Organic Mixtures and Their Applications in Organic Electronic Devices

Abstract

A mixture and its application in organic electronic devices, particularly in organic light-emitting diodes. An organic electronic device comprising the mixture, particularly an organic light-emitting diode, and its application in display and lighting technologies. Through device structure optimization, better device performance can be achieved, particularly high-performance OLED devices can be realized, providing better material and fabrication technology options for full-color display and lighting applications.

Description

Technical Field

[0001] The present invention relates to the technical field of organic electroluminescence, and particularly to a mixture and its application in the field of organic electronics, especially in the field of electroluminescence. Background Art

[0002] Due to the diversity in synthesis, relatively low manufacturing cost, and excellent optical and electrical properties of organic semiconductor materials, organic light-emitting diodes (OLEDs) have great potential in the application of optoelectronic devices (such as flat panel displays and lighting).

[0003] Organic electroluminescence refers to the phenomenon of converting electrical energy into light energy using organic substances. An organic electroluminescent element utilizing the organic electroluminescence phenomenon usually has a structure including a positive electrode and a negative electrode with an organic layer therebetween. To improve the efficiency and lifespan of the organic electroluminescent element, the organic layer has a multi-layer structure, and each layer contains different organic substances. Specifically, it may include a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, etc. In such an organic electroluminescent element, when a voltage is applied between the two electrodes, holes are injected into the organic layer from the positive electrode, and electrons are injected into the organic layer from the negative electrode. When the injected holes and electrons meet, excitons are formed, and light is emitted when the excitons transition back to the ground state. Such an organic electroluminescent element has characteristics such as self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast ratio, and high responsiveness.

[0004] To improve the luminous efficiency of organic electroluminescent elements, various luminescent material systems based on fluorescence and phosphorescence have been developed. For both fluorescent materials and phosphorescent materials, the development of excellent blue light materials is a huge challenge. Generally speaking, currently used organic light-emitting diodes with blue fluorescent materials have higher reliability. Nevertheless, restricted by quantum statistics, the internal quantum efficiency of most current blue fluorescent materials is at most 25%, resulting in low overall luminous efficiency; and the emission spectrum is too wide, and the color purity is poor, which is not conducive to high-end displays. The synthesis of such fluorescent materials is also relatively complex, which is not conducive to large-scale production. At the same time, the stability of OLEDs with such blue fluorescent materials still needs to be further improved. Therefore, developing high-efficiency and stable blue fluorescent materials is an urgent problem in the industry.

[0005] In the prior art, the light-emitting layer of a blue organic electroluminescent device adopts a host-guest doping structure. As the existing blue host material, it is a polycyclic derivative based on anthracene, as described in patents such as CN1914293B, CN102448945B, US2015287928A1, etc. However, these compounds have problems of insufficient luminous efficiency and brightness, and poor device lifetime. As the existing blue-light-emitting guest compound, an arylvinylamine compound can be used (WO 04 / 013073, WO 04 / 016575, WO 04 / 018587). However, these compounds have poor thermal stability and are prone to decomposition, resulting in poor device lifetime, which is the main drawback of OLED materials in the current industry. In order to achieve high efficiency and long lifetime of blue-light devices, patents such as WO2017010489A1 disclose a blue host material with steric hindrance limitation, which can obtain better luminous efficiency and device lifetime.

[0006] In order to further improve the efficiency and lifetime of blue-light devices, materials still need to be further improved. For blue OLEDs, the host material is the key material determining its lifetime. High-performance blue host materials have always been the focus of people's development. Summary of the Invention

[0007] Based on this, the purpose of the present invention is to provide a mixture and its application in electronic devices.

[0008] The specific technical solution is as follows:

[0009] The present invention provides a mixture, comprising a first organic compound H 1 and a second organic compound H 2 , characterized in that

[0010] 1) ΔE ST (H 1 ) ≥ 0.6 eV, E X -T 1 (H 1 ) ≥ 0.6 eV; and / or

[0011] 2) ΔE ST (H 2 ) ≥ 0.6 eV, E X -T 1 (H 2 ) ≥ 0.6 eV; and

[0012] 3) LUMO(H 2 ) ≤ LUMO(H 1 ) + 0.10 eV;

[0013] wherein, ΔE ST is E S1 -ET1 , E X is min(|HOMO(H 1 ) - LUMO(H 2 )|, |HOMO(H 2 ) - LUMO(H 1 )|), E S1 is the singlet energy level, E T1 is the triplet energy level, HOMO is the highest occupied molecular orbital energy level, and LUMO is the lowest unoccupied molecular orbital energy level.

