KR20180083888A - COMPOSITIONS FOR ELECTRONIC DEVICE PRINTING AND APPLICATIONS IN ELECTRONIC DEVICES - Google Patents

Abstract

The disclosure discloses a formulation for printing electronic devices comprising at least one functional material and an organic solvent based on at least one alicyclic structure. In some preferred embodiments, the viscosity of the organic solvent at 25 占 폚 is 1 cPs to 100 cPs; The surface tension at 25 占 폚 is between 19 dyne / cm and 50 dyne / cm; And the boiling point is higher than 150 ° C. The disclosure also relates to the printing process of the formulations and the application of the formulations to electronic devices, in particular electroluminescent devices. The disclosure also relates to electronic devices made using the formulations.

Description

COMPOSITIONS FOR ELECTRONIC DEVICE PRINTING AND APPLICATIONS IN ELECTRONIC DEVICES

This disclosure relates to formulations for printing on electronic devices and their applications in electronic devices, particularly electroluminescent devices.

Presently, organic light emitting diodes (OLEDs) as next generation displays are manufactured by evaporation methods, so their material utilization is low, and this method requires a fine metal mask (FMM) which increases cost and lowers yield. In order to solve the above problems, a printing technique for realizing a high resolution full-color display is getting more attention. For example, large-area functional material films can be produced by ink-jet printing at low cost. Compared to conventional semiconductor manufacturing processes, ink-jet printing has great advantages and potential due to its low energy consumption, low water consumption and its environmentally friendly properties. Other new display technologies include quantum dot light-emitting diodes (QLEDs), which can not be fabricated by evaporation methods, but can only be manufactured by printing. Therefore, in order to realize a printed display, there is a need to provide a breakthrough in printing ink and solve the main problems of the related printing process. Viscosity and surface tension are important parameters affecting printing inks and printing processes. Promotable printing inks require moderate viscosity and surface tension.

Organic semiconductor materials have received widespread attention due to their solution processability and have made significant advances in electronic and optoelectronic devices. Solution processability allows the organic functional material to form a film of such a functional material in a device through specific coating and printing processes. Such techniques can effectively reduce the processing cost of electronic and optoelectronic devices and satisfy the needs of large area manufacturing. So far, several companies have reported printing inks for organic semiconducting materials. For example, KATEEVA, INC discloses an ink comprising a low molecular organic material based on an ester solvent that can be applied to the printing of OLEDs (US2015044802A1); UNIVERSAL DISPLAY CORPORATION discloses a printable ink comprising a low molecular weight organic material based on an aromatic ketone or aromatic ether solvent (US20120205637); SEIKO EPSON CORPORATION disclosed a printable ink comprising an organic polymeric material based on a substituted benzene derivative solvent. Other examples involving organic functional material printing inks include CN102408776A, CN103173060A, CN103824959A, CN1180049C, CN102124588B, US2009130296A1, and US2014097406A1.

Other types of functional materials suitable for printing are inorganic nanomaterials, especially quantum dots. The quantum dot is a nano-sized semiconductor material with quantum confinement effect. Quantum dots can emit fluorescence of a specific energy when they are stimulated with light or electricity, and the color (energy) of such fluorescence is determined by the chemical composition, particle size and shape of the quantum dot. Therefore, adjustment of the particle size and shape of the quantum dot can effectively control the electron and optical properties of the quantum dot. Currently, many countries are conducting research in the fields of quantum dots for full-color emission, mainly display. Recently, as reported by Peng et al., Nature Vol 51596 (2015) and Qian et al., Nature Photonics Vol 9259 (2015), electroluminescent devices QLED including quantum dots as a light emitting layer are rapidly developed And the lifetime of such devices has been greatly extended. To date, several companies have reported printing quantum dot inks: Nanoco Technologies Ltd. of England has disclosed a method of printing ink formulations containing nanoparticles (CN101878535B). Printable nanoparticle inks and corresponding films containing nanoparticles are obtained by selecting suitable solvents such as toluene and dodecane selenol. Samsung Electronics has disclosed a quantum dot for ink-jet printing (US8765014B2). The ink contains a specific concentration of quantum dots, an organic solvent and a polyalcohol additive. A quantum dot film is printed from the ink to produce a quantum dot electroluminescence device. QD Vision Inc. discloses a quantum dot ink formulation comprising a host material, a quantum dot material, and an additive (US2010264371A1).

Other patents related to quantum dot printing inks include US2008277626A1, US2015079720A1, US2015075397A1, TW201340370A, US2007225402A1, US2008169753A1, US2010265307A1, US2015101665A1, and WO2008105792A2. However, in these published patents all quantum dot inks contain other additives such as alcohol polymers to control the physical parameters of the ink. The introduction of insulating polymer additives tends to reduce the charge transport capability of the film and adversely affects the optoelectronic properties of the device and thus limits the application of quantum dot ink in optoelectronic devices.

One of the purposes of this disclosure is to provide novel formulations for printing on electronic devices.

The technical solution of the disclosure is as follows:

A formulation for printing on an electronic device comprises a solvent system containing at least one functional material and at least one organic solvent based on an alicyclic structure and having the general formula (I)

[Formula I]

Wherein R ¹ is an alicyclic or heteroalicyclic structure having 3 to 20 ring atoms; n is an integer of 0 or more, and R < ² > is a substituent when n > The boiling point of the organic solvent is 150 DEG C or higher, and the organic solvent can be evaporated from the solvent system to form a film of the functional material.

In one embodiment of the above-described electronic device printing formulation, the organic solvent based on the alicyclic structure and having the general formula (I) has a viscosity of 1 cPs to 100 cPs at 25 占 폚.

In one embodiment of the above-described electronic device printing formulation, the organic solvent based on alicyclic structure and having formula (I) has a surface tension of from 19 dyne / cm to 25 dyne / cm at 25 ° C.

In one embodiment of the above-described electronic device printing formulation, in an organic solvent based on an alicyclic structure and having formula (I), R ¹ has any one of the structures selected from the following general formulas:

Wherein X is selected from CR ³ R ⁴ , C (= O), S, S (= O) ₂ , O, SiR ⁵ R ⁶ , NR ⁷ , or P (= O) R ⁸ ; Each R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ is independently selected from any of H, D, straight chain alkyl containing from 1 to 20 carbon atoms, straight chain alkoxy, or Straight chain thioalkoxy, branched or cyclic alkyl containing from 3 to 20 carbon atoms each, branched or cyclic alkoxy, branched or cyclic thioalkoxy, or branched or cyclic silyl, having from 1 to 20 carbon atoms Alkoxycarbonyl containing 2 to 20 carbon atoms, aryloxycarbonyl containing 7 to 20 carbon atoms, cyano (-CN), carbamoyl (-C (= O) (= O) -NH ₂ ), haloformyl (-C (= O) -X wherein X represents a halogen atom), formyl (-C (= O) -H), isocyanato, isocyanate, cyanate, hydroxy, nitro, CF _3, also the ring atoms of Cl, Br, F, crosslinkable functional groups, 5 to 40 Aryloxy or heteroaryloxy, which contains a substituted or unsubstituted aromatic or heteroaromatic ring system, or a 5 to 40 ring atoms which; When one or more of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are present at the same time, they may be present independently or together with each other and / or R ¹ or R ² , Aliphatic or aromatic ring system.

In one embodiment of the above-described electronic device printing formulation, each R < ² > can be the same or different selected from any one of the following: straight chain alkyl containing from 1 to 20 carbon atoms, straight chain alkoxy, Thioalkoxy, branched or cyclic alkyl, branched or cyclic alkoxy, branched or cyclic thioalkoxy or silyl each containing from 3 to 20 carbon atoms, substituted keto containing from 1 to 20 carbon atoms, Alkoxycarbonyl containing from 2 to 20 carbon atoms, aryloxycarbonyl containing from 7 to 20 carbon atoms, cyano (-CN), carbamoyl (-C (= O) NH ₂ ), haloformyl ( -C (= O) -X wherein X represents a halogen atom, formyl (-C (= O) -H), isocyanato, isocyanate, thiocyanate or isothiocyanate, , CF ₃ , Cl, Br, F, a crosslinkable functional group or A substituted or unsubstituted aromatic or heteroaromatic ring system optionally containing 5 to 40 ring atoms, or aryloxy or heteroaryloxy containing 5 to 40 ring atoms; Here, when one or a part of R < ² > is present at the same time, they may be present independently or together with each other and / or functional groups may form a monocyclic or polycyclic aliphatic or aromatic ring system.

In one embodiment of the above-described electronic device printing formulation, the organic solvent based on alicyclic structure and having the general formula (I) is selected from the group consisting of tetralin, cyclohexylbenzene, decahydronaphthalene, 2-phenoxytetrahydrofuran, Butyl cyclohexane, ethyl abietate, benzyl abietate, ethylene glycol carbonate, styrene oxide, isophorone, 3,3,5-trimethylcyclohexanone, cycloheptanone, fenchone, Tetralone, 2- tetralone, 2- (phenyl epoxy) tetralone, 6- (methoxy) tetralone,? -Butyrolactone,? -Valerolactone, 6- N, N-diethylcyclohexylamine, sulfolane, 2,4-dimethylsulfone, or a mixture of any two or more thereof.

In one embodiment of the above-described electronic device printing formulation, the solvent system is a mixture further comprising at least one other organic solvent, wherein the organic solvent based on alicyclic structure and having formula (I) It accounts for more than 50% of the weight.

In one embodiment of the above-described electronic device printing formulation, the functional material is an inorganic nanomaterial.

In one embodiment of the above-described electronic device printing formulation, the functional material is a quantum dot material, that is, the particle size of the functional material has a monodisperse distribution, the shape of which is a spherical nano-shape, a cube nano- Shapes, nano-shapes of a branched structure, and the like.

In one embodiment of the above-described electronic device printing formulation, the functional material is a luminescent quantum dot material and its emission wavelength is from 380 nm to 2500 nm.

III-VI, III-VI, IV-VI, and I-III-VI of the Periodic Table of the Elements Functional compound selected from bimetallic, II-IV-VI, II-IV-V or any two or more thereof.

In one embodiment of the above-described electronic device printing formulation, the functional material is a perovskite nanoparticle material, preferably a luminescent perovskite nanomaterial, a metal nanoparticle material, a metal oxide nanoparticle material, ≪ / RTI >

In one embodiment of the above-described electronic device printing formulation, the functional material is an organofunctional material.

In one embodiment of the above-described electronic device printing formulation, the organic functional material is selected from the group consisting of a hole injection material (HIM), a hole transport material (HTM), an electron transport material (ETM), an electron injection material (EIM) EBM), a hole blocking material (HBM), an emitter, a host material, an organic dye, or a mixture of any two or more thereof.

In one embodiment of the above-described electronic device printing formulation, the organic functional material may comprise at least one host material and at least one emitter.

In one embodiment of the above-described electronic device printing formulation, the functional material accounts for 0.3-30% of the total weight of the formulation, and the organic solvent contained may comprise 70-99.7% of the total weight of the formulation.

Another object of the present disclosure is to provide an electronic device comprising a functional layer printed from any of the above-described electronic device printing formulations, wherein the organic material based on the alicyclic structure contained in the formulation and having the general formula (I) The solvent may be evaporated from the solvent system to form a functional material film.

