CN110041758B - Perovskite nanocrystalline ink, electroluminescent device and preparation method - Google Patents
Perovskite nanocrystalline ink, electroluminescent device and preparation method Download PDFInfo
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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
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- C09D11/32—Inkjet printing inks characterised by colouring agents
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- 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 perovskite nanocrystalline ink, an electroluminescent device and a preparation method, and belongs to the field of printing display. The perovskite nanocrystal ink comprises: a perovskite nanocrystalline material, a solvent system for dispersing the perovskite nanocrystalline material, the solvent system comprising: a low boiling point solvent having a boiling point of 115 ℃ to 175 ℃; a high boiling point solvent having a boiling point of 230 ℃ to 260 ℃; the surface tension and viscosity of the low boiling point solvent are less than the surface tension and viscosity of the high boiling point solvent, respectively. By adjusting the volume ratio of the low-boiling-point solvent to the high-boiling-point solvent, the boiling point of the solvent system can be adjusted to a desired range, so that the ink is suitable for dispersing perovskite nanocrystals, desired volatility can be obtained, the ink jetting feasibility is ensured, the nozzle blockage is avoided, and the coffee ring phenomenon can be effectively avoided. By adjusting the surface tension and viscosity of the solvent system to a desired range, the spreading capability of the perovskite nanocrystalline ink and the printability after ink jetting are ensured, and the printing effect is improved.
Description
Technical Field
The invention relates to the field of nanocrystal display, in particular to perovskite nanocrystal ink, an electroluminescent device and a preparation method.
Background
The perovskite quantum dots are widely applied to the electroluminescent device and the related display field on the basis of the advantages of easy tuning of luminescence, narrow emission spectral line, high quantum efficiency, high color purity, low production cost and the like. At present, perovskite quantum dot inks are mostly subjected to inkjet printing to prepare patterned quantum dot light emitting layers. Therefore, it is necessary to provide a perovskite quantum dot ink.
The perovskite quantum dot ink provided by the prior art comprises: non-polar solvents such as hexane and octane, and perovskite quantum dot materials dispersed in the non-polar solvents.
The inventor finds that at least the following problems exist in the prior art:
the perovskite quantum dot ink provided by the prior art is easy to block a spray head in the ink-jet printing process, and is easy to generate a coffee ring phenomenon.
Disclosure of Invention
In view of this, the invention provides a perovskite nanocrystal ink, an electroluminescent device and a preparation method. Specifically, the method comprises the following technical scheme:
in one aspect, there is provided a perovskite nanocrystal ink comprising: a perovskite nanocrystalline material, the perovskite nanocrystalline ink further comprising: a solvent system for dispersing the perovskite nanocrystalline material, the solvent system comprising: a low boiling point solvent having a boiling point of 115 ℃ to 175 ℃; and
a high boiling point solvent having a boiling point of 230 ℃ to 260 ℃;
wherein the surface tension and viscosity of the low boiling point solvent are less than the surface tension and viscosity of the high boiling point solvent, respectively.
In one possible implementation, the solvent system further comprises: a medium boiling point solvent having a boiling point of 175 ℃ to 230 ℃ and a surface tension of the medium boiling point solvent between that of the high boiling point solvent and that of the low boiling point solvent;
the viscosity of the medium-boiling point solvent is between the viscosity of the high-boiling point solvent and the viscosity of the low-boiling point solvent.
In one possible implementation, the perovskite nanocrystalline material is a perovskite quantum dot material.
In one possible implementation, the mass concentration of the perovskite nanocrystalline material is 5mg/mL to 60 mg/mL.
In one possible implementation, the solvent in the solvent system is a weakly polar solvent and/or a non-polar solvent.
In one possible implementation, the solvent in the solvent system is selected from at least one of alkanes, cycloalkanes, alkenes, aromatics, long chain fatty acids, esters, amines, ethers.
In one possible implementation, the perovskite nanocrystal ink has a surface tension of 25dyn/cm to 40dyn/cm and a viscosity of 1.0mPa · S to 10mPa · S.
