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WO2019105326A1 - Mélange organique, composition le comprenant, composant électronique organique, et applications - Google Patents

Mélange organique, composition le comprenant, composant électronique organique, et applications Download PDF

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Publication number
WO2019105326A1
WO2019105326A1 PCT/CN2018/117517 CN2018117517W WO2019105326A1 WO 2019105326 A1 WO2019105326 A1 WO 2019105326A1 CN 2018117517 W CN2018117517 W CN 2018117517W WO 2019105326 A1 WO2019105326 A1 WO 2019105326A1
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organic
organic mixture
homo
lumo
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Chinese (zh)
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潘君友
黄宏
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Guangzhou Chinaray Optoelectronic Materials Ltd
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Guangzhou Chinaray Optoelectronic Materials Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/611—Charge transfer complexes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/40—Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/90—Multiple hosts in the emissive layer
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • H10K2102/103—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising indium oxides, e.g. ITO
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers

Definitions

  • the present invention relates to the field of electroluminescent materials, and more particularly to an organic mixture, a composition comprising the same, an organic electronic device, and its use in an organic electronic device, particularly in an electroluminescent device.
  • OLEDs Organic light-emitting diodes
  • the main material is the key to achieving high performance LEDs.
  • Organic light-emitting diodes using phosphorescent materials can achieve nearly 100% internal electroluminescence quantum efficiency, and thus become the mainstream material system in the industry.
  • the phosphorescent host material with practical use value is a bipolar transport compound or a co-host compound, and its material composition is relatively complicated. If it is applied to a device, it is easy to cause hole and electron transport imbalance, so the lifetime of the phosphorescent device is not long.
  • Kim proposed the concept of exciplex as a phosphorescent host material, which can use two different organic compounds to form an intermediate state, namely an exciplex, thereby improving the device. Lifespan (see Kim et al., Adv. Mater., Vol 26, 5864, (2014)).
  • the solubility is poor, and on the other hand, even if it is soluble, the molecular weight is low, printability and film formability are poor, and thus it is not suitable for printing. Process.
  • a major aspect of the present invention provides an organic mixture which provides a new organic mixture material for solving the problem that existing exciplex materials are not suitable for printing processes. Problems that improve device performance.
  • Another aspect of the invention provides an organic electronic device comprising the organic mixture, and uses thereof.
  • An organic mixture comprising an organic material P and another organic material H, wherein at least one of P and H is a polymer, and min((LUMO(P)-HOMO(H), LUMO(H)-HOMO( P)) ⁇ min(E T (P), E T (H)) + 0.1eV, where HOMO(H), LUMO(H) and E T (H) respectively represent the highest occupied orbit of H and the lowest unoccupied orbit And the triplet level, HOMO(P), LUMO(P), and E T (P) represent the highest occupied orbital, the lowest unoccupied orbit, and the triplet level of P, respectively.
  • An organic mixture as described above comprising: 1) a polymer P1 and a small molecule organic material H2; or 2) a polymer P1 and a polymer P2; or 3) a polymer P2 and a small molecule organic material H1, wherein P1 comprises As a repeating unit represented by Chemical Formula 1 or 1b, P2 contains a repeating unit as shown in Chemical Formula 2 or 2b, n, n1, m and m1 represent the number of repeating units, and n, n1, m and m1 are natural numbers greater than or equal to 1. , SP is a non-conjugated spacer group.
  • An organic mixture as described above preferably, at least one of H1 and H2 satisfies ((HOMO-(HOMO-1)) ⁇ 0.3 eV.
  • H1 and H2 have the structure shown by structural formula (I) or (II) below:
  • Ar is a substituted or unsubstituted aromatic or heteroaromatic structural unit
  • D may be independently selected from the same or different electron-donating groups when it is present multiple times, and A may be independently selected from each other when it occurs multiple times.
  • the same or different electron withdrawing groups, p, r are integers between 1 and 6, and q, s are 0 or 1;
  • the organic mixture further comprises a luminescent material selected from the group consisting of a singlet illuminant (fluorescent illuminant), a triplet illuminant (phosphorescent illuminant) or a TADF illuminant .
  • a luminescent material selected from the group consisting of a singlet illuminant (fluorescent illuminant), a triplet illuminant (phosphorescent illuminant) or a TADF illuminant .
  • Another aspect of the invention provides a composition comprising an organic mixture as described above, and at least one organic solvent.
  • Yet another aspect of the invention provides the use of an organic mixture as described above in an organic electronic device.
  • Another aspect of the invention provides an organic electronic device comprising an organic mixture as described above.
  • Another aspect of the invention provides an organic electronic device comprising a light-emitting layer, wherein the light-emitting layer comprises an organic mixture as described above.
  • the organic mixture of the present invention is easy to form an exciplex, and has good stability when used for a host material, and can improve the performance of the device. At the same time, since the organic mixture of the invention has good solubility in an organic solvent, the film forming property is good, thereby providing a better material solution for printing OLED.
  • the present invention provides an organic mixture and its use in an organic electroluminescent device.
  • the present invention will be further described in detail below in order to make the objects, technical solutions and effects of the present invention more clear and clear. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
  • the host material In the present invention, the host material, the matrix material, the Host material, and the Matrix material have the same meaning and are interchangeable.
  • the singlet and singlet states have the same meaning and are interchangeable.
  • triplet and triplet states have the same meaning and are interchangeable.
  • composition and the printing ink, or ink have the same meaning and are interchangeable.
  • the complex excited state, exciplex and Exciplex have the same meaning and are interchangeable.
  • small molecule refers to a molecule that is not a polymer, oligomer, dendrimer or blend. In particular, there are no repeating structures in small molecules.
  • the molecular weight of the small molecule is ⁇ 3000 g/mol, preferably ⁇ 2000 g/mol, most preferably ⁇ 1500 g/mol.
  • the polymer ie, Polymer
  • the polymer also includes a dendrimer.
  • a dendrimer For the synthesis and application of the tree, see [Dendrimers and Dendrons, Wiley-VCH Verlag GmbH & Co. KGaA, 2002, Ed. George R. Newkome, Charles. N. Moorefield, Fritz Vogtle.].
  • a conjugated polymer is a polymer whose main chain is mainly composed of sp2 hybrid orbitals of C atoms. Typical examples include, but are not limited to, polyacetylene and poly(phenylene) [poly(phenylene) Vinylene]], the C atom in its main chain can also be substituted by other non-C atoms, and when the sp2 hybridization in the main chain is interrupted by some natural defects, it is still considered to be a conjugated polymer. Further, in the present invention, the conjugated polymer also includes a polymer comprising an arylamine, an arylphosphine, and other heterocyclic aromatic hydrocarbons, an organic metal complex or the like in the main chain.
