WO2017080317A1 - Composition pour l'impression de dispositif électronique et son utilisation dans un dispositif électronique - Google Patents

Composition pour l'impression de dispositif électronique et son utilisation dans un dispositif électronique Download PDF

Info

Publication number
WO2017080317A1
WO2017080317A1 PCT/CN2016/099784 CN2016099784W WO2017080317A1 WO 2017080317 A1 WO2017080317 A1 WO 2017080317A1 CN 2016099784 W CN2016099784 W CN 2016099784W WO 2017080317 A1 WO2017080317 A1 WO 2017080317A1
Authority
WO
WIPO (PCT)
Prior art keywords
printing
solvent
composition
solvent component
group
Prior art date
Application number
PCT/CN2016/099784
Other languages
English (en)
Chinese (zh)
Inventor
杨曦
潘君友
闫晓林
Original Assignee
广州华睿光电材料有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 广州华睿光电材料有限公司 filed Critical 广州华睿光电材料有限公司
Priority to CN201680059822.4A priority Critical patent/CN108137969A/zh
Publication of WO2017080317A1 publication Critical patent/WO2017080317A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent

Definitions

  • the present invention relates to a composition for printing electronic devices, to the printing process of such compositions and to applications in optoelectronic devices, particularly in electroluminescent devices.
  • Quantum dots are nano-sized semiconductor materials with quantum confinement effects. When stimulated by light or electricity, quantum dots emit fluorescence with specific energy. The color (energy) of fluorescence is determined by the chemical composition and size of quantum dots. Therefore, the control of the size and shape of quantum dots can effectively regulate its electrical and optical properties. At present, countries are studying the application of quantum dots in full color, mainly in the display field.
  • quantum dots have been rapidly developed as electroluminescent devices (QLEDs), and device lifetimes have been greatly improved, as in Peng et al., Nature Vol515 96 (2015) and Qian et al., in Nature Photonics Vol9 259 ( Reported in 2015).
  • QLEDs electroluminescent devices
  • electrons and holes are injected into the light-emitting layer to illuminate under an applied electric field.
  • Spin coating is currently the primary method for forming quantum dot luminescent layer films.
  • spin coating techniques are difficult to apply to the fabrication of large area electroluminescent devices.
  • inkjet printing can produce quantum dot films on a large scale and low cost; compared with traditional semiconductor production processes, inkjet printing has low energy consumption, low water consumption, and environmental protection, which is a great advantage and potential for production. technology. Viscosity and surface tension are important parameters that affect the printing ink and printing process. A promising printing ink needs to have the proper viscosity and surface tension. At present, several companies have reported quantum dot inks for printing:
  • Nanoco Technologies Ltd. discloses a method of printing a printable ink formulation comprising nanoparticles (CN101878535B).
  • a printable ink formulation comprising nanoparticles (CN101878535B).
  • a suitable ink substrate such as toluene and dodecyl selenol
  • a printable nanoparticle ink and a corresponding nanoparticle-containing film are obtained.
  • the ink contains a concentration of quantum dot material, an organic solvent, and an alcohol polymer additive having a high viscosity.
  • a quantum dot film was obtained by printing the ink, and a quantum dot electroluminescent device was prepared.
  • QD Vision discloses a quantum dot ink formulation comprising a host material, a quantum dot material and an additive (US2010264371A1).
  • these quantum dot inks contain other additives such as alcohol polymers.
  • the introduction of polymer additives with insulating properties tends to reduce the charge transport capability of the film, which has a negative impact on the photoelectric performance of the device, and limits its wide application in optoelectronic devices. So looking for It is particularly important to have an organic solvent system for dispersing quantum dots with appropriate surface tension and viscosity.
  • One of the objects of the present invention is to provide a composition for printing electrons.
  • the first solvent component a higher boiling point and a lower solubility/dispersibility (poor solvent) for the inorganic nanomaterial;
  • the second solvent component has a lower boiling point and a higher solubility/dispersibility (good solvent) for the inorganic nanomaterial.
  • the first solvent and the second solvent are mutually soluble, the first solvent component has a boiling point greater than 180 ° C, the second solvent component has a boiling point between 100 ° C and 250 ° C, and the inorganic nanomaterial is in the first
  • the solubility/dispersibility in a solvent component is ⁇ 1 wt%
  • the solubility/dispersibility of the inorganic nanomaterial in the second solvent component is ⁇ 1.5 wt%
  • the two solvent components can be evaporated from the solvent system.
  • the boiling point of the first solvent component is at least 30 ° C higher than the boiling point of the second solvent component.
  • the solubility/dispersibility of the inorganic nanomaterial in the second solvent component is at least 2 times greater than that in the first solvent component.
  • the surface tension at 25 ° C of at least one of the first solvent component and the second solvent component is at 19 dyne / Cm to the range of 50 dyne/cm.
  • the viscosity of at least one of the first solvent component and the second solvent component at 25 ° C, from 1 cPs to 100 cPs within the scope.
  • the first solvent component accounts for 10% to 70% of the total volume of the solvent of the composition for printing electrons, and the second solvent component 30% to 90% of the total volume of the solvent of the composition for printing electrons, and the amount of the inorganic nano material in the composition for printing electrons and the ratio of the two solvent components satisfy :
  • the concentration of the inorganic nanomaterial in the first solvent component should be in a saturated or supersaturated state.
  • At least one of the first solvent component and the second solvent component is based on an aromatic or heteroaromatic solvent, aromatic A ketone solvent, an aromatic ether solvent, an ester solvent, a linear aliphatic solvent, an alicyclic solvent, an aliphatic ketone solvent, an aliphatic ether solvent or an alcohol solvent.
  • At least one of the first solvent component and the second solvent component is selected from any one of the following: dodecylbenzene , dipentylbenzene, xylene, diethylbenzene, trimethylbenzene, tetramethylbenzene, triphenylbenzene, pentyltoluene, 1-methylnaphthalene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, pentylbenzene , tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1-tetralone, 3-phenoxytoluene, 1-methoxynaphthalene, cyclohexylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-Methyl cumene, benzyl benzoate, benzyl ether
  • the inorganic nanomaterial is a quantum dot material, that is, its particle size has a monodisperse size distribution, and its shape may be selected from a sphere, a cube, a rod, or Different nanotopography such as branched structures.
  • the composition for printing electrons comprises at least one luminescent quantum dot material having an emission wavelength between 380 nm and 2500 nm.
  • the at least one inorganic nanomaterial is selected from Group IV, Group II-VI, Group II-V, Group III-V of the Periodic Table of the Elements a binary or polyvalent semiconductor compound of Groups III-VI, IV-VI, I-III-VI, II-IV-VI, II-IV-V or a mixture of any two or more thereof.
  • the at least one inorganic nanomaterial is a luminescent quantum dot selected from the group consisting of CdSe, CdS, CdTe, ZnO, ZnSe, ZnS, ZnTe, HgS , HgSe, HgTe, CdZnSe or a mixture of any two or more thereof.
  • the at least one inorganic nanomaterial is a luminescent quantum dot selected from the group consisting of InAs, InP, InN, GaN, InSb, InAsP, InGaAs, GaAs Any one of GaP, GaSb, AlP, AlN, AlAs, AlSb, CdSeTe, ZnCdSe, or a mixture of any two or more thereof.
  • the at least one inorganic nanomaterial is a perovskite nanoparticle material, particularly a luminescent perovskite nanoparticle, a metal nanoparticle A material, a metal oxide nanoparticle material or a mixture of any two or more thereof.
  • composition for printing electrons further comprising at least one organic functional material, which may be selected from a hole injection material (HIM), a hole transport material (HTM) Any of electron transporting material (ETM), electron injecting material (EIM), electron blocking material (EBM), hole blocking material (HBM), emitter (Emitter), host material (Host), and organic dye, Or a mixture of any two or more of them.
  • HIM hole injection material
  • HTM hole transport material
  • EIM electron injecting material
  • EBM electron blocking material
  • HBM hole blocking material
  • Emitter emitter
  • host material Hos
  • organic dye Or a mixture of any two or more of them.
  • the inorganic nanomaterial accounts for 0.3% to 70% by weight of the composition for printing electrons
  • the organic solvent accounts for The composition for printing electrons has a weight percentage of 30% to 99.7%.
  • the present invention also provides a method of preparing a composition for printing electrons as described above, comprising the steps of:
  • the volume percentage of the second solvent is 30% to 90% with respect to the total volume of the total solvent, and the first and second solvents are mutually soluble.