In another aspect, an embodiment of the present invention provides a method for preparing perovskite nanocrystal ink, where the method includes: dispersing a perovskite nanocrystalline material in a solvent system to obtain the perovskite nanocrystalline ink;
the solvent system comprises: a low boiling point solvent having a boiling point of 115 ℃ to 175 ℃; and
a high boiling point solvent having a boiling point of 230 ℃ to 260 ℃;
wherein the surface tension and viscosity of the low boiling point solvent are less than the surface tension and viscosity of the high boiling point solvent, respectively.
In one possible implementation, the solvent system further comprises: a medium boiling point solvent having a boiling point of 175 ℃ to 230 ℃ and a surface tension of the medium boiling point solvent between that of the high boiling point solvent and that of the low boiling point solvent;
the viscosity of the medium-boiling point solvent is between the viscosity of the high-boiling point solvent and the viscosity of the low-boiling point solvent.
In another aspect, an embodiment of the present invention provides an electroluminescent device, including a nanocrystalline light-emitting layer, where the nanocrystalline light-emitting layer is prepared from the perovskite nanocrystalline ink by an inkjet printing technology.
The technical scheme provided by the embodiment of the invention has the beneficial effects that at least:
according to the perovskite nanocrystalline ink provided by the embodiment of the invention, two solvents with different boiling points can be selected to form a solvent system, the boiling point ranges of the two solvents are limited as above, and the volume ratio of the low boiling point solvent to the high boiling point solvent is adjusted, so that the boiling point of the solvent system can be adjusted to a desired range on one hand, the perovskite nanocrystalline ink is suitable for dispersing perovskite nanocrystals, desired volatility can be obtained, the ink jet feasibility of the perovskite nanocrystalline ink is ensured, and the nozzle blockage is avoided. In addition, based on the non-azeotropic characteristic of the multiple solvents, the volatilization processes of the solvents are not synchronous, so that the volatility of the solvent system is adjustable, and the coffee ring phenomenon can be effectively avoided. On the other hand, by adjusting the volume ratio of the low-boiling point solvent to the high-boiling point solvent, the surface tension and viscosity of the solvent system can be adjusted to a desired range, so that the spreading capability of the perovskite nanocrystalline ink and the printability after ink jetting are ensured, and the printing effect is improved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a surface topography of a nanocrystalline light-emitting layer prepared from the perovskite nanocrystalline ink provided in example 2;
FIG. 2 is a graph showing a current density-voltage-light emission luminance characteristic of an electroluminescent device provided in example 3;
FIG. 3 is a graph showing the current efficiency-light emission luminance-power efficiency characteristics of an electroluminescent device provided in example 3;
fig. 4 is a graph showing external quantum efficiency-light emission luminance characteristics of an electroluminescent device provided in example 3.
Detailed Description
In order to make the technical solutions and advantages of the present invention clearer, the following will describe embodiments of the present invention in further detail with reference to the accompanying drawings.
In addition, when the particle size of the perovskite nanocrystal according to the embodiment of the present invention is within the quantum dot particle size range (for example, 2 to 20nm), the perovskite nanocrystal is perovskite quantum dot, and in this case, the perovskite nanocrystal ink provided by the embodiment of the present invention may be referred to as perovskite quantum dot ink.
In one aspect, an embodiment of the present invention provides a perovskite nanocrystal ink, including: a perovskite nanocrystalline material, and a solvent system for dispersing the perovskite nanocrystalline material. Wherein the solvent system comprises: a low boiling point solvent having a boiling point of 115 ℃ to 175 ℃; and a high boiling point solvent having a boiling point of 230 ℃ to 260 ℃; the surface tension and viscosity of the low boiling point solvent are less than the surface tension and viscosity of the high boiling point solvent, respectively.
According to the perovskite nanocrystalline ink provided by the embodiment of the invention, two solvents with different boiling points can be selected to form a solvent system, the boiling point ranges of the two solvents are limited as above, and the volume ratio of the low boiling point solvent to the high boiling point solvent is adjusted, so that the boiling point of the solvent system can be adjusted to a desired range on one hand, the perovskite nanocrystalline ink is suitable for dispersing perovskite nanocrystals, desired volatility can be obtained, the ink jet feasibility of the perovskite nanocrystalline ink is ensured, and the nozzle blockage is avoided. In addition, based on the non-azeotropic characteristic of the multiple solvents, the volatilization processes of the solvents are not synchronous, so that the volatility of the solvent system is adjustable, and the coffee ring phenomenon can be effectively avoided. On the other hand, by adjusting the volume ratio of the low-boiling point solvent to the high-boiling point solvent, the surface tension and viscosity of the solvent system can be adjusted to a desired range, so that the spreading capability of the perovskite nanocrystalline ink and the printability after ink jetting are ensured, and the printing effect is improved.
