalkyl group, cycloalkenyl group, heterocycloalkyl group, heterocycloalkenyl group, aryl group, heteroaryl group, cycloalkyl group, heterocycloalkyl group, arylalkyl group, heteroarylalkyl group, arylalkenyl group, cycloalkylheteroalkyl group, heterocycloalkylheteroalkyl group, heteroarylheteroalkyl group, arylheteroalkyl group, hydroxyl group, hydroxyalkyl group, alkoxy group, alkoxyalkyl group, alkoxyaryl group, alkenyloxy group, alkynyloxy group, cycloalkyloxy group, heterocycloalkyloxy group, aryloxy group, arylalkoxy group, phenoxy group, benzyloxy group, heteroaryloxy group, amino group, alkylamino group, aminoalkyl group, acylamino group, arylamino group, sulfonylamino group, sulfinylamino group, hydroxyl group, or the like, -COOH, -COR, -COOR, -CONHR, -NHCOR, -NHCOOR, -NHCONHR, alkoxycarbonyl, alkylaminocarbonyl, sulfonyl, alkylsulfonyl, alkylsulfinyl, arylsulfonyl, arylsulfinyl, aminosulfonyl-R, 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, and the substitution site of said substituent is arbitrary, wherein R, R1, R2, R3 are each independently selected from one of H, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, cycloalkyl, heterocycloalkyl, arylalkyl, heteroarylalkyl, and acyl.
Wherein the alkyl group has the general formula CnH2n+1Wherein n is a positive integer of 1 to 25, and the alkyl group includes a branched or straight chain saturated aliphatic hydrocarbon group, a cyclic alkyl group; the aryl group includes substituents having the following structure: comprises benzene, biphenyl, triphenyl, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene and azulene; the heteroaryl group includes substituents having the following structure: dibenzothiophene, dibenzofuran, furan, thiophene, benzofuran, benzothiophene, carbazole, pyrazole, imidazole, triazole, benzisoxazole, oxathiazine, oxadiazole, oxatriazole, bisoxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, thiazine, oxadiazine, indole, benzimidazole, indazole, indolizine, benzoxazole, isoxazole, benzothiazole, quinoline, isoquinoline, ortho-dinitrogen (hetero) naphthalene, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, dibenzoselenophene, benzoselenophene, benzofuropyridine, indolocarbazole, pyridylindole, pyrrolobipyridine, furanbipyridine, benzothienopyridine, thienopyridine, benzoselenenopyridine, and selenophenedipyridine.
As a preferred embodiment, the structural unit of the positive charge transport agent is an arylamine derivative compound. Specifically, the structural unit of the positive charge transport agent includes, but is not limited to, the structures shown in the following formulas 11 to 18:
ar1 and Ar 2-Ar 13 are independently selected from one of aryl compounds and heteroaryl compounds, wherein the aryl compounds comprise benzene, biphenyl, triphenyl, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene and derivatives thereof; the heteroaryl compound includes dibenzothiophene, dibenzofuran, furan, thiophene, benzofuran, benzothiophene, carbazole, pyrazole, imidazole, triazole, isoxazole, oxathiazine, oxadiazole, oxatriazole, bisoxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, thiazine, oxadiazine, indole, benzimidazole, indazole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, o-diaza (hetero) naphthalene, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, dibenzoselenophene, benzoselenophene, benzofuropyridine, indocarbazole, pyridylindole, pyrrolobipyridine, furanbipyridine, benzothienopyridine, thienobipyridine, benzoselenenopyridine, and selenophene bipyridine, and derivatives thereof.
As another preferred embodiment, the structural unit of the positive charge transport agent is a group comprising 2 to 10 ring structures, which are aryl groups or heteroaryl groups of the same or different types, the ring structures being directly connected to each other; or the ring structures are connected through at least one of the following heteroatoms or connecting groups, wherein the heteroatoms are at least one of oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms and boron atoms, and the connecting groups are at least one of methylene groups and aliphatic ring groups.
