CN109021701A - The preparation method of quantum dot ink and light emitting diode with quantum dots - Google Patents
The preparation method of quantum dot ink and light emitting diode with quantum dots Download PDFInfo
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- CN109021701A CN109021701A CN201710433462.6A CN201710433462A CN109021701A CN 109021701 A CN109021701 A CN 109021701A CN 201710433462 A CN201710433462 A CN 201710433462A CN 109021701 A CN109021701 A CN 109021701A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/36—Inkjet printing inks based on non-aqueous solvents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
- H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
Abstract
The present invention provides the preparation methods of a kind of quantum dot ink and light emitting diode with quantum dots.Quantum dot ink of the present invention includes at least one quanta point material and at least one sulfoxide type organic solvent, and the molecular structural formula of the sulfoxide type organic solvent is as shown in general structure I or/and II:Wherein, the R contained by the general structure I1、R2It is identical or different for C1‑30Any group in aliphatic series, aromatic group；Or the R1、R2A wherein group H, another group are C1‑30Any group in aliphatic series, aromatic group；The R contained by the general structure II3For C1‑30Any group in aliphatic series, aromatic group.The preparation method of light emitting diode with quantum dots of the present invention includes the steps that preparing quantum dot light emitting layer using ink-jet printing using quantum dot ink of the present invention.
Description
Technical field
The invention belongs to light emitting diode with quantum dots technical field more particularly to a kind of quantum dot ink and quantum dot light emitting
The preparation method of diode.
Background technique
Quantum dot is made of a limited number of atom, and three dimensions are in nanometer scale.Quantum dot is generally
It is spherical or spherical, it is made of semiconductor material (being usually made of the A of IIB~VI or IIIA~VA element), stable diameter
In the nanoparticle of 2~20nm.Quantum dot is the aggregate of the atom and molecule on nanoscale.As a kind of novel half
Conductor nano material, quantum dot have many unique nanometer properties.Fluorescence can be emitted after being excited.In recent years, quantum dot
(QD) luminescent material has played very big effect in fields such as LED illumination, liquid crystal displays, and quantum dot substitutes traditional fluorescent powder,
Effectively improve the colour gamut of LED and liquid crystal display.Recently, light emitting diode with quantum dots of the luminescent material as luminescent layer
(QLED) it is with a wide range of applications in fields such as solid-state lighting, FPD, receives the wide of academia and industrial circle
General concern.
The solution processing properties of quantum dot allow quantum dot light emitting layer to pass through spin coating, blade coating, injection, inkjet printing etc.
Various ways preparation.Opposite front several method, inkjet printing technology can be accurately in the desired amount by quantum dot light emitting material
It deposits in place, allows semiconductor material uniform deposition to form film layer, very high to the utilization rate of material, manufacturer can be with
Production cost is reduced, manufacture craft is simplified, universal volume production is easy, reduces cost.Inkjet printing technology be it is generally acknowledged at present can be with
Solve the effective ways of the manufacture problem of large scale QLED screen
Quantum dot ink is essentially all that quantum dot is directly dispersing in solvent at present, is such as disclosing a kind of printing ink
In composition, use substituted aromatics or heteroaromatic organic solvent as solvent, although those solvents further include toluene, chlorine
Imitative equal to have relative distribution good quantum dot, but obtained quantum dot ink viscosity is very small, boiling point is also very low, when being dissolved in
It is again very poor to the dispersion effect of quantum dot when some biggish solvent of viscosity such as long alkane alcohols solvents, system is directly resulted in this way
Standby quantum dot film thickness is inconsistent, and uniformity is very poor, and the introducing of the polymeric additive with insulating property (properties) is toward contact
The charge transport ability that film can be reduced has negative effect to the photoelectric properties of device, limits it in the opto-electronic device
It is widely applied.Therefore, viscosity can be improved, have preferably dispersibility again by how researching and developing one kind, can be facilitated in last handling process
The solvent of removal, and can satisfy inkjet printing requirement, stablizes out of ink, and stabilization is sprawled, and uniform drying, form a film uniform quantum dot
Ink is particularly important.
Summary of the invention
The purpose of the present invention is to provide a kind of quantum dot ink, it is intended to solve dispersion solvent viscosity mistake in quantum dot ink
Small and low boiling point or viscosity is excessive causes quantum dot dispersion uneven and lead to that quantum dot film thickness is inconsistent and uniformity is very poor
Technical problem.
Another object of the present invention is to provide a kind of preparation method of light emitting diode with quantum dots, existing using spray to solve
Ink printing formed quantum dot light emitting layer thickness is inconsistent and the very poor technical problem of uniformity.
