WO2017080324A1 - Printing composition containing inorganic nanomaterial and application therefor - Google Patents

Abstract

A printing composition containing an inorganic nanomaterial contains an inorganic nanomaterial and a solvent composition. The solvent composition comprises an aliphatic ketone and/or an aliphatic ether. The boiling point of the aliphatic ketone or the aliphatic ether is more than or equal to 180 ℃ and the viscosity of the aliphatic ketone or the aliphatic ether under the temperature of 25 ℃ C is within the range of 1 cPs to 100 cPs. The printing composition obtained on the basis of the solvent system is capable of forming a functional material film having uniform thickness and composition property.

Description

Printing composition containing inorganic nano material and application thereof Technical field

The invention relates to the field of electroluminescence technology, in particular to a printing composition containing inorganic nanoparticles and an application thereof.

Background technique

Quantum dots are nano-sized semiconductor materials with quantum confinement effects. When stimulated by light or electricity, quantum dots emit fluorescence with specific energy. The color (energy) of fluorescence is determined by the chemical composition and size of quantum dots. Therefore, the control of the size and shape of quantum dots can effectively regulate its electrical and optical properties. At present, countries are studying the application of quantum dots in full color, mainly in the display field.

In recent years, quantum dots have been rapidly developed as electroluminescent devices (QLEDs), and device lifetimes have been greatly improved, as in Peng et al., Nature Vol515 96 (2015) and Qian et al., in Nature Photonics Vol9 259 ( Reported in 2015). In the electroluminescent device, electrons and holes are injected into the light-emitting layer to illuminate under an applied electric field. Spin coating is currently the primary method for forming quantum dot luminescent layer films. However, spin coating techniques are difficult to apply to the fabrication of large area electroluminescent devices. In contrast, inkjet printing can produce quantum dot films on a large scale and low cost; compared with traditional semiconductor production processes, inkjet printing has low energy consumption, low water consumption, and environmental protection, which is a great advantage and potential for production. technology. Viscosity and surface tension are important parameters that affect the printing ink and printing process. A promising printing ink needs to have the proper viscosity and surface tension. At present, several companies have reported quantum dot inks for printing:

Nanoco Technologies Ltd. discloses a method of printing a printable ink formulation comprising nanoparticles (CN101878535B). By selecting a suitable ink substrate, such as toluene and dodecyl selenol, a printable nanoparticle ink and a corresponding nanoparticle-containing film are obtained.

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 was obtained by printing the ink, and a quantum dot electroluminescent device was prepared.

QD Vision (Ind.) discloses a quantum dot ink formulation comprising a host material, a quantum dot material and an additive (US2010264371A1).

Other patents relating to quantum dot printing inks are: US2008277626A1, US2015079720A1, US2015075397A1, TW201340370A, US2007225402A1, US2008169753A1, US2010265307A1, US2015101665A1, WO2008105792A2. In these published patents, in order to regulate the physical parameters of the ink, these quantum dot inks contain other additives such as alcohol polymers. The introduction of polymer additives with insulating properties tends to reduce the charge transport capability of the film, which has a negative impact on the photoelectric performance of the device, and limits its wide application in optoelectronic devices. Therefore, it has become particularly important to find an organic solvent system for dispersing quantum dots with appropriate surface tension and viscosity.

Summary of the invention

Based on this, it is an object of the present invention to provide a printing composition comprising an inorganic nanomaterial.

The specific technical solutions are as follows:

A printing composition comprising an inorganic nano material comprising an inorganic nano material and a solvent composition, the solvent composition comprising an aliphatic ketone and/or an aliphatic ether, the boiling point of the aliphatic ketone and the aliphatic ether ≥180 ° C, and the viscosity range at 25 ° C is 1 cPs-100 cPs.

In some of these embodiments, the aliphatic ketone and the aliphatic ether each have a boiling point of > 250 ° C and a viscosity at 25 ° C ranging from 1 cPs to 40 cPs.

In some of these embodiments, the aliphatic ketone and the aliphatic ether have a surface tension ranging from 19 dyne/cm to 50 dyne/cm at 25 °C.

In some of these embodiments, the aliphatic ketone and the aliphatic ether have a surface tension in the range of 22 dyne/cm to 35 dyne/cm at 25 °C.

In some of these embodiments, the inorganic nanomaterial comprises from 0.3% to 70% of the total mass of the printing composition, and the solvent composition comprises from 30% to 99.7% of the total mass of the printing composition.

In some of these embodiments, the aliphatic ketone is selected from the group consisting of the structure represented by the formula (I), and the aliphatic ether is selected from the structure represented by the formula (II):

Wherein R ¹ , R ² and R ³ are the same or different from each other, and are each independently selected from a linear alkyl group of 1 to 10 C atoms, a branched alkyl group or a cyclic alkyl group;

n is an integer of 0 to 4, and when n ≥ 2, R ^{3 is the} same or different from each other.

In some of these embodiments, the aliphatic ketone is selected from the group consisting of 2-nonanone, 3-fluorenone, 5-nonanone, 2-nonanone, 2,5-hexanedione, 2,6,8-trimethyl Ketoketone, phorone or di-n-pentyl ketone.

In some of these embodiments, the aliphatic ether is selected from the group consisting of pentyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol II Butyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether or tetraethylene glycol dimethyl ether.

In some of these embodiments, the solvent composition further includes a third solvent, the third solvent being an aromatic or heteroaromatic compound, and the third solvent comprising 20%-99 of the total mass of the solvent composition. %.

In some of the embodiments, the third solvent is selected from the group consisting of 1-tetralone, 3-phenoxytoluene, acetophenone, 1-methoxynaphthalene, p-diisopropylbenzene, pentylbenzene, and tetra Hydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, o-diethylbenzene, m-diethylbenzene, p-pair Ethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, 1-methylnaphthalene 1,2,4-trichlorobenzene, 1,3-dipropoxybenzene, 4,4-difluorodiphenylmethane, diphenyl ether, 1,2-dimethoxy-4-(1-propene Benzo, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether, N-methyldiphenylamine , 4-isopropylbiphenyl, α,α-dichlorodiphenylmethane, 4-(3-phenylpropyl)pyridine, benzyl benzoate, 1,1-bis(3,4-dimethylbenzene Ethyl) and 2-isopropylnaphthalene or dibenzyl ether.

In some of the embodiments, the inorganic nanomaterial is a luminescent quantum dot material, and the luminescent quantum dot material has an emission wavelength between 380 nm and 2500 nm.

In some of the embodiments, the inorganic nanomaterial is selected from Group IV, II-VI, II-V, III-V, III-VI, IV-VI, and I-III-VI of the Periodic Table of the Elements. Groups, Groups II-IV-VI, Group II-IV-V binary or multi-component semiconductor compounds or mixtures of these compounds.

In some of these embodiments, the inorganic nanomaterial is a metal nanoparticle material or a metal oxide nanoparticle material or a mixture thereof.

In some of these embodiments, the inorganic nanomaterial is a perovskite nanoparticle material.

In some of the embodiments, the printing composition further comprises an organic functional material selected from the group consisting of a hole injecting material, a hole transporting material, an electron transporting material, an electron injecting material, an electron blocking material, and a hole blocking Material, illuminant, host material or organic dye.

Another object of the present invention is to provide the use of the above inorganic nanomaterial-containing printing composition.

The specific technical solutions are as follows:

The use of the above inorganic nanomaterial-containing printing composition for the preparation of electronic devices.

Another object of the present invention is to provide an electronic device.

The specific technical solutions are as follows:

An electronic device for producing a functional film using the inorganic nanomaterial-containing printing composition according to any one of claims 1-13.

In some of these embodiments, the method of preparing the functional film includes the step of applying the printing composition to a substrate.

In some of these embodiments, the method of coating is selected from the group consisting of: inkjet printing, jet printing, letterpress printing, screen printing, dip coating, spin coating, knife coating, roller printing, torsion roll printing, lithography Printing, flexographic, rotary printing, spray coating, brush coating, pad printing or slit extrusion coating.

