CN105694590B - Quantum dot ink, luminescent film and electroluminescent device - Google Patents
Quantum dot ink, luminescent film and electroluminescent device Download PDFInfo
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- CN105694590B CN105694590B CN201610033845.XA CN201610033845A CN105694590B CN 105694590 B CN105694590 B CN 105694590B CN 201610033845 A CN201610033845 A CN 201610033845A CN 105694590 B CN105694590 B CN 105694590B
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- quantum dot
- polymer material
- dot ink
- ink
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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
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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
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- 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
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- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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Abstract
The present invention provides a kind of quantum dot ink, luminescent film and electroluminescent devices.The quantum dot ink includes polymer material, quantum dot and solvent, and the mass ratio of polymer material and quantum dot is 1:1000~1:10, and viscosity of the polymer material at 25 DEG C is more than or equal to 10000pa.s.There is above-mentioned quantum dot ink less polymer material can have biggish viscosity, and using the polymer material with above-mentioned larger viscosity can also effectively quantum point ink viscosity, so that quantum dot ink be enable to apply in the coating means of large area；Also, due to the content of polymer material in above-mentioned quantum dot ink is less and the content of quantum dot is larger, to enable the luminescent film conductive capability with higher using the preparation of above-mentioned quantum dot ink.
Description
Technical field
The present invention relates to technical field of semiconductors, in particular to a kind of quantum dot ink, luminescent film and electroluminescent
Device.
Background technique
Relative to traditional fluorescent material, quantum dot has bigger application advantage in luminescent device, it can not only be compared with
Good regulation launch wavelength, and have relatively high luminous efficiency.In the preparation of quanta point electroluminescent device, need to measure
Son point ink, which is uniformly dispersed, is made into nanoscale film, has quantum dot is directly dispersed directly into suitable solvent in the prior art
In, and relatively thin luminescent film is prepared using the method for spin coating, to be fabricated to the technical solution of luminescent device.But spin coating is logical
The method for crossing rotation ink to disperse is not appropriate for the even spread of large area, and limitation is larger in practical applications, Er Qiezhi
Connect be distributed to it is also unfavorable to the stability of quantum dot in solvent.
Quanta point electroluminescent device generally comprises cathode, electron injecting layer, electron transfer layer, luminescent layer, hole transport
Layer, hole injection layer, anode.With the maturation of solution preparation, inkjet printing, slot coated, spraying, intaglio printing and silk screen
The technologies such as printing are to make the important method of quanta point electroluminescent device.The above method has the range of viscosities of quantum dot ink
Different requirements.Number of polymers is typically used for as matrix in quantum dot light photoluminescence film preparation to protect quantum dot
Stability and film forming, and above-mentioned luminescent film is nonconducting, however the luminescent film of luminescent device will meet electric conductivity demand.
Therefore, it is urgent to provide a kind of inks can meet industrial production demand and device photism simultaneously in the prior art
It can demand.
Summary of the invention
The main purpose of the present invention is to provide a kind of quantum dot ink, luminescent film and electroluminescent devices, to provide one
Kind has the quantum dot ink of larger viscosity.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of quantum dot ink includes polymer
Material, quantum dot and solvent, and the mass ratio of polymer material and quantum dot is 1:1000~1:10, polymer material is at 25 DEG C
Under viscosity be more than or equal to 10000pa.s.
Further, the mass ratio of polymer material and quantum dot is 1:1000~1:100, and polymer material is at 25 DEG C
Under viscosity be more than or equal to 108pa.s。
Further, the absolute value of polymer material highest occupied molecular orbital(HOMO) HOMO energy level is more than or equal to 7eV, and polymerize
The band gap of object material is more than or equal to 2.8eV.
Further, the weight average molecular weight of selected polymer material is more than or equal to 100,000, preferably greater than or equal to 2,000,000.
Further, quantum dot is that red quantum dot, green quantum dot and blue quantum dot are any one or more of.
Further, quantum dot ink further includes additive, and additive be adhesive, surfactant, defoaming agent and
Moisturizer is any one or more of.
Further, the viscosity of quantum dot ink is 1~50mPa.s.
Further, the viscosity of quantum dot ink is 8~12mPa.s.
According to another aspect of the present invention, a kind of luminescent film is provided, comprising: supporting part；Luminescent layer is set to carrying
In portion, and luminescent layer after above-mentioned quantum dot ink dried by forming.
Further, the thickness of luminescent layer is less than or equal to 150nm.
Further, luminescent layer is using inkjet printing, slot coated, spraying, intaglio printing or silk-screen printing by quantum
The luminescent layer that point ink is set to supporting part and will be formed after quantum dot ink dried.
