CN110041758A - The nanocrystalline ink of perovskite, electroluminescent device and preparation method - Google Patents
The nanocrystalline ink of perovskite, electroluminescent device and preparation method Download PDFInfo
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- CN110041758A CN110041758A CN201910323360.8A CN201910323360A CN110041758A CN 110041758 A CN110041758 A CN 110041758A CN 201910323360 A CN201910323360 A CN 201910323360A CN 110041758 A CN110041758 A CN 110041758A
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- 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
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
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- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/36—Inkjet printing inks based on non-aqueous solvents
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- 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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- 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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- 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
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Abstract
The invention discloses the nanocrystalline ink of perovskite, electroluminescent device and preparation methods, belong to typographical display field.The nanocrystalline ink of the perovskite includes: perovskite nanocrystalline material, the dicyandiamide solution for dispersing perovskite nanocrystalline material, and dicyandiamide solution includes: the low boiling point solvent that boiling point is 115 DEG C -175 DEG C；The high boiling solvent that boiling point is 230 DEG C -260 DEG C；The surface tension and viscosity of low boiling point solvent are respectively smaller than the surface tension and viscosity of high boiling solvent.By adjusting the volume ratio of low boiling point solvent and high boiling solvent, the boiling point of dicyandiamide solution is adjusted to expected range, so that the ink is suitable for dispersion perovskite nanocrystalline, and desired volatility can be obtained, ensure ink-jet feasibility, avoid blocking spray head, and also can effectively avoid the appearance of coffee ring phenomenon.By the surface tension and viscosity that adjust dicyandiamide solution to expected range, it is ensured that the spreading ability and the printing after ink-jet of the nanocrystalline ink of perovskite improve printing effect.
Description
Technical field
The present invention relates to nanocrystalline display fields, the in particular to nanocrystalline ink of perovskite, electroluminescent device and preparation
Method.
Background technique
Perovskite it is quantum dot-based in its shine easily tuning, the spectral line of emission is narrow, quantum efficiency is high, colour purity is high, production cost is low
Etc. advantages, be widely used in electroluminescent device and related display field.Currently, perovskite quantum dot ink is mostly carried out ink-jet
Printing is to prepare patterned quantum dot light emitting layer.So it is very necessary for providing a kind of perovskite quantum dot ink.
The perovskite quantum dot ink that the prior art provides includes: the nonpolar solvents such as hexane, octane, and is scattered in this
Perovskite quanta point material in nonpolar solvent.
Inventor discovery in the prior art the prior art has at least the following problems:
The perovskite quantum dot ink that the prior art provides, easily blocks spray head, and be also easy to produce coffee in ink jet printing process
Coffee ring phenomenon.
Summary of the invention
In consideration of it, the present invention provides a kind of nanocrystalline ink of perovskite, electroluminescent device and preparation method.It is specific and
Speech, including technical solution below:
On the one hand, a kind of nanocrystalline ink of perovskite is provided, comprising: perovskite nanocrystalline material, the perovskite are received
The brilliant ink of rice further include: for dispersing the dicyandiamide solution of the perovskite nanocrystalline material, the dicyandiamide solution includes: that boiling point is
115 DEG C -175 DEG C of low boiling point solvent；And
The high boiling solvent that boiling point is 230 DEG C -260 DEG C；
Wherein, the surface tension and viscosity of the low boiling point solvent be respectively smaller than the high boiling solvent surface tension and
Viscosity.
In one possible implementation, the dicyandiamide solution further include: boiling point is that 175 DEG C -230 DEG C of mid-boiling point is molten
Agent, and the surface tension of the medium-boiling solvent between the surface tension of the high boiling solvent and the low boiling point solvent it
Between；
The viscosity of the medium-boiling solvent is between the high boiling solvent and the viscosity of the low boiling point solvent.
In one possible implementation, the perovskite nanocrystalline material is perovskite quanta point material.
In one possible implementation, the mass concentration of the perovskite nanocrystalline material is 5mg/mL-60mg/
mL。
In one possible implementation, the solvent in the dicyandiamide solution is that weak polar solvent and/or nonpolarity are molten
Agent.
In one possible implementation, the solvent in the dicyandiamide solution is selected from alkane, cycloalkane, alkene, fragrance
At least one of hydrocarbon, long chain fatty acids, esters, amine, ethers.
In one possible implementation, the surface tension of the nanocrystalline ink of the perovskite is 25dyn/cm-
40dyn/cm, viscosity 1.0mPaS-10mPaS.