  • the present invention also provides an electronic device comprising a functional layer printed or coated by a composition for printing electrons according to any of the above, wherein the composition for printing electrons comprises
  • the two organic solvent components can be evaporated from the solvent system to form a functional film comprising the inorganic nanomaterial.
  • the electronic device is selected from the group consisting of a quantum dot light emitting diode (QLED), a quantum dot photovoltaic cell (QPV), a quantum dot luminescent cell (QLEEC), a quantum dot field effect transistor (QFET). ), quantum dot luminescence field effect transistors, quantum dot lasers, quantum dot sensors, and the like.
  • QLED quantum dot light emitting diode
  • QPV quantum dot photovoltaic cell
  • QLEEC quantum dot luminescent cell
  • QFET quantum dot field effect transistor
  • the present invention also provides a preparation method comprising: applying a composition for printing electrons according to any one of the above methods to a substrate by printing or coating, wherein the method of printing or coating may be selected from ( But not limited to): inkjet printing, jet printing (Nozzle Printing), typography, screen printing, dip coating, spin coating, blade coating, roller printing, twist roll printing, lithography, flexographic printing, rotation Printing, spraying, brushing, pad printing, slit type extrusion coating.
  • the invention has the beneficial effects that the printing composition of the invention can adjust the viscosity and surface tension to a suitable range according to a specific printing method, especially inkjet printing, in use, to facilitate printing, and to form a uniform surface. film.
  • the organic solvent can be effectively removed by post-treatment, such as heat treatment or vacuum treatment, to ensure the performance of the electronic device.
  • the present invention therefore provides a printing ink for the preparation of high quality functional films comprising inorganic nanomaterials, in particular quantum dots, providing a technical solution for printed electronic or optoelectronic devices.
  • FIG. 1 is a structural view of a preferred embodiment of a light emitting device according to the present invention, in which 101 is a substrate, 102 is an anode, 103 is a hole injection layer (HIL) or a hole transport layer (HTL), 104 is A light-emitting layer (electroluminescence device) or a light absorbing layer (photovoltaic cell), 105 is an electron injection layer (EIL) or an electron transport layer (ETL), and 106 is a cathode.
  • HIL hole injection layer
  • HTL hole transport layer
  • 104 is A light-emitting layer (electroluminescence device) or a light absorbing layer (photovoltaic cell)
  • 105 is an electron injection layer (EIL) or an electron transport layer (ETL)
  • 106 is a cathode.
  • composition for printing electrons comprises at least one inorganic nanomaterial and at least two organic solvent components, wherein the first solvent component has a higher boiling point, and the inorganic nanomaterial It has a lower solubility/dispersibility (poor solvent); the second solvent component has a lower boiling point and a higher solubility/dispersibility (good solvent) for inorganic nanomaterials.
  • the two organic solvents Among the components, the viscosity of at least one solvent at 25 ° C is in the range of 1 cPs to 100 cPs; or the surface tension of at least one solvent at 25 ° C is in the range of 19 dyne / cm to 50 dyne / cm.
  • the invention also relates to the printing process of such compositions and their use in optoelectronic devices, particularly in electroluminescent devices. The invention still further relates to electronic devices made using such compositions.
  • composition for printing electrons of the present invention has the same meaning as the printing ink or ink, and is interchangeable between them.
  • the present invention provides a composition for printing electrons comprising at least one inorganic nanomaterial and at least two organic solvent components having the following characteristics:
  • the first solvent component a higher boiling point and a lower solubility/dispersibility (poor solvent) for the inorganic nanomaterial;
  • the second solvent component has a lower boiling point and a higher solubility/dispersibility (good solvent) for the inorganic nanomaterial.
  • the two solvent components can be evaporated from the solvent system to form a thin film of inorganic nanomaterial.
  • the first solvent component has a boiling point that is at least 30 ° C higher than the boiling point of the second solvent component.
  • the first solvent component has a boiling point greater than 180 ° C
  • the second solvent component has a boiling point between 100 ° C and 250 ° C
  • the composition for printing electrons of the present invention has a certain limit on the boiling points of the two solvent components.
  • the boiling point of the first solvent component is relatively high: in a particular embodiment, the first solvent component has a boiling point > 180 °C. In certain embodiments, the first solvent component has a boiling point ⁇ 200 ° C; in certain preferred embodiments, the first solvent component has a boiling point ⁇ 250 ° C; in other preferred embodiments The first solvent component has a boiling point of ⁇ 275 ° C or ⁇ 300 ° C.
  • the boiling points within these ranges are beneficial for preventing nozzle clogging of the inkjet printhead.
  • the second solvent component has a relatively low boiling point: in a particular embodiment, the second solvent component has a boiling point between 100 ° C and 250 ° C. In certain embodiments, the second solvent component has a boiling point between 120 ° C and 225 ° C; in certain embodiments, the second solvent component has a boiling point between 120 ° C and 200 ° C. In other preferred embodiments, the second solvent component has a boiling point between 120 ° C and 180 ° C. The boiling point within these ranges ensures that during the heat drying process after the composition for printing electrons is sprayed onto the substrate, the second solvent component first evaporates to form a saturation of the inorganic nanoparticles in the first solvent component. Or droplets of supersaturated solution.
  • the difference in boiling point of the two solvent components is at least 30 ° C, more preferably 35 ° C, more preferably 40 ° C, still more preferably 45 ° C, and most preferably 50 ° C.
  • the composition for printing electrons of the present invention has limitations on the solubility/dispersibility of the two nano-solvent components to the inorganic nanomaterial.
  • the inorganic nanoparticles have a lower solubility/dispersibility in the first solvent component and a higher solubility/dispersibility in the second solvent component.
  • the solubility/dispersibility of the inorganic nanomaterial in the first solvent component It is not more than 1% by weight, more preferably in the range of 0.1% by weight to 1% by weight, still more preferably in the range of 0.1% by weight to 0.75% by weight, and most preferably in the range of 0.1% by weight to 0.5% by weight.
  • the solubility/dispersibility of the inorganic nanomaterial in the second solvent component is ⁇ 1.5 wt%, more preferably ⁇ 1.75 wt%, more preferably ⁇ 2.0 wt%, and most preferably ⁇ 2.25 wt%.
  • the composition of the present invention has a solubility/dispersibility of the inorganic nanomaterial in the second solvent component that is at least 2 times greater than the first solvent component. .
  • the solubility/dispersibility of the inorganic nanomaterial in the second solvent component is at least 3 times greater than in the first solvent component; in a more preferred embodiment, The solubility/dispersibility of the inorganic nanomaterial in the second solvent component is at least 4 times greater than that in the first solvent component; in a most preferred embodiment, the inorganic nanomaterial is in the second solvent component
  • the solubility/dispersibility in it is at least 5 times greater than in the first solvent component.
  • the solubility/dispersibility, surface tension, and viscosity in the present invention refer to solubility/dispersibility, surface tension, and viscosity at ambient temperature (or working temperature) at the time of printing, unless otherwise specified.
  • the ambient temperature (or working temperature) at the time of printing is generally from 15 to 30 ° C, more preferably from 18 to 28 ° C, still more preferably from 20 to 25 ° C, and most preferably from 23 to 25 ° C.
  • the solubility/dispersibility of the inorganic nano material can be determined by various methods, such as by the following method, but is not limited thereto: 1) preparing a saturated solution of the inorganic nano material in the solvent to be tested, and promoting dissolution by heating or the like. Then, the temperature is lowered to the working temperature; 2) the weight of the inorganic nanomaterial in the saturated solution is measured, and the percentage of the total weight of the solution is calculated, which is the solubility/dispersibility of the contained solvent to the inorganic nanomaterial.
  • Different measurement methods and processes may have a certain influence on solubility/dispersibility. More preferably, all of the solubility/dispersibility should be measured under exactly the same conditions, including the working temperature, heating temperature and time, heating rate, stirring conditions, and the like.
  • the surface tension of at least one solvent component of the composition for printing electrons of the present invention is from 19 dyne/cm to 50 dyne/cm at an operating temperature or at 25 °C. In the range.