According to a further aspect of the invention, a kind of electroluminescent device, including luminescent film are provided, which is upper
The luminescent film stated.
It applies the technical scheme of the present invention, which includes polymer material, quantum dot and solvent, due to above-mentioned
The mass ratio of polymer material and quantum dot is 1:1000~1:10, and viscosity of the polymer material at 25 DEG C is more than or equal to
10000pa.s to make above-mentioned quantum dot ink that there is less polymer material can have biggish viscosity, and is utilized
Polymer material with above-mentioned larger viscosity can also effectively quantum point ink viscosity, to make quantum dot ink
It can apply in the coating means of large area；Also, due to the content of polymer material in above-mentioned quantum dot ink it is less and
The content of quantum dot is larger, to enable the luminescent film conductive capability with higher using the preparation of above-mentioned quantum dot ink.
Other than objects, features and advantages described above, there are also other objects, features and advantages by the present invention.
Below with reference to figure, the present invention is described in further detail.
Detailed description of the invention
The Figure of description for constituting a part of the invention is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 shows the structural schematic diagram of luminescent film provided by embodiment of the present invention.
Specific embodiment
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the present invention can phase
Mutually combination.The present invention will be described in detail below with reference to the accompanying drawings and embodiments.
In order to enable those skilled in the art to better understand the solution of the present invention, below in conjunction in the embodiment of the present invention
Attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is only
The embodiment of a part of the invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill people
The model that the present invention protects all should belong in member's every other embodiment obtained without making creative work
It encloses.
It should be noted that description and claims of this specification and term " first " in above-mentioned attached drawing, "
Two " etc. be to be used to distinguish similar objects, without being used to describe a particular order or precedence order.It should be understood that using in this way
Data be interchangeable under appropriate circumstances, so as to the embodiment of the present invention described herein.In addition, term " includes " and " tool
Have " and their any deformation, it is intended that cover it is non-exclusive include, for example, containing a series of steps or units
Process, method, system, product or equipment those of are not necessarily limited to be clearly listed step or unit, but may include without clear
Other step or units listing to Chu or intrinsic for these process, methods, product or equipment.
It can be seen from background technology that, in the prior art it is urgent to provide a kind of ink can meet simultaneously industrial production demand and
Device luminescent properties demand.The present inventor studies regarding to the issue above, provides a kind of quantum dot ink, including
Polymer material, quantum dot and solvent, and the mass ratio of polymer material and quantum dot is 1:1000~1:10, polymer material
Viscosity at 25 DEG C is more than or equal to 10000pa.s.
In above-mentioned quantum dot ink of the invention, since the mass ratio of above-mentioned polymer material and quantum dot is 1:1000
~1:10, viscosity of the polymer material at 25 DEG C are more than or equal to 10000pa.s, so that it is less to have above-mentioned quantum dot ink
Polymer material can have biggish viscosity, and using the polymer material with above-mentioned larger viscosity and pass through adjusting
The dosage of solvent, additionally it is possible to which the effectively viscosity of quantum point ink enables quantum dot ink to apply to the painting of large area
In cloth means, such as inkjet printing, slot coated and intaglio printing etc.；Also, due to polymer material in above-mentioned quantum dot ink
Content is less and the content of quantum dot is larger, to make the luminescent film prepared using above-mentioned quantum dot ink is with higher to lead
Electric energy power.
It in quantum dot ink provided by the invention, is adjusted by the content to solvent, makes the viscous of quantum dot ink
Degree range reaches between 1~50mPa.s, thus suitable for the coating means of the large area such as slot coated and intaglio printing；It is excellent
Selection of land can make the viscosity of quantum dot ink reach 8~12mPa.s by adjusting the content of solvent, by the viscous of quantum dot ink
Degree is limited in above-mentioned preferred parameter area, and quantum dot ink when inkjet printing can be made both not flow out from inkjet mouth,
Inkjet mouth will not be blocked, to better adapt to inkjet printing.
In quantum dot ink provided by the invention, it is preferable that the preferred mass of polymer material and quantum dot ratio is 1:
1000~1:100, and viscosity of the polymer material at 25 DEG C is more than or equal to 108pa.s.By polymer material and quantum dot
Mass ratio is limited in above-mentioned preferred parameter area the content that can further decrease polymer material in quantum dot ink, and
And the viscosity by further increasing polymer material, the viscosity of quantum dot ink is more effectively had adjusted, further the amount of making
Son point ink can apply in the coating means of the large area such as inkjet printing；Also, due to further improving above-mentioned quantum
The content of quantum dot in point ink, to enable the luminescent film prepared using above-mentioned quantum dot ink that there is higher conductive energy
Power.
