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WO2017080316A1 - 用于印刷电子的组合物及其在电子器件中的应用 - Google Patents

用于印刷电子的组合物及其在电子器件中的应用 Download PDF

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WO2017080316A1
WO2017080316A1 PCT/CN2016/099783 CN2016099783W WO2017080316A1 WO 2017080316 A1 WO2017080316 A1 WO 2017080316A1 CN 2016099783 W CN2016099783 W CN 2016099783W WO 2017080316 A1 WO2017080316 A1 WO 2017080316A1
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group
printing
composition
organic
atoms
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PCT/CN2016/099783
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English (en)
French (fr)
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潘君友
杨曦
何锐锋
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广州华睿光电材料有限公司
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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 KR1020187016327A priority Critical patent/KR20180083889A/ko
Priority to CN201680059869.0A priority patent/CN108137971B/zh
Priority to US15/775,396 priority patent/US20180320066A1/en
Publication of WO2017080316A1 publication Critical patent/WO2017080316A1/zh

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    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
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    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
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    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
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Definitions

  • the present invention relates to a composition suitable for printing electronics and its use in printed electronic devices, particularly in electroluminescent devices.
  • the organic light-emitting diode which is a new-generation display technology
  • OLED organic light-emitting diode
  • FMM fine mask
  • Low yield In order to solve the above problems, techniques for realizing high-resolution full-color display using a printing process have received increasing attention. For example, inkjet printing can produce functional material films in a large area and at low cost. Compared with traditional semiconductor production processes, inkjet printing has low energy consumption, low water consumption, and environmental protection, and is a production technology with great advantages and potential.
  • QLED quantum dot light-emitting diode
  • Organic semiconductor materials have gained widespread attention and significant progress in their use in electronic and optoelectronic devices due to their solution processability.
  • Solution processability allows the organic functional material to form a thin film of the functional material in the device by certain coating and printing techniques. Such a technology can effectively reduce the processing cost of electronic and optoelectronic devices, and meet the process requirements of large-area preparation.
  • KATEEVA discloses an ester solvent-based organic small molecule material ink for printing OLEDs (US2015044802A1)
  • UNIVERSALDISPLAYCORPORATION discloses a A printable organic small molecular material ink based on an aromatic ketone or an aromatic ether solvent (US20120205637)
  • SEIKOEPSON CORPORATION discloses a printable organic polymer material ink based on a substituted benzene derivative solvent.
  • printing inks involving organic functional materials are: CN102408776A, CN103173060A, CN103824959A, CN1180049C, CN102124588B, US2009130296A1, US2014097406A1, and the like.
  • 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.
  • countries are studying the application of quantum dots in full color, mainly in the display field.
  • quantum light-emitting devices QLEDs
  • QLEDs quantum light-emitting devices
  • NanocoTechnologies Ltd. discloses a method of printing a printable ink formulation comprising nanoparticles (CN101878535B).
  • Printable nanoparticle inks and corresponding nanoparticle-containing films are obtained by selecting suitable solvents such as toluene and dodecyl selenol; Samsung Electronics discloses a quantum dot ink for inkjet printing ( US8765014B2).
  • 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 is obtained by printing the ink, and a quantum dot electroluminescent device is prepared;
  • QD Vision QDVision, Inc. discloses a quantum dot ink preparation comprising a host material and a quantum dot material.
  • an additive US2010264371A1.
  • these quantum dot inks contain Its additives, such as alcohol polymers.
  • additives such as alcohol polymers.
  • 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.
  • One of the objects of the present invention is to provide a composition for electronic printing.
  • a composition for printing electrons comprising at least one functional material and a solvent system comprising at least one organic solvent, the organic solvent comprising at least one organic based on heteroaromatic and having the general formula (I) Solvent:
  • Ar 1 is a heteroaromatic ring having 5 to 10 carbon atoms, n is an integer greater than or equal to 0, and R is a substituent characterized by being heteroaromatic-based and having an organic solvent of the formula (I)
  • the boiling point is ⁇ 150 ° C and can be evaporated from the solvent system to form a film containing the inorganic nanomaterial.
  • the composition for printing electrons has a viscosity based on a heteroaromatic and organic solvent of the formula (I) at 25 ° C in the composition for printing electrons described above. , in the range of 1cPs to 100cPs.
  • the composition for printing electrons is used in a composition for printing electrons as described above, the organic solvent based on heteroaromatic and having the general formula (I) at 25 ° C Surface tension, in the range of 19 dyne/cm to 50 dyne/cm.
  • the composition for printing electrons in the composition for printing electrons described above, the organic solvent based on heteroaromatic and having the general formula (I) has a general formula selected from the group consisting of The structure shown in either one:
  • X is CR 1 or N
  • At least one X or Y in each formula is a non-C atom (so-called hetero atom);
  • composition for printing electrons in the composition for printing electrons described above, the Ar 1 in the formula (I) is selected from any one of the following structural units:
  • R in the formula (I) is selected from the group consisting of a linear alkyl group having 1 to 20 C atoms, an alkoxy group or a thioalkyl group.
  • the heteroaromatic based organic solvent having the general formula (I) is selected from the group consisting of: 2-phenylpyridine, 3-phenylpyridine, 4 -(3-phenylpropyl)pyridine, quinoline, isoquinoline, 8-hydroxyquinoline, methyl 2-furancarboxylate, ethyl 2-furancarboxylate or a mixture of any two or more thereof.
  • the solvent system may be a mixed solvent further comprising at least one other solvent, and the Organic of formula (I) The solvent accounts for more than 50% of the total weight of the mixed solvent.
  • the composition for printing electrons is in the composition for printing electrons described above, the functional material being an inorganic nano material.
  • the composition for printing electrons is used in a composition for printing electrons as described above, the functional material being a quantum dot material, that is, a particle size having a monodisperse size distribution, a shape thereof It can be selected from different nanotopography such as spheres, cubes, rods or branched structures.
  • the functional material being a quantum dot material, that is, a particle size having a monodisperse size distribution, a shape thereof It can be selected from different nanotopography such as spheres, cubes, rods or branched structures.
  • the composition for printing electrons is a composition for printing electrons as described above, the functional material being a luminescent quantum dot material having an emission wavelength between 380 nm and 2500 nm.
  • the composition for printing electrons includes the inorganic functional material selected from the group consisting of: Group IV, II- Binary or multi-component semiconductor compounds of group VI, II-V, III-V, III-VI, IV-VI, I-III-VI, II-IV-VI, II-IV-V Any one of them, or a mixture of any two or more thereof.
  • the composition for printing electrons is used in a composition for printing electrons as described above, the functional material being a perovskite nanoparticle material, preferably a luminescent perovskite nanomaterial, a metal A nanoparticle material, a metal oxide nanoparticle material, or a mixture of any two or more thereof.
  • the composition for printing electrons is used in a composition for printing electrons as described above, the functional material being an organic functional material.
  • the composition for printing electrons is used in a composition for printing electrons as described above, and the organic functional material may be selected from a hole injection material (HIM), a hole transport material (HTM). ), electron transport material (ETM), electron injecting material (EIM), electron blocking material (EBM), hole blocking material (HBM), illuminator (Emitter), host material (Host), and organic dye , or a mixture of any two or more thereof.
  • HIM hole injection material
  • HTM hole transport material
  • ETM electron transport material
  • EIM electron injecting material
  • EBM electron blocking material
  • HBM hole blocking material
  • Emitter illuminator
  • host material Host
  • organic dye or a mixture of any two or more thereof.
  • the composition for printing electrons is described above for use in a composition for printing electrons, the organic functional material comprising at least one host material and at least one illuminant.
  • the composition for printing electrons described above is characterized in that the functional material accounts for 0.3% to 30% by weight of the composition for printing electrons, and the solvent system is included.
  • the weight percentage of the composition for printing electrons is 70% to 99.7%.
  • the present invention also provides an electronic device comprising a functional layer printed or coated by any of the compositions described above, wherein the organic solvent based on heteroaromatic and having the general formula (I) is included Evaporation from the solvent system to form a functional film.
  • the electronic device described above wherein the electronic device may be selected from the group consisting of: a quantum dot light emitting diode (QLED), a quantum dot photovoltaic cell (QPV), a quantum dot light emitting cell (QLEEC), a quantum dot field effect.
  • Tube QFET
  • quantum dot luminescence field effect transistor quantum dot laser, quantum dot sensor
  • organic light emitting diode OLED
  • organic photovoltaic cell OLED
  • OLED organic light emitting cell
  • OFEC organic light emitting cell
  • OFET organic field effect transistor
  • organic Luminescent field effect transistors organic lasers, and organic sensors.
  • the present invention also provides a method for preparing a film of a functional material, wherein a coating according to any of the above-described compositions is applied 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 (NozzlePrinting), typography, screen printing, dip coating, spin coating, blade coating, roller printing, torsion roll printing, lithography, flexographic printing, rotary printing , spraying, brushing, pad printing, slit type extrusion coating, etc.
  • the present invention also provides a printing process for a composition for printing electrons as described above and its use in electronic devices, particularly in electroluminescent devices.
  • the invention has the beneficial effects that the composition for printing electrons 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, so as to facilitate Print and form a film with a uniform surface.
  • 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 provides a printing ink for preparing a high quality functional film, particularly a printing ink comprising quantum dots and an organic semiconductor material, which provides an excellent 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.
  • the present invention provides a composition for printing electrons, and also relates to a printing process of the composition and its use in electronic devices, particularly in optoelectronic devices, especially in electroluminescent devices.
  • the invention still further relates to electronic devices made using such compositions.
  • composition for printing electrons of the present invention and the term printing ink, or ink, have the same meaning and are interchangeable.
  • composition for printing electrons comprising at least one functional material and a solvent system comprising at least one organic solvent, the organic solvent comprising at least one heteroaromatic based And having the organic solvent of the formula (I):
  • Ar 1 is a heteroaromatic ring having 5 to 10 carbon atoms, n is an integer greater than or equal to 0, and R is a substituent characterized in that the organic solvent having a heteroaromatic group and having the general formula (I) has a boiling point ⁇ 120 ° C and can be evaporated from the solvent system to form a film of functional material.
  • Ar 1 is a heteroaromatic ring having 5 to 10 carbon atoms.
  • 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 polycyclic rings may have 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 a heteroaromatic group.
  • 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-diazine, quinoxaline, Phenanthrene, benzidine, quinazoline, quinazolinone, and derivatives thereof.
  • the total number of atoms other than H in all substituents R in formula (I) as described above is greater than or equal to two.
  • the atoms other than H in all the substituents R described herein include atoms of C, Si, N, P, O, S, F, Cl, Br, I, etc., but are not limited thereto.
  • a methoxy substituent and two chlorine substituents thereof and the like are within the scope of the present invention.
  • the total number of atoms other than H in all substituents R is greater than or equal to 2, preferably from 2 to 20, more preferably from 2 to 10, most preferably from 3 to 10.
  • the composition for printing electrons of the present invention comprises a heteroaromatic-based organic solvent having the general formula (I) which may have a structure represented by the following 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);
  • the composition for printing electrons according to the present invention comprises a heteroaromatic-based organic solvent having the general formula (I), wherein Ar 1 is preferred from Any of the following structural units:
  • organic solvent based on heteroaromatic and having the general formula (I) for dissolving functional materials, the boiling point parameters of which are to be taken into consideration when selecting.
  • the organic solvent based on heteroaromatic and having the general formula (I) has a boiling point > 150 °C.
  • the organic solvent based on heteroaromatic and having the general formula (I) has a boiling point of ⁇ 180 ° C; In some embodiments, the organic solvent based on heteroaromatic and having the general formula (I) has a boiling point ⁇ 200 ° C; in certain embodiments, the organic solvent based on heteroaromatic and having the general formula (I) Its boiling point is ⁇ 250 ° C; in other preferred embodiments, the organic solvent based on heteroaromatic and having the general formula (I) 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 organic solvent based on heteroaromatic and having the general formula (I) can be evaporated from a solvent system to form a film comprising a functional material.
  • the composition for printing electrons according to the invention comprises a heteroaromatically based heteroaromatic compound having the general formula (I) and having an organic solvent of the formula (I)
  • the surface tension at 25 ° C is in the range of 19 dyne / cm to 50 dyne / cm.
  • an organic solvent based on heteroaromatics and having the general formula (I) for dissolving functional materials the surface tension parameters of which are to be taken into consideration when selecting. Suitable ink surface tension parameters are suitable for a particular substrate and a particular printing method.
  • the heteroaromatic based organic solvent of formula (I) has a surface tension at 25 ° C in the range of from about 19 dyne / cm to 50 dyne / cm;
  • the organic solvent based on heteroaromatic and having the general formula (I) has a surface tension at 25 ° C in the range of from about 22 dyne / cm to 35 dyne / cm;
  • the organic solvent based on heteroaromatic and having the general formula (I) has a surface tension at 25 ° C in the range of from about 25 dyne/cm to 33 dyne/cm.
  • the ink of the present invention has a surface tension at 25 ° C in the range of about 19 dyne / cm to 50 dyne / cm; more preferably in the range of 22 dyne / cm to 35 dyne / cm; It is preferably in the range of 25 dyne/cm to 33 dyne/cm.
  • a composition according to the present invention wherein the organic solvent based on heteroaromatic and having the general formula (I) has a viscosity at 25 ° C in the range of 1 cPs to 100 cPs.
  • the viscosity parameter of the ink is taken into consideration when selecting.
  • the viscosity can be adjusted by different methods, such as by the selection of a suitable organic solvent and the concentration/weight ratio of the functional material in the ink.
  • the content of the solvent system of the present invention containing a heteroaromatic based organic solvent having the general formula (I) in the printing ink can be conveniently adjusted to an appropriate range in accordance with the printing method used.
  • the composition for printing electrons according to the present invention comprises a functional material in a weight ratio of 0.3% to 30% by weight, more preferably 0.5% by weight of the composition for printing electrons.
  • the organic solvent based on heteroaromatic and having the general formula (I) has a viscosity of less than 100 cps; in a more preferred embodiment, the heteroaromatic based and general formula The organic solvent of (I) has a viscosity of less than 50 cps; in a most preferred embodiment, the heteroaromatic based organic solvent of the formula (I) has a viscosity of from 1.5 to 20 cps.
  • the viscosity herein refers to the viscosity at ambient temperature at the time of printing, and is generally 15 to 30 ° C, more preferably 18 to 28 ° C, still more preferably 20 to 25 ° C, and most preferably 23 to 25 ° C.
  • Compositions so formulated will be particularly suitable for ink jet printing.
  • the composition for printing electrons of the present invention has a viscosity at 25 ° C of about 1 cps to 100 cps when it is formulated according to the above ratio; more preferably at 1 cps. Up to the range of 50 cps; most preferably in the range of 1.5 cps to 20 cps.
  • the resulting ink is capable of forming a thin film of functional material having uniform thickness and compositional properties.
  • heteroaromatic-based organic solvent of the formula (I) are, but not limited to, 2-phenylpyridine, 3-phenylpyridine, 4-(3-phenylpropyl)pyridine , quinoline, isoquinoline, methyl 2-furancarboxylate, ethyl 2-furancarboxylate, and the like.
  • the printing inks of the present invention comprise a single heteroaromatic based organic solvent of formula (I), preferably quinoline or isoquinoline.
  • the printing inks of the present invention comprise a mixture of two or more heteroaromatic based organic solvents of formula (I).
  • the printing ink of the present invention comprises an organic solvent which is a mixture of quinoline and isoquinoline.
  • the printing inks of the present invention comprise an organic solvent based on heteroaromatic and having the general formula (I) and at least one other solvent, and are heteroaromatic based and have a general formula
  • the organic solvent of (I) accounts for 50% or more of the total weight of the mixed solvent.
  • the organic solvent represented by the general formula (I) is at least 70% by weight based on the total weight of the solvent; more preferably, the organic solvent based on heteroaromatic and having the general formula (I) accounts for at least 80% by weight based on the total weight of the mixed solvent. %.
  • the organic solvent based on heteroaromatic and having the general formula (I) comprises at least 90% by weight based on the total weight of the mixed solvent, or the mixed solvent consists essentially of an organic solvent based on heteroaromatic and having the general formula (I), Or consists entirely of an organic solvent based on heteroaromatics and having the general formula (I).
  • another organic solvent as described above is selected from the group consisting of an optionally substituted or unsubstituted aromatic solvent.
  • the printing inks of the present invention comprise an organic solvent which is a mixture of quinoline and dodecylbenzene.
  • the printing inks of the present invention comprise an organic solvent which is a mixture of isoquinoline and dodecylbenzene.
  • the printing inks of the present invention comprise an organic solvent which is a mixture of quinoline and 3-phenoxytoluene.
  • the printing inks of the present invention comprise an organic solvent which is a mixture of isoquinoline and 3-phenoxytoluene.
  • examples of another organic solvent as described above include, but are not limited to, methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-di Chlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane Alkane, 3-phenoxytoluene, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethyl Acetamide, dimethyl sulfoxide, tetrahydronaphthalene, decalin, hydrazine, or a mixture of any two or more thereof.