In some of these embodiments, the electronic device is selected from the group consisting of a quantum dot light emitting diode, a quantum dot photovoltaic cell, a quantum dot luminescent cell, a quantum dot field effect transistor, a quantum dot luminescence field effect transistor, a quantum dot laser, a quantum dot sensor.

The beneficial effects of the present invention are as follows:

The above inorganic nanomaterial-containing printing composition comprises at least one inorganic nanomaterial, in particular a quantum dot material, and at least one organic solvent based on an aliphatic ketone or an aliphatic ether. The aliphatic ketone or the aliphatic ether has a boiling point of ≥180 ° C, and a viscosity at 25 ° C ranging from 1 cPs to 100 cPs, and a surface tension ranging from 19 dyne/cm to 50 dyne/cm. A printing composition obtained from an aliphatic ketone or aliphatic ether-based solvent system that satisfies the above boiling point and surface tension parameters and viscosity parameters is capable of forming a functional material film having uniform thickness and composition properties.

The above printing composition can control the viscosity and surface tension of the printing composition by selecting a specific organic solvent. 1-100 cPs and 19 dyne/cm-50 dyne/cm are suitable for ink jet printing and form a film having a uniform surface. At the same time, the organic solvent based on the aliphatic ketone or the aliphatic ether can be effectively removed by post-treatment, such as heat treatment or vacuum treatment, which is advantageous for ensuring the performance of the electronic device. The present invention therefore provides a printing ink for the preparation of high quality functional films, which provides an effective technical solution for printing quantum dot electronic or optoelectronic devices.

DRAWINGS

1 is a schematic structural view of an organic electroluminescent device according to an embodiment of 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), and 104 is a light emitting layer. (Electroluminescent device) or light absorbing layer (photovoltaic cell), 105 is an electron injection layer (EIL) or an electron transport layer (ETL), and 106 is a cathode.

detailed description

In order to facilitate the understanding of the present invention, the present invention will be described more fully hereinafter with reference to the accompanying drawings. Preferred embodiments of the invention are shown in the drawings. However, the invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that the understanding of the present disclosure will be more fully understood.

All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, unless otherwise defined. The terminology used in the description of the present invention is for the purpose of describing particular embodiments and is not intended to limit the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.

In the present invention, the printing composition and the printing ink, or ink, have the same meaning and are interchangeable.

The present invention provides a printing composition comprising an inorganic nanomaterial, comprising at least one inorganic nanomaterial, and at least one organic solvent based on an aliphatic ketone or an aliphatic ether, based on an aliphatic ketone or an aliphatic ether The organic solvent has a boiling point higher than 180 ° C, and its viscosity is @25 ° C. In the range of 1 cPs to 100 cPs, the organic solvent based on aliphatic ketone or aliphatic ether can be evaporated from the solvent system to form an inorganic nano material film. .

In a specific embodiment, the aliphatic ketone or aliphatic ether-based organic solvent has a boiling point of ≥180 °C. In certain embodiments, the aliphatic ketone or aliphatic ether-based organic solvent has a boiling point of ≥200 ° C; in certain embodiments, the aliphatic ketone or aliphatic ether-based organic solvent The boiling point is ≥ 250 ° C; in other preferred embodiments, the aliphatic ketone or aliphatic ether-based organic solvent has a boiling point of ≥ 275 ° C or ≥ 300 ° C. The boiling point within these ranges is to prevent Nozzle clogging of the inkjet printhead is beneficial. The organic solvent may be completely evaporated from the solvent system by heating, vacuum drying or the like to form a film comprising the inorganic nano material.

In a preferred embodiment, in the printing ink according to the present invention, the viscosity of the selected aliphatic ketone or aliphatic ether-based organic solvent at 25 ° C is in the range of about 1 cps to 90 cps; preferably from 1 cps to 60 cps. Range; better in the range of 1 cps to 40 cps; preferably in the range of 1.5 cps to 20 cps.

The viscosity of the printing composition can be adjusted by different methods, such as by selection of a suitable organic solvent and concentration of inorganic nanomaterials in the ink. The organic solvent containing an aliphatic ketone or an aliphatic ether according to the present invention can facilitate the adjustment of the printing ink to an appropriate range in accordance with the printing method used. Generally, the printing ink according to the present invention comprises the inorganic nanomaterial in a weight percentage ranging from 0.3% to 70% by weight, preferably from 0.5% to 50% by weight, more preferably from 0.5% to 30% by weight, most preferably It is in the range of 0.5% to 10% by weight. In a preferred embodiment, the ink comprising the aliphatic ketone or aliphatic ether-based organic solvent has a viscosity at the above composition ratio of less than 100 cps; in a more preferred embodiment, the ink is included The ink of the organic solvent based on the aliphatic ketone or the aliphatic ether has a viscosity at the above composition ratio of less than 60 cps; in a more preferred embodiment, the organic based on the aliphatic ketone or the aliphatic ether is contained. The solvent ink has a viscosity at a composition ratio of less than 40 cps; in a most preferred embodiment, the ink containing the aliphatic ketone or aliphatic ether-based organic solvent has a viscosity of 1.5 at the above composition ratio. To 20cps. The viscosity herein refers to the viscosity at ambient temperature at the time of printing, and is usually 15 to 30 ° C, preferably 18 to 28 ° C, more preferably 20 to 25 ° C, and most preferably 23 to 25 ° C. The printing ink thus formulated will be particularly suitable for ink jet printing.

In some preferred embodiments, the present invention relates to printing inks comprising an aliphatic ketone or aliphatic ether based organic solvent having a surface tension @25 ° C in the range of 19 dyne/cm to 50 dyne/cm.

Suitable ink surface tension parameters are suitable for a particular substrate and a particular printing method. For example, for ink jet printing, in a preferred embodiment, the organic solvent based on an aliphatic ketone or an aliphatic ether has a surface tension at 25 ° C in the range of about 19 dyne / cm to 50 dyne / cm; In a preferred embodiment, the surface temperature of the aliphatic ketone or aliphatic ether-based organic solvent at 25 ° C is in the range of about 22 dyne / cm to 35 dyne / cm; in a most preferred embodiment, the The surface tension of the organic solvent based on the aliphatic ketone or the aliphatic ether at 25 ° C is in the range of about 25 dyne/cm to 33 dyne/cm.

In a preferred embodiment, the printing ink according to the invention has a surface tension at 25 ° C in the range of from about 19 dyne/cm to 50 dyne/cm; more preferably in the range of from 22 dyne/cm to 35 dyne/cm; preferably in 25 dyne. /cm to 33 Dyne/cm range.

An ink obtained by a solvent system of an aliphatic ketone or an aliphatic ether-based organic solvent satisfying the above boiling point and surface tension parameters and viscosity parameters can form a functional material film having uniform thickness and composition properties.

In some preferred embodiments, the printing ink according to the invention comprises an organic solvent having the structural formula shown in formula (I) or (II):

among them,

n is an integer of 0 to 4, and when n ≥ 2, R ₃ may be the same or different from each other;

R ¹ , R ² is H, or D, or a linear alkyl, alkoxy or thioalkoxy group having 1 to 10, more preferably 1 to 5 C atoms, or having 3 to 10 More preferably, a branched or cyclic alkyl, alkoxy or thioalkoxy group of 3 to 5 C atoms or a silyl group, or 1 to 10, more preferably a substituted keto group of 1 to 5 C atoms, or an alkoxycarbonyl group having 2 to 10, more preferably 2 to 5 C atoms, or an aryloxy group having 7 to 10 C atoms a carbonyl group, a cyano group (-CN), a carbamoyl group (-C(=O)NH ₂ ), a haloformyl group (-C(=O)-X wherein X represents a halogen atom), Formyl group (-C(=O)-H), isocyano group, isocyanate group, thiocyanate group or isothiocyanate group, hydroxyl group, nitro group, CF _a group of ₃ , Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 20, more preferably 5 to 10 ring atoms, or 5 to 20, more preferably an aryloxy or heteroaryloxy group of 5 to 10 ring atoms, or a combination of these systems;

R ³ , when n ≥ 2, R ₃ may be the same or different from each other, and is a linear alkyl group, alkoxy group or thioalkoxy group having 1 to 10, more preferably 1 to 5 C atoms. Or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 10, more preferably 3 to 5 C atoms, or a silyl group, or having 1 to 10, more preferably a substituted keto group of 1 to 5 C atoms, or an alkoxycarbonyl group of 2 to 10, more preferably 2 to 5 C atoms, or 7 to 10 An aryloxycarbonyl group of a C atom, a cyano group (-CN), a carbamoyl group (-C(=O)NH ₂ ), a haloformyl group (-C(=O)-X wherein X represents a halogen atom), a formyl group (-C(=O)-H), an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, a CF ₃ group, a Cl, a Br, a F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaryl having 5 to 20, more preferably 5 to 10 ring atoms. a family ring system, or an aryloxy or heteroaryloxy group having 5 to 20, more preferably 5 to 10 ring atoms, or these systems Combination;

Wherein at least one of R ¹ , R ² and R ³ is an aliphatic group, and a chain which may be bonded to each other and/or to the group may form a monocyclic or polycyclic structure.