On the other hand, the embodiment of the invention provides a kind of preparation method of the nanocrystalline ink of perovskite, the method packets
It includes: dispersing perovskite nanocrystalline material in dicyandiamide solution, obtain the nanocrystalline ink of the perovskite；
The dicyandiamide solution includes: the low boiling point solvent that boiling point is 115 DEG C -175 DEG C；And
The high boiling solvent that boiling point is 230 DEG C -260 DEG C；
Wherein, the surface tension and viscosity of the low boiling point solvent be respectively smaller than the high boiling solvent surface tension and
Viscosity.
In one possible implementation, the dicyandiamide solution further include: boiling point is that 175 DEG C -230 DEG C of mid-boiling point is molten
Agent, and the surface tension of the medium-boiling solvent between the surface tension of the high boiling solvent and the low boiling point solvent it
Between；
The viscosity of the medium-boiling solvent is between the high boiling solvent and the viscosity of the low boiling point solvent.
In another aspect, the embodiment of the invention provides a kind of electroluminescent device, including nanocrystalline luminescent layer, wherein institute
Nanocrystalline luminescent layer is stated to be prepared by the above-mentioned nanocrystalline ink of perovskite by inkjet printing technology.
The beneficial effect of technical solution provided in an embodiment of the present invention includes at least:
The nanocrystalline ink of perovskite provided in an embodiment of the present invention can be selected two different component solvents of boiling point and constitute solvent
System, and it is defined as above the boiling spread of the two, by adjusting the volume ratio of low boiling point solvent and high boiling solvent, on the one hand may be used
It is nanocrystalline to be not only adapted to dispersion perovskite to expected range to adjust the boiling point of dicyandiamide solution, and can obtain desired
Volatility, it is ensured that the ink-jet feasibility of the nanocrystalline ink of perovskite avoids blocking spray head.In addition, the non-azeotrope based on multi-solvent
Characteristic, the volatilization process of each solvent is simultaneously asynchronous, so that the volatility of dicyandiamide solution is adjustable, can effectively avoid coffee ring phenomenon and goes out
It is existing.On the other hand, by adjusting the volume ratio of low boiling point solvent and high boiling solvent, the surface of dicyandiamide solution can also be adjusted
Power and viscosity are to expected range, it is ensured that the spreading ability and the printing after ink-jet of the nanocrystalline ink of perovskite improve printing
Effect.
Detailed description of the invention
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for
For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings other
Attached drawing.
Fig. 1 is the surface topography map of the nanocrystalline luminescent layer for the nanocrystalline ink preparation of perovskite that embodiment 2 provides；
Fig. 2 is the Current density-voltage-light emission luminance performance diagram for the electroluminescent device that embodiment 3 provides；
Fig. 3 is the current efficiency-light emission luminance-power efficiency characteristic curve graph for the electroluminescent device that embodiment 3 provides；
Fig. 4 is the external quantum efficiency-light emission luminance performance diagram for the electroluminescent device that embodiment 3 provides.
Specific embodiment
To keep technical solution of the present invention and advantage clearer, below in conjunction with attached drawing to embodiment of the present invention make into
One step it is described in detail.
It should be noted that perovskite involved in the embodiment of the present invention is nanocrystalline, when its partial size is in quantum point grain diameter model
In enclosing when (such as 2-20nm), the nanocrystalline perovskite is perovskite quantum dot, at this point, perovskite provided in an embodiment of the present invention
Nanocrystalline ink can be referred to as perovskite quantum dot ink.
On the one hand, the embodiment of the invention provides a kind of nanocrystalline ink of perovskite, the nanocrystalline ink of the perovskite includes:
Perovskite nanocrystalline material, and the dicyandiamide solution for dispersing perovskite nanocrystalline material.Wherein, which includes:
The low boiling point solvent that boiling point is 115 DEG C -175 DEG C；And the high boiling solvent that boiling point is 230 DEG C -260 DEG C；Low boiling point solvent
Surface tension and viscosity are respectively smaller than the surface tension and viscosity of high boiling solvent.
The nanocrystalline ink of perovskite provided in an embodiment of the present invention can be selected two different component solvents of boiling point and constitute solvent
System, and it is defined as above the boiling spread of the two, by adjusting the volume ratio of low boiling point solvent and high boiling solvent, on the one hand may be used
It is nanocrystalline to be not only adapted to dispersion perovskite to expected range to adjust the boiling point of dicyandiamide solution, and can obtain desired
Volatility, it is ensured that the ink-jet feasibility of the nanocrystalline ink of perovskite avoids blocking spray head.In addition, the non-azeotrope based on multi-solvent
Characteristic, the volatilization process of each solvent is simultaneously asynchronous, so that the volatility of dicyandiamide solution is adjustable, can effectively avoid coffee ring phenomenon and goes out
It is existing.On the other hand, by adjusting the volume ratio of low boiling point solvent and high boiling solvent, the surface of dicyandiamide solution can also be adjusted
Power and viscosity are to expected range, it is ensured that the spreading ability and the printing after ink-jet of the nanocrystalline ink of perovskite improve printing
Effect.