As a particularly preferred embodiment, the structural unit of the positive charge transport agent may be an arylamine derivative structure represented by the following formulas 19 to 24:
the positive charge transport agent may be an arylamine derivative polymer structure having a structure represented by formulas 25-28 below:
in the embodiment of the invention, the structural unit of the positive charge transport agent can also be a metal complex. Specifically, the structure of the metal complex can be represented by the following formula 29, wherein M and n are integers, the maximum coordination number of M is not less than 1, M and not more than M, M + n is the maximum coordination number of M, M is a metal element with an atomic weight of more than 40, L is an auxiliary ligand, (Y1-Y2) is a bidentate ligand, or (Y1-Y2) is an aromatic heterocyclic ring containing at least one of C, N, O, P, S,
when the (Y1-Y2) is a bidentate ligand, Y1 and Y2 are independently selected from C, N, O, P, S. When the (Y1-Y2) is an aromatic heterocyclic ring, the aromatic heterocyclic ring includes dibenzothiophene, dibenzofuran, furan, thiophene, benzofuran, benzothiophene, carbazole, pyrazole, imidazole, triazole, isoxazole, oxathiazine, oxadiazole, oxatriazole, bisoxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, thiazine, oxadiazine, indole, benzimidazole, indazole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, benzodiazepine, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, dibenzoselenophene, benzoselenophene, benzofuropyridine, indocarbazole, pyridylindole, pyrrolobipyridine, furanbipyridine, benzothienopyridine, thienobipyridine, benzoselenenopyridine and selenophenedipyridine, and derivatives thereof.
As a preferred embodiment, the structural unit of the negative charge transport agent is a structure represented by the following formulas 30 to 59:
wherein N is an integer of 1-20, X1 to X1 are independently selected from CH or N, Ar1 to Ar5 are independently selected from one of aryl compounds and heteroaryl compounds, R1 is selected from one of hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, heteroalkyl, aryl and heteroaryl, or R1 is selected from one of alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, heteroalkyl, aryl and heteroaryl containing a combinable/polymerizable substituent group;
wherein the aryl compound comprises benzene, biphenyl, triphenyl, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene and derivatives thereof; the heteroaryl compound, such as dibenzothiophene, dibenzofuran, furan, thiophene, benzofuran, benzothiophene, carbazole, pyrazole, imidazole, triazole, isoxazole, oxathiazine, oxadiazole, oxatriazole, bisoxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, thiazine, oxadiazine, indole, benzimidazole, indazole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, o-diaza (hetero) naphthalene, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, dibenzoselenophene, benzoselenophene, benzofuropyridine, indocarbazole, pyridylindole, pyrrolobipyridine, furanbipyridine, benzothienopyridine, thienobipyridine, benzoselenenopyridine, and selenophenedipyridine, and derivatives thereof.
The negative charge transport agent may have a polymer structure represented by the following formula 59-62:
in the embodiment of the invention, the structural unit of the negative charge transport agent can also be a metal complex. Specifically, the structure of the metal complex can be represented by the following formula 63-66, wherein z is an integer, z is not less than 1 and not more than z and not more than the maximum coordination number of the metal, L is an auxiliary ligand, and (O-N) or (N-N) is a bidentate ligand, the metal is coordinated with (O-N) or (N-N),
in the quantum dot ink provided by the embodiment of the invention, the distribution states of the positive charge transport agent and the negative charge transport agent in a quantum dot light-emitting layer are different according to different types (small molecule compounds or polymers) of the positive charge transport agent and the negative charge transport agent.
As a specific example, the positive charge transport agent is a small molecule compound and the negative charge transport agent is a polymer. At this time, the positive charge transport agent and the negative charge transport agent are uniformly dispersed with each other.
As yet another specific example, the positive charge transport agent is a polymer and the negative charge transport agent is a small molecule compound. At this time, the positive charge transport agent and the negative charge transport agent are uniformly dispersed with each other.
As yet another specific example, the positive charge transport agent and the negative charge transport agent are both small molecule compounds. At this time, the positive charge transport agent and the negative charge transport agent are uniformly dispersed with each other.
As another specific example, the positive charge transport agent and the negative charge transport agent are both polymers, and the positive charge transport agent and the negative charge transport agent form an interpenetrating polymer. The interpenetrating polymer includes an interpenetrating network polymer (IPN) or a semi-interpenetrating network polymer.
Wherein the interpenetrating network polymer is formed by mutually interpenetrating networks formed by respectively crosslinking the crosslinked polymer of the positive charge transport agent and the crosslinked polymer of the negative charge transport agent continuously. The interpenetrating network polymers can be classified into chemical interpenetrating network polymers and physical interpenetrating network polymers according to their crosslinking properties.