[0014] The present invention also provides another mixture, comprising at least one mixture as described above and at least one other organic functional material, and the at least one other organic functional material can be selected from hole (also called electric hole) injection material (HIM), hole transport material (HTM), hole blocking material (HBM), electron injection material (EIM), electron transport material (ETM), electron blocking material (EBM), organic matrix material (Host), singlet emitter (fluorescent emitter), triplet emitter (phosphorescent emitter), thermally activated delayed fluorescence material (TADF material), and organic dye.

[0015] The present invention also provides a composition, comprising at least one mixture as described above and at least one organic solvent.

[0016] The present invention also provides an organic electronic device, comprising a mixture as described above.

[0017] Advantageous effects: For the mixture satisfying a certain energy level structure relationship according to the present invention, a transition excited state in an intermediate state can be formed between its two organic compounds (i.e., the first organic compound H 1 and the second organic compound H 2 ). The exciton energy of this transition excited state is in a high energy state relative to the T 1 excited state of the two organic compounds, and has much higher energy than T 1 , so a normal exciplex cannot be formed. However, the mixture according to the present invention is based on polycyclic compounds and has a special energy level structure, which is beneficial to the formation of an efficient transition excited state; when the energy difference between this transition excited state and the S 1 state of the two organic compounds is small enough, energy transfer from the transition excited state to the S 1 state can occur quickly; or when there is another emitter (guest), this transition excited state can quickly transfer energy to the S 1 state of the guest; the organic electroluminescent device prepared with such a mixture as the light-emitting layer material has high luminous efficiency and long device life. A possible reason is that in the described transition excited state, S 1 and T1 The ratio is higher than 1:3. Detailed implementation mode

[0018] The present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, these embodiments are provided to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0019] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field to which the present invention belongs. The terms used in the description of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0020] In the present invention, the host material, matrix material, Host material, and Matrix material have the same meaning and can be interchanged.

[0021] In the present invention, metal-organic complex, metal-organic coordination compound, and organometallic coordination compound have the same meaning and can be interchanged.

[0022] In the present invention, composition, printing ink, ink, and ink have the same meaning and can be interchanged.

[0023] The present invention provides a mixture comprising a first organic compound H 1 and a second organic compound H 2 , and

[0024] 1) ΔE ST (H 1 ) ≥ 0.6 eV, E X -T 1 (H 1 ) ≥ 0.6 eV; and / or

[0025] 2) ΔE ST (H 2 ) ≥ 0.6 eV, E X -T 1 (H 2 ) ≥ 0.6 eV; and

[0026] 3) LUMO(H 2 ) ≤ LUMO(H 1 ) + 0.10 eV;

[0027] wherein, ΔE ST is E S1 -E T1 , E X is min(|HOMO(H 1) - LUMO(H 2 )|,|HOMO(H 2 ) - LUMO(H 1 )|), E S1 is the singlet energy level, E T1 is the triplet energy level, HOMO is the highest occupied molecular orbital energy level, and LUMO is the lowest unoccupied molecular orbital energy level.

[0028] In some preferred embodiments, ΔE ST (H 1 ) ≥ 0.7 eV; in some more preferred embodiments, ΔE ST (H 1 ) ≥ 0.8 eV; in some most preferred embodiments, ΔE ST (H 1 ) ≥ 0.9 eV; in some most most preferred embodiments, ΔE ST (H 1 ) ≥ 1.0 eV.

[0029] In some other preferred embodiments, ΔE ST (H 2 ) ≥ 0.7 eV; in some other more preferred embodiments, ΔE ST (H 2 ) ≥ 0.8 eV; in some other most preferred embodiments, ΔE ST (H 2 ) ≥ 0.9 eV; in some other most most preferred embodiments, ΔE ST (H 2 ) ≥ 1.0 eV.

[0030] In some preferred embodiments, E X - T 1 (H 1 ) ≥ 0.7 eV; in some more preferred embodiments, E X - T 1 (H 1 ) ≥ 0.8 eV; in some most preferred embodiments, E X - T 1 (H 1 ) ≥ 0.9 eV; in some most most preferred embodiments, E X - T 1 (H 1 ) ≥ 1.0 eV.