  • the present invention relates to an organic mixture comprising an organic material P and another organic material H, wherein at least one of P and H is a polymer, and min((LUMO(P)-HOMO(H), LUMO(H) )-HOMO(P)) ⁇ min(E T (P), E T (H))+0.1eV, where HOMO(H), LUMO(H) and E T (H) respectively represent the highest occupied orbit of H, The lowest unoccupied orbital and triplet energy levels, HOMO(P), LUMO(P), and E T (P) represent the highest occupied orbit, the lowest unoccupied orbit, and the triplet level of P, respectively.
  • the organic mixture satisfies the following formula: min((LUMO(H)-HOMO(P), LUMO(P)-HOMO(H)) ⁇ min(E T (H), E T (P)) +0.05 eV;
  • the organic mixture satisfies the following formula: min((LUMO(H)-HOMO(P), LUMO(P)-HOMO(H)) ⁇ min(E T (H), E T (P));
  • the organic mixture satisfies the following formula: min((LUMO(H)-HOMO(P), LUMO(P)-HOMO(H)) ⁇ min(E T (H), E T (P))-0.1eV;
  • the organic mixture satisfies the following formula: min((LUMO(H)-HOMO(P), LUMO(P)-HOMO(H)) ⁇ min(E T (H), E T (P)) - 0.15 eV;
  • the organic mixture satisfies the following formula: min((LUMO(H)-HOMO(P), LUMO(P)-HOMO(H)) ⁇ min(E T (H), E T (P)) - 0.2 eV;
  • the energy level structure of the organic material the triplet energy levels E T , HOMO, and LUMO play a key role.
  • the following is an introduction to the determination of these energy levels.
  • the HOMO and LUMO levels can be measured by photoelectric effect, such as XPS (X-ray photoelectron spectroscopy) and UPS (UV photoelectron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV).
  • photoelectric effect such as XPS (X-ray photoelectron spectroscopy) and UPS (UV photoelectron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV).
  • quantum chemical methods such as density functional theory (hereinafter referred to as DFT) have also become effective methods for calculating molecular orbital energy levels.
  • the triplet energy level E T of organic materials can be measured by low temperature time-resolved luminescence spectroscopy, or by quantum simulation calculations (eg by Time-dependent DFT), as by commercial software Gaussian 03W (Gaussian Inc.), specific simulation methods. See WO2011141110 or the following examples.
  • the absolute values of HOMO, LUMO, E T depend on the measurement method or calculation method used. Even for the same method, different evaluation methods, such as starting point and peak point on the CV curve, can give different HOMO/ LUMO value. Therefore, reasonable and meaningful comparisons should be made using the same measurement method and the same evaluation method.
  • the values of HOMO, LUMO, and E T are simulations based on Time-dependent DFT, but do not affect the application of other measurement or calculation methods.
  • At least one of P and H in the organic mixture according to the present invention is a conjugated polymer.
  • Conjugated polymers are widely reported and are well known to those skilled in the art.
  • the triplet energy level of the conjugated polymer is low, and thus a mixture containing a conjugated polymer can be preferably used as the red phosphorescent host.
  • At least one of P and H in the organic mixture according to the invention is a non-conjugated polymer.
  • the organic mixture according to the invention comprises: 1) a polymer P1 and a small molecule organic material H2; or 2) a polymer P1 and a polymer P2; or 3) a polymer P2 and a small molecule organic material H1, wherein P1 comprises As a repeating unit represented by Chemical Formula 1 or 1b, P2 contains a repeating unit as shown in Chemical Formula 2 or 2b, n, n1, m and m1 represent the number of repeating units, and n, n1, m and m1 are natural numbers greater than or equal to 1. , SP is a non-conjugated spacer group.
  • the organic mixture satisfies the following formula: min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1)) ⁇ min(E T (H1), E T (H2))+0.1 eV, where HOMO(H1), LUMO(H1), and E T (H1) represent the highest occupied orbit, the lowest unoccupied orbit, and the triplet level of H1, HOMO(H2), LUMO(H2), and E T (H2, respectively). ) indicates the highest occupied orbit, the lowest unoccupied orbit, and the triplet level of H2, respectively.
  • the above organic mixture satisfies the following formula: min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1)) ⁇ min(E T (H1), E T ( H2)) +0.05 eV;
  • the above organic mixture satisfies the following formula: min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1)) ⁇ min(E T (H1), E T (H2));
  • the above organic mixture satisfies the following formula: min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1)) ⁇ min(E T (H1), E T (H2)) - 0.1 eV;
  • the above organic mixture satisfies the following formula: min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1)) ⁇ min(E T (H1), E T (H2)) -0.15eV;
  • the above organic mixture satisfies the following formula: min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1)) ⁇ min(E T (H1), E T (H2)) -0.2eV;
  • SP represents a non-conjugated spacer unit, specifically a structural unit whose conjugation structure is interrupted, such as interrupted by at least one sp3-hybridized atom such as C. Similarly, its conjugated structure can also be interrupted by a non-sp3-hybrid atom, such as O, S or Si.
  • R 11 to R 13 independently of each other represent hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or substituted 5- to 60- Meta-heteroaryl.
  • the non-conjugated spacer unit SP may comprise a single non-conjugated atom between two conjugated groups, or the SP comprises a non-conjugated at least 2 atoms separating the two conjugated groups chain.
  • the non-conjugated spacer unit SP may comprise two or more atoms to separate two conjugated groups, for example a linear or branched alkyl chain of 1 to 20 carbon atoms, wherein one or more of the chains
  • the spacer group SP comprises at least one sp3-hybridized carbon atom to separate the two conjugated groups.
  • Preferred spacer groups SP are selected from alkyl chains of 1 to 20 carbon atoms in which one or more non-adjacent C atoms are replaced by O.
  • the preferred non-conjugated spacer unit SP is selected from the following structures:
  • Ar-1 represents an aromatic or heteroaromatic group having 5 to 60 ring atoms.
  • the non-conjugated spacer unit may be selected from linear or bifurcated alkylene, cycloalkylene, alkylsilylene, silylene, arylsilylene, An alkylalkoxyalkylene group, an arylalkoxyalkylene group, an alkylthioalkylene group, a sulfone, an alkylene sulfone, a sulfone oxide, an alkylene sulfone oxide, wherein the alkylene group
  • the groups in each case independently of 1 to 12 C atoms, and one or more H atoms may be D, F, Cl, Br, I, alkyl, heteroalkyl, cycloalkyl, aryl Or substituted with a heteroaryl group.