  • the surface tension parameters of suitable compositions are suitable for the particular substrate and the particular printing process.
  • the surface tension of the two solvent components at an operating temperature or at 25 ° C is in the range of from about 19 dyne/cm to 50 dyne/cm; in a more preferred embodiment
  • the surface tension of the two solvent components at an operating temperature or at 25 ° C is in the range of from about 22 dyne/cm to 35 dyne/cm; in a most preferred embodiment, the two solvent components are working.
  • the temperature or surface tension at 25 ° C is in the range of about 25 dyne / cm to 33 dyne / cm.
  • the composition for printing electrons of the present invention has a surface tension at an operating temperature or at 25 ° C in the range of from about 19 dyne/cm to 50 dyne/cm; more preferably from 22 dyne/cm to 35dyne/cm range; most preferably in the range of 25dyne/cm to 33dyne/cm.
  • the viscosity of at least one solvent component is in the range of from 1 cPs to 100 cPs at an operating temperature or at 25 °C.
  • the solvent system based on at least two solvent components has a viscosity of less than 100 cps; more preferably less than 50 cps; more preferably from 1.5 to 20 cps; most preferably from 4.0 to 20 cps.
  • Viscosity can also be adjusted by the concentration of inorganic nanomaterials in the composition.
  • the invention includes at least two types
  • the organic solvent component can be conveniently adjusted to the composition for printing electrons in an appropriate range depending on the printing method used.
  • the composition for printing electrons of the present invention comprises a weight ratio of inorganic nanomaterials in the range of 0.3% to 70% by weight, more preferably in the range of 0.5% to 50% by weight, still more preferably 0.5% to 30% by weight.
  • the range of % is most preferably in the range of 0.5% to 10% by weight.
  • the composition for printing electrons of the present invention has a viscosity at 25 ° C in the range of about 1 cps to 100 cps; more preferably in the range of 1 cps to 50 cps; more preferably in the range of 1.5 cps to 20 cps. Range; most preferably in the range of 4.0 cps to 20 cps. Compositions so formulated will be particularly suitable for ink jet printing.
  • compositions based on at least two organic solvent components that satisfies the above boiling point, surface tension parameters, and viscosity parameters facilitates the formation of an inorganic nanomaterial film having uniform thickness and composition properties.
  • the first solvent component comprises from 10% to 70% of the total volume of the solvent
  • the second solvent component comprises from 30% to 90% of the total volume of the solvent. %
  • the amount of the inorganic nano material in the composition and the ratio of the two solvent components satisfy: when the second solvent component is removed, the concentration of the inorganic nano material in the first solvent component should be saturated or supersaturated .
  • the first solvent component comprises from 10% to 60%, more preferably from 20% to 50%, by total volume of the solvent.
  • the second solvent component comprises from 40% to 90%, more preferably from 50% to 80%, by total volume of the solvent.
  • the second solvent component having a low boiling point is rapidly evaporated, leaving a first solvent component having a high boiling point, and at this time, the inorganic nanomaterial is in the first solvent component. In saturated or supersaturated state, this facilitates rapid precipitation of inorganic nanomaterials.
  • the purpose of this is to cause the inorganic nanomaterial to start to precipitate at the early stage of droplet drying, that is, to start sedimentation when most of the solvent has not evaporated, and prevent it from flowing radially in the droplet, such precipitation
  • the process is beneficial to the uniform distribution of inorganic nanomaterials during the drying process, which can effectively reduce the deposition of inorganic nanomaterials at the edges, weaken the "coffee ring effect", and make the dried film have good uniformity and flatness.
  • the composition for printing electrons of the present invention comprises at least one of two organic solvent components, including an aromatic or heteroaromatic based solvent, particularly an aliphatic chain/ring.
  • an aromatic or heteroaromatic based solvent particularly an aliphatic chain/ring.
  • a substituted aromatic solvent, an aromatic ketone solvent, or an aromatic ether solvent is included in the composition for printing electrons of the present invention.
  • the composition for printing electrons of the present invention comprises at least two organic solvent components, and wherein at least one of the organic solvents has the following general formula (I):
  • Ar 1 is an aromatic or heteroaromatic ring having 5 to 10 ring atoms, n ⁇ 0, and R is a substituent.
  • An aromatic group refers to a hydrocarbon group containing at least one aromatic ring, including a monocyclic group and a polycyclic ring system.
  • a heteroaromatic group refers to a hydrocarbon group (containing a hetero atom) comprising at least one heteroaromatic ring, including a monocyclic group and a polycyclic ring system.
  • These multi-ring rings can There are two or more rings in which two carbon atoms are shared by two adjacent rings, a fused ring. At least one of these rings of the polycyclic ring is aromatic or heteroaromatic.
  • examples of the aromatic group may be selected from, but not limited to, benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, anthracene, benzopyrene, triphenylene, anthracene, anthracene, and derivatives thereof. Things.
  • heteroaromatic group may be selected from, but not limited to, furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetra Azole, anthracene, oxazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrol, furanfuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole , pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-naphthyridine, quinoxaline, phenanthridine, pyridine, quinazoline, quinazolinone, and derivatives thereof
  • the composition for printing electrons comprises an organic solvent having the general formula (I), which preferably has a structure represented by the following general formula:
  • X can be CR 1 or N
  • At least one X or Y in each formula is a non-C atom (so-called hetero atom);
  • Ar 1 in the formula (I is preferably selected from any of the following structural units:
  • aromatic or heteroaromatic solvent examples include, but not limited to, p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene.
  • the composition for printing electrons the two organic solvent components contained, at least one of which is an aromatic ketone-based organic solvent.
  • the solvent of the aromatic ketone may be a tetralone.
  • the tetralone involved in the present invention include 1-tetralone and 2-tetralone.
  • the tetralone solvent may comprise a derivative of 1-tetralone and 2-tetralone, ie, a tetralone substituted with at least one substituent.
  • substituents may include an aliphatic group, an aryl group, a heteroaryl group, a halogen, and the like. Specific examples are 2-(phenyl epoxy)tetralone and 6-(methoxy)tetralone, but are not limited thereto.
  • the solvent of the aromatic ketone may be selected from the group consisting of acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone. , 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, but is not limited thereto.
  • the composition for printing electrons the two organic solvent components contained, at least one of which may be a ketone solvent containing no aromatic or heteroaromatic groups, examples of which are: Isophorone, 2,6,8-trimethyl-4-indanone, anthrone, 2-nonanone, 3-fluorenone, 5-fluorenone, 2-nonanone, 2,5-hexanedione , phorone, di-n-pentyl ketone, but is not limited thereto.
  • a ketone solvent containing no aromatic or heteroaromatic groups examples of which are: Isophorone, 2,6,8-trimethyl-4-indanone, anthrone, 2-nonanone, 3-fluorenone, 5-fluorenone, 2-nonanone, 2,5-hexanedione , phorone, di-n-pentyl ketone, but is not limited thereto.
  • composition for printing electrons the two organic solvent components contained, at least one of which is an aromatic ether-based organic solvent.
  • aromatic ether solvent suitable for use in the present invention examples include 3-phenoxytoluene, butoxybenzene, benzylbutylbenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy- 2H-pyran, 1,2-dimethoxy-4-(1-propenyl)benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-dimethoxy Toluene, 4-ethyl ether, 1,2,4-trimethoxybenzene, 4-(1-propenyl)-1,2-dimethoxybenzene, 1,3-dimethoxybenzene, shrinkage Glycerylphenyl ether, dibenzyl ether, 4-tert-butyl anisole, trans-p-propenyl anisole, 1,2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2 - phenoxy
  • the aromatic ether solvent is 3-phenoxytoluene.
  • the composition for printing electrons the two organic solvent components contained, at least one of which may be an ether solvent containing no aromatic or heteroaromatic groups, examples of which are: Pentyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol Alcohol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, but is not limited thereto.
  • Pentyl ether Pentyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene
  • composition for printing electrons may comprise two organic solvent components, at least one of which is an ester-based organic solvent.