Specifically, the interpenetrating network polymer can be a positive charge transport substance polymer and a negative charge transport agent cross-linked polymer, which are mixed with the quantum dots together with respective cross-linking agents (and catalysts) to form a chemical interpenetrating network polymer in a film forming process. The interpenetrating network polymer can also be a chemical interpenetrating network polymer which is formed by the cross-linking polymerization of the small molecular structural units of the positive charge transport agent, the small molecular structural units of the negative charge transport agent, the respective cross-linking agents (and catalysts) and the initiator (or activating agent) after being mixed with the quantum dots in the film forming process. The interpenetrating network polymer can also be formed by mixing the small molecular structure unit of the positive (or negative) charge transport agent, the cross-linking agent and the initiating agent (or activating agent), the polymer of the negative (or positive) charge transport agent and the cross-linking agent (and the catalyst) thereof, and then mixing the mixture with the quantum dots, in-situ polymerizing the small molecular structure unit of the positive (or negative) charge transport agent and cross-linking the small molecular structure unit of the negative (or positive) charge transport agent to form the polymer in the film forming process, and cross-linking the polymer of the negative (or positive) charge transport agent to form the chemical cross-linked interpenetrating network polymer. The interpenetrating network polymer can also be a small molecular structure unit of a positive charge transport agent, a small molecular structure unit of a negative charge transport agent and respective initiators (or activators) which are polymerized into a positive charge transport substance polymer and a negative charge transport substance polymer, and then mixed with quantum dots to form a physical interpenetrating network polymer in the film forming process.
The semi-interpenetrating network polymer is a network formed by two polymers, wherein one polymer is an uncrosslinked linear molecule which is interpenetrating into the other polymer which is crosslinked, and the semi-interpenetrating network is called. Wherein the crosslinked polymer I/the linear polymer II is referred to as semi-I; the linear polymer I/crosslinked polymer II is referred to as semi-II.
Specifically, the semi-interpenetrating network polymer can be a polymer cross-linking agent (and catalyst) formed by a small molecular structural unit of a positive charge transport agent, a small molecular structural unit of a negative charge transport agent, a respective initiator (or activator), and one of small molecular compounds, and after being mixed with quantum dots, the cross-linking polymerization is carried out in a film forming process to form a chemically cross-linked semi-interpenetrating network polymer. The semi-interpenetrating network polymer can also be a polymer of a positive charge transport agent and a polymer of a negative charge transport agent, and a crosslinking agent (and a catalyst) of one of the polymers are mixed with the quantum dots to form a chemically crosslinked semi-interpenetrating network polymer in the film forming process. The semi-interpenetrating network polymer can also be a chemically crosslinked semi-interpenetrating network polymer formed by mixing the small molecular structural unit of the positive (or negative) charge transport agent, an initiator (or an activating agent), a polymer of the negative (or positive) charge transport agent and a crosslinking agent (and a catalyst) thereof with the quantum dots, and polymerizing the small molecular structural unit of the positive (or negative) charge transport agent in situ during film formation to form the polymer of the positive (or negative) charge transport agent, wherein the polymer is crosslinked, and the polymer of the negative (or positive) charge transport agent is interpenetrated in the crosslinked polymer of the positive (or negative) charge transport agent. The semi-interpenetrating network polymer can also be a chemically crosslinked semi-interpenetrating network polymer formed by mixing the small molecular structural units of the positive (or negative) charge transport agent, the crosslinking agent and the initiator (or activating agent) with the polymer of the negative (or positive) charge transport agent and the quantum dots, and polymerizing the small molecular structural units of the positive (or negative) charge transport agent in situ and crosslinking the small molecular structural units to form the positive (or negative) charge transport agent in a film forming process, wherein the polymer of the negative (or positive) charge transport agent is interpenetrated in the crosslinked polymer of the positive (or negative) charge transport agent.
In the quantum dot ink, the charge transport agent should be added in a suitable ratio. The content of the organic silicon compound is too low, so that the effects of improving the charge transmission effectiveness, reducing the threshold voltage and improving the energy efficiency are difficult to achieve; if the content of the quantum dot is too high, the charge transport performance is too strong, and the charge transport agent forms a conductive path, so that electron-hole transport does not transmit charges through the quantum dot, and the quantum dot does not emit light and loses the function. Therefore, in the embodiment of the present invention, the amount of the charge transport agent is 0.1 to 15.0% based on 100% of the total weight of the quantum dot ink, and as a specific embodiment, the amount of the charge transport agent may 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%, and other specific content values.
The solvent is used as a main component of the quantum dot ink of the embodiment of the invention, and in order to fully realize the full dissolution and dispersion of each component in the quantum dot ink, the solvent is divided into a main solvent and a cosolvent. In the embodiment of the invention, the main solvent is a non-polar solvent, and the cosolvent is a polar solvent.