In order to achieve the above-mentioned object of the invention, one aspect of the present invention provides a kind of quantum dot ink.The quantum dot ink
Including at least one quanta point material and at least one sulfoxide type organic solvent, the structural formula of the sulfoxide type organic solvent is as tied
Shown in structure general formula I or/and II:
Wherein, the R contained by the general structure I1For C1-30Any group in aliphatic series, aromatic group, the R2
For C1-30Any group in aliphatic series, aromatic group；Or the R1、R2Wherein a group is H, and another group is C1-30Aliphatic series,
Any group in aromatic group；
The R contained by the general structure II3For C1-30Any group in aliphatic series, aromatic group.
Another aspect of the invention provides a kind of preparation method of light emitting diode with quantum dots.The preparation method includes
Following steps:
Quantum dot ink is printed into quantum dot ink layer by the way of inkjet printing；
The quantum dot ink layer is dried, quantum dot light emitting layer is formed；
Wherein, the quantum dot ink is quantum dot ink of the present invention.
Compared with prior art, quantum dot ink of the present invention is using sulfoxide type organic solvent shown in general structure I or/and II
As organic solvent, the characteristic of the one side organic solvent itself, with being suitable for, quanta point material is evenly dispersed, assigns this hair
The uniformity and stability of bright quantum dot ink dispersion system have high storage stability；On the other hand present invention amount is assigned
Son point ink viscosity compatible with inkjet printing and surface tension, so that quantum dot ink of the present invention is beaten suitable for ink-jet
Print, and guarantee that stablizing for printing process is out of ink, stabilization is sprawled, and it is uniform to print the thicknesses of layers formed；Another aspect, it is contained
Sulfoxide type organic solvent has volatility, so that printing forms no solvent residue after film layer drying, guarantees quantum dot light emitting layer
Low start voltage drops in charge-transporting, improves luminous efficiency.
The preparation method of light emitting diode with quantum dots of the present invention uses quantum dot ink combination ink-jet printing shape of the present invention
At quantum dot light emitting layer, the quantum light emitting layer thickness for forming printing is uniform, and charge-transporting is high, starts voltage
Low, luminous efficiency is high；On the other hand, guarantee ink-jet printing process is stablized out of ink, and ink stability is sprawled, and thicknesses of layers is uniform,
Improve yields and production efficiency.
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
(1) quantum dot ink
On the one hand, the embodiment of the present invention provides a kind of quantum dot ink suitable for inkjet printing.The quantum dot ink packet
At least one quanta point material and at least one sulfoxide type organic solvent are included, the molecular structural formula of the sulfoxide type organic solvent is such as
Shown in general structure I or/and II:
Wherein, described contained by general structure I in an embodiment for above structure general formula I sulfoxide type organic solvent
R1、R2Can be identical or not identical, and the two is C1-30Any group in aliphatic series, aromatic group.In another embodiment,
The R1、R2Wherein a group is H, and another group is C1-30Any group in aliphatic series, aromatic group.Wherein, the C1-30
Aliphatic series, aromatic group can be unsubstituted group, be also possible to substituted group.
In further embodiment, R contained by above structure general formula I sulfoxide type organic solvent1、R2In an at least group be
Substituted C1-30Aliphatic series or aromatic group.In one embodiment, C1-30The substituent group of aliphatic series or aromatic group is alkyl, aryl, nitre
Base, cyano, amino ,-N (R ') (R "), halogen, hydroxyl, carboxyl, ester group, ether, carbonyl, alkenyl, alkynyl, naphthenic base, alcoxyl
Base, aryloxy group, heteroaryloxy, alkoxy carbonyl group, perfluoroalkyl, perfluoro alkoxy, aryloxy group, thio alkoxy ,-S (O)2-N
(R ') (R ") ,-C (=O)-N (R ') (R "), (R ') (R ") alkyl, (R ') (R ") positive alkoxy, (R ') (R ") alkyl virtue oxygen
At least one of base alkyl ,-S (O) s- aryl ,-S (O) s- heteroaryl, silicyl；Wherein, the s is the integer of 0-2,
The R ' and R " is identical or not identical, and is alkyl, naphthenic base or aryl.
In a particular embodiment, when abovementioned alkyl substituent group can be the saturated fat alkyl of branch and straight chain, for example
C1-25The saturated fat alkyl of branch and straight chain；Such as can be but not just for methyl, ethyl, propyl, isopropyl, isobutyl group,
Sec-butyl, tert-butyl, amyl, isopentyl, neopentyl, cyclopenta, hexyl, cyclohexyl, isohesyl.
In another embodiment, the aryl substituent is but not just for phenyl, xenyl, triphenyl base, benzene
And at least one of base, naphthalene, anthryl, non-that alkenyl (phenalene), phenanthryl, fluorenyl, pyrenyl, Qu Ji, base, azulenyl.
