WO2019105326A1

WO2019105326A1 - Organic mixture, composition comprising same, organic electronic component, and applications

Info

Publication number: WO2019105326A1
Application number: PCT/CN2018/117517
Authority: WO
Inventors: 潘君友; 黄宏
Original assignee: 广州华睿光电材料有限公司
Priority date: 2017-11-28
Filing date: 2018-11-26
Publication date: 2019-06-06
Also published as: CN107978692A; CN107978692B

Abstract

Disclosed are an organic mixture, a composition comprising same, an organic electronic component, and applications. The organic mixture comprises an organic material P and another organic material H, where at least one of P and H is a polymer, and min((LUMO(P)-HOMO(H), LUMO(H)-HOMO(P)) ≤ min(ET(P), ET(H)) + 0.1eV. The organic mixture of the present invention easily forms an exciplex, facilitates the preparation of a solution suitable for printing, has improved stability, and provides an effective solution for OLED printing.

Description

Organic mixture, composition comprising the same, organic electronic device and application

The present application claims priority to Chinese Patent Application No. 200911218633.X entitled "Organic Mixture, Compositions Containing the Same, Organic Electronic Devices and Applications", filed on November 28, 2017, all of which are incorporated herein by reference. The content is incorporated herein by reference.

Technical field

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.

Background technique

Organic light-emitting diodes (OLEDs) are considered to be the most promising next-generation displays in the industry due to their light weight, active illumination, wide viewing angle, high contrast ratio, high luminous efficiency, low power consumption, ease of preparation of flexible and large-sized panels. technology.

In order to improve the luminous efficiency of organic light-emitting diodes and promote the industrialization process of organic light-emitting diodes, the key problem of organic light-emitting diodes that are urgently needed to be solved is the light-emitting performance and lifetime. Therefore, it is still necessary to further develop a high-performance organic photoelectric material system.

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. However, to date, 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. In order to solve this problem, 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)).

At present, several companies have reported the use of exciplex as a co-host. For example, Rohm and Haas Electronic Materials Korea Ltd. discloses a co-subject in which a first body and a second body are respectively associated. Carbazole derivatives and carbazole derivatives (US2017/0062730). Samsung discloses a co-host with two host materials selected from the group consisting of an electron transport host and a hole transport body (KR20160026744). However, the organic materials capable of forming exciplex disclosed in these articles or disclosed in the patent are all small molecule materials, which are suitable for the preparation of vapor-deposited OLEDs. It is easy to prepare multi-layer, complex and high-efficiency OLED devices by vacuum evaporation method, but the production cost is expensive, time-consuming, and material utilization is not high; especially for RGBside-by-side technology, due to the use of precision metal masks (FMM), it is difficult to achieve the production of large-size displays. In contrast, solution-processed OLEDs have the advantages of being able to prepare large-area, flexible devices through inexpensive inkjet printing, printing and other solution processing methods, and thus have broad application prospects and commercial value. For the small molecule co-hosts of the presently disclosed excimer complexes, on the one hand, 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.

Therefore, new materials suitable for the printing process, especially new luminescent layer materials, are yet to be developed.

Summary of the invention

In view of the above deficiencies of the prior art, 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.

The technical solution provided in one aspect of the invention is as follows:

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. Also, 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, respectively. HOMO(H2), LUMO(H2) and E _T (H2) respectively represent the highest occupied orbit of H2. , the lowest unoccupied orbit and the triplet level.

An organic mixture as described above, preferably, at least one of H1 and H2 satisfies ((HOMO-(HOMO-1)) ≥ 0.3 eV.

An organic mixture as described above, wherein at least one of H1 and H2 comprises an electron donating group D or/and at least one comprises an electron withdrawing group A.

In certain preferred embodiments, H1 and H2 have the structure shown by structural formula (I) or (II) below:

Wherein Ar is a substituted or unsubstituted aromatic or heteroaromatic structural unit, and 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;

In some particularly preferred embodiments, 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 .

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.

Advantageous Effects: 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.

Detailed ways

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.

In the present invention, the host material, the matrix material, the Host material, and the Matrix material have the same meaning and are interchangeable.

In the present invention, the singlet and singlet states have the same meaning and are interchangeable.

In the present invention, the triplet and triplet states have the same meaning and are interchangeable.