In a specific embodiment, the main solvent is a single nonpolar solvent or a mixed solvent of two or more nonpolar solvents. As a preferable embodiment, the main solvent uses one of long-chain alkane, alcohol, ester and ether with the boiling point of 60-250 ℃ and at least containing 6 carbon atoms, or a mixture of two or more of the long-chain alkane, alcohol, ester and ether. The optimized main solvent can prevent the solvent from volatilizing to influence the performance of the obtained quantum dot luminescent layer in the process of ink-jet printing of the quantum dot luminescent layer; meanwhile, the boiling point of the main solvent is not too high, so that the solvent is not required to be removed at high temperature, and the quantum dots are ensured not to undergo fluorescence quenching. In particular, the primary solvent is preferably a straight or branched chain alkane, for example an alkane of 6 to 10 carbon atoms. Further, the main solvent is at least one of chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, n-hexane, dichloromethane, trichloromethane, 1, 4-dioxane, 1, 2-dichloroethane, 1,1, 1-trichloroethane, 1,1,2, 2-tetrachloroethane, tetrahydronaphthalene and decalin. In order to sufficiently achieve sufficient dispersion of quantum dots and sufficient dissolution of the less polar component in the quantum dot ink, the weight of the main solvent accounts for 50% or more of the total weight of the solvent.
The cosolvent is alcohol or a composite solvent formed by alcohol and other polar solvents. Wherein, the alcohol includes but is not limited to methanol, ethanol, isopropanol, butanol, pentanol, 2-methoxyethanol, and the other polar solvent includes but is not limited to various esters, ethers, amides, specifically including but not limited to acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, or monoalkyl ethers of ethylene glycol, propylene glycol and polyethylene glycol, such as one or more of ethylene glycol monobutyl ether, dipropylene glycol monomethyl ether. Further, the other polar solvent preferably uses the ether. As a preferred example, in order to sufficiently achieve sufficient dissolution of the polar component in the quantum dot ink, the weight of the co-solvent is 1.0 to 20.0% of the total weight of the solvent, and further, the weight of the co-solvent is preferably 1.0 to 10% of the total weight of the solvent.
When the quantum dot ink provided by the embodiment of the invention is used for ink-jet printing of a quantum dot light-emitting layer, the fluidity greatly affects the printing effect. As a preferred example, in order to ensure a proper solid content and thus a proper fluidity of the quantum dot ink, the solvent is used in an amount of 40.0 to 90.0% based on 100% by weight of the total quantum dot ink. Further, the amount of the solvent is preferably 40.0 to 70 wt%; further, the amount of the solvent is preferably 40.0 to 65%.
In the embodiment of the invention, the solvent can be removed by heating and pressurizing in the post-treatment process.
In the quantum dot ink, a dispersant can be selectively added according to actual needs. The dispersant may be effective to uniformly disperse the quantum dots in the solvent and to stabilize the dispersion. In particular, the dispersant may be one or more surfactants. The surfactant may be an anionic, cationic, nonionic or amphoteric surfactant.
As specific examples, the nonionic surfactant includes, but is not limited to, at least one of linear or secondary alcohol ethoxylates, alkylphenol ethoxylates, fluorosurfactants, fatty acid polyoxyethylene esters, fatty amine polyoxyethylene ethers, polyoxyethylene block copolymers and propoxylated block copolymers, polyoxyethylene and propylsilicone oxide resin-based surfactants, alkyl polyglycosides, and acetylene polyethylene oxide surfactants. The anionic surfactant includes, but is not limited to, at least one of carboxylates (e.g., ether carboxylates and sulfosuccinates), sulfates (e.g., sodium lauryl sulfate), sulfonates (e.g., dodecylbenzene sulfonate, alpha-olefin sulfonate, alkyl diphenyl oxide disulfonate, fatty acid taurates, alkyl naphthalene sulfonates), phosphates (e.g., phosphate esters of alkyl and aryl alcohols), phosphonates and amine oxide surfactants, and anionic fluorinated surfactants. The amphoteric surfactant includes, but is not limited to, at least one of trimethylamine ethylester, sultaine, and aminopropionate. The cationic surfactant includes, but is not limited to, at least one of quaternary ammonium compounds, cationic amine oxides, ethoxylated fatty amines, and imidazoline surfactants.
The amount of the dispersant is 0-15% based on 100% of the total weight of the quantum dot ink. As a specific example, the dispersant may be used in an amount of 0, 0.1%, 0.2%, 0.5%, 0.8%, 1.0%, 2.0%, 3.0%, 4.0%, 5.0%, 10%, 15%, or other specific content values.