In one embodiment, the electronic device described above is a light emitting diode (LED), such as a quantum dot light emitting diode (QLED), a quantum dot photovoltaic cell (QPV), a quantum dot light emitting electrochemical cell (QLEEC), a quantum dot field effect transistor , An organic light emitting diode (OLED), an organic photovoltaic (OPV), an organic light emitting electrochemical cell (OLEEC), an organic field effect transistor (OFET), an organic luminescence field effect transistor, an organic laser, have.

Another object of the disclosure is to provide a method of producing a functional material film comprising placing the above-described electronic device printing formulation on a substrate by printing or coating methods, wherein the printing or coating methods are inkjet printing, From typographic printing, screen printing, dip coating, spin coating, blade coating, roller printing, torsion roller printing, lithographic printing, flexographic printing, rotary printing, spray coating, brush coating, (But not limited to).

In addition, another object of the disclosure is the printing process of the formulation and the application of the formulation to an electronic device, particularly an electroluminescent device.

The beneficial effects of the disclosure are that the viscosity and surface tension of the formulation for printing on an electronic device can be adjusted to a suitable range of use in accordance with a particular printing process, particularly inkjet printing, and thus can facilitate the printing process and form a film having a uniform surface . Moreover, the organic solvent is effectively removed by a post-treatment process such as a heat treatment or a vacuum treatment, thus ensuring the performance of the electronic device. Accordingly, the disclosure provides ink formulations, particularly printing inks comprising quantum dots and organic semiconductor materials, for producing high-quality functional films to provide an effective technical solution for printed or optoelectronic devices.

1 is a structural view of a preferred embodiment of the present disclosure of a light emitting device, wherein 101 is a substrate; 102 is a cathode; 103 is a hole injection layer (HIL) or a hole transport layer (HTL); 104 is a light emitting layer (electroluminescent device) or a light absorbing layer (photovoltaic cell); 105 is an electron injection layer (EIL) or an electron transport layer (ETL); 106 is an anode.

The present disclosure provides novel formulations for printing on electronic devices. The formulations provided comprise at least one functional solvent and at least one organic solvent based on an alicyclic structure. Preferably, the organic solvent based on the alicyclic structure has a viscosity of 1 cPs to 100 cPs at 25 캜, a surface tension of 19 dyne / cm to 25 dyne / cm at 25 캜, and a boiling point of 150 캜 or higher. The disclosure also relates to the printing process of the formulations and the application of the formulations to electronic devices, in particular electroluminescent devices. The disclosure also relates to electronic devices made from the formulations.

In order that the objectives, technical solution and advantages of the disclosure become more apparent and clearer, specific descriptions of the disclosure are set forth below. It should be understood that the specific description of the disclosure is used only to illustrate the disclosure, rather than to limit the disclosure.

One embodiment of the disclosure provides a formulation for printing electronic devices, the formulation comprising a solvent system containing at least one organic solvent based on at least one functional material and an alicyclic structure and having the general formula (I) :

[Formula I]

Here, R ¹ is an alicyclic or heteroalicyclic structure having 3 to 20 ring atoms, n is an integer of 0 or more, and R ² is a substituent when n is 1. The boiling point of the organic solvent is 150 DEG C or higher, and the organic solvent can be evaporated from the solvent system to form a film of the functional material.

The boiling point is a parameter that should be considered when selecting a solvent to dissolve the functional material. In some embodiments of the disclosure, the organic solvent based on the alicyclic structure and having formula (I) has a boiling point of at least 150 캜. In some embodiments, the organic solvent based on the alicyclic structure and having the general formula (I) has a boiling point of 180 占 폚 or higher or 200 占 폚 or higher; In some embodiments, the organic solvent based on the alicyclic structure and having the general formula (I) has a boiling point of 220 캜 or higher; In other preferred embodiments, the organic solvent based on the alicyclic structure and having the general formula (I) has a boiling point of 250 ° C or higher or 300 ° C or higher. The boiling points within these ranges are useful for preventing nozzle clogging of the inkjet printhead. The organic solvent may be evaporated from the solvent system by vacuum drying or other methods to form a film containing the functional material.

In one embodiment of the disclosure, the organic solvent based on the alicyclic structure contained in the formulation and having the general formula (I) has a viscosity of 1 cPs to 100 cPs at 25 占 폚.

Viscosity is a parameter that should be considered when selecting a solvent to dissolve a functional material. The viscosity can be adjusted by selecting different methods, for example, by selecting a suitable organic solvent or concentration of functional material in the ink. In a preferred embodiment of the disclosure, the organic solvent based on the alicyclic structure and having the general formula (I) has 1 cPs to 100 cPs at 25 占 폚, more preferably 1 cPs to 50 cPs, most preferably 1.5 cPs to 20 cPs.

The content of the organic solvent based on the alicyclic structure of the disclosure in the ink can be easily adjusted within a suitable range according to the printing method applied. Typically, in the printing ink of the present disclosure, the functional material is present in an amount of 0.3% to 30% of the total weight of the formulation, preferably 0.5% to 20% of the total weight of the formulation, more preferably 0.5% To 15%, and most preferably from 1% to 10% of the total weight of the formulation. In a preferred embodiment, the viscosity of the ink containing the organic solvent based on the alicyclic structure is less than 100 cPs in the composition ratio. In a more preferred embodiment, the viscosity of the ink containing the organic solvent based on the alicyclic structure is less than 50 cPs in the composition ratio. In a most preferred embodiment, the viscosity of the ink containing the organic solvent based on the alicyclic structure is in the range of 1.5 to 20 cPs in the composition ratio. Wherein the viscosity is at least equal to the ambient temperature during printing, usually at a temperature of from 15 to 30 占 폚, relatively preferably at a temperature of from 18 to 28 占 폚, more preferably at a temperature of from 20 to 25 占 폚, Lt; 0 > C. Printing inks formulated in this manner are particularly suitable for inkjet printing.

In one embodiment of the disclosure, the organic solvent based on alicyclic structure and contained in the formulation having formula (I) has a surface tension of from 19 dyne / cm to 25 dyne / cm at 25 ° C.

Suitable surface tension parameters of the ink are suitable for certain substrates and special printing methods. For example, in a preferred embodiment, for ink jet printing, the surface tension of an organic solvent based on an alicyclic structure and having formula (I) is about 19 dyne / cm to 50 dyne / cm at 25 占 폚; In a more preferred embodiment, the surface tension of an organic solvent based on an alicyclic structure and having the general formula (I) is 22 dyne / cm to 35 dyne / cm at 25 占 폚; In a most preferred embodiment, the surface tension of the organic solvent based on the alicyclic structure and having the general formula (I) is 25 dyne / cm to 33 dyne / cm at 25 占 폚.

In a preferred embodiment, the surface tension of the inks of the present disclosure is from about 19 dyne / cm to 50 dyne / cm at 25 占 폚; More preferably, the surface tension of the inks of this disclosure is from 22 dyne / cm to 35 dyne / cm at 25 占 폚; Most preferably, the surface tension of the inks of this disclosure is 25 dyne / cm to 33 dyne / cm at 25 占 폚.

Using a solvent system having the above-mentioned boiling point, surface tension parameter and viscosity parameter, based on an alicyclic structure and containing an organic solvent having the general formula (I), the resulting ink has a uniform thickness and uniform formulation properties Can be formed.

In a preferred embodiment of the above-described electronic device printing formulation, in an organic solvent based on an alicyclic structure and having the general formula (I), R ¹ has a structure selected from any of the general formulas shown below:

Wherein X is selected from CR ³ R ⁴ , C (= O), S, S (= O) ₂ , O, SiR ⁵ R ⁶ , NR ⁷ , or P (= O) R ⁸ ; Each R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ is independently selected from any of H, D, straight chain alkyl containing from 1 to 20 carbon atoms, straight chain alkoxy, or Straight chain thioalkoxy, branched or cyclic alkyl containing from 3 to 20 carbon atoms each, branched or cyclic alkoxy, branched or cyclic thioalkoxy, or branched or cyclic silyl, having from 1 to 20 carbon atoms Alkoxycarbonyl containing 2 to 20 carbon atoms, aryloxycarbonyl containing 7 to 20 carbon atoms, cyano (-CN), carbamoyl (-C (= O) (= O) -NH ₂ ), haloformyl (-C (= O) -X wherein X represents a halogen atom), formyl (-C (= O) -H), isocyanato, isocyanate, cyanate, hydroxy, nitro, CF _3, also the ring atoms of Cl, Br, F, crosslinkable functional groups, 5 to 40 Aryloxy or heteroaryloxy, which contains a substituted or unsubstituted aromatic or heteroaromatic ring system, or a 5 to 40 ring atoms which; When one or more of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are present at the same time, they may be present independently or together with each other and / or R ¹ or R ² , Aliphatic or aromatic ring system.

In some preferred embodiments, each of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ can be the same or different from any one of the following: H, D, Straight chain alkoxy, or straight chain thioalkoxy, branched or cyclic alkyl containing from 3 to 10 carbon atoms each, branched or cyclic alkoxy, branched or cyclic thioalkoxy, or branched Substituted silyl, cyclic silyl, substituted keto containing 1 to 10 carbon atoms, alkoxycarbonyl containing 2 to 10 carbon atoms, aryloxycarbonyl containing 7 to 10 carbon atoms, cyano (-CN ), Carbamoyl (-C (= O) NH ₂ ), haloformyl (-C (= O) -X wherein X represents a halogen atom), formyl cyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, nitro, CF _3, Cl, Br, F, crosslinked Results Functional groups, aryloxy or heteroaryloxy, which contains a substituted or unsubstituted aromatic or heteroaromatic ring atoms of the ring system, or 5 to 20 ring atoms, which contains from 5 to 20; When one or more of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are present at the same time, they may be present independently or together with each other and / or R ¹ or R ² , Aliphatic or aromatic ring system.

In another preferred embodiment of the formulations for printing electronic devices in the present disclosure, each R < ² > contained in an organic solvent based on an alicyclic structure and having formula (I) may be the same or different from any one of Straight chain alkyl, straight chain alkoxy, or straight chain thioalkoxy each containing from 1 to 20 carbon atoms, branched or cyclic alkyl containing from 3 to 20 carbon atoms each, branched or cyclic alkoxy, branched or cyclic Substituted thioalkoxy or silyl, substituted keto containing 1 to 20 carbon atoms, alkoxycarbonyl containing 2 to 20 carbon atoms, aryloxycarbonyl containing 7 to 20 carbon atoms, cyano (- CN), carbamoyl _{(-C (= O) NH 2} ), halo-formyl (-C (= O) -X; wherein, X represents a halogen atom), formyl (-C (= O) -H) , Isocyanato, isocyanate, thiocyanate or isothi A cyanate, hydroxy, nitro, CF _3, Cl, Br, F, crosslinkable functional groups, or optionally 5 to substituted or unsubstituted containing the ring atoms of the 40-ring aromatic or heteroaromatic ring systems, or 5-40 Aryloxy or heteroaryloxy containing ring atoms; Here, when one or a part of R < ² > is present at the same time, they may be present independently or may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with functional groups.