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

In the present invention, the complex excited state, exciplex and Exciplex have the same meaning and are interchangeable.

The term "small molecule" as defined herein 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, includes homopolymers, copolymers, and block copolymers. Also in the present invention, the polymer also includes 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.

In a preferred embodiment, 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;

In a more preferred embodiment, the organic mixture satisfies the following formula: min((LUMO(H)-HOMO(P), LUMO(P)-HOMO(H)) ≤ min(E _T (H), E _T (P));

In a more preferred embodiment, 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;

In a highly preferred embodiment, 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;

In a most preferred embodiment, 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;

In the embodiment of the present invention, 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). Recently, 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.

It should be noted that 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. In the description of the embodiments of the present invention, 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.

In certain embodiments, 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.

In a particularly preferred embodiment, at least one of P and H in the organic mixture according to the invention is a non-conjugated polymer.

Preferably, 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. And, 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.

In a preferred embodiment, 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;

In a more preferred embodiment, the above organic mixture satisfies the following formula: min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1)) ≤ min(E _T (H1), E _T (H2));

In a more preferred embodiment, 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;

In a highly preferred embodiment, 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;

In a most preferred embodiment, 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;

In Chemical Formulas 1b and 2b, 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.

In a preferred embodiment, the non-conjugated spacer unit SP represents a linear or branched alkyl chain having from 1 to 20 carbon atoms, wherein one or more non-adjacent C atoms of the chain may be O, S, -NR ₁₁ -, -CR ₁₂ R ₁₃ -, -C(=O)- or -COO- replacement. 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.

In Chemical Formulas 1b and 2b, 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 non-adjacent C atoms may be replaced by O, S, -NR ₁₁ -, -CR ₁₂ R ₁₃ -, -C(=O)- or -COO-. Preferably, 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:

Wherein Ar-1 represents an aromatic or heteroaromatic group having 5 to 60 ring atoms.

In another preferred embodiment, 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.

Particularly preferably, 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.

In another preferred embodiment, the non-conjugated spacer unit SP may be selected from the following structural formula:

Wherein Ar-2, Ar-3 and Ar-4 independently of each other represent an aromatic or heteroaromatic group having 5 to 60 ring atoms, and 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:

The meaning of the symbols is the same as above.

Preferred non-limiting examples of polymers according to formula 1b are shown in the following table:

A non-limiting example of a preferred polymer according to Chemical Formula 2b is shown in the following table:

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.

In a preferred embodiment, the organic mixture according to the invention can be used as a phosphorescent host material.

In a preferred embodiment, 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.

In another preferred embodiment, 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.

In another preferred embodiment, 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.

In the invention, (HOMO-1) is defined as the second highest occupied orbital level, (HOMO-2) is the third highest occupied orbital level, and so on. (LUMO+1) is defined as the second lowest unoccupied orbital level, (LUMO+2) is the third lowest occupied orbital level, and so on.

In a preferred embodiment, according to the organic mixture of the invention, 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.

In a particularly preferred embodiment, according to the organic mixture of the invention, 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.

In another preferred embodiment, according to the organic mixture of the present invention, ((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.

In another particularly preferred embodiment, according to the organic mixture of the present invention, ((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.

In some particularly preferred embodiments, according to the organic mixture of the invention, 1) at least one of 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; 2) ((LUMO+1)-LUMO) of the other of H1 and H2 ≥0.15 eV, preferably ≥0.20 eV, Preferably ≥ 0.25 eV, more preferably ≥ 0.30 eV, very preferably ≥ 0.35 eV, most preferably ≥ 0.40 eV.

X is the mass ratio of P1/H2, P1/P2, and P2/H1 in the above organic mixture. In certain embodiments, the organic mixture according to the present invention has a X selected from 0.1 to 10.

In a preferred embodiment, the organic mixture according to the invention wherein X is selected from the range of 0.2 to 5.

In a more preferred embodiment, the organic mixture according to the invention wherein X is selected from the range of 0.25 to 4.

In a more preferred embodiment, X is selected from the range of 0.5 to 2 in accordance with the organic mixture of the present invention.

In a particularly preferred embodiment, X is selected from the range of 0.8 to 1.25 in accordance with the organic mixture of the present invention.

In a most preferred embodiment, X is selected to be 1 according to the organic mixture of the present invention.

In a preferred embodiment, 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.