  • the non-conjugated spacer unit SP is selected from linear or bifurcated alkylene or alkoxyalkylene groups comprising from 1 to 12 C atoms, and one or more H atoms may be substituted by F.
  • non-conjugated spacer unit SP may be selected from the following structural formula:
  • Ar-2, Ar-3 and Ar-4 independently of each other represent an aromatic or heteroaromatic group having 5 to 60 ring atoms
  • R-1, R-2 and R-3R-4 are independently represented by each other.
  • -C alkylene, cycloalkylene, alkylsilylene, silylene, arylsilylene, alkylalkoxyalkylene, arylalkoxyalkylene, alkane a thioalkylene group, a phosphine, a phosphine oxide, a sulfone, an alkylene sulfone, a sulfone oxide, an alkylene sulfone oxide, wherein the alkylene group in each case comprises 1 to 12 C independently of each other.
  • Atom, and one or more H atoms may be substituted by D, F, Cl, Br, I, alkyl, heteroalkyl, cycloalkyl, aryl or heteroaryl.
  • the substituents R-1 to R-4 may be one atom bonded to Ar-2, Ar-3 and Ar-4, or two adjacent to each other between Ar-2, Ar-3 and Ar-4. On the atom.
  • the atom to which R-1 to R-4 are bonded may be an atom on the aromatic ring or a hetero atom.
  • the dotted line represents the position of the functional group linkage on the non-conjugated spacer unit SP.
  • a particularly preferred non-conjugated spacer unit SP is selected from the following structural units:
  • An advantage of the organic mixture according to the present invention is that the organic mixture contains at least one polymer compared to the organic small molecule mixture, has better solubility and better film formation quality, and thus can simplify the device processing process.
  • Another advantage of the organic mixture according to the present invention is that the organic mixture may form an Exciplex which, when used in the luminescent layer material, can improve device efficiency and increase device lifetime.
  • the organic mixture according to the invention can be used as a phosphorescent host material.
  • the organic mixture according to the invention has min ((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1))) in the range of 1.9-2.4 eV.
  • the mixture may preferably be used as a red phosphorescent host material.
  • the organic mixture according to the invention has a min ((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1))) in the range of 2.4-2.7 eV.
  • the organic mixture can be preferably used as a green phosphorescent host material.
  • the organic mixture according to the invention has min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1)) in the range of 2.7-3.1 eV.
  • the organic mixture may preferably be used as a blue phosphorescent host material.
  • (HOMO-1) is defined as the second highest occupied orbital level
  • (HOMO-2) is the third highest occupied orbital level
  • (LUMO+1) is defined as the second lowest unoccupied orbital level
  • (LUMO+2) is the third lowest occupied orbital level, and so on.
  • At least one of said H1 and H2 (HOMO-(HOMO-1)) ⁇ 0.2 eV, preferably ⁇ 0.25 eV, more preferably ⁇ 0.3 eV, more More preferably ⁇ 0.35 eV, very preferably ⁇ 0.4 eV, most preferably ⁇ 0.45 eV.
  • each of said H1 and H2 (HOMO-(HOMO-1)) ⁇ 0.2 eV, preferably one of them (HOMO-(HOMO-1) )) ⁇ 0.25 eV, more preferably ⁇ 0.3 eV, still more preferably ⁇ 0.35 eV, very preferably ⁇ 0.4 eV, most preferably ⁇ 0.45 eV.
  • ((LUMO+1)-LUMO) of at least one of H1 and H2 is ⁇ 0.15 eV, preferably ⁇ 0.20 eV, more preferably ⁇ 0.25 eV, More preferably, it is ⁇ 0.30 eV, very preferably ⁇ 0.35 eV, and most preferably ⁇ 0.40 eV.
  • ((LUMO+1)-LUMO) of each of H1 and H2 is ⁇ 0.15 eV, preferably one of ((LUMO+1) -LUMO) ⁇ 0.20 eV, more preferably ⁇ 0.25 eV, still more preferably ⁇ 0.30 eV, very preferably ⁇ 0.35 eV, most preferably ⁇ 0.40 eV.
  • H1 and H2 HOMO-(HOMO-1)
  • H1 and H2 HOMO-(HOMO-1)
  • ⁇ 0.2 eV preferably ⁇ 0.25 eV, more preferably ⁇ 0.3 More preferably, ⁇ 0.35 eV, very preferably ⁇ 0.4 eV, most preferably ⁇ 0.45 eV
  • X is the mass ratio of P1/H2, P1/P2, and P2/H1 in the above organic mixture.
  • the organic mixture according to the present invention has a X selected from 0.1 to 10.
  • the organic mixture according to the invention wherein X is selected from the range of 0.2 to 5.
  • the organic mixture according to the invention wherein X is selected from the range of 0.25 to 4.
  • X is selected from the range of 0.5 to 2 in accordance with the organic mixture of the present invention.
  • X is selected from the range of 0.8 to 1.25 in accordance with the organic mixture of the present invention.
  • X is selected to be 1 according to the organic mixture of the present invention.
  • the organic mixture according to the invention wherein at least one of said H1 and H2 comprises an electron-donating group D, and/or at least one comprises an electron-withdrawing group A.
  • the organic mixture according to the invention wherein at least one of H1 and H2 comprises a structure represented by the following structural formula (I):
  • Ar is an aromatic or heteroaromatic structural unit
  • D may be independently selected from the same or different electron-donating groups when present multiple times
  • p is an integer between 1 and 6, and q is equal to 0 or 1;
  • the above electron donating group D may preferably be selected from a structure comprising any of the following groups:
  • Y represents an aromatic group having 6 to 40 carbon atoms or 3 to 40 carbon atoms; preferably, Y is selected from the group consisting of benzene, naphthalene, anthracene, phenanthrene, triphenylene, anthracene, and pyridine.
  • R, R 1 and R 2 each independently represent alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, heteroalkyl, aryl and heteroaryl;
  • R, R 1 and R 2 are an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 40 carbon atoms or carbon.
  • R, R 1 and R 2 are an alkyl group having 1 to 15 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms, and a more preferred embodiment.