In a particularly preferred embodiment, each R < ² > may be the same or different from any one of the following: straight chain alkyl, straight chain alkoxy, or straight chain thioalkoxy each containing from 1 to 10 carbon atoms, Branched or cyclic alkyl, branched or cyclic alkoxy, branched or cyclic thioalkoxy or silyl containing 1 to 10 carbon atoms, a substituted keto containing 2 to 10 carbon atoms (-C (= O) NH ₂ ), haloformyl (-C (= O) -X (= O) -X ; wherein, X represents a halogen atom), formyl (-C (= O) -H) , isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxy, nitro, CF _3, Cl, Br, F, a crosslinkable functional group or alternatively from 5 to 20 Substituted or unsubstituted aromatic or heteroaromatic ring systems containing ring atoms, or aryloxy or heteroaryloxy containing 5 to 20 ring atoms; Here, when one or a part of R < ² > is present at the same time, they may be present independently or may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with functional groups.

In the formulation for printing electronic devices described in this disclosure, the organic solvent based on alicyclic structure and having the general formula (I) is selected from the group consisting of tetralin, cyclohexylbenzene, decahydronaphthalene, 2-phenoxytetrahydrofuran, Butyl cyclohexane, ethyl abietate, benzyl abietate, ethylene glycol carbonate, styrene oxide, isophorone, 3,3,5-trimethylcyclohexanone, cycloheptanone, Tetralone, 2- tetralone, 2- (phenyl epoxy) tetralone, 6- (methoxy) tetralone,? -Butyrolactone,? -Valerolactone, 6-hexanolactone, N-diethylcyclohexylamine, sulfolane, 2,4-dimethylsulfone, or a mixture of any two or more thereof, but is not limited thereto.

In some other embodiments, the formulation of the disclosure comprises at least two organic solvents, wherein the solvent mixture is based on an alicyclic structure and comprises at least one organic solvent having the general formula (I) and at least one other organic solvent .

In a preferred embodiment, the organic solvent based on the alicyclic structure and having the general formula (I) accounts for at least 50% of the total weight of the mixed solvent; In a preferred embodiment, the organic solvent based on the alicyclic structure and having the general formula (I) accounts for at least 70% of the total weight of the mixed solvent; In a more preferred embodiment, the organic solvent based on the alicyclic structure and having the general formula (I) accounts for 80% or more of the total weight of the mixed solvent; In a most preferred embodiment, the organic solvent based on the alicyclic structure and having the general formula (I) accounts for at least 90% of the total weight of the mixed solvent; Or the mixed solvent consists essentially of an organic solvent based on an alicyclic structure and having the general formula (I); Or the mixed solvent is composed entirely of an organic solvent based on an alicyclic structure and having the general formula (I).

In a preferred embodiment, the organic solvent based on the alicyclic structure and having the general formula (I) is cyclohexylbenzene.

In another preferred embodiment, the solvent is a mixture of cyclohexylbenzene and at least one other solvent, wherein cyclohexylbenzene accounts for at least 50% of the total weight of the mixed solvent, preferably at least 80% of the total weight of the mixed solvent And most preferably accounts for 90% or more of the total weight of the mixed solvent.

In some preferred embodiments, the organic solvent based on the alicyclic structure and having the general formula (I) is 1,1'-bicyclohexyl.

In a preferred embodiment, the mixed solvent is a mixture of 1,1'-bicyclohexyl and at least one other solvent, wherein the 1,1'-bicyclohexyl accounts for at least 50% of the total weight of the mixed solvent, Accounts for at least 80% of the total weight of the mixed solvent, and most preferably accounts for at least 90% of the total weight of the mixed solvent.

In some preferred embodiments, the organic solvent based on the alicyclic structure and having the general formula (I) is gamma-valerolactone.

In a preferred embodiment, the solvent is a mixture of gamma -valerolactone and at least one other solvent, wherein gamma -valerolactone accounts for at least 50% of the total weight of the mixed solvent, preferably the total weight of the mixed solvent Of the total weight of the mixed solvent, and most preferably accounts for 90% or more of the total weight of the mixed solvent.

In some preferred embodiments, the organic solvent based on the alicyclic structure and having the general formula (I) is sulfolane.

In a preferred embodiment, the solvent is a mixture of sulfolane and at least one other solvent, wherein the sulfolane comprises at least 50% of the total weight of the mixed solvent, preferably at least 80% of the total weight of the mixed solvent And most preferably accounts for 90% or more of the total weight of the mixed solvent.

Examples of at least one other solvent as described above include but are not limited to methanol, ethanol, 2-methoxyethanol, dichloromethane, trichloromethane, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o Xylene, p-xylene, 1,4-dioxane, acetone, methyl ethyl ketone, 1,2-dichloroethane, 3-phenoxy toluene, 1,1,1-trichloroethane, But not limited to, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethyl formamide, dimethyl acetamide, dimethylsulfoxide, tetrahydronaphthalene, decahydronaphthalene, indene or any mixture of any two or more thereof But is not limited thereto.

The organic solvent based on the alicyclic structure and having the general formula (I) can be used in place of the commonly used dispersants for dispersing functional materials such as toluene, xylene, chloroform, chlorine benzene, dichlorobenzene, n-heptane and the like As a new dispersant capable of dispersing the functional substance, it is possible to effectively disperse the functional substance.

The boiling point, surface tension and viscosity parameters of the examples are listed below:

designation constitutional formula Boiling point
(° C) Surface tension
@RT
(dyne / cm) Viscosity
@RT
(cPs) Tetralin

207 35.9 2 Cyclohexylbenzene

238 34 4 Decahydronaphthalene

196 29 3.4 1,1'-bicyclohexyl

239 33 3.75 Butyl cyclohexane

181 27 1.2 Butyrolactone

204 35 1.7 Ethylene glycol carbonate

238 37 2 Styrene oxide

194 43 2 Isophorone 215 32 2.6 Cycloheptanone

181 31.5 2.6 Fencing

193 31 3.6 1-Tetralone

256 42 8.6 ? -butyrolactone

204 35 1.8 gamma -valerolactone

207 29 3.4 6-hexanolactone

215 32 1.1 Sulpolan

287 35 10 2,4-dimethylsulfone

280 28 7.9

The printing ink may further comprise one or more components such as a surfactant, a lubricant, a wetting agent, a dispersing agent, a hydrophobicity imparting agent, a binder, etc., for adjusting viscosity and film forming properties and adhesion improvement.

The functional material film can be formed by depositing printing ink by various printing or coating techniques. The printing or coating techniques may be applied to a variety of applications including inkjet printing, nozzle printing, typographic printing, screen printing, dip coating, spin coating, blade coating, roller printing, torsion roller printing, lithographic printing, flexographic printing, rotary printing, Coatings, pad printing, or slot die coatings. Preferred printing techniques are inkjet printing, screen printing and typographic printing. Specific information relating to printing techniques and requirements for solutions such as solvent, concentration and viscosity are set forth in the Handbook of Print Media: Technologies and Production Methods, Helmut Kipphan, ISBN 3-540-67326-1: Technologies and Production Methods, Helmut Kipphan , ISBN 3-540-67326-1. In general, different printing techniques have different characteristic requirements for the ink used. For example, printing inks suitable for inkjet printing need to adjust the surface tension, viscosity and wettability of the ink, so that the ink can be dried at a printing temperature (e. G., Room temperature, 25 캜) Or it may form a continuous, flat, defect-free film on a particular substrate.

The electronic printing formulations described in this disclosure comprise at least one functional material.

In the present disclosure, the functional material is preferably a material having photoelectric function. The photoelectric function includes, but is not limited to, a hole injection function, a hole transport function, an electron transport function, an electron injection function, an electron blocking function, a hole blocking function, a light emitting function, and a host function. The corresponding functional materials are selected from the group consisting of a hole injecting material (HIM), a hole transporting material (HTM), an electron transporting material (ETM), an electron injecting material (EIM), an electron blocking material (EBM), a hole blocking material (HBM) A host material, an organic dye, or a mixture of two or more thereof.

The functional material may be an organic material or an inorganic material.

In a preferred embodiment, the at least one functional material contained in the electronic printing formulations described in this disclosure is an inorganic nanomaterial.

Preferably, the inorganic nanomaterial is an inorganic semiconductor nanoparticle material.

In the present disclosure, the inorganic nanomaterials have an average particle size of from about 1 nm to about 1000 nm. In some preferred embodiments, the inorganic nanomaterial has an average particle size of from about 1 nm to about 100 nm. In some more preferred embodiments, the inorganic nanomaterial has an average particle size of from about 1 nm to about 20 nm, most preferably from 1 to 10 nm.

The inorganic nanomaterials may be particles having different nano-shapes and various shapes, such as spherical nano-shapes, cube nano-shapes, rod-shaped nano-shapes, disk-shaped nano-shapes, Including, but not limited to, mixtures of two or more of the following: < RTI ID = 0.0 >

In a preferred embodiment, the inorganic nanomaterial is a quantum dot material with a very narrow monodisperse size distribution, i.e. a very small intergranular size difference. Preferably, the mean square deviation of the size of the monodisperse quantum dots is less than 15% rms. More preferably, the mean square deviation of the size of the monodisperse quantum dots is less than 10% rms. Most preferably, the mean square deviation of the size of the monodisperse quantum dots is less than 5% rms.

In a more preferred embodiment, the inorganic nanomaterial is a luminescent material. In a more preferred embodiment, the luminescent inorganic nanomaterial is a luminescent quantum dot material.

Generally, the light emitting quantum dots can emit light in the wavelength range of 380 nm to 2500 nm. For example, the wavelength of light emitted from a quantum dot having a CdS core ranges from about 400 nm to about 560 nm, the wavelength of light emitted from a quantum dot having a CdSe core ranges from about 490 nm to about 620 nm, the CdTe core Wherein the wavelength of the light emitted from the quantum dot having a PbS core is in a range of about 620 nm to about 680 nm and the wavelength of light emitted from a quantum dot having an InGaP core is in a range of about 600 nm to about 700 nm, The wavelength of the light is in the range of about 800 nm to about 2500 nm and the wavelength of the light emitted from the quantum dot having the PbSe core is in the range of about 1200 nm to about 2500 nm and the wavelength of the light emitted from the quantum dot having the CuInGaS core is about 600 nm To about 680 nm, the wavelength of the light emitted from the quantum dot having the ZnCuInGaS core is in the range of about 500 nm to about 620 nm, and the quantum dot having the CuInGaSe core From the emitted light wavelength was found to be in the range of from about 700 nm to about 1000 nm.

In a preferred embodiment, the quantum dot material is a blue light having an emission peak wavelength range in the range of 450 nm to 460 nm, or a green light having an emission peak wavelength range in the range of 520 nm to 540 nm, or an emission peak in the range of 615 nm to 630 nm At least one substance capable of emitting red light having a wavelength range or a mixture of any two or more thereof.

The quantum dots contained in the material can be selected from quantum dots having a particular chemical composition, morphological structure, and / or size to obtain the required wavelength of light emitted under electrical stimulation.

The narrow size distribution of the quantum dot allows the quantum dot to have a narrower emission spectrum. Further, in application, the size of the quantum dot needs to be adjusted within the above-mentioned size range according to different chemical composition and structure in order to obtain luminescence characteristics having the required wavelength.

Preferably, the luminescent quantum dot is a semiconductor nanocrystal. In one embodiment, the size of the semiconductor nanocrystals ranges from about 2 nm to about 15 nm. In addition, the size of the quantum dot needs to be adjusted within the above-mentioned size range according to different chemical composition and structure in order to obtain luminescence characteristics having the required wavelength.