  • the heteroaromatic-based solvent system of the present invention is capable of effectively dissolving functional materials, that is, a solvent for replacing a conventionally used dissolving functional material as a new solvent, such as toluene, xylene, chloroform, chlorobenzene, dichlorobenzene, positive Heptane and the like.
  • the printing ink may further comprise one or more components, such as surface active compounds, lubricants, wetting agents, dispersing agents, hydrophobic agents, adhesives, etc., for adjusting viscosity, film forming properties, and improving adhesion. Wait.
  • components such as surface active compounds, lubricants, wetting agents, dispersing agents, hydrophobic agents, adhesives, etc., for adjusting viscosity, film forming properties, and improving adhesion. Wait.
  • the printing ink can be deposited to obtain a functional film by a variety of printing or coating techniques including, but not limited to, ink jet printing, inkjet printing, letterpress printing, screen printing, dip coating. , spin coating, blade coating, roller printing, torsion roller printing, lithography, flexographic printing, rotary printing, spraying, brushing, pad printing, slit-type extrusion coating, and the like.
  • Preferred printing techniques are ink jet printing, jet printing and gravure printing.
  • HelmutKipphan's Printing Media Handbook: Techniques and Production Methods" (Hand book of Print Media: Technologies and Production Methods).
  • printing inks suitable for inkjet printing require adjustment of the surface tension, viscosity, and wettability of the ink so that the ink can be ejected through the nozzle at a printing 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.
  • composition for printing electrons of the present invention comprises at least one functional material.
  • the functional material preferably refers to a material having certain photoelectric functions.
  • Photoelectric functions include, but are not limited to, hole injection function, hole transport function, electron transport function, electron injection function, electron blocking function, hole blocking function, light emitting function, main body function, and 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 organic dyes.
  • the functional material may be an organic material or an inorganic material.
  • the composition for printing electrons of the present invention comprises at least one functional material that is an inorganic nanomaterial.
  • the 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 is less than 15% rms; more preferably, the deviation of the monodisperse quantum dots in size is less than 10% rms; most preferably, monodisperse Quantum dots have a root mean square deviation of less than 5% rms in size.
  • 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 dots comprise 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 any two or The above mixture.
  • this material can be 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, 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 core-shell structures.
  • 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, HgSe, HgTe, InAs, InN, InSb, AlAs, AlN, AlP, AlSb, PbO, PbS, PbSe, PbTe, Ge, Si, or an alloy thereof 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, HgTe, InAs, InN, InSb, AlAs, AlN, AlP, AlSb, PbO, PbS, PbSe, PbTe, Ge, Si, or an alloy thereof 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, etc.
  • 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 is a metal nanoparticle material, preferably a luminescent metal nanoparticle material.
  • 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 of metals such as zinc (Zn), palladium (Pd), gold (Au), hungry (Os), ruthenium (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 compound, a metal phosphorus group element 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.
  • Preferred n-type inorganic semiconductor materials may be selected from, but not limited to, ZnO, ZnS, ZnSe, TiO 2 , ZnTe, GaN, GaP, AlN, CdSe, CdS, CdTe, CdZnSe or a mixture of any two or more thereof.
  • 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 selected from 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.
  • composition for printing electrons of the present invention may comprise at least one organic functional material.
  • the organic functional material may include, but is not limited to, holes (also called holes) injection or transport materials (HIM/HTM), hole blocking materials (HBM), electron injection or transport materials (EIM/ETM), electrons.
  • Barrier material EBM
  • organic host material Host
  • singlet illuminant fluorescent illuminant
  • thermally activated delayed fluorescent luminescent material TADF
  • triplet illuminant phosphorescent illuminant
  • the solubility of the organic functional material in the heteroaromatic solvent of the present invention may be at least 0.2 wt%, more preferably at least 0.3 wt%, more preferably at least 0.6 wt%, still more preferably at least 1.0 wt%, most preferably at least 1.5 wt%.
  • the organic functional material may be a small molecule and a high polymer material.
  • the small molecule organic material means a material having a molecular weight of at most 4000 g/mol, and the material having a molecular weight higher than 4000 g/mol is collectively referred to as a high polymer.
  • the composition for printing electrons of the present invention comprises a functional material that is an organic small molecule material.
  • the composition for printing electrons of the present invention wherein the organic functional material may comprise at least one host material and at least one illuminant.
  • the organic functional material may comprise a host material and a singlet emitter.
  • the organic functional material may comprise a host material and a triplet state Light body.
  • the organic functional material may comprise a host material and a thermally activated delayed fluorescent luminescent material.
  • the organic functional material may comprise a hole transporting material (HTM), and more preferably, the HTM comprises a crosslinkable group.
  • HTM hole transporting material
  • organic small molecule functional materials suitable for the preferred embodiment will be described in some detail below (but are not limited thereto).
  • Suitable organic HIM/HTM materials may optionally comprise compounds having the following structural units: phthalocyanine, porphyrin, amine, aromatic amine, biphenyl triarylamine, thiophene, thiophene such as dithienothiophene and thiophene, pyrrole , aniline, carbazole, azide and azepine and its derivatives, but are not limited thereto.
  • suitable HIMs also include fluorocarbon-containing polymers, conductively doped polymers, conductive polymers such as PEDOT:PSS, but are not limited thereto.
  • An electron blocking layer is used to block electrons from adjacent functional layers, particularly the luminescent layer.
  • the presence of an EBL generally results in an increase in luminous efficiency.
  • the electron blocking material (EBM) of the electron blocking layer (EBL) requires a higher LUMO than an adjacent functional layer such as a light emitting layer.
  • the HBM has a larger excited state level than the adjacent luminescent layer, such as a singlet or triplet, depending on the illuminant, while the EBM has a hole transport function.
  • HIM/HTM materials that typically have high LUMO levels can be used as EBMs.
  • cyclic aromatic amine-derived compounds useful as HIM, HTM or EBM include, but are not limited to, the following general structures:
  • Each of Ar 1 to Ar 9 may be independently selected from the group consisting of a cyclic aromatic hydrocarbon compound such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalrene, phenanthrene, anthracene, anthracene, fluorene, anthracene, anthracene; Heterocyclic compounds such as dibenzothiophene, dibenzofuran, furan, thiophene, benzofuran, benzothiophene, oxazole, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, evil Triazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, acesulfazine, oxadiazine, hydrazine
  • each of Ar may be further substituted, and the substituent may be selected from, but not limited to, hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl or heteroaryl.
  • Ar 1 to Ar 9 may be independently selected from the group consisting of the following, but are not limited thereto:
  • n is an integer from 1 to 20; X 1 to X 8 are CH or N; and Ar 1 is as defined above.
  • metal complexes that can be used as HTM or HIM include, but are not limited to, the following general structures:
  • M is a metal having an atomic weight greater than 40
  • (Y 1 -Y 2 ) is a bidentate ligand, Y 1 and Y 2 are independently selected from C, N, O, P and S; L is an ancillary ligand; m is an integer selected from 1 to this metal The maximum coordination number; m+n is the maximum coordination number of this metal.
  • (Y 1 -Y 2 ) is a 2-phenylpyridine derivative.
  • (Y 1 -Y 2 ) is a carbene ligand.
  • M can be selected from the group consisting of Ir, Pt, Os, and Zn.
  • the HOMO of the metal complex is greater than -5.5 eV (relative to the vacuum level).
  • HIM/HTM compounds are listed in the table below, but are not limited thereto:
  • the example of the triplet host material is not particularly limited, and any metal complex or organic compound may be used as a host as long as its triplet energy is higher than that of the illuminant, particularly the triplet illuminant or the phosphorescent illuminant.
  • metal complexes that can be used as the triplet host include, but are not limited to, the following general structure:
  • M is a metal
  • (Y 3 -Y 4 ) is a bidentate ligand, Y 3 and Y 4 are independently selected from C, N, O, P, and S
  • L is an ancillary ligand
  • m is an integer, the value thereof The maximum coordination number selected from 1 to this metal
  • m+n is the maximum coordination number of this metal.
  • the metal complex that can be used as the triplet host can have one of the following forms:
  • (O-N) is a two-dentate ligand in which the metal is coordinated to the O and N atoms.
  • M is selectable from Ir and Pt.
  • Examples of the organic compound which can be a host of a triplet state may be selected from, but not limited to, a compound containing a cyclic aromatic hydrocarbon group such as benzene, biphenyl, triphenyl, benzo, anthracene; a compound containing an aromatic heterocyclic group, Such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, carbazole, pyridinium, pyrrole dipyridine, Pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxazine , o
  • each Ar may be further substituted, and the substituent may be hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl or heteroaryl, but is not limited thereto.
  • the triplet host material can be selected from compounds containing at least one of the following groups, but is not limited thereto:
  • the R 1 -R 7 may be independently of one another selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl, but not limited thereto, when they are an aryl group or a heteroaryl group, which is the same meaning as above 2 Ar 1 and Ar; n is an integer from 0 to 20; X 1 -X 8 is selected in CH or N; X 9 is selected from At CR 1 R 2 or NR 1 .
  • triplet host materials examples include but are not limited to this:
  • the example of the singlet host material is not particularly limited, and any organic compound may be used as a host as long as its singlet energy is higher than that of the illuminant, particularly the singlet illuminant or the luminescent illuminant.
  • Examples of the organic compound used as the singlet host material may be selected from, but not limited to, a cyclic aromatic compound such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, anthracene, phenanthrene, anthracene, anthracene.
  • a cyclic aromatic compound such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, anthracene, phenanthrene, anthracene, anthracene.
  • aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, oxime Carbazole, pyridinium, pyrrole dipyridine, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, Pyrazine, triazine, oxazine, oxazine, oxadiazine, hydrazine, benzimidazole, oxazole, pyridazine, benzoxazole, benzoisoxazole, benzothiazole, quinoline, isoquine Porphy
  • the singlet host material may be selected from, but not limited to, a compound comprising at least one of the following groups:
  • R 1 may be independently selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl;
  • Ar 1 is aryl or a heteroaryl group, but is not limited thereto, which has the same meaning as Ar 1 defined in the above HTM;
  • n is an integer from 0 to 20;
  • X 1 -X 8 is selected from CH or N;
  • X 9 and X 10 are selected from CR 1 R 2 or NR 1 .
  • Singlet emitters tend to have longer conjugated pi-electron systems. To date, there have been many examples such as styrylamine and its derivatives and indenoindene and its derivatives.
  • the singlet emitter may be selected from the group consisting of monobasic styrylamine, dibasic styrylamine, ternary styrylamine, quaternary styrylamine, styrene phosphine, styrene ether and arylamine, But it is not limited to this.
  • the monostyrylamine refers to a compound comprising an unsubstituted or optionally substituted styrene group and at least one amine, preferably an aromatic amine.
  • the dibasic styrylamine refers to a compound comprising two unsubstituted or optionally substituted styrene groups and at least one amine, preferably an aromatic amine.
  • the ternary styrylamine refers to a compound comprising three unsubstituted or optionally substituted styrene groups and at least one amine, preferably an aromatic amine.
  • Tetrastyrylamine refers to a compound comprising four unsubstituted or optionally substituted styrene groups and at least one amine, preferably an aromatic amine.
  • the preferred styrene is stilbene, which may be further substituted. Accordingly, the definitions of phosphines and ethers are similar to those of amines.
  • An arylamine or an aromatic amine refers to a compound comprising three unsubstituted or optionally substituted aromatic ring or heterocyclic systems directly bonded to a nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably selected from the fused ring system, and most preferably has at least 14 aromatic ring atoms.
  • Aromatic decylamine refers to a compound in which one of the diarylamine groups is attached directly to the oxime, preferably at the position of 9.
  • Aromatic quinone diamine refers to a compound in which two diarylamine groups are attached directly to the oxime, preferably at the 9,10 position.
  • the aromatic decylamine, the aromatic guanidine diamine, the aromatic thiamine and the aromatic thiamine are similarly defined, wherein the diarylamine group is preferably attached to the 1 or 1,6 position of the oxime.
  • Further preferred singlet emitters may be selected from the group consisting of indeno-amine and indeno-diamine, benzindole-amine and benzoindole-diamine, dibenzoindenoquinone-amine And dibenzoindenoindole-diamine and the like.
  • polycyclic aromatic hydrocarbon compounds in particular derivatives of the following compounds: for example, 9,10-bis(2-naphthoquinone), naphthalene, tetraphenyl, xanthene, phenanthrene , ⁇ (such as 2,5,8,11-tetra-t-butyl fluorene), anthracene, phenylene such as (4,4'-bis(9-ethyl-3-carbazolevinyl)-1 , 1'-biphenyl), di-indeno pyrene, chrysene, decacyclene, coronene, fluorene, spirobifluorene, pyrene aryl group, arylene group ethylene, cyclopentadiene such as tetraphenyl cyclopentadiene, Rubrene, coumarin, rhodamine, quinacridone, pyran such as 4
  • TDF Thermally activated delayed fluorescent luminescent material
  • the thermally activated delayed fluorescent luminescent material is a third generation organic luminescent material developed after organic fluorescent materials and organic phosphorescent materials.
  • Such materials generally have a small singlet-triplet energy level difference ( ⁇ E st ), and triplet excitons can be converted into singlet exciton luminescence by inter-system crossing. This can make full use of the singlet excitons and triplet excitons formed under electrical excitation.
  • the quantum efficiency in the device can reach 100%.
  • the TADF material needs to have a small singlet-triplet energy level difference, typically ⁇ E st ⁇ 0.3eV, more preferably ⁇ E st ⁇ 0.2eV, more preferably ⁇ E st ⁇ 0.1eV, and most preferably ⁇ E st ⁇ 0.05eV.
  • TADF has a more preferred fluorescence quantum efficiency.
  • TADF luminescent materials are listed in the table below, but are not limited to this:
  • Triplet emitters are also known as phosphorescent emitters.
  • the triplet emitter is a metal complex of the formula M(L) n , wherein M is a metal atom, and each occurrence of L may be the same or different, which is an organic ligand Connected to the metal atom M by one or more position linkages or coordination, n is an integer greater than 1, more preferably 1, 2, 3, 4, 5 or 6.
  • these metal complexes are coupled to one polymer by one or more positions, most preferably by an organic ligand.
  • the metal atom M may be selected from transition metal elements or lanthanides or actinides, etc., preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy, Re, Cu or Ag is particularly preferably Os, Ir, Ru, Rh, Re, Pd or Pt, but is not limited thereto.
  • the triplet emitter may comprise a chelating ligand, ie a ligand, coordinated to the metal by at least two bonding sites, it being particularly preferred to consider that the triplet emitter comprises two or three identical or different Double or multidentate ligand.
  • Chelating ligands are beneficial for increasing the stability of metal complexes.
  • organic ligand examples may be selected from, but not limited to, a phenylpyridine derivative, a 7,8-benzoquinoline derivative, a 2(2-thienyl)pyridine derivative, and a 2(1-naphthyl)pyridine derivative. Or a 2 phenylquinoline derivative. All of these organic ligands may be substituted, for example by fluorine or trifluoromethyl.
  • the ancillary ligand may preferably be selected from the group consisting of acetone acetate or picric acid.
  • the metal complex that can be used as the triplet emitter has the following form:
  • M is a metal selected from the group consisting of transition metal elements or lanthanides or actinides;
  • Ar 1 may be the same or different at each occurrence, which is a cyclic group containing at least one donor atom, that is, an atom having a lone pair of electrons, such as nitrogen or phosphorus, coordinated to the metal through its cyclic group Connection;
  • Ar 2 may be the same or different each time it appears, which is a cyclic group containing at least one C atom through which a cyclic group is attached to the metal;
  • Ar 1 and Ar 2 are bonded by a covalent bond Together, each may carry one or more substituent groups, or may be further joined together by a substituent group;
  • each occurrence of L may be the same or different, which is an auxiliary ligand, preferably a bidentate chelate ligand, Most preferred is a monoanionic bidentate chelating ligand;
  • m is 1, 2 or 3, preferably 2 or 3, particularly preferably 3;
  • n is 0, 1, or 2, preferably 0 or 1, in particular Preferably 0;
  • triplet emitters Some examples of suitable triplet emitters are listed in the table below, but are not limited to this:
  • the functional material for printing electronic compositions of the present invention may comprise a polymeric material.
  • the above organic small molecule functional materials may include HIM, HTM, ETM, EIM, Host, fluorescent illuminants, phosphorescent emitters, TADF, etc., and all of them may be included as a repeating unit in a high polymer.
  • the high polymer suitable for the present invention may be a conjugated high polymer.
  • conjugated polymers have the following general formula:
  • A can independently select the same or different structural units when appearing multiple times
  • B ⁇ -conjugated structural unit having a larger energy gap, also called a backbone unit (Backbone Unit), selected from single or multiple rings
  • Backbone Unit backbone Unit
  • preferred unit form is benzene, biphenylene, naphthalene, anthracene, phenanthrene, dihydrophenanthrene, 9,10-dihydrophenanthrene, anthracene, diterpene, spirobifluorene, pair Phenylacetylene, ruthenium and oxime, cis hydrazine, dibenzo-indole fluorene, anthracene naphthalene and its derivatives.