In a more preferred embodiment, 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):

Wherein Ar is an aromatic or heteroaromatic structural unit, and 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;

In certain preferred embodiments, the above electron donating group D may preferably be selected from a structure comprising any of the following groups:

among them,

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.

Z ¹ , Z ² , and Z ³ each independently represent a single bond, N(R), C(R) ₂ , Si(R) ₂ , O, S, C=N(R), C=C(R) ₂ or P(R), Z ² and Z ^{3 are} not simultaneously a single bond; in a preferred embodiment, Z ¹ , Z ² , Z ³ are a single bond, N(R), C(R) ₂ , Si(R) ₂ , O or S, but Z ² and Z ^{3 are} not single bonds at the same time.

Wherein R, R ¹ and R ² each independently represent alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, heteroalkyl, aryl and heteroaryl;

In certain preferred embodiments, 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. In a more preferred embodiment, 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. The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 3 to 30 carbon atoms; in a most preferred embodiment, R, R ¹ and R ² are an alkyl group having 1 to 10 carbon atoms. And a cycloalkyl group having 3 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms or an aromatic heterocyclic group having 3 to 20 carbon atoms.

In a 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, phenanthrene, benzophenanthrene, or snail .

In a preferred embodiment, the electron-donating group D is selected from any one of the following formulas:

Here, the meanings of Y, Z ² , Z ³ and R are as described above.

In a more preferred embodiment, the electron-donating group D is selected from any one of the following formulas:

Wherein, the meanings of R and R1 are as described above.

In a most preferred embodiment, the electron-donating group D is selected from structural units comprising groups wherein the H on the ring can be further optionally substituted:

In some preferred embodiments, the structural formula represented by the general formula (1) according to the present invention is selected from any one of the following structural formulas:

Wherein Ar, Z2, Z3, Y have the meanings as described above.

In another preferred embodiment, 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):

Wherein 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.

In a preferred embodiment, 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:

Wherein m2 is 1, 2 or 3; X ¹ -X ^{8 is} selected from CR or N, and at least one is N;

M ¹ , M ² , and M ³ independently represent N(R), C(R) ₂ , Si(R) ₂ , O, C=N(R), C=C(R) ₂ , P(R), P(=O)R, S, S=O, SO ₂ or none; in a preferred embodiment, the above M ¹ , M ² , M ^{3 are} preferably N(R), C(R) ₂ , Si (R) ₂ , O, S or none.

The meanings of R, R ¹ and R ² are as described above.

In a preferred embodiment, a suitable electron withdrawing group A is a cyano group.

In some preferred embodiments, the structural formula represented by the general formula (II) according to the present invention is selected from any one of the following structural formulas:

Wherein Ar means as described above.

In certain preferred embodiments, 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 group or an aromatic hetero group of 6 to 60; in a highly preferred embodiment, Ar is an aromatic group or an aromatic hetero group having 6 to 50 ring atoms; in a most preferred embodiment, Ar is an aromatic group or an aromatic hetero group having a ring number of 6 to 40.

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. At least one of these rings of the polycyclic ring is aromatic or heteroaromatic. In various aspects of the invention, 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). Thus, 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.

Specifically, non-limiting examples of aromatic groups are: benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, anthracene, benzopyrene, triphenylene, anthracene, anthracene, and derivatives thereof.

Specifically, 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.

In a preferred embodiment, 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芴 and other groups.

In a preferred embodiment, Ar in Structural Formulas (I) and (II) may comprise one or more of the following structural groups:

among them,

X ¹ -X ⁸ respectively represent CR ³ or N;

Y ¹ and Y ² each independently represent CR ⁴ R ⁵ , SiR ⁴ R ⁵ , NR ³ , C(=O), S or O;

R ³ , R ⁴ , R ⁵ are H, D, or a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branch having 3 to 20 C atoms Or a cyclic alkyl, alkoxy or thioalkoxy group or a silyl group, or a substituted keto group having 1 to 20 C atoms, or having 2 to 20 C atoms Alkoxycarbonyl group, or an aryloxycarbonyl group having 7 to 20 C atoms, a cyano group (-CN), a carbamoyl group (-C(=O)NH2), a halogen Acyl group (-C(=O)-X wherein X represents a halogen atom), formyl group (-C(=O)-H), isocyano group, isocyanate group, thiocyanate group Or isothiocyanate group, hydroxyl group, nitro group, CF ₃ group, Cl, Br, F, crosslinkable group or substituted or unsubstituted aryl having 5 to 40 ring atoms a family or heteroaromatic ring system, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems, wherein one or more of the groups R ³ , R ⁴ , R ⁵ may The rings bonded to each other and/or to the groups form a monocyclic or polycyclic aliphatic or aromatic ring.