Further, dicyandiamide solution provided in an embodiment of the present invention further include: boiling point is that 175 DEG C -230 DEG C of mid-boiling point is molten
Agent, and, the surface tension of the medium-boiling solvent is between high boiling solvent and the surface tension of low boiling point solvent, the mid-boiling point
The viscosity of solvent is between high boiling solvent and the viscosity of low boiling point solvent.
By the addition of the moderate medium-boiling solvent of boiling point, surface tension and viscosity, can get by three component solvent structures
At dicyandiamide solution so that volatile adjustability of the dicyandiamide solution is stronger, for avoiding spray head from blocking and coffee
Ring phenomenon is advantageously.
In summary, the nanocrystalline ink of perovskite provided in an embodiment of the present invention, by adjusting the above multi-component solvent
System, or further adjust perovskite nanocrystalline material concentration, can make boiling point, the viscosity of the nanocrystalline ink of perovskite with
And surface tension reaches expected range, in order to carry out inkjet printing using ink-jet printing technology, so as to avoid other surfaces
The use of activating agent, levelling agent, moisturizer, stabilizer or other organic principles, and then avoid the hair to subsequent printing film layer
Optical property impacts.
Illustratively, the viscosity of low boiling point solvent can be less than 1.0mPaS, and the viscosity of high boiling solvent can be greater than 2mPa
S, further can be greater than 10.0mPaS, and the viscosity of medium-boiling solvent can between 1.0mPaS-10.0mPaS,
It further, can be between 1.0mPaS-2.0mPaS.
The surface tension of low boiling point solvent is smaller than 25dyn/cm, and the surface tension of high boiling solvent can be greater than 25dyn/
Cm can further be greater than 40dyn/cm, and the surface tension of medium-boiling solvent can be between 25dyn/cm-40dyn/cm.
It should be noted that viscosity and surface tension involved in the embodiment of the present invention, refer in 25 DEG C of conditions
Under the data that measure.
In the embodiment of the present invention, the surface tension 25dyn/cm-40dyn/cm of the nanocrystalline ink of perovskite can be made, glued
Degree is 1.0mPaS-10mPaS, is limited to range as above by the surface tension and viscosity that make the nanocrystalline ink of perovskite,
Make it be conducive to carry out inkjet printing, and obtains good printing effect.
For the dicyandiamide solution of two solvent compositions, wherein the volume of low boiling point solvent and high boiling solvent can phase
Together, it can also be different, also, low boiling point solvent volume is higher or lower than what high boiling solvent was possible to, as long as being constituted
Dicyandiamide solution boiling point, viscosity and the surface tension of the nanocrystalline ink of perovskite can be made to reach in expected range.
For the dicyandiamide solution of three solvent compositions, wherein the volume of medium-boiling solvent is respectively greater than low boiling point solvent
With the volume of high boiling solvent.By keeping the volume of medium-boiling solvent maximum, more conducively optimizes said effect, obtain desired calcium
The nanocrystalline ink of titanium ore.
For example, the 50%-80% that can make the volume dicyandiamide solution volume of medium-boiling solvent, makes low boiling point solvent
Volume with high boiling solvent is the 10%-25% of dicyandiamide solution volume.
In the embodiment of the present invention, the solvent in dicyandiamide solution is weak polar solvent and/or nonpolar solvent, passes through such as upper limit
Determine solvent polarity, can avoid organic ligand on perovskite nanocrystalline material and fall off, and then prevent nanocrystalline reunion, improve dispersion
Property.
In a kind of possible example, the solvent in dicyandiamide solution is nonpolar solvent；In a kind of possible example,
Solvent in dicyandiamide solution may include weak polar solvent and nonpolar solvent, also, the volume of nonpolar solvent is greater than low pole
The volume of solvent.
It is understood that the interpretation solvent polarity can be carried out according to the size of solvent relative dielectric constant.Usual situation
Under, solvent of the relative dielectric constant greater than 3.6 is considered polar solvent；Solvent of the relative dielectric constant within the scope of 2.8-3.6
It is considered weak polar solvent；Solvent of the relative dielectric constant less than 2.8 is regarded as nonpolar solvent.
Under the premise of meeting above-mentioned each condition, the solvent in dicyandiamide solution can be selected from alkane, cycloalkane, alkene, fragrance
At least one of hydrocarbon, long chain fatty acids, esters, amine, ethers.