The semiconductor nanocrystals comprise at least one semiconductor material and the semiconductor material is selected from the group consisting of Group IV, II-VI, II-V, III-V, III-VI, IV-VI, A binary semiconducting compound of the group VI, a group II-IV-VI, a group II-IV-V, or a multi-semiconductor compound or mixtures thereof. Specific examples of semiconductor materials are group IV semiconductor compounds such as element Si, element Ge, bicomponent SiC and bicomponent SiGe; CdSeS, CdSeTe, CdSe, CdSe, ZnSe, ZnTe, ZnO, HgO, HgS, HgSe, HgTe, or a Group II-VI semiconductor compound such as CdSe, CdTe, CdO, CdSe, temples include CdZnSe, CdZnTe, CgHgS, CdHgSe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, HgZnS, three won compound and CgHgSeS containing HgSeSe, CdHgSeTe, CgHgSTe, CdZnSeS, CdZnSeTe, HgZnSeTe, HgZnSTe, CdZnSTe, HgZnSeS compound; AlNs, AlNSs, AlPAs, AlPSb, AlNb, AlNb, AlNb, AlNb, GaN, GaN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, InNP, InNAs, InNSb, InPAs, InPSb and GaNNAs, GaAlNSb, GaAlPAs, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb ; A binary compound including an IV-VI group semiconductor compound such as SnS, SnSe, SnTe, PbSe, PbS, PbTe, a ternary compound including SnSeS, SnSeTe, SnSTe, SnPbS, SnPbSe, SnPbTe, PbSTe, PbSeS, PbSeTe And a silane compound including SnPbSSe, SnPbSeTe, and SnPbSTe.

In a preferred embodiment, the luminescent quantum dot preferably comprises a II-VI semiconductor material selected from dSe, CdS, CdTe, ZnO, ZnSe, ZnS, ZnTe, HgS, HgSe, HgTe, CdZnSe and any combination thereof. In a preferred embodiment, CdSe and CdS can be used as luminescent quantum dots of visible light since their synthesis process is relatively well developed.

In another preferred embodiment, the luminescent quantum dot is preferably a mixture of any two or more of InAs, InP, InN, GaN, InSb, InAsP, InGaAs, GaAs, GaP, GaSb, AlP, AlN, AlAs, AlSb, CdSeTe, ZnCdSe, Lt; RTI ID = 0.0 > III-V < / RTI > semiconductor material.

In another preferred embodiment, the luminescent quantum dot is preferably selected from the group consisting of PbSe, PbTe, PbS, PbSnTe, Tl ₂ SnTe ₅ And mixtures of any two or more thereof.

In one preferred embodiment, the quantum dot has a core-shell structure. The core and shell each include one or more types of semiconductor material, either equally or differently.

The cores of the quantum dots are composed of Group IV, Group II-VI, Group II-V, Group III-V, Group III-VI, Group IV-VI, Group I-III-VI, Group II-IV- -IV-V group semiconductor compound or a multi-semiconductor compound. Specific examples used in the cores of the quantum dots are 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 and any two or more alloys or mixtures thereof.

The shell of the quantum dot includes a semiconductor material that is the same as or different from the core of the quantum dot. The semiconductor material of the shell may be selected from the group consisting of Group IV, Group II-VI, Group II-V, Group III-V, Group III-VI, Group IV-VI, Group I- Or a binary semiconductor compound or a multi-semiconductor compound of group II-IV-V. Specific examples of the shells of the quantum dots are ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, MgS, MgSe, GaAs, GaN, GaP, GaSe, GaSb, HgO, HgS, HgSe, HgTe, InAs, , AlAs, AlN, AlP, AlSb, PbO, PbS, PbSe, PbTe, Ge, Si and any two or more alloys or mixtures thereof.

In a quantum dot having a core-shell structure, the shell may be a single layer or a multiple layer structure. The shell may comprise one or more semiconductor materials that are the same or different from the material of the core. In a preferred embodiment, the shell has a thickness of from about 1 to about 20 layers. In a more preferred embodiment, the shell has a thickness from about 5 to about 10 layers. In some embodiments, two or more shells are grown on the surface of the core of the quantum dot.

In a preferred embodiment, the semiconductor material of the shell may have a larger bandgap than the core. Particularly preferably, the shell and the core have an I-type semiconductor heterojunction structure.

In another preferred embodiment, the semiconductor material of the shell may have a smaller bandgap than the core.

In a preferred embodiment, the semiconductor material of the shell may have the same or similar atomic crystal structure as the core. This selection is beneficial for reducing the stress between the shell and the core to make the quantum dots more stable.

Suitable examples of luminescent quantum dots using a core-shell structure include, but are not limited to,

Red light: CdSe / CdS, CdSe / CdS / ZnS, CdSe / CdZnS and the like;

Green light: CdZnSe / CdZnS, CdSe / ZnS and the like;

Blue light: CdS / CdZnS, CdZnS / ZnS and the like.

A preferred method of producing the quantum dot is a colloidal growth method. In a preferred embodiment, the preparation for producing monodisperse quantum dots is selected from a hot-injection method and / or a heating method. The methods are described in Nano Res, 2009, 2, 425-447 and Chem. Mater., 2015, 27 (7), 2246-2285.

In a preferred embodiment, the surface of the quantum dot may have an organic ligand. The organic ligand can control the growth process of the quantum dots, control the shape of the quantum dots, reduce the surface defects of the quantum dots, and increase the emission efficiency and stability of the quantum dots. The organic ligand can be selected from, but not limited to, pyridine, pyrimidine, furan, amine, alkylphosphine, alkylphosphine oxide, alkylphosphonic acid or alkylphosphinic acid, alkylthiol and the like. Specific examples of organic ligands include tri-n-octylphosphine, tri-n-octylphosphine oxide, trihydroxypropylphosphine, tributylphosphine, tri (dodecyl) phosphine, dibutylphosphite, tributyl (Tridecyl) phosphate, hexadecylamine, oleylamine, octadecylphosphate, octadecylphosphite, tridecylphosphite, tridodecylphosphite, triisodecylphosphite, di (2-ethylhexyl) amine, octylamine, dioctylamine, trioctylamine, dodecylamine, didodecylamine, tridodecylamine, hexadecylamine, trioctadecylamine, Octylphosphonic acid, propylenic diphosphonic acid, dioctyl ether, diphenyl ether, octanethiol, dodecanethiol, etc., or any two or more thereof, such as, for example, phenylphosphonic acid, hexylphosphonic acid, tetradecylphosphonic acid, octylphosphonic acid,Including one compound, it is not limited.

In another preferred embodiment, the surface of the quantum dot may have an inorganic ligand. Quantum dots protected by inorganic ligands can be obtained by ligand exchange with organic ligands on the surface of the quantum dots. Specific examples of the inorganic ligand are the ^{S 2-, HS -, Se 2} -, HSe -, Te 2 -, HTe -, TeS 3 2 -, OH -, NH 2 -, PO 4 3-, MoO 4 2 - or a But is not limited to, any combination of two or more.

In some embodiments, the surface of the quantum dot may have one or more of the same or different ligands.

In one preferred embodiment, the luminescence spectra performed by monodisperse quantum dots have a symmetrical peak shape and a full width at half maxima (FWHM) at half maximum. Generally, the better the monodispersity of a quantum dot is, the more luminescent peak is more symmetrical, and the FWHM becomes narrower. Preferably, the FWHM of the emission spectrum of the quantum dot is smaller than 70 nm. More preferably, the FWHM of the emission spectrum of the quantum dot is smaller than 40 nm. Most preferably, the FWHM of the emission spectrum of the quantum dot is smaller than 30 nm.

In general, the quantum dot emission quantum efficiency is greater than 10%, preferably greater than 50%, more preferably greater than 60%, and most preferably greater than 70%.

In other preferred embodiments, the luminescent semiconductor nanocrystals are nanorods. The properties of nanorods are different from spherical nanocrystalline particles. For example, light emitted from the nanorods is polarized along the long axis of the nanorod, and light emitted from spherical nanocrystalline particles is not polarized. In addition, the light emission of the nanorod can be turned on and off reversibly under the control of an external electric field. These features of the nanorod are preferably incorporated into the device of this disclosure in certain situations.

In other preferred embodiments, in the formulations for printing electronic devices described in this disclosure, the inorganic nanomaterial is a perovskite nanoparticle material, in particular a luminescent perovskite nanoparticle material.

The perovskite nanoparticle material may have a general formula of AMX ₃ , where A may be selected from organic amine or alkali metal cations, M may be selected from metal cations, X is oxygen or a halogen anion Lt; / RTI > Specific examples of perovskite nanoparticle materials are 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 _{/ Br) 3, CH 3 NH} 3 PbBr 3, CH 3 NH 3 Pb (I / Br) 3, including, such as CH ₃ NH ₃ PbI _3, are not limited.

In another preferred embodiment, in the formulations for printing electronic devices described in this disclosure, the inorganic nanomaterial can be a metal nanoparticle material, preferably a luminescent metal nanoparticle material. The metal nanoparticles may be at least one selected from the group consisting of Cr, molybdenum, tungsten, ruthenium, rhodium, nickel, silver, copper, But are not limited to, nanoparticles of palladium (Pd), gold (Au), osmium (Os), rhenium (Re), iridium (Ir) and platinum (Pt).

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

In a preferred embodiment, the inorganic nanomaterial has an electron transporting capability. Preferably, such inorganic nanomaterials are selected from n-type semiconductor materials. Examples of n-type inorganic semiconductor materials include metal chalcogenides, metal nitride, or elemental semiconductors such as metal oxides, metal sulfides, metal selenides, metal tellurides, metal nitrides, metal phosphides or metal arsenide But is not limited thereto. Preferred n- type inorganic semiconductor material may be selected from ZnO, ZnS, ZnSe, TiO _2, ZnTe, GaN, GaP, AlN, CdSe, CdS, CdTe, CdZnSe, or mixtures of any two or more thereof, but are not limited to .

In some embodiments, the inorganic nanomaterial has hole transport capability. Preferably, such inorganic nanomaterials can be selected from p-type semiconductor materials. The inorganic p-type semiconductor nanomaterial can be selected from, but not limited to, NiOx, WOx, MoOx, RuOx, VOx, CuOx, or mixtures of any two or more thereof.

In some embodiments, the printing ink described in this disclosure may comprise two or more types of inorganic nanomaterials.

In another particularly preferred embodiment, the electronic printing formulations described in this disclosure may comprise at least one type of organic functional material.

The organic functional material may be a hole transport material (HIM / HTM), a hole blocking material (HBM), an electron injection or transport material (EIM / ETM), an electron blocking material (EBM) (Phosphorescent emitters), thermally activated delayed fluorescent (TADF), triplet emitters (phosphorescent emitters), in particular luminescent organometallic complexes, organic dyes or derivatives thereof But is not limited to, any combination of two or more.

In general, the solubility of a suitable organic functional material in a solvent based on the alicyclic structure described in this disclosure and having the general formula (I) is at least 0.2 wt%, preferably at least 0.3 wt%, more preferably at least 0.6 wt%, even more preferably at least 1.0 wt%, and most preferably at least 1.5 wt%.

The organic functional material may be a low molecular weight or a high molecular weight material. In the present disclosure, a low-molecular organic material refers to a material having a molecular weight of at most 4000 g / mol, and a material having a molecular weight of more than 4000 g / mol is collectively referred to as a polymer.