As the solvent, the molecular weight needs to be in an appropriate range. In certain embodiments, the printing ink according to the invention, wherein the solvent according to formula (I) or (II) has a molecular weight of from 100 to 350 Dalton, preferably from 120 to 330 Dalton, more preferably from 140 to 310 Dalton. More preferably, it is at 160-280 Dalton, preferably at 180-260 Dalton.

In a particularly preferred embodiment, the printing ink according to the invention comprises an organic solvent having an aliphatic ketone of the formula (I), wherein R ¹ , R ² , R ³ may be in each other The same or different, a linear alkyl group or a branched alkyl group of 1 to 10 C atoms;

n is an integer of 0 to 4, and when n ≥ 2, R ³ may be the same or different from each other.

In some preferred embodiments, the organic solvent of the aliphatic ketone has the structure of formula (I), and n is preferably 0 or 1.

Suitable organic solvents for the aliphatic ketones according to the invention may preferably be selected from, but not limited to, 2-nonanone, 3-fluorenone, 5-fluorenone, 2-nonanone, 2,5-hexanedione , 2,6,8-trimethyl-4-indolone, phorone, di-n-pentyl ketone, and the like.

In another particularly preferred embodiment, the printing ink according to the invention comprises an organic solvent having an aliphatic ether of the formula shown in formula (II):

among them,

R ¹ , R ² , and R ³ may be the same or different from each other, and are a linear alkyl group or a branched alkyl group of 1 to 10 C atoms; n is an integer of 0 to 4, and when n≥2, R ³ may be Same or different from each other.

In some preferred embodiments, the organic solvent of the aliphatic ether has a structure of the formula (II), and n is preferably from 2 to 4. Such a choice would result in better stability and desolvation of the ink based on the solvent. At the same time, it helps to increase the boiling point of the ink solvent and prevent clogging of the nozzle by the ink material during inkjet printing.

In certain preferred embodiments, the organic solvent of the aliphatic ether has the structure of formula (II), and R ³ preferably has 2 to 3 C atoms. Such a choice helps to effectively dissolve (disperse) the inorganic nanomaterial in the solvent.

Suitable organic solvents for the aliphatic ethers according to the invention may preferably be selected from, but not limited to, pentanyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol Alcohol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, etc. .

In certain preferred embodiments, the aliphatic ketone or aliphatic ether-based solvent system comprises a system comprising a single aliphatic ketone solvent, or a mixture of a plurality of aliphatic ketone solvents, or an aliphatic ketone solvent and a mixture of other solvents; or a single aliphatic ether solvent, or a mixture of a plurality of aliphatic ether solvents, or a mixture of an aliphatic ether solvent and other solvents; or a mixture of an aliphatic ketone solvent and an aliphatic ether solvent, or a mixture thereof Further mixtures with other solvents.

In certain embodiments, the organic solvent contained in the printing ink of the present invention is a mixture of an aliphatic ketone solvent and a good solvent for another inorganic nanoparticle. In other embodiments, the organic solvent contained in the printing ink of the present invention is a mixture of an aliphatic ether solvent and a good solvent for another inorganic nanoparticle. The purpose of this is to effectively dissolve or disperse the inorganic nanomaterial into the solvent system when the inorganic nanomaterial is only soluble in the non-aqueous solvent; and it can be adjusted by adjusting the aliphatic ketone/ether solvent and the good solvent of the inorganic nanoparticle. The ratio adjusts the viscosity and surface tension of the ink to the desired value.

In some preferred embodiments, the aliphatic ketone/ether solvent comprises from 1% to 80%, preferably from 5% to 70%, more preferably from 10% to 70%, based on the total weight of the mixed solvent of the other inorganic nanoparticles. % to 60%; preferably 20% to 50%.

In some preferred embodiments, the good solvent of the other inorganic nanoparticle is preferably selected from aromatic or heteroaromatic based solvents.

In a preferred embodiment, the aromatic or heteroaromatic solvent as described above has a structure of the formula (III):

among them,

Ar ¹ is an aromatic or heteroaryl ring having 5 to 10 carbon atoms, n is an integer of 0 or more, and R is a substituent.

In certain preferred embodiments, the aromatic or heteroaromatic based solvent of formula (III) wherein Ar ¹ is an aromatic or heteroaromatic ring having from 5 to 10 carbon atoms. An aromatic group refers to a hydrocarbon group containing at least one aromatic ring, including a monocyclic group and a polycyclic ring system. A heteroaromatic group refers to a hydrocarbon group (containing a hetero atom) comprising at least one heteroaromatic ring, including a monocyclic group and a polycyclic ring system. These 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 aromatic or heteroaromatic.

Specifically, examples of the aromatic group are: benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, anthracene, benzofluorene, triphenylene, anthracene, anthracene, and derivatives thereof.

Specifically, examples of heteroaromatic groups are: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, anthracene, anthracene Oxazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrol, furanfuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, Pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-diazine, quinoxaline, phenanthridine, carbaidine, quinazoline, quinazolinone, and derivatives thereof.

In a preferred embodiment, the total number of atoms other than H in all substituents R in the formula (III) as described above is greater than or equal to 1, preferably from 2 to 20, more preferably from 2 to 10, most preferably It is 3 to 10. . 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 and the like. For example, a methoxy substituent and three chlorine substituents are all included in the scope of the benzene invention, and specific examples are 1-methoxynaphthalene and trichlorobenzene.

In a preferred embodiment, the aromatic or heteroaromatic based solvent has a boiling point of ≥ 100 ° C, preferably ≥ 140 ° C, more preferably ≥ 180 ° C, most preferably ≥ 200 ° C.

In certain more preferred embodiments, the organic solvent of formula (III) as described above may be further selected from the following formula:

among them,

X is CR ⁴ or N;

Y is selected from CR ⁵ R ⁶ , SiR ⁷ R ⁸ , NR ⁹ or, C(=O), S, or O;

R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ are H, or D, or a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms or a silyl group or a substituted ketone group having 1 to 20 C atoms a group, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, a cyano group (-CN), a carbamoyl group (- C(=O)NH ₂ ), haloformyl group (-C(=O)-X wherein X represents a halogen atom), formyl group (-C(=O)-H), isocyanato group , isocyanate group, thiocyanate group or isothiocyanate group, hydroxyl group, nitro group, CF ₃ group, Cl, Br, F, crosslinkable group or having 5 to a substituted or unsubstituted aromatic or heteroaromatic ring system of 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems, one or more of which radicals R ^4, R ^5, R ⁶ may be and / or are formed monocyclic or polycyclic group with each other and the ring bonded Aliphatic or aromatic ring system

In some preferred embodiments, R ⁴ , R ⁵ , R ⁶ are H, or D, or a linear alkyl, alkoxy or thioalkoxy group having from 1 to 10 C atoms, or A branched or cyclic alkyl, alkoxy or thioalkoxy group of 3 to 10 C atoms is either a silyl group or a substituted keto group having 1 to 10 C atoms. Or an alkoxycarbonyl group having 2 to 10 C atoms, or an aryloxycarbonyl group having 7 to 10 C atoms, a cyano group (-CN), a carbamoyl group (-C) (=O)NH ₂ ), haloformyl group (-C(=O)-X wherein X represents a halogen atom), formyl group (-C(=O)-H), isocyanato group, Isocyanate group, thiocyanate group or isothiocyanate group, hydroxyl group, nitro group, CF ₃ group, Cl, Br, F, crosslinkable group or having 5 to 20 a substituted or unsubstituted aromatic or heteroaromatic ring system of one ring atom, or an aryloxy or heteroaryloxy group having 5 to 20 ring atoms, or a combination of these systems, wherein one or more groups groups ^{R 4, R 5, R 6} , R 7, R 8, R 9 can each other and / or with the group key Ring form an aliphatic or aromatic ring system monocyclic or polycyclic.