[0031] In some other preferred embodiments, E X - T 1 (H 2 ) ≥ 0.7 eV; in some other more preferred embodiments, E X-T 1 (H 2 ) ≥ 0.8 eV; In some most preferred embodiments, E X -T 1 (H 2 ) ≥ 0.9 eV; In some even more preferred embodiments, E X -T 1 (H 2 ) ≥ 1.0 eV.

[0032] In some preferred embodiments, LUMO(H 2 ) ≤ LUMO(H 1 ) + 0.08 eV; In some preferred embodiments, LUMO(H 2 ) ≤ LUMO(H 1 ) + 0.06 eV; In some preferred embodiments, LUMO(H 2 ) ≤ LUMO(H 1 ) + 0.04 eV; In some preferred embodiments, LUMO(H 2 ) ≤ LUMO(H 1 ) + 0.02 eV; In some preferred embodiments, LUMO(H 2 ) ≤ LUMO(H 1 ).

[0033] A mixture according to the present invention, wherein, |E X -E S1 (H 1 )| ≤ 0.4 eV or |E X -E S1 (H 2 )| ≤ 0.4 eV.

[0034] In some preferred embodiments, |E X -S 1 (H 1 )| ≤ 0.3 eV or |E X -S 1 (H 2 )| ≤ 0.3 eV; In some more preferred embodiments, |E X -S 1 (H 1 )| ≤ 0.2 eV or |E X -S 1 (H 2 )| ≤ 0.2 eV; In some most preferred embodiments, |E X -S 1 (H 1 )| ≤ 0.1 eV or |E X -S 1 (H2 )| ≤ 0.1 eV; In some most preferred embodiments, |E X -S 1 (H 1 )| ≤ 0.05 eV or |E X -S 1 (H 2 )| ≤ 0.05 eV.

[0035] For the mixture satisfying the above energy and structural relationships according to the present invention, a transition excited state in an intermediate state can be formed between its two organic compounds (i.e., the first organic compound H 1 and the second organic compound H 2 ). The exciton energy of this transition excited state is in a high energy state relative to the T 1 excited state of the two organic compounds, and has a much higher energy than T 1 . At the same time, the energy difference between this transition excited state and the S 1 state of the two organic compounds is small enough to enable rapid energy transfer from the transition excited state to the S 1 state.

[0036] For a mixture according to the present invention, the two organic compounds H 1 and H 2 are each independently selected from substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 40 ring atoms, or aryloxy or heteroaryloxy groups having 5 to 40 ring atoms, or combinations of these systems, wherein one or more groups may form monocyclic or polycyclic aliphatic or aromatic ring systems with each other and / or with the rings to which the groups are bonded.

[0037] In some preferred embodiments, for a mixture according to the present invention, the two organic compounds H 1 and H 2 are each independently selected from substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 30 ring atoms, or aryloxy or heteroaryloxy groups having 5 to 30 ring atoms, or combinations of these systems, wherein one or more groups may form monocyclic or polycyclic aliphatic or aromatic ring systems with each other and / or with the rings to which the groups are bonded.

[0038] In some preferred embodiments, for a mixture according to the present invention, the two organic compounds H 1 and H 2 are each independently selected from substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 20 ring atoms, or aryloxy or heteroaryloxy groups having 5 to 20 ring atoms, or combinations of these systems, wherein one or more groups may form monocyclic or polycyclic aliphatic or aromatic ring systems with each other and / or with the rings to which the groups are bonded.

[0039] One or more H in the various groups described above may further be replaced by D.

[0040] In a more preferred embodiment, the aromatic ring system contains 5 to 15 carbon atoms in the ring system, more preferably 5 to 10 carbon atoms, the heteroaromatic ring system contains 2 to 15 carbon atoms in the ring system, more preferably 2 to 10 carbon atoms, and at least one heteroatom, provided that the total number of carbon atoms and heteroatoms is at least 4. The heteroatom is preferably selected from Si, N, P, O, S and / or Ge, particularly preferably selected from Si, N, P, O and / or S, and even more particularly preferably selected from N, O or S.