In quantum dot ink provided by the invention, it is preferable that the electronics highest occupied molecular orbital(HOMO) of polymer material
The absolute value of HOMO (Highest Occupied Molecular Orbital) energy level is more than or equal to 7eV, band gap (Band
Gap) it is more than or equal to 2.8eV.Since the absolute value of the HOMO energy level of red quantum dot, green quantum dot and blue quantum dot is general
Less than 7eV, to select the polymer material that HOMO energy level absolute value is greater than 7eV and band gap is less than or equal to 2.8eV, can guarantee
Electrons and holes transmission when at first by quantum dot capture and pass through quantum dot it is compound or transmit, without by quantum dot ink
Polymer capture, and then further increase using above-mentioned quantum dot ink preparation luminescent film conductive capability；Also,
Due to blue quantum dot band gap about 2.8eV, to select polymer material of the energy level greater than 2.8eV that can be effectively prevented from charge
It is captured by polymer.
In quantum dot ink provided by the invention, quantum dot can be red quantum dot, green quantum dot and amount of blue
Son point is any one or more of, when quantum dot includes red quantum dot, green quantum dot and blue quantum dot, can pass through
RGB three primary colors realize high color gamut value.Preferably, quantum dot includes quantum dot main body and is set to matching in quantum dot main body
Body, ligand are sulfydryl class ligand, phosphate radical class ligand, amido ligand or carboxylate radical class ligand；The molecular weight of quantum dot is at this time
Molecular weight including quantum dot main body and ligand.The presence that above-mentioned ligand not only allows quantum dot more stable, but also make quantum
Point and polymer material can be preferably dispersed in same solvent, so as to improve the compatible of quantum dot and polymer material
Property, the service life of quantum dot is improved, the quantum efficiency of the electroluminescent device by the production of above-mentioned quantum dot ink is also improved.
In order to make the viscosity of polymer material be greater than 10000pa.s, polymer material is preferably polyacrylic resin, poly- carbon
Acid esters, polystyrene, polyethylene, polypropylene, polyisobutene, polyketone, polyether-ether-ketone, polyester, polyamide, polyimides, poly- third
Acrylamide, polyolefin, polyacetylene, polyisoprene, polybutadiene, polyvinyladine floride, polyvinyl chloride, ethane-acetic acid ethyenyl are total
Polymers, polyethylene terephthalate, polyurethane, cellulose, ethyl cellulose, nitrocellulose, trimethylolpropane tris third
Olefin(e) acid ester-lauryl methacrylate mixture, the poly- isobutyl of trimethylolpropane trimethacrylate-lauryl methacrylate-
Alkene mixture, trimethylol-propane trimethacrylate-lauryl methacrylate-PIPS mixture, isobornyl
In the group of sour-two propyl alcohol diacrylate mixture of rouge, acrylic acid-polystyrene-toluene mixture and polycarbonate composition
It is one or more.
Above-mentioned preferred polymer material can not only have preferable chemical compatibility with the organic group of quantum dot surface,
And the quantum efficiency of the electroluminescent device using the production of above-mentioned quantum dot ink will not be reduced, additionally it is possible to further regulated quantity
The viscosity and surface tension of son point ink, can higher apply in the coating means of large area, narrow such as inkjet printing
Seam coating and intaglio printing.It is further preferable that the weight average molecular weight of above-mentioned preferred polymer material is greater than 100,000, preferably greater than
Equal to 2,000,000.The weight average molecular weight of polymer material is limited in above-mentioned preferred range, can effectively guarantee polymer
Material has bigger viscosity.
In quantum dot ink provided by the invention, the content of quantum dot, solvent and polymer material can be according to existing
Technology is set, it is preferable that the mass percent of quantum dot is 1-30% in quantum dot ink, and the mass percent of solvent is
65-99%, the mass percent of polymer material are 0.001-5%.Above-mentioned solvent can be selected from chloroform, chlorobenzene, dimethylbenzene, first
Benzene, benzene, n-hexane, hexamethylene, normal heptane, octane, decane, hendecane, dodecane, n-tetradecane, hexadecane and n-octadecane
It is any one or more of, but it is not limited to mentioned kind, those skilled in the art can be according to the steaming in practical preparation process
The technological factors such as fermentation product, vacuum degree and temperature select suitable solvent type.