In some embodiments, Ar ¹ in formula (III) is preferably selected from the group consisting of:

In some embodiments, at least one substituent R in formula (III) is selected from a linear alkyl, alkoxy or thioalkoxy group having from 1 to 20 C atoms, or from 3 to 20 a branched or cyclic alkyl, alkoxy or thioalkoxy group of a C atom or a silyl group, or a substituted keto group having 1 to 20 C atoms, or An alkoxycarbonyl group of 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, a cyano group (-CN), a carbamoyl group (-C(=O) NH ₂ ), haloformyl group (-C(=O)-X wherein X represents a halogen atom), formyl group (-C(=O)-H), isocyano group, isocyanate group , thiocyanate group or isothiocyanate group, hydroxyl group, nitro group, CF ₃ group, Cl, Br, F, crosslinkable group or having 5 to 40 ring atoms a substituted or unsubstituted aromatic or heteroaromatic ring system, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems, wherein one or more groups R may Rings bonded to each other and/or to the group form a monocyclic or polycyclic lipid Family or aromatic ring system.

In some preferred embodiments, at least one substituent R in the formula (III) is selected from a linear alkyl, alkoxy or thioalkoxy group having from 1 to 10 C atoms, or has 3 a branched or cyclic alkyl, alkoxy or thioalkoxy group of up to 10 C atoms or a silyl group, or a substituted keto group having 1 to 10 C atoms, Or an alkoxycarbonyl group having 2 to 10 C atoms, or an aryloxycarbonyl group having 7 to 10 C atoms, a cyano group (-CN), a carbamoyl group (-C ( =O)NH ₂ ), haloformyl group (-C(=O)-X wherein X represents a halogen atom), formyl group (-C(=O)-H), isocyanato group, isocyanate a group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, a CF ₃ group, a Cl, a Br, a F, a crosslinkable group or having 5 to 20 a substituted or unsubstituted aromatic or heteroaromatic ring system of a ring atom, or an aryloxy or heteroaryloxy group having 5 to 20 ring atoms, or a combination of these systems, wherein one or more groups R may form a single ring or more with each other and/or a ring bonded to the group A ring of aliphatic or aromatic ring systems.

In certain preferred embodiments, one or more of the groups R in the above formula (III) may form a monocyclic or polycyclic aliphatic or aromatic group with each other and/or a ring bonded to the group. Ring system. Examples of such solvents are, but not limited to, 1-tetralone, 2-tetralone, 1-methoxynaphthalene, 2-methoxynaphthalene, tetrahydronaphthalene, 1-chloronaphthalene, 2-chloro Naphthalene, 1,4-dimethylnaphthalene, 1-methylnaphthalene, 2-methylnaphthalene, and the like.

Examples of aromatic or heteroaromatic solvents suitable for use with the printing inks of the present invention are, but are not limited to, 1-tetralone, 3-phenoxytoluene, acetophenone, 1-methoxynaphthalene, p-Diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, adjacent Diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, Dodecylbenzene, 1-methylnaphthalene, 1,2,4-trichlorobenzene, 1,3-dipropoxybenzene, 4,4-difluorodiphenylmethane, diphenyl ether, 1,2- Dimethoxy-4-(1-propenyl)benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2 -naphthyl ether, N-methyldiphenylamine, 4-isopropylbiphenyl, α,α-dichlorodiphenylmethane, 4-(3-phenylpropyl)pyridine, benzyl benzoate, 1,1 - bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, dibenzyl ether, and the like.

In other embodiments, the printing ink further comprises another organic solvent. Examples of another organic solvent include, but are not limited to, methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine , toluene, o-xylene, m-xylene, p-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1, 1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrogen Naphthalene, decalin, hydrazine and/or mixtures thereof.

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.

The solvent system according to the present invention containing an aliphatic ketone or an aliphatic ether can effectively disperse inorganic nanomaterials, particularly quantum dot materials, as a new dispersing solvent to replace the solvent of the conventionally used dispersed inorganic nanoparticles, such as Toluene, xylene, chloroform, chlorobenzene, dichlorobenzene, n-heptane, and the like.

The printing ink can be deposited by a variety of printing or coating techniques to obtain quantum dot films. Suitable printing or coating techniques include, but are not limited to, ink jet printing, Nozzle Printing, typography, screen printing. , dip coating, spin coating, blade coating, roller printing, reverse roll printing, lithography, flexographic printing, rotary printing, spraying, brushing or pad printing, slit type extrusion coating, and the like. Preferred printing techniques are ink jet printing, jet printing and gravure printing. For more information on printing techniques and their related ink requirements, such as solvents and concentrations, viscosity, etc., see Handbook of Print Media: Technologies and Production Methods, edited by Helmut Kipphan. , ISBN 3-540-67326-1. In general, different printing techniques have different characteristics for the inks used. For example, printing inks suitable for inkjet printing require adjustment of the surface tension, viscosity, and wettability of the ink so that the ink is in At the printing temperature (e.g., room temperature, 25 ° C), it is possible to eject well through the nozzle without drying on the nozzle or clogging the nozzle, or to form a continuous, flat and defect-free film on a specific substrate.

The printing ink according to the invention comprises at least one inorganic nanomaterial.

In certain embodiments, the inorganic nanomaterials have an average particle size in the range of from 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 about 20 nm. In certain most preferred embodiments, the inorganic nanomaterials have an average particle size of from about 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.

In a preferred embodiment, 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. Preferably, the deviation of the monodisperse quantum dots in the size of the root mean square is less than 15% rms; more preferably, the deviation of the monodisperse quantum dots in the size of the root mean square is less than 10% rms; optimally, monodisperse Quantum dots have a root mean square deviation of less than 5% rms in size.

In certain preferred embodiments, the inorganic nanomaterial is an inorganic semiconductor material.

In another preferred embodiment, the inorganic nanomaterial is a luminescent material.

In certain preferred embodiments, the luminescent inorganic nanomaterial is a quantum dot luminescent material.

Generally, luminescent quantum dots can illuminate at wavelengths between 380 nanometers and 2500 nanometers. For example, it has been found that the luminescent wavelength of a quantum dot having a CdS core is in the range of about 400 nm to 560 nm; the luminescent wavelength of a quantum dot having a CdSe nucleus is in the range of about 490 nm to 620 nm; the luminescent wavelength of a quantum dot having a CdTe core Located in the range of about 620 nm to 680 nm; the quantum wavelength of the quantum dots having the InGaP core is in the range of about 600 nm to 700 nm; the wavelength of the quantum dots having the PbS core is in the range of about 800 nm to 2500 nm; the quantum having the PbSe nucleus The illuminating wavelength of the point is in the range of about 1200 nm to 2500 nm; the luminescent wavelength of the quantum dot having the CuInGaS nucleus is in the range of about 600 nm to 680 nm; and the luminescent wavelength of the quantum dot having the ZnCuInGaS nucleus is in the range of about 500 nm to 620 nm; The luminescence wavelength of the quantum dots of the CuInGaSe core is in the range of about 700 nm to 1000 nm;

In a preferred embodiment, the quantum dot material comprises at least one blue light having a peak wavelength of 450 nm to 460 nm, or green light having a peak wavelength of 520 nm to 540 nm, or a peak wavelength of 615 nm to 630 nm. Red light, or a mixture of them.