  • Possible ester solvents suitable for use in the present invention may be selected from, but not limited to, alkyl octanoate, alkyl sebacate, alkyl stearate, alkyl benzoate, alkyl phenyl acetate, alkyl cinnamate, oxalic acid Ester, alkyl maleate, alkanolide, alkyl oleate, and the like.
  • ester solvent suitable for use in the present invention may be selected from octyl octanoate or diethyl sebacate.
  • one of the two organic solvent components included in the composition of the present invention may be selected from at least one organic solvent selected from, but not limited to, a linear aliphatic or alcohol solvent, for example.
  • a linear alkane such as decane, decane, undecane or dodecane
  • an alcohol such as n-butanol, n-pentanol or n-hexanol
  • an alicyclic group such as decalin or 2-phenoxy.
  • Tetrahydrofuran 1,1'-bicyclohexane, butylcyclohexane, ethyl rosinate, benzyl rosinate, ethylene glycol carbonate, styrene oxide, 3,3,5-trimethylcyclohexanone, cycloheptane Ketone, 2-(phenyl epoxy) tetralone, 6-(methoxy)tetralone, ⁇ -butyrolactone, ⁇ -valerolactone, 6-caprolactone, N, N-di Ethylcyclohexylamine, sulfolane, 2,4-dimethylsulfolane and the like.
  • At least one of the two organic solvent components may be selected from, but not limited to, an aliphatic ketone, for example, 2-nonanone or 3-fluorenone. , 5-fluorenone, 2-nonanone, 2,5-hexanedione, 2,6,8-trimethyl-4-indolone, phorone, di-n-pentyl ketone, etc.; or an aliphatic ether,
  • the composition based on the two organic solvent components may further comprise another organic solvent.
  • another organic solvent include, but are not limited to, methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine , toluene, o-xylene, m-xylene, p-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1, 1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrogen Naphthalene, decalin, hydrazine, etc., or a mixture of any two or more
  • a composition of the invention comprises at least two organic solvent components, each of which may be a mixture of two or more organic solvents.
  • the first solvent component may comprise one or more organic solvents having a higher boiling point and a lower solubility/dispersibility to the inorganic nanomaterial.
  • the second solvent component may also comprise one or more organic solvents having a lower boiling point and a higher solubility/dispersibility to the inorganic nanomaterial.
  • the solvent system based on two organic solvents can effectively disperse functional materials, that is, as a new dispersing solvent to replace the solvent of the conventionally used dispersing functional materials, such as toluene, xylene, chloroform, chlorobenzene, dichlorobenzene, positive Heptane and the like.
  • the composition for printing electrons may additionally include one or more other components such as a surface active compound, a lubricant, a wetting agent, a dispersing agent, a hydrophobic agent, a binder, etc., for adjusting the viscosity. , film forming properties, improved adhesion and the like.
  • the composition for printing electrons can be obtained as a functional film by a variety of printing or coating techniques including, but not limited to, ink jet printing, Nozzle Printing, typography, Screen printing, dip coating, spin coating, blade coating, roller printing, torsion roller printing, lithography, flexographic printing, rotary printing, spray coating, brush coating, pad printing, slit extrusion coating, etc. .
  • Preferred printing techniques are ink jet printing, jet printing and gravure printing.
  • printing inks suitable for inkjet printing need to regulate the surface tension, viscosity, and wettability of the ink so that the ink can be sprayed through the nozzle at an operating temperature (such as room temperature, 25 ° C) without being sprayed. Drying on the nozzle or clogging the nozzle, or forming a continuous, flat and defect-free film on a particular substrate.
  • the composition for printing electrons of the present invention comprises at least one inorganic material, particularly an inorganic material having a certain photoelectric function.
  • the photoelectric function includes, but is not limited to, a hole injection function, a hole transport function, an electron transport function, an electron injection function, an electron blocking function, a hole blocking function, a light emitting function, a main body function, and a light absorbing function.
  • the corresponding functional materials are called hole injection material (HIM), hole transport material (HTM), electron transport material (ETM), electron injecting material (EIM), electron blocking material (EBM), hole blocking material (HBM). ), Emitter, Host and dye.
  • composition for printing electrons of the present invention comprises at least one inorganic nanomaterial.
  • the at least one inorganic nano material is an inorganic semiconductor nanoparticle material.
  • the inorganic nanomaterial has an average particle diameter in the range of about 1 to 1000 nm. In certain preferred embodiments, the inorganic nanomaterials have an average particle size of from about 1 to 100 nm. In certain more preferred embodiments, the inorganic nanomaterials have an average particle size of from about 1 to 20 nm, most preferably from 1 to 10 nm.
  • the inorganic nanomaterials may be selected from different shapes including, but not limited to, different nanotopography such as spheres, cubes, rods, discs, or branched structures, as well as mixtures of particles of various shapes.
  • the inorganic nanomaterial is a quantum dot material having a very narrow, monodisperse size distribution, i.e., the size difference between the particles and the particles is very small.
  • the deviation of the monodisperse quantum dots in size The root mean square is less than 15% rms; more preferably, the deviation of the monodisperse quantum dots in the size is less than 10% rms; optimally, the deviation of the monodispersed quantum dots in the size is less than 5% Rms.
  • the inorganic nanomaterial is a luminescent material.
  • the luminescent inorganic nanomaterial is a quantum dot luminescent material.
  • luminescent quantum dots can illuminate at wavelengths between 380 nanometers and 2500 nanometers.
  • quantum dots having a CdS core have an emission wavelength in the range of about 400 nm to 560 nm; quantum dots having a CdSe core have an emission wavelength in the range of about 490 nm to 620 nm; and a quantum having a CdTe core
  • the illuminating wavelength of the dot is in the range of about 620 nm to 680 nm;
  • the luminescent wavelength of the quantum dot having the InGaP nucleus is in the range of about 600 nm to 700 nm;
  • the luminescent wavelength of the quantum dot having the PbS nucleus is about 800 nm to 2500 In the range of nanometers;
  • the wavelength of the quantum dots having the PbSe core is in the range of about 1200 nm to 2500 nm;
  • the wavelength of the quantum dots having the CuInGaS core is in the range
  • the quantum dot material comprises at least one material capable of emitting blue light having an emission peak wavelength of 450 nm to 460 nm, a green light having an emission peak wavelength of 520 nm to 540 nm, and an emission peak wavelength of 615 nm.
  • the quantum dots contained may be selected from a particular chemical composition, topographical structure, and/or size to achieve light that emits the desired wavelength under electrical stimulation.
  • the narrow particle size distribution of quantum dots enables quantum dots to have a narrower luminescence spectrum. Furthermore, depending on the chemical composition and structure employed, the size of the quantum dots needs to be adjusted accordingly within the above-described size range to achieve the luminescent properties of the desired wavelength.
  • the luminescent quantum dots are semiconductor nanocrystals.
  • semiconductor nanocrystals range in size from about 2 nanometers to about 15 nanometers.
  • the size of the quantum dots needs to be adjusted accordingly within the above-described size range to achieve the luminescent properties of the desired wavelength.
  • the semiconductor nanocrystal comprises at least one semiconductor material, wherein the semiconductor material may be selected from group IV, II-VI, II-V, III-V, III-VI, IV-VI, I of the periodic table. a binary or polyvalent semiconductor compound of Groups III-VI, II-IV-VI, II-IV-V or a mixture of any two or more thereof.
  • the semiconductor material include, but are not limited to, Group IV semiconductor compounds including, for example, elemental Si, Ge, and binary compounds SiC, SiGe; Group II-VI semiconductor compounds, for example, wherein the binary compound includes CdSe, CdTe, CdO, CdS, CdSe, ZnS, ZnSe, ZnTe, ZnO, HgO, HgS, HgSe, HgTe, ternary compounds including CdSeS, CdSeTe, CdSTe, CdZnS, CdZnSe, CdZnTe, CgHgS, CdHgSe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, HgZnS, HgSeSe, and quaternary compounds include CgHgSeS, CdHgSeTe, CgHgSTe, CdZnS, H
  • the luminescent quantum dot comprises a Group II-VI semiconductor material, preferably selected from the group consisting of CdSe, CdS, CdTe, ZnO, ZnSe, ZnS, ZnTe, HgS, HgSe, HgTe, CdZnSe. Or a mixture of any two or more of them. In a suitable embodiment, this material is used as a luminescent quantum dot for visible light due to the relatively mature synthesis of CdSe, CdS.
  • the luminescent quantum dots comprise a III-V semiconductor material, preferably selected from the group consisting of InAs, InP, InN, GaN, InSb, InAsP, InGaAs, GaAs, GaP, GaSb, AlP, AlN, AlAs, Any one of AlSb, CdSeTe, ZnCdSe, or a mixture of any two or more thereof.
  • the luminescent quantum dots comprise a Group IV-VI semiconductor material, preferably selected from the group consisting of PbSe, PbTe, PbS, PbSnTe, Tl 2 SnTe 5 or a mixture of any two or more thereof.