  • R, R 1 , and R 2 are each selected from the group consisting of methyl, isopropyl, t-butyl, isobutyl, hexyl, octyl, 2-ethylhexyl, benzene, biphenyl, Naphthalene, anthracene, phenanthrene, benzophenanthrene, anthracene, pyridine, pyrimidine, triazine, anthracene, thioindigo, silicon germanium, carbazole, thiophene, furan, thiazole, triphenylamine, triphenylphosphine, tetraphenyl silicon, a group such as a snail or a spirosilicone; more preferably a group such as methyl, isopropyl, t-butyl, isobutyl, benzene, biphenyl, naphthalene, anthracene, phen
  • the electron-donating group D is selected from any one of the following formulas:
  • the electron-donating group D is selected from any one of the following formulas:
  • the electron-donating group D is selected from structural units comprising groups wherein the H on the ring can be further optionally substituted:
  • the structural formula represented by the general formula (1) according to the present invention is selected from any one of the following structural formulas:
  • the organic mixture according to the present invention wherein at least one of H1 and H2 comprises a structure represented by the following structural formula (II):
  • Ar is a substituted or unsubstituted aromatic or heteroaromatic structural unit, and A, when multiple occurrences, may be independently selected from the same or different electron withdrawing groups, r is an integer between 1 and 6, s is 0 or 1.
  • a suitable electron withdrawing group A may be selected from the group consisting of F, cyano or a group having any of the following formulas:
  • n2 is 1, 2 or 3;
  • X 1 -X 8 is selected from CR or N, and at least one is N;
  • R, R 1 and R 2 are as described above.
  • a suitable electron withdrawing group A is a cyano group.
  • the structural formula represented by the general formula (II) according to the present invention is selected from any one of the following structural formulas:
  • Ar in the structural formulae (I) and (II) is an aromatic group or an aromatic heterocyclic group having 6 to 70 ring atoms; in a more preferred embodiment, Ar is a ring atom.
  • An aromatic ring system or an aromatic group refers to a hydrocarbon group containing at least one aromatic ring, including a monocyclic group and a polycyclic ring system.
  • the aromatic heterocyclic or aromatic hetero group refers to a hydrocarbon group (containing a hetero atom) containing at least one aromatic heterocyclic ring, and includes a monocyclic group and a polycyclic ring system.
  • the heteroatoms are preferably selected from the group consisting of Si, N, P, O, S and/or Ge, particularly preferably selected from the group consisting of Si, N, P, O and/or S.
  • These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, a fused ring.
  • the aromatic or aromatic heterocyclic ring system includes not only a system of an aryl or a aryl group, but also a plurality of aryl or aryl groups may also be interrupted by short non-aromatic units ( ⁇ 10). % of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms).
  • systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, etc., are also considered to be aromatic ring systems in the aspect of the invention.
  • aromatic groups are: benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, anthracene, benzopyrene, triphenylene, anthracene, anthracene, and derivatives thereof.
  • non-limiting examples of the aromatic hetero group are: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, anthracene Anthracene, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrazole, furanfuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, Pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-diazine, quinoxaline, phenanthridine, carbaidine, quinazoline, quinazolinone, and derivatives thereof.
  • Ar is preferably selected from the group consisting of benzene, biphenyl, naphthalene, anthracene, phenanthrene, triphenylene, anthracene, pyridine, pyrimidine, triazine, anthracene, thioindigo, silicon germanium, carbazole, thiophene, a group such as furan, thiazole, triphenylamine, triphenylphosphine oxide, tetraphenyl silicon, spirulina, spirosilicone or the like; more preferably selected from the group consisting of: benzene, biphenyl, naphthalene, anthracene, phenanthrene, benzophenanthrene, snail ⁇ and other groups.
  • Ar in Structural Formulas (I) and (II) may comprise one or more of the following structural groups:
  • X 1 -X 8 respectively represent CR 3 or N;
  • the organic mixture according to the invention wherein in said structural formulae (I) and (II), Ar may be selected from the group consisting of:
  • n2 is 1 or 2 or 3 or 4.
  • the H1 or H2 is selected from a compound or a formula (p-type) represented by one of the following formulae (1) to (8):
  • L 1 represents a single bond, an aromatic group having 6 to 30 carbon atoms or an aromatic hetero group having 3 to 30 carbon atoms, and the linking position of L 1 may be any one of carbon atoms on the benzene ring;
  • L 2 , L 3 , L 4 and L 5 represent an aromatic group having 6 to 30 carbon atoms or an aromatic hetero group having 3 to 30 carbon atoms;
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 represent an aromatic group having 6 to 30 carbon atoms or an aromatic hetero group having 3 to 30 carbon atoms;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R each independently represent H, D, F, CN, alkenyl, alkynyl, nitrile, amine, nitro, acyl, alkoxy a carbonyl group, a sulfone group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic ring having 3 to 60 carbon atoms. a group wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 may be bonded to any carbon atom on the fused ring.
  • N3 and n4 represent an integer of 1 to 6.
  • H1 or H2 is selected from the group consisting of:
  • the H1 or H2 is selected from a compound or formula (p-type) as shown in one of the following formulae:
  • Each of Ar 5 -Ar 13 may be independently selected from the group consisting of: cyclic aromatic hydrocarbon compounds such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalylene, phenanthrene, anthracene, pyrene, fluorene, fluorene, fluorene; Aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, furan, thiophene, benzofuran, benzothiophene, oxazole, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, Oxtriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxazine, dioxazin, hydrazine, benzimid
  • each Ar may be further substituted, and the substituent may be selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, heteroalkyl, aryl and heteroaryl.
  • a further non-limiting example of a structural unit (p-type) useful for H1 or H2 according to the organic mixture of the invention is as follows:
  • repeating structural units H1 and H2 in the polymer P1 or P2, when present in plurality, may be independently selected from the same or different structural groups as described above.
  • the organic mixture according to the present invention, wherein the method for synthesizing the polymer is selected from the group consisting of SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA- , HARTWIG-BUCHWALD- and ULLMAN.
  • the organic mixture according to the invention has a polymer having a glass transition temperature (Tg) ⁇ 100 ° C, preferably ⁇ 120 ° C, more preferably ⁇ 140 ° C, still more preferably ⁇ 160 ° C. Most preferably ⁇ 180 °C.
  • Tg glass transition temperature
  • the organic mixture according to the invention has a polymer having a molecular weight distribution (PDI) in the range of preferably from 1 to 5, more preferably from 1 to 4, still more preferably from 1 to 3, more preferably It is preferably 1 to 2, and most preferably 1 to 1.5.
  • PDI molecular weight distribution
  • the organic mixture according to the present invention has a weight average molecular weight (Mw) of the polymer preferably in the range of 10,000 to 1,000,000, more preferably 50,000 to 500,000, more preferably 10 10,000 to 400,000, more preferably 150,000 to 300,000, and most preferably 200,000 to 250,000.