In a preferred embodiment, the functional material contained in the electronic printing formulations described in this disclosure may be a low molecular organic material.

In some preferred embodiments, the organic functional material contained in the printing form for printing electronic devices described in this disclosure may comprise at least one host material and at least one emitter.

In a preferred embodiment, the organic functional material may comprise one kind of host material and one kind of mono-terminated emitter.

In another preferred embodiment, the organic functional material may comprise one kind of host material and one kind of triplet emitter.

In another preferred embodiment, the organic functional material may comprise one type of host material and one thermally activated delayed fluorescent material.

In other preferred embodiments, the organic functional material may comprise one type of hole transport material (HTM), and more preferably the HTM may comprise a cross-linkable functional group.

Suitable low molecular organic functional materials of the preferred embodiments are described more specifically below, but the invention is not limited to these materials.

1. HIM / HTM / EBM

Suitable organic HIM / HTMs include, but are not limited to, compounds having the following structural units: phthalocyanine, porphyrin, amine, aromatic amine, biphenyltriacrylamine, thiophene, dithienothiophene, The same fused thiophene, pyrrole, aniline, carbazole, indolocarbazole and derivatives thereof. In addition, suitable HIMs also include, but are not limited to, polymers containing fluorocarbons, polymers containing conductive dopants, and conductive polymers such as PEDOT: PSS.

The electron blocking layer (EBL) is used for blocking electrons from the adjacent functional layers, particularly the light emitting layer. In contrast to light-emitting devices without barrier layers, the presence of EBL generally improves the luminous efficiency. The electron blocking material (EBM) of the electron blocking layer (EBL) needs to have a higher LUMO than the adjacent functional layer, for example, the light emitting layer. In a preferred embodiment, the HBM has a state energy level that is more excited than an adjacent light emitting layer, for example a singlet or triplet state depending on the emitter. Furthermore, EBM has a hole transport function. In general, HIM / HTM materials with high LUMO energy levels can be used as EBMs.

Embodiments of cyclic aromatic amine derivatives that may be applied with HIM, HTM or EBM include, but are not limited to, the following general structures:

Each of Ar ¹ to Ar ⁹ is independently a cyclic aromatic group such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, Hydrocarbon compounds; Benzothiophene, carbazole, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, oxatriazole, dioxolane, oxadiazole, dibenzothiophene, dibenzofuran, furan, thiophene, benzofuran, Thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indolizine, benzoxazole, benzsulfazole, benzothiazole , Quinoline, isoquinoline, naphthalene (cinoline), quinazoline, quinoxaline, naphthalene, phthalene, phthyridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, dibenzoselenophene, Aromatic heterocyclic compounds such as naphthene, benzopyropyridine, indolocarbazole, pyridylindole, pyrrolodipyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine ; Or a cyclic aromatic hydrocarbon group or a heterocyclic aromatic group of the same or different type and may be selected from functional groups containing 2 to 10 rings which are connected to each other directly or via at least one of the following functional groups: , A nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and a cyclic alicyclic functional group. Each Ar may be further substituted by a substituent. The substituent may be selected from hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, heteroalkyl, aryl and heteroaryl, but is not limited thereto.

In one embodiment, Ar ¹ to Ar ⁹ may include, but are not limited to, one functional group independently selected from the following functional groups:

Wherein n is an integer from 1 to 20; X ¹ to X ⁸ are CH or N; Ar ¹ is defined as above.

Examples of metal complexes that can be used as HTM or HIM include, but are not limited to, the following general structures:

Here, M is a metal having an atomic weight exceeding 40.

(Y ¹ -Y ² ) is a bidentate ligand. Y ¹ and Y ² can be independently selected from C, N, O, P and S; L is an ancillary ligand; m is an integer from 1 to the maximum coordination number of the metal; m + n is the maximum coordination number of the metal.

In one embodiment, (Y ¹ -Y ² ) is a 2-phenylpyridine derivative.

In another embodiment, (Y < ^{1 >} -Y < ² >) is a carban ligand.

In other embodiments, M may be selected from Ir, Pt, Os, and Zn.

In another embodiment, the HOMO of the metal complex is greater than -5.5 eV (relative to the vacuum energy level).

Examples of suitable HIM / HTM compounds are listed below, but are not limited thereto.

2. Triplet host material (triplet host)

The triplet host material is not particularly limited, and any metal complex or organic compound can be used as a host if its triplet energy is higher than the emitter, especially the triplet emitter or phosphorescent emitter. Examples of metal complexes that can be used as triplet hosts include, but are not limited to, the following general structures:

Wherein M is a metal; (Y ³ -Y ⁴ ) is a bidentate ligand, Y ³ and Y ⁴ can be independently selected from C, N, O, P and S; L is an ancillary ligand; m is an integer from 1 to the maximum coordination number of the metal; And m + n is the maximum coordination number of the metal.

In a preferred embodiment, the metal complex which may be used as a triplet host may have one of the following forms:

(O-N) is a bidentate ligand in which the metal is coordinated with O and N atoms.

In one embodiment, M may be selected from Ir and Pt.

Examples of organic compounds that can be used as triplet hosts include compounds containing cyclic aromatic hydrocarbon functional groups such as benzene, biphenyl, triphenyl, benzo, fluorine; Benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, pyrazole, pyrrolidine, pyrazole, A pyridazine, a pyridazine, a pyridine, a pyrazine, a triazine, an oxazine, an oxathiazine, an oxadiazine, a thiazole, a thiazole, a thiadiazole, a thiadiazole, , Indole, benzimidazole, indazole, oxazole, dibenzoxazole, benzsulfazole, benzothiazole, quinoline, isoquinoline, phthalazine (cininoline), quinazoline, quinoxaline, naphthalene, phthalide Aromatic compounds such as benzenesulfonylpyridines, benzenesulfonylbenzenes, benzenesulfonylbenzenes, benzenesulfonylbenzenes, benzenesulfonylbenzenes, benzenesulfonylbenzenes, benzenesulfonylbenzenes, benzenesulfonylbenzenesulfonamides, A compound containing a heterocyclic functional group; A cyclic aromatic hydrocarbon functional group or aromatic heterocyclic functional group of the same or different type or may be selected from functional groups comprising 2 to 10 rings which may be connected to each other directly or via at least one of the following functional groups, But are not limited to, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an alicyclic ring functional group. Wherein each Ar may be further substituted and the substituent may be selected from hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, heteroalkyl, aryl and heteroaryl.

In a preferred embodiment, the triplet host material can be selected from compounds having at least one of the following functional groups, but is not limited thereto:

Wherein R ¹ -R ⁷ may independently be selected from the following functional groups: but not limited to: hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, heteroalkyl, aryl, and heteroaryl ; When R ¹ -R ⁷ is aryl or heteroaryl, they have the same definitions as Ar ¹ and Ar ² above; n is an integer from 0 to 20, and each X ¹ -X ⁸ is selected from CH or N; X ⁹ is CR ¹ R ² Or NR < ^{1 &} gt ;.

Examples of suitable triplet host materials include, but are not limited to, the following:

3. Single-host material (single-host)

The single-term host material is not particularly limited, and any organic compound can be used as a host if its singlet state energy is higher than that of the emitter, especially the single-term emitter or fluorescent emitter.

Examples of organic compounds that can be used as monohydric host materials include organic compounds such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, Type aromatic hydrocarbon compound; Benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, pyrazole, pyrrolidine, pyrazole, Wherein the substituent is selected from the group consisting of imidazole, triazole, isoxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, The present invention relates to a process for the preparation of a compound represented by the general formula (1) or a salt thereof, wherein the compound is selected from the group consisting of benzene, indole, benzimidazole, indazole, indolizine, benzoxazole, benzisothiazole, benzothiazole, quinoline, isoquinoline, Heteroaromatic compounds such as xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine; May be selected from functional groups comprising 2 to 10 rings which may be the same or different types of cyclic aromatic hydrocarbon functionalities or aromatic heterocyclic functionalities connected directly or through at least one of the following functional groups, But are not limited to: an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an alicyclic ring.

In a preferred embodiment, the monovalent host material can be selected from compounds containing at least one of the following functional groups, but is not limited thereto:

Wherein R ¹ may independently be selected from the following functional groups: but not limited to: hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, heteroalkyl, aryl, and heteroaryl; Ar ¹ is aryl or heteroaryl, the definition of which is the same as Ar ¹ of HTM; n is an integer from 0 to 20; Each of X < ^{1 >} -X < ⁸ > is selected from CH or N; X ⁹ and X ¹⁰ are CR ¹ R ² Or NR < ^{1 &} gt ;.

Some examples of anthryl monolithic host materials are listed below, but are not limited to:

4. Single-ended emitter (single-ended emitter)

A single-termed emitter usually has a relatively long conjugated pi electron system. So far, there have been many examples, such as styrylamines and derivatives thereof and indenofluorene and derivatives thereof.

In a preferred embodiment, the single-termed emitter can be selected from, but not limited to, monostyrylamine, distyrylamine, tristyrylamine, tetrastyrylamine, styrylphosphine, styrylether and arylamine .

Monostyrylamines refer to compounds having unsubstituted or substituted styryls and at least one amine (preferably an aromatic amine). Distyrylamine refers to compounds having two unsubstituted or substituted styryl groups and at least one amine (preferably an aromatic amine). Tristyrylamine refers to compounds having three unsubstituted or substituted styryl groups and at least one amine (preferably an aromatic amine). Tetrastyrylamine refers to compounds having four unsubstituted or substituted styryl groups and at least one amine (preferably an aromatic amine). A preferred styryl is distyryl which may be further substituted. Correspondingly, phosphines and ethers are defined analogously to amines. An arylamine or an aromatic amine refers to a compound having three unsubstituted or optionally substituted aromatic rings or a heterocyclic ring system in which nitrogen is directly linked. At least one of these aromatic rings or heterocyclic systems is preferably selected from fused ring systems having at least 14 atoms in the aromatic ring. Preferred embodiments thereof include, but are not limited to, aromatic anthracene amines, aromatic anthracene diamines, aromatic pyrene amines, aromatic pyrene diamines, aromatic chrysene amines, and aromatic chrysene diamines. An aromatic anthracene amine refers to a compound having one diarylamino group directly linked to anthracene, preferably at position 9. An aromatic anthracene diamine refers to a compound having two diarylamino groups directly linked to anthracene, preferably at positions 9 and 10. The definitions of aromatic pyrene amines, aromatic pyrene diamines, aromatic chrysene amines and aromatic chrysene diamines are similar, and diaryl amino groups are preferably linked to pyrene at position 1 or positions 1 and 6.

Further preferred mono-terminated emitters include, but are not limited to, indenofluorene-amine and indenofluorene-diamine, benzindenofluorene-amine and benzidineindenofluorene-diamine, dibenzylindenofluorene- Fluorene-diamine, and the like.

Other materials that can be used as monophasic emitters include, but are not limited to, polycyclic aromatic hydrocarbon compounds, particularly derivatives of the following compounds: anthracene such as 9,10-di (2-naphthanthracene), naphthalene, Tetracene, xanthene, phenanthrene, pyrene (e.g., 2,5,8,11-tetra-t-butyl pyrene), indenopylene, (4,4'- Phenylene), such as phenylene, dicyandiophene, decanediol, tetramethylenediamine, tetramethylenediamine, tetramethylenediamine, triethyleneterephthalate, Such as cyclopentadiene, such as cyclopentadiene, rubrene, coumarin, rhodamine, quinacridone and 4 (dicyanomethylene) -6- (4-p-dimethylaminostyryl- , Thiopyran, di (azinyl) iminoborone compounds, bis (azinyl) methane compounds, carbostyril compounds, pentoxazone, benzoxazole, benzothiazole, And diketopyrrolopyrrole.