The viscosity modifier is an important component for adjusting the viscosity of the quantum dot ink. In order to obtain quantum dot inks with appropriate viscosity, in the present embodiment, the viscosity modifier is preferably at least one of polyhydric alcohol, alkyl glycol ether or trimethylolpropane, trimethylolethane, casein, carboxymethyl cellulose. Specifically, the polyhydric alcohol is at least one of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1, 3-butylene glycol, 1, 4-butylene glycol, 1, 5-pentanediol, 2-butene-1, 4-diol, 2-methyl-2-pentanediol, 1,2, 6-hexanetriol, glycerol, polyethylene glycol, dipropylene glycol and polyvinyl alcohol. The alkyl glycol ether is at least one of polyethylene glycol monobutyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether and propylene glycol n-propyl ether.
In an embodiment, the amount of the viscosity modifier is 0.1 to 15.0%, and in an embodiment, the amount of the viscosity modifier may 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%, or other specific content values, based on 100% of the total weight of the quantum dot ink.
In order to ensure that the ink is properly released from a nozzle of an ink-jet printing head without blockage when the quantum dot ink is subjected to ink-jet printing, and simultaneously has good film forming characteristics, the viscosity and the surface tension of the quantum dot ink need to meet certain conditions. As a preferable example, the viscosity of the quantum dot ink at room temperature (25 ℃) is preferably 0.1 to 50.0mPa.s, and specifically may 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, 50 mPa.s; further, the viscosity of the quantum dot ink is preferably 0.5 to 20.0 mpa.s. As another preferred example, the surface tension of the quantum dot ink is 15.0 to 50.0mN/m, and specifically 15.0mN/m, 20.0mN/m, 25.0mN/m, 30.0mN/m, 35.0mN/m, 40.0mN/m, 55.0mN/m, 50.0 mN/m. Further, the surface tension of the quantum dot ink is preferably 20.0-40.0 mN/m.
The quantum dot ink provided by the embodiment of the invention has proper viscosity and surface tension, and can be deposited to form a quantum dot light-emitting layer with a pixel lattice, high resolution and electro-excitation by an ink-jet printing method; meanwhile, the quantum dot ink contains positive and negative charge transport agents which can facilitate charge transport, so that charge transport of a quantum dot light-emitting layer prepared by using the quantum dot ink is smoother and more effective, the threshold voltage is reduced, and electrons and holes can carry out composite radiation luminescence. In addition, the proportion of the added positive and negative charge transport agents can be controlled, and the dispersion state of the positive and negative charge transport agents, such as uniform dispersion or formation of network interpenetrating or semi-interpenetrating polymer, can be regulated and controlled, so that the charge transport in the quantum dot light-emitting layer is balanced, the starting voltage is reduced, and electrons and holes can perform radiation composite luminescence.
The quantum dot ink of the embodiment of the invention can be prepared by, but is not limited to, the following method.
Correspondingly, the embodiment of the invention also provides a preparation method of the quantum dot ink, which comprises the following steps:
s01, weighing the formula components of the quantum dot ink;
s02, dissolving quantum dots, a charge transport agent, a dispersing agent and a viscosity regulator in a solvent to form a blend;
and S03, mixing the blend.
Specifically, in the step S01, the formula of the quantum dot ink, and the preferred components and contents thereof are described above, and are not described herein again for brevity.
In the above step S02, the quantum dots, the charge transport agent, the dispersant, and the viscosity modifier are dissolved in the solvent in an unlimited manner. As a preferred embodiment, the quantum dots are dissolved in the solvent before the other components are added. As another preferred embodiment, polar components such as the quantum dots and the like may be dissolved in the main solvent to form a non-polar mixed solution, and relatively more polar components such as the charge transport agent and the like may be dissolved in the co-solvent to form a polar mixed solution, and then the non-polar mixed solution and the polar mixed solution may be mixed to form a blend. The optimized method can realize the full dissolution and dispersion of the components, thereby improving the overall performance of the quantum dot ink.
In the above step S03, the manner of mixing the blend is not limited as long as sufficient blending can be achieved. As a preferred embodiment, the mixing treatment is realized by stirring, and the stirring time is 25 to 35min, and more preferably 30 min.
Correspondingly, the embodiment of the invention also provides a quantum dot light-emitting diode which comprises a quantum dot light-emitting layer, wherein the quantum dot light-emitting layer is formed by printing the quantum dot ink.