Above-mentioned quantum dot ink can also include additive, and above-mentioned additive includes adhesive, surfactant, defoaming agent
Any one or more of with moisturizer, the mass percent of polymer material is preferably 0.03-1% at this time.Above-mentioned add is added
The quantum efficiency for the electroluminescent device for adding agent that can further increase by the production of above-mentioned quantum dot ink；Also, due to being added
Additive to reduce the polymer material ratio as non-conducting material, and then is further improved by quantum dot ink
The electric conductivity of the luminescent film of water preparation.The content in quantum dot ink of above-mentioned additive can be carried out according to the prior art
Setting, if mass percent is 0.01-4%.Wherein, adhesive is selected from celluosic resin, maleic anhydride resin, acrylic compounds tree
One or more of rouge, polyurethane based resin, phenolic resin, epoxy resin, polyvinyl acetate, polyvinyl acetate are with any
Ratio mixing etc.；Surfactant stearic acid, oleic acid, lauric acid, dodecyl sodium sulfate, triethanolamine, sldium lauryl sulfate,
Neopelex, quaternary ammonium compound, hydroxypropyl cellulose, mosanom, pectic acid sodium, hydroxymethyl cellulose, metering system
Sour graft starch, shell polyacids, vinylpyridine copolymer, polysiloxanes, polyvinylether, polyvinyl alcohol, polyacrylamide, polyethylene
The block copolymerization of imines, maleic acid and polyoxyethylene, polyethyleneimine, polyoxypropylene, polybutylene, polystyrene
Object, the U.S. is aerochemical 465, Bayer N-75, one of DOW CORNING DC-29, EFKA-3580, BYK-345, BYK-020 or
The combination of several arbitrary proportions；Defoaming agent is selected from polysiloxanes, polyethers, silicone emulsion, higher alcohols, tributyl phosphate, high-carbon
One or more of polyol fatty acid ester complexes, polyoxypropylene or polyether-modified organosilicon are mixed with arbitrary proportion；Moisturizing
Agent is selected from ethylene glycol, polyethylene glycol, xylitol, propylene glycol diethylene glycol, glycerol, triethylene glycol butyl ether, NMP, DMSO, 1,5- penta
One or more of glycol, trimethylolpropane, 1,6-HD, 2- methyl -2,4-PD, PVP are with any comparative group
It closes.
According to another aspect of the present invention, a kind of luminescent film is provided, as shown in Figure 1, including supporting part 10 and setting
Luminescent layer on supporting part 10, and luminescent layer after above-mentioned quantum dot ink dried by forming；Above-mentioned quantum dot ink includes
The mass ratio of polymer material 210, quantum dot 220 and solvent, polymer material 210 and quantum dot 220 is 1:1000~1:10,
Viscosity of the polymer material 210 at 25 DEG C is more than or equal to 10000pa.s.Wherein, above-mentioned luminescent layer is by by quantum dot ink
Solvent therein is removed in drying, to form above-mentioned cured luminescent layer.
What is leaned on due to electroluminescent is that electrons and holes are transferred to luminescent film, and the two is compound to make quantum dot light emitting, works as quantum
After introducing too many polymer material in point, electronics may be compound in the polymeric material with hole, is not converted into light, the amount of causing
Sub- efficiency can reduce；And in above-mentioned luminescent film of the invention, since polymer material 210 and the mass ratio of quantum dot 220 are
1:1000~1:10, viscosity of the polymer material 210 at 25 DEG C is more than or equal to 10000pa.s, to make to polymerize in luminescent film
The content of object material 210 is less and the content of quantum dot 220 is more, and then improves by the electroluminescent cell of the film production that shines
The quantum efficiency of part.
In luminescent film provided by the invention, luminescent layer can use inkjet printing, slot coated, spraying, intaglio printing
Or the quantum dot ink is set to the supporting part 10 and by shape after the quantum dot ink dried by the methods of silk-screen printing
At.Quantum dot ink is placed in hair first with the methods of inkjet printing, slot coated, spraying, intaglio printing or silk-screen printing
The supporting part 10 of light film；Then the quantum dot ink for being located at supporting part 10 is dried, forms luminescent film after so that solvent is volatilized.
Supporting part 10 can be substrate perhaps electrode perhaps other each functional layers in electroluminescent device or other suitable
Play the component of carrying.Quantum dot 220 in luminescent layer is interconnected to form conductive channel, and the surface of luminescent film is by portion
Quantum dot 220 and partial polymer material 210 is divided to constitute or be made of part quantum dot 220, as shown in Figure 1.By by quantum
Point 220 is interconnected to form conductive channel, keeps luminescent film conductive.
In luminescent film provided by the invention, it is preferable that the thickness of luminescent layer is less than or equal to 150nm.By polymer material
210 are limited to 1:1000~1:10 with the mass ratio of quantum dot 220, and the thickness limit of luminescent layer is less than or equal to 150nm, energy
Enough make luminescent film electric conductivity with higher.It is further preferable that the thickness of above-mentioned luminescent layer is less than or equal to 50nm.In polymer
In the case that the mass ratio of material 210 and quantum dot 220 is constant, the thickness of above-mentioned luminescent film is reduced to above-mentioned preferred range
It can make luminescent film that there is higher electric conductivity.