Some examples of single-termed emitters are listed below, but are not limited to:

5. Thermally activated delayed fluorescent material (TADF)

Traditional organic fluorescent materials can only emit light by 25% of the singlet excitons produced by electrical excitation, and the device's internal quantum efficiency is low (up to 25%). Although the inter-crossover of the phosphor is enhanced due to strong spin-orbit coupling at the center of the atom, the singlet anti-exciton and triplet excitons formed by the electrical excitation emit light and achieve 100% internal quantum efficiency of the device Can be effectively used. However, problems with the phosphors, such as high cost, poor stability and severe rolling-off of the device, limit their application in OLEDs. The thermally activated delayed fluorescent material is the third generation of the organic light emitting material developed after the organic fluorescent material and the organic phosphorescent material. Since this type of material generally has a small singlet-triplet energy level difference (ΔEst), triplet excitons can be converted to mono-excitons through inter-station crossings to emit light. In this way, singlet excitons and triplet excitons formed by electrical excitation can be fully utilized, and the internal quantum efficiency of the device can reach 100%.

The TADF material generally has a relatively small singlet-triplet energy level difference of DELTA Est <0.3 eV, preferably DELTA Est <0.2 eV, more preferably DELTA Est <0.1 eV, most preferably DELTA Est < . In a preferred embodiment, TADF has better fluorescence quantum efficiency.

Examples of suitable TADF luminescent materials are listed in the following table, but are not limited thereto.

6. Triplet Emitter

Triplet emitters are also called phosphorescent emitters. In a preferred embodiment, the triplet emitter can be a metal complex of the general formula M (L) _n , wherein M is a metal atom; L in each occurrence may be the same or different and is an organic ligand connected or coordinated to the metal atom M at one or more positions; n is an integer of 1 or more, more preferably 1, 2, 3, 4, 5, or 6. Alternatively, these metal complexes are preferably linked to the polymer at one or more positions by an organic ligand.

In a preferred embodiment, the metal atom M is selected from transition metal elements, lanthanide elements, or actinide elements, preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb , Dy, Re, Cu or Ag, more preferably Os, Ir, Ru, Rh, Re, Pd or Pt.

Preferably, the triplet emitter can contain a chelating ligand, i. E., A ligand coordinated to the metal at at least two binding sites. Preferably, the triplet emitter contains two or three identical or different bidentate ligands or multidentate ligands. The chelating ligand is beneficial in increasing the stability of the metal complex.

Examples of organic ligands are selected from phenyl pyridine derivatives, 7,8-benzoquinoline derivatives, 2 (2-thienyl) pyridine derivatives, 2 (1-naphthyl) pyridine derivatives or 2-phenylquinoline derivatives But is not limited thereto. Both of these organic ligands may be substituted, for example, by fluoromethyl or trifluoromethyl. Preferably, the ancillary ligand can be selected from acetylacetonate or picric acid.

In a preferred embodiment, the metal complex which can be used as a triplet emitter has the form:

Where M is a metal selected from transition metal elements, lanthanide elements or actinide elements.

The cyclic functional group Ar ¹ may be the same or different in each occurrence, and the cyclic functional group is an atom having at least one donor atom, that is, an atom containing a lone pair of electrons such as N or P . Ar ^{2 as the} cyclic functional group may be the same or different in each occurrence, and the cyclic functional group contains at least one carbon atom as the cyclic functional group is connected to the metal. Ar ¹ and Ar ² are linked together through a covalent bond, each of which may carry one or more substituents, which may also be joined together by substituents. The auxiliary ligand L can be the same or different in each occurrence and is preferably a bidentate chelating ligand, more preferably a monovalent anionic 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, and particularly preferably 0. [

Examples of suitable triplet emitters are listed in the following table, but are not limited thereto.

In another preferred embodiment, the functional material contained in the electronic printing formulations of the present disclosure may be a polymeric material.

In general, the above-described low molecular weight organic functional materials may include HIM, HTM, ETM, EIM, host, fluorescent emitter, phosphorescent emitter, TADF and the like. have.

In a preferred embodiment, the polymer suitable for the present disclosure may be a conjugated polymer. Generally, a conjugated polymer has the following formula:

[Chemical Formula 1]

Here, when B and A appear multiple times, they may independently select the same or different structural units.

B is a monovalent aryl or polycyclic aryl or heteroaryl, preferably benzene, biphenylene, naphthalene, anthracene, phenanthrene, dihydrophenanthrene, 9,10-dihydrophenanthrene, fluorene, difluorene, A larger energy gap, also referred to as a backbone unit selected from spirofluor fluorene, p-phenylacetylene, trans-indenofluorene, cis-indeno, dibenzo-indenofluorene, indenonaphthalene and derivatives thereof Conjugated structural units.

A is a pi-conjugated structural unit with a smaller energy gap, also referred to as a functional unit. According to other functional requirements, A may be a hole injection or hole transport material (HIM / HTM), an electron injection or transport material (EIM / ETM), a host material (Host) ) And triplet emitters (phosphorescent emitters), but are not limited thereto.

x and y are larger than 0, and x + y = 1.

In some preferred embodiments, the functional material contained in the electronic printing formulations described in this disclosure is a polymeric HTM.

In a preferred embodiment, the polymeric HTM material is a homopolymer and the homopolymer is preferably selected from polythiophene, polypyrrole, polyaniline, polybiphenyltriallyamine, polyvinylcarbazole and derivatives thereof.

In another particularly preferred embodiment, the polymeric HTM is a conjugated polymer represented by Formula 1,

A is a functional group having hole transport ability and can be selected equally or differently from the structural units containing the hole injection or transport material (HIM / HTM) described above. In a preferred embodiment, A is selected from the group consisting of amines, biphenyl triaryl amines, thiophenes, dithienothiophenes and thioctenes such as thioctene, pyrrole, aniline, carbazole, indenocarbazole, indolocarbazole, Phthalocyanine, porphyrin and derivatives thereof.

x and y are greater than 0 and x + y = 1; Usually y? 0.10; Preferably y? 0.15; More preferably y? 0.20; Most preferably, x = y = 0.5.

Examples of suitable conjugated polymers that can be used as HTM are listed below, but are not limited to:

Wherein each R is independently hydrogen, straight chain alkyl containing from 1 to 20 carbon atoms each, straight chain alkoxy, or straight chain thioalkoxy, branched or cyclic alkyl containing from 3 to 20 carbon atoms, Branched or cyclic thioalkoxy, or branched or cyclic silyl, substituted keto containing from 1 to 20 carbon atoms, alkoxycarbonyl containing from 2 to 20 carbon atoms, from 7 to 20 carbon atoms (-C (= O) NH ₂ ), haloformyl (-C (= O) -X, wherein X represents a halogen atom. ), formyl (-C (= O) -H) , isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, nitro, CF _3, Cl, Br, F, crosslinkable functional groups, 5 to Substituted or unsubstituted aromatic or heteroaromatic rings containing up to 40 ring atoms Selected from the aryloxy or heteroaryloxy containing the ring atoms of the ring system, or 5 to 40, and; Wherein one or more of the R groups and / or R groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with respect to each other;

r is selected from 0, 1, 2, 3, or 4;

s is selected from 0, 1, 2, 3, 4, or 5;

x and y are greater than 0 and x + y = 1; Usually y? 0.10; Preferably y? 0.15; More preferably y? 0.20; Most preferably, x = y = 0.5.

Other types of preferred organic functional materials may be polymers with electron transport capabilities, including conjugated polymers and non-conjugated polymers.

Preferred polymeric ETMs are preferably homopolymers selected from polyphenanthrene, polyphenanthroline, polyindenofluorene, polystyprobifluorene, polyfluorene and derivatives thereof.

A preferred polymeric ETM may be a conjugated polymer represented by formula (1), and when A appears multiple times, A may be the same or different from the following forms:

A is a functional group having an electron transporting ability and is preferably a tris (8-hydroxyquinoline) aluminum (AlQ3), benzene, biphenylene, naphthalene, anthracene, phenanthrene, dihydrophenanthrene, fluorene, , P-phenylacetylene, pyrene, perylene, 9,10-dihydrophenanthrene, phenazine, phenanthroline, trans-indenofluorene, cis-indeno, dibenzo-indeno Fluorene, indenonaphthalene, benzoanthracene and derivatives thereof.

x and y are greater than 0 and x + y = 1; Usually y? 0.10; Preferably y? 0.15; More preferably y? 0.20; Most preferably, x = y = 0.5.

In another preferred embodiment, the functional material contained in the printing form for electronic device described in this disclosure is a luminescent polymer.

In a particularly preferred embodiment, the luminescent polymer is a conjugated polymer having the formula:

(2)

B has the same definition as that in formula (1).

A ₁ is a functional group having hole or electron transport ability and can be selected from structural units containing the above-described hole injection or transport material (HIM / HTM) or electron injection or transport material (EIM / ETM) But is not limited to.

A ₂ is a functional group having a light emitting ability, and may be selected from structural units including, but not limited to, a single-termed emitter (fluorescent emitter) and a triplet emitter (phosphorescent emitter).

x, y, and z are greater than 0, and x + y + z = 1.

In other embodiments, the polymer suitable for the present disclosure may be a non-conjugated polymer. Non-conjugated polymers can be the backbone with all the functional groups in the side chain. Examples of non-conjugated polymers may be selected from, but are not limited to, non-conjugated polymers used as phosphorescent host or phosphorescent materials and non-conjugated polymers used as fluorescent emissive materials. In addition, the non-conjugated polymer may also be a polymer in which the conjugated functional units in the backbone are linked together by non-conjugated connecting units.

The present disclosure also relates to a method of making a functional material film, wherein the step of placing the electronic device printing formulation on a substrate is by printing or coating and the printing or coating methods are inkjet printing, nozzle printing, typographic printing, (Such as, but not limited to, dip coating, spin coating, blade coating, roller printing, torsion roller printing, lithographic printing, flexographic printing, rotary printing, spray coating, brush coating, pad printing or slot die coating Not).

In a preferred embodiment, the film containing the functional material is produced by inkjet printing. An ink jet printer that may be used to print the inks of this disclosure may be a commercially available printer and includes a drop-on-demand print head. 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 Limited (Rishon Le Zion, Isreal). For example, this disclosure uses a Dimatix Materials Printer DMP-3000 (Fujifilm) for printing.

The disclosure is also directed to an electronic device comprising at least one functional film layer, wherein at least one functional film layer is formed using the printing ink formulation of the disclosure described in this disclosure, in particular by the method of printing or coating do.

Examples of suitable electronic devices include, but are not limited to, quantum dot light emitting diodes (QLEDs), quantum dot photovoltaic cells (QPVs), quantum dot luminescent electrochemical cells (QLEECs), quantum dot field effect transistors (QFETs), quantum dot luminescence field effect transistors, But are not limited to, a diode (OLED), an organic photovoltaic (OPV), an organic light emitting electrochemical cell (OLEEC), an organic field effect transistor (OFET), an organic luminescence field effect transistor, an organic laser,

1, the electronic device is an electroluminescent device or a photovoltaic cell and includes a substrate 101, a cathode 102, at least one light-emitting or light-absorbing layer 104, and a cathode 106. In this embodiment, . The following description only uses an electroluminescent device as an example.