Further, the solvent system provided by the embodiment of the present invention further includes: the medium boiling point solvent has a boiling point of 175-230 ℃, the surface tension of the medium boiling point solvent is between the surface tension of the high boiling point solvent and the surface tension of the low boiling point solvent, and the viscosity of the medium boiling point solvent is between the viscosity of the high boiling point solvent and the viscosity of the low boiling point solvent.
By adding the medium boiling point solvent with moderate boiling point, surface tension and viscosity, the solvent system consisting of three component solvents can be obtained, so that the solvent system has stronger adjustability of volatility and is more favorable for avoiding the blockage of a spray head and the coffee ring phenomenon.
In summary, the perovskite nanocrystalline ink provided by the embodiment of the invention can make the boiling point, viscosity and surface tension of the perovskite nanocrystalline ink reach the desired range by adjusting the above multi-component solvent system or further adjusting the concentration of the perovskite nanocrystalline material, so as to facilitate inkjet printing by adopting the inkjet printing technology, thereby avoiding the use of other surfactants, leveling agents, humectants, stabilizers or other organic components, and further avoiding the influence on the luminescence performance of the subsequent printed film layer.
Illustratively, the low-boiling solvent may have a viscosity of less than 1.0 mPaS, the high-boiling solvent may have a viscosity of greater than 2 mPaS, and further greater than 10.0 mPaS, and the medium-boiling solvent may have a viscosity of between 1.0 mPaS and 10.0 mPaS, and further between 1.0 mPaS and 2.0 mPaS.
The low boiling point solvent may have a surface tension of less than 25dyn/cm, the high boiling point solvent may have a surface tension of greater than 25dyn/cm, and further may have a surface tension of greater than 40dyn/cm, and the medium boiling point solvent may have a surface tension of between 25dyn/cm and 40 dyn/cm.
It should be noted that the viscosity and surface tension referred to in the examples of the present invention refer to data measured at 25 ℃.
In the embodiment of the present invention, the surface tension of the perovskite nano-crystal ink is 25dyn/cm to 40dyn/cm, the viscosity is 1.0 mPa.S to 10 mPa.S, and the surface tension and the viscosity of the perovskite nano-crystal ink are limited to the above ranges, so that the perovskite nano-crystal ink is favorable for ink-jet printing and obtains a good printing effect.
For a two-solvent component solvent system, the volumes of the low boiling point solvent and the high boiling point solvent may be the same or different, and the volume of the low boiling point solvent may be higher or lower than that of the high boiling point solvent, provided that the solvent system is configured to achieve the boiling point, viscosity, and surface tension of the perovskite nanocrystal ink within the desired ranges.
For a three solvent component solvent system, the volume of the medium boiling solvent is greater than the volume of the low boiling solvent and the high boiling solvent, respectively. By maximizing the volume of the medium boiling point solvent, it is more advantageous to optimize the above effects, and the desired perovskite nanocrystal ink is obtained.
For example, the volume of the medium boiling point solvent may be 50% to 80% of the volume of the solvent system, and the volumes of the low boiling point solvent and the high boiling point solvent may each be 10% to 25% of the volume of the solvent system.
In the embodiment of the invention, the solvent in the solvent system is a weak polar solvent and/or a non-polar solvent, and the falling-off of the organic ligand on the perovskite nanocrystalline material can be avoided by limiting the polarity of the solvent as above, so that the agglomeration of the nanocrystals is prevented, and the dispersibility is improved.
In one possible example, the solvents in the solvent system are all non-polar solvents; in one possible example, the solvent in the solvent system may include a weakly polar solvent and a non-polar solvent, and the volume of the non-polar solvent is greater than the volume of the weakly polar solvent.
It will be appreciated that the polarity of the solvent may be interpreted according to the magnitude of its relative dielectric constant. In general, solvents having a relative dielectric constant greater than 3.6 are considered to be polar solvents; solvents having a relative dielectric constant in the range of 2.8 to 3.6 are considered to be weakly polar solvents; solvents having a relative dielectric constant of less than 2.8 may be considered non-polar solvents.