Specifically, the method for preparing the quantum dot light-emitting layer in the quantum dot light-emitting diode by using the quantum dot ink is preferably realized by adopting a piezoelectric or thermal ink jet printing mode. The thickness of the dry film formed by ink-jet printing is preferably 10-100 nm; further, the dry film thickness formed by the ink-jet printing is 20-50 nm.
The quantum dot light-emitting diode provided by the embodiment of the invention comprises a quantum dot light-emitting layer printed by the quantum dot ink. The quantum dot ink contains the charge transport agent, so that the charge transport efficiency of the quantum dot light-emitting layer is improved, and the effects of reducing threshold voltage and improving energy efficiency are achieved.
The following description will be given with reference to specific examples.
Example 1
The quantum dot ink comprises the components with the weight percentage content shown in the following table 1 and example 1, wherein the quantum dots are oleylamine-stabilized red CdSe/ZnS quantum dots, the positive charge transport agent is polyvinyl carbazole PVK and has the structure shown in the following structural formula 67, the negative charge transport agent is oxadiazole acrylate polymer and has the structure shown in the following structural formula 68, the main solvent is high-purity chlorobenzene, the cosolvent is dimethylformamide, the dispersing agent is trimethylamine ethyl lactone surfactant, and the viscosity regulator is glycerol, wherein the components are calculated by taking the weight percentage content of the quantum dot ink as 100%.
The preparation method of the quantum dot ink comprises the following steps:
s11, weighing the formula components of the quantum dot ink;
s12, adding the components into a 500mL high-density polyethylene bottle containing a solvent under the stirring condition to form a blend;
and S13, stirring and mixing the blend for 30 minutes to obtain the physically-connected quantum dot ink.
Further, the quantum dot ink was printed into a quantum dot layer of 70 × 200um with a resolution of 80 × 80ppi by an inkjet printer. Heating the mixture on a hot plate to 100 ℃, and volatilizing and drying the mixture for 30min under nitrogen flow to obtain the monochromatic quantum dot light-emitting layer.
Example 2
The three quantum dot inks comprise the components with the weight percentages shown in the following table 1 and example 2, wherein the quantum dots are oleylamine-stabilized quantum dots, the positive charge transport agent is triphenylamine methacrylate and a small amount of azodiisobutyronitrile and ditrimethylolpropane tetraacrylic acid, the structure of the positive charge transport agent is shown in the following structural formula 69, the negative charge transport agent is polypyridine-alkoxy phenyl, the structure of the negative charge transport agent is shown in the following structural formula 70, the main solvent is high-purity toluene, the cosolvent is dimethyl sulfoxide, the dispersing agent is an ethoxy aliphatic amine surfactant, and the viscosity regulator is propylene glycol n-propyl ether;
the quantum dots in the first quantum dot ink are blue CdS/CdZnS quantum dots, the quantum dots in the second quantum dot ink are green CdZnSe/CdZnS quantum dots, and the quantum dots in the third quantum dot ink are red CdSe/ZnS quantum dots.
The preparation method of the quantum dot ink comprises the following steps:
s11, weighing the formula components of the quantum dot ink;
s12, under the stirring condition, sequentially adding the components into a 500mL high-density polyethylene bottle containing a solvent according to the following sequence: quantum dots, a charge transport agent, a dispersant and a viscosity modifier to form a blend;
and S13, stirring and mixing the blend for 30 minutes to obtain the quantum dot ink.
The quantum dot printing ink with three different colors is prepared according to the method.
Further, the three quantum dot inks are printed into blue, green and red side-by-side quantum dot layers with the resolution of 80X 80ppi and the thickness of 50X 150um by an ink-jet printer. Heating the mixture on a hot plate to 100 ℃, and volatilizing and drying the mixture for 30min under nitrogen flow to obtain the tricolor quantum dot light-emitting layer.
TABLE 1
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (18)
1. The quantum dot ink is characterized by comprising the following components in percentage by weight based on 100% of the quantum dot ink:
wherein the charge transport agent comprises a positive charge transport agent and a negative charge transport agent, the solvent comprises a primary solvent and a co-solvent,
the positive charge transport agent is at least one of a small molecule compound or a polymer containing the following structural units: amines, bifluorenes, azaindenoazafluorenes, phthalocyanines, porphyrins, organometallic complexes, metal complexes, fluorocarbons, and derivatives thereof; and/or
The negative charge transport agent is at least one of a small molecule compound or a polymer containing the following structural units: anthracene, phenanthrene, triazine, pyrene, perylene, phenazine, phenanthroline, oxadiazole, imidazole, oxazole, triazole, benzodiazole, pyridine, pyrimidine, pyrazine, quinoline, quinoxaline, thiophene, dithienothiophene, bithiophene, organosilicon, metal complexes, and derivatives thereof;
the weight ratio of the positive charge transport agent to the negative charge transport agent is 1:9 to 9: 1.