The substrate 101 may be opaque or transparent. The transparent substrate can be used for producing a transparent light emitting device. The substrate may be rigid or resilient. The substrate can be plastic, metal, semiconductor wafer or glass. Most preferably, the substrate has a smooth surface. A substrate having a defect free surface is a particularly preferred option. In a preferred embodiment, the substrate can be selected from polymer films or plastics, and the glass transition temperature Tg is at least 150 ° C, preferably greater than 200 ° C, more preferably greater than 250 ° C, and most preferably at least 300 ° C Respectively. Suitable examples of substrates include, but are not limited to, poly (ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).

The cathode 102 may comprise a conductive metal or a metal oxide, or a conductive polymer. The cathode can easily inject holes into the HIL or HTL or the light emitting layer. In one embodiment, the absolute value of the difference between the work function of the cathode and the HOMO level or valence band level of the p-type semiconductor material as HIL or HTL is less than 0.5 ev, preferably less than 0.3 ev, It is smaller than 0.2 ev. Examples of negative electrode materials include but are not limited to Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, Al-doped zinc oxide (AZO) Other suitable cathode materials are known, and those skilled in the art can readily select and use them. The negative electrode material can be deposited by any suitable technique, such as, for example, radio-frequency magnetron sputtering, vacuum thermal evaporation, e-beam, or the like.

In some embodiments, the cathode has a patterned structure. A patterned ITO conductive substrate available on the market can be used to make the devices of this disclosure.

The anode 106 may comprise a conductive metal or a metal oxide. The anode can easily inject electrons into the EIL or ETL or the light emitting layer. In one embodiment, the absolute value of the difference between the work function of the anode 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, preferably less than 0.3 ev, Is smaller than 0.2 ev. In particular, all materials used for the anode of an OLED can be used as the anode material of the device in this disclosure. Examples of anode materials include Al, Au, Ag, Ca, Ba, Mg, LiF / Al, MgAg alloy, BaF ₂ / Al, Cu, Fe, Co, Ni, Mn, Pd, include, Pt, ITO, etc., whereby But is not limited to. The anode material can be deposited by any suitable technique, for example, by suitable physical vapor deposition methods including radio-frequency magnetron sputtering, vacuum thermal evaporation, e-beam, and the like.

The light emitting layer 104 may include at least one layer of a luminescent functional material having a thickness of 2 nm to 200 nm. In a preferred embodiment, the light emitting device of the present disclosure comprises a light emitting layer printed from the printing ink of the present disclosure, and the printing ink comprises at least one luminescent functional material described above, especially a quantum dot or organic functional materials.

In a preferred embodiment, the light emitting device of the present disclosure may further include a hole injection layer (HIL) or a hole transport layer (HTL) 103 including the above-described organic HTM or inorganic p-type material. In a preferred embodiment, the HIL or HTL can be printed from the printing ink of the present disclosure, and the printing ink comprises a functional material having hole transport ability, especially a quantum dot or organic HTM material.

In another preferred embodiment, the light emitting device of the present disclosure may further comprise an electron injection layer (EIL) or an electron transport layer (ETL) 105, such as the organic ETM or inorganic n-type material described above. In certain preferred embodiments, the EIL or ETL may be printed from a printing ink of the present disclosure, and the printing ink comprises a functional material having an electron transporting capability, particularly a quantum dot or an organic ETM.

The present disclosure also relates to the use of the present disclosure in various contexts, including without limitation, various display devices, backlight units, light sources, and the like.

The present disclosure will be described below with reference to preferred embodiments, but the disclosure is not limited to the following embodiments. It is to be understood that the appended claims are intended to summarize the scope of the disclosure. Those skilled in the art will appreciate that any changes to the various embodiments of the disclosure should be included within the spirit and scope of the claims of this disclosure.

Example 1: Preparation of a quantum dot (CdZnS / ZnS) as a blue emitter

The first solution is prepared by adding 0.0512 g of S and 2.4 mL of ODE to a 25 mL 1-necked flask and heating S to 80 DEG C in an oil bath. The second solution is prepared by adding 0.1280 g of S and 5 mL of OA to a 25-mL volumetric flask and dissolving S by heating to 90 캜 in an oil bath. Then, 0.1028 g of CdO, 1.4680 g of zinc acetate and 5.6 mL of OA were added to a 50 mL three-necked flask, then the two necks were covered with rubber spatula, the top side was connected to the condenser, Leave the heating jacket in a 150-mL capacity while connected to the manifold. The three-necked flask is heated to 150 占 폚, vacuum-treated for 40 minutes, and purged with nitrogen gas. Then inject 12 mL of ODE into a three-necked flask using an injector. When the mixture in a three-necked flask is heated to 310 DEG C, 1.92 mL of the first solution is rapidly injected into a three-necked flask using an injector, and the time is calculated as a maximum of 12 minutes. When 12 minutes is reached, 4 mL of the second solution is added to the three-necked flask at a rate of about 0.5 mL / min using an injector. After 3 hours the reaction is stopped and the three-necked flask is immediately placed in water and cooled to 150 ° C.

Excess hexane is added to the three-necked flask. The liquid in the three-necked flask was transferred to several centrifuge tubes of 10 mL capacity, followed by centrifugation and removal of the bottom sediment three times. After the post-treatment 1, acetone is added until the liquid precipitates, and the supernatant is removed after centrifugation to obtain a precipitate. The precipitate is again dissolved in hexane, acetone is added until precipitation occurs, centrifugation is carried out, the supernatant is removed to obtain a precipitate, and the above step is repeated three times. Finally, the precipitate is dissolved in toluene and transferred to a glass container for storage.

Example 2: Preparation of quantum dot (CdZnSeS / ZnS) as green emitter

The first solution is prepared by adding 0.0079 g Se and 0.1122 g S to a 25 mL 1-necked flask, weighing 2 mL of TOP, purging nitrogen and stirring. Then, 0.0128 g of CdO, 0.3670 g of zinc acetate and 2.5 mL of OA were added to a 25-mL three-necked flask, the two necks of the three-necked flask were covered with rubber spatulas, the top was connected to a condenser, The condenser is connected to the dual manifold on the other side. The three-necked flask was then placed in a 50 mL heating jacket and subjected to the following vacuum treatment steps, purged with nitrogen, heated to 150 DEG C, vacuumed for 30 minutes, 7.5 mL of ODE was introduced Heat again to 300 ° C, quickly inject 1 mL of the first solution, and hold for 10 minutes. Upon reaching 10 minutes, the reaction is stopped immediately, and the three-necked flask is placed in water and allowed to cool.

Then, 5 mL of hexane is added to the three-necked flask. Transfer the mixture to several 10-mL centrifuge tubes, add acetone until precipitation occurs, centrifuge and remove the supernatant to obtain a precipitate. The precipitate is dissolved in hexane, then acetone is added until precipitation occurs, centrifugation is performed, and the above steps are repeated three times. Finally, the precipitate is dissolved in a small amount of toluene and transferred to a glass container for storage.

Example 3: Preparation of a quantum dot (CdSe / CdS / ZnS) as a red emitter

Cd (OA) ₂ The precursor is prepared by adding 1 mmol of CdO, 4 mmol of OA and 20 mL of ODE to a 100 mL three-necked flask, purging with nitrogen and heating to 300 ° C. At this temperature, 0.25 mL of TOP containing 0.25 mmol of Se powder is rapidly injected into the flask. The reaction solution was reacted at this temperature for 90 seconds to grow a CdSe core of about 3.5 nm size. 0.75 mmol of octanethiol was added dropwise to the reaction solution at 300 ° C. and reacted for 30 minutes to grow a CdS shell having a thickness of about 1 nm. Then, 2 mL of TBP in which 4 mmol of Zn (OA) ₂ and 4 mmol of S powder are dissolved is added to the reaction solution to form a ZnS shell having a thickness of about 1 nm. After reacting for 10 minutes, cool the reaction solution to room temperature.

Then, 5 mL of hexane is added to the three-necked flask. Transfer the mixture to several 10-mL centrifuge tubes, add acetone until precipitation occurs, centrifuge and remove the supernatant to obtain a precipitate. Dissolve the precipitate in hexane, add acetone until precipitation occurs, perform centrifugation and repeat the above step three times. Finally, the precipitate is dissolved in a small amount of toluene and transferred to a glass container for storage.

Example 4: Preparation of ZnO nanoparticles

The first solution is prepared by adding 1.475 g of zinc acetate to 62.5 mL of methanol. The second solution is prepared by dissolving 0.74 g of KOH in 32.5 mL of methanol. The first solution is heated to 60 DEG C and vigorously stirred. The second solution is added dropwise to the first solution with the sample injector, and the mixed solution system is continuously stirred at 60 캜 for 2 hours. The heating source is removed and the solution system is kept quiet for 2 hours. The reaction solution was centrifuged at least three times for 5 minutes under centrifugation at 4500 rpm for washing, and finally the resulting white solid was ZnO nanoparticles having a diameter of about 3 nm.

Example 5: Production of quantum dot printing ink containing cyclohexylbenzene

The stirrer is placed in a vial, cleaned and transferred to a glove box. 9.5 g of cyclohexylbenzene solvent is prepared in the vial. After centrifugation, the quantum dots are separated from one solution using acetone to obtain solid quantum dots. 0.5 g of quantum solid is weighed in a glovebox, added to the solvent system in the vial, dispersed at 60 캜 until the quantum dots are completely dispersed, and allowed to cool to room temperature. The resulting quantum dot solution is filtered with a 0.2 μm PTFE membrane, sealed and stored.

Example 6: Preparation of ZnO nanoparticle printing ink containing 1,1'-bicyclohexane

The stirrer is placed in a vial, cleaned and transferred to a glove box. 9.5 g of 1,1'-bicyclohexane solvent is prepared in the vial. 0.5 g of ZnO nanoparticle solids are weighed in a glovebox and added to the solvent system in the vial, stirred at 60 DEG C until the ZnO nanoparticles are completely dispersed and cooled to room temperature. The resulting ZnO nanoparticle solution is filtered with a 0.2 μm PTFE membrane, sealed and stored.

All of the functional organic materials included in the following examples are commercially available, for example, from Jilin OLED Material Tech Co., Ltd. (www.jl-oled.com) or synthesized by methods reported in the literature.

Example 7: Preparation of printing ink for organic luminescent layer containing? -Valerolactone

In this embodiment, the organic functional material of the luminescent layer comprises a phosphorescent host material and a phosphorescent emitter material, and the phosphorescent host material is selected from carbazole derivatives as follows:

And the phosphorescent emitter material is selected from an iridium complex as follows:

The stirrer is placed in a vial, cleaned and transferred to a glove box. 9.8 g of gamma-valerolactone solvent is prepared in the vial. 0.18 g of phosphorescent host material and 0.02 g of phosphorescent emitter material are weighed in a glovebox and added to the solvent system in the vial. The mixture is stirred at 60 DEG C until the organic compound is completely dispersed, and then the mixture is cooled to room temperature. The resulting organic compound solution is filtered with a 0.2 탆 PTFE membrane, sealed and stored.