[0041] The aromatic ring system or aromatic group described above refers to a hydrocarbon group containing at least one aromatic ring, including monocyclic groups and polycyclic ring systems. The heteroaromatic ring system or heteroaromatic group described above refers to a hydrocarbon group (containing heteroatoms) containing at least one heteroaromatic ring, including monocyclic groups and polycyclic ring systems. These polycyclic rings can have two or more rings, where two carbon atoms are shared by two adjacent rings, i.e., fused rings. Among these polycyclic rings, at least one is aromatic or heteroaromatic. For the purposes of the present invention, the aromatic or heteroaromatic ring system includes not only systems of aromatic or heteroaromatic groups, but also, where multiple aromatic or heteroaromatic groups can also be interrupted by short non-aromatic units (<10% non-H atoms, preferably less than 5% 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 aromatic ring systems for the purposes of this invention.

[0042] Specifically, examples of aromatic groups are: benzene, naphthalene, anthracene, phenanthrene, coronene, tetracene, pyrene, benzopyrene, triphenylene, acenaphthene, fluorene, spirofluorene and their derivatives.

[0043] Specifically, examples of heteroaromatic groups are: furan, benzofuran, dibenzofuran, thiophene, benzothiophene, dibenzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thiophenopyrrole, thiophenothiophene, furanopyrrole, furanofuran, thiophenofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, phthalazine, quinoxaline, phenanthridine, perimidine, quinazoline, quinazolinone, and their derivatives.

[0044] According to a mixture of the present invention, the second organic compound H 2 contains an electron-withdrawing group.

[0045] In some preferred embodiments, the second organic compound H 2 contains two electron-withdrawing groups.

[0046] In some preferred embodiments, the second organic compound H 2 contains three electron-withdrawing groups.

[0047] In some other preferred embodiments, the second organic compound H 2 contains more than three electron-withdrawing groups.

[0048] The above-mentioned electron-withdrawing groups can be selected from one of F, cyano group or the following groups:

[0049]

[0050] wherein, n is 1, 2 or 3; X 1 -X 8 is selected from CR or N, and at least one of them is N; M 1 、M 2 、M 3 respectively and 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; R 4 、R 5 are selected from the following structures: H, or D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, or a substituted or unsubstituted silyl group, or a substituted keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, cyano group (-CN), carbamoyl group (-C(=O)NH 2 ), halocarbonyl group (-C(=O)-X where X represents a halogen atom), formyl group (-C(=O)-H), isocyano group, isocyanate, thiocyanate or isothiocyanate, hydroxyl group, nitro group, CF 3 , Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems, wherein one or more of the said groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which they are bonded. R, being the same or different, respectively and independently represent a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group or aromatic heterocyclic group having 5 to 60 ring atoms.

[0051] In some preferred embodiments, the second organic compound H 2 contains -F.

[0052] In some preferred embodiments, the second organic compound H 2 contains -CN.

[0053] A mixture according to the present invention, the first organic compound H 1 or the second organic compound H 2 is selected from the following structures:

[0054]

[0055] wherein R 11 -R 28 is H, or D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, or a substituted or unsubstituted silyl group, or a substituted keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, cyano (-CN), carbamoyl (-C(=O)NH 2 ), halocarbonyl (-C(=O)-X where X represents a halogen atom), formyl (-C(=O)-H), isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxyl, nitro, CF 3 , Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems, wherein one or more of said groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which they are bonded.

[0056] In some preferred embodiments, R 11 -R 28 is H, or D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 10 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 10 C atoms, or a substituted or unsubstituted silyl group, or a substituted keto group having 1 to 10 C atoms, or an alkoxycarbonyl group having 2 to 10 C atoms, or an aryloxycarbonyl group having 7 to 10 C atoms, cyano (-CN), carbamoyl (-C(=O)NH 2 ), halocarbonyl (-C(=O)-X where X represents a halogen atom), formyl (-C(=O)-H), isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxyl, nitro, CF 3, Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 20 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 20 ring atoms, or a combination of these systems, wherein one or more of said groups may form, together with each other and / or with the ring to which they are bonded, a monocyclic or polycyclic aliphatic or aromatic ring system.