  • a ⁇ -conjugated structural unit having a smaller energy gap may be selected from, but not limited to, a hole injection or transport material (HIM/) as described above.
  • HTM hole injection or transport material
  • EIM/ETM electron injecting or transporting material
  • host material Host
  • singlet illuminant fluorescent illuminant
  • structural unit of heavy illuminant phosphorescent illuminant
  • the functional composition for printing electronic compositions of the present invention comprises a polymeric HTM.
  • the high polymer HTM material is a homopolymer, and the preferred homopolymer is selected from the group consisting of polythiophene, polypyrrole, polyaniline, polybiphenyl triarylamine, polyvinyl carbazole and derivatives thereof. .
  • the high polymer HTM material is a conjugated copolymer represented by Chemical Formula 1, wherein
  • A a functional group having a hole transporting ability, which may be the same or differently selected from the structural unit containing the hole injection or transport material (HIM/HTM) described above; in a preferred embodiment, A is selected From amines, biphenyls, triarylamines, thiophenes, and thiophenes such as dithienothiophenes and thiophenes, pyrrole, aniline, carbazole, indenocarbazole, indolocarbazide, pentacene, phthalocyanine, porphyrin and derivatives thereof .
  • HIM/HTM hole injection or transport material
  • R is each independently selected from the group consisting of hydrogen, a linear alkyl group having 1 to 20 C atoms, an alkoxy group or a thioalkoxy group, and a branched or cyclic alkane having 3 to 20 C atoms.
  • a base alkoxy or thioalkoxy group or a silyl group, a substituted keto group of 1 to 20 C atoms, an alkoxycarbonyl group of 2 to 20 C atoms, 7
  • r 0, 1, 2, 3 or 4;
  • s 0, 1, 2, 3, 4 or 5;
  • Another preferred class of organic functional materials can be polymers having electron transport capabilities, including conjugated high polymers and non-conjugated high polymers.
  • Preferred high polymer ETM materials may be homopolymers, and preferred homopolymers are selected from the group consisting of polyphenanthrene, polyphenanthroline, polyfluorene, polyspiroquinone, polyfluorene and derivatives thereof.
  • a preferred high polymer ETM material may be a conjugated copolymer represented by Chemical Formula 1, wherein A may independently select the same or different forms in multiple occurrences:
  • A a functional group having an electron transporting ability, preferably selected from the group consisting of tris(8-hydroxyquinoline)aluminum (AlQ3), benzene, diphenylene, naphthalene, anthracene, phenanthrene, dihydrophenanthrene, anthracene, diterpene, Spirobiindole, p-phenylacetylene, anthracene, anthracene, 9,10-dihydrophenanthrene, phenazine, phenanthroline, ruthenium, fluorene, dibenzo-indole, anthracene, naphthalene, benzo Bismuth and its derivatives
  • the composition for printing electrons of the present invention comprises a functional material that is a luminescent polymer.
  • the luminescent polymer is a conjugated high polymer having the following general formula:
  • A1 a functional group having a hole or electron transporting ability, which may be selected from, but not limited to, inclusion of the above hole injection or Transmission material (HIM/HTM), or structural unit of electron injection or transport material (EIM/ETM).
  • HIM/HTM hole injection or Transmission material
  • EIM/ETM structural unit of electron injection or transport material
  • A2 a group having a light-emitting function, which may be selected from, but not limited to, a structural unit containing the above-described singlet light emitter (fluorescent light-emitting body) and heavy light-emitting body (phosphorescent light-emitting body).
  • a high polymer suitable for the present invention may be a non-conjugated high polymer.
  • This can be that all functional groups are on the side chain and the backbone is a non-conjugated high polymer. Examples thereof may be selected from, but not limited to, such non-conjugated high polymers used as phosphorescent host or phosphorescent materials, and such non-conjugated high polymers used as fluorescent materials.
  • the non-conjugated high polymer may also be a high polymer in which functional units conjugated in the main chain are linked by a non-conjugated linking unit.
  • the present invention also relates to a method of preparing a film comprising a functional material by a method of printing or coating, wherein any one of the compositions described above is applied to a substrate by printing or coating, wherein printing or coating
  • the cloth method can be selected from, but not limited to, inkjet printing, jet printing (Nozzle Printing), typography, screen printing, dip coating, spin coating, blade coating, roller printing, torsion roller printing, lithography, Flexographic printing, rotary printing, spraying, brushing, pad printing, slit-type extrusion coating, etc.
  • the film comprising the functional material is prepared by a method of ink jet printing.
  • Inkjet printers that can be used to print the inks of the present invention are commercially available printers and include drop-on-demand printheads. These printers are available, for example, 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 LeZion, Isreal). Purchased.
  • 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 (QPVs), quantum dot luminescent cells (QLEEC), quantum dot field effect transistors (QFETs), quantum dot luminescence field effect transistors, quantum dots.
  • QLEDs quantum dot light emitting diodes
  • QPVs quantum dot photovoltaic cells
  • QLEEC quantum dot luminescent cells
  • QFETs quantum dot field effect transistors
  • Quant dot luminescence field effect transistors quantum dots.
  • 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), at least one luminescent layer or a light absorbing layer (104). ), cathode (106).
  • an electroluminescent device will be described as an example.
  • 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.
  • the anode material 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 RF magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), etc.
  • a suitable physical vapor deposition process including RF magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), etc.
  • 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 light-emitting functional material as described above, in particular Quantum dots or organic functional materials.
  • 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 a functional material having a hole transporting ability, particularly a quantum dot or an organic HTM material.
  • the light emitting device of the present invention further comprises an electron injection layer (EIL) or an electron transport layer (ETL) (105) containing the organic ETM or inorganic n-type material as described above.
  • EIL electron injection layer
  • ETL electron transport layer
  • the EIL or ETL can be prepared by printing a printing ink of the present invention, wherein the printing ink contains functional materials having electron transport capabilities, particularly quantum dots or organic ETM materials.
  • the invention further relates to the use of the light-emitting device of the invention in various applications, including, but not limited to, various display devices, backlights, illumination sources, and the like.
  • the two sides of the bottle were stoppered with a rubber stopper.
  • the upper part was connected to a condenser tube, and then connected to a double-row tube, heated to 150 ° C, vacuumed for 40 min, and then passed through a nitrogen gas; 12 mL of a syringe was used.
  • ODE was added to a three-necked flask.
  • 1.92 mL of the solution 1 was quickly injected into a three-necked flask with a syringe for 12 min.
  • After 12 min, 4 mL of the solution was added to the three-necked flask with a syringe.
  • 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.
  • the 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 into a glove box, added to the solvent system in the vial, and stirred and mixed. After stirring at a temperature of 60 ° C until the quantum dots were completely dispersed, it was cooled to room temperature.
  • the obtained quantum dot solution was filtered through a 0.2 ⁇ m PTFE filter. Seal and store.
  • a mixed solvent of 9.5 g of isoquinoline and 3-phenoxytoluene (weight ratio of 60:40) was prepared in a vial.
  • 0.5 g of ZnO nanoparticle solids were weighed into a glove box, added to the solvent system in the vial, and stirred and mixed. After stirring at a temperature of 60 ° C until the ZnO nanoparticles were completely dispersed, they were cooled to room temperature.
  • the obtained ZnO nanoparticle solution was filtered through a 0.2 ⁇ m PTFE filter. Seal and store.
  • organic functional materials referred to in the following examples are all commercially available, such as Jilin O'Reilly. (Jilin OLED Material Technology Co., Ltd, www.jl-oled.com), or synthesized according to the methods reported in the literature.