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. For a relationship between the luminescent properties of quantum dots and their chemical composition, morphology, and/or size, see Annual Review of Material Sci., 2000, 30, 545-610; Optical Materials Express., 2012, 2, 594-628; Nano Res, 2009, 2, 425-447. The entire contents of the above-listed patent documents are hereby incorporated by reference.

The narrow particle size distribution of the quantum dots enables quantum dots to have a narrower luminescence spectrum (J. Am. Chem. Soc., 1993, 115, 8706; US 20150108405). 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.

Preferably, the luminescent quantum dots are semiconductor nanocrystals. In one embodiment, the semiconductor nanocrystals have a size in the range of from about 5 nanometers to about 15 nanometers. 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 semiconductor nanocrystal includes 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 of the periodic table, Group I-III-VI, Group II-IV-VI, Group II-IV-V binary or multi-component semiconductor compounds or mixtures thereof. Specific examples of the semiconductor material include, but are not limited to, Group IV semiconductor compounds composed of elemental Si, Ge, and binary compounds SiC, SiGe; Group II-VI semiconductor compounds, including binary compounds including 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, CdZnSeS, CdZnSeTe, HgZnSeTe, HgZnSTe, CdZnSTe, HgZnSeS, composition; III-V semiconductor compounds, from binary compounds including AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, ternary compounds include AlNP, AlNAs, AlNSb, AlPAs, AlPSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, InNP, InNAs, InNSb, InPAs, InPSb, and quaternary compounds include GaAlNAs, GaAlNSb, GaAlPAs, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb; IV-VI half Conductor compounds, including binary compounds including SnS, SnSe, SnTe, PbSe, PbS, PbTe, ternary compounds including SnSeS, SnSeTe, SnSTe, SnPbS, SnPbSe, SnPbTe, PbSTe, PbSeS, PbSeTe, and quaternary compounds including SnPbSSe, SnPbSeTe, SnPbSTe composition.

In a preferred embodiment, the luminescent quantum dots comprise a Group II-VI semiconductor compound, preferably selected from the group consisting of CdSe, CdS, CdTe, ZnO, ZnSe, ZnS, ZnTe, HgS, HgSe, HgTe, CdZnSe, and any combination thereof. In a suitable embodiment, this material is used as a luminescent quantum dot for visible light due to the relatively mature synthesis of CdSe due to CdSe.

In another preferred embodiment, the luminescent quantum dots comprise a Group III-V semiconductor compound, preferably selected from the group consisting of InAs, InP, InN, GaN, InSb, InAsP, InGaAs, GaAs, GaP, GaSb, AlP, AlN, AlAs, AlSb, CdSeTe, ZnCdSe and any combination thereof.

In another preferred embodiment, the luminescent quantum dots comprise a Group IV-VI semiconductor compound, preferably selected from the group consisting of PbSe, PbTe, PbS, PbSnTe, Tl ₂ SnTe _5, and any combination thereof.

In a preferred embodiment, the quantum dots are a core-shell structure. The core and the shell respectively comprise one or more semiconductor materials, either identically or differently.

The core of the quantum dot may be selected from the group IV, II-VI, II-V, III-V, III-VI, IV-VI, I-III-VI of the periodic table, Group II-IV-VI, Group II-IV-V binary or multi-element semiconductor compounds. Specific examples for quantum dot nuclei include, but are not limited to, ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, MgS, MgSe, GaAs, GaN, GaP, GaSe, GaSb, HgO, HgS, HgSe, An alloy or mixture of HgTe, InAs, InN, InSb, AlAs, AlN, AlP, AlSb, PbO, PbS, PbSe, PbTe, Ge, Si, and any combination thereof.

The shell of the quantum dot comprises a semiconductor material that is the same or different from the core, preferably selected from a semiconductor material that is 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. Specific examples for quantum dot nuclei include, but are not limited to, ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, MgS, MgSe, GaAs, GaN, GaP, GaSe, GaSb, HgO, HgS, HgSe, An alloy or mixture of HgTe, InAs, InN, InSb, AlAs, AlN, AlP, AlSb, PbO, PbS, PbSe, PbTe, Ge, Si, and any combination thereof.

The quantum dots having a core-shell structure may include a single layer or a multilayer structure. The shell includes one or more semiconductor materials that are the same or different from the core. In a preferred embodiment, 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 certain embodiments, two or more shells are grown on the surface of the quantum dot core.

In a preferred embodiment, the semiconductor material used for the shell has a larger band gap than the core. Particularly preferably, the shell core has a type I semiconductor heterojunction structure.

In another preferred embodiment, the semiconductor material used for the shell has a smaller band gap than the core.

In a preferred embodiment, the semiconductor material used for the shell has an atomic crystal structure that is the same as or close to 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 (but not limited to) are:

Red light: CdSe/CdS, CdSe/CdS/ZnS, CdSe/CdZnS, etc.

Green light: CdZnSe/CdZnS, CdSe/ZnS, etc.

Blue light: CdS/CdZnS, CdZnS/ZnS, etc.

A preferred method of preparing quantum dots is a colloidal growth method. In a preferred embodiment, 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 literature Nano Res, 2009, 2, 425-447; Chem. Mater., 2015, 27(7), pp 2246-2285. The entire contents of the above-listed documents are hereby incorporated by reference.

In a preferred embodiment, the surface of the quantum dot comprises an organic ligand. Organic ligands can control the growth process of quantum dots, regulate the appearance of quantum dots and reduce surface defects of quantum dots to improve the luminous efficiency and stability of quantum dots. The organic ligand may be selected from the group consisting of pyridine, pyrimidine, furan, amine, alkylphosphine, alkylphosphine oxide, alkylphosphonic acid or alkylphosphinic acid, alkyl mercaptan and the like. Examples of specific 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, octylamine, dioctylamine, trioctane Amine, dodecylamine, dodecylamine, tridodecylamine, hexadecylamine, phenylphosphoric acid, hexylphosphoric acid, tetradecylphosphoric acid, octylphosphoric acid, n-octadecylphosphoric acid, propylene diphosphate, dioctyl ether , diphenyl ether, octyl mercaptan, dodecyl mercaptan.

In another preferred embodiment, the surface of the quantum dot comprises an inorganic ligand. Quantum dots protected by inorganic ligands can be obtained by ligand exchange of organic ligands on the surface of quantum dots. Examples of specific inorganic ligands include, but are not limited to, S ^2- , HS ^- , Se ^2- , HSe ^- , Te ^2- , HTe ^- , TeS ₃ ^2- , OH ^- , NH ₂ ^- , PO ₄ ^3- , MoO ₄ ^2- , and so on. Examples of such inorganic ligand quantum dots can be found in documents: J. Am. Chem. Soc. 2011, 133, 10612-10620; ACS Nano, 2014, 9, 9388-9402. The entire contents of the above-listed documents are hereby incorporated by reference.

In certain embodiments, the quantum dot surface has one or more of the same or different ligands.

In a preferred embodiment, the luminescence spectrum exhibited by the monodisperse quantum dots has a symmetrical peak shape and a narrow half width. In general, the better the monodispersity of quantum dots, the more symmetric the luminescence peaks are and the narrower the half-width. Preferably, 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 half-width of the quantum dot is smaller than 30 nanometers.

Generally, the quantum dots have a luminescence quantum efficiency of greater than 10%, preferably greater than 50%, more preferably greater than 60%, and most preferably greater than 70%.

Other materials, techniques, methods, applications, and other information relating to quantum dots that may be useful in the present invention are described in the following patent documents, WO2007/117698, WO2007/120877, WO2008/108798, WO2008/105792, WO2008/111947, WO2007/092606, WO2007/117672, WO2008/033388, WO2008/085210, WO2008/13366, WO2008/063652, WO2008/063653, WO2007/143197, WO2008/070028, WO2008/063653, US6207229, US6251303, US6319426, US6426513, US6576291, US Pat. No. 6,670,829, US Pat. No. 6,861,155, US Pat. No. 6,692, 496, US Pat. No. 7,060, 243, US Pat. No. 7,125, 605, US Pat. No. 7,138,098, US Pat.