2. The quantum dot ink of claim 1, wherein the amine comprises an aromatic amine and the bifluorene comprises a spirobifluorene.
3. The quantum dot ink of claim 2, wherein the aromatic amine comprises a triarylamine biphenyl.
4. The quantum dot ink of claim 1, wherein the structural unit of the positive charge transport agent or the structural unit of the negative charge transport agent comprises at least one combinable/polymerizable group comprising a vinyl group, an acrylate group, a perfluorovinyl ether group, an enediphosphate group, an allylamine group, an allylalcohol group, an allylthiol group, an acrylic group, a methacrylate hydroxyl ester group, a primary amine, a secondary amine, an epoxy group, an α, β unsaturated carbonyl compound group, an alcoholic hydroxyl compound group, a carboxylic acid group, an acid chloride group, an acid anhydride group, a cyclic lactone group, an aldehyde compound group.
5. The quantum dot ink of claim 4, wherein the acrylate group comprises an acrylate hydroxy ester comprising a hydroxyl functional group; and/or
The epoxy compound group includes a propylene oxide compound group.
6. The quantum dot ink according to claim 4, wherein the positive charge transport agent is a side chain type positive charge transport polymer formed by addition polymerization of the structural unit via a polymerizable group; and/or
The negative charge transport agent is a side chain type negative charge transport polymer formed by the addition polymerization reaction of the structural unit through a polymerizable group,
the polymerizable group comprises a vinyl group, an acrylate group, a perfluorovinyl ether group, an alkene diphosphate group, an allylamine group, an allylalcohol group, an allylthiol group and an acrylic group.
7. The quantum dot ink according to claim 4, wherein the positive charge transport agent and/or the negative charge transport agent is at least one of main chain type charge transport polymers obtained by addition reaction of a primary amine and/or a secondary amine to an epoxy compound, Michael addition reaction of a primary amine and/or a secondary amine to an α, β unsaturated carbonyl compound, condensation reaction of an alcoholic hydroxyl compound with at least one of carboxylic acid, acid chloride, and acid anhydride, ring-opening polymerization reaction of a glycidyl compound and a cyclic lactone, and schiff base reaction of a primary amine and an aldehyde compound, in the structural unit having a polymerizable group.
8. The quantum dot ink of claim 1, wherein the structural unit of the positive charge transport agent or the structural unit of the negative charge transport agent contains at least one substituent group comprising halogen, alkyl, alkenyl, alkynyl, haloalkenyl, heteroalkyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, heterocycloalkenyl, aryl, heteroaryl, arylalkyl, heteroarylalkyl, arylalkenyl, cycloalkylheteroalkyl, heterocycloalkylheteroalkyl, heteroarylheteroalkyl, arylheteroalkyl, hydroxy, hydroxyalkyl, alkoxy, alkoxyalkyl, alkoxyaryl, alkenyloxy, alkynyloxy, cycloalkyloxy, heterocycloalkyloxy, aryloxy, arylalkoxy, heteroaryloxy, amino, alkylamino, aminoalkyl, acylamino, arylamino, sulfonylamino, sulfinylamino, -COOH, carboxyl, amino, carboxyl, -COR, -COOR, -CONHR, -NHCOR, -NHCOOR, -NHCONHR, alkoxycarbonyl, alkylaminocarbonyl, sulfonyl, alkylsulfonyl, alkylsulfinyl, arylsulfonyl, arylsulfinyl, 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, and the substitution site of the substitution group is arbitrary, wherein R is selected from one of alkenyl, alkynyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, arylalkyl, heteroarylalkyl and acyl; the R1, R2 and R3 are respectively and independently selected from one of H, alkyl, alkenyl, alkynyl, halogenated alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, arylalkyl, heteroarylalkyl and acyl, and at least one of R1 and R3 in R1S (O) R3 is not selected from H and alkyl, 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) -at least one of R1, R2 and R3 is not selected from H and alkyl.