  • the luminescent layer organic functional material comprises a phosphorescent host material and a phosphorescent illuminant material.
  • the phosphorescent host material is selected from the group consisting of carbazole derivatives as follows:
  • the phosphorescent emitter material is selected from the group consisting of ruthenium complexes as follows:
  • the luminescent layer organic functional material comprises a fluorescent host material and a fluorescent illuminant material.
  • the fluorescent host material is selected from the group consisting of the following spiro derivatives:
  • the fluorescent emitter material is selected from the group consisting of:
  • Example 11 Preparation of organic light-emitting layer material containing quinoline and 3-phenoxytoluene
  • the luminescent layer organic functional material comprises a host material and a TADF material.
  • the host material is selected from the group consisting of the following structures:
  • the TADF material is selected from the group consisting of the following structures:
  • a mixed solvent of 9.8 g of quinoline and 3-phenoxytoluene (weight ratio of 60:40) was prepared in a vial. 0.19 g of the host material and 0.01 g of the TADF material were weighed in a glove box, added to the solvent system in the vial, and stirred and mixed. After stirring at a temperature of 60 ° C until the organic functional material was completely dissolved, it was cooled to room temperature. The obtained organic functional material solution was filtered through a 0.2 ⁇ m PTFE filter. Sealed and saved
  • the printing ink comprises a hole transport layer material having a hole transporting ability.
  • the hole transporting material is selected from the following triarylamine derivatives:
  • the viscosity of the functional material ink was tested by a DV-IPrime Brookfield rheometer; the surface tension of the functional material ink was tested by a SITA bubble pressure tomometer.
  • Example 14 Preparation of an electronic device functional layer using the printing ink of the present invention
  • 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 printing ink containing the functional material based on the heteroaromatic and organic solvent of the general formula (I) prepared above. Specific steps are as follows.
  • the ink containing the functional material is loaded into an ink tank which is mounted on an ink jet printer such as Dimatix Materials Printer DMP-3000 (Fujifilm).
  • the waveform, pulse time and voltage of the ejected ink are adjusted to optimize ink ejection and to stabilize within the range of ink ejection.
  • the substrate of the OLED/QLED is 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

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Abstract

一种用于印刷电子的组合物，包含至少一种功能材料及至少一种基于杂芳族的有机溶剂。该组合物的印刷工艺及在电子器件中的应用，特别是在电致发光器件中的应用。利用该组合物制备的电子器件。

Description

用于印刷电子的组合物及其在电子器件中的应用 技术领域
本发明涉及一种适合于印刷电子的组合物及其在印刷电子器件中的应用，特别是在电致发光器件中的应用。
背景技术
目前作为新一代显示技术的有机发光二极管(OLED)是用蒸镀方法制备的，其制备过程中涉及大量的真空制程，材料利用率低，同时需要精细掩模(FMM)，成本较高，同时良率低。为了解决上述问题，采用印刷工艺实现高分辨全彩色显示的技术越来越受到关注。例如，喷墨打印能够大面积低成本地制备功能材料薄膜，相比传统的半导体生产工艺，喷墨打印低能耗，耗水量少，绿色环保，是具有极大的优势和潜力的生产技术。另一种新型显示技术，量子点发光二极管(QLED)，无法蒸镀，必须以印刷的方法制备。因此，实现印刷显示，必须突破印刷油墨及相关印刷工艺等关键问题。粘度和表面张力是影响印刷油墨及打印过程的重要参数。一种有前景的印刷墨水需要具备适当的粘度和表面张力。
有机半导体材料由于其溶液加工性，在电子和光电子器件中的应用已获得了广泛的关注并取得了显著的进展。溶液加工性使得有机功能材料可以通过一定的涂覆和印刷技术在器件中形成该功能材料的薄膜。这样的技术可以有效降低电子和光电子器件的加工成本，且满足大面积制备的工艺需求。目前，已有数家公司报道了用于打印的有机半导体材料油墨，例如：KATEEVA，INC公开了一种用于可印刷OLED的基于酯类溶剂的有机小分子材料油墨(US2015044802A1)；UNIVERSALDISPLAYCORPORATION公开了一种可印刷的基于芳族酮或芳族醚类溶剂的有机小分子材料油墨(US20120205637)；SEIKOEPSONCORPORATION公开了可印刷的基于取代的苯衍生物溶剂的有机聚合物材料油墨。其它的涉及有机功能材料的印刷油墨的例子有：CN102408776A、CN103173060A、CN103824959A、CN1180049C、CN102124588B、US2009130296A1、US2014097406A1等。
另一类可适合于印刷的功能材料是无机纳米材料，特别是量子点。量子点是具有量子限制效应的纳米尺寸的半导体材料，当受到光或电的刺激，量子点会发出具有特定能量的荧光，荧光的颜色(能量)由量子点的化学组成和尺寸形状决定。因此，对量子点尺寸形状的控制能有效调控其电学和光学性质。目前，各国都在研究量子点在全彩方面的应用，主要集中在显示领域。最近，量子点作为发光层的电致发光器件(QLED)得到了迅速发展，器件寿命得到很大的提高，如Peng等，在NatureVol51596(2015)及Qian等，在NaturePhotonicsVol9259(2015)中所报道的。目前，已有数家公司报道了用于打印的量子点油墨：英国纳米技术有限公司(NanocoTechnologiesLtd)公开了一种包含纳米粒子的可印刷的油墨制剂的方法(CN101878535B)。通过选用合适的溶剂，比如甲苯和十二烷硒醇，得到了可印刷的纳米粒子油墨及相应的包含纳米粒子的薄膜；三星(SamsungElectronics)公开了一种用于喷墨打印的量子点油墨(US8765014B2)。这种油墨包含一定浓度的量子点材料、有机溶剂和具有高粘度的醇类聚合物添加剂。通过打印该油墨得到了量子点薄膜，并制备了量子点电致发光器件；QD视光(QDVision，Inc.)公开了一种量子点的油墨制剂，包含一种主体材料、一种量子点材料和一种添加剂(US2010264371A1)。
其它的涉及量子点印刷油墨的专利有：US2008277626A1，US2015079720A1，US2015075397A1，TW201340370A，US2007225402A1，US2008169753A1，US2010265307A1，US2015101665A1，WO2008105792A2。
但是，在这些已公开的专利中，为了调控油墨的物理参数，这些量子点油墨都包含有其 它的添加剂，如醇类聚合物。具有绝缘性质的聚合物添加剂的引入往往会降低薄膜的电荷传输能力，对器件的光电性能具有负面影响，限制了其在光电器件中的广泛应用。
发明内容
本发明的目的之一，在于提供一种电子印刷用组合物。
本发明的技术方案如下：
一种用于印刷电子的组合物，包含有至少一种功能材料和含有至少一种有机溶剂的溶剂体系，所述有机溶剂中包括至少一种基于杂芳族且具有通式(I)的有机溶剂：
Figure PCTCN2016099783-appb-000001
其中，
Ar1是具有5～10个碳原子的杂芳环，n是大于或等于0的整数，R是取代基，其特征在于，所述基于杂芳族且具有通式(I)的有机溶剂的沸点≥150℃，且可从溶剂体系中蒸发，以形成含有所述无机纳米材料的薄膜。
在其中一个实施例中，所述用于印刷电子的组合物以上所述用于印刷电子的组合物中，所述基于杂芳族且具有通式(I)的有机溶剂在25℃下的粘度，在1cPs到100cPs的范围内。
在其中一个实施例中，所述用于印刷电子的组合物以上所述用于印刷电子的组合物中，所述基于杂芳族且具有通式(I)的有机溶剂其在25℃下的表面张力，在19dyne/cm到50dyne/cm的范围内。
在其中一个实施例中，所述用于印刷电子的组合物以上所述用于印刷电子的组合物中，所述基于杂芳族且具有通式(I)的有机溶剂具有选自如下通式中任一种所示的结构：
Figure PCTCN2016099783-appb-000002
其中，
X是CR1或N；
Y选自CR2R3，SiR4R5，NR6，C(＝O)，S，S(＝O)2或O；
且每一个通式中至少有一个X或Y是非C的原子(即所谓的杂原子)；
每个所述R1，R2，R3，R4，R5，R6独立选自以下各项中的任一种：H，D，具有1至20个C原子的直链烷基、烷氧基或硫代烷氧基基团，具有3至20个C原子的支链或环状的烷基、烷氧基或硫代烷氧基基团或者是甲硅烷基基团，具有1至20个C原子的取代的酮基基团，具有2至20个C原子的烷氧基羰基基团，具有7至20个C原子的芳氧基羰基基团，氰基基团(-CN)，氨基甲酰基基团(-C(＝O)NH2)，卤甲酰基基团(-C(＝O)-X其中X代表卤素原 子)，甲酰基基团(-C(＝O)-H)，异氰基基团，异氰酸酯基团，硫氰酸酯基团或异硫氰酸酯基团，羟基基团，硝基基团，CF3基团，Cl，Br，F，可交联的基团或者具有5至40个环原子的任选取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团；其中R1，R2，R3，R4，R5，R6中的一个或多个同时存在时，可以彼此独立存在或可以在彼此之间和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。
在其中一个实施例中，所述用于印刷电子的组合物以上所述用于印刷电子的组合物中，所述通式(I)中的Ar1选自如下结构单元中的任一种：
Figure PCTCN2016099783-appb-000003
在其中一个实施例中，以上所述用于印刷电子的组合物中，通式(I)中的R选自：具有1至20个C原子的直链烷基、烷氧基或硫代烷氧基基团，具有3至20个C原子的支链或环状的烷基、烷氧基或硫代烷氧基基团或者是甲硅烷基基团，具有1至20个C原子的取代的酮基基团，具有2至20个C原子的烷氧基羰基基团，具有7至20个C原子的芳氧基羰基基团，氰基基团(-CN)，氨基甲酰基基团(-C(＝O)NH2)，卤甲酰基基团(-C(＝O)-X其中X代表卤素原子)，甲酰基基团(-C(＝O)-H)，异氰基基团，异氰酸酯基团，硫氰酸酯基团或异硫氰酸酯基团，羟基基团，硝基基团，CF3基团，Cl，Br，F，可交联的基团或者具有5至40个环原子的任选取代或未取代的芳族或杂芳族环系，具有5至40个环原子的芳氧基或杂芳氧基基团；其中一个或多个所述R可以彼此独立存在或可以在彼此之间和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。
在其中一个实施例中，以上所述用于印刷电子的组合物，所述基于杂芳族且具有通式(I)的有机溶剂选自：2-苯基吡啶、3-苯基吡啶、4-(3-苯基丙基)吡啶、喹啉、异喹啉、8-羟基喹啉、2-呋喃甲酸甲酯、2-呋喃甲酸乙酯或其中任意两种或以上的混合物。
在其中一个实施例中，所述用于印刷电子的组合物以上所述用于印刷电子的组合物中，所述溶剂体系可以是进一步包含至少一种其它溶剂的混合溶剂，且所述具有通式(I)的有机 溶剂占混合溶剂总重量的50％以上。
在其中一个实施例中，所述用于印刷电子的组合物以上所述用于印刷电子的组合物中，所述功能材料是无机纳米材料。
在其中一个实施例中，所述用于印刷电子的组合物以上所述用于印刷电子的组合物中，所述功能材料是量子点材料，即其粒径具有单分散的尺寸分布，其形状可选自球形、立方体、棒状或支化结构等不同纳米形貌。
在其中一个实施例中，所述用于印刷电子的组合物以上所述用于印刷电子的组合物中，所述功能材料是发光波长位于380nm～2500nm之间的发光量子点材料。
在其中一个实施例中，所述用于印刷电子的组合物以上所述用于印刷电子的组合物中，包含有无机功能材料，所述无机功能材料选自：元素周期表IV族、II-VI族、II-V族、III-V族、III-VI族、IV-VI族、I-III-VI族、II-IV-VI族、II-IV-V族的二元或多元半导体化合物中的任一种，或其中任意两种或以上的混合物。
在其中一个实施例中，所述用于印刷电子的组合物以上所述用于印刷电子的组合物中，所述功能材料是钙钛矿纳米粒子材料，优选为发光钙钛矿纳米材料、金属纳米粒子材料、金属氧化物纳米粒子材料，或其中任意两种或以上的混合物。
在其中一个实施例中，所述用于印刷电子的组合物以上所述用于印刷电子的组合物中，所述功能材料是有机功能材料。
在其中一个实施例中，所述用于印刷电子的组合物以上所述用于印刷电子的组合物中，所述有机功能材料可选自空穴注入材料(HIM)、空穴传输材料(HTM)、电子传输材料(ETM)、电子注入材料(EIM)、电子阻挡材料(EBM)、空穴阻挡材料(HBM)、发光体(Emitter)、主体材料(Host)和有机染料中的任一种，或其中任意两种或以上的混合物。
在其中一个实施例中，所述用于印刷电子的组合物以上所述用于印刷电子的组合物中，所述有机功能材料包含有至少一种的主体材料和至少一种的发光体。
在其中一个实施例中，以上所述用于印刷电子的组合物，其特征在于，所述功能材料占所述用于印刷电子的组合物的重量百分比为0.3％～30％，包含的溶剂体系占所述用于印刷电子的组合物的重量百分比为70％～99.7％。
本发明还提供了一种电子器件，包含有由如上所述任一种组合物印刷或涂布而成的功能层，其中所包含的基于杂芳族且具有通式(I)的有机溶剂可从溶剂体系中蒸发，以形成功能薄膜。
在其中一个实施例中，以上所述电子器件，其中所述电子器件可选自：量子点发光二极管(QLED)、量子点光伏电池(QPV)、量子点发光电池(QLEEC)、量子点场效应管(QFET)、量子点发光场效应管、量子点激光器，量子点传感器，有机发光二极管(OLED)、有机光伏电池(OPV)、有机发光电池(OLEEC)、有机场效应管(OFET)、有机发光场效应管、有机激光器和有机传感器等。
本发明还提供了一种功能材料薄膜的制备方法，其中将根据如上所述的任一种组合物用印刷或涂布的方法涂布于基板上，其中印刷或涂布的方法可选自(但不限于)：喷墨打印，喷印(NozzlePrinting)、活版印刷、丝网印刷、浸涂、旋转涂布、刮刀涂布、辊筒印花、扭转辊印刷、平版印刷、柔版印刷、轮转印刷、喷涂、刷涂、移印，狭缝型挤压式涂布等。
本发明还提供如上所述的用于印刷电子的组合物的印刷工艺及在电子器件中的应用，特别是在电致发光器件中的应用。
本发明的有益效果在于，本发明所述用于印刷电子的组合物，可以在使用中根据特定的印刷方法，特别是喷墨印刷，将粘度和表面张力调节到合适的的范围内，以便于打印，并形成表面均匀的薄膜。同时，有机溶剂可以通过后处理有效移除，如热处理或真空处理，有利于保证电子器件的性能。因此，本发明提供了一种用于制备高质量功能薄膜的印刷油墨，特别是包含有量子点和有机半导体材料的印刷油墨，为印刷电子或光电子器件提供了一种效果卓越的技术解决方案。
附图说明
图1是根据本发明所述的发光器件的一个优选实施例的结构图，图中101是基板，102是阳极，103是空穴注入层(HIL)或空穴传输层(HTL)，104是发光层(电致发光器件)或光吸收层(光伏电池)，105是电子注入层(EIL)或电子传输层(ETL)，106是阴极。
具体实施方式
本发明提供一种用于印刷电子的组合物，还涉及此组合物的印刷工艺及在电子器件中的应用，特别是在光电器件，尤其特别是在电致发光器件中的应用。本发明还进一步涉及利用此组合物制备的电子器件。
为使本发明的目的、技术方案及效果更加清楚、明确，以下对本发明进一步详细说明。应当理解，此处所描述的详细说明和具体实施例仅仅用以解释本发明，并不用于限定本发明。
在本申请的叙述中，本发明所述的用于印刷电子的组合物和术语印刷油墨，或油墨具有相同的含义，它们之间可以互换。
本发明的一个实施例中，提供一种用于印刷电子的组合物，包含有至少一种功能材料和含有至少一种有机溶剂的溶剂体系，所述有机溶剂中包括至少一种基于杂芳族且具有通式(I)的有机溶剂：
Figure PCTCN2016099783-appb-000004
其中，
Ar1是具有5～10个碳原子的杂芳环，n大于或等于0的整数，R是取代基，其特征在于，所述基于杂芳族且具有通式(I)的有机溶剂沸点≥120℃，且可从溶剂体系中蒸发，以形成功能材料的薄膜。
按照通式(I)所示的基于杂芳族的溶剂中，Ar1是具有5～10个碳原子的杂芳族环。杂芳族基团指包含至少一个杂芳环的烃基(含有杂原子)，包括单环基团和多环的环系统。这些多环的环可以具有两个或多个环，其中两个碳原子被两个相邻的环共用，即稠环。多环的这些环中，至少一个是杂芳族。
具体地，杂芳族基团的例子可以选自，但不限于：呋喃、苯并呋喃、噻吩、苯并噻吩、吡咯、吡唑、三唑、咪唑、噁唑、噁二唑、噻唑、四唑、吲哚、咔唑、吡咯并咪唑、吡咯并吡咯、噻吩并吡咯、噻吩并噻吩、呋喃并吡咯、呋喃并呋喃、噻吩并呋喃、苯并异噁唑、苯并异噻唑、苯并咪唑、吡啶、吡嗪、哒嗪、嘧啶、三嗪、喹啉、异喹啉、邻二氮萘、喹喔啉、 菲啶、伯啶、喹唑啉、喹唑啉酮，及其衍生物。