On the premise that the above conditions are met, the solvent in the solvent system can be at least one selected from alkanes, cycloalkanes, alkenes, aromatics, long-chain fatty acids, esters, amines and ethers.
For example, in the embodiment of the present invention, the low boiling point solvent may be selected from n-octane, 2,3, 3-tetramethylbutane, 2-methylheptane, 2,3, 3-trimethylpentane, 2, 3-dimethylhexane, 2, 5-dimethylhexane, 4-methylheptane, 2, 3-trimethylpentane, 3-methylheptane, 3, 4-dimethylhexane, 2-methyl-3-ethylpentane, 2, 4-trimethylpentane, 3, 3-dimethylhexane, 3-ethylhexane, 2,3, 4-trimethylpentane, 2-dimethylhexane, 2, 5-trimethylhexane, n-nonane, 3, 3-dimethyloctane, n-decane, trans-1, 2-dimethylcyclohexane, 1, 3-dimethylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, butylcyclohexane, 1-isopropyl-4-methylcyclohexane, 1-octene, 1-nonene, 1-decene, 1-methylcyclohexene, 1, 5-cyclooctadiene, alpha-pinene (l), beta-pinene (l), phenylacetylene, 2-phenylpropene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, propylbenzene, isopropylbenzene, 1,2, 4-trimethylbenzene, 1,3, 5-trimethylbenzene, tert-butylbenzene, tetrachloroethylene, p-dichlorobenzene, bromobenzene, butyl ether, At least one of trioxane, butyric acid, isobutyric acid, diethyl carbonate, dibutylamine, diisobutylamine, and the like.
The suitable medium boiling point solvent may be selected from at least one of n-undecane, n-dodecane, cis-decalin, trans-decalin, 1, 8-limonene, 1-undecene, 1-dodecene, 1,2, 3-trimethylbenzene, 1,3, 5-trimethylbenzene, o-diethylbenzene, m-diethylbenzene, p-methylisopropylbenzene, 1,2, 3, 5-tetramethylbenzene, butylbenzene, sec-butylbenzene, tert-butylbenzene, durene, isobutylbenzene, pentylbenzene, tert-pentylbenzene, pentyltoluene, naphthalene, tetrahydronaphthalene, indene, 2, 3-indane, pentyl ether, isopentyl ether, diethyl oxalate.
The high boiling point solvent used may be at least one selected from the group consisting of n-tridecane, n-tetradecane, 1-tetradecene, cyclohexylcyclohexane, dipentylbenzene, biphenyl, 1-methylnaphthalene, octanoic acid, butyl stearate, and cyclohexylbenzene.
For the perovskite nanocrystalline ink of the embodiment of the invention, the mass concentration of the perovskite nanocrystalline material is 5mg/mL-60mg/mL, for example, 10mg/mL, 20mg/mL, 30mg/mL, 40mg/mL, 50mg/mL, 60mg/mL, and the like.
It is understood that perovskite nanocrystalline materials include: perovskite nanocrystalline and lie in the organic ligand of perovskite nanocrystalline surface. Wherein the perovskite nanocrystal can be all-inorganic perovskite type nanocrystal (CsPbX)3X ═ Cl, Br, I), organic-inorganic hybrid perovskite type nanocrystals (CH)3NH3PbX3X ═ Cl, Br, I), other ion-doped (elements such as manganese, aluminum, cerium), perovskite nanocrystals, lead-free perovskite nanocrystals, or the like.
For example, the perovskite nanocrystalline material may be a perovskite quantum dot material, none of whose dimensions are greater than twice the exciton bohr radius of its corresponding semiconductor material, with particle sizes typically between 2nm and 20 nm.
The perovskite quantum dot material comprises: titanium ore quantum dots and organic ligands positioned on the surface of the perovskite nanocrystals. Wherein the perovskite quantum dot can be an all-inorganic perovskite quantum dot (CsPbX)3X ═ Cl, Br, I), organic-inorganic hybrid perovskite quantum dots (CH)3NH3PbX3X ═ Cl, Br, I), other ion-doped (elements such as manganese, aluminum, cerium), perovskite quantum dots of the perovskite type, lead-free perovskite quantum dots, and the like.