  • Mw weight average molecular weight
  • the invention further relates to another mixture comprising an organic mixture as described above, and at least one other organic functional material, which may be selected from the group consisting of: hole (also known as a hole) injection or transport material (HIM) /HTM), hole blocking material (HBM), electron injecting or transporting material (EIM/ETM), electron blocking material (EBM), organic matrix material (Host), singlet illuminant (fluorescent illuminant), triplet state Luminescent (phosphorescent) and TADF materials, in particular luminescent organic metal complexes.
  • hole also known as a hole injection or transport material (HIM) /HTM
  • HBM hole blocking material
  • EIM/ETM electron injecting or transporting material
  • EBM electron blocking material
  • organic matrix material Host
  • singlet illuminant fluorescent illuminant
  • triplet state Luminescent phosphorescent
  • TADF materials in particular luminescent organic metal complexes.
  • organic functional materials are described in detail in, for example
  • the further mixture comprises an organic mixture and a luminescent material according to the invention, the luminescent material being selected from the group consisting of singlet emitters (fluorescent emitters), triplet emitters (phosphorescence) Body) or TADF illuminant.
  • the other mixture comprises an organic mixture and a fluorescent illuminant according to the invention.
  • the organic mixture according to the invention here can be used as a fluorescent host material, wherein the fluorescent illuminant is ⁇ 10% by weight, preferably ⁇ 9wt%, more preferably ⁇ 8wt%, particularly preferably ⁇ 7wt%, most preferably ⁇ 5wt%.
  • the further mixture comprises an organic mixture and a phosphorescent emitter according to the invention.
  • the organic mixture according to the invention here can be used as a phosphorescent host material, wherein the phosphorescent emitter is ⁇ 25 wt%, preferably ⁇ 20 wt%, more preferably ⁇ 15 wt%.
  • the further mixture comprises an organic mixture, a phosphorescent emitter and a host material according to the invention.
  • the organic mixture according to the invention may be used as an auxiliary luminescent material in a weight ratio to phosphorescent emitter of from 1:2 to 2:1.
  • the energy level of the exciplex of the mixture according to the invention is higher than that of the phosphorescent emitter.
  • the other mixture comprises an organic mixture and a TADF material according to the invention.
  • the organic mixture according to the invention here can be used as a TADF host material, wherein the weight percentage of the TADF host material is ⁇ 15% by weight, preferably ⁇ 10% by weight, more preferably ⁇ 8% by weight.
  • Singlet emitters tend to have longer conjugated pi-electron systems.
  • styrylamines and derivatives thereof disclosed in JP 2913116 B and WO 2001021729 A1
  • indenoindenes and their derivatives disclosed in WO 2008/006449 and WO 2007/140847 and in US Pat. No. 7,233,019, KR2006-0006760 A disclosed triarylamine derivative of hydrazine.
  • the singlet emitter can be selected from the group consisting of: monostyrylamine, dibasic styrylamine, ternary styrylamine, quaternary styrylamine, styrene phosphine, styrene ether, and arylamine .
  • Monostyrylamine refers to a compound comprising an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine.
  • Dibasic styrylamine refers to a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • Ternary styrylamine refers to a compound comprising three unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • Tetrastyrylamine refers to a compound comprising four unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • a preferred styrene is stilbene, which may be further substituted.
  • the corresponding phosphines and ethers are defined similarly to amines.
  • An arylamine or an aromatic amine refers to a compound comprising three unsubstituted or substituted aromatic ring or heterocyclic systems directly bonded to nitrogen. At least one of these aromatic or heterocyclic ring systems preferably has a self-fused ring system and most preferably has at least 14 aromatic ring atoms.
  • Preferred non-limiting examples thereof are: aromatic decylamine, aromatic quinone diamine, aromatic decylamine, aromatic quinone diamine, aromatic thiamine and aromatic quinone diamine.
  • Aromatic decylamine refers to a compound in which one of the diarylamine groups is attached directly to the oxime, most preferably at the position of 9.
  • Aromatic quinone diamine refers to a compound in which two diaryl arylamine groups are attached directly to the oxime, most preferably at the 9,10 position.
  • the definitions of aromatic decylamine, aromatic guanidine diamine, aromatic thiamine and aromatic quinone diamine are similar, wherein the diaryl aryl group is most preferably bonded to the 1 or 1,6 position of hydrazine.
  • Examples of singlet emitters based on vinylamines and arylamines are also preferred examples and can be found in the following patent documents: WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549, WO 2007 /115610, US Pat. No. 7,250,532, B2, DE 102005058557 A1, CN 1583691 A, JP 08053397 A, US Pat. No. 6,215,531, B1, US 2006/210830 A, EP 1 957 606 A1, and US 2008/0113101 A1, the entire contents of which are incorporated herein by reference. This article serves as a reference.
  • Further preferred singlet emitters may be selected from the indolo-amines and indeno-quinone-diamines as disclosed in WO 2006/122630, such as the benzoindeno-amines and benzoses disclosed in WO 2008/006449
  • An indeno-diamine such as dibenzoindeno-amine and dibenzoindeno-diamine as disclosed in WO2007/140847.
  • Further preferred singlet emitters may be selected from the group consisting of ruthenium-based fused ring systems as disclosed in US2015333277A1, US2016099411A1, US2016204355A1.
  • More preferred singlet emitters may be selected from the group consisting of: a derivative of ruthenium, such as the structure disclosed in US Pat. No. 1, 1975, 509, A1; a triarylamine derivative of ruthenium, such as a triarylamine derivative of ruthenium containing a dibenzofuran unit disclosed in CN102232068B; Other triarylamine derivatives of hydrazine having a specific structure are disclosed in CN105085334A, CN105037173A.
  • polycyclic aromatic hydrocarbon compounds in particular derivatives of the following compounds: for example, 9,10-bis(2-naphthoquinone), naphthalene, tetraphenyl, xanthene, phenanthrene , ⁇ (such as 2,5,8,11-tetra-t-butyl fluorene), anthracene, phenylene such as (4,4'-bis(9-ethyl-3-carbazolevinyl)-1 , 1 '-biphenyl), indenyl hydrazine, decacycloolefin, hexacene benzene, anthracene, spirobifluorene, aryl hydrazine (such as US20060222886), arylene vinyl (such as US5121029, US5130603), cyclopentane Alkene such as tetraphenylcyclopentadiene, rub
  • Non-limiting examples of some suitable singlet emitters are listed in the table below:
  • TDF Thermally activated delayed fluorescent luminescent material
  • the thermally activated delayed fluorescent luminescent material is a third generation organic luminescent material developed after organic fluorescent materials and organic phosphorescent materials.