在某些优选的实施例中，如上所述通式(I)中所有取代基R中除H以外的原子总数大于或等于2。这里所述所有取代基R中除H以外的原子包括C、Si、N、P、O、S、F、Cl、Br、I等原子，但不限于此。例如，甲氧基取代基及其两个氯取代基等都在本发明的包含的范围内。在某些实施例中，所有取代基R中除H以外的原子总数大于或等于2，优选为2～20，，更优为2～10，最优为3～10。
在本发明的一些实施例中，本发明所述的用于印刷电子的组合物，所包含的基于杂芳族且具有通式(I)的有机溶剂可以具有如下通式所示的结构：
Figure PCTCN2016099783-appb-000005
其中，
X可以是CR1或N；
Y可以选自CR2R3，SiR4R5，NR6，C(＝O)，S，S(＝O)2或O；
且每一个通式中至少有一个X或Y是非C的原子(即所谓的杂原子)；
每个R1，R2，R3，R4，R5，R6可以独立选自以下各项中的任一种：H，D，具有1至20个C原子的直链烷基、烷氧基或硫代烷氧基基团，具有3至20个C原子的支链或环状的烷基、烷氧基或硫代烷氧基基团或者是甲硅烷基基团，具有1至20个C原子的取代的酮基基团，具有2至20个C原子的烷氧基羰基基团，具有7至20个C原子的芳氧基羰基基团，氰基基团(-CN)，氨基甲酰基基团(-C(＝O)NH2)，卤甲酰基基团(-C(＝O)-X其中X代表卤素原子)，甲酰基基团(-C(＝O)-H)，异氰基基团，异氰酸酯基团，硫氰酸酯基团或异硫氰酸酯基团，羟基基团，硝基基团，CF3基团，Cl，，Br，F，可交联的基团或者具有5至40个环原子的任选取代或未取代的芳族或杂芳族环系，具有5至40个环原子的芳氧基或杂芳氧基基团；，但不限于此；其中R1，R2，R3，R4，R5，R6中的一个或多个同时存在时，可以彼此独立存在或可以在彼此之间和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。
在一些优选的实施例中，每个R1，R2，R3，R4，R5，R6可以独立选自以下各项中的任一种：H，D，具有1至10个C原子的直链烷基、烷氧基或硫代烷氧基基团，或者具有3至10个C原子的支链或环状的烷基、烷氧基或硫代烷氧基基团或者是甲硅烷基基团，具有1至10个C原子的取代的酮基基团，具有2至10个C原子的烷氧基羰基基团，具有7至10个C原子的芳氧基羰基基团，氰基基团(-CN)，氨基甲酰基基团(-C(＝O)NH2)，卤甲酰基基团(-C(＝O)-X其中X代表卤素原子)，甲酰基基团(-C(＝O)-H)，异氰基基团，异氰酸酯基团，硫氰酸酯基团或异硫氰酸酯基团，羟基基团，硝基基团，CF3基团，Cl，Br，F，可交联的基团或者具有5至20个环原子的任选取代或未取代的芳族或杂芳族环系，具有5至20个环原子的芳氧基或杂芳氧基基团；其中R1，R2，R3，R4，R5，R6中的一个或多个同时存在时，可以彼此独立存在或可以在彼此之间和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。
在本发明的一些实施例中，本发明所述的用于印刷电子的组合物包含的基于杂芳族且具有通式(I)的有机溶剂具有通式(I)，其中的Ar1优选自如下结构单元中的任一种：
Figure PCTCN2016099783-appb-000006
在某些实施例中，通式(I)中的R可以选自，但不限于：具有1至20个C原子的直链烷基、烷氧基或硫代烷氧基基团，具有3至20个C原子的支链或环状的烷基、烷氧基或硫代烷氧基基团或者是甲硅烷基基团，具有1至20个C原子的取代的酮基基团，具有2至20个C原子的烷氧基羰基基团，具有7至20个C原子的芳氧基羰基基团，氰基基团(-CN)，氨基甲酰基基团(-C(＝O)NH2)，卤甲酰基基团(-C(＝O)-X其中X代表卤素原子)，甲酰基基团(-C(＝O)-H)，异氰基基团，异氰酸酯基团，硫氰酸酯基团或异硫氰酸酯基团，羟基基团，硝基基团，CF3基团，Cl，Br，F，可交联的基团或者具有5至40个环原子的任选取代或未取代的芳族或杂芳族环系，具有5至40个环原子的芳氧基或杂芳氧基基团；，但不限于此；其中一个或多个所述R可以彼此独立存在或可以在彼此之间和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。
在一些优选的实施例中，通式(I)中的至少一个取代基R可以选自，但不限于：具有1至10个C原子的直链烷基、烷氧基或硫代烷氧基基团，具有3至10个C原子的支链或环状的烷基、烷氧基或硫代烷氧基基团或者是甲硅烷基基团，具有1至10个C原子的取代的酮基基团，具有2至10个C原子的烷氧基羰基基团，具有7至10个C原子的芳氧基羰基基团，氰基基团(-CN)，氨基甲酰基基团(-C(＝O)NH2)，卤甲酰基基团(-C(＝O)-X其中X代表卤素原子)，甲酰基基团(-C(＝O)-H)，异氰基基团，异氰酸酯基团，硫氰酸酯基团或异硫氰酸酯基团，羟基基团，硝基基团，CF3基团，Cl，Br，F，可交联的基团或者具有5至20个环原子的任选取代或未取代的芳族或杂芳族环系，具有5至20个环原子的芳氧基或杂芳氧基基团；其中一个或多个所述R可以彼此独立存在或可以在彼此之间和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。
用于溶解功能材料的基于杂芳族且具有通式(I)的有机溶剂，在选取时需考虑其沸点参数。在本发明的一些实施例中，所述基于杂芳族且具有通式(I)的有机溶剂的沸点≥150℃。在某些优选的实施例中，所述基于杂芳族且具有通式(I)的有机溶剂的沸点≥180℃；在某 些实施例中，所述基于杂芳族且具有通式(I)的有机溶剂其沸点≥200℃；在某些实施例中，所述基于杂芳族且具有通式(I)的有机溶剂其沸点≥250℃；在另一些优选实施例中，所述基于杂芳族且具有通式(I)的有机溶剂其沸点≥275℃或≥300℃。这些范围内的沸点对防止喷墨印刷头的喷嘴堵塞是有益的。所述基于杂芳族且具有通式(I)的有机溶剂可从溶剂体系中蒸发，以形成包含功能材料薄膜。
在本发明的一些实施例中，本发明所述的用于印刷电子的组合物所包含的基于杂芳族且具有通式(I)的基于杂芳族且具有通式(I)的有机溶剂在25℃下的表面张力在19dyne/cm到50dyne/cm的范围内。
用于溶解功能材料的基于杂芳族且具有通式(I)的有机溶剂，在选取时需考虑其表面张力参数。合适的油墨表面张力参数适合于特定的基板和特定的印刷方法。例如对喷墨印刷，在一个优选的实施例中，所述基于杂芳族且具有通式(I)的有机溶剂在25℃下的表面张力约在19dyne/cm到50dyne/cm的范围内；在一个更为优选的实施例中，所述基于杂芳族且具有通式(I)的有机溶剂在25℃下的表面张力约在22dyne/cm到35dyne/cm的范围内；在一个最为优选的实施例中，所述基于杂芳族且具有通式(I)的有机溶剂在25℃下的表面张力约在25dyne/cm到33dyne/cm的范围内。
在一个优选的实施例中，本发明所述的油墨在25℃下的表面张力约在19dyne/cm到50dyne/cm的范围内；更优选是在22dyne/cm到35dyne/cm的范围内；最优选是在25dyne/cm到33dyne/cm的范围内。
本发明所述的一种组合物，其中所包含的基于杂芳族且具有通式(I)的有机溶剂在25℃下的粘度在1cPs到100cPs的范围内。
用于溶解功能材料的基于杂芳族且具有通式(I)的有机溶剂，在选取时需考虑其油墨的粘度参数。粘度可以通过不同的方法调节，如通过合适的有机溶剂的选取和油墨中功能材料的浓度/重量比。本发明所述的包含有基于杂芳族且具有通式(I)的有机溶剂的溶剂体系在印刷油墨中的含量，可以方便地按照所用的印刷方法在适当的范围进行调节。一般地，本发明所述的用于印刷电子的组合物包含的功能材料的重量比为占所述用于印刷电子的组合物的0.3％～30wt％的范围内，较优选的为0.5％～20wt％的范围内，更优选的为0.5％～15wt％的范围内，最优选的为0.5％～10wt％的范围内。在一个优选的实施例中，所述基于杂芳族且具有通式(I)的有机溶剂的粘度低于100cps；在一个更为优选的实施例中，所述基于杂芳族且具有通式(I)的有机溶剂的粘度低于50cps；在一个最为优选的实施例中，所述基于杂芳族且具有通式(I)的有机溶剂的粘度为1.5到20cps。这里的粘度是指在印刷时的环境温度下的粘度，一般在15-30℃，较优选的是18-28℃，更优选是20-25℃，最优选是23-25℃。如此配制的组合物将特别适合于喷墨印刷。
在一个优选的实施例中，本发明所述的用于印刷电子的组合物，当其按照如上配比配制后，在25℃下的粘度约在1cps到100cps的范围内；更优选是在1cps到50cps的范围内；最优选是在1.5cps到20cps的范围内。
使用满足上述沸点、表面张力参数及粘度参数的基于杂芳族的溶剂体系，获得的油墨能够形成具有均匀厚度及组成性质的功能材料薄膜。
本发明所述的基于杂芳族且具有通式(I)的有机溶剂的例子有，但不限于：2-苯基吡啶、3-苯基吡啶、4-(3-苯基丙基)吡啶、喹啉、异喹啉、2-呋喃甲酸甲酯、2-呋喃甲酸乙酯等。
在一些优选的实施例中，本发明所述的印刷油墨包含单一的基于杂芳族且具有通式(I)的有机溶剂，优选为喹啉或异喹啉。
在另一些优选的实施例中，本发明所述的印刷油墨包含两种及两种以上的基于杂芳族且具有通式(I)的有机溶剂的混合物。
在一些优选的实施例中，本发明所述的印刷油墨包含的有机溶剂是喹啉和异喹啉的混合物。
在另一些优选的实施例中，本发明所述的印刷油墨包含一种基于杂芳族且具有通式(I)的有机溶剂和至少另一种其它溶剂，且基于杂芳族且具有通式(I)的有机溶剂占混合溶剂总重量的50％以上。优选地，包含如通式(I)所示的有机溶剂占溶剂总重量的至少70％；更优选地，基于杂芳族且具有通式(I)的有机溶剂占混合溶剂总重量的至少80％。最优选地，基于杂芳族且具有通式(I)的有机溶剂占混合溶剂总重量的至少90％，或混合溶剂基本上由基于杂芳族且具有通式(I)的有机溶剂组成，或完全由基于杂芳族且具有通式(I)的有机溶剂组成。
在一个优选的实施例种，如上所述另一种有机溶剂选自任选取代或未取代的芳族溶剂。
在一些优选的实施例中，本发明涉及的印刷油墨包含的有机溶剂是喹啉和十二烷基苯的混合物。
在一些优选的实施例中，本发明涉及的印刷油墨包含的有机溶剂是异喹啉和十二烷基苯的混合物。
在一些优选的实施例中，本发明涉及的印刷油墨包含的有机溶剂是喹啉和3-苯氧基甲苯的混合物。
在一些优选的实施例中，本发明涉及的印刷油墨包含的有机溶剂是异喹啉和3-苯氧基甲苯的混合物。
在另一些实施例中，如上所述另一种的有机溶剂的例子，包括(但不限于)：甲醇、乙醇、2-甲氧基乙醇、二氯甲烷、三氯甲烷、氯苯、邻二氯苯、四氢呋喃、苯甲醚、吗啉、甲苯、邻二甲苯、间二甲苯、对二甲苯、1，4二氧杂环己烷、丙酮、甲基乙基酮、1，2二氯乙烷、3-苯氧基甲苯、1，1，1-三氯乙烷、1，1，2，2-四氯乙烷、醋酸乙酯、醋酸丁酯、二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、四氢萘、萘烷、茚，或其中任意两种或以上的混合物。
本发明所述的基于杂芳族的溶剂体系能够有效地溶解功能材料，即作为新的溶剂取代传统使用的溶解功能材料的溶剂，如甲苯、二甲苯、氯仿、氯苯、二氯苯、正庚烷等。
所述印刷油墨还可以另外包括一个或多个组份，例如表面活性化合物、润滑剂、润湿剂、分散剂、疏水剂、粘接剂等，用于调节粘度，成膜性能，提高附着性等。
所述印刷油墨可以通过多种打印或涂布技术沉积得到功能薄膜，适合的打印或涂布技术包括(但不限于)喷墨打印，喷印(NozzlePrinting)，活版印刷，丝网印刷，浸涂，旋转涂布，刮刀涂布，辊筒印花，扭转辊印刷，平版印刷，柔版印刷，轮转印刷，喷涂，刷涂、移印，狭缝型挤压式涂布等。优选的打印技术是喷墨印刷，喷印及凹版印刷。有关打印技术，及其对有关油墨的相关要求，如溶剂及浓度，粘度等，的详细信息请参见HelmutKipphan主编的《印刷媒体手册：技术和生产方法》(Hand book of Print Media：Technologies and Production Methods)，ISBN3-540-67326-1。一般地，不同的打印技术对所采用的油墨有不同的特性要求。例如，适用于喷墨打印的印刷油墨，需要对油墨的表面张力、粘度、及浸润性进行调控，使得油墨在印刷温度下(比如室温，25℃)能够很好地经由喷嘴喷出而不至于干燥于喷嘴上或堵塞喷嘴，或能在特定的基板上形成连续、平整和无缺陷的薄膜。
本发明所述的用于印刷电子的组合物包含至少一种功能材料。
在本发明中，功能材料优选是指具有某些光电功能的材料。光电功能包括、但不限于、空穴注入功能、空穴传输功能、电子传输功能、电子注入功能、电子阻挡功能、空穴阻挡功能、发光功能、主体功能和光吸收功能。相应的功能材料被称为空穴注入材料(HIM)、空穴传输材料(HTM)、电子传输材料(ETM)、电子注入材料(EIM)、电子阻挡材料(EBM)、空穴阻挡材料(HBM)、发光体(Emitter)、主体材料(Host)和有机染料。
所述功能材料可以是有机材料或无机材料。
在一个优选的实施例中，本发明所述的用于印刷电子的组合物包含的至少一种功能材料是无机纳米材料。
优选地，所述用于印刷电子的组合物中，所述无机纳米材料是无机半导体纳米粒子材料。
本发明中，无机纳米材料的平均粒径约在1到1000nm范围内。在某些优选的实施例中，无机纳米材料的平均粒径约在1到100nm。在某些更为优选的实施例中，无机纳米材料的平均粒径约在1到20nm，最优选在1到10nm。
所述无机纳米材料可以选自不同的形状，包含但不限于球形、立方体、棒状、盘形或支化结构等不同纳米形貌，以及各种形状颗粒的混合物。
在一个优选的实施例中，所述无机纳米材料是量子点材料，具有非常狭窄的、单分散的尺寸分布，即颗粒与颗粒之间的尺寸差异非常小。优选地，单分散的量子点在尺寸上的偏差均方根小于15％rms；更优选地，单分散的量子点在尺寸上的偏差均方根小于10％rms；最优选地，单分散的量子点在尺寸上的偏差均方根小于5％rms。
在一个优选的实施例中，所述无机纳米材料是发光材料。
在一个更加优选的实施例中，所述发光无机纳米材料是量子点发光材料。
一般地，发光量子点可以在波长380纳米到2500纳米之间发光。例如，已发现，具有CdS核的量子点的发光波长位于约400纳米到560纳米的范围内；具有CdSe核的量子点的发光波长位于约490纳米到620纳米的范围内；具有CdTe核的量子点的发光波长位于约620纳米到680纳米的范围内；具有InGaP核的量子点的发光波长位于约600纳米到700纳米的范围内；具有PbS核的量子点的发光波长位于约800纳米到2500纳米的范围内；具有PbSe核的量子点的发光波长位于约1200纳米到2500纳米的范围内；具有CuInGaS核的量子点的发光波长位于约600纳米到680纳米的范围内；具有ZnCuInGaS核的量子点的发光波长位于约500纳米到620纳米的范围内；具有CuInGaSe核的量子点的发光波长位于约700纳米到1000纳米的范围内；
在一个优选的实施例中，所述量子点材料包含至少一种能够发出发光峰值波长位于450nm～460nm的蓝光的材料、发光峰值波长位于520nm～540nm的绿光的材料、发光峰值波长位于615nm～630nm的红光的材料，或其中任意两种或以上的混合物。
所包含的量子点可以选自特殊的化学组成、形貌结构和/或大小尺寸，以获得在电刺激下发出所需波长的光。
量子点的窄的粒径分布能使量子点具有更窄的发光光谱。此外，根据所采用的化学组成和结构的不同，量子点的尺寸需在上述的尺寸范围内做相应调节，以获得所需波长的发光性质。
优选地，发光量子点是半导体纳米晶体。一般地，半导体纳米晶体的尺寸为约2纳米到约15纳米的范围内。此外，根据所采用的化学组成和结构的不同，量子点的尺寸需在上述的尺寸范围内做相应调节，以获得所需波长的发光性质。
所述半导体纳米晶体包括至少一种半导体材料，其中半导体材料可选为元素周期表IV族、II-VI族、II-V族、III-V族、III-VI族、IV-VI族、I-III-VI族、II-IV-VI族、II-IV-V族的二元或多元半导体化合物或其中任意两种或以上的混合物。具体所述半导体材料的实例包括，但不限制于：IV族半导体化合物，例如包括由单质Si、Ge和二元化合物SiC、SiGe；II-VI族半导体化合物，例如，其中二元化合物包括CdSe、CdTe、CdO、CdS、CdSe、ZnS、ZnSe、ZnTe、ZnO、HgO、HgS、HgSe、HgTe，三元化合物包括CdSeS、CdSeTe、CdSTe、CdZnS、CdZnSe、CdZnTe、CgHgS、CdHgSe、ZnSeS、ZnSeTe、ZnSTe、HgSeS、HgSeTe、HgSTe、HgZnS、HgSeSe，及四元化合物包括CgHgSeS、CdHgSeTe、CgHgSTe、CdZnSeS、CdZnSeTe、HgZnSeTe、HgZnSTe、CdZnSTe、HgZnSeS、；III-V族半导体化合物，例如，其中二元化合物包括AlN、AlP、AlAs、AlSb、GaN、GaP、GaAs、GaSb、InN、InP、InAs、InSb，三元化合物包括AlNP、AlNAs、AlNSb、AlPAs、AlPSb、GaNP、GaNAs、GaNSb、GaPAs、GaPSb、InNP、InNAs、InNSb、InPAs、InPSb，及四元化合物包括GaAlNAs、GaAlNSb、GaAlPAs、GaInNP、GaInNAs、GaInNSb、GaInPAs、GaInPSb、InAlNP、InAlNAs、InAlNSb、InAlPAs、InAlPSb；IV-VI族半导体化合物，例如，其中二元化合物包括SnS、SnSe、SnTe、PbSe、PbS、PbTe，三元化合物包括SnSeS、SnSeTe、SnSTe、SnPbS、SnPbSe、SnPbTe、PbSTe、PbSeS、PbSeTe，以及四元化合物包括SnPbSSe、SnPbSeTe、SnPbSTe。
在一个优选的实施例中，发光量子点包含有II-VI族半导体材料，优选选自CdSe、CdS、CdTe、ZnO、ZnSe、ZnS、ZnTe、HgS、HgSe、HgTe、CdZnSe或其中任意两种或以上的混合物。在合适的实施例中，由于CdSe、CdS的合成相对成熟，而可以将此材料用作用于可见光的发光量子点。
在另一个优选的实施例中，发光量子点包含有III-V族半导体材料，优选选自InAs、InP、InN、GaN、InSb、InAsP、InGaAs、GaAs、GaP、GaSb、AlP、AlN、AlAs、AlSb、CdSeTe、ZnCdSe或其中任意两种或以上的混合物。
在另一个优选的实施例中，发光量子点包含有IV-VI族半导体材料，优选选自PbSe、PbTe、PbS、PbSnTe、Tl2SnTe5或其中任意两种或以上的混合物。
在一个优选的实施例中，量子点为核壳结构。核与壳分别相同或不同地包括一种或多种半导体材料。
所述量子点的核可以选自上述的元素周期表IV族、II-VI族、II-V族、III-V族、III-VI族、IV-VI族、I-III-VI族、II-IV-VI族、II-IV-V族的二元或多元半导体化合物。具体的用于量子点核的实例包括，但不限制于：ZnO、ZnS、ZnSe、ZnTe、CdO、CdS、CdSe、CdTe、MgS、MgSe、GaAs、GaN、GaP、GaSe、GaSb、HgO、HgS、HgSe、HgTe、InAs、InN、InSb、AlAs、AlN、AlP、AlSb、PbO、PbS、PbSe、PbTe、Ge、Si，或其合金或其中任意两种或以上的混合物。
所述量子点的壳包含有与核相同或不同的半导体材料。可用于壳的半导体材料包括元素周期表IV族、II-VI族、II-V族、III-V族、III-VI族、IV-VI族、I-III-VI族、II-IV-VI族、II-IV-V族二元或多元半导体化合物。具体的用于量子点核的实例包括但不限制于ZnO、ZnS、ZnSe、ZnTe、CdO、CdS、CdSe、CdTe、MgS、MgSe、GaAs、GaN、GaP、GaSe、GaSb、HgO、HgS、HgSe、HgTe、InAs、InN、InSb、AlAs、AlN、AlP、AlSb、PbO、PbS、PbSe、PbTe、Ge、Si，或其合金或其中任意两种或以上的混合物。
所述具有核壳结构的量子点中，其壳可以包括单层或多层的结构。所述壳可以包括一种或多种与核相同或不同的半导体材料。在一个优选的实施例中，壳具有约1到20层的厚度。在一个更为优选的实施例中，壳具有约5到10层的厚度。在某些实施例中，在量子点核的表面包含有两种或两种以上的壳。
在一个优选的实施例中，用于壳的半导体材料可以具有比核更大的带隙。特别优选地，壳核具有I型的半导体异质结结构。
在另一个优选的实施例中，用于壳的半导体材料可以具有比核更小的带隙。
在一个优选的实施例中，用于壳的半导体材料可以具有与核相同或接近的原子晶体结构。这样的选择有利于减小核壳间的应力，使量子点更为稳定。
合适的采用核壳结构的发光量子点的例子(但不限制于)有：
红光：CdSe/CdS、CdSe/CdS/ZnS、CdSe/CdZnS等；
绿光：CdZnSe/CdZnS、CdSe/ZnS等；
蓝光：CdS/CdZnS、CdZnS/ZnS等。