In a more preferred embodiment, the organic mixture according to the invention, wherein in said structural formulae (I) and (II), Ar may be selected from the group consisting of:

Wherein n2 is 1 or 2 or 3 or 4.

In a preferred embodiment, the H1 or H2 is selected from a compound or a formula (p-type) represented by one of the following formulae (1) to (8):

among them,

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;

B ¹ and B ² independently represent N(R), C(R) ₂ , Si(R) ₂ , O, C=N(R), C=C(R) ₂ , P(R), P(= O) R, S, S=O or SO ₂ ;

B ³ and B ⁴ each independently represent a single bond, N(R), C(R) ₂ , Si(R) ₂ , O, C=N(R), C=C(R) ₂ , P(R), P(=O)R, S, S=O or SO ₂ , but not the same as a single bond;

Y ¹ to Y ⁸ independently represent N(R), C(R) ₂ , Si(R) ₂ , O, C=N(R), C=C(R) ₂ , P(R), P(= O) R, S, S=O or SO ₂ ;

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.

In a preferred embodiment, in the mixture according to the invention, in the formulae (1) to (8), H1 or H2 is selected from the group consisting of:

In other preferred embodiments, 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, benzimidazole, oxazole, pyridazine, Benzooxazole, benzoxazole, benzothiazole, quinoline, isoquinoline, o-diaza(hetero)naphthalene, quinazoline, quinoxaline, naphthalene, anthracene, pteridine, xanthene, acridine , phenazine, phenothiazine, phenoxazine, dibenzoselenophene, benzoselenophene, benzofuranpyridine, carbazole, pyridinium, pyrrole dipyridine, furobipyridine, benzothiophenepyridine, Thiophenepyridine, benzoselenopyridine and selenophene dipyridine; a group comprising a 2 to 10 ring structure, which may be the same or different types of cyclic aromatic hydrocarbon groups or aromatic heterocyclic groups, and This is linked directly or through at least one of the following groups, such as an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit, and an aliphatic ring group. Wherein 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.

In a preferred embodiment, further non-limiting examples of structural units (n-type) that can be used for H1 or H2 in accordance with the organic mixtures of the present invention are as follows:

In a preferred embodiment, 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:

In the present invention, the 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.

In a preferred embodiment, 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.

In a preferred embodiment, 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.

In a preferred embodiment, 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.

In a preferred embodiment, 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.

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. Various organic functional materials are described in detail in, for example, WO2010135519A1, US2009134784A1, and WO2011110277A1, the entire disclosure of each of which is hereby incorporated by reference. Organic functional materials can be small molecules and polymeric materials.

In a more preferred embodiment, 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.

In certain embodiments, 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%.

In a particularly preferred embodiment, 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%.

In another preferred embodiment, the further mixture comprises an organic mixture, a phosphorescent emitter and a host material according to the invention. In such an embodiment, 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. In another preferred embodiment, the energy level of the exciplex of the mixture according to the invention is higher than that of the phosphorescent emitter.

In another more preferred embodiment, 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.

Some more detailed and non-limiting descriptions of fluorescent or singlet emitters, phosphorescent or triplet emitters and TADF materials are provided below.

1. Singlet emitter (Singlet Emitter)

Singlet emitters tend to have longer conjugated pi-electron systems. To date, there have been many examples, such as the styrylamines and derivatives thereof disclosed in JP 2913116 B and WO 2001021729 A1, the 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.

In a preferred embodiment, 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.

An example of a singlet emitter based on a stilbene extreme derivative is US 5121029.