In another preferred embodiment, the luminescent semiconductor nanocrystals are nanorods. The properties of nanorods are different from those of spherical nanocrystals. For example, the luminescence of the nanorods is polarized along the long rod axis, while the luminescence of the spherical grains is unpolarized (see Woggon et al, Nano Lett., 2003, 3, p509). Nanorods have excellent optical gain characteristics, making them possible to use as laser gain materials (see Banin et al. Adv. Mater. 2002, 14, p317). In addition, the luminescence of the nanorods can be reversibly turned on and off under the control of an external electric field (see Banin et al, Nano Lett. 2005, 5, p1581). These characteristics of the nanorods may be preferably incorporated into the device of the present invention under certain circumstances. Examples of the preparation of the semiconductor nanorods are, for example, WO03097904A1, US2008188063A1, US2009053522A1, and KR20050121443A, the entire contents of each of which are hereby incorporated by reference.

In still other preferred embodiments, in the printing ink according to the invention, the inorganic nanomaterial is a perovskite nanoparticle material, in particular a luminescent perovskite nanoparticle material.

The perovskite nanoparticle material has the structural formula of AMX ₃ wherein A comprises an organic amine or an alkali metal cation, M comprises a metal cation, and X comprises an oxygen or halogen anion. Specific examples include, but are not limited to, 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. For literature on perovskite nanoparticle materials, see NanoLett., 2015, 15, 3692-3696; ACS Nano, 2015, 9, 4533-4542; Angewandte Chemie, 2015, 127(19): 5785-5788; Nano Lett. , 2015, 15(4), pp 2640-2644; Adv. Optical Mater. 2014, 2, 670-678; The Journal of Physical Chemistry Letters, 2015, 6(3): 446-450; J. Mater. A, 2015, 3, 9187-9193; Inorg. Chem. 2015, 54, 740-745; RSC Adv., 2014, 4, 55908-55911; J. Am. Chem. Soc., 2014, 136(3), Pp 850-853; Part.Part.Syst.Charact.2015, doi: 10.1002/ppsc.201400214; Nanoscale, 2013, 5(19): 8752-8780. The entire contents of the above-listed patent documents are hereby incorporated by reference.

In another preferred embodiment, in the printing ink according to the invention, the inorganic nanomaterial is a 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 zinc (Zn), palladium (Pd), gold (Au), hungry (Os), ruthenium (Re), iridium (Ir), and platinum (Pt). The types, morphologies and synthetic methods of common metal nanoparticles can be found in: Angew. Chem. Int. Ed. 2009, 48, 60-103; Angew. Chem. Int. Ed. 2012, 51, 7656-7673; Adv. Mater. 2003, 15, No. 5, 353-389; Adv. Mater. 2010, 22, 1781-1804; Small. 2008, 3, 310-325; Angew. Chem. Int. Ed. 2008, 47, 2- The disclosures of the above-cited documents are hereby incorporated by reference.

In another preferred embodiment, the inorganic nanomaterial has charge transport properties.

In a preferred embodiment, the inorganic nanomaterial has electron transport capabilities. Preferably, such inorganic nanomaterials are selected from the group consisting of n-type semiconductor materials. Examples of n-type inorganic semiconductor materials include, but are not limited to, metal chalcogen compounds, metal phosphorus group compounds, or elemental semiconductors such as metal oxides, metal sulfides, metal selenides, metal tellurides, metal nitrides, Metal phosphide, or metal arsenide. Preferred n-type inorganic semiconductor materials are selected from the group consisting of ZnO, ZnS, ZnSe, TiO ₂ , ZnTe, GaN, GaP, AlN, CdSe, CdS, CdTe, CdZnSe, and any combination thereof.

In certain embodiments, the inorganic nanomaterial has a hole transporting ability. Preferably, such inorganic nanomaterials are selected from p-type semiconductor materials. The inorganic p-type semiconductor material can be selected from the group consisting of NiOx, WOx, MoOx, RuOx, VOx, CuOx, and any combination thereof.

In certain embodiments, the printing ink according to the present invention comprises at least two and two or more inorganic nanomaterials.

In certain embodiments, the printing ink according to the present invention further comprises at least one organic functional material. As described above, it is an object of the present invention to prepare an electronic device from a solution which, due to its solubility in an organic solution and its inherent flexibility, can be incorporated into the functional layer of the electronic device under certain conditions. Come to other benefits, such as increase Strong device flexibility, improved film forming properties, etc. In principle, all organic functional materials for OLEDs, including but not limited to hole injection materials (HIM), hole transport materials (HTM), electron transport materials (ETM), electron injecting materials (EIM), electron blocking materials (EBM), a hole blocking material (HBM), an illuminator, a host material and an organic dye can all be used in the printing ink of the present invention. Various organic functional materials are described in detail in, for example, WO2010135519A1 and US20090134784A1, the entire disclosure of each of each of each of

The invention further relates to an electronic device comprising one or more functional films, at least one of which is prepared by means of a printing ink according to the invention, in particular by printing or coating.

The invention further relates to a process for the preparation of functional films comprising nanoparticles, in particular by printing or coating. In a preferred embodiment, the nanoparticle-containing film is prepared by a method of inkjet printing. Inkjet printers for printing inks comprising quantum dots of the present invention are commercially available printers and include drop-on-demand printheads. These printers are available from Fujifilm Dimatix (Lebanon, NH), Trident International (Brookfield, Conn.), Epson (Torrance, Calif), Hitachi Data systems Corporation (Santa Clara, Calif), Xaar PLC (Cambridge, United Kingdom), and Idanit. Technologies, Limited (Rishon Le Zion, Isreal) purchased. For example, the present invention can be printed using Dimatix Materials Printer DMP-3000 (Fujifilm).

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. Lasers, quantum dot sensors, etc.

In a preferred embodiment, the electronic device described above is an electroluminescent device or a photovoltaic cell, as shown in FIG. 1, comprising a substrate (101), an anode (102), and at least one luminescent layer (electrically A light emitting device) or a light absorbing layer (photovoltaic cell) (104), a cathode (106). The substrate (101) may be opaque or transparent. The following is only for the description of the electroluminescent device.

A transparent substrate can be used to make a transparent light-emitting component. See, for example, Bulovic et al. Nature 1996, 380, p29, and Gu et al, Appl. Phys. Lett. 1996, 68, p2606. The substrate can be rigid or elastic. The substrate can be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice. In a preferred embodiment, the substrate may be selected from a polymer film or plastic having a glass transition temperature Tg of 150 ° C or higher, 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).

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. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or the valence band level of the p-type semiconductor material as the HIL or HTL is less than 0.5 eV, preferably less than 0.3 eV, and preferably less than 0.2eV. Examples of 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. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.

In certain embodiments, 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. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO level or the conduction band level of the n-type semiconductor material as EIL or ETL or HBL is less than 0.5 eV, preferably less than 0.3 eV, preferably It is less than 0.2eV. In principle, all materials which can be used as cathodes for OLEDs are possible as cathode materials for the devices of the invention. Examples of the cathode material 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) includes at least one luminescent nanomaterial having a thickness between 2 nm and 200 nm. In a preferred embodiment, in the light-emitting device according to the invention, the light-emitting layer is prepared by printing a printing ink according to the invention, wherein the printing ink comprises a luminescent nanomaterial as described above, in particular a quantum point.

In a preferred embodiment, the light emitting device according to the present invention further comprises a hole injection layer (HIL) or hole transport layer (HTL) (103) containing the organic HTM or inorganic p type as described above. material. In a preferred embodiment, the HIL or HTL can be prepared by printing the printing ink of the present invention, wherein the printing ink contains inorganic nanomaterials having hole transporting ability, particularly quantum dots.

In another preferred embodiment, the light emitting device according to the present invention further comprises an electron injection layer (EIL) or an electron transport layer (ETL) (105) comprising the organic ETM or inorganic n-type material as described above. . In a preferred embodiment, the EIL or ETL can be prepared by printing the printing ink of the present invention, wherein the printing ink contains inorganic nanomaterials having electron transporting ability, particularly quantum dots.