Example 8: Preparation of a printing ink for an organic light emitting layer containing 2,4-dimethylsulfolane

In this embodiment, the organic functional material of the light emitting layer comprises a fluorescent host material and a fluorescent emitter material, and the fluorescent host material is selected from derivatives of spirofluorene as follows:

And the fluorescent emitter material is selected from the following compounds:

The stirrer is placed in a vial, cleaned and transferred to a glove box. 9.8 g of 2,4-dimethylsulfolane solvent is prepared in the vial. 0.19 g of fluorescent host material and 0.01 g of fluorescent emitter material are weighed in a glove box and added to the solvent system in the vial. The mixture is stirred at 60 DEG C until the functional organic material is completely dissolved, and then the mixture is cooled to room temperature. The resulting functional organic material solution is filtered with a 0.2 탆 PTFE membrane, sealed and stored.

Example 9: Preparation of a printing ink for an organic light emitting layer including a fountain

In this embodiment, the organic functional material of the light emitting layer comprises a host material and a TADF material, and the host material is selected from a compound having the structure:

And the TADF material is selected from compounds having the structure:

The stirrer is placed in a vial, cleaned and transferred to a glove box. 9.8 g of a fungicide solvent is prepared in the vial. 0.19 g of host material and 0.01 g of TADF are weighed in a glovebox and added to the solvent system in the vial. The mixture is stirred at 60 DEG C until the functional organic material is completely dissolved, and then the mixture is cooled to room temperature. The resulting functional organic material solution is filtered with a 0.2 탆 PTFE membrane, sealed and stored.

Example 10: Preparation of printing ink for hole transport material containing sulfolane

In this embodiment, the printing ink includes a hole transporting layer material having hole transporting ability.

The hole transport material is selected from derivatives of triaryl amines as follows:

The stirrer is placed in a vial, cleaned and transferred to a glove box. 9.8 g of sulfolane solvent is prepared in the vial. 0.2 g of hole transport material is weighed in a glovebox and added to the solvent system in the vial. The mixture is stirred at 60 DEG C until the organic compound is completely dispersed, and then the mixture is cooled to room temperature. The resulting organic compound solution is filtered with a 0.2 탆 PTFE membrane, sealed and stored.

Example 11: Viscosity and surface tension test

The viscosity of the functional material ink is measured with a DV-I Prime Brookfield rheometer, and the surface tension of the functional material ink is measured with a SITA bubble pressure tensiometer.

According to the test, the viscosity and surface tension data of the functional material inks prepared in Examples 5 to 10 are listed in the following table:

Example Viscosity (cPs) Surface tension (dyne / cm) 5 5.1 ± 0.5 32.5 ± 0.3 6 4.8 ± 0.5 31.8 ± 0.3 7 4.6 ± 0.5 28.8 ± 0.5 8 8.7 ± 0.5 27.2 ± 0.3 9 4.7 ± 0.5 29.8 ± 0.5 10 10.5 ± 0.3 33.5 ± 0.3

Example 12: Fabrication of functional layer of an electronic device having printing ink of the present disclosure

The functional layer such as the light emitting layer and the charge transport layer of the light emitting diode can be produced from the printing ink of the present disclosure through inkjet printing, the printing ink using the alicyclic solvent system, and the functional material.

The printing method includes the following steps: filling the ink containing the functional material in an ink cartridge mounted on an inkjet printer such as Dimatix Materials Printer DMP-3000 (Fujifilm); And adjusting the waveform, pulse time, and voltage for ejecting the ink to optimize the ejection of the ink and to realize stability from the ink ejection. A method of manufacturing a QLED device including a functional material film as a light emitting layer includes using a 0.7 nm thick glass piece in which an indium tin oxide (ITO) electrode pattern is sputtered as a substrate of a QLED. A pixel defining layer is patterned on ITO to form holes for depositing printing ink therein. The HIL / HTL material is then injected into the holes and dried under high vacuum to remove the solvent to obtain a HIL / HTL film. Thereafter, the printing ink containing the luminescent functional material is sprayed onto the HIL / HTL film and dried under high temperature vacuum to remove the solvent to obtain a film of the light emitting layer. A printing ink containing a functional material having an electron transporting ability is sprayed onto a film of a light emitting layer and dried under a high temperature vacuum to remove the solvent to obtain an electron transport layer (ETL). When using an organic electron transport material, the ETL can also be formed by vacuum thermal evaporation and finally the QLED device is packaged.

What has been described above are some implementations of the disclosure, and they are specific and specific, but are not intended to limit the scope of the disclosure. Those skilled in the art will appreciate that various modifications and improvements can be made without departing from the concept of the disclosure, and all such modifications and improvements are within the scope of the present disclosure. The scope of the disclosure is to be accorded the scope of the appended claims.

Claims (20)

At least one functional material; And a solvent system based on an alicyclic structure and containing at least one organic solvent having the general formula (I).
[General Formula (I)]

here,
R ¹ is an alicyclic or heteroalicyclic structure having 3 to 20 ring atoms, n is an integer of 0 or more, and R ² is a substituent when n is 1;
The boiling point of the organic solvent is? 150 ° C, and the organic solvent can be evaporated from the solvent system to form the functional material film. The method according to claim 1,
Wherein the organic solvent based on alicyclic structure and having formula (I) has a viscosity of from 1 cPs to 100 cPs at 25 占 폚. The method according to claim 1,
Wherein the organic solvent based on alicyclic structure and having formula (I) has a surface tension of from 19 dyne / cm to 50 dyne / cm at 25 占 폚. The method of claim 3,
R ¹ of an organic solvent based on an alicyclic structure and having the general formula (I) has a structure selected from any of the following general formulas:

Wherein X is selected from CR ³ R ⁴ , C (= O), S, S (= O) ₂ , O, SiR ⁵ R ⁶ , NR ⁷ , or P (= O) R ⁸ ; Each R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ is independently selected from any of H, D, straight chain alkyl containing from 1 to 20 carbon atoms, straight chain alkoxy or straight chain Branched or cyclic alkyl, branched or cyclic alkoxy, branched or cyclic thioalkoxy, branched or cyclic silyl containing from 1 to 20 carbon atoms Alkoxycarbonyl containing from 2 to 20 carbon atoms, aryloxycarbonyl containing from 7 to 20 carbon atoms, cyano (-CN), carbamoyl (-C (= O) NH _2), halo-formyl (-C (= O) -X, wherein, X represents a halogen atom), formyl (-C (= O) -H) , isocyano, isocyanate, thiocyanate, isothiocyanate N, hydroxy, nitro, CF ₃ , Cl, Br, F, a crosslinkable functional group, 5 to 40 ring atoms A substituted or unsubstituted aromatic or heteroaromatic ring system, or aryloxy or heteroaryloxy containing from 5 to 40 ring atoms; When one or more of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are present at the same time, they may be present independently or together with each other and / or R ¹ or R ² , Form an aliphatic or aromatic ring system. The method according to claim 1,
Wherein each R &lt; ² &gt; contained in the organic solvent based on the alicyclic structure and having the general formula (I) is the same or different from any one of the following:
Straight chain alkyl, straight chain alkoxy or straight chain thioalkoxy each containing from 1 to 20 carbon atoms, branched or cyclic alkyl containing from 3 to 20 carbon atoms each, branched or cyclic alkoxy, branched or cyclic thio Alkoxy or silyl, substituted keto containing from 1 to 20 carbon atoms, alkoxycarbonyl containing from 2 to 20 carbon atoms; Of 7 to 20 containing the carbon atoms aryloxycarbonyl, cyano (-CN), carbamoyl _{(-C (= O) NH 2} ), halo-formyl (-C (= O) -X; wherein, X is represents a halogen atom), formyl (-C (= O) -H) , isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxy, nitro, CF _3, Cl, Br, F, crosslinkable A functional group or a substituted or unsubstituted aromatic or heteroaromatic ring system containing 5 to 40 ring atoms, or aryloxy or heteroaryloxy containing 5 to 40 ring atoms; Wherein when one or more of R &lt; ² &gt; are present at the same time, they are independently present or together with each other and / or functional groups form a single ring or polycyclic aliphatic or aromatic ring system. The method according to claim 1,
The organic solvent based on the alicyclic structure and having the general formula (I) includes tetralin, cyclohexylbenzene, decahydronaphthalene, 2-phenoxytetrahydrofuran, 1,1'-bicyclohexyl, butylcyclohexane, 2-tetralone, 2-tetralone, 2-tetralone, 2-ethylhexyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl acrylate, - (phenyl epoxy) tetralone, 6- (methoxy) tetralone,? -Butyrolactone,? -Valerolactone, 6-hexanololactone, N, N-diethylcyclohexylamine, 2,4-dimethylsulfone, and any combination thereof. The method according to claim 1,
Wherein the solvent system is a mixture further comprising at least one other organic solvent, wherein the organic solvent based on the alicyclic structure and having the general formula (I) accounts for at least 50% of the total weight of the mixed solvent. The method according to claim 1,
Wherein the functional material is an inorganic nanomaterial. The method according to claim 1,
Wherein the functional material is a quantum dot material. The method according to claim 1,
Wherein the functional material is a luminescent quantum dot material having an emission wavelength in the range of 380 nm to 2500 nm. The method according to claim 1,
II-VI-VI, III-VI, IV-VI, I-III-VI, II-IV-VI and II-IV-V of the Periodic Table of the Elements And an inorganic functional material that is a binary or multi-semiconductor compound selected from the group consisting of any combination thereof. The method according to claim 1,
Wherein the functional material is a perovskite nanoparticle material. 13. The method of claim 12,
Wherein the perovskite nanoparticle material is selected from the group consisting of a luminescent perovskite nanomaterial, a metal nanoparticle material, a metal oxide nanoparticle material, and any combination thereof. The method according to claim 1,
Wherein the functional material is an organic functional material. 15. The method of claim 14,
The organic functional material is 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, a hole blocking material, an emitter, a host material, an organic dye, Formulation for printing. 16. The method of claim 15,
Wherein the organic functional material comprises at least one host material and at least one emitter. The method according to claim 1,
Wherein the functional material comprises 0.3-30% of the total weight of the formulation and the organic solvent comprises 70-99.7% of the total weight of the formulation. An organic solvent based on an alicyclic structure contained in a formulation and printed or coated by the formulation for printing an electronic article of claim 1, wherein the organic solvent having the general formula (I) is evaporated from the solvent system to form a functional material film The electronic device can. 19. The method of claim 18,
Electronic devices include, but are not limited to, quantum dot light emitting diodes (QLEDs), quantum dot photovoltaic cells (QPV), quantum dot luminescent electrochemical cells (QLEECs), quantum dot field effect transistors (QFETs), quantum dot luminescence field effect transistors, ), An organic photovoltaic (OPV), an organic luminescent electrochemical cell (OLEEC), an organic field effect transistor (OFET), an organic luminescence field effect transistor and an organic sensor. The method of printing or coating according to claim 1, wherein the printing or coating method comprises the steps of: placing an electronic printing formulation of claim 1 on a substrate by a printing or coating method, wherein the printing or coating method is selected from the group consisting of inkjet printing, nozzle printing, typographic printing, screen printing, dip coating, Wherein the functional material film is selected from the group consisting of printing, torsion roller printing, lithographic printing, flexographic printing, rotary printing, spray coating, brush coating, pad printing and slot die coating.

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