  • the quantum dots are a core-shell structure.
  • the core and the shell respectively comprise one or more semiconductor materials, either identically or differently.
  • the core of the quantum dot may be selected from the group IV, II-VI, II-V, III-V, III-VI, IV-VI, I-III-VI, II of the Periodic Table of the Elements above. a binary or polyvalent semiconductor compound of Group IV-VI, Group II-IV-V.
  • quantum dot nuclei include, but are not limited to, ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, MgS, MgSe, GaAs, GaN, GaP, GaSe, GaSb, HgO, HgS, An alloy of HgSe, HgTe, InAs, InN, InSb, AlAs, AlN, AlP, AlSb, PbO, PbS, PbSe, PbTe, Ge, Si, or a mixture of any two or more thereof.
  • the shell of the quantum dot contains a semiconductor material that is the same as or different from the core.
  • Semiconductor materials that can be used for the shell include Group IV, II-VI, II-V, III-V, III-VI, IV-VI, I-III-VI, II-IV-VI of the Periodic Table of the Elements. Group, II-IV-V binary or multi-component semiconductor compounds.
  • quantum dot nuclei include, but are not limited to, ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, MgS, MgSe, GaAs, GaN, GaP, GaSe, GaSb, HgO, HgS, HgSe, An alloy of HgTe, InAs, InN, InSb, AlAs, AlN, AlP, AlSb, PbO, PbS, PbSe, PbTe, Ge, Si, or a mixture of any two or more thereof.
  • the shell may include a single layer or a multilayer structure.
  • the shell may comprise one or more semiconductor materials that are the same or different from the core.
  • the shell has a thickness of from about 1 to 20 layers. In a more preferred embodiment, the shell has a thickness of about 5 to 10 layers. In some embodiments, two or more shells are included on the surface of the quantum dot core.
  • the semiconductor material used for the shell may have a larger band gap than the core.
  • the shell core has a type I semiconductor heterojunction structure.
  • the semiconductor material used for the shell may have a smaller band gap than the core.
  • the semiconductor material used for the shell may have the same or close atomic crystal structure as the core. Such a choice is beneficial to reduce the stress between the core shells and make the quantum dots more stable.
  • Examples of suitable luminescent quantum dots using a core-shell structure are:
  • Red light CdSe/CdS, CdSe/CdS/ZnS, CdSe/CdZnS, etc.;
  • Green light CdZnSe/CdZnS, CdSe/ZnS, etc.
  • Blue light CdS/CdZnS, CdZnS/ZnS, and the like.
  • a preferred method of preparing quantum dots is a colloidal growth method.
  • the method of preparing monodisperse quantum dots is selected from the group consisting of hot-inject and/or heating-up.
  • the preparation method is contained in the document NanoRes, 2009, 2, 425-447; Chem. Mater., 2015, 27(7), pp 2246-2285.
  • the surface of the quantum dots may comprise an organic ligand.
  • the organic ligand can control the growth process of the quantum dots, regulate the morphology of the quantum dots and reduce the surface defects of the quantum dots, thereby improving the luminous efficiency and stability of the quantum dots.
  • the organic ligand may be selected from, but not limited to, pyridine, pyrimidine, furan, amine, alkylphosphine, alkylphosphine oxide, alkylphosphonic acid or alkylphosphinic acid, alkyl mercaptan, and the like.
  • organic ligands include, but are not limited to, tri-n-octylphosphine, tri-n-octylphosphine oxide, trihydroxypropylphosphine, tributylphosphine, tris(dodecyl)phosphine, dibutyl phosphite , tributyl phosphite, octadecyl phosphite, trilauryl phosphite, tris(dodecyl) phosphite, triisodecyl phosphite, bis(2-ethylhexyl) phosphate, Tris(tridecyl)phosphate, hexadecylamine, oleylamine, octadecylamine, bisoctadecylamine, octadecylamine, bis(2-ethylhexyl)amine, oleyl
  • the surface of the quantum dots may comprise an inorganic ligand.
  • Quantum dots protected by inorganic ligands can be obtained by ligand exchange of organic ligands on the surface of quantum dots. Examples of specific inorganic ligands include, but are not limited to, S 2- , HS - , Se 2- , HSe - , Te 2- , HTe - , TeS 3 2- , OH - , NH 2 - , PO 4 3- , MoO 4 2- , and so on.
  • the quantum dot surface can have one or more of the same or different ligands.
  • the luminescence spectrum exhibited by the monodisperse quantum dots may have a symmetrical peak shape and a narrow half width.
  • the quantum dot has a half-width of light emission of less than 70 nanometers; more preferably, the quantum half-width of the quantum dot is less than 40 nanometers; most preferably, the quantum dot has a half-width of light emission of less than 30 nanometers.
  • the quantum dots have a luminescence quantum efficiency of greater than 10%, more preferably greater than 50%, more preferably greater than 60%, and most preferably greater than 70%.
  • the luminescent semiconductor nanocrystals are nanorods.
  • the properties of nanorods are different from those of spherical nanocrystals.
  • the luminescence of the nanorods is polarized along the long rod axis, while the luminescence of the spherical grains is unpolarized.
  • Nanorods have excellent optical gain characteristics, making them possible to use as laser gain materials.
  • the luminescence of the nanorods can be reversibly turned on and off under the control of an external electric field. These characteristics of the nanorods may be preferably incorporated into the device of the present invention under certain circumstances.
  • the inorganic nanomaterial is a perovskite nanoparticle material, particularly a luminescent perovskite nanoparticle material.
  • the perovskite nanoparticle material may have the structural formula of AMX 3 wherein A may be selected from an organic amine or an alkali metal cation, M may be selected from a metal cation, and X may be selected from an oxygen or a halogen anion.
  • CsPbCl 3 CsPb (Cl/Br) 3 , CsPbBr 3 , CsPb (I/Br) 3 , CsPbI 3 , CH 3 NH 3 PbCl 3 , CH 3 NH 3 Pb (Cl/Br 3 , CH 3 NH 3 PbBr 3 , CH 3 NH 3 Pb(I/Br) 3 , CH 3 NH 3 PbI 3 and the like.
  • the inorganic nanomaterial in the composition for printing electrons of the present invention, is a metal nanoparticle material. Particularly preferred are luminescent metal nanoparticle materials.
  • the metal nanoparticles include, but are not limited to, chromium (Cr), molybdenum (Mo), tungsten (W), ruthenium (Ru), rhenium (Rh), nickel (Ni), silver (Ag), copper (Cu). Nanoparticles such as zinc (Zn), palladium (Pd), gold (Au), hungry (Os), strontium (Re), iridium (Ir), and platinum (Pt).
  • the inorganic nanomaterial has charge transport properties.
  • the inorganic nanomaterial has electron transport capabilities.
  • such inorganic nanomaterials are selected from the group consisting of n-type semiconductor materials.
  • the n-type inorganic semiconductor material may include, but are not limited to, a metal chalcogen compound, a metal phosphorus group compound, or an elemental semiconductor such as a metal oxide, a metal sulfide, a metal selenide, a metal telluride, a metal nitride. , metal phosphide, or metal arsenide.
  • the preferred n-type inorganic semiconductor material may be selected from, but not limited to, any one of ZnO, ZnS, ZnSe, TiO 2 , ZnTe, GaN, GaP, AlN, CdSe, CdS, CdTe, CdZnSe, or any two of them. Kind or a mixture of the above.
  • the inorganic nanomaterial has a hole transporting ability.
  • such inorganic nanomaterials may be selected from p-type semiconductor materials.
  • the inorganic p-type semiconductor material may be any one of NiOx, WOx, MoOx, RuOx, VOx, CuOx, or a mixture of any two or more thereof.
  • the printing ink of the present invention may comprise at least two and two or more inorganic nanomaterials.
  • the composition for printing electrons of the present invention may further comprise at least one organic functional material.
  • organic functional materials for OLEDs including but not limited to hole injection materials (HIM), hole transport materials (HTM), electron transport materials (ETM), electron injecting materials (EIM), electron blocking materials Any one of (EBM), hole blocking material (HBM), illuminator, host material, and organic dye, or a mixture of any two or more thereof, can be used for the printing ink of the present invention in.
  • HIM hole injection materials
  • HTM hole transport materials
  • ETM electron transport materials
  • EIM electron injecting materials
  • EBM electron blocking material
  • illuminator illuminator
  • host material illuminator
  • organic dye or a mixture of any two or more thereof
  • the present invention also relates to a method of preparing a composition for printing electrons as described above, comprising the steps of:
  • the volume percentage of the second solvent component is from 30% to 90% relative to the total volume of the total solvent, and the first and second solvent components are mutually soluble.
  • the dissolution may be assisted by heating, the heating temperature does not exceed 100 ° C, more preferably does not exceed 90 ° C, more preferably does not exceed 80 ° C.
  • the present invention also relates to a method of preparing a film comprising an inorganic nanomaterial by a method of printing or coating, comprising coating a composition for printing electrons according to any one of the above, by printing or coating.
  • a step on the substrate wherein the method of printing or coating may be selected from, but not limited to, inkjet printing, Nozzle Printing, typography, screen printing, dip coating, spin coating, knife coating, Roller printing, torsion roll printing, lithography, flexographic printing, rotary printing, spraying, brushing, pad printing, slit-type extrusion coating, etc.