9. The quantum dot ink of claim 8, wherein the aryloxy groups comprise phenoxy, benzyloxy.
10. The quantum dot ink of claim 1, wherein the positive charge transport agent is formed by direct reaction of the same or different structural units; or said positive charge transport agent is formed by the same or different of said building blocks being linked via at least one heteroatom or linking group; and/or
The negative charge transport agent is formed by direct reaction of the same or different structural units; or said negative charge transport agent is formed by the same or different of said building blocks being linked via at least one heteroatom or linking group;
wherein the heteroatom is at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom and boron atom, and the connecting group is at least one of methylene, aliphatic ring group, aryl and heteroaryl.
11. The quantum dot ink of claim 10, wherein the aliphatic cyclic group, the aryl group, and the heteroaryl group are aliphatic cyclic groups, aryl groups, and heteroaryl groups independently comprising at least one substituent group comprising halogen, alkyl, alkenyl, alkynyl, haloalkenyl, heteroalkyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, heterocycloalkenyl, aryl, heteroaryl, arylalkyl, heteroarylalkyl, arylalkenyl, cycloalkylheteroalkyl, heterocycloalkylheteroalkyl, heteroarylheteroalkyl, arylheteroalkyl, hydroxy, hydroxyalkyl, alkoxy, alkoxyalkyl, alkoxyaryl, alkenyloxy, alkynyloxy, cycloalkyloxy, heterocycloalkyloxy, aryloxy, arylalkoxy, heteroaryloxy, amino, alkylamino, aminoalkyl, acylamino, arylamino, sulfonylamino, sulfinylamino, hydroxyl, cycloalkenyl, and heteroaryl groups, -COOH, -COR, -COOR, -CONHR, -NHCOR, -NHCOOR, -NHCONHR, alkoxycarbonyl, alkylaminocarbonyl, sulfonyl, alkylsulfonyl, alkylsulfinyl, arylsulfonyl, arylsulfinyl, R1S (O) R3-, R1C (O) N (R2) (R3) -, R1S (O) N (R2) (R3) -, R1N (R2) c (O) R3-, R1N (R2) SOR3-, R1N (R2) c (R2) (R3) -and acyl, and the substitution site of the substituent group is arbitrary, wherein R is selected from one of alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, arylalkyl, heteroarylalkyl and acyl; the R1, R2 and R3 are respectively and independently selected from one of H, alkyl, alkenyl, alkynyl, halogenated alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, arylalkyl, heteroarylalkyl and acyl, and at least one of R1 and R3 in R1S (O) R3 is not selected from H and alkyl, 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) -at least one of R1, R2 and R3 is not selected from H and alkyl.
12. The quantum dot ink of claim 11, wherein the aryloxy groups comprise phenoxy, benzyloxy.
13. The quantum dot ink according to claim 1, wherein the structural unit of the positive charge transport agent is at least one of an arylamine derivative compound and a metal complex; and/or
The structural unit of the negative charge transport agent is at least one of metal complexes.
14. The quantum dot ink of any of claims 1 to 6, wherein the positive charge transport agent and the negative charge transport agent each have a molecular weight of 102-105g/mol。
15. The quantum dot ink of any of claims 1-6, wherein the positive charge transport agent and the negative charge transport agent are both small molecule compounds; and/or
The positive charge transport agent and the negative charge transport agent are both polymers, and the positive charge transport agent and the negative charge transport agent form an interpenetrating polymer.
16. The quantum dot ink of any of claims 1-6, wherein the positive charge transport agent is a small molecule compound and the negative charge transport agent is a polymer; and/or
The positive charge transport agent is a polymer, and the negative charge transport agent is a small molecule compound.
17. A preparation method of quantum dot ink comprises the following steps:
weighing the formulation components of the quantum dot ink as defined in any one of claims 1 to 16;
dissolving quantum dots, a charge transport agent, a dispersing agent and a viscosity regulator in a solvent to form a blend;
and (3) mixing the blend.
18. A quantum dot light emitting diode comprising a quantum dot light emitting layer printed from the quantum dot ink of any one of claims 1-16.
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| CN105810851B (en) * | 2016-05-03 | 2018-03-06 | 深圳市华星光电技术有限公司 | The preparation method and light emitting diode with quantum dots display of light emitting diode with quantum dots 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 |
| CN106374046A (en) * | 2016-09-12 | 2017-02-01 | Tcl集团股份有限公司 | Positively-arranged structure quantum dot light-emitting diode and fabrication method thereof |
| 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 |
| CN108276826B (en) * | 2016-12-30 | 2022-06-24 | Tcl科技集团股份有限公司 | Quantum dot ink and preparation method thereof |
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