In order to improve the quantum efficiency of the electroluminescent device by above-mentioned luminous film production, by by polymer material 210
It is limited within the above range with the mass ratio of quantum dot 220, enables the content with higher of quantum dot 220 in luminescent film, i.e.,
Polymer material 210 has lower content, however the content of polymer material 210 compared to quantum dot 220 in luminescent film
Lower to be possible to will lead to luminescent film not easily molded during the preparation process, and adhesiveness is lower.Therefore, selection is at 25 DEG C or less
Viscosity is greater than the polymer material 210 of 10000pa.s, and luminescent film can be made in polymer material 210 lower with content
Also molding can be effectivelyed prepared；Also, the polymer material 210 with above-mentioned range of viscosities can pass through quantum point
The viscosity and surface tension of ink, can apply in the coating means of large area, such as inkjet printing, slot coated and recessed
The means such as version printing.
According to another aspect of the present invention, a kind of preparation method of above-mentioned luminescent film is additionally provided, comprising: prepare above-mentioned amount
Son point ink, quantum dot ink is arranged on a supporting part 10 and is dried.Above-mentioned quantum dot ink includes polymerization
Object material, quantum dot and solvent, wherein the mass ratio of polymer material and quantum dot is 1:1000~1:10, and polymeric material
Expect that the viscosity at 25 DEG C is more than or equal to 10000pa.s.Preferably, the mass percent of quantum dot is 0.5- in quantum dot ink
30%, the mass percent of solvent is 65-99%, and the mass percent of polymer material is 0.01-5%.
What is leaned on due to electroluminescent is that electrons and holes are transferred to luminescent film, and the two is compound to make quantum dot light emitting, and equivalent
After introducing too many polymer material in son point, electronics may be compound in the polymeric material with hole, is not converted into light, causes
Quantum efficiency can reduce.And in the above preparation method, since the mass ratio of polymer material and quantum dot is 1:10~1:
1000, viscosity of the polymer material at 25 DEG C is more than or equal to 10000pa.s, to keep above-mentioned quantum dot ink with higher
Viscosity, and using the polymer material with above-mentioned larger viscosity can also effectively quantum point ink viscosity, the amount of making
Son point ink can apply in the coating means of large area, such as inkjet printing, slot coated and intaglio printing etc..
The exemplary implementation of the preparation method of the luminescent film provided according to the present invention is provided below in conjunction with Fig. 1
Mode.However, these illustrative embodiments can be implemented by many different forms, and it is not construed as only limiting
In embodiments set forth herein.It should be understood that thesing embodiments are provided so that disclosure herein is thorough
Bottom and complete, and the design of these illustrative embodiments is fully conveyed to those of ordinary skill in the art.
Firstly, will include that polymer material 210, quantum dot 220 and the raw material of solvent are mixed to form quantum dot ink, quantum
The mass ratio of polymer material and quantum dot is 1:1000~1:10 in point ink, and viscosity of the polymer material at 25 DEG C is big
In equal to 10000pa.s.Preferably, the mass percent of quantum dot 220 is 1-30%, and the mass percent of solvent is 65-
99%, the mass percent of polymer material 210 is 0.001-5%.Above-mentioned solvent can be selected from chloroform, chlorobenzene, dimethylbenzene, first
Benzene, benzene, n-hexane, hexamethylene, normal heptane, octane, decane, hendecane, dodecane, n-tetradecane, hexadecane and n-octadecane
It is any one or more of, but it is not limited to mentioned kind, those skilled in the art can be according to the steaming in practical preparation process
The technological factors such as fermentation product, vacuum degree and temperature select suitable solvent type.
Above-mentioned quantum dot ink can also include the additive that mass percent is 0.01-4%, which may include
Adhesive, surfactant, defoaming agent and moisturizer are any one or more of, at this time the quality percentage of polymer material 210
Than being preferably 0.03-3%.The mass percent of polymer material 210 is limited to can be further in above-mentioned preferred range
Improve the quantum efficiency of the electroluminescent device made by above-mentioned quantum dot ink；Also, due to reducing as non-conductive material
210 ratio of polymer material of material, to further improve the electric conductivity of luminescent film.