  • the film comprising the inorganic nanomaterial is prepared by a method of ink jet printing.
  • An inkjet printer for printing inks comprising quantum dots of the present invention may be a commercially available printer and include drop-on-demand printheads. These printers can for example be from Fujifilm Dimatix (Lebanon, NH), Trident International (Brookfield, Conn.), Epson (Torrance, Calif), Hitachi Data systems Corporation (Santa Clara, Calif), Xaar PLC (Cambridge, United Kingdom), and Idanit Technologies, Limited (Rishon Le Zion, Isreal).
  • the present invention can be printed using Dimatix Materials Printer DMP-3000 (Fujifilm).
  • the invention further relates to an electronic device comprising one or more functional films, wherein at least one functional film is prepared using the printing ink composition of the invention, in particular by printing or coating Prepared.
  • Suitable electronic devices include, but are not limited to, quantum dot light emitting diodes (QLEDs), quantum dot photovoltaic cells (QPV), quantum dot luminescent cells (QLEEC), quantum dot field effect transistors (QFETs), quantum dot luminescence field effect transistors, quantum Point laser, quantum dot sensor, etc.
  • QLEDs quantum dot light emitting diodes
  • QPV quantum dot photovoltaic cells
  • QLEEC quantum dot luminescent cells
  • QFETs quantum dot field effect transistors
  • quantum dot luminescence field effect transistors quantum Point laser, quantum dot sensor, etc.
  • the electronic device described above is an electroluminescent device or a photovoltaic cell, as shown in FIG. 1, comprising a substrate (101), an anode (102), and at least one luminescent layer (electroluminescent device). Or a light absorbing layer (photovoltaic cell) (104), a cathode (106).
  • a photovoltaic cell photovoltaic cell
  • 106 cathode
  • the substrate (101) may be opaque or transparent. Transparent substrates can be used to make transparent light-emitting components.
  • the substrate can be rigid or elastic.
  • the substrate can be plastic, metal, semiconductor wafer or glass. Most preferably, the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice.
  • the substrate may be selected from polymeric films or plastics having a glass transition temperature Tg of 150 ° C or higher, more preferably more than 200 ° C, more preferably more than 250 ° C, and most preferably more than 300 ° C. Examples of suitable substrates are poly(ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN), but are not limited thereto.
  • the anode (102) may comprise a conductive metal or metal oxide, or a conductive polymer.
  • the anode can easily inject holes into the HIL or HTL or the luminescent layer.
  • the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the p-type semiconductor material as the HIL or HTL is less than 0.5 eV, more preferably less than 0.3 eV, and most preferably less than 0.2eV.
  • Examples of anode materials include, but are not limited to, Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like.
  • anode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
  • a suitable physical vapor deposition process including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
  • the anode is patterned.
  • Patterned ITO conductive substrates are commercially available and can be used to prepare devices in accordance with the present invention.
  • the cathode (106) can comprise a conductive metal or metal oxide.
  • the cathode can easily inject electrons into the EIL or ETL or directly into the luminescent layer.
  • the absolute value of the difference between the work function of the cathode and the LUMO level or conduction band level of the n-type semiconductor material as EIL or ETL or HBL is less than 0.5 eV, more preferably less than 0.3 eV, most preferably It is less than 0.2eV.
  • all materials which can be used as cathodes for OLEDs are possible as cathode materials for the devices of the invention.
  • cathode material examples include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, and the like.
  • the cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
  • the luminescent layer (104) may include at least one layer of luminescent functional material having a thickness between 2 nm and 200 nm.
  • the light-emitting layer is prepared by printing the printing ink of the present invention, wherein the printing ink comprises at least one of the above-mentioned light-emitting functional inorganic nano-materials. Especially quantum dots.
  • the light emitting device of the present invention further comprises a hole injection layer (HIL) or a hole transport layer (HTL) (103) containing the organic HTM or inorganic p type as described above. material.
  • HIL hole injection layer
  • HTL hole transport layer
  • the HIL or HTL can be prepared by printing the printing ink of the present invention, wherein the printing ink contains an inorganic nanomaterial having a hole transporting ability.
  • the electroluminescent device of the present invention further comprises an electron injection layer (EIL) or electron transport layer (ETL) (105) comprising organic ETM or inorganic n as described above.
  • EIL electron injection layer
  • ETL electron transport layer
  • the EIL or ETL can be prepared by printing the printing ink of the present invention, wherein the printing ink contains an inorganic nanomaterial having electron transporting ability.
  • the invention further relates to the use of the electroluminescent device of the invention in various applications, including, but not limited to, various display devices, backlights, illumination sources, and the like.
  • n-hexane was added to the three-necked flask, and then the liquid in the three-necked flask was transferred to a plurality of 10 mL centrifuge tubes, centrifuged to remove the lower layer precipitate, and repeated three times; acetone was added to the liquid after the post-treatment 1 to precipitate Centrifuge, remove the supernatant, leave a precipitate; then dissolve the precipitate with n-hexane, add acetone to precipitate, centrifuge, remove the supernatant, leave a precipitate, repeat three times; finally dissolve the precipitate with toluene, transfer to glass Stored in the bottle.
  • solution 1 Weigh 0.0079 g of selenium and 0.1122 g of sulfur in a 25 mL single-necked flask, measure 2 mL of TOP, pass nitrogen, stir, and reserve, hereinafter referred to as solution 1; weigh 0.0128 g of CdO and 0.3670 g of zinc acetate. Take 2.5mL of OA in a 25mL three-necked flask, plug the two sides of the bottle with a rubber stopper, connect a condenser tube at the top, connect to the double-row tube, place the three-necked flask in a 50mL heating jacket, and vacuum the nitrogen.
  • quantum dots were precipitated from the solution with acetone and centrifuged to obtain a quantum dot solid.
  • 0.5 g of quantum dot solids were weighed in a glove box, and added to 3.8 g of 3-phenoxytoluene (boiling point 272 ° C) to be dispersed, and then 5.7 g of o-xylene (boiling point 144 ° C) was added to the quantum dot dispersion, and stirred.
  • Mixing weight ratio of 3-phenoxytoluene to o-xylene in the mixed solvent was 40:60). After stirring at a temperature of 60 ° C until the quantum dots were completely dissolved, it was cooled to room temperature.
  • the obtained quantum dot solution was filtered through a 0.2 ⁇ m PTFE filter. Seal and store.
  • quantum dot solids were weighed in a glove box, and added to 3.8 g of cyclohexylbenzene (boiling point 238 ° C) to be dispersed, and then 5.7 g of o-xylene (boiling point 144 ° C) was added to the quantum dot dispersion, and the mixture was stirred and mixed ( The weight ratio of cyclohexylbenzene to ortho-xylene in the mixed solvent was 40:60). After stirring at a temperature of 60 ° C until the quantum dots were completely dissolved, it was cooled to room temperature. The obtained quantum dot solution was filtered through a 0.2 ⁇ m PTFE filter. Seal and store.
  • Example 7 Preparation of ZnO nanoparticle printing ink containing 1-tetralone and n-butanol
  • the viscosity of the nanoparticle ink was tested by a DV-I Prime Brookfield rheometer; the surface tension of the nanoparticle ink was tested by a SITA bubble pressure tomometer.
  • the functional layer in the light-emitting diode such as the light-emitting layer and the charge transport layer, can be prepared by inkjet printing using the composition of the inorganic nano-material based on the two organic solvent components prepared above, and the specific steps are as follows.
  • the composition comprising the inorganic nanomaterial is loaded into an ink tank which is assembled to an ink jet printer such as Dimatix Materials Printer DMP-3000 (Fujifilm).
  • the waveform, pulse time and voltage of the jetted ink are adjusted to optimize ink jetting and to stabilize the ink jet range.
  • the substrate of the QLED is a 0.7 mm thick glass sputtered with an indium tin oxide (ITO) electrode pattern.
  • ITO indium tin oxide
  • the HIL/HTL material is then inkjet printed into the well and the solvent is removed by drying at elevated temperature in a vacuum to obtain a HIL/HTL film.
  • the printing ink containing the luminescent functional material is ink-jet printed onto the HIL/HTL film, and the solvent is removed by drying at a high temperature in a vacuum atmosphere to obtain a luminescent layer film.
  • a printing ink containing a functional material having electron transporting properties is ink-jet printed onto the luminescent layer film, and the solvent is removed by drying at a high temperature in a vacuum atmosphere to form an electron transport layer (ETL).
  • ETL electron transport layer
  • ETL electron transport layer