The invention further relates to the use of a light emitting device according to the invention in various applications, including, but not limited to, various display devices, backlights, illumination sources, and the like.

Example:

Example 1: Preparation of blue light quantum dots (CdZnS/ZnS)

Weigh 0.0512g of S and weigh 2.4mLODE in a 25mL single-mouth flask, put it in an oil pan and heat it to 80 °C to dissolve S, standby, hereinafter referred to as solution 1; weigh 0.1280g of S and weigh 5mL OA in 25mL In a single-mouth flask, put it in an oil pan and heat it to 90 ° C to dissolve S, standby, hereinafter referred to as solution 2; weigh 0.1028 g of CdO and 1.4680 g of zinc acetate, and measure 5.6 mL of OA in a 50 mL three-necked flask. The three-necked flask was placed in a 150-mL heating mantle. 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. When the temperature was raised to 310 ° C, 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. About 0.5mL / min, reaction 3h, stop the reaction, immediately put the three-necked flask into water and cooled to 150 ° C;

An excess of n-hexane was added to the three-necked flask, and then the liquid in the three-necked flask was transferred to a plurality of 10 mL centrifuge tubes, centrifuged to remove the lower layer precipitate, and repeated three times; acetone was added to the liquid after the post-treatment 1 to precipitate Centrifuge, remove the supernatant, leave a precipitate; then dissolve the precipitate with n-hexane, add acetone to precipitate, centrifuge, remove the supernatant, leave a precipitate, repeat three times; finally dissolve the precipitate with toluene, transfer to glass Stored in the bottle.

Example 2: Preparation of green light quantum dots (CdZnSeS/ZnS)

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. Heat to 150 ° C, vacuum for 30 min, inject 7.5 mL of ODE, then heat to 300 ° C to quickly inject 1 mL of solution 1 for 10 min; 10 min, immediately stop the reaction, the three-necked flask was placed in water to cool.

Add 5 mL of n-hexane to the three-necked flask, then add the mixture to a number of 10 mL centrifuge tubes and add C. The ketone is precipitated and centrifuged. The precipitate was taken, the supernatant was removed, the precipitate was dissolved with n-hexane, acetone was added until precipitation occurred, and centrifugation was carried out. repeat three times. The final precipitate was dissolved in a small amount of toluene and transferred to a glass vial for storage.

Example 3: Preparation of red light quantum dots (CdSe/CdS/ZnS)

1 mmol of CdO, 4 mmol of OA and 20 ml of ODE were added to a 100 ml three-necked flask, and nitrogen gas was bubbled to 300 ° C to form a Cd(OA) ₂ precursor. At this temperature, 0.25 mL of 0.25 mmol of Se was rapidly injected. Powder TOP. The reaction solution was reacted at this temperature for 90 seconds to grow to obtain a CdSe core of about 3.5 nm. 0.75 mmol of octyl mercaptan was added dropwise to the reaction solution at 300 ° C, and a CdS shell of about 1 nm thick was grown after 30 minutes of reaction. 4 mmol of Zn(OA) ₂ and 2 ml of TBP in which 4 mmol of S powder was dissolved were then added dropwise to the reaction solution to grow a ZnS shell (about 1 nm). After the reaction was continued for 10 minutes, it was cooled to room temperature.

5 mL of n-hexane was added to the three-necked flask, and the mixture was added to a plurality of 10 mL centrifuge tubes, acetone was added until precipitation occurred, and centrifugation was carried out. The precipitate was taken, the supernatant was removed, the precipitate was dissolved with n-hexane, acetone was added until precipitation occurred, and centrifugation was carried out. repeat three times. The final precipitate was dissolved in a small amount of toluene and transferred to a glass vial for storage.

Example 4: Preparation of ZnO nanoparticles

1.475 g of zinc acetate was dissolved in 62.5 mL of methanol to obtain a solution 1. 0.74 g of KOH was dissolved in 32.5 mL of methanol to obtain a solution 2. Solution 1 was warmed to 60 ° C and stirred vigorously. Solution 2 was added dropwise to Solution 1 using an injector. After the completion of the dropwise addition, the mixed solution system was further stirred at 60 ° C for 2 hours. The heat source was removed and the solution system was allowed to stand for 2 hours. The reaction solution was centrifuged three times or more using a centrifugal condition of 4500 rpm for 5 minutes. Finally, a white solid was obtained as ZnO nanoparticles having a diameter of about 3 nm.

The boiling point and rheological parameters of the aliphatic ketone or aliphatic ether solvent involved in the examples of the present invention are shown in Table 1 below.

Table 1

The boiling point and rheological parameters of the aromatic solvent involved in the examples of the present invention are shown in Table 2 below.

Table 2

Example 5: Preparation of a quantum dot printing composition containing dioctyl ether

Put the stirrer in the vial, clean it and transfer it to the glove box. 9.5 g of dioctyl ether was prepared in a vial. 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 μm PTFE filter. Seal and store.

Example 6: Preparation of quantum dot printing ink containing 2,6,8-trimethyl-4-indanone

Put the stirrer in the vial, clean it and transfer it to the glove box. 9.5 g of 2,6,8-trimethyl-4-indanone was prepared in a vial. The quantum dots were precipitated from the solution with acetone and centrifuged to obtain a quantum dot solid. Weigh 0.5g of quantum dot solid in the glove box The body was added to the solvent system in the vial and stirred for mixing. 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 μm PTFE filter. Seal and store.

Example 7: Preparation of ZnO Nanoparticle Printing Ink Containing Triethylene Glycol Dimethyl Ether

Put the stirrer in the vial, clean it and transfer it to the glove box. 9.5 g of triethylene glycol dimethyl ether 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 μm PTFE filter. Seal and store.

Example 8: Preparation of quantum dot printing ink containing a mixture of diethylene glycol dibutyl ether and 1,4-dimethylnaphthalene

Put the stirrer in the vial, clean it and transfer it to the glove box. 9.5 g of diethylene glycol dibutyl ether and 1,4-dimethylnaphthalene (weight ratio of 1:9) were prepared in a vial. 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 μm PTFE filter. Seal and store.

Example 9: Preparation of a quantum dot printing ink containing a mixture of 2,5-hexanedione and 1,4-dimethylnaphthalene

Put the stirrer in the vial, clean it and transfer it to the glove box. 9.5 g of 2,5-hexanedione and 1,4-dimethylnaphthalene (weight ratio of 1:9) were prepared in a vial. 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 μm PTFE filter. Seal and store.

Example 10: Preparation of a quantum dot printing ink containing a mixture of triethylene glycol dimethyl ether and 3-phenoxytoluene

Put the stirrer in the vial, clean it and transfer it to the glove box. 9.5 g of triethylene glycol dimethyl ether and 3-phenoxytoluene (weight ratio of 2:8) were prepared in a vial. 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 μm PTFE filter. Seal and store.

Example 11: Preparation of a quantum dot printing ink containing a mixture of phorone and 1-tetralone

Put the stirrer in the vial, clean it and transfer it to the glove box. 9.5 g of phorone and 1-tetralone were prepared in a vial (weight ratio of 2:8). 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 μm PTFE filter. Seal and store.

Example 12: Viscosity and Surface Tension Test

The viscosity of the quantum dot ink was tested by a DV-I Prime Brookfield rheometer; the surface tension of the quantum dot ink was tested by a SITA bubble pressure tomometer.

Through the above test, the quantum dot ink obtained in Example 5 had a viscosity of 4.2 ± 0.3 cPs and a surface tension of 27.8 ± 0.3 dyne/cm.

Through the above test, the quantum dot ink obtained in Example 6 had a viscosity of 2.4 ± 0.5 cPs and a surface tension of 25.7 ± 0.3 dyne/cm.

Through the above test, the quantum dot ink obtained in Example 7 had a viscosity of 4.5 ± 0.3 cPs and a surface tension of 30.1 ± 0.3 dyne/cm.

Through the above test, the quantum dot ink obtained in Example 8 had a viscosity of 5.7 ± 0.5 cPs and a surface tension of 35.1 ± 0.5 dyne/cm.