优选的量子点的制备方法是胶状生长法。在一个优选的实施例中，制备单分散的量子点的方法选自热注射法(hot-inject)和/或加热法(heating-up)。制备方法包含在文件NanoRes，2009，2，425-447；Chem.Mater.，2015，27(7)，pp2246-2285中。
在一个优选的实施例中，所述量子点的表面可以包含有有机配体。有机配体可以控制量子点的生长过程，调控量子点的形貌和减小量子点表面缺陷，从而提高量子点的发光效率及稳定性。所述有机配体可以选自，但不限于：吡啶、嘧啶、呋喃、胺、烷基膦、烷基膦氧化物、烷基膦酸或烷基次膦酸、烷基硫醇等。具体的有机配体的实例包括但不限制于三正辛基膦、三正辛基氧化膦、三羟基丙基膦、三丁基膦、三(十二烷基)膦、亚磷酸二丁酯、亚磷酸三丁酯、亚磷酸十八烷基酯、亚磷酸三月桂酯、亚磷酸三(十二烷基)酯、亚磷酸三异癸酯、双(2-乙基己基)磷酸酯、三(十三烷基)磷酸酯、十六胺、油胺、十八胺、双十八胺、三十八胺、双(2-乙基己基)胺、辛胺、二辛胺、三辛胺、十二胺、双十二胺、三十二胺、十六胺、苯基磷酸、己基磷酸、四癸基磷酸、辛基磷酸、正十八烷基磷酸、丙烯二磷酸、二辛醚、二苯醚、辛硫醇、十二烷基硫醇等。
在另一个优选的实施例中，所述量子点的表面可以包含有无机配体。由无机配体保护的量子点可以通过对量子点表面有机配体进行配体交换得到。具体的无机配体的实例包括但不限制于：S2-、HS-、Se2-、HSe-、Te2-、HTe-、TeS3 2-、OH-、NH2 -、PO4 3-、MoO4 2等。
在某些实施例中，量子点表面可以具有一种或多种相同或不同的配体。
在一个优选的实施例中，具有单分散的量子点所表现出的发光光谱可以具有对称的峰形和窄的半峰宽。一般地，量子点的单分散性越好，其所表现的发光峰越对称，且半峰宽越窄。优选地，所述量子点的发光半峰宽小于70纳米；更优选地，所述量子点的发光半峰宽小于40纳米；最优选地，所述量子点的发光半峰宽小于30纳米。
一般地，所述量子点的发光量子效率大于10％，较优选是大于50％，更优选是大于60％，最优选是大于70％。
在另一个优选的实施例中，发光半导体纳米晶体是纳米棒。纳米棒的特性不同于球形纳米晶粒。例如，纳米棒的发光沿长棒轴偏振化，而球形晶粒的发光是非偏振的。纳米棒具有优异的光学增益特性，使得它们可能用作激光增益材料。此外，纳米棒的发光可以可逆地在外部电场的控制下打开和关闭。纳米棒的这些特性可以在某种情况下优选地结合到本发明的器件中。
在另一些优选的实施例中，本发明所述的用于印刷电子的组合物中，所述无机纳米材料是钙钛矿纳米粒子材料，特别是发光钙钛矿纳米粒子材料。
钙钛矿纳米粒子材料可以具有AMX3的结构通式，其中A可选自有机胺或碱金属阳离子，M可选自金属阳离子，X可选自氧或卤素阴离子。具体的实例包括但不限制于：CsPbCl3、CsPb(Cl/Br)3、CsPbBr3、CsPb(I/Br)3、CsPbI3、CH3NH3PbCl3、CH3NH3Pb(Cl/Br)3、CH3NH3PbBr3、CH3NH3Pb(I/Br)3、CH3NH3PbI3等。
在另一优选的实施例中，本发明所述的用于印刷电子的组合物中，所述无机纳米材料是金属纳米粒子材料，优选是发光金属纳米粒子材料。
所述金属纳米粒子包括但不限制于：铬(Cr)、钼(Mo)、钨(W)、钌(Ru)、铑(Rh)、镍(Ni)、银(Ag)、铜(Cu)、锌(Zn)、钯(Pd)、金(Au)、饿(Os)、铼(Re)、铱(Ir)和铂(Pt)等金属的纳米粒子。
在另一个优选的实施例中，所述无机纳米材料具有电荷传输的性能。
在一个优选的实施例中，所述无机纳米材料具有电子传输能力。优选地，这类无机纳米材料选自n型半导体材料。n型无机半导体材料的例子可以包括，但不限于，金属硫族元素化合物、金属磷族元素化合物、或元素半导体、如金属氧化物、金属硫化物、金属硒化物、金属碲化物、金属氮化物、金属磷化物，或金属砷化物。优选的n-型无机半导体材料可以选自，但不限于：ZnO，ZnS，ZnSe，TiO2，ZnTe，GaN，GaP，AlN，CdSe，CdS，CdTe，CdZnSe或其中任意两种或以上的混合物。
在某些实施例中，所述无机纳米材料具有空穴传输能力。优选地，这类无机纳米材料可以选自p型半导体材料。无机p-型半导体材料可选NiOx、WOx、MoOx、RuOx、VOx、CuOx或其中任意两种或以上的混合物。
在某些的实施例中，本发明所述的印刷油墨，可以包含至少两种及两种以上的无机纳米材料。
在另一个特别优选的实施例中，本发明所述的用于印刷电子的组合物可以包含有至少一种有机功能材料。
所述有机功能材料可以包括，但不限于，空穴(也称电洞)注入或传输材料(HIM/HTM)、空穴阻挡材料(HBM)、电子注入或传输材料(EIM/ETM)、电子阻挡材料(EBM)、有机主体材料(Host)、单重态发光体(荧光发光体)、热激活延迟荧光发光材料(TADF)、三重态发光体(磷光发光体)，特别是发光有机金属络合物，有机染料。
一般地，有机功能材料在本发明所述的杂芳族溶剂中的溶解度可以至少是0.2wt％，较优选为至少是0.3wt％，更优选为至少是0.6wt％，更更优选为至少是1.0wt％，最优选为至少是1.5wt％。
有机功能材料可以是小分子和高聚物材料。在本发明中，小分子有机材料是指分子量至多为4000g/mol的材料，分子量高于4000g/mol的材料统称为高聚物。
在一个优选的实施例中，本发明所述的用于印刷电子的组合物包含的功能材料为有机小分子材料。
在某些优选的实施例中，本发明所述的用于印刷电子的组合物，其中所述有机功能材料可以包含有至少一种的主体材料和至少一种发光体。
在一个优选的实施例中，所述有机功能材料可以包含有一种主体材料和一种单重态发光体。
在另一个优选的实施例中，所述有机功能材料可以包含有一种主体材料和一种三重态发 光体。
在另一个优选的实施例中，所述有机功能材料可以包含有一种主体材料和一种热激活延迟荧光发光材料。
在另一些优选的实施例中，所述有机功能材料可以包含有一种空穴传输材料(HTM)，更加优选地，所述HTM包含有可交联基团。
下面对将对适合优选的实施例的有机小分子功能材料作一些较详细的描述(但不限于此)。
1.HIM/HTM/EBM
合适的有机HIM/HTM材料可以可选地包含有如下结构单元的化合物：酞菁、卟啉、胺、芳香胺、联苯类三芳胺、噻吩、并噻吩如二噻吩并噻吩和并噻吩、吡咯、苯胺、咔唑、氮茚并氮芴及其衍生物，但不限于此。另外，合适的HIM也包括含有氟烃的聚合物、含有导电掺杂的聚合物、导电聚合物，如PEDOT：PSS，但不限于此。
电子阻挡层(EBL)用来阻挡来自相邻功能层，特别是发光层的电子。对比没有阻挡层的发光器件，EBL的存在通常会使得发光效率的提高。电子阻挡层(EBL)的电子阻挡材料(EBM)需要有比相邻功能层，如发光层更高的LUMO。在一个优选的实施例中，HBM有比相邻发光层更大的激发态能级，如单重态或三重态，取决于发光体，同时，EBM有空穴传输功能。通常具有高的LUMO能级的HIM/HTM材料可以作为EBM。
可用作HIM，HTM或EBM的环芳香胺衍生化合物的例子包括(但不限于)如下的一般结构：
Figure PCTCN2016099783-appb-000007
每个Ar1到Ar9可独立选自环芳香烃化合物，如苯、联苯、三苯基、苯并、萘、蒽、非那烯、菲、芴、芘、屈、苝、薁；芳香杂环化合物，如二苯并噻吩、二苯并呋喃、呋喃、噻吩、苯并呋喃、苯并噻吩、咔唑、吡唑、咪唑、三氮唑、异恶唑、噻唑、恶二唑、恶三唑、二恶唑、噻二唑、吡啶、哒嗪、嘧啶、吡嗪、三嗪、恶嗪、恶噻嗪、恶二嗪、吲哚、苯并咪唑、吲唑、吲哚嗪、苯并恶唑、苯异恶唑、苯并噻唑、喹啉、异喹啉、邻二氮(杂)萘、喹唑啉、喹喔啉、萘、酞、蝶啶、氧杂蒽、吖啶、吩嗪、吩噻嗪、吩恶嗪、二苯并硒吩、苯并硒吩、苯并呋喃吡啶、吲哚咔唑、吡啶吲哚、吡咯二吡啶、呋喃二吡啶、苯并噻吩吡啶、噻吩吡啶、苯并硒吩吡啶和硒吩二吡啶；包含有2至10环结构的基团，可以是相同或不同类型的环芳香烃基团或芳香杂环基团，并彼此直接或通过例如至少一个以下的基团连接在一起：氧原子、氮原子、硫原子、硅原子、磷原子、硼原子、链结构单元和脂肪环基团，但不限于此。其中，每个Ar可以进一步被取代，取代基可以选自，但不限于：氢、烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基或杂芳基。
在一个方面，Ar1到Ar9可独立选自包含如下基团，但不限于此：
Figure PCTCN2016099783-appb-000008
其中n是1到20的整数；X1到X8是CH或N；Ar1如以上所定义。
可用作HTM或HIM的金属络合物的例子包括(但不限于)如下的一般结构：
Figure PCTCN2016099783-appb-000009
其中M是金属，有大于40的原子量；
(Y1-Y2)是两齿配体，Y1和Y2独立地选自C、N、O、P和S；L是辅助配体；m是整数，其值选自从1到此金属的最大配位数；m+n是此金属的最大配位数。
在一个实施例中，(Y1-Y2)是2-苯基吡啶衍生物。
在另一个实施例中，(Y1-Y2)是一卡宾配体。
在另一个实施例中，M可以选自Ir、Pt、Os和Zn。
在另一个方面，金属络合物的HOMO大于-5.5eV(相对于真空能级)。
在下面的表中列出了合适的可作为HIM/HTM化合物的例子，但不限于此：
Figure PCTCN2016099783-appb-000010
2.三重态主体材料(TripletHost)：
三重态主体材料的例子并不受特别的限制，任何金属络合物或有机化合物都可能用作为主体，只要其三重态能量比发光体，特别是三重态发光体或磷光发光体更高接口。可用作三重态主体(Host)的金属络合物的例子包括(但不限于)如下的一般结构：
Figure PCTCN2016099783-appb-000011
其中M是金属；(Y3-Y4)是两齿配体，Y3和Y4独立地选自C，N，O，P，和S；L是辅助配体；m是整数，其值选自从1到此金属的最大配位数；m+n是此金属的最大配位数。
在一个优选的实施例中，可用作三重态主体的金属络合物可以有如下形式之一：
Figure PCTCN2016099783-appb-000012
其中，(O-N)是一两齿配体，其中金属与O和N原子配位。
在某一个实施例中，M可选于Ir和Pt。
可作为三重态主体的有机化合物的例子可以选自，但不限于：包含有环芳香烃基的化合物，例如苯、联苯、三苯基、苯并、芴；包含有芳香杂环基的化合物，如二苯并噻吩、二苯并呋喃、二苯并硒吩、呋喃、噻吩、苯并呋喃、苯并噻吩、苯并硒吩、咔唑、吲哚咔唑、吡啶吲哚、吡咯二吡啶、吡唑、咪唑、三唑类、恶唑、噻唑、恶二唑、恶三唑、二恶唑、噻二唑、吡啶、哒嗪、嘧啶、吡嗪、三嗪类、恶嗪、恶噻嗪、恶二嗪、吲哚、苯并咪唑、吲唑、恶唑、二苯并恶唑、苯异恶唑、苯并噻唑、喹啉、异喹啉、邻二氮杂萘、喹唑啉、喹喔啉、萘、酞、蝶啶、氧杂蒽、吖啶、吩嗪、吩噻嗪、吩恶嗪、苯并呋喃吡啶、呋喃并吡啶、苯并噻吩吡啶、噻吩吡啶、苯并硒吩吡啶和硒吩苯并二吡啶；包含有2至10环结构的基团，其可以是相同或不同类型的环芳香烃基团或芳香杂环基团，并彼此直接或通过例如至少一个以下的基团连接在一起，如氧原子、氮原子、硫原子、硅原子、磷原子、硼原子、链结构单元和脂肪环基团，但不限于此。其中，每个Ar可以进一步被取代，取代基可选为氢、烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基和杂芳基，但不限于此。
在一个优选的实施例中，三重态主体材料可选于包含至少一个以下基团的化合物，但不限于此：
Figure PCTCN2016099783-appb-000013
Figure PCTCN2016099783-appb-000014
所述R1-R7可相互独立地选于如下的基团：氢，烷基，烷氧基，氨基，烯，炔，芳烷基，杂烷基，芳基和杂芳基，但不限于此，当它们是芳基或杂芳基时，其与上述的Ar1和Ar2意义相同；n是一个从0到20的整数；X1-X8选于CH或N；X9选于CR1R2或NR1。
下面的表中列出了合适的三重态主体材料的例子，但不限于此：
Figure PCTCN2016099783-appb-000015
3.单重态主体材料(SingletHost)：
单重态主体材料的例子并不受特别的限制，任何有机化合物都可能被用作为主体，只要其单重态能量比发光体，特别是单重态发光体或荧光发光体更高即可。
作为单重态主体材料使用的有机化合物的例子可以选自，但不限于：含有环芳香烃化合物，如苯、联苯、三苯基、苯并、萘、蒽、萉、菲、芴、芘、屈、苝、薁；芳香杂环化合物，如二苯并噻吩、二苯并呋喃、二苯并硒吩、呋喃、噻吩、苯并呋喃、苯并噻吩、苯并硒吩、咔唑、吲哚咔唑、吡啶吲哚、吡咯二吡啶、吡唑、咪唑、三氮唑、异恶唑、噻唑、恶二唑、恶三唑、二恶唑、噻二唑、吡啶、哒嗪、嘧啶、吡嗪、三嗪、恶嗪、恶噻嗪、恶二嗪、吲哚、苯并咪唑、吲唑、吲哚嗪、苯并恶唑、苯异恶唑、苯并噻唑、喹啉、异喹啉、噌啉、喹唑啉、喹喔啉、萘、酞、蝶啶、氧杂蒽、吖啶、吩嗪、吩噻嗪、吩恶嗪、苯并呋喃吡啶、呋喃二吡啶、苯并噻吩吡啶、噻吩二吡啶、苯并硒吩吡啶和硒吩二吡啶；包含有2至10环结构的基团，它们可以是相同或不同类型的环芳香烃基团或芳香杂环基团，并彼此直接或通过至少一个以下的基团连接在一起，如氧原子、氮原子、硫原子、硅原子、磷原子、硼原子、链结构单元 和脂肪环基团，但不限于此。
在一个优选的实施例中，单重态主体材料可以选自，但不限于包含至少一个以下基团的化合物：
Figure PCTCN2016099783-appb-000016
其中，R1可相互独立地选于如下的基团：氢、烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基和杂芳基；Ar1是芳基或杂芳基，但不限于此，它与上述的HTM中定义的Ar1意义相同；n是一个从0到20的整数；X1-X8选于CH或N；X9和X10选于CR1R2或NR1。
下面的表中列出了一些蒽基单重态主体材料的例子，但不限于此：
Figure PCTCN2016099783-appb-000017
4.单重态发光体(SingletEmitter)
单重态发光体往往有较长的共轭π电子系统。迄今，已有许多例子，例如苯乙烯胺及其衍生物和茚并芴及其衍生物。
在一个优选的实施例中，单重态发光体可选自一元苯乙烯胺，二元苯乙烯胺，三元苯乙烯胺，四元苯乙烯胺，苯乙烯膦，苯乙烯醚和芳胺，但不限于此。
一元苯乙烯胺是指包含一个无取代或任选取代的苯乙烯团基团和至少一个胺(优选为芳香胺)的化合物。二元苯乙烯胺是指包含二个无取代或任选取代的苯乙烯基团和至少一个胺(优选为芳香胺)的化合物。三元苯乙烯胺是指包含三个无取代或任选取代的苯乙烯基团和至少一个胺(优选为芳香胺)的化合物。四元苯乙烯胺是指包含四个无取代或任选取代的苯乙烯基团和至少一个胺(优选为芳香胺)的化合物。优选的苯乙烯是二苯乙烯，其可能会进一步被取代。相应地，膦类和醚类的定义与胺类相似。芳基胺或芳香胺是指包含三个直接联接氮的无取代或任选取代的芳香环或杂环系统的化合物。这些芳香族或杂环的环系统中至少有一个优选地选于稠环系统，并最优选为有至少14个芳香环原子。其中优选的例子有芳香蒽胺，芳香蒽二胺，芳香芘胺，芳香芘二胺，芳香屈胺和芳香屈二胺，但不限于此。芳香蒽胺是指其中一个二元芳基胺基团直接连到蒽上，最好是在9的位置上的化合物。芳香蒽二胺是指其中二个二元芳基胺基团直接连到蒽上，最好是在9，10的位置上的化合物。芳香芘胺，芳香芘二胺，芳香屈胺和芳香屈二胺的定义类似，其中二元芳基胺基团最好连到芘的1或1，6位置上。
进一步的优选的单重态发光体可选自茚并芴-胺和茚并芴-二胺，苯并茚并芴-胺和苯并茚并芴-二胺，二苯并茚并芴-胺和二苯并茚并芴-二胺等。
其他可用作单重态发光体的材料有多环芳烃化合物，特别是如下化合物的衍生物：蒽如9，10-二(2-萘并蒽)，萘，四苯，氧杂蒽，菲，芘(如2，5，8，11-四-t-丁基苝)，茚并芘，苯撑如(4，4’-双(9-乙基-3-咔唑乙烯基)-1，1’-联苯)，二茚并芘，十环烯，六苯并苯，芴，螺二芴，芳基芘，亚芳香基乙烯，环戊二烯如四苯基环戊二烯，红荧烯，香豆素，若丹明，喹吖啶酮，吡喃如4(二氰基亚甲基)-6-(4-对二甲氨基苯乙烯基-2-甲基)-4H-吡喃(DCM)，噻喃，双(吖嗪基)亚胺硼化合物，双(吖嗪基)亚甲基化合物，carbostyryl化合物，噁嗪酮，苯并恶唑，苯并噻唑，苯并咪唑及吡咯并吡咯二酮，但不限于此。
下面的表中列出了一些合适的单重态发光体的例子，但不限于此：
Figure PCTCN2016099783-appb-000018
Figure PCTCN2016099783-appb-000019
5.热激活延迟荧光发光材料(TADF)：
传统有机荧光材料只能利用电激发形成的25％单线态激子发光，器件的内量子效率较低(最高为25％)。尽管磷光材料由于重原子中心强的自旋-轨道耦合增强了系间穿越，可以有效利用电激发形成的单线态激子和三线态激子发光，使器件的内量子效率达到100％。但磷光材料昂贵，材料稳定性差，器件效率滚降严重等问题限制了其在OLED中的应用。热激活延迟荧光发光材料是继有机荧光材料和有机磷光材料之后发展的第三代有机发光材料。该类材料一般具有小的单线态-三线态能级差(ΔEst)，三线态激子可以通过反系间穿越转变成单线态激子发光。这可以充分利用电激发下形成的单线态激子和三线态激子。器件内量子效率可达到100％。
TADF材料需要具有较小的单线态-三线态能级差，一般是ΔEst＜0.3eV，较优选是ΔEst＜0.2eV，更优选是ΔEst＜0.1eV，最优选是ΔEst＜0.05eV。在一个优选的实施例中，TADF有较优选的荧光量子效率。
下面的表中列出了一些合适的TADF发光材料的例子，但不限于此：
Figure PCTCN2016099783-appb-000020
Figure PCTCN2016099783-appb-000021
Figure PCTCN2016099783-appb-000022
6.三重态发光体(TripletEmitter)
三重态发光体也称磷光发光体。在一个优选的实施例中，三重态发光体是有通式M(L)n的金属络合物，其中M是一金属原子，L每次出现时可以是相同或不同，其为有机配体，通过一个或多个位置键接或配位连接到金属原子M上，n是一个大于1的整数，较优选选是1，2，3，4，5或6。可选地，这些金属络合物通过一个或多个位置联接到一个聚合物上，最优选是通过有机配体。
在一个优选的实施例中，金属原子M可以选自过渡金属元素或镧系元素或锕系元素等，优选Ir，Pt，Pd，Au，Rh，Ru，Os，Sm，Eu，Gd，Tb，Dy，Re，Cu或Ag，特别优选Os，Ir，Ru，Rh，Re，Pd或Pt，但不限于此。
优选地，三重态发光体可以包含有螯合配体，即配体，通过至少两个结合点与金属配位，特别优选考虑的是三重态发光体包含有两个或三个相同或不同的双齿或多齿配体。螯合配体有利于提高金属络合物的稳定性。
有机配体的例子可以选自，但不限于：苯基吡啶衍生物，7，8-苯并喹啉衍生物，2(2-噻吩基)吡啶衍生物，2(1-萘基)吡啶衍生物，或2苯基喹啉衍生物。所有这些有机配体都可能被取代，例如被含氟或三氟甲基取代。辅助配体可优选选自乙酸丙酮或苦味酸。
在一个优选的实施例中，可用作三重态发光体的金属络合物有如下形式：
Figure PCTCN2016099783-appb-000023
其中M是金属，选自过渡金属元素或镧系元素或锕系元素；
Ar1每次出现时可以是相同或不同，其为环状基团，其中至少包含有一个施主原子，即有一孤对电子的原子，如氮或磷，通过其环状基团与金属配位连接；Ar2每次出现时可以是相同或不同，其为环状基团，其中至少包含有一个C原子，通过其环状基团与金属连接；Ar1和Ar2由共价键联接在一起，可各自携带一个或多个取代基团，也可再通过取代基团联接在一起；L每次出现时可以是相同或不同，其为辅助配体，优选为双齿螯合配体，最优选是单阴离子双齿螯合配体；m是1，2或3，优选地是2或3，特别优选地是3；n是0，1，或2，优选地是0或1，特别优选地是0；
下面的表中列出一些合适的三重态发光体的例子，但不限于此：
Figure PCTCN2016099783-appb-000024
Figure PCTCN2016099783-appb-000026
在另一个优选的实施例中，本发明所述的用于印刷电子的组合物包含的功能材料可以为高聚物材料。
一般地，以上所述有机小分子功能材料，可以包括HIM，HTM，ETM，EIM，Host，荧光发光体，磷光发光体，TADF等，且其都可以作为重复单元包含在一高聚物中。
在一个优选的实施例中，适合于本发明的高聚物可以是共轭高聚物。一般地，共轭高聚物有如下通式：
Figure PCTCN2016099783-appb-000027
化学式1
其中B，A在多次出现时可独立选择相同或不同的结构单元
B：具有较大的能隙的π-共轭结构单元，也称骨干单元(BackboneUnit)，选自单环或多环 芳基或杂芳基，优选的单元形式为苯，联二亚苯(Biphenylene)，萘，蒽，菲，二氢菲，9，10-二氢菲，芴，二芴，螺二芴，对苯乙炔，反茚并芴，顺茚并，二苯并-茚并芴，茚并萘及其衍生物.