The organic ligand may be at least one selected from the group consisting of an acid ligand, an amine ligand, a quaternary ammonium salt, a silane ligand, an (oxy) phosphine ligand and a thiol ligand.
Further, the acid ligand may be selected from at least one of oleic acid, n-dodecanoic acid, n-octanoic acid;
the amine ligand can be at least one selected from oleylamine, dodecylamine and n-octylamine;
the quaternary ammonium salt ligand can be at least one selected from didodecyl dimethyl ammonium bromide, tetraoctyl ammonium bromide and hexadecyl trimethyl ammonium bromide;
the silane ligand can be selected from at least one of cage polysilsesquioxane, hexamethyldisiloxane and tetramethoxysilane;
the (oxy) phosphine ligand may be selected from at least one of trioctylphosphine, trioctylphosphine;
the thiol ligand may be at least one selected from octaalkylthiols, dodecylthiols, and octadecylthiols.
The perovskite nanocrystalline material may have an average size of between 5nm and 100nm, such as 5nm, 10nm, 20nm, 30nm, 40nm, 50nm, 70nm, 90nm, and the like. Moreover, the color of the perovskite nanocrystalline material can be common in the field, such as red, blue, green, yellow, orange, and the like, so as to meet the requirements of different color development applications.
On the other hand, the embodiment of the invention also provides a preparation method of the perovskite nanocrystalline ink, which comprises the following steps: and dispersing the perovskite nanocrystalline material in a solvent system to obtain the perovskite nanocrystalline ink. Wherein the solvent system comprises: a low boiling point solvent having a boiling point of 115 ℃ to 175 ℃; and a high boiling point solvent having a boiling point of 230 ℃ to 260 ℃; the surface tension and viscosity of the low boiling point solvent are less than the surface tension and viscosity of the high boiling point solvent, respectively.
Further, the solvent system further comprises: a medium boiling point solvent with a boiling point of 175-230 ℃, wherein the surface tension of the medium boiling point solvent is between the surface tension of the high boiling point solvent and the surface tension of the low boiling point solvent; wherein the viscosity of the medium-boiling-point solvent is between that of the high-boiling-point solvent and that of the low-boiling-point solvent.
In the above preparation method, there is no particular requirement on the order of addition of each solvent, for example, for a two-solvent system, the perovskite nanocrystalline material may be first added to a low boiling point solvent, and then a high boiling point solvent is added thereto; alternatively, the order of both may be replaced.
For a three-solvent system, the perovskite nanocrystalline material may be first added to a mid-boiling point solvent to obtain a first mixed solution, and its boiling point adjusted to a desired range by adjusting the volume of the mid-boiling point solvent. Subsequently, a low boiling point solvent may be added to the first mixed solution to obtain a second mixed solution, and the surface tension of the second mixed solution may be adjusted by adjusting the volume of the low boiling point solvent. Subsequently, a high boiling point solvent may be added to the second mixed solution to obtain a third mixed solution, and the viscosity of the second mixed solution may be adjusted by adjusting the volume of the high boiling point solvent, thereby obtaining the perovskite nanocrystal ink having a boiling point, a surface tension, and a viscosity within a desired range. Of course, the order of addition of the three solvents may be changed as long as the above object is satisfied.
In another aspect, an embodiment of the present invention further provides an electroluminescent device, where the electroluminescent device includes a nanocrystalline light-emitting layer, where the nanocrystalline light-emitting layer is prepared from any one of the above perovskite nanocrystalline inks by an inkjet printing technology.
In summary, the electroluminescent device provided by the embodiment of the invention is not only beneficial to preparation by adopting an inkjet printing technology and has a good printing effect because the perovskite nanocrystalline ink is adopted.
In one possible example, the nanocrystal light emitting layer may be a quantum dot light emitting layer, and the structure of the electroluminescent device is common in the art, and in addition to the nanocrystal light emitting layer, considering that it further includes other functional layers, and the structure of the formed electroluminescent device is different based on the arrangement of the functional layers, which is described below:
as an example one, the electroluminescent device may include: the transparent conductive electrode, the hole transport layer, the nanocrystalline light emitting layer, the electron transport layer and the metal electrode are sequentially stacked from bottom to top.
As example two, the electroluminescent device may include: the electroluminescent device may include: the light-emitting diode comprises a transparent conductive electrode, a hole injection layer, a hole transport layer, a nanocrystalline light-emitting layer, an electron injection layer, an electron transport layer and a metal electrode which are sequentially stacked from bottom to top.