[0057] A mixture according to the invention, R 11 -R 28 Identical or different and selected from one or more combinations of the structures shown in Table 1 below:

[0058] Table 1

[0059]

[0060] Wherein Y is CR 701 or N; A is selected from O, S, CR 702 R 703 , NR 704 ; R 701 -R 704 , which are identical or different when occurring multiple times, may be a site for connection to other groups, or H, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, or a substituted or unsubstituted silyl group, or a substituted keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, cyano (-CN), carbamoyl (-C(=O)NH 2 ), halocarbonyl (-C(=O)-X where X represents a halogen atom), formyl (-C(=O)-H), isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxyl, nitro, CF 3 , Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems, wherein one or more of said groups may form, together with each other and / or with the ring to which they are bonded, a monocyclic or polycyclic aliphatic or aromatic ring system.

[0061] In some preferred embodiments, all Y are CR 701 ;

[0062] In some other preferred embodiments, at least one Y in each structure is N;

[0063] In some other more preferred embodiments, at least two Y in each structure are N;

[0064] In still other more preferred embodiments, at least three Ys in each structure are N;

[0065] More preferably, R 701 -R 704 , when occurring multiple times, may be the same or different, and may be a single bond connecting to other groups, or H, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 10 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 10 C atoms, or a substituted or unsubstituted silyl group, or a substituted keto group having 1 to 10 C atoms, or an alkoxycarbonyl group having 2 to 10 C atoms, or an aryloxycarbonyl group having 7 to 10 C atoms, cyano (-CN), carbamoyl (-C(=O)NH 2 ), halocarbonyl (-C(=O)-X where X represents a halogen atom), formyl (-C(=O)-H), isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxyl, nitro, CF 3 , Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 20 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 20 ring atoms, or a combination of these systems, where one or more of the said groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which they are bonded. One or more Hs in the above various said groups may further be replaced by D.

[0066] A mixture according to the present invention, H 1 or H 2 is selected from the following structures:

[0067]

[0068] wherein, R 11 -R 20 is H, or D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, or a substituted or unsubstituted silyl group, or a substituted keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, cyano (-CN), carbamoyl (-C(=O)NH 2 ), halocarbonyl (-C(=O)-X where X represents a halogen atom), formyl (-C(=O)-H), isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxyl, nitro, CF 3, Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems, wherein one or more of said groups may form, with each other and / or with the ring to which they are bonded, a monocyclic or polycyclic aliphatic or aromatic ring system.

[0069] Preferably, R 11 -R 20 is H, or D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 10 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 10 C atoms, or a substituted or unsubstituted silyl group, or a substituted keto group having 1 to 10 C atoms, or an alkoxycarbonyl group having 2 to 10 C atoms, or an aryloxycarbonyl group having 7 to 10 C atoms, cyano (-CN), carbamoyl (-C(=O)NH 2 ), halocarbonyl (-C(=O)-X where X represents a halogen atom), formyl (-C(=O)-H), isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxy, nitro, CF 3 , Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 20 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 20 ring atoms, or a combination of these systems, wherein one or more of said groups may form, with each other and / or with the ring to which they are bonded, a monocyclic or polycyclic aliphatic or aromatic ring system.

[0070] In a particularly preferred embodiment, R 11 , R 12 , R 14 , R 15 , R 16 , R 17 , R 19 , R 20 is selected from H, or D; R 13 , R 18 is selected from one or more combinations of the structures shown in Table 1.

[0071] A mixture according to the invention, H 1 or H 2 is selected from the following structures:

[0072]

[0073] wherein, R 21 -R 28is H, or D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, or a substituted or unsubstituted silyl group, or a substituted keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, cyano (-CN), carbamoyl (-C(=O)NH 2 ), halocarbonyl (-C(=O)-X where X represents a halogen atom), formyl (-C(=O)-H), isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxyl, nitro, CF 3 , Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems, where one or more of said groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which they are bonded.

[0074] Preferably, R 21 -R 28 is H, or D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 10 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 10 C atoms, or a substituted or unsubstituted silyl group, or a substituted keto group having 1 to 10 C atoms, or an alkoxycarbonyl group having 2 to 10 C atoms, or an aryloxycarbonyl group having 7 to 10 C atoms, cyano (-CN), carbamoyl (-C(=O)NH 2 ), halocarbonyl (-C(=O)-X where X represents a halogen atom), formyl (-C(=O)-H), isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxyl, nitro, CF 3 , Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 20 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 20 ring atoms, or a combination of these systems, where one or more of said groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which they are bonded.