In still another embodiment, the heteroaryl substituent is dibenzothiophene, dibenzofuran group, furans
Base, thienyl, benzofuranyl, benzothienyl, carbazyl, pyrazolyl, imidazole radicals, triazol radical, isoxazolyl, thiazole
Base, oxadiazoles base, diazole (oxatriazole) base, dioxazole base, thiadiazolyl group, pyridyl group, pyridazinyl, pyrimidine radicals, pyrazine
Base, triazine radical, oxazines base, thiazine (oxathiazine) base, oxadiazines (oxadiazine) base, indyl, benzimidazolyl,
Indazolyl, indolizine (indoxazine) base, benzoxazolyl, isoxazole (benzisoxazole) base, benzothiazolyl, quinoline
Quinoline base, isoquinolyl, cinnoline base, quinazolyl, quinoxalinyl, naphthalene, phthalidyl, pteridyl, oxa- anthryl, acridine
Base, phenazinyl, phenothiazinyl, phenoxazine base, dibenzo selenophen (dibenzoselenophene) base, benzo selenophen
(benzoselenophene) base, benzofuran and pyridine (benzofuropyridine) base, indole carbazole
(indolocarbazole) base, pyridyl group indoles (pyridylindole) base, two pyridine of pyrroles (pyrrolodipyridine)
Base, two pyridine of furans (furodipyridine) base, benzothiophene and pyridine (benzothienopyridine) base, thiophene two
Pyridine (thienodipyridine) base, benzo selenophen and pyridine (benzoselenophenopyridine) base, two pyrrole of selenophen
At least one of pyridine (selenophenodipyridine).
For above structure general formula II sulfoxide type organic solvent, in an embodiment, the R contained by general structure II3
For C1-30Any group in aliphatic series, aromatic group.Wherein, the C1-30Aliphatic series, aromatic group are also possible to unsubstituted base
Group, is also possible to substituted group.
In further embodiment, as described in general structure I sulfoxide type organic solvent above, above structure general formula II sulfoxide type
R contained by organic solvent3For substituted C1-30Aliphatic series or aromatic group.In one embodiment, C1-30The substitution of aliphatic series or aromatic group
Group be alkyl, aryl, nitro, cyano, amino ,-N (R ') (R "), halogen, hydroxyl, carboxyl, ester group, ether, carbonyl, alkenyl,
Alkynyl, naphthenic base, alkoxy, aryloxy group, heteroaryloxy, alkoxy carbonyl group, perfluoroalkyl, perfluoro alkoxy, aryloxy group, thio alkane
Oxygroup ,-S (O)2- N (R ') (R ") ,-C (=O)-N (R ') (R "), (R ') (R ") alkyl, (R ') (R ") positive alkoxy, (R ')
At least one of (R ") alkyl aryloxy alkyl ,-S (O) s- aryl ,-S (O) s- heteroaryl, silicyl；Wherein, described
S is the integer of 0-2, and the R ' and R " is identical or not identical, and is alkyl, naphthenic base or aryl.
In a particular embodiment, when abovementioned alkyl substituent group can be the saturated fat alkyl of branch and straight chain, for example
C1-25The saturated fat alkyl of branch and straight chain；Such as can be but not just for methyl, ethyl, propyl, isopropyl, isobutyl group,
Sec-butyl, tert-butyl, amyl, isopentyl, neopentyl, cyclopenta, hexyl, cyclohexyl, isohesyl.
In another embodiment, the aryl substituent is but not just for phenyl, xenyl, triphenyl base, benzene
And at least one of base, naphthalene, anthryl, non-that alkenyl (phenalene), phenanthryl, fluorenyl, pyrenyl, Qu Ji, base, azulenyl.
In still another embodiment, the heteroaryl substituent is dibenzothiophene, dibenzofuran group, furans
Base, thienyl, benzofuranyl, benzothienyl, carbazyl, pyrazolyl, imidazole radicals, triazol radical, isoxazolyl, thiazole
Base, oxadiazoles base, diazole (oxatriazole) base, dioxazole base, thiadiazolyl group, pyridyl group, pyridazinyl, pyrimidine radicals, pyrazine
Base, triazine radical, oxazines base, thiazine (oxathiazine) base, oxadiazines (oxadiazine) base, indyl, benzimidazolyl,
Indazolyl, indolizine (indoxazine) base, benzoxazolyl, isoxazole (benzisoxazole) base, benzothiazolyl, quinoline
Quinoline base, isoquinolyl, cinnoline base, quinazolyl, quinoxalinyl, naphthalene, phthalidyl, pteridyl, oxa- anthryl, acridine
Base, phenazinyl, phenothiazinyl, phenoxazine base, dibenzo (dibenzoselenophene) base, benzo selenium
(benzoselenophene) base, benzofuran and pyrazoles (benzofuropyridine) base, indole carbazole
(indolocarbazole) base, pyridyl group indoles (pyridylindole) base, pyrrolo-indole (pyrrolodipyridine)
Base, two pyridine of furans (furodipyridine) base, furopyridine (benzothienopyridine) base, thienopyridine
(thienodipyridine) base, benzo selenophen and pyridine (benzoselenophenopyridine) base, two pyridine of selenophen
(selenophenodipyridine) at least one of base.