Through the above test, the quantum dot ink obtained in Example 9 had a viscosity of 5.5 ± 0.3 cPs and a surface tension of 38.2 ± 0.5 dyne/cm.

Through the above test, the quantum dot ink obtained in Example 10 had a viscosity of 5.0 ± 0.5 cPs and a surface tension of 34.8 ± 0.5 dyne/cm.

Through the above test, the quantum dot ink obtained in Example 11 had a viscosity of 6.5 ± 0.3 cPs and a surface tension of 35.6 ± 0.5 dyne/cm.

The functional layer in the quantum dot light-emitting diode, such as the light-emitting layer and the charge transport layer, can be prepared by inkjet printing using the above-prepared printing ink containing quantum dots based on an aliphatic ketone or aliphatic ether solvent system. as follows.

The ink containing the quantum dots is loaded into an ink tank, and the ink tank is assembled in an inkjet printer such as Dimatix Materials Printer DMP-3000 (Fujifilm). The waveform, pulse time and voltage of the jetted ink are adjusted to optimize ink jetting and to stabilize the ink jet range. In the preparation of a QLED device in which the quantum dot film is a light-emitting layer, the following technical solution is adopted: the substrate of the QLED is a 0.7 mm thick glass sputtered with an indium tin oxide (ITO) electrode pattern. The pixels are patterned on the ITO to form a layer of holes for depositing printing ink. 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. Thereafter, the printing ink containing the luminescent quantum dots 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 quantum dot luminescent layer film. Subsequently, a printing ink containing quantum dots having electron transporting properties is ink-jet printed onto the light-emitting layer film, and the solvent is removed by drying at a high temperature in a vacuum atmosphere to form an electron transport layer (ETL). When using organic electron transport materials, ETL can also be formed by vacuum thermal evaporation. Then, the Al cathode is formed by vacuum thermal evaporation, and finally the QLED device is completed by packaging.

The technical features of the above-described embodiments may be arbitrarily combined. For the sake of brevity of description, all possible combinations of the technical features in the above embodiments are not described. However, as long as there is no contradiction between the combinations of these technical features, All should be considered as the scope of this manual.

The above-described embodiments are merely illustrative of several embodiments of the present invention, and the description thereof is more specific and detailed, but is not to be construed as limiting the scope of the invention. It should be noted that a number of variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of the invention should be determined by the appended claims.

Claims (20)

1. A printing composition comprising an inorganic nano material, comprising an inorganic nano material and a solvent composition, the solvent composition comprising an aliphatic ketone and/or an aliphatic ether, the aliphatic ketone and the aliphatic The ethers have a boiling point of ≥180 ° C and a viscosity in the range of 1 cPs to 100 cPs at 25 ° C.
2. The inorganic nanomaterial-containing printing composition according to claim 1, wherein the aliphatic ketone and the aliphatic ether have a boiling point of ≥250 ° C and a viscosity range of 1 cPs at 25 ° C. 40cPs.
3. The inorganic nanomaterial-containing printing composition according to claim 1, wherein the aliphatic ketone and the aliphatic ether have a surface tension ranging from 19 dyne/cm to 50 dyne/cm at 25 °C.
4. The inorganic nanomaterial-containing printing composition according to claim 1, wherein the aliphatic ketone and the aliphatic ether have a surface tension in the range of 22 dyne/cm to 35 dyne/cm at 25 °C.
5. The inorganic nanomaterial-containing printing composition according to claim 1, wherein the inorganic nanomaterial accounts for 0.3% to 70% of the total mass of the printing composition, and the solvent composition accounts for the printing combination. 30%-99.7% of the total mass of the material.
6. The inorganic nanomaterial-containing printing composition according to any one of claims 1 to 5, wherein the aliphatic ketone is selected from the structures represented by the formula (I), and the aliphatic ether is selected from the group consisting of The structure shown in formula (II):

   

   Wherein R ¹ , R ² and R ³ are the same or different from each other, and are each independently selected from a linear alkyl group of 1 to 10 C atoms, a branched alkyl group or a cyclic alkyl group;

   n is an integer of 0 to 4, and when n ≥ 2, R ^{3 is the} same or different from each other.
7. The inorganic nanomaterial-containing printing composition according to claim 6, wherein the aliphatic ketone is selected from the group consisting of 2-nonanone, 3-fluorenone, 5-nonanone, 2-nonanone, 2, 5 -hexanedione, 2,6,8-trimethyl-4-indolone, phorone or di-n-pentyl ketone.
8. The inorganic nanomaterial-containing printing composition according to claim 6, wherein the aliphatic ether is selected from the group consisting of pentyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, and diethylene glycol diethyl ether. , diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether or tetraethylene glycol Dimethyl ether.
9. The inorganic nanomaterial-containing printing composition according to any one of claims 1 to 5, wherein the solvent composition further comprises a third solvent, the third solvent being an aromatic or heteroaromatic compound, The third solvent comprises from 20% to 99% of the total mass of the solvent composition.
10. The inorganic nanomaterial-containing printing composition according to claim 9, wherein the third solvent is selected from the group consisting of 1-tetralone, 3-phenoxytoluene, acetophenone, and 1-methoxyl. Naphthalene, p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, oxynaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylcumene, dipentylbenzene , o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butyl Benzene, dodecylbenzene, 1-methylnaphthalene, 1,2,4-trioxobenzene, 1,3-dipropoxybenzene, 4,4-difluorodiphenylmethane, diphenyl ether, 1, 2-dimethoxy-4-(1-propenyl)benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl -2-naphthyl ether, N-methyldiphenylamine, 4-isopropylbiphenyl, α,α-dioxydiphenylmethane, 4-(3-phenylpropyl)pyridine, benzyl benzoate, 1 , 1-bis(3,4-dimethylphenyl)ethane and 2-isopropylnaphthalene or dibenzyl ether.
11. The inorganic nanomaterial-containing printing composition according to any one of claims 1 to 5, wherein the inorganic nanomaterial is a luminescent quantum dot material, and the luminescent quantum dot material has an illuminating wavelength of 380 nm to 2500 nm. between.
12. The inorganic nanomaterial-containing printing composition according to claim 11, wherein the inorganic nanomaterial is selected from the group consisting of Group IV, Group II-VI, Group II-V, Group III-V, III- Group VI, Group IV-VI, Group I-III-VI, Group II-IV-VI, Group II-IV-V binary or multi-component semiconductor compounds or mixtures of these compounds.
13. The inorganic nanomaterial-containing printing composition according to claim 12, wherein the inorganic nanomaterial is a metal nanoparticle material or a metal oxide nanoparticle material or a mixture thereof.
14. The inorganic nanomaterial-containing printing composition according to claim 12, wherein the inorganic nanomaterial is a perovskite nanoparticle material.
15. The inorganic nanomaterial-containing printing composition according to any one of claims 1 to 5, wherein the printing composition further comprises an organic functional material selected from the group consisting of a hole injecting material and a hole transporting Material, electronics Transmission material, electron injecting material, electron blocking material, hole blocking material, illuminant, host material or organic dye.
16. Use of the inorganic nanomaterial-containing printing composition of any of claims 1-15 in the preparation of an electronic device.
17. An electronic device characterized by using the inorganic nanomaterial-containing printing composition according to any one of claims 1 to 15 to prepare a functional film.
18. The electronic device according to claim 17, wherein the method of preparing the functional film comprises the step of applying the printing composition to a substrate.
19. The electronic device according to claim 18, wherein said coating method is selected from the group consisting of: inkjet printing, jet printing, letterpress printing, screen printing, dip coating, spin coating, blade coating, and roller Printing, twist roll printing, lithography, flexographic printing, rotary printing, spray coating, brush coating, pad printing or slit extrusion coating.
20. The electronic device according to any one of claims 17 to 19, wherein the electronic device is selected from the group consisting of a quantum dot light emitting diode, a quantum dot photovoltaic cell, a quantum dot luminescent cell, a quantum dot field effect transistor, and a quantum dot illuminating field. Effect tube, quantum dot laser, quantum dot sensor.

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