[0075] In a particularly preferred embodiment, R 21 , R 24 , R 25 , R 28 are selected from H, or D; R 22 , R 23 , R 26 , R 27 are selected from H, D or a combination of one or more of the structures shown in Table 1.

[0076] In some preferred embodiments, the R 11 -R 20 and R 21 -R 28 are the same or different and each independently selected from one of the structures shown below:

[0077]

[0078] In certain preferred embodiments, the mixture, wherein H 1 and H 2 form a type I heterojunction structure.

[0079] In a preferred embodiment, the mixture, wherein H 1 and H 2 have a molar ratio ranging from 2:8 to 8:2; a preferred molar ratio is from 3:7 to 7:3; a more preferred molar ratio is from 4:6 to 6:4.

[0080] In certain preferred embodiments, the mixture, wherein H 1 and / or H 2 has a relatively large resonance factor (f(S 1 ), f(S 2 ), f(S 3 )); preferably, at least one is greater than 0.05, more preferably at least one is greater than 0.10, and most preferably at least one is greater than 0.15. The resonance factor can be obtained through quantum chemical simulations, as described in the following examples.

[0081] In a more preferred embodiment, the mixture, wherein H 1 and / or H 2 has a resonance factor (f(S 1 )) greater than or equal to 0.05, preferably greater than or equal to 0.10, more preferably greater than or equal to 0.15, and most preferably greater than or equal to 0.18.

[0082] In a preferred embodiment, in the mixture according to the present invention, for H 1 and H 2 , at least one has a glass transition temperature T g ≥100 °C; in a preferred embodiment, at least one has a T g ≥120 °C; in a more preferred embodiment, at least one has a T g ≥140 °C; in a still more preferred embodiment, at least one has a T g ≥160 °C; in a most preferred embodiment, at least one has a T g ≥180 °C.

[0083] In a more preferred embodiment, for the mixture according to the present invention, H 1 and H 2 , at least one of them is partially deuterated. Preferably, 10% of H is deuterated, more preferably 20% of H is deuterated, very preferably 30% of H is deuterated, and most preferably 40% of H is deuterated.

[0084] In a preferred embodiment, for the mixture according to the present invention, H 1 and H 2 are both small molecule materials.

[0085] An object of the present invention is to provide a material solution for evaporation-type OLEDs.

[0086] In a preferred embodiment, the mixture material according to the present invention is used for evaporation-type OLED devices. For this purpose, in the mixture according to the present invention, H 1 and H 2 have a molecular weight ≤ 1000 g / mol, preferably ≤ 900 g / mol, very preferably ≤ 850 g / mol, more preferably ≤ 800 g / mol, and most preferably ≤ 700 g / mol.

[0087] In a preferred embodiment, for the mixture, the difference in molecular weight between H 1 and H 2 does not exceed 100 Dalton; preferably does not exceed 60 Dalton; more preferably does not exceed 30 Dalton.

[0088] In another preferred embodiment, for the mixture, the difference in sublimation temperature between H 1 and H 2 does not exceed 30 K; preferably does not exceed 20 K; more preferably the difference does not exceed 10 K.

[0089] Another object of the present invention is to provide a material solution for printed OLEDs.

[0090] For this purpose, in the mixture according to the present invention, H 1 and H 2, , at least one, preferably both, have a molecular weight ≥ 700 g / mol, preferably ≥ 800 g / mol, very preferably ≥ 900 g / mol, more preferably ≥ 1000 g / mol, and most preferably ≥ 1100 g / mol.

[0091] In the co-host in the form of Premix in vapor deposition type OLEDs, it is required that the two host materials have similar chemical properties or physical properties, such as molecular weight, sublimation temperature; in solution-processed OLEDs, two host materials with different properties may improve the film-forming performance, thereby improving the device performance. The properties mentioned above, in addition to molecular weight and sublimation temperature, can also be others, such as glass transition temperature, different molecular volumes, etc. For these purposes, the preferred embodiments of the mixture according to the present invention are also as follows:

[0092] 1) The difference in molecular weight between H 1 and H 2 is ≥120 g / mol, preferably ≥140 g / mol, more preferably ≥160 g / mol, and most preferably ≥180 g / mol.