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention concerne une composition destinée à l'impression d'un dispositif électronique comprenant : au moins un nanomatériau minéral ; et au moins deux constituants solvants organiques. Le premier constituant solvant organique a un point d'ébullition supérieur à 180 °C, et une solubilité/dispersibilité du nanomatériau minéral dans le premier constituant solvant organique est inférieure ou égale à 1 % en poids. Le second constituant solvant organique a un point d'ébullition compris entre 100 °C et 250 °C, et la solubilité/dispersibilité du nanomatériau minéral dans le second constituant solvant organique est supérieure ou égale à 1,5 % en poids. Le premier constituant solvant organique et le second constituant solvant organique sont mutuellement solubles, et les deux constituants solvants organiques peuvent s'évaporer à partir d'un système de solvants pour former un film mince formé du nanomatériau minéral. La composition est applicable à des dispositifs optoélectroniques, et plus particulièrement à des dispositifs électroluminescents. L'invention concerne également un dispositif électronique fabriqué au moyen de cette composition.
PCT/CN2016/099784 2015-11-12 2016-09-23 Composition pour l'impression de dispositif électronique et son utilisation dans un dispositif électronique WO2017080317A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201680059822.4A CN108137969A (zh) 2015-11-12 2016-09-23 用于印刷电子的组合物及其在电子器件中的应用