In the various embodiments described above on the basis of sulfoxide type organic solvent shown in general structure I or/and II, the sulfoxide type
Organic solvent specifically can be with but not just for dimethyl sulfoxide, ethyl-sulfoxide, diisopropyl sulfoxide, methyl phenyl sulfoxide, allyl
The thio methyl sulfone of base phenylsulfone, methyl, tetramethylene sulfoxide, tiacyclopentane 1- oxide (thiirane 1-oxide),
At least one of oxydemeton_methyl.
Sulfoxide type organic solvent shown in general structure I or/and II has the viscosity of appropriateness in the various embodiments described above, such as sub-
The viscosity of sulfone class organic solvent is at 25 DEG C between 0.5cPs-50cPs, and surface tension is at 25 DEG C between 20-80mN/m.The spy
The sulfoxide type organic solvent of property can effectively disperse quanta point material, and guarantee the stabilization of above-mentioned quantum dot ink dispersion system
Property, and above-mentioned quantum dot ink viscosity compatible with inkjet printing and surface tension are assigned, so that the various embodiments described above
In quantum dot ink be suitable for inkjet printing, guarantee printing process stablize it is out of ink, stabilization sprawl, meet thickness requirement；Meanwhile
Sulfoxide type organic solvent has volatility in the various embodiments described above, if sulfoxide type solvents boiling spread is at 100 DEG C -350 DEG C.So that
Printing forms no solvent residue after film layer drying, guarantees the charge-transporting of quantum dot light emitting layer, drops low start voltage, improves hair
Light efficiency.
On the basis of the various embodiments described above, the solvent of above-mentioned quantum dot ink can be entirely above-mentioned sulfoxide type solvents,
It can be above-mentioned sulfoxide type solvents and other conventional organic solvents for being suitable for quantum dot ink.When above-mentioned quantum dot ink also contains
When other organic solvents, which together forms the molten of above-mentioned quantum dot ink with above-mentioned sulfoxide type organic solvent
Agent system.It therefore, is in terms of 100% by the quantum dot total weight of printing ink, there is sulfoxide type in the various embodiments described above in an embodiment
Content of the solvent in quantum dot ink is 0.01%-99.9%, and at the same time, the content for controlling quanta point material is
0.01%-20.0%, preferably in 4%-15%；The content 0-99.8% of other class organic solvents.By organic molten to sulfoxide type
Agent and quanta point material or further to other organic solvent contents control, realize to the viscosity of quantum dot ink carry out control and
Optimize, in an embodiment, the viscosity for assigning above-mentioned quantum dot ink is 0.5-50.0mPa.s at 25-35 DEG C, is preferably existed
On the one hand 1.0mPa.s-15.0mPa.s makes quantum dot ink be suitable for inkjet printing, and guarantee that stablizing for printing process is out of ink,
Stabilization is sprawled, and it is uniform to print the thicknesses of layers formed；On the other hand guarantee the uniformity of quantum dot ink dispersion system and steady
It is qualitative.
Specifically, other above-mentioned organic solvents can be alcoholic solvent conventional contained by quantum dot ink, be also possible to quantum
Conventional alkanes and/or arene organic solvent contained by point ink.Wherein, the alkanes organic solvent includes branch
Saturated fat hydro carbons organic solvent CnH2n+2And/or the saturated fat hydro carbons organic solvent C of straight chainnH2n+2And/or cycloalkane
Organic solvent CmH2m；Wherein n and m is positive integer, 10≤n, m≤18.Preferably, alkanes organic solvent may include decane,
Hendecane, dodecane, tridecane, the tetradecane, pentadecane, hexadecane, heptadecane, octadecane, cyclodecane, in ring hendecane extremely
Few one kind also may include decane isomer, hendecane isomer, dodecane isomer, same point of tridecane
Isomers, tetradecane isomer, pentadecane isomer, hexadecane isomer, heptadecane isomer, ten
At least one of eight alkane isomers, cyclodecane isomer, ring hendecane isomer.