  • Such materials generally have a small singlet-triplet energy level difference ( ⁇ E st ), and triplet excitons can be converted into singlet exciton luminescence by inter-system crossing. This can make full use of the singlet excitons and triplet excitons formed under electrical excitation.
  • the quantum efficiency in the device can reach 100%.
  • the material structure is controllable, the property is stable, the price is cheap, no precious metal is needed, and the application prospect in the OLED field is broad.
  • the TADF material needs to have a small singlet-triplet energy level difference, typically ⁇ Est ⁇ 0.3 eV, preferably ⁇ Est ⁇ 0.25 eV, more preferably ⁇ Est ⁇ 0.20 eV, and most preferably ⁇ Est ⁇ 0.1 eV.
  • the TADF material has a relatively small ⁇ Est, and in another preferred embodiment, the TADF has a better fluorescence quantum efficiency.
  • Non-limiting examples of TADF luminescent materials can be found in the following patent documents: CN103483332(A), TW201309696(A), TW201309778(A), TW201343874(A), TW201350558(A), US20120217869(A1), WO2013133359(A1) , WO2013154064 (A1), Adachi, et.al. Adv. Mater., 21, 2009, 4802, Adachi, et. al. Appl. Phys. Lett., 98, 2011, 083302, Adachi, et.al. Appl. Phys. Lett., 101, 2012, 093306, Adachi, et. al. Chem.
  • TADF luminescent materials are listed in the table below:
  • Triplet emitters are also known as phosphorescent emitters.
  • the triplet emitter is a metal complex of the formula M(L)n, wherein M is a metal atom and each time L can be the same or a different organic ligand, it Attached to the metal atom M by one or more position linkages or coordination, n is an integer greater than 1, preferably 1, 2, 3, 4, 5 or 6.
  • these metal complexes are coupled to the polymer by one or more positions, most preferably to the polymer via an organic ligand.
  • the metal atom M may be selected from transition metal elements or lanthanides or actinides, preferably selected from the group consisting of Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb.
  • Dy, Re, Cu or Ag is particularly preferably selected from the group consisting of Os, Ir, Ru, Rh, Re, Pd, Au or Pt.
  • the triplet emitter may comprise a chelating ligand, ie a ligand, coordinated to the metal by at least two bonding sites, with particular preference being given to the triplet emitter comprising two or three identical or different Double or multidentate ligand.
  • Chelating ligands are beneficial for increasing the stability of metal complexes.
  • Non-limiting examples of organic ligands may be selected from the group consisting of: phenylpyridine derivatives, 7,8-benzoquinoline derivatives, 2(2-thienyl)pyridine derivatives, 2(1-naphthyl)pyridine derivatives Or a 2 phenylquinoline derivative. All of these organic ligands may be substituted, for example by fluorine or trifluoromethyl.
  • the ancillary ligand may preferably be selected from the group consisting of acetone acetate or picric acid.
  • the metal complex that can be used as the triplet emitter can have the following form:
  • M is a metal selected from a transition metal element or a lanthanide or lanthanide element, particularly preferably selected from the group consisting of Ir, Pt, and Au;
  • Each occurrence of Ar 1 may be the same or different cyclic group, which contains at least one donor atom, that is, an atom having a lone pair of electrons, such as nitrogen or phosphorus, through which a cyclic group is coordinated to the metal;
  • Each occurrence of Ar 2 may be the same or different cyclic group, which contains at least one C atom through which a cyclic group is bonded to the metal;
  • Ar 1 and Ar 2 are linked by a covalent bond, respectively Carrying one or more substituent groups, which may also be linked together by a substituent group;
  • each occurrence of L' may be the same or a different bidentate chelated auxiliary ligand, most preferably a monoanionic bidentate chelate
  • Non-limiting examples of materials for some triplet emitters and their use can be found in the following patent documents and documents: WO 200070655, WO 200141512, WO 200202714, WO 200215645, EP 1191613, EP 1191612, EP 1191614, WO 2005033244, WO 2005019373, US 2005/0258742, WO 2009146770, WO 2010015307, WO 2010031485, WO 2010054731, WO 2010054728, WO 2010086089, WO 2010099852, WO 2010102709, US 20070087219 A1, US 20090061681 A1, US 20010053462 A1, Baldo, Thompson et al.
  • triplet emitters Some non-limiting examples of suitable triplet emitters are listed in the table below:
  • Another aspect of the invention relates to a solution for providing printing inks for printing OLEDs.
  • the solubility of the mixture according to the invention in toluene is > 10 mg/ml, preferably > 15 mg/ml, most preferably > 20 mg/ml at 25 °C.
  • Another aspect of the invention still further relates to a composition or ink comprising an organic mixture as described above and at least one organic solvent.
  • the viscosity and surface tension of the ink are important parameters when used in the printing process. Suitable surface tension parameters for the ink are suitable for the particular substrate and the particular printing method.
  • the surface tension of the ink according to the invention is in the range of from about 19 dyne/cm to 50 dyne/cm at the working temperature or at 25 ° C; preferably in the range of 22 dyne/cm to 35 dyne/cm; most preferably 25dyne/cm to 33dyne/cm range.
  • the viscosity of the ink according to the invention is in the range of from about 1 cps to 100 cps at the working temperature or at 25 ° C; preferably in the range of from 1 cps to 50 cps; more preferably in the range of from 1.5 cps to 20 cps; most preferably 4.0cps to 20cps range.
  • the composition so formulated will facilitate ink jet printing.
  • the viscosity can be adjusted by different methods, such as by selection of a suitable solvent and concentration of the functional material in the ink.
  • the ink containing the metal organic complex or polymer according to the present invention can facilitate the adjustment of the printing ink in an appropriate range in accordance with the printing method used.
  • the composition according to the invention comprises a functional material in a weight ratio ranging from 0.3% to 30% by weight, preferably from 0.5% to 20% by weight, more preferably from 0.5% to 15% by weight, even more preferably from 0.5% to ⁇
  • the at least one organic solvent is selected from the group consisting of aromatic or heteroaromatic based solvents, particularly aliphatic chain/ring substituted aromatic solvents, aromatic ketone solvents, or Aromatic ether solvent.