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. Other materials which can be used as singlet emitters are polycyclic aromatic hydrocarbon compounds, in particular derivatives of the following compounds: for example, 9,10-bis(2-naphthoquinone), naphthalene, tetraphenyl, xanthene, phenanthrene , 芘 (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, rubrene, coumarin, rhodamine, quinacridone, pyran such as 4 (dicyanomethylidene)-6-(4-p-dimethylaminobenzene Vinyl-2-methyl)-4H-pyran (DCM), thiopyran, bis(pyridazinyl)imine boron compound (US 2007/0092753 A1), bis(pyridazinyl)methylene compound, carbostyryl Compounds, oxazinone, benzoxazole, benzothiazole, benzimidazole and pyrrolopyrroledione. Materials for some singlet illuminants can be found in the following patent documents: US 20070252517 A1, US 4769292, US 6020078, US 2007/0252517 A1, US 2007/0252517 A1. The entire contents of the above-listed patent documents are hereby incorporated by reference.

Non-limiting examples of some suitable singlet emitters are listed in the table below:

2. Thermally activated delayed fluorescent luminescent material (TADF)

Traditional organic fluorescent materials can only use 25% singlet excitons formed by electrical excitation, and the internal quantum efficiency of the device is low (up to 25%). Although the phosphorescent material enhances the inter-system traversal due to the strong spin-orbit coupling of the center of the heavy atom, it can effectively utilize the singlet excitons and triplet exciton luminescence formed by electrical excitation, so that the internal quantum efficiency of the device reaches 100%. However, the problems of expensive phosphorescent materials, poor material stability, and severe roll-off of device efficiency limit their application in OLEDs. 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 (ΔE _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%. At the same time, 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 ΔEst < 0.3 eV, preferably ΔEst < 0.25 eV, more preferably ΔEst < 0.20 eV, and most preferably ΔEst < 0.1 eV. In a preferred embodiment, the TADF material has a relatively small ΔEst, 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. Commun., 48, 2012, 11392, Adachi, et. al. Nature Photonics, 6, 2012, 253, Adachi, et. al. , 492, 2012, 234, Adachi, et. al. J. Am. Chem. Soc, 134, 2012, 14706, Adachi, et. al. Angew. Chem. Int. Ed, 51, 2012, 11311, Adachi, et .al.Chem.Commun.,48,2012,9580,Adachi,et.al.Chem.Commun.,48,2013,10385,Adachi,et.al.Adv.Mater.,25,2013,3319,Adachi, et.al.Adv.Mater., 25, 2013, 3707, Adachi, et. al. Chem. Mater., 25, 2013, 3038, Adachi, et. al. Chem. Mater., 25, 2013, 3766, Adachi , et.al.J.Mater.Chem.C., 1, 2013, 4599, Adachi, et.al. J. Phys.Chem.A., 117 2013,5607, the entire contents of which patents are hereby articles or documents are incorporated herein by reference.

Some non-limiting examples of suitable TADF luminescent materials are listed in the table below:

3. Triplet illuminator (Triplet Emitter)

Triplet emitters are also known as phosphorescent emitters. In a preferred embodiment, 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. Optionally, these metal complexes are coupled to the polymer by one or more positions, most preferably to the polymer via an organic ligand.

In a preferred embodiment, 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.

Preferably, 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.

In a preferred embodiment, the metal complex that can be used as the triplet emitter can have the following form:

Wherein 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 The ligand; q1 may be 0, 1, 2 or 3, preferably 2 or 3; q2 may be 0, 1, 2 or 3, preferably 1 or 0.

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. 403, (2000), 750-753, US 20090061681 A1, US 20090061681 A1, Adachi et al. Appl. Phys. Lett. 78 (2001), 1622-1624, J. Kido et al. Appl. Phys. Lett. (1994), 2124, Kido et al. Chem. Lett. 657, 1990, US 2007/0252517 A1, Johnson et al., JACS 105, 1983, 1795, Wrighton, JACS 96, 1974, 998, Ma et al., Synth.Metals 94,1998,245, US 6824895, US 7029766, US 6835469, US 6830828, US 20010053462 A1, WO 2007095118 A1, US 2012004407A1, WO 2012007088A1, WO2 012007087A1, WO 2012007086A1, US 2008027220A1, WO 2011157339A1, CN 102282150A, WO 2009118087A1, WO 2013107487A1, WO 2013094620A1, WO 2013174471A1, WO 2014031977A1, WO 2014112450A1, WO 2014007565A1, WO 2014038456A1, WO 2014024131A1, WO 2014008982A1, WO2014023377A1. The entire contents of the aforementioned patent documents and documents are hereby incorporated herein by reference.