Above-mentioned arene organic solvent include but is not limited to ethylbenzene, ortho-xylene (o-), meta-xylene (m-), to diformazan
Benzene (p-), ortho-chlorotolu'ene, p-chlorotoluene, m-chlorotoluene, adjacent diethylbenzene (o-), NSC 62102 (m-), p-Diethylbenzene (p-), neighbour two
Chlorobenzene, m-dichlorobenzene, paracide, trimethylbenzene, durene, 3 penta benzene, amyl toluene, 1- methyl naphthalene, dihexyl benzene, butylbenzene,
Sec-butylbenzene, tert-butyl benzene, isobutyl-benzene, dibutyl benzene, isopropylbenzene, p-Methylisopropylbenzene, to diisopropyl benzene, penta benzene, two
Penta benzene, detergent alkylate, naphthane, cyclohexyl benzene, 1,3,5- trimethylbenzene cyclohexyl benzene, 1- chloronaphthalene, 1-tetralone, 3- benzene oxygen
Base toluene, 1- methoxynaphthalene, dimethylnaphthalene, 3- isopropyl biphenyl, 1,2,4- trimethylbenzene biphenyl, Ergol, benzyl ether, benzene
At least one of benzyl formate, indenes, benzyl benzene, divinylbenzene, indane, Styryl oxide.
In the above embodiments, above-mentioned quanta point material can be conventional quanta point material, such as in one embodiment,
Above-mentioned quanta point material is period of element Table IV race, II-VI group, II-V race, iii-v, III-VI race, group IV-VI, I-III-
VI race, II-IV-VI race, mixture II-IV-V race binary the above semiconducting compound or be made of these compounds.Another
In one embodiment, above-mentioned quanta point material be selected from CdSe, CdS, CdTe, ZnO, ZnSe, ZnS, ZnTe, HgS, HgSe, HgTe,
CdZnSe and any combination of them.In another embodiment, above-mentioned quanta point material be selected from InAs, InP, InN, GaN,
InSb, InAsP, InGaAs, GaAs, GaP, GaSb, AlP, AlN, AlAs, AlSb, CdSeTe, ZnCdSe and their any group
It closes.In another embodiment, above-mentioned quanta point material is that (especially shine perovskite nanometer particle material perovskite nanoparticle
Son), metal nano particle material or metal oxide nanoparticles material or their mixture.Above-mentioned each quanta point material tool
There are quantum dot characteristics, there is high efficiency of giving out light.
In further embodiment, the quanta point material in the various embodiments described above is luminescent quantum dot, the luminescent quantum dot
Surface also incorporates ligand, and the ligand is sour ligand, mercaptan ligand, amine ligand, Phosphine ligands, phosphine oxide ligand, phosphatide, soft phosphorus
One of rouge, polyvinylpyridine etc. are a variety of.Specifically, the sour ligand is ten acid, undecenoic acid, tetradecylic acid, oleic acid
With one of stearic acid or a variety of；The mercaptan ligand is in eight alkyl hydrosulfides, lauryl mercaptan and Stearyl mercaptan
It is one or more；The amine ligand is one of oleyl amine, octadecylamine and eight amine or a variety of；The Phosphine ligands are trioctylphosphine
Phosphine；The phosphine oxide ligand is trioctylphosphine oxide (TOPO).
In addition, above-mentioned each quanta point material can also be auto-dope or undoped quantum dot, it can also be and it is
Uniform mixed type, gradient mixed type, core-shell structure copolymer type or union type.Preferred quanta point material selects oil-soluble quantum
Point.In one embodiment, 1~20nm of average feature size of the quanta point material in the various embodiments described above.Pass through the control to size
System improves the stability of its dispersibility and quantum dot ink dispersion system in quantum dot ink.
Therefore, sulfoxide type organic solvent contained by quantum dot ink, and can due to self-characteristic in the various embodiments described above
So that quanta point material is evenly dispersed, the uniformity and stability of above-mentioned quantum dot ink dispersion system are assigned, there is high storage
Deposit stability；And above-mentioned quantum dot ink viscosity compatible with inkjet printing and surface tension are assigned, guarantee printing process
Stablize out of ink, stabilization is sprawled, and it is uniform to print the thicknesses of layers formed, and make printing formed film layer it is dry after it is solvent-free residual
It stays, guarantees the charge-transporting of quantum dot light emitting layer, drop low start voltage, improve luminous efficiency.
In addition, the quantum dot ink formulation method in the various embodiments described above, which can be, directly has sulfoxide type described above
Solvent and quanta point material directly carry out mixing treatment, so that quantum dot is fully dispersed uniformly.It is as described above to obtain
With proper viscosity, surface tension quantum dot ink.The boiling point of all quantum dot ink is controlled at 350 DEG C or less.