It completes to include that the raw material of polymer material 210, quantum dot 220 and solvent is mixed to form the step of quantum dot ink
After rapid, luminescent film is formed using quantum dot ink, light emitting layer thickness is preferably smaller than equal to 150nm.In a kind of preferred implementation
In mode, quantum dot ink is placed in luminescent film first with inkjet printing, slot coated, spraying, intaglio printing or silk-screen printing
Supporting part 10；Then the quantum dot ink for being located at supporting part 10 is dried, forms luminescent film after so that solvent is volatilized.
It is further preferable that in above-mentioned quantum dot ink the mass ratio of polymer material 210 and quantum dot 220 be 1:1000~
1:100, and viscosity of the polymer material 210 at 25 DEG C is more than or equal to 108pa.s.The above parameter range energy further limited
Enough make luminescent film that can also be effectivelyed prepared molding in polymer material 210 lower with content；Also, have above-mentioned
The polymer material 210 of range of viscosities can more have by the viscosity and surface tension of quantum point ink
Effect ground applies in the coating means of large area, such as inkjet printing, slot coated and intaglio printing etc..
According to another aspect of the present invention, a kind of electroluminescent device, including above-mentioned luminescent film are additionally provided.Due to electroluminescent
Shining, lean on is that electrons and holes are transferred to luminescent film, and the two is compound to make quantum dot light emitting, and too many when introducing in quantum dot
After polymer material, electronics may be compound in the polymeric material with hole, is not converted into light, causes quantum efficiency that can reduce.
And in above-mentioned electroluminescent device, since the mass ratio of polymer material and quantum dot is 1:1000~1:10 in luminescent film,
And viscosity of the polymer material at 25 DEG C be more than or equal to 10000pa.s, thus make the content of polymer material in luminescent film compared with
Less and the content of quantum dot is more, and then improves the quantum efficiency of electroluminescent device.
Quantum dot ink provided by the invention and luminescent film are further illustrated below in conjunction with embodiment and comparative example.
Embodiment 1
Quantum dot ink provided in this embodiment includes polymer material, quantum dot and solvent, wherein polymer material with
The mass ratio of quantum dot is 1:10, and quantum dot is blue quantum dot, and solvent is chloroform, and polymer material is polyurethane, viscosity
For 20000Pa.s, weight average molecular weight 25000.
Embodiment 2
Quantum dot ink provided in this embodiment includes polymer material, quantum dot and solvent, wherein polymer material with
The mass ratio of quantum dot is 1:10, and quantum dot is blue quantum dot, and solvent is chloroform, and polymer material is polyisobutene, is glued
Degree is 1 × 108Pa.s, weight average molecular weight 400000.
Embodiment 3
Quantum dot ink provided in this embodiment includes polymer material, quantum dot and solvent, wherein polymer material with
The mass ratio of quantum dot is 1:100, and quantum dot is blue quantum dot, and solvent is n-hexane, and polymer material is polyisobutene,
Viscosity is 1 × 108Pa.s, weight average molecular weight 400000.
Embodiment 4
Quantum dot ink provided in this embodiment includes polymer material, quantum dot and solvent, wherein polymer material with
The mass ratio of quantum dot is 1:1000, and quantum dot is blue quantum dot, and solvent is n-hexane, and polymer material is polyurethane third
Olefin(e) acid ester, viscosity are 1 × 109Pa.s, weight average molecular weight are 2,000,000.
Embodiment 5
Quantum dot ink provided in this embodiment includes polymer material, quantum dot and solvent, wherein polymer material with
The mass ratio of quantum dot is 1:1000, and quantum dot is blue quantum dot, and solvent is toluene, and polymer material is polyurethane propylene
Acid esters, viscosity are 3 × 106Pa.s, weight average molecular weight are 100,000.
Embodiment 6
Quantum dot ink provided in this embodiment includes polymer material, quantum dot and solvent, wherein polymer material with
The mass ratio of quantum dot is 1:10, and quantum dot is blue quantum dot, and solvent is toluene, and polymer material is polyurethane acroleic acid
Ester, viscosity are 3 × 106Pa.s, weight average molecular weight are 100,000.
Embodiment 7
Quantum dot ink provided in this embodiment includes polymer material, quantum dot and solvent, wherein polymer material with
The mass ratio of quantum dot is 1:10, and quantum dot is blue quantum dot, and solvent is toluene, and polymer material is polyurethane acroleic acid
Ester, viscosity are 5 × 106Pa.s, weight average molecular weight are 130,000.