  • Non-limiting examples of solvents suitable for the present invention are: aromatic or heteroaromatic based solvents: p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethyl Naphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, triphenylbenzene, pentyltoluene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene , p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexyl Benz
  • the at least one solvent may be selected from the group consisting of aliphatic ketones, for example, 2-fluorenone, 3-fluorenone, 5-fluorenone, 2-nonanone, 2,5-hexyl Diketone, 2,6,8-trimethyl-4-indanone, phorone, di-n-pentyl ketone, etc.; or an aliphatic ether, for example, pentyl ether, hexyl ether, dioctyl ether, ethylene glycol Dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, three Propylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and the like.
  • aliphatic ketones for example, 2-fluorenone, 3-fluoren
  • the printing ink further comprises another organic solvent.
  • another organic solvent include, but are not limited to, methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, O-xylene, m-xylene, p-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1,1,1 -trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene, naphthalene Alkanes, hydrazines and/or mixtures thereof.
  • the composition according to the invention is a solution.
  • composition according to the invention is a suspension.
  • composition in the examples of the invention may comprise from 0.01 to 20% by weight of the organic mixture according to the invention, preferably from 0.1 to 15% by weight, more preferably from 0.2 to 10% by weight, most preferably from 0.25 to 5% by weight of the organic mixture.
  • Another aspect of the invention also relates to the use of the composition as a coating or printing ink in the preparation of an organic electronic device, particularly preferably the use of the composition for the preparation of an organic electronic device by printing or coating.
  • suitable printing or coating techniques include, but are not limited to, inkjet printing, Nozzle Printing, typography, screen printing, dip coating, spin coating, blade coating, roller printing, torsion rolls. Printing, lithography, flexographic printing, rotary printing, spraying, brushing or pad printing, slit-type extrusion coating, etc. Preferred are gravure, inkjet and inkjet printing.
  • the solution or suspension may additionally comprise one or more components such as surface active compounds, lubricants, wetting agents, dispersing agents, hydrophobic agents, binders and the like for adjusting viscosity, film forming properties, adhesion, and the like.
  • the present invention also provides an application of the organic mixture as described above, that is, the organic mixture is applied to an organic electronic device, and the organic electronic device may be selected from, but not limited to, an organic light emitting diode (OLED), an organic photovoltaic cell. (OPV), organic light-emitting battery (OLEEC), organic field effect transistor (OFET), organic light-emitting field effect transistor, organic laser, organic spintronic device, organic sensor and organic plasmon emitting diode (Organic Plasmon Emitting Diode) Etc. Especially OLED.
  • the organic compound is preferably used in the luminescent layer of an OLED device.
  • the organic electronic device comprises at least one cathode, one anode, and a functional layer between the cathode and the anode, wherein the functional layer contains at least one organic mixture as described above.
  • the organic electronic device may be selected from, but not limited to, an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, an organic laser.
  • Organic spintronic devices organic sensors and organic plasmon emitting diodes (Organic Plasmon Emitting Diode), etc., particularly preferred are organic electroluminescent devices such as OLED, OLEEC, organic light-emitting field effect transistors.
  • the luminescent layer of the electroluminescent device comprises or comprises the organic mixture and phosphorescent emitter, or comprises the organic mixture and host material, or comprises The organic mixture, the phosphorescent emitter, and the host material.
  • the above-mentioned light emitting device particularly an OLED, includes a substrate, an anode, at least one light emitting layer, and a cathode.
  • the substrate can be opaque or transparent. Transparent substrates can be used to make transparent light-emitting components. See, for example, Bulovic et al. Nature 1996, 380, p29, and Gu et al, Appl. Phys. Lett. 1996, 68, p2606.
  • the substrate can be rigid or elastic.
  • the substrate can be made of plastic, metal, semiconductor wafer or glass. Most preferably, the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice.
  • the substrate is flexible and may be selected from polymeric films or plastics having a glass transition temperature Tg of 150 ° C or higher, preferably more than 200 ° C, more preferably more than 250 ° C, and most preferably more than 300 ° C.
  • suitable flexible substrates are poly(ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).
  • the anode can include a conductive metal or metal oxide, or a conductive polymer.
  • the anode can easily inject holes into a hole injection layer (HIL), a hole transport layer (HTL), or a light-emitting layer.
  • HIL hole injection layer
  • HTL hole transport layer
  • the work function of the anode and the absolute value of the difference between the HOMO level or the valence band level of the luminescent material in the luminescent layer as the p-type semiconductor material of the HIL, HTL or electron blocking layer (EBL) is less than 0.5 eV. Preferably, it is less than 0.3 eV, and most preferably less than 0.2 eV.
  • anode material examples include, but are not limited to, Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like.
  • suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art.
  • the anode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
  • the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices in accordance with the present invention.
  • the cathode can include a conductive metal or metal oxide.
  • the cathode can easily inject electrons into the EIL or ETL or directly into the luminescent layer.
  • the work function of the cathode and the LUMO level or conduction band of the n-type semiconductor material of the illuminant in the luminescent layer as an electron injection layer (EIL), an electron transport layer (ETL) or a hole blocking layer (HBL)
  • EIL electron injection layer
  • ETL electron transport layer
  • HBL hole blocking layer
  • the absolute value of the difference in energy levels is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV.
  • all materials which can be used as cathodes for OLEDs are possible as cathode materials for the devices of the invention.
  • cathode material examples include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF 2 /Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, and the like.
  • the cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
  • the OLED may further include other functional layers such as a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), an electron injection layer (EIL), an electron transport layer (ETL), a hole blocking layer. (HBL).
  • HIL hole injection layer
  • HTL hole transport layer
  • EBL electron blocking layer
  • EIL electron injection layer
  • ETL electron transport layer
  • HBL hole blocking layer
  • the light-emitting device according to the invention has an emission wavelength of between 300 and 1000 nm, preferably between 350 and 900 nm, more preferably between 400 and 800 nm.
  • Another aspect of the invention also relates to the use of an electroluminescent device according to the invention in various electronic devices, including but not limited to display devices, illumination devices, light sources, sensors, and the like.
  • H1-1, H1-2, H2-1, and H2-1 are all prior art, and the details of the prior art are not described herein.
  • the H1-1 synthesis method can be found in WO2015156449A1
  • the H2-1 synthesis method can be found in WO2015023034A1.
  • the energy structure of the organic small molecule material can be obtained by quantum calculation, for example, by TD-DFT (time-dependent density functional theory) by Gaussian 03W (Gaussian Inc.), and the specific simulation method can be found in WO2011141110.
  • TD-DFT time-dependent density functional theory
  • Gaussian 03W Gaussian Inc.
  • the specific simulation method can be found in WO2011141110.