(2) preparation method of light emitting diode with quantum dots
On the other hand, the embodiment of the invention also provides a kind of preparation methods of light emitting diode with quantum dots.The quantum
Point luminescent diode preparation method is included the steps that such as to anode grid substrate processing, the injection of preparation hole and/or hole on anode
The step of transport layer, forms the step of quantum dot light emitting layer, and electron transfer layer and/or electronics note are formed on quantum dot light emitting layer
The step of entering layer and the step of prepare cathode etc..In addition to the preparation step of quantum dot light emitting layer, other steps can be according to
It is prepared by the step of light emitting diode with quantum dots routine.Wherein the step of quantum dot light emitting layer is prepared as follows in quantum dot light emitting layer
It is rapid:
A. quantum dot ink is printed into quantum dot ink layer by the way of inkjet printing；
B. the quantum dot ink layer is dried, forms quantum dot light emitting layer.
Wherein, the quantum dot ink in step A is quantum dot ink described above.Component contained by the quantum dot ink
As described above with content, in order to save length, details are not described herein.
Inkjet printing in step A is piezoelectricity or thermal inkjet-printing.The work of piezoelectric ink jet printing or thermal inkjet-printing
Skill condition is referred to the process conditions of conventional piezoelectric ink jet printing or thermal inkjet-printing, as long as using amount described above
Son point ink is that ink is printed.
Drying process in step B is preferably dried using any one of heating, cooling and/or reduced vacuum；
Wherein, in an embodiment, the heat treatment is that PULSE HEATING or continuous heating are handled, and the temperature of the heating is 60-180
DEG C, the time of heating can be enough, such as it is not more than 30min, but whether how long, it may be that guarantee contained solvent
All volatilizations.In another embodiment, it is described cooling processing temperature be 0-20 DEG C, the time of cooling can be it is enough, if not
Greater than 30min；In another embodiment, when being dried using the reduced vacuum, the vacuum degree of reduced vacuum drying process
It is [1 × 10-6Torr- normal pressure), the time be also it is enough, such as be not more than 30min, but whether how long, it may be that guarantee
Contained solvent all volatilizees.
Furthermore it is possible to control inkjet printing, can control the thickness for the quantum dot light emitting layer that printing is formed, such as with a thickness of
10-100nm.It is, of course, also possible to according to the actual needs, flexibly the thickness of quantum dot light emitting layer be adjusted and arrives other thickness.
Therefore, because the preparation method of above-mentioned light emitting diode with quantum dots combines spray using quantum dot ink described above
Black impact system forms quantum dot light emitting layer, and the quantum light emitting layer thickness for forming printing is uniform, and charge-transporting is high,
It is low to start voltage, luminous efficiency is high；On the other hand, guarantee ink-jet printing process is stablized out of ink, and ink stability is sprawled, and film layer is thick
Degree uniformly, improves yields and production efficiency.
Now in conjunction with specific example, the present invention will be described in further detail.
Embodiment 1
A kind of quantum dot ink is present embodiments provided, CdSe/ZnS quantum dot and the 5wt% decahydronaphthalene for wrapping 5wt% are molten
Agent, 90wt% ethyl-sulfoxide solvent；Wherein, decahydronaphthalene, ethyl-sulfoxide form mixed solvent, and various solvents are all made of corresponding side
Method water removal, deoxygenation are refined to purity greater than 99.9%.
Its configuration method:
Following components is added in container, in the case of stirring, order of addition are as follows: stable red of the oleyl amine of 5wt%
Color CdSe/ZnS quantum dot, 5wt% decahydronaphthalene solvent 90wt% ethyl-sulfoxide stirring solvent mixture 30 minutes, obtain quantum
Point printing ink composition.
The quantum dot ink provided using the present embodiment 1 is printed as 20 × 30um, resolution ratio 200 by ink-jet printer
The red quantum dot layer of × 200ppi, after 120 DEG C, vacuum 1 × 10 are heated on hot plate-6Volatile dry 30min under Torr, obtains
To monochromatic quantum dot luminescent layer.
Embodiment 2
A kind of quantum dot ink is present embodiments provided, CdZnSe/CdZnS quantum dot and the 80%wt for wrapping 13wt% are adjacent
Dimethoxy benzene, 7%wt tetramethylene sulfoxide solvent；Wherein, o-dimethoxybenzene, tetramethylene sulfoxide solvent form mixed solvent,
Various solvents are all made of corresponding method water removal, deoxygenation is refined to purity greater than 99.9%.
Its configuration method:
Following components is added in container, in the case of stirring, order of addition are as follows: stable green of the oleyl amine of 13wt%
Color CdZnSe/CdZnS, 80%wt o-dimethoxybenzene, 7%wt tetramethylene sulfoxide solvent stir mixture 30 minutes, the amount of obtaining
Son point printing ink composition.