A：具有较小能隙的π-共轭结构单元，也称功能单元(FunctionalUnit)，按照不同的功能要求，可以选自，但不限于包含有以上所述空穴注入或传输材料(HIM/HTM)，电子注入或传输材料(EIM/ETM)，主体材料(Host)，单重态发光体(荧光发光体)，重态发光体(磷光发光体)的结构单元。
x，y：＞0，且x+y＝1；
在某些较为优选的实施例中，本发明所述的用于印刷电子的组合物包含的功能材料为高聚物HTM。
在一个优选的实施例中，高聚物HTM材料为均聚物，优选的均聚物选自聚噻吩，聚吡咯，聚苯胺，聚联苯类三芳胺，聚乙烯基咔唑及其衍生物.
在另一个特别优选的实施例中，高聚物HTM材料为化学式1表示的共轭共聚物，其中
A：具有空穴输运能力的功能基团，可相同或不同地选自包含有以上所述空穴注入或传输材料(HIM/HTM)的结构单元；在一个优选的实施例中，A选自胺，联苯类三芳胺，噻吩，并噻吩如二噻吩并噻吩和并噻吩，吡咯，苯胺，咔唑，indenocarbazole，氮茚并氮芴，并五苯，酞菁，卟啉及其衍生物.
x，y：＞0，且x+y＝1；通常y≥0.10，比较优选为≥0.15，更优选为≥0.20，最优选为x＝y＝0.5.
下面列出合适的可作为HTM的共轭高聚物的例子，但不限于此：
Figure PCTCN2016099783-appb-000028
Figure PCTCN2016099783-appb-000029
其中，
R各自彼此独立地选自：氢，具有1至20个C原子的直链烷基、烷氧基或硫代烷氧基基团，具有3至20个C原子的支链或环状的烷基、烷氧基或硫代烷氧基基团或者是甲硅烷基基团，1至20个C原子的取代的酮基基团，2至20个C原子的烷氧基羰基基团，7至20个C原子的芳氧基羰基基团，氰基基团(-CN)，氨基甲酰基基团(-C(＝O)NH2)，卤甲酰基基团(-C(＝O)-X其中X代表卤素原子)，甲酰基基团(-C(＝O)-H)，异氰基基团，异氰酸酯基团，硫氰酸酯基团或异硫氰酸酯基团，羟基基团，硝基基团，CF3基团，Cl，Br，F，可交联的基团或者具有5至40个环原子的任选取代或未取代的芳族或杂芳族环系，具有5至40个环原子的芳氧基或杂芳氧基基团；其中一个或多个所述R可以彼此独立存在或可以在彼此之间和/或与所述基团R键合的环形成单环或多环的脂族或芳族环系；
r是0，1，2，3或4；
s是0，1，2，3，4或5；
x，y：＞0，且x+y＝1；通常y≥0.10，较优选为≥0.15，更优选为≥0.20，最优选为x＝y＝0.5。
另一类优选的有机功能材料可以是具有电子传输能力的高聚物，包括共轭高聚物和非共轭高聚物。
优选的高聚物ETM材料可以为均聚物，优选的均聚物选自聚菲，聚菲罗啉，聚茚并芴，聚螺二芴，聚芴及其衍生物。
优选的高聚物ETM材料可以为化学式1表示的共轭共聚物，其中A在多次出现时可独立选择相同或不同的形式：
A：具有电子输运能力的功能基团，优选选自三(8-羟基喹啉)铝(AlQ3)，苯，联二亚苯，萘，蒽，菲，二氢菲，芴，二芴，螺二芴，对苯乙炔，芘，苝，9，10-二氢菲，吩嗪，菲罗啉，反茚并芴，顺茚并，二苯并-茚并芴，茚并萘，苯并蒽及其衍生物
x，y：＞0，且x+y＝1.通常y≥0.10，较优选为≥0.15，更优选为≥0.20，最优选为x＝y＝0.5.
在另一个优选的实施例中，本发明所述的用于印刷电子的组合物包含的功能材料为发光高聚物。
在一个特别优选的实施例中，发光高聚物是有如下通式的共轭高聚物高聚物有如下通式：
Figure PCTCN2016099783-appb-000030
化学式2
B：与化学式1的定义相同。
A1：具有空穴或电子输运能力的功能基，可以选自，但不限于包含有以上所述空穴注入或 传输材料(HIM/HTM)，或电子注入或传输材料(EIM/ETM)的结构单元。
A2：具有发光功能的基团，可以选自，但不限于包含有以上所述单重态发光体(荧光发光体)，重态发光体(磷光发光体)的结构单元。
x，y，z：＞0，且x+y+z＝1；
在另一个实施例中，适合于本发明的高聚物可以是非共轭高聚物。这可以是所有功能基团都在侧链上，而主链是非共轭的高聚物。其示例可以选自，但不限于：用作磷光主体或磷光发光材料的这类非共轭高聚物，一用作荧光发光材料的这类非共轭高聚物。另外，非共轭高聚物也可以是主链上共轭的功能单元通过非共轭的连接单元连接起来的高聚物。
本发明还涉及一种通过打印或涂布的方法制备包含功能材料的薄膜的方法，其中将如上所述任何一种组合物用印刷或涂布的方法涂布于一基板上，其中印刷或涂布的方法可选于(但不限于)喷墨打印，喷印(NozzlePrinting)，活版印刷，丝网印刷，浸涂，旋转涂布，刮刀涂布，辊筒印花，扭转辊印刷，平版印刷，柔版印刷，轮转印刷，喷涂，刷涂、移印，狭缝型挤压式涂布等。
在一个优选的实施例中，包含功能材料的薄膜为通过喷墨打印的方法制备。可用于打印本发明所述的油墨的喷墨打印机为可以是市售打印机，且包含按需打印喷头(drop-on-demandprintheads)。这些打印机可以从例如FujifilmDimatix(Lebanon，N.H.)，TridentInternational(Brookfield，Conn.)，Epson(Torrance，Calif)，HitachiDatasystemsCorporation(SantaClara，Calif)，XaarPLC(Cambridge，UnitedKingdom)，和IdanitTechnologies，Limited(RishonLeZion，Isreal)购得。例如，本发明可以使用DimatixMaterialsPrinterDMP-3000(Fujifilm)进行打印。
本发明进一步涉及一种电子器件，且包含有一层或多层功能薄膜，其中至少有一层功能薄膜是利用本发明所述的印刷油墨组合物制备而成的，特别是通过打印或涂布的方法制备的。
合适的电子器件包括但不限于量子点发光二极管(QLED)、量子点光伏电池(QPV)、量子点发光电池(QLEEC)、量子点场效应管(QFET)、量子点发光场效应管、量子点激光器，量子点传感器，有机发光二极管(OLED)、有机光伏电池(OPV)、有机发光电池(OLEEC)、有机场效应管(OFET)、有机发光场效应管、有机激光器，有机传感器等。
在一个优选的实施例中，以上所述电子器件是电致发光器件或光伏电池，如图1所示，包括基片(101)，阳极(102)，至少一个发光层或光吸收层(104)，阴极(106)。以下仅以电致发光器件为例做说明。
基片(101)可以是不透明或透明的。透明的基板可以用来制造透明的发光元器件。基材可以是刚性的或弹性的。基片可以是塑料，金属，半导体晶片或玻璃。最优选是基片有一个平滑的表面。无表面缺陷的基板是特别理想的选择。在一个优选的实施例中，基片可选于聚合物薄膜或塑料，其玻璃化温度Tg为150℃以上，较优选是超过200℃，更优选是超过250℃，最优选是超过300℃。合适的基板的例子有聚(对苯二甲酸乙二醇酯)(PET)和聚乙二醇(2，6-萘)(PEN)，但不限于此。
阳极(102)可包括导电金属或金属氧化物，或导电聚合物。阳极可以容易地注入空穴到HIL或HTL或发光层中。在一个的实施例中，阳极的功函数和作为HIL或HTL的p型半导体材料的HOMO能级或价带能级的差的绝对值小于0.5eV，较优选是小于0.3eV，最优选是小于0.2eV。阳极材料的例子包括但不限于，Al，Cu，Au，Ag，Mg，Fe，Co，Ni，Mn，Pd，Pt，ITO，铝掺杂氧化锌(AZO)等。其他合适的阳极材料是已知的，本领域普通技术人员可容易地选择使用。阳极材料可以使用任何合适的技术沉积，如一合适的物理气相沉积法，包括 射频磁控溅射，真空热蒸发，电子束(e-beam)等。
在某些实施例中，阳极是图案结构化的。图案化的ITO导电基板可在市场上买到，并且可以用来制备根据本发明的器件。
阴极(106)可包括一导电金属或金属氧化物。阴极可以容易地注入电子到EIL或ETL或直接到发光层中。在一个的实施例中，阴极的功函数和作为EIL或ETL或HBL的n型半导体材料的LUMO能级或导带能级的差的绝对值小于0.5eV，较优选是小于0.3eV，最优选是小于0.2eV。原则上，所有可用作OLED的阴极的材料都可能作为本发明器件的阴极材料。阴极材料的例子包括但不限于，Al，Au，Ag，Ca，Ba，Mg，LiF/Al，MgAg合金，BaF2/Al，Cu，Fe，Co，Ni，Mn，Pd，Pt，ITO等。阴极材料可以使用任何合适的技术沉积，如一合适的物理气相沉积法，包括射频磁控溅射，真空热蒸发，电子束(e-beam)等。
发光层(104)中可以至少包含有一层发光功能材料，其厚度可以在2nm到200nm之间。在一个优选的实施例中，本发明所述的发光器件中，其发光层是通过打印本发明的印刷油墨制备而成，其中印刷油墨中包含有至少一种如上所述发光功能材料，特别是量子点或有机功能材料。
在一个优选的实施例中，本发明所述的发光器件进一步包含有一个空穴注层(HIL)或空穴传输层(HTL)(103)，其中包含有如上所述有机HTM或无机p型材料。在一个优选的实施例中，HIL或HTL可以通过打印本发明的印刷油墨制备而成，其中印刷油墨中包含有具有空穴传输能力的功能材料，特别是量子点或有机HTM材料。
在另一个优选的实施例中，本发明所述的发光器件进一步包含有一个电子注层(EIL)或电子传输层(ETL)(105)，其中包含有如上所述有机ETM或无机n型材料。在某些实施例中，EIL或ETL可以通过打印本发明的印刷油墨制备而成，其中印刷油墨中包含有具有电子传输能力的功能材料，特别是量子点或有机ETM材料。
本发明还涉及本发明所述的发光器件在各种场合的应用，包括，但不限于，各种显示器件，背光源，照明光源等。
下面将结合优选实施例对本发明进行了说明，但本发明并不局限于下述实施例，应当理解，所附权利要求概括了本发明的的范围内在本发明构思的引导下本领域的技术人员应意识到，对本发明的各实施例所进行的一定的改变，都将被本发明的权利要求书的精神和的范围内所覆盖。
实施例：
实施例1：蓝光量子点的制备(CdZnS/ZnS)
称取0.0512g的S和量取2.4mLODE于25mL的单口烧瓶中，置于油浴中加热至80℃使S溶解，备用，以下简称溶液1；称取0.1280g的S和量取5mLOA于25mL的单口烧瓶中，置于油浴中加热至90℃使S溶解，备用，以下简称溶液2；称量0.1028gCdO和1.4680g的乙酸锌，量取5.6mL的OA于50mL的三口烧瓶中，将三口烧瓶置于150mL的加热套中，两边瓶口用胶塞塞住，上方连接一个冷凝管，再连接至双排管，加热至150℃，抽真空40min，再通氮气；用注射器将12mL的ODE加入到三口烧瓶中，升温至310℃时快速用注射器将1.92mL的溶液1打进三口烧瓶中，计时12min；12min一到，用注射器将4mL的溶液2滴加至三口烧瓶中，滴加速度大约为0.5mL/min，反应3h，停止反应，立刻把三口烧瓶放入水中冷却至150℃；
将过量的正己烷加入至三口烧瓶中，然后将三口烧瓶中的液体转移至多个10mL的离心 管中，离心，除去下层沉淀，重复三次；在经过后处理1的液体中加入丙酮至有沉淀产生，离心，除去上层清液，留下沉淀；再用正己烷溶解沉淀，后加丙酮至有沉淀出来，离心，除去上层清液，留下沉淀，重复三次；最后用甲苯溶解沉淀，转移至玻璃瓶中存储。
实施例2：绿光量子点的制备(CdZnSeS/ZnS)
称量0.0079g的硒和0.1122g的硫于25mL的单口烧瓶中，量取2mL的TOP，通氮气，搅拌，备用，以下简称溶液1；称量0.0128g的CdO和0.3670g的乙酸锌，量取2.5mL的OA于25mL的三口烧瓶中，两边瓶口用胶塞塞住，上方连接一个冷凝管，再连接至双排管，将三口烧瓶置于50mL的加热套中，抽真空通氮气，加热至150℃，抽真空30min，注射7.5mL的ODE，再加热至300℃快速注射1mL的溶液1，计时10min；10min一到，立刻停止反应，将三口烧瓶置于水中冷却。
往三口烧瓶中加入5mL的正己烷，然后就混合液加入至多个10mL的离心管中，加入丙酮至有沉淀出来，离心。取沉淀，除去上层清液，用正己烷将沉淀溶解，加入丙酮至有沉淀产生，离心。重复三次。最后的沉淀用少量的甲苯溶解，转移至玻璃瓶中储存。
实施例3：红光量子点的制备(CdSe/CdS/ZnS)
1mmol的CdO，4mmol的OA和20ml的ODE加入到100ml三口烧瓶中，鼓氮气，升温至300℃形成Cd(OA)2前驱体.在此温度下，快速注入0.25mL的溶有0.25mmol的Se粉的TOP。反应液在此温度下反应90秒，生长得到约3.5纳米的CdSe核。0.75mmol的辛硫醇在300℃下逐滴加入到反应液中，反应30分钟后生长约1纳米厚的CdS壳。4mmol的Zn(OA)2和2ml的溶有4mmol的S粉的TBP随后逐滴加入到反应液中，用以生长ZnS壳(约1纳米)。反应持续10分钟后，冷却至室温。
往三口烧瓶中加入5mL的正己烷，然后就混合液加入至多个10mL的离心管中，加入丙酮至有沉淀出来，离心。取沉淀，除去上层清液，用正己烷将沉淀溶解，加入丙酮至有沉淀产生，离心。重复三次。最后的沉淀用少量的甲苯溶解，转移至玻璃瓶中储存。
实施例4：ZnO纳米粒子的制备
将1.475g醋酸锌溶于62.5mL甲醇中，得到溶液1。将0.74gKOH溶于32.5mL甲醇中，得到溶液2。溶液1升温至60℃，激烈搅拌。使用进样器将溶液2逐滴滴加进溶液1。滴加完成后，该混合溶液体系在60℃下继续搅拌2小时。移去加热源，将溶液体系静置2小时。采用4500rpm，5min的离心条件，对反应溶液离心清洗三遍以上。最终得到白色固体为直径约3nm的ZnO纳米粒子。
下面列出本发明例子中所使用的部分杂芳族溶剂的沸点、表面张力及粘度参数：