Embodiment 8
Present embodiments provide a kind of electroluminescent device, production method the following steps are included:
PEDOT:PSS material (cas:155090-83-8) is formed on ito anode layer, then through vacuum low-pressure heat
The dry hole injection layer formed with a thickness of 35nm of plate, then forms PVK material (cas:25067-59- on hole injection layer
8) and using the hole transmission layer formed with a thickness of 5nm dry after the hot pressing of vacuum low-pressure hot plate, in the hole biography as supporting part
The quantum dot ink in printing of inkjet printer embodiment 1 is utilized on defeated layer and utilizes shape dry after the hot pressing of vacuum low-pressure heating platen
At the luminescent layer with a thickness of 150nm, the ethanol solution of ZnO is formed on the light-emitting layer and is done using after the hot pressing of vacuum low-pressure heating platen
Dry formation is with a thickness of the electron transfer layer of 100nm, and finally vapor deposition silver forms the electrode layer with a thickness of 100nm, and encapsulation forms electroluminescent
Luminescent device.
Embodiment 9
Electroluminescent device provided in this embodiment uses production method same as Example 6, and difference is, in sky
In the transport layer of cave print embodiment 2 in quantum dot ink, and luminescent film with a thickness of 100nm.
Embodiment 10
Electroluminescent device provided in this embodiment uses production method same as Example 6, and difference is, in sky
In the transport layer of cave print embodiment 3 in quantum dot ink, and luminescent film with a thickness of 100nm.
Embodiment 11
Electroluminescent device provided in this embodiment uses production method same as Example 6, and difference is, in sky
In the transport layer of cave print embodiment 4 in quantum dot ink, and luminescent film with a thickness of 30nm.
Embodiment 12
Electroluminescent device provided in this embodiment uses production method same as Example 6, and difference is, in sky
In the transport layer of cave print embodiment 5 in quantum dot ink, and luminescent film with a thickness of 30nm.
Embodiment 13
Electroluminescent device provided in this embodiment uses production method same as Example 6, and difference is, in sky
Using the quantum dot ink in slit coater coating Examples 6 in the transport layer of cave, and luminescent film with a thickness of 60nm.
Embodiment 14
Electroluminescent device provided in this embodiment uses production method same as Example 6, and difference is, in sky
Using the quantum dot ink in slit coater coating Examples 7 in the transport layer of cave, and luminescent film with a thickness of 60nm.
Comparative example 1
This comparative example provide quantum dot ink include polymer material, quantum dot and solvent, wherein polymer material with
The mass ratio of quantum dot is 1:2, and quantum dot is blue quantum dot, and polymer material is polyacrylate, and viscosity is
500Pa.s, weight average molecular weight 200.
Comparative example 2
The electroluminescent device that this comparative example provides uses production method same as Example 6, and difference is, in sky
The quantum dot ink in comparative example 1 is printed in the transport layer of cave.
Comparative example 3
This comparative example provide quantum dot ink include conductive organic matter, quantum dot and solvent, wherein polymer material with
The mass ratio of quantum dot is 1:10, and quantum dot is blue quantum dot, and solvent is chloroform, and conductive organic matter is a-NPD (N '-two
Phenyl-N, N '-two (1- naphthalene) -1,1 '-xenyl -4,4 "-diamines), molecular weight 588.
Comparative example 4
The electroluminescent device that this comparative example provides uses production method same as Example 6, and difference is, in sky
The quantum dot ink in comparative example 3 is printed in the transport layer of cave.
It is adjusted by the content to solvent in embodiment 1 to 7, comparative example 1 and comparative example 3, is printed with adjustment
The viscosity of quantum dot ink, and the viscosity of the above-mentioned quantum dot ink printed is tested, using Brookfield model
For the viscosimeter of DV-2T, test temperature is maintained at 25 DEG C, and sample size 1ml, test result is as follows shown in table:
| Embodiment | 25 DEG C of viscosity/mPa.s |
| Embodiment 1 | 1.2 |
| Embodiment 2 | 13.5 |
| Embodiment 3 | 11.8 |
| Embodiment 4 | 13.0 |
| Embodiment 5 | 8.1 |
| Embodiment 6 | 49.6 |
| Embodiment 7 | 67.0 |
| Comparative example 1 | 1.3 |
| Comparative example 3 | 0.7 |
The viscosity that can be seen that quantum dot ink in embodiment 1 to 7 from above-mentioned test result is above comparative example 1 and right
The viscosity of quantum dot ink in ratio 3, it is seen then that the quantum dot ink in the application has bigger viscosity, to be more suitable for transporting
For in the coating means of large area, and the viscosity of embodiment 3 and embodiment 5 can satisfy 8~12mPa.s, so as to very
Well suitable for the coating means of inkjet printing.