The quantum dot ink provided using the present embodiment 2 is printed as 20 × 30um, resolution ratio 200 by ink-jet printer
The green quantum dot layer of × 200ppi, after 180 DEG C are heated on hot plate, volatile dry 30min under nitrogen stream, obtain monochromatic amount
Son point luminescent layer.
Embodiment 3
A kind of quantum dot ink is present embodiments provided, the oleyl amine of 10wt% stable blue CdS/CdZnS (green is wrapped
CdZnSe/CdZnS, red CdSe/ZnS quantum dot) and 15%wt dodecane, 40%wt decahydronaphthalenes, 35wt% aminomethyl phenyl
Sulfoxide；Wherein, dodecane, decahydronaphthalenes and methyl phenyl sulfoxide form mixed solvent, and various solvents are all made of corresponding method
Water removal, deoxygenation are refined to purity greater than 99.9%.
Its configuration method:
Following components is added in container, in the case of stirring, order of addition are as follows: 15%wt dodecane, 40%wt
The stable blue CdS/CdZnS of oleyl amine of decahydronaphthalenes, 10wt%, (green CdZnSe/CdZnS, red CdSe/ZnS quantum
Point), 35wt% methyl phenyl sulfoxide stir mixture 30 minutes, obtain quantum dot printing ink composition.
The quantum dot ink provided using the present embodiment 3 is printed as 20 × 30um, resolution ratio 200 by ink-jet printer
Blue, green, the red side-by-side quantum dot layer of × 200ppi, after 150 DEG C, vacuum degree 1 × 10 are heated on hot plate- 5Volatile dry 30min under Torr obtains three primary colours quantum dot light emitting layer.
Embodiment 4
A kind of quantum dot ink is present embodiments provided, CdSe/ZnS quantum dot and the 90wt% diformazan for wrapping 10wt% are sub-
Sulfoxide solvent；Wherein, dimethylsulfoxide solvent is refined to purity greater than 99.9% using the water removal of corresponding method, deoxygenation.
Its configuration method:
Following components is added in container, in the case of stirring, order of addition are as follows: stable red of the oleyl amine of 10wt%
Color CdSe/ZnS quantum dot, 90wt% dimethylsulfoxide solvent stir mixture 30 minutes, obtain quantum dot printing ink composition.
The quantum dot ink provided using the present embodiment 4 is printed as 20 × 30um, resolution ratio 200 by ink-jet printer
The red quantum dot layer of × 200ppi, after 100 DEG C, vacuum 1 × 10 are heated on hot plate-6Volatile dry 30min under Torr, obtains
To monochromatic quantum dot luminescent layer.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (12)
1. a kind of quantum dot ink, it is characterised in that: organic molten including at least one quanta point material and at least one sulfoxide type
Agent, the molecular structural formula of the sulfoxide type organic solvent is as shown in general structure I or/and II:
Wherein, the R contained by the general structure I1For C1-30Any group in aliphatic series, aromatic group, the R2For
C1-30Any group in aliphatic series, aromatic group；Or the R1、R2Wherein a group is H, and another group is C1-30Aliphatic series, virtue
Any group in race's group；
The R contained by the general structure II3For C1-30Any group in aliphatic series, aromatic group.
2. quantum dot ink according to claim 1, it is characterised in that: the R1、R2、R3In an at least group be take
The C in generation1-30Aliphatic series or aromatic group, and substituent group be alkyl, aryl, nitro, cyano, amino ,-N (R ') (R "), halogen,
It is hydroxyl, carboxyl, ester group, ether, carbonyl, alkenyl, alkynyl, naphthenic base, alkoxy, aryloxy group, heteroaryloxy, alkoxy carbonyl group, complete
Fluoroalkyl, perfluoro alkoxy, aryloxy group, thio alkoxy ,-S (O)2- N (R ') (R ") ,-C (=O)-N (R ') (R "), (R ')
(R ") alkyl, (R ') (R ") positive alkoxy, (R ') (R ") alkyl aryloxy alkyl ,-S (O) s- aryl ,-S (O) s- heteroaryl
At least one of base, silicyl；Wherein, the s is the integer of 0-2, and the R ' and R " is identical or not identical, and the R '
And R " is alkyl, naphthenic base or aryl.