  • the semi-empirical method “Ground State/Semi-empirical/Default Spin/AM1” (Charge 0/Spin Singlet) is used to optimize the molecular geometry, and then the energy structure of the organic molecule is determined by TD-DFT (time-dependent density functional theory) method.
  • TD-SCF/DFT/Default Spin/B3PW91 the base group "6-31G(d)” (Charge 0/Spin Singlet).
  • the energy structure of the polymer can be obtained by calculating functional groups such as H1 or H2 on the side chain, where H1 or H2 is linked to other units. Replace with methyl.
  • the HOMO and LUMO levels are calculated according to the following calibration formula, and S1 and T1 are used directly.
  • HOMO(eV) ((HOMO(G) ⁇ 27.212)-0.9899)/1.1206
  • HOMO(G) and LUMO(G) are direct calculation results of Gaussian 09W, and the unit is eV.
  • the following reaction route using a format reagent, first reacts with an anthrone to form 9-nonanol, and then uses Eton reagent to strongly absorb water to form a polymer P1, the reaction yield is high, and the reaction treatment is easy, and the molecular weight of the finally obtained polymer Both distribution and molecular weight give better results.
  • the bipoxazole and 3,4'-dibromomethylbiphenyl are polymerized by a Hartwig reaction to obtain a polymer P2.
  • the main synthetic steps are as follows: taking the synthesis of the P1-1 polymer as an example, 0.5 mmol of H1-1 monomer is dissolved in a toluene solvent under nitrogen protection, and 0.01 mmol 2 is added by a syringe. 2-Azobisisobutyronitrile (AIBN initiator), sealed, reacted at 60 ° C for 4 hours, when the reaction was completed, cooled to room temperature, and the polymer was precipitated with methanol. The precipitate was dissolved in tetrahydrofuran (THF) and precipitated with methanol. Repeat this way The vacuum was dried to give a solid of the polymer P1-1.
  • AIBN initiator 2-Azobisisobutyronitrile
  • the synthesis steps for the polymers P1-2, P2-1 and P2-2 are similar to those of the polymer P1-1, except that the H1-1 monomer is converted into a monomer corresponding to the polymer, and the polymer is relative to the single
  • the body is shown in the following table:
  • the calculation method of polymer energy level structure is the same as the calculation method of small molecule energy level structure.
  • the mixing manner of the organic mixture in the examples of the present invention is as follows:
  • An alternative embodiment of the present invention comprises an organic mixture and a fluorescent emitter mixed as in Table 5, or an organic mixture and a phosphorescent emitter mixed as in Table 5, or an organic mixture and a TADF material mixed as in Table 5.
  • the specifics are shown in Table 6:
  • Compound A is as follows:
  • the preparation process of the OLED device using the mixture shown in Table 4 will be described in detail below by way of a specific embodiment.
  • the structure of the OLED device is: ITO/HIL/HTL/EML/ETL/cathode, and the preparation steps are as follows:
  • ITO indium tin oxide
  • a conductive glass substrate cleaning using a variety of solvents (such as one or several of chloroform, acetone or isopropanol) cleaning, and then UV ozone treatment;
  • HIL hole injection layer, 60nm
  • 60nm is of PEDOT (polyethylene dioxythiophene, Clevios TM AI4083) in a clean room as HIL spin coated from, and heat-treated at 180 [deg.] C for 10 minutes plate ;
  • HTL hole transport layer, 20 nm
  • 20 nm TFB or PVK (Sigma Aldrich, average Mn 25,000-50,000) was prepared by spin coating in a nitrogen glove box, and the solution used was TFB added to the toluene solvent.
  • PVK Sigma Aldrich
  • solution solubility 5mg / ml was treated on a hot plate at 180 ° C for 60 minutes;
  • TFB H.W.SandsCorp.
  • EML organic light-emitting layer
  • EML is formed by spin coating in a nitrogen glove box, and the solution used is a mixture (1-6) or a mixture (A/B/C) added to a toluene solvent and a certain amount.
  • Compound D having the structural formula shown below, having a solution solubility of 10 mg/ml, followed by treatment on a hot plate at 180 ° C for 10 minutes; Table 7 lists the composition and thickness of the EML of the device;
  • OLED device HTL EML composition and thickness OLED1 PVK Mixture 1 (15%) Compound D (80 nm)
  • OLED2 PVK Mixture 2 (15%) Compound D (65 nm) OLED3 TFB Mixture 3: (15%) Compound D (80 nm) OLED4 TFB Mixture 4: (15%) Compound D (80 nm) OLED5 TFB Mixture 5: (15%) Compound D (80 nm) OLED6 PVK Mixture 6: (15%) Compound D (65 nm) OLED7 PVK Mixture 7: (15%) Compound D (65 nm) OLED8 PVK Mixture A: (15%) Compound D (65 nm) OLED9 TFB Mixture B: (15%) Compound D (80 nm) OLED10 TFB Mixture C: (15%) Compound D (80 nm)
  • cathode Ba / Al (2nm / 100nm) in a high vacuum (1 ⁇ 10 -6 mbar) in the thermal evaporation;
  • the device was encapsulated in a UV glove box with a UV curable resin.
  • the current and voltage (IVL) characteristics of each OLED device are characterized by characterization equipment while recording important parameters such as efficiency, lifetime and drive voltage.
  • the performance of OLED devices is summarized in Table 8.

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  • Electroluminescent Light Sources (AREA)

Abstract

L'invention concerne un mélange organique, une composition le comprenant, un composant électronique organique, et des applications. Le mélange organique comprend un matériau organique (P) et un autre matériau organique (H), au moins un matériau parmi P et H étant un polymère, et min((LUMO(P)−HOMO(H), LUMO(H)−HOMO(P)) ≤ min(ET(P), ET(H)) + 0,1 eV. Le mélange organique selon la présente invention forme facilement un exciplexe, facilite la préparation d'une solution convenant à l'impression, a une stabilité améliorée, et constitue une solution efficace pour l'impression de DELO.
PCT/CN2018/117517 2017-11-28 2018-11-26 Mélange organique, composition le comprenant, composant électronique organique, et applications Ceased WO2019105326A1 (fr)

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CN111384299B (zh) * 2018-12-29 2024-02-09 固安鼎材科技有限公司 一种有机发光二极管及其制备方法
CN109734928B (zh) * 2019-01-04 2021-08-17 中国科学院长春应用化学研究所 一种空间电荷转移树枝状荧光材料及其制备方法、有机电致发光器件
CN112319081A (zh) * 2019-12-12 2021-02-05 广东聚华印刷显示技术有限公司 喷墨打印方法、喷墨打印装置及发光器件
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