The quantum efficiency and bright voltage of the electroluminescent device printed to embodiment 8 to 14 and comparative example 2 are surveyed
Examination, wherein bright voltage is that the brightness of device reaches 1cd/m2When operating voltage.Test result is as follows shown in table:
| Embodiment | External quantum efficiency@2mA/cm2 | Bright voltage/volt |
| Embodiment 8 | 4.69% | 7.3 |
| Embodiment 9 | 5.01% | 7.1 |
| Embodiment 10 | 5.93% | 5 |
| Embodiment 11 | 9.67% | 4.2 |
| Embodiment 12 | 8.58% | 4.5 |
| Embodiment 13 | 5.23% | 7.1 |
| Embodiment 14 | 5.69% | 7.2 |
| Comparative example 2 | 3.89% | 8 |
| Comparative example 4 | 4.12% | 7.6 |
The external quantum efficiency that can be seen that the electroluminescent device made in embodiment 8 and 14 from above-mentioned test result is equal
Greater than the external quantum efficiency of the electroluminescent device made in comparative example 2 and 4, it is seen then that polymer content is got in quantum dot ink
Few, the quantum efficiency using the electroluminescent device of its production is bigger；Also, the electroluminescent cell made in embodiment 8 and 14
The bright voltage of part is respectively less than the bright voltage of the electroluminescent device made in comparative example 2 and 4, it is seen then that in quantum dot ink
Polymer content is fewer, and the bright voltage using the electroluminescent device of its production is lower, further relates to utilize the application quantum
The luminescent film of point ink preparation being capable of conductive capability with higher.
It can be seen from the above description that the above embodiments of the present invention realized the following chievements:
1, there is above-mentioned quantum dot ink of the invention less polymer material can have biggish viscosity, and benefit
With the polymer material with above-mentioned larger viscosity can also effectively quantum point ink viscosity, to keep quantum dot black
Water energy enough applies in the coating means of large area, such as inkjet printing, slot coated and intaglio printing etc.；
2, due to the content of polymer material in above-mentioned quantum dot ink is less and the content of quantum dot is larger, to make benefit
It can not only electric conductivity with higher with luminescent film prepared by above-mentioned quantum dot ink；
3, by adjusting the content of solvent, the viscosity of quantum dot ink is made to reach 8~12mPa.s, inkjet printing can be made
When quantum dot ink will not both be flowed out from inkjet mouth, inkjet mouth will not be blocked, to better adapt to inkjet printing；
It 4, can also quantum efficiency with higher and lower using the electroluminescent device of above-mentioned quantum dot ink preparation
Bright voltage.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (12)
1. a kind of quantum dot ink, which is characterized in that including polymer material, quantum dot and solvent, and the polymer material
Mass ratio with the quantum dot is 1:1000~1:10, and viscosity of the polymer material at 25 DEG C is more than or equal to
The weight average molecular weight of 10000Pas, selected polymer material are more than or equal to 100,000.
2. the mass ratio of quantum dot ink according to claim 1, the polymer material and the quantum dot is 1:
1000~1:100, and viscosity of the polymer material at 25 DEG C is more than or equal to 108Pa·s 。
3. quantum dot ink according to claim 1 or 2, which is characterized in that the polymer material highest occupied molecular
The absolute value of track HOMO energy level is more than or equal to 7eV, and the band gap of the polymer material is more than or equal to 2.8eV.
4. quantum dot ink according to claim 1, which is characterized in that the weight average molecular weight of selected polymer material is greater than
Equal to 2,000,000.
5. quantum dot ink according to claim 1, which is characterized in that the quantum dot is red quantum dot, green amount
Son point and blue quantum dot are any one or more of.
6. quantum dot ink according to claim 1, which is characterized in that the quantum dot ink further includes additive, and
The additive is that adhesive, surfactant, defoaming agent and moisturizer are any one or more of.
7. quantum dot ink according to claim 1 or 2, which is characterized in that the viscosity of the quantum dot ink be 1~
50mPa·s 。
8. quantum dot ink according to claim 7, which is characterized in that the viscosity of the quantum dot ink be 8~
12mPa·s 。
9. a kind of luminescent film characterized by comprising
Supporting part；
Luminescent layer is set on the supporting part, and luminescent layer amount as described in any one of the claims 1 to 8
It is formed after son point ink dried.
10. luminescent film according to claim 9, which is characterized in that the thickness of the luminescent layer is less than or equal to 150nm.
11. luminescent film according to claim 10, which is characterized in that the luminescent layer is to be applied using inkjet printing, slit
The quantum dot ink is set to the supporting part and by the quantum dot ink by cloth, spraying, intaglio printing or silk-screen printing
The luminescent layer formed after drying.
12. a kind of electroluminescent device, including luminescent film, which is characterized in that the luminescent film is any in claim 9 to 11
Luminescent film described in.
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