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201510771727 2015-11-12
CN201510771727.4 2015-11-12

Publications (1)

Publication Number Publication Date
WO2017080317A1 true WO2017080317A1 (fr) 2017-05-18

Family

ID=58694728

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2016/099784 WO2017080317A1 (fr) 2015-11-12 2016-09-23 Composition pour l'impression de dispositif électronique et son utilisation dans un dispositif électronique

Country Status (2)

Country Link
CN (1) CN108137969A (fr)
WO (1) WO2017080317A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109651887A (zh) * 2018-11-15 2019-04-19 苏州星烁纳米科技有限公司 钙钛矿量子点墨水及发光膜
CN110041758A (zh) * 2019-04-22 2019-07-23 京东方科技集团股份有限公司 钙钛矿纳米晶墨水、电致发光器件及制备方法
CN110270485A (zh) * 2019-06-11 2019-09-24 南京邮电大学 一种钙钛矿纳米颗粒厚膜的制备方法
EP3546532A4 (fr) * 2016-11-23 2019-12-04 Guangzhou Chinaray Optoelectronic Materials Ltd. Composition d'encre d'impression, son procédé de préparation et ses utilisations
CN111370495A (zh) * 2018-12-26 2020-07-03 Tcl集团股份有限公司 薄膜晶体管有源层墨水及一种薄膜晶体管的制备方法
CN114106623A (zh) * 2020-12-15 2022-03-01 广东聚华印刷显示技术有限公司 量子点墨水、量子点薄膜、电致发光二极管及显示器件
CN116218283A (zh) * 2023-04-13 2023-06-06 义乌清越光电技术研究院有限公司 一种用于tfb空穴传输层的量子点墨水及其应用

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200006652A (ko) 2018-07-10 2020-01-21 삼성디스플레이 주식회사 잉크조성물, 그 제조 방법, 및 이를 이용한 양자점-폴리머 복합체 패턴 제조방법
CN113122070A (zh) * 2019-12-31 2021-07-16 Tcl集团股份有限公司 组合物及其制备方法和发光二极管
CN113130791A (zh) * 2019-12-31 2021-07-16 Tcl集团股份有限公司 复合材料及其制备方法、发光二极管和制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102408776A (zh) * 2010-08-24 2012-04-11 精工爱普生株式会社 成膜用油墨、成膜方法、液滴喷出装置、发光元件的制造方法、发光元件、发光装置及电子设备
CN102916097A (zh) * 2011-08-01 2013-02-06 潘才法 一种电致发光器件
CN105038408A (zh) * 2015-08-14 2015-11-11 广州华睿光电材料有限公司 印刷油墨及应用其印刷而成的电子器件

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102145424B1 (ko) * 2013-11-11 2020-08-18 엘지디스플레이 주식회사 표시장치 제조용 잉크 및 이를 이용한 표시장치의 제조방법

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102408776A (zh) * 2010-08-24 2012-04-11 精工爱普生株式会社 成膜用油墨、成膜方法、液滴喷出装置、发光元件的制造方法、发光元件、发光装置及电子设备
CN102916097A (zh) * 2011-08-01 2013-02-06 潘才法 一种电致发光器件
CN105038408A (zh) * 2015-08-14 2015-11-11 广州华睿光电材料有限公司 印刷油墨及应用其印刷而成的电子器件

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11248138B2 (en) 2016-11-23 2022-02-15 Guangzhou Chinaray Optoelectronic Materials Ltd. Printing ink formulations, preparation methods and uses thereof
EP3546532A4 (fr) * 2016-11-23 2019-12-04 Guangzhou Chinaray Optoelectronic Materials Ltd. Composition d'encre d'impression, son procédé de préparation et ses utilisations
CN109651887A (zh) * 2018-11-15 2019-04-19 苏州星烁纳米科技有限公司 钙钛矿量子点墨水及发光膜
CN109651887B (zh) * 2018-11-15 2022-06-10 苏州星烁纳米科技有限公司 钙钛矿量子点墨水及发光膜
CN111370495A (zh) * 2018-12-26 2020-07-03 Tcl集团股份有限公司 薄膜晶体管有源层墨水及一种薄膜晶体管的制备方法
CN111370495B (zh) * 2018-12-26 2022-05-03 Tcl科技集团股份有限公司 薄膜晶体管有源层墨水及一种薄膜晶体管的制备方法
CN110041758A (zh) * 2019-04-22 2019-07-23 京东方科技集团股份有限公司 钙钛矿纳米晶墨水、电致发光器件及制备方法
WO2020215864A1 (fr) * 2019-04-22 2020-10-29 京东方科技集团股份有限公司 Encre nanocristalline de pérovskite, dispositif électroluminescent et procédé de préparation
CN110270485A (zh) * 2019-06-11 2019-09-24 南京邮电大学 一种钙钛矿纳米颗粒厚膜的制备方法
CN114106623A (zh) * 2020-12-15 2022-03-01 广东聚华印刷显示技术有限公司 量子点墨水、量子点薄膜、电致发光二极管及显示器件
CN114106623B (zh) * 2020-12-15 2023-04-07 广东聚华印刷显示技术有限公司 量子点墨水、量子点薄膜、电致发光二极管及显示器件
CN116218283A (zh) * 2023-04-13 2023-06-06 义乌清越光电技术研究院有限公司 一种用于tfb空穴传输层的量子点墨水及其应用
CN116218283B (zh) * 2023-04-13 2024-04-05 义乌清越光电技术研究院有限公司 一种用于tfb空穴传输层的量子点墨水及其应用

Also Published As

Publication number Publication date
CN108137969A (zh) 2018-06-08

Similar Documents

Publication Publication Date Title
WO2017028639A1 (fr) Encre d'impression et dispositif électronique fabriqué par impression avec celle-ci
WO2017028640A1 (fr) Composition d'encre d'impression et dispositif électronique
WO2017028638A1 (fr) Encre d'impression et dispositif électronique
WO2017080317A1 (fr) Composition pour l'impression de dispositif électronique et son utilisation dans un dispositif électronique
EP3546532B1 (fr) Composition d'encre d'impression, son procédé de préparation et ses utilisations
WO2017080325A1 (fr) Composition d'impression et application associée
US20180331312A1 (en) Electroluminescent device, preparation method thereof, and ink formulation
WO2018095380A1 (fr) Composition pour composant électronique imprimé, son procédé de préparation, et utilisations associées
WO2017080323A1 (fr) Composition d'impression et son application
WO2017080307A1 (fr) Composition pour l'impression de dispositifs électroniques et son application dans des dispositifs électroniques
US20180346748A1 (en) Formulation for printing electronic device and application thereof in electronic device
WO2018103747A1 (fr) Polymère et dispositif electroluminescent
US11555128B2 (en) Printing composition, electronic device comprising same and preparation method for functional material thin film
CN108137972B (zh) 印刷电子组合物、包含其的电子器件及功能材料薄膜的制备方法
WO2017080316A1 (fr) Composition pour composants électroniques imprimés et son utilisation dans un dispositif électronique
WO2017080324A1 (fr) Composition d'impression contenant un nanomatériau inorganique et application correspondante
CN116606568A (zh) 量子点墨组合物和量子点电致发光器件

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16863494

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16863494

Country of ref document: EP

Kind code of ref document: A1