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.

In certain embodiments, 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.

In a preferred embodiment, 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.

In another preferred embodiment, 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. In general, 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 range of 10 wt%, most preferably in the range of 1% to 5 wt%. In some embodiments, the ink according to the present invention, 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 Benzene, dibutylbenzene, p-diisopropylbenzene, 1-methoxynaphthalene, cyclohexylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene 1,2,4-trichlorobenzene, 1,3-dipropoxybenzene, 4,4-difluorodiphenylmethane, 1,2-dimethoxy-4-(1-propenyl)benzene, Diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α,α-dichlorodiphenylmethane, 4-(3-phenylpropyl Pyridine, benzyl benzoate, 1,1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, dibenzyl ether, etc.; ketone-based solvent: 1-tetralone 2-tetrahydrogen Ketone, 2-(phenyl epoxy) tetralone, 6-(methoxy)tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylbenzene Ethyl ketone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, isophorone, 2,6,8 -trimethyl-4-indolone, anthrone, 2-nonanone, 3-fluorenone, 5-fluorenone, 2-nonanone, 2,5-hexanedione, phorone, di-n-pentanone Aromatic ether solvent: 3-phenoxytoluene, butoxybenzene, benzylbutylbenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4-(1-propenyl)benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-dimethoxytoluene, 4-ethylamine Ethyl ether, 1,2,4-trimethoxybenzene, 4-(1-propenyl)-1,2-dimethoxybenzene, 1,3-dimethoxybenzene, glycidyl phenyl ether, two Benzyl ether, 4-tert-butyl anisole, trans-p-propenyl anisole, 1,2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether, pentyl ether c-hexyl ether, dioctyl ether, B 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 , tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether; ester solvent: alkyl octanoate, alkyl sebacate, alkyl stearate, alkyl benzoate, alkyl phenyl acetate, alkyl cinnamate, oxalic acid An alkyl ester, an alkyl maleate, an alkanolide, an alkyl oleate or the like.

Further, according to the ink of the present invention, 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.

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

In a preferred embodiment, the composition according to the invention is a solution.

In another preferred embodiment, the composition according to the invention is a suspension.

The 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.

Among them, 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. For information on printing techniques and their requirements for solutions, such as solvents and concentrations, viscosity, etc., please refer to Helmut Kipphan's "Printing Media Handbook: Techniques and Production Methods" (Handbook of Print Media: Technologies and Production Methods). ), ISBN 3-540-67326-1.

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. In an embodiment of the invention, the organic compound is preferably used in the luminescent layer of an OLED device.

Yet another aspect of the invention further relates to an organic electronic device comprising at least one organic mixture as described above. Generally, 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.

In certain particularly preferred embodiments, 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. In a preferred embodiment, 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. Non-limiting examples of 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. In one embodiment, 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. Examples of the anode material include, but are not limited to, Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices in accordance with the present invention.

The cathode 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. In one embodiment, 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) 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. In principle, all materials which can be used as cathodes for OLEDs are possible as cathode materials for the devices of the invention. Examples of the cathode material include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, 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). Materials suitable for use in these functional layers are described in detail above and in WO2010135519A1, US20090134784A1, and WO2011110277A1, the entire disclosure of each of which is incorporated herein by reference.

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.

The present invention will be described with reference to the preferred embodiments thereof, but the present invention is not limited to the embodiments described below. It is to be understood that the scope of the invention is intended to be It is to be understood that the modifications of the various embodiments of the invention are intended to be

Example

1. Synthesis of small molecular organic materials

The methods for synthesizing the above materials H1-1, H1-2, H2-1, and H2-1 are all prior art, and the details of the prior art are not described herein. For example, the H1-1 synthesis method can be found in WO2015156449A1, and the H2-1 synthesis method can be found in WO2015023034A1.

2. Organic material energy level structure

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. First, 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. Calculated "TD-SCF/DFT/Default Spin/B3PW91" and the base group "6-31G(d)" (Charge 0/Spin Singlet).

For non-conjugated polymers as shown in Chemical Formulas 1, 1b, 2 and 2b, 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

LUMO(eV)=((LUMO(G)×27.212)-2.0041)/1.385

Among them, HOMO(G) and LUMO(G) are direct calculation results of Gaussian 09W, and the unit is eV. The results are shown in Table 1, where ΔHOMO=HOMO-(HOMO-1):

Table 1

Table 2

3. Synthesis of polymers

3.1 Synthesis of P1 and P2

The synthetic steps of P1 are as follows:

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.