Figure PCTCN2016099783-appb-000031
Figure PCTCN2016099783-appb-000032
下面列出本发明例子中所使用的另一种溶剂的沸点、表面张力及粘度参数：
Figure PCTCN2016099783-appb-000033
实施例5：含喹啉的量子点印刷油墨的制备
在小瓶内放入搅拌子，清洗干净后转移至手套箱中。在小瓶中配制9.5g喹啉溶剂。用丙酮将量子点从溶液中析出，离心得到量子点固体。在手套箱中称取0.5g量子点固体，加到小瓶中的溶剂体系中，搅拌混合。在60℃温度下搅拌直至量子点完全分散后，冷却至室温。将得到的量子点溶液经0.2μmPTFE滤膜过滤。密封并保存。
实施例6：含喹啉与十二烷基苯的量子点印刷油墨的制备
在小瓶内放入搅拌子，清洗干净后转移至手套箱中。在小瓶中配制9.5g喹啉与十二烷基苯的混合溶剂(重量比为60∶40)。用丙酮将量子点从溶液中析出，离心得到量子点固体。在手套箱中称取0.5g量子点固体，加到小瓶中的溶剂体系中，搅拌混合。在60℃温度下搅拌直至量子点完全分散后，冷却至室温。将得到的量子点溶液经0.2μmPTFE滤膜过滤。密封并保存。
实施例7：含异喹啉的ZnO纳米粒子印刷油墨的制备
在小瓶内放入搅拌子，清洗干净后转移至手套箱中。在小瓶中配制9.5g异喹啉溶剂。在手套箱中称取0.5gZnO纳米粒子固体，加到小瓶中的溶剂体系中，搅拌混合。在60℃温度下搅拌直至ZnO纳米粒子完全分散后，冷却至室温。将得到的ZnO纳米粒子溶液经0.2μmPTFE滤膜过滤。密封并保存。
实施例8：含异喹啉与3-苯氧基甲苯的ZnO纳米粒子印刷油墨的制备
在小瓶内放入搅拌子，清洗干净后转移至手套箱中。在小瓶中配制9.5g异喹啉与3-苯氧基甲苯的混合溶剂(重量比为60∶40)。在手套箱中称取0.5gZnO纳米粒子固体，加到小瓶中的溶剂体系中，搅拌混合。在60℃温度下搅拌直至ZnO纳米粒子完全分散后，冷却至室温。将得到的ZnO纳米粒子溶液经0.2μmPTFE滤膜过滤。密封并保存。
以下实施例中所涉及的有机功能材料均是可商业购得，如吉林奥莱德 (JilinOLEDMaterialTechCo.，Ltd，www.jl-oled.com)，或按照文献报道的方法合成而得。
实施例9：含喹啉的有机发光层材料印刷油墨的制备
在该实施例中，发光层有机功能材料包含一种磷光主体材料和一种磷光发光体材料。磷光主体材料选自如下的咔唑衍生物：
Figure PCTCN2016099783-appb-000034
磷光发光体材料选自如下铱配合物：
Figure PCTCN2016099783-appb-000035
在小瓶内放入搅拌子，清洗干净后转移至手套箱中。在小瓶中配制9.8g喹啉溶剂。在手套箱中称取0.18g磷光主体材料和0.02g磷光发光体材料，加到小瓶中的溶剂体系中，搅拌混合。在60℃温度下搅拌直至有机功能材料完全溶解后，冷却至室温。将得到的有机功能材料溶液经0.2μmPTFE滤膜过滤。密封并保存。
实施例10：含异喹啉的有机发光层材料印刷油墨的制备
在该实施例中，发光层有机功能材料包含一种荧光主体材料和一种荧光发光体材料。
荧光主体材料选自如下的螺芴衍生物：
Figure PCTCN2016099783-appb-000036
荧光发光体材料选自如下化合物：
Figure PCTCN2016099783-appb-000037
在小瓶内放入搅拌子，清洗干净后转移至手套箱中。在小瓶中配制9.8g异喹啉溶剂。在手套箱中称取0.19g荧光主体材料和0.01g荧光发光体材料，加到小瓶中的溶剂体系中，搅拌混合。在60℃温度下搅拌直至有机功能材料完全溶解后，冷却至室温。将得到的有机功能材 料溶液经0.2μmPTFE滤膜过滤。密封并保存
实施例11：含喹啉与3-苯氧基甲苯的有机发光层材料印刷油墨的制备
在该实施例中，发光层有机功能材料包含一种主体材料和一种TADF材料。
主体材料选自如下结构的化合物：
Figure PCTCN2016099783-appb-000038
TADF材料选自如下结构的化合物：
Figure PCTCN2016099783-appb-000039
在小瓶内放入搅拌子，清洗干净后转移至手套箱中。在小瓶中配制9.8g喹啉与3-苯氧基甲苯的混合溶剂(重量比为60∶40)。在手套箱中称取0.19g主体材料和0.01gTADF材料，加到小瓶中的溶剂体系中，搅拌混合。在60℃温度下搅拌直至有机功能材料完全溶解后，冷却至室温。将得到的有机功能材料溶液经0.2μmPTFE滤膜过滤。密封并保存
实施例12：含喹啉的空穴传输材料印刷油墨的制备
在该实施例中，印刷油墨包含一种具有空穴传输能力的空穴传输层材料。
空穴传输材料选自如下的三芳胺衍生物：
Figure PCTCN2016099783-appb-000040
在小瓶内放入搅拌子，清洗干净后转移至手套箱中。在小瓶中配制9.8g喹啉溶剂。在手套箱中称取0.2g空穴传输材料，加到小瓶中的溶剂体系中，搅拌混合。在60℃温度下搅拌直至有机功能材料完全溶解后，冷却至室温。将得到的有机功能材料溶液经0.2μmPTFE滤膜过滤。密封并保存。
实施例13：粘度及表面张力测试
功能材料油墨的粘度由DV-IPrimeBrookfield流变仪测试；功能材料油墨的表面张力由SITA气泡压力张力仪测试。
经上述测试，根据本发明实施例5至实施例12中制备得到的功能材料油墨的粘度和表面张力如下表所示：
实施例 粘度(cPs) 表面张力(dyne/cm)
5 5.4±0.5 41.0±0.5
6 5.5±0.5 37.2±0.5
7 4.5±0.3 41.7±0.5
8 4.7±0.3 40.1±0.5
9 5.6±0.5 41.3±0.5
10 5.1±0.5 42.1±0.2
11 5.8±0.5 38.3±0.5
12 5.9±0.5 41.6±0.5
实施例14：利用本发明的印刷油墨制备电子器件功能层
利用上述制备的基于杂芳族且具有通式(I)的有机溶剂的包含功能材料的印刷油墨，通过喷墨打印的方式，可制备发光二极管中的功能层，如发光层和电荷传输层，具体步骤如下。
将包含功能材料的油墨装入油墨桶中，油墨桶装配于喷墨打印机，如DimatixMaterialsPrinterDMP-3000(Fujifilm)。调节喷射油墨的波形、脉冲时间和电压，使油墨喷射达到最优，且实现油墨喷射的范围内的稳定化。在制备功能材料薄膜为发光层的OLED/QLED器件时，按照如下技术方案：OLED/QLED的基板为溅射有氧化铟锡(ITO)电极图案的0.7mm厚的玻璃。在ITO上使像素界定层图案话，形成内部用于沉积打印油墨的孔。然后将HIL/HTL材料喷墨打印至该孔中，真空环境下高温干燥移除溶剂，得到HIL/HTL薄膜。此后，将包含发光功能材料的印刷油墨喷墨打印到HIL/HTL薄膜上，真空环境下高温干燥移除溶剂，得到发光层薄膜。随后将包含有电子传输性能的功能材料的印刷油墨喷墨打印到发光层薄膜上，真空环境下高温干燥移除溶剂，形成电子传输层(ETL)。在使用有机电子传输材料时，ETL也可通过真空热蒸镀而成。然后Al阴极通过真空热蒸镀而成，最后封装完成OLED/QLED器件制备。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (20)

  1. 一种用于印刷电子的组合物，包含有至少一种功能材料和含有至少一种有机溶剂的溶剂体系，所述有机溶剂中包括至少一种基于杂芳族且具有通式(I)的有机溶剂：
    Figure PCTCN2016099783-appb-100001
    其中，
    Ar1是具有5～10个碳原子的杂芳环，n是大于或等于0的整数，R是取代基，其特征在于，所述基于杂芳族且具有通式(I)的有机溶剂的沸点≥150℃，且能够从溶剂体系中蒸发，以形成功能材料的薄膜。
  2. 根据权利要求1所述的用于印刷电子的组合物，其特征在于，其中所述基于杂芳族且具有通式(I)的有机溶剂在25℃下的粘度在1cPs到100cPs的范围内。
  3. 根据权利要求1所述的用于印刷电子的组合物，其特征在于，所述基于杂芳族且具有通式(I)的有机溶剂在25℃下的表面张力在19dyne/cm到50dyne/cm的范围内。
  4. 根据权利要求1所述的用于印刷电子的组合物，其特征在于，所述基于杂芳族且具有通式(I)的有机溶剂具有选自如下通式中任一种所示的结构：
    Figure PCTCN2016099783-appb-100002
    其中，
    X是CR1或N；
    Y选自CR2R3，SiR4R5，NR6，C(＝O)，S，S(＝O)2或O；
    且每一个通式中至少有一个X或Y是非C的原子；
    每个所述R1，R2，R3，R4，R5，R6独立选自以下各项中的任一种：H，D，具有1至20个C原子的直链烷基、烷氧基或硫代烷氧基基团，具有3至20个C原子的支链或环状的烷基、烷氧基或硫代烷氧基基团或者是甲硅烷基基团，具有1至20个C原子的取代的酮基基团，具有2至20个C原子的烷氧基羰基基团，具有7至20个C原子的芳氧基羰基基团，氰基基团，氨基甲酰基基团，卤甲酰基基团，甲酰基基团，异氰基基团，异氰酸酯基团，硫氰酸酯基团或异硫氰酸酯基团，羟基基团，硝基基团，CF3基团，Cl，Br，F，具有5至40个环原子的任选取代或未取代的芳族或杂芳族环系，具有5至40个环原子的芳氧基或杂芳氧基基团；其中R1，R2，R3，R4，R5，R6中的一个或多个基团能够彼此和/或与其键合的环形成单环或多环的脂族或芳族环系。
  5. 根据权利要求1所述的用于印刷电子的组合物，其特征在于，其中所述Ar1选自如下结构单元中的任一种：
    Figure PCTCN2016099783-appb-100003
  6. 根据权利要求1所述的用于印刷电子的组合物，其特征在于，所述R选自：具有1至20个C原子的直链烷基、烷氧基或硫代烷氧基基团，具有3至20个C原子的支链或环状的烷基、烷氧基或硫代烷氧基基团或者是甲硅烷基基团，具有1至20个C原子的取代的酮基基团，具有2至20个C原子的烷氧基羰基基团，具有7至20个C原子的芳氧基羰基基团，氰基基团，氨基甲酰基基团，卤甲酰基基团，甲酰基基团，异氰基基团，异氰酸酯基团，硫氰酸酯基团或异硫氰酸酯基团，羟基基团，硝基基团，CF3基团，Cl，Br，F，具有5至40个环原子的任选取代或未取代的芳族或杂芳族环系，具有5至40个环原子的芳氧基或杂芳氧基基团；其中一个或多个所述R能够彼此和/或与其键合的环形成单环或多环的脂族或芳族环系。
  7. 根据权利要求1所述的用于印刷电子的组合物，其特征在于，所述基于杂芳族且具有通式(I)的有机溶剂选自：2-苯基吡啶、3-苯基吡啶、4-(3-苯基丙基)吡啶、喹啉、异喹啉、8-羟基喹啉、2-呋喃甲酸甲酯、2-呋喃甲酸乙酯或其中任意两种或以上的混合物。
  8. 根据权利要求1所述的用于印刷电子的组合物，其特征在于，所述溶剂体系是进一步包含至少一种其它溶剂的混合溶剂，且所述具有通式(I)的有机溶剂占所述混合溶剂总重量的50％以上。
  9. 根据权利要求1所述的用于印刷电子的组合物，其特征在于，所述功能材料是无机纳米材料。
  10. 根据权利要求1所述的用于印刷电子的组合物，其特征在于，所述功能材料是量子点材料。
  11. 根据权利要求1所述的用于印刷电子的组合物，其特征在于，所述功能材料是发光波长位于380nm～2500nm之间的发光量子点材料，其。
  12. 根据权利要求1所述的用于印刷电子的组合物，其特征在于，所述用于印刷电子的组合物包含有无机功能材料，所述无机功能材料选自：元素周期表IV族、II-VI族、II-V族、III-V族、III-VI族、IV-VI族、I-III-VI族、II-IV-VI族、II-IV-V族的二元或多元半导体化合物中的任一种，或其中任意两种或以上的混合物。
  13. 根据权利要求1所述的用于印刷电子的组合物，其特征在于，所述功能材料为选自发光钙钛矿纳米材料、金属纳米粒子材料、金属氧化物纳米粒子材料的任一种，或其中任意两种或以上的混合物。
  14. 根据权利要求1所述的用于印刷电子的组合物，其特征在于，所述功能材料是有机功能材料。
  15. 根据权利要求14所述的用于印刷电子的组合物，其特征在于，所述有机功能材料为选自空穴注入材料、空穴传输材料、电子传输材料、电子注入材料、电子阻挡材料、空穴阻挡材料、发光体、主体材料或有机染料，或其中任意两种或以上的混合物。
  16. 根据权利要求14所述的用于印刷电子的组合物，其特征在于，所述有机功能材料包含有至少一种主体材料和至少一种发光体。
  17. 根据权利要求1所述的用于印刷电子的组合物，其特征在于，所述功能材料占所述用于印刷电子的组合物的重量百分比为0.3％～30％，所述溶剂体系占所述用于印刷电子的组合物的重量百分比为70％～99.7％。
  18. 一种电子器件，其包含有由如权利要求1所述的用于印刷电子的组合物印刷或涂布而成的功能层。
  19. 根据权利要求18所述的电子器件，其特征在于，所述电子器件选自以下任一种：量子点发光二极管、量子点光伏电池、量子点发光电池、量子点场效应管、量子点发光场效应管、量子点激光器、量子点传感器、有机发光二极管、有机光伏电池、有机发光电池、有机场效应管、有机发光场效应管、有机激光器或有机传感器。
  20. 一种功能材料薄膜的制备方法，包括：将根据权利要求1所述的用于印刷电子的组合物，用印刷或涂布的方法铺设于基板上，其中所述印刷或涂布的方法选自以下任一种：喷墨打印、喷印、活版印刷、丝网印刷、浸涂、旋转涂布、刮刀涂布、辊筒印花、扭转辊印刷、平版印刷、柔版印刷、轮转印刷、喷涂、刷涂、移印，或狭缝型挤压式涂布。
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