3. quantum dot ink according to claim 2, it is characterised in that: the alkyl substituent is C1-25Alkyl；
The aryl substituent be phenyl, xenyl, triphenyl base, benzo base, naphthalene, anthryl, that non-alkenyl, phenanthryl, fluorenyl,
At least one of pyrenyl, Qu Ji, base, azulenyl；
The heteroaryl substituent is dibenzothiophene, dibenzofuran group, furyl, thienyl, benzofuranyl, benzo
Thienyl, carbazyl, pyrazolyl, imidazole radicals, triazol radical, isoxazolyl, thiazolyl, oxadiazoles base, di azoly, dioxazole
Base, thiadiazolyl group, pyridyl group, pyridazinyl, pyrimidine radicals, pyrazinyl, triazine radical, oxazines base, thiazinyl, oxadiazines base, indyl,
Benzimidazolyl, indazolyl, indolizine base, benzoxazolyl, isoxazolyl, benzothiazolyl, quinolyl, isoquinolyl, neighbour
Phenodiazine (miscellaneous) naphthalene, quinazolyl, quinoxalinyl, naphthalene, phthalidyl, pteridyl, oxa- anthryl, acridinyl, phenazinyl, phenthazine
Base, phenoxazine base, dibenzo selenophen base, benzo selenophen base, benzofuran and pyridyl group, indole carbazole base, pyridyl group indyl,
Pyrroles's bipyridyl, furans bipyridyl, benzothiophene and pyridyl group, thiophene bipyridyl, benzo selenophen and pyridyl group, selenophen
At least one of bipyridyl.
4. quantum dot ink according to claim 1, it is characterised in that: the sulfoxide type organic solvent be dimethyl sulfoxide,
Ethyl-sulfoxide, diisopropyl sulfoxide, methyl phenyl sulfoxide, allyl phenyl sulfoxide, the thio methyl sulfone of methyl, tetramethylene are sub-
At least one of sulfone, tiacyclopentane 1- oxide, oxydemeton_methyl.
5. quantum dot ink according to claim 1 to 4, it is characterised in that: be with the quantum dot total weight of printing ink
100% meter, the content of the quanta point material are 0.01%-20.0%；The content of the sulfoxide type organic solvent is 0.01%-
99.9%, the content of other class organic solvents is 0-99.8%.
6. quantum dot ink according to claim 5, it is characterised in that: the quantum dot ink is viscous at 25-35 DEG C
Degree is 0.5-50.0mPa.s.
7. -4,6 any quantum dot ink according to claim 1, it is characterised in that: the quanta point material is element week
Phase Table IV race, II-VI group, II-V race, iii-v, III-VI race, group IV-VI, I-III-VI race, II-IV-VI race, II-IV-
Mixture V race binary the above semiconducting compound or be made of these compounds；Or
The quanta point material be selected from CdSe, CdS, CdTe, ZnO, ZnSe, ZnS, ZnTe, HgS, HgSe, HgTe, CdZnSe and
Any combination of them；Or
The quanta point material be selected from InAs, InP, InN, GaN, InSb, InAsP, InGaAs, GaAs, GaP, GaSb, AlP,
AlN, AlAs, AlSb, CdSeTe, ZnCdSe and any combination of them；Or
The quanta point material is perovskite nanometer particle material, metal nano particle material, metal oxide nanoparticles material
Material or their mixture.
8. -4,6 any quantum dot ink according to claim 1, it is characterised in that: the average spy of the quanta point material
Levy 1~20nm of size.
9. -4,6 any quantum dot ink according to claim 1, it is characterised in that: tie on the surface of the quanta point material
Conjunction has ligand, and the ligand is sour ligand, mercaptan ligand, amine ligand, Phosphine ligands, phosphine oxide ligand, phosphatide, soft phosphatide, polyethylene
One of yl pyridines etc. are a variety of.
10. quantum dot ink according to claim 9, it is characterised in that: the acid ligand is ten acid, undecenoic acid, ten
One of tetracid, oleic acid and stearic acid are a variety of；The mercaptan ligand is eight alkyl hydrosulfides, lauryl mercaptan and octadecane
One of base mercaptan is a variety of；The amine ligand is one of oleyl amine, octadecylamine and eight amine or a variety of；The Phosphine ligands are
Tri octyl phosphine；The phosphine oxide ligand is trioctylphosphine oxide (TOPO).
11. a kind of preparation method of light emitting diode with quantum dots, which is characterized in that the step including preparing quantum dot light emitting layer as follows
It is rapid:
Quantum dot ink is printed into quantum dot ink layer by the way of inkjet printing；
The quantum dot ink layer is dried, quantum dot light emitting layer is formed；
Wherein, the quantum dot ink is any quantum dot ink of claim 1-10.
12. preparation method according to claim 11, it is characterised in that: the inkjet printing is that piezoelectricity or thermal inkjet are beaten
Print；And/or
The drying process is dried using at least one of heating, cooling and/or reduced vacuum；Wherein, described to add
Heat treatment is that PULSE HEATING or continuous heating are handled, and the temperature of the heating is 60-180 DEG C；The temperature of the cooling processing
It is 0-20 DEG C；The vacuum degree that the reduced vacuum is dried is [1 × 10-6Torr- normal pressure)；And/or
The quantum dot light emitting layer with a thickness of 10-100nm.
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