Polymer P1 synthetic route

The synthetic steps of P2 are as follows:

The bipoxazole and 3,4'-dibromomethylbiphenyl are polymerized by a Hartwig reaction to obtain a polymer P2.

Polymer P2 synthetic route

3.2 Synthesis of P1-1, P1-2, P2-1, P2-2

For the synthesis of the polymer, 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.

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:

table 3

聚合物polymer	对应单体Corresponding monomer
P1-1P1-1	H1-1H1-1
P1-2P1-2	H1-2H1-2
P2-1P2-1	H2-1H2-1
P2-2P2-2	H2-2H2-2

4. Energy level structure of the polymer

The calculation method of polymer energy level structure is the same as the calculation method of small molecule energy level structure.

Table 4

5. Mixing of organic mixtures

For the monomers and polymers synthesized in the above examples, the mixing manner of the organic mixture in the examples of the present invention is as follows:

table 5

混合物mixture	包括组分Including components	X(质量比)X (mass ratio)
混合物1Mixture 1	P1-1，H2-2P1-1, H2-2	11
混合物2Mixture 2	P1-2，H2-1P1-2, H2-1	11
混合物3Mixture 3	P1-1，P2-2P1-1, P2-2	11
混合物4Mixture 4	P1-2，P2-1P1-2, P2-1	11
混合物5Mixture 5	P2-1，H1-2P2-1, H1-2	11
混合物6Mixture 6	P2-2，H2-1P2-2, H2-1	11
混合物7Mixture 7	P1，P2P1, P2	11

6. Mixing of another mixture

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:

Table 6

Among them, Compound A, Compound B, and Compound C are as follows:

7. Preparation and measurement of OLED devices

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:

a, ITO (indium tin oxide) 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;

B, 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 ;

c, 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. Or PVK (Sigma Aldrich), solution solubility 5mg / ml, and then treated on a hot plate at 180 ° C for 60 minutes;

Among them, TFB (H.W.SandsCorp.) is a hole transporting material for HTL, and its structural formula is as follows:

d, 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;

Table 7

OLED器件OLED device	HTLHTL	EML组成及厚度EML composition and thickness
OLED1OLED1	PVKPVK	混合物1：(15％)化合物D(80nm)Mixture 1: (15%) Compound D (80 nm)

OLED2OLED2	PVKPVK	混合物2：(15％)化合物D(65nm)Mixture 2: (15%) Compound D (65 nm)
OLED3OLED3	TFBTFB	混合物3：(15％)化合物D(80nm)Mixture 3: (15%) Compound D (80 nm)
OLED4OLED4	TFBTFB	混合物4：(15％)化合物D(80nm)Mixture 4: (15%) Compound D (80 nm)
OLED5OLED5	TFBTFB	混合物5：(15％)化合物D(80nm)Mixture 5: (15%) Compound D (80 nm)
OLED6OLED6	PVKPVK	混合物6：(15％)化合物D(65nm)Mixture 6: (15%) Compound D (65 nm)
OLED7OLED7	PVKPVK	混合物7：(15％)化合物D(65nm)Mixture 7: (15%) Compound D (65 nm)
OLED8OLED8	PVKPVK	混合物A：(15％)化合物D(65nm)Mixture A: (15%) Compound D (65 nm)
OLED9OLED9	TFBTFB	混合物B：(15％)化合物D(80nm)Mixture B: (15%) Compound D (80 nm)
OLED10OLED10	TFBTFB	混合物C：(15％)化合物D(80nm)Mixture C: (15%) Compound D (80 nm)

e, cathode: Ba / Al (2nm / 100nm) in a high vacuum (1 × 10 ^-6 mbar) in the thermal evaporation;

f. Package: 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.