As example three, the electroluminescent device includes: the transparent conductive electrode, the electron transport layer, the nanocrystalline light emitting layer, the hole transport layer and the metal electrode are sequentially stacked from bottom to top.
As example four, the electroluminescent device may comprise: the light-emitting diode comprises a transparent conductive electrode, an electron injection layer, an electron transport layer, a nanocrystal light-emitting layer, a hole transport layer, a hole injection layer and a metal electrode which are sequentially stacked from bottom to top.
As example five, the electroluminescent device may comprise: the transparent conductive electrode, the nanocrystalline light-emitting layer and the metal electrode are sequentially stacked from bottom to top.
Each of the above functional layers may be conventional in the art, and the following are examples:
the electron injection layer can be LiF, NaF, Liq, Cs2CO3、CsN3。
The electron transport layer may be a metal oxide, a metal composite oxide, a metal complex compound or an organic substance, and may be, for example, ZnO, ZnMgO, ZnAlOInorganic nanoparticles, such as TPBi (1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene), Alq3(8-quinolinylaluminum), BPhen (4, 7-diphenyl-1, 10-phenanthroline), and the like.
The material of the hole transport layer may be PEDOT: PSS (where PEDOT is a polymer of EDOT (3, 4-ethylenedioxythiophene monomer) and PSS is polystyrene sulfonate), ((poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine)) (TFB), (polyvinylcarbazole) (PVK), poly [ bis (4-phenyl) (4-butylphenyl) amine ]) (poly-TPD), N '-diphenyl-N, N' (α -naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPD) or N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB).
The material of the hole injection layer may be PEDOT: PSS (where PEDOT is a polymer of EDOT (3, 4-ethylenedioxythiophene monomer) and PSS is polystyrene sulfonate), poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid), polyaniline.
The transparent conductive electrode can be ITO (indium tin oxide) or FTO (SnO doped with fluorine)2Transparent conductive glass (SnO)2: F) or silver nanoparticles/wire mesh, etc.
The electrode material of the metal electrode can be gold Au, silver Ag, aluminum Al, Al/Nd, Mg/Ag and the like.
Based on the above, in the preparation of the electroluminescent device, the perovskite nanocrystal ink may be printed on the hole transport layer, the electron transport layer, or the transparent conductive electrode.
The invention will be further described by the following specific examples:
example 1
The present embodiment provides a perovskite quantum dot ink, including: the mass concentration of the CsPbCl is 40mg/mL3Perovskite quantum dot materials, and solvent systems containing low boiling point solvents and high boiling point solvents. Wherein, in the solvent system, the low boiling point solvent is mesitylene with the volume percentage of 20 percent, the high boiling point solvent is n-dodecane with the volume percentage of 80 percent.
The perovskite quantum dot ink is tested by a Marvens rheometer and a surface tension tester, and the test result shows that the viscosity of the perovskite quantum dot ink is 2.1mPa & S, and the surface tension of the perovskite quantum dot ink is 30.1 dyn/cm..
And printing the perovskite quantum dot ink on the hole transport layer by using a DMP-2831 ink-jet printer of Fujifilm Dimatix company to form the quantum dot light-emitting layer. Scanning electron microscope tests show that the surface roughness of the quantum dot light-emitting layer is 3.52nm, which is superior to that of a quantum dot light-emitting layer prepared by taking n-dodecane as a solvent system (6.95 nm).
Example 2
The present embodiment provides a perovskite quantum dot ink, including: the mass concentration of CsPbBr is 20mg/mL3Perovskite quantum dot material, and contain low boiling point solvent, medium boiling point solvent and the solvent system of high boiling point solvent. In the solvent system, the low-boiling point solvent is cyclooctane, the volume percentage is 10%, the medium-boiling point solvent is tetralin, the volume percentage is 70%, and the high-boiling point solvent is cyclohexylcyclohexane, the volume percentage is 20%.
The perovskite quantum dot ink is tested by a Marvens rheometer and a surface tension tester, and the test result shows that the viscosity of the perovskite quantum dot ink is 3.4 mPa.S, and the surface tension is 32.2 dyn/cm.