[0093] 2) The difference in sublimation temperature between H 1 and H 2 is ≤80 K, preferably ≤75 K, more preferably ≤70 K, and most preferably ≤60 K.

[0094] 3) The difference in glass transition temperature between H 1 and H 2 is ≤45 K, preferably ≤40 K, more preferably ≤30 K, and most preferably ≤35 K.

[0095] 4) The difference in molecular volume between H 1 and H 2 is ≥20%, preferably ≥30%, more preferably ≥40%, and most preferably ≥45%.

[0096] In some other embodiments, in the mixture according to the present invention, H 1 and H 2 , at least one, preferably both, have a solubility in toluene of ≥2 mg / ml at 25°C, preferably ≥3 mg / ml, more preferably ≥4 mg / ml, and most preferably ≥5 mg / ml.

[0097] The term "small molecule" as defined herein refers to a molecule that is not a polymer, oligomer, dendrimer, or blend. In particular, there is no repeating structure in the small molecule. The molecular weight of the small molecule is ≤3000 g / mol, preferably ≤2000 g / mol, and most preferably ≤1500 g / mol.

[0098] Polymers, namely polymers, include homopolymers, copolymers, and block copolymers. Additionally, in the present invention, polymers also include dendrimers. For the synthesis and applications of dendrimers, please refer to [Dendrimers and Dendrons, Wiley-VCH Verlag GmbH&Co.KGaA, 2002, Ed. George R. Newkome, Charles N. Moorefield, Fritz Vogtle.].

[0099] Conjugated polymers are polymers whose backbone is mainly composed of sp2 hybrid orbitals of carbon atoms. Well-known examples include polyacetylene and poly(phenylenevinylene). The carbon atoms on the backbone can also be replaced by other non-carbon atoms, and when the sp2 hybridization on the backbone is interrupted by some natural defects, it is still considered a conjugated polymer. Additionally, in the present invention, conjugated polymers also include those containing arylamine, aryl phosphine, other heteroaromatics, organometallic complexes, etc. on the backbone.

[0100] According to the mixture of the present invention, specific examples of H 1 are as follows, but are not limited thereto:

[0101]

[0102]

[0103]

[0104] According to a mixture of the present invention, specific examples of H 2 are as follows, but are not limited thereto:

[0105]

[0106]

[0107]

[0108]

[0109] The present invention also provides a mixture, comprising at least one of the mixtures described above and at least one other organic functional material, where the at least one other organic functional material can be selected from hole (also known as electric hole) injection material (HIM), hole transport material (HTM), hole blocking material (HBM), electron injection material (EIM), electron transport material (ETM), electron blocking material (EBM), organic matrix material (Host), singlet emitter (fluorescent emitter), triplet emitter (phosphorescent emitter), thermally activated delayed fluorescence material (TADF material), and organic dye. For example, various organic functional materials are described in detail in WO2010135519A1, US20090134784A1, and WO 2011110277A1. The entire contents of these three patent documents are hereby incorporated herein by reference.

[0110] In a more preferred embodiment, the E of the mixture X (i.e., min(|HOMO(H 1 ) - LUMO(H 2 )|, |HOMO(H 2 ) - LUMO(H 1 )|)) is greater than or equal to the S of the other organic functional material 1 . A possible advantage of this is that the transition excited state of the mixture can quickly transfer energy to the S state of the other organic functional material; the possible mechanism of energy transfer can be Foester transfer or Dexter transfer. 1

[0111] In a most preferred embodiment, the mixture comprises an organic mixture according to the present invention and a fluorescent guest material. Here, the organic compound according to the present invention can be used as the host, and the weight percentage of the guest is ≤15 wt%, preferably ≤10 wt%, more preferably ≤8 wt%, even more preferably ≤7 wt%, and most preferably ≤5 wt%.

[0112] In certain embodiments, the mixture comprises an organic mixture according to the present invention and a TADF material.

[0113] Some more detailed descriptions (but not limited to this) of the singlet emitter and the TADF material are given below.

[0114] 1. Singlet Emitter

[0115] Singlet emitters often have a long conjugated π - electron system. So far, there have been many examples, such as styrylamines and their derivatives disclosed in JP2913116B and WO2001021729A1, and indeno[1,2 - b]fluorene and its derivatives disclosed in WO2008 / 006449 and WO2007 / 140847.

[0116] In a preferred embodiment, the