Table 8

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

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

Claims

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 according to claim 1, 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 a repeating unit as shown in Chemical Formula 1 or Chemical Formula 1b, and P2 comprises a repeating unit as shown in Chemical Formula 2 or Chemical Formula 2b:

Wherein: n, n1, m and m1 represent the number of repeating units, n, n1, m and m1 are natural numbers greater than or equal to 1, and SP is a non-conjugated spacer group;

And, min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1)) ≤ min(E T (H1), E T (H2))+0.1eV, where HOMO(H1), LUMO(H1) and E T (H1) respectively represent the highest occupied orbit, the lowest unoccupied orbit, and the triplet level, HOMO(H2), LUMO(H2), and E T (H2) of H1, respectively, indicating the highest occupied orbit of H2. , the lowest unoccupied orbit and the triplet level.
The organic mixture according to claim 2, wherein at least one of H1 and H2 satisfies the following formula: (HOMO-(HOMO-1)) ≥ 0.3 eV.
The organic mixture according to claim 2, wherein X is selected in the range of 0.1 to 10, wherein X is the mass ratio of P1/H2, P1/P2, and P2/H1 in the organic mixture.
The organic mixture according to any one of claims 2 to 4, wherein at least one of H1 and H2 comprises an electron-donating group D, and at least one of H1 and H2 comprises an electron-withdrawing group A.
The organic mixture according to claim 5, wherein at least one of H1 and H2 has a structure represented by the following structural formula (I) or (II):

Wherein, Ar is a substituted or unsubstituted aromatic or heteroaromatic structural unit, and D may be independently selected from the same or different electron-donating groups when present multiple times, and p is an integer between 1 and 6, q Equal to 0 or 1; A may be independently selected from the same or different electron withdrawing groups when present multiple times, r is an integer between 1 and 6, and s is equal to 0 or 1.
The organic mixture according to claim 6, wherein said electron donating group D is selected from the group consisting of:

among them,

Y represents an aromatic group having 6 to 40 carbon atoms or an aromatic hetero group having 3 to 40 carbon atoms;

Z 1 , Z 2 , and Z 3 are each independently selected from a single bond, N(R), C(R) 2 , Si(R) 2 , O, S, C=N(R), C=C(R) 2 Or P(R), Z 2 and Z 3 are not single bonds at the same time;

Wherein R, R 1 and R 2 are each independently selected from the group consisting of alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, heteroalkyl, aryl and heteroaryl.
The organic mixture according to claim 6, wherein the electron-donating group D is selected from structural units containing a group whose ring H can be further optionally substituted:
The organic mixture according to claim 6, wherein the electron-withdrawing group A is selected from F, a cyano group or a structural unit selected from the group consisting of: H on the ring may be further optionally substituted:

Wherein m2 is 1, 2 or 3; X 1 -X 8 is selected from CR or N, and at least one is N; M 1 , M 2 and M 3 independently represent N(R), C(R) 2 , Si (R) 2 , O, C=N(R), C=C(R) 2 , P(R), P(=O)R, S, S=O, SO 2 or none; wherein R, R 1 And R 2 each independently represents an alkyl group, an alkoxy group, an amino group, an alkenyl group, an alkynyl group, an aralkyl group, a heteroalkyl group, an aryl group, and a heteroaryl group.
The organic mixture according to claim 6, wherein Ar is selected from structural units including a group, and H on the ring may be further optionally substituted:

Wherein n2 is 1 or 2 or 3 or 4.
The organic mixture of claim 2 wherein said SP is selected from the group consisting of:

Wherein Ar-1 represents an aromatic or heteroaromatic group having 5 to 60 ring atoms.
The organic mixture of claim 2 wherein said SP is selected from the group consisting of:

Wherein R-1, R-2, R-3 and R-4 are independently selected from -C, an alkylene group, a cycloalkylene group, an alkylsilylene group, a silylene group, an aryl group Oxidation of silyl, alkylalkoxyalkylene, arylalkoxyalkylene, alkylthioalkylene, phosphine, phosphine oxide, sulfone, alkylene sulfone, sulfone oxide or alkylene sulfone Things.
The organic mixture according to any one of claims 1 to 12, further comprising a luminescent material selected from the group consisting of a singlet illuminant, a triplet illuminant or a TADF illuminant.
A composition comprising an organic mixture according to any one of claims 1 to 13, and at least one organic solvent.
An organic electronic device characterized by comprising at least one organic mixture according to any one of claims 1-13.
The organic electronic device according to claim 15, wherein the electroluminescent device comprises at least a light-emitting layer, the light-emitting layer comprising an organic mixture according to any one of claims 1-13.