And printing the perovskite quantum dot ink on a hole transport layer by using a DMP-2831 ink-jet printer of Dimatix company to form a quantum dot light-emitting layer. The surface morphology test of the quantum dot light-emitting layer shows that the surface roughness of the quantum dot light-emitting layer is 2.92nm (see figure 1), which is superior to the surface roughness (6.95nm) of the quantum dot light-emitting layer prepared by taking n-dodecane as a solvent system.
Example 3
The embodiment provides an electroluminescent device, which is prepared by the following method:
ITO glass having a sheet resistance of 10. omega./□ was used as a substrate and also used as a transparent conductive electrode. And (3) cleaning the ITO glass by using acetone cotton and detergent cotton, sequentially and ultrasonically cleaning the cleaned ITO glass for 15min by using a glass cleaning agent, deionized water, ethanol, acetone and deionized water, and drying the cleaned ITO glass by using dry high-purity nitrogen.
Before use, a cleaned ITO glass substrate was irradiated with oxygen plasma for 3 minutes, and then, a PEDOT: PSS hole injection layer was spin-coated on the ITO glass at 4000 revolutions for 45 seconds, followed by hot-stage annealing at 140 ℃ in the atmosphere for 15 minutes to remove the remaining solvent, thereby obtaining a hole injection layer having a film thickness of 30 nm.
A prepared 8mg/mL solution of Poly-TPD in chlorobenzene was spin coated onto the PEDOT: PSS layer at 4000 revs for 45 seconds. Followed by annealing at 120 ℃ for 20 minutes in a hot stage to obtain a hole transporting layer having a film thickness of 30 nm.
A layer of the perovskite quantum dot ink provided in example 2 was printed on the hole transport layer using a DMP-2831 ink jet printer of Dimatix corporation, and annealed and dried at 60 ℃ in vacuum for 1 hour to obtain a quantum dot light emitting layer with a thickness of 30 nm. Finally, the whole body is placed in a vacuum coating machine, an electron transport layer TPBi with the thickness of 40nm and an electron injection layer Liq with the thickness of 2nm are sequentially deposited, an Al metal electrode is evaporated, and finally the electroluminescent device expected by the embodiment is packaged.
The light emitting performance of the electroluminescent device is tested, and the test results are respectively shown in fig. 2-4:
as shown in FIG. 2, it shows that the current-voltage curve of the printed device is normal and the maximum luminance reaches 13100cd m-2；
As shown in FIG. 3, it shows that the maximum current efficiency of the printed device reaches 12.0cd A-1The power efficiency reaches 11.6 LmW-1；
As shown in fig. 4, it shows that the maximum external quantum efficiency of the printed device reaches 5.0%.
As can be seen from the above, the electroluminescent device provided in this embodiment has good light emission performance and more stable light emission performance.
The above description is only for facilitating the understanding of the technical solutions of the present invention by those skilled in the art, and is not intended to limit the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A perovskite nanocrystalline ink comprising: a perovskite nanocrystalline material, wherein the perovskite nanocrystalline ink further comprises: a solvent system for dispersing the perovskite nanocrystalline material, the solvent system comprising: a low boiling point solvent having a boiling point of 115 ℃ to 175 ℃; and
a high boiling point solvent having a boiling point of 230 ℃ to 260 ℃;
wherein the surface tension and viscosity of the low boiling point solvent are less than the surface tension and viscosity of the high boiling point solvent, respectively;
the solvent system further comprises: a medium boiling point solvent with a boiling point of 175 ℃ to 230 ℃ and a surface tension of the medium boiling point solvent between that of the high boiling point solvent and that of the low boiling point solvent;
the viscosity of the medium-boiling point solvent is between the viscosity of the high-boiling point solvent and the viscosity of the low-boiling point solvent;
the volume of the medium-boiling point solvent is 50-80% of the volume of the solvent system, and the volumes of the low-boiling point solvent and the high-boiling point solvent are both 10-25% of the volume of the solvent system;
the low boiling point solvent is selected from the group consisting of n-octane, 2-methylheptane, 2,3, 3-trimethylpentane, 2, 3-dimethylhexane, 4-methylheptane, 3, 4-dimethylhexane, 2-methyl-3-ethylpentane, 3, 3-dimethylhexane, 3-ethylhexane, 2, 5-trimethylhexane, n-nonane, 3, 3-dimethyloctane, n-decane, trans-1, 2-dimethylcyclohexane, 1, 3-dimethylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, 1-isopropyl-4-methylcyclohexane, 1-octene, 1-nonene, 1-decene, 1-methylcyclohexene, 1, 5-cyclooctadiene, and mixtures thereof, At least one of α -pinene (levo), α -pinene (dextro), β -pinene (levo), β -pinene (dextro), phenylacetylene, 2-phenylpropylene, tetrachloroethylene, p-dichlorobenzene, bromobenzene, butyl ether, trioxane, butyric acid, isobutyric acid, dibutylamine, diisobutylamine;
the medium-boiling point solvent is selected from at least one of n-undecane, n-dodecane, cis-decalin, trans-decalin, 1, 8-limonene, 1-undecene, 1-dodecene, tetralin, indene, 2, 3-indane and amyl ether;
the high boiling point solvent is at least one selected from the group consisting of n-tridecane, n-tetradecane, 1-tetradecene, cyclohexylcyclohexane, and octanoic acid.