For example, in the embodiment of the present invention, the low boiling point solvent being applicable in can be selected from normal octane, 2,2,3,3- tetramethyls
Base butane, 2- methyl heptane, 2,3,3- trimethylpentane, 2,3- dimethylhexane, 2,5- dimethylhexane, 4- methyl heptane,
2,2,3- trimethylpentane, 3- methyl heptane, 3,4- dimethylhexane, 2,4- dimethylhexane, 2- methyl -3- ethylpentane,
2,2,4- trimethylpentane, 3,3- dimethylhexane, 3- ethyl hexane, 3- ethyl hexane, 2,3,4- trimethylpentane, 2,2- bis-
Methyl hexane, 2,2,5- trimethyl cyclohexanes, n -nonane, 3,3- dimethyl octane, n-decane, anti-form-1,2- dimethyl cyclohexane,
1,3- dimethyl cyclohexane, ethyl cyclohexane, cycloheptane, cyclooctane, butyl cyclohexane, 1- isopropyl-4-methyl hexamethylene, 1-
Octene, 1- nonene, 1- decene, 1- methylcyclohexene, 1,5- cyclo-octadiene, australene (left-handed), australene (dextrorotation), nopinene
(left-handed), nopinene (dextrorotation), phenylacetylene, 2- propenyl benzene, toluene, ortho-xylene, meta-xylene, paraxylene, dimethylbenzene, second
Benzene, propyl benzene, isopropylbenzene, 1,2,4- trimethylbenzenes, 1,3,5- trimethylbenzenes, 2-methyl-2-phenylpropane, tetrachloro-ethylene, paracide, bromobenzene, butyl ether,
At least one of trioxane, butyric acid, isobutyric acid, diethyl carbonate, dibutyl amine, di-iso-butylmanice etc..
The medium-boiling solvent being applicable in can be selected from n-undecane, n-dodecane, cis- naphthalane, trans- naphthalane, 1,8- terpene two
Alkene, 1- hendecene, 1- laurylene, 1,2,3- trimethylbenzenes, 1 are 3,5- trimethylbenzenes, adjacent diethylbenzene, NSC 62102, p-Diethylbenzene, right
Cymene, 1,2,3,5- durenes, butylbenzene, sec-butylbenzene, tert-butyl benzene, durol, isobutyl-benzene, penta benzene, uncle penta
At least one of base benzene, amyl toluene, naphthalene, tetrahydronaphthalene, indenes, 2,3- indane, amyl ether, isoamyl ether, diethy-aceto oxalate.
Used high boiling solvent can be selected from n-tridecane, n-tetradecane, 1-tetradecylene, cyclohexyl ring hexane, two
At least one of penta benzene, biphenyl, 1- methyl naphthalene, octanoic acid, butyl stearate, cyclohexyl benzene.
For the nanocrystalline ink of perovskite of the embodiment of the present invention, the mass concentration for the perovskite nanocrystalline material being applicable in
For 5mg/mL-60mg/mL, for example, 10mg/mL, 20mg/mL, 30mg/mL, 40mg/mL, 50mg/mL, 60mg/mL etc..
It is understood that perovskite nanocrystalline material include: perovskite it is nanocrystalline and be located at the nanocrystalline table of perovskite
The organic ligand in face.Wherein, it can be the nanocrystalline (CsPbX of full-inorganic Ca-Ti ore type that perovskite is nanocrystalline3, X=Cl, Br, I),
Nanocrystalline (the CH of organic inorganic hybridization Ca-Ti ore type3NH3PbX3, X=Cl, Br, I), other ion dopings (elements such as manganese, aluminium, cerium)
One of type perovskite is nanocrystalline or unleaded perovskite is nanocrystalline etc..
For example, perovskite nanocrystalline material can be perovskite quanta point material, and the size in three of them dimension is all
Twice of the exciton Bohr radius of semiconductor material corresponding no more than its, partial size is usually between 2nm-20nm.
The perovskite quanta point material includes: titanium ore quantum dot and the organic ligand positioned at perovskite nanocrystal surface.
Wherein, perovskite quantum dot can be full-inorganic Ca-Ti ore type quantum dot (CsPbX3, X=Cl, Br, I), organic inorganic hybridization calcium
Titanium ore type quantum dot (CH3NH3PbX3, X=Cl, Br, I), other ion doping (elements such as manganese, aluminium, cerium) type perovskite quantum dots
Or one of unleaded perovskite quantum dot etc..
Above-mentioned organic ligand can be selected from sour ligand, amine ligand, quaternary ammonium salt, silane ligand, (oxygen) Phosphine ligands, mercaptan ligand
At least one of.
Further, sour ligand can be selected from least one of oleic acid, positive lauric acid/dodecanoic acid, caprylic acid；
Amine ligand can be selected from least one of oleyl amine, lauryl amine, n-octyl amine；
Quaternary ammonium salt ligand can be selected from didodecyldimethylammbromide bromide, ammonium bromide and tetraoctyl ammonium bromide, cetyl trimethyl
At least one of ammonium bromide；
Silane ligand can be in cage modle polysilsesquioxane, hexamethyldisiloxane, tetramethoxy-silicane at least
It is a kind of；
(oxygen) Phosphine ligands can be selected from least one of trioctylphosphine oxygen phosphorus, trioctylphosphine phosphorus；
Mercaptan ligand can be selected from least one of eight alkyl hydrosulfides, lauryl mercaptan, Stearyl mercaptan.
The average-size of above-mentioned perovskite nanocrystalline material can between 5nm-100nm, such as 5nm, 10nm,
20nm, 30nm, 40nm, 50nm, 70nm, 90nm etc..Also, the color of the perovskite nanocrystalline material can be for this field institute often
See, such as red, blue, green, yellow, orange etc., to meet different colour developing application demands.
On the other hand, the embodiment of the invention also provides a kind of preparation method of the nanocrystalline ink of perovskite, this method packets
It includes: dispersing perovskite nanocrystalline material in dicyandiamide solution, obtain the nanocrystalline ink of perovskite.Wherein, dicyandiamide solution includes:
The low boiling point solvent that boiling point is 115 DEG C -175 DEG C；And the high boiling solvent that boiling point is 230 DEG C -260 DEG C；Low boiling point solvent
Surface tension and viscosity are respectively smaller than the surface tension and viscosity of high boiling solvent.
Further, dicyandiamide solution further include: the medium-boiling solvent that boiling point is 175 DEG C -230 DEG C, and medium-boiling solvent
Surface tension between high boiling solvent and the surface tension of low boiling point solvent；Wherein, the viscosity of medium-boiling solvent between
Between high boiling solvent and the viscosity of low boiling point solvent.
In above-mentioned preparation method, particular/special requirement is had no to the order of addition of each solvent, for example, for the molten of two solvents
Perovskite nanocrystalline material can be firstly added in low boiling point solvent, high boiling solvent is then being added thereto by agent system；
Alternatively, can also be by the sequential replacement of the two.
For the dicyandiamide solution of three solvents, perovskite nanocrystalline material can be firstly added in medium-boiling solvent, be obtained
First mixed solution, and the volume by adjusting medium-boiling solvent adjusts its boiling point to expected range.It then, can be mixed to first
It closes and low boiling point solvent is added in solution, obtain the second mixed solution, and adjust second by the volume of adjusting low boiling point solvent
The surface tension of mixed solution.Then, high boiling solvent can be added into the second mixed solution, obtain third mixed solution,
And the volume by adjusting high boiling solvent adjusts the viscosity of the second mixed solution, and then obtain boiling point, surface tension and
The nanocrystalline ink of perovskite of the viscosity in expected range.It is of course also possible to the order of addition of three kinds of solvents be exchanged, as long as energy
Meet above-mentioned purpose.
In another aspect, the electroluminescent device includes nanometer the embodiment of the invention also provides a kind of electroluminescent device
Trichite photosphere, wherein the nanocrystalline luminescent layer passes through inkjet printing technology system by the above-mentioned nanocrystalline ink of any perovskite
It is standby to obtain.
In summary, electroluminescent device provided in an embodiment of the present invention, based on which employs above-mentioned perovskite is nanocrystalline
Ink is not only conducive to be prepared using inkjet printing technology, and has good printing effect.
In a kind of possible example, nanocrystalline luminescent layer can be quantum dot light emitting layer, also, electroluminescent device
Structure is common for this field, other than nanocrystalline luminescent layer, it is contemplated that it further includes other function layer, also, is based on
The arrangement mode of functional layer is different, and the structure for being formed by electroluminescent device is also different, gives illustrate individually below:
As example one, the electroluminescent device can include: transparent conductive electrode, the hole biography stacked gradually from the bottom to top
Defeated layer, nanocrystalline luminescent layer, electron transfer layer, metal electrode.
As example two, the electroluminescent device can include: the electroluminescent device can include: stack gradually from the bottom to top
Transparent conductive electrode, hole injection layer, hole transmission layer, nanocrystalline luminescent layer, electron injecting layer, electron transfer layer, metal
Electrode.
As example three, which includes: the transparent conductive electrode stacked gradually from the bottom to top, electron-transport
Layer, nanocrystalline luminescent layer, hole transmission layer, metal electrode.
As example four, the electroluminescent device can include: the transparent conductive electrode that stacks gradually from the bottom to top, electronics note
Enter layer, electron transfer layer, nanocrystalline luminescent layer, hole transmission layer, hole injection layer, metal electrode.
As example five, the electroluminescent device can include: the transparent conductive electrode that stacks gradually from the bottom to top, nanocrystalline
Luminescent layer, metal electrode.
Above each functional layer all can be this field it is common, individually below for example:
Electron injecting layer can be LiF, NaF, Liq, Cs2CO3、CsN3。
Electron transfer layer can be metal oxide, composite oxide of metal, metal complex or organic matter, example
Such as, can be the inorganic nano-particles such as ZnO, ZnMgO, ZnAlO, or electron-transporting small organic molecule, as TPBi (1,
3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene), Alq3(8- quinoline aluminum), BPhen (4,7- diphenyl -1,10- phenanthrene hello
Quinoline) etc..
The material of hole transmission layer can (wherein, PEDOT be EDOT (3,4-rthylene dioxythiophene list for PEDOT:PSS
Body) polymer, PSS is poly styrene sulfonate.), (poly- (9,9- dioctyl fluorene-CO-N- (4- butyl phenyl) diphenylamines))
(TFB), (polyvinyl carbazole) (PVK), poly- [bis- (4- phenyl) (4- butyl phenyl) amine]) (poly-TPD), N, N '-hexichol
Base-N, N ' (Alpha-Naphthyl) -1,1 '-biphenyl -4,4 '-diamines (NPD) or N, N'- diphenyl-N, N'- (1- naphthalene) -1,1'- connection
Benzene -4,4'- diamines (NPB).
The material of hole injection layer can (wherein, PEDOT be EDOT (3,4-rthylene dioxythiophene list for PEDOT:PSS
Body) polymer, PSS is poly styrene sulfonate.), poly- (3,4- Ethylenedioxy Thiophene)-poly- (styrene sulfonic acid), polyphenyl
Amine.
Related transparent conductive electrode can be ITO (tin indium oxide), the FTO (SnO of doping fluorine2Transparent conducting glass
(SnO2: F)) or silver nano-grain/wire grid etc..
The electrode material of related metal electrode can be gold Au, silver Ag, aluminium Al, Al/Nd, Mg/Ag etc..
Based on above-mentioned it is found that the nanocrystalline ink printed of perovskite can be made in sky when preparing above-mentioned electroluminescent device
In cave transport layer, electron transfer layer or transparent conductive electrode.
Hereinafter the present invention will be further described by specific embodiment:
Embodiment 1
Present embodiments provide a kind of perovskite quantum dot ink comprising: mass concentration is 40mg/mL CsPbCl3Calcium
Titanium ore quanta point material, and the dicyandiamide solution containing low boiling point solvent and high boiling solvent.Wherein, low in the dicyandiamide solution
Boiling point solvent is mesitylene, and percent by volume 20%, high boiling solvent is n-dodecane, percent by volume 80%..
The perovskite quantum dot ink is tested by Malvern rheometer and surface tension tester, test result
The viscosity for showing the perovskite quantum dot ink is 2.1mPaS, surface tension 30.1dyn/cm..
Above-mentioned perovskite quantum dot ink is beaten using the DMP-2831 ink-jet printer of Fujifilm Dimatix company
Print on the hole transport layer, forms quantum dot light emitting layer.Electronic Speculum test is scanned to the quantum dot light emitting layer, the results showed that,
The surface roughness of the quantum dot light emitting layer is 3.52nm, is the quantum dot light emitting that dicyandiamide solution is prepared better than n-dodecane
The surface roughness (6.95nm) of layer.
Embodiment 2
Present embodiments provide a kind of perovskite quantum dot ink comprising: mass concentration is 20mg/mL CsPbBr3Calcium
Titanium ore quanta point material, and the dicyandiamide solution containing low boiling point solvent, medium-boiling solvent and high boiling solvent.Wherein, this is molten
In agent system, low boiling point solvent is cyclooctane, and percent by volume 10%, medium-boiling solvent is tetrahydronaphthalene, percent by volume
It is 70%, high boiling solvent is cyclohexyl ring hexane, percent by volume 20%.
The perovskite quantum dot ink is tested by Malvern rheometer and surface tension tester, test result
The viscosity for showing the perovskite quantum dot ink is 3.4mPaS, surface tension 32.2dyn/cm.
Above-mentioned perovskite quantum dot ink printed is passed in hole using the DMP-2831 ink-jet printer of Dimatix company
On defeated layer, quantum dot light emitting layer is formed.Surface topography test is carried out to the quantum dot light emitting layer, the results showed that, quantum dot hair
The surface roughness of photosphere is 2.92nm (referring to Fig. 1), is the quantum dot light emitting that dicyandiamide solution is prepared better than n-dodecane
The surface roughness (6.95nm) of layer.
Embodiment 3
A kind of electroluminescent device is present embodiments provided, which is prepared via a method which to obtain:
It is 10 Ω/ ito glass as substrate, and transparent conductive electrode using sheet resistance.Ito glass is through acetone cotton and washes clean
After smart cotton rub is washed, each 15min, cleaning are successively cleaned by ultrasonic using glass cleaner, deionized water, ethyl alcohol, acetone, deionized water
After, it is dried up with dry high pure nitrogen.
Before use, the ito glass substrate of wash clean irradiates 3 minutes under oxygen plasma, then, on ito glass
With 4000 turns 45 seconds, spin coating PEDOT:PSS hole injection layer, then 140 DEG C of thermal station are annealed 15 minutes in an atmosphere, remove residual
Solvent, obtain the hole injection layer of 30nm film thickness.
By the chlorobenzene solution of the Poly-TPD of the 8mg/mL prepared, it is spun on PEDOT:PSS layer within 45 seconds with 4000 turns.With
It anneals 20 minutes at 120 DEG C of thermal station afterwards, obtains the hole transmission layer of 30nm film thickness.
It is provided on the hole transport layer using one layer of embodiment 2 of the DMP-2831 printing of inkjet printer of Dimatix company
Perovskite quantum dot ink, 60 DEG C of annealing of vacuum are 1 hour dry, obtain the quantum dot light emitting layer of 30nm thickness.It is last whole
It is placed in vacuum coating equipment, is sequentially depositing the electron injecting layer Liq of electron transfer layer TPBi, the 2nm thickness of 40nm thickness, then evaporating Al
Metal electrode, the last desired electroluminescent device of packaging cost embodiment.
The luminescent properties of the electroluminescent device are tested, test result difference is as in Figure 2-4:
As shown in Fig. 2, which show printing device i-v curve is normal, maximum brightness reaches 13100cd m-2；
As shown in Fig. 3, which show printing device maximum current efficiency to reach 12.0cd A-1, power efficiency reaches
11.6l m W-1；
As shown in Fig. 4, which show printing device maximum external quantum efficiencys to reach 5.0%.
In summary, the luminescent properties of electroluminescent device provided in this embodiment are good, and luminescent properties are more stable.
The above is merely for convenience of it will be understood by those skilled in the art that technical solution of the present invention, not to limit
The present invention.All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in this
Within the protection scope of invention.
Claims (10)
1. a kind of nanocrystalline ink of perovskite, comprising: perovskite nanocrystalline material, which is characterized in that the perovskite is nanocrystalline
Ink further include: for dispersing the dicyandiamide solution of the perovskite nanocrystalline material, the dicyandiamide solution includes: that boiling point is 115
DEG C -175 DEG C of low boiling point solvent；And
The high boiling solvent that boiling point is 230 DEG C -260 DEG C；
Wherein, the surface tension and viscosity of the low boiling point solvent are respectively smaller than the surface tension of the high boiling solvent and glue
Degree.
2. the nanocrystalline ink of perovskite according to claim 1, which is characterized in that the dicyandiamide solution further include: boiling point
For 175 DEG C -230 DEG C of medium-boiling solvent, and the surface tension of the medium-boiling solvent is between the high boiling solvent and described
Between the surface tension of low boiling point solvent；
The viscosity of the medium-boiling solvent is between the high boiling solvent and the viscosity of the low boiling point solvent.
3. the nanocrystalline ink of perovskite according to claim 1, which is characterized in that the perovskite nanocrystalline material is calcium
Titanium ore quanta point material.
4. the nanocrystalline ink of perovskite according to claim 1, which is characterized in that the matter of the perovskite nanocrystalline material
Amount concentration is 5mg/mL-60mg/mL.
5. the nanocrystalline ink of perovskite according to claim 1, which is characterized in that the solvent in the dicyandiamide solution is weak
Polar solvent and/or nonpolar solvent.
6. the nanocrystalline ink of perovskite according to claim 5, which is characterized in that the solvent in the dicyandiamide solution is selected from
At least one of alkane, cycloalkane, alkene, aromatic hydrocarbon, long chain fatty acids, esters, amine, ethers.
7. the nanocrystalline ink of perovskite according to claim 1-6, which is characterized in that the perovskite is nanocrystalline
The surface tension of ink is 25dyn/cm-40dyn/cm, viscosity 1.0mPaS-10mPaS.
8. a kind of preparation method of the nanocrystalline ink of perovskite, which is characterized in that the described method includes: by the nanocrystalline material of perovskite
Material is scattered in dicyandiamide solution, obtains the nanocrystalline ink of the perovskite；
The dicyandiamide solution includes: the low boiling point solvent that boiling point is 115 DEG C -175 DEG C；And
The high boiling solvent that boiling point is 230 DEG C -260 DEG C；
Wherein, the surface tension and viscosity of the low boiling point solvent are respectively smaller than the surface tension of the high boiling solvent and glue
Degree.
9. preparation method according to claim 8, which is characterized in that the dicyandiamide solution further include: boiling point be 175 DEG C-
230 DEG C of medium-boiling solvent, and the surface tension of the medium-boiling solvent is molten between the high boiling solvent and the low boiling point
Between the surface tension of agent；
The viscosity of the medium-boiling solvent is between the high boiling solvent and the viscosity of the low boiling point solvent.
10. a kind of electroluminescent device, including nanocrystalline luminescent layer, which is characterized in that the nanocrystalline luminescent layer is wanted by right
The nanocrystalline ink of the described in any item perovskites of 1-7 is asked to be prepared by inkjet printing technology.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110718645A (en) * | 2019-09-24 | 2020-01-21 | 华中科技大学 | Preparation method and product of perovskite quantum dot light-emitting diode |
| CN111129354A (en) * | 2019-12-20 | 2020-05-08 | 深圳市华星光电半导体显示技术有限公司 | Blue-light perovskite ink, preparation method thereof and perovskite light-emitting device |
| WO2020215864A1 (en) * | 2019-04-22 | 2020-10-29 | 京东方科技集团股份有限公司 | Perovskite nanocrystalline ink, electroluminescent device, and preparation method |
| CN112391085A (en) * | 2020-11-27 | 2021-02-23 | 南京邮电大学 | Perovskite nanocrystalline ink for ink-jet printing and preparation method thereof |
| CN113233499A (en) * | 2021-06-09 | 2021-08-10 | 曲阜师范大学 | Preparation method for regulating morphology and fluorescence wavelength of inorganic perovskite nanocrystalline by using pH value of aqueous solution |
| CN113292096A (en) * | 2021-06-09 | 2021-08-24 | 曲阜师范大学 | Preparation method for synthesizing inorganic perovskite nanocrystalline by non-injection one-step method |
| CN115029134A (en) * | 2022-05-27 | 2022-09-09 | 广西大学 | Efficient Mn-doped CsPbCl based on aluminum chloride auxiliary preparation 3 Method for producing nanocrystals |
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| CN116218283B (en) * | 2023-04-13 | 2024-04-05 | 义乌清越光电技术研究院有限公司 | Quantum dot ink for TFB hole transport layer and application thereof |
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| CN108727902A (en) * | 2017-04-21 | 2018-11-02 | Tcl集团股份有限公司 | Inorganic nano material prints ink and preparation method thereof |
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| WO2017080317A1 (en) * | 2015-11-12 | 2017-05-18 | 广州华睿光电材料有限公司 | Composition for printing electronic device and use thereof in electronic device |
| CN108727902A (en) * | 2017-04-21 | 2018-11-02 | Tcl集团股份有限公司 | Inorganic nano material prints ink and preparation method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020215864A1 (en) * | 2019-04-22 | 2020-10-29 | 京东方科技集团股份有限公司 | Perovskite nanocrystalline ink, electroluminescent device, and preparation method |
| CN110718645A (en) * | 2019-09-24 | 2020-01-21 | 华中科技大学 | Preparation method and product of perovskite quantum dot light-emitting diode |
| CN111129354A (en) * | 2019-12-20 | 2020-05-08 | 深圳市华星光电半导体显示技术有限公司 | Blue-light perovskite ink, preparation method thereof and perovskite light-emitting device |
| CN111129354B (en) * | 2019-12-20 | 2022-07-12 | 深圳市华星光电半导体显示技术有限公司 | Blue-light perovskite ink, preparation method thereof and perovskite light-emitting device |
| CN112391085A (en) * | 2020-11-27 | 2021-02-23 | 南京邮电大学 | Perovskite nanocrystalline ink for ink-jet printing and preparation method thereof |
| CN113233499A (en) * | 2021-06-09 | 2021-08-10 | 曲阜师范大学 | Preparation method for regulating morphology and fluorescence wavelength of inorganic perovskite nanocrystalline by using pH value of aqueous solution |
| CN113292096A (en) * | 2021-06-09 | 2021-08-24 | 曲阜师范大学 | Preparation method for synthesizing inorganic perovskite nanocrystalline by non-injection one-step method |
| CN113233499B (en) * | 2021-06-09 | 2022-12-02 | 曲阜师范大学 | Preparation method for regulating morphology and fluorescence wavelength of inorganic perovskite nanocrystal by using pH value of aqueous solution |
| CN115029134A (en) * | 2022-05-27 | 2022-09-09 | 广西大学 | Efficient Mn-doped CsPbCl based on aluminum chloride auxiliary preparation 3 Method for producing nanocrystals |
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| WO2020215864A1 (en) | 2020-10-29 |
| CN110041758B (en) | 2021-04-09 |
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