2. The perovskite nanocrystalline ink according to claim 1, wherein the perovskite nanocrystalline material is a perovskite quantum dot material.
3. The perovskite nanocrystalline ink according to claim 1, wherein the perovskite nanocrystalline material has a mass concentration of 5mg/mL to 60 mg/mL.
4. The perovskite nanocrystalline ink according to any one of claims 1 to 3, characterized in that the perovskite nanocrystalline ink has a surface tension of 25dyn/cm to 40dyn/cm and a viscosity of 1.0 mPa-S to 10 mPa-S.
5. A method of preparing a perovskite nanocrystalline ink, the method comprising: dispersing a perovskite nanocrystalline material in a solvent system to obtain the perovskite nanocrystalline ink;
the solvent system comprises: a low boiling point solvent having a boiling point of 115 ℃ to 175 ℃; and
a high boiling point solvent having a boiling point of 230 ℃ to 260 ℃;
wherein the surface tension and viscosity of the low boiling point solvent are less than the surface tension and viscosity of the high boiling point solvent, respectively;
the solvent system further comprises: a medium boiling point solvent having a boiling point of 175 ℃ to 230 ℃ and a surface tension of the medium boiling point solvent between that of the high boiling point solvent and that of the low boiling point solvent;
the viscosity of the medium-boiling point solvent is between the viscosity of the high-boiling point solvent and the viscosity of the low-boiling point solvent;
the volume of the medium-boiling point solvent is 50-80% of the volume of the solvent system, and the volumes of the low-boiling point solvent and the high-boiling point solvent are both 10-25% of the volume of the solvent system;
the low boiling point solvent is selected from the group consisting of n-octane, 2-methylheptane, 2,3, 3-trimethylpentane, 2, 3-dimethylhexane, 4-methylheptane, 3, 4-dimethylhexane, 2-methyl-3-ethylpentane, 3, 3-dimethylhexane, 3-ethylhexane, 2, 5-trimethylhexane, n-nonane, 3, 3-dimethyloctane, n-decane, trans-1, 2-dimethylcyclohexane, 1, 3-dimethylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, 1-isopropyl-4-methylcyclohexane, 1-octene, 1-nonene, 1-decene, 1-methylcyclohexene, 1, 5-cyclooctadiene, and mixtures thereof, At least one of α -pinene (levo), α -pinene (dextro), β -pinene (levo), β -pinene (dextro), phenylacetylene, 2-phenylpropylene, tetrachloroethylene, p-dichlorobenzene, bromobenzene, butyl ether, trioxane, butyric acid, isobutyric acid, dibutylamine, diisobutylamine;
the medium-boiling point solvent is selected from at least one of n-undecane, n-dodecane, cis-decalin, trans-decalin, 1, 8-limonene, 1-undecene, 1-dodecene, tetralin, indene, 2, 3-indane and amyl ether;
the high boiling point solvent is at least one selected from the group consisting of n-tridecane, n-tetradecane, 1-tetradecene, cyclohexylcyclohexane, and octanoic acid.
6. An electroluminescent device comprising a nanocrystalline light-emitting layer, wherein the nanocrystalline light-emitting layer is prepared from the perovskite nanocrystalline ink according to any one of claims 1 to 4 by an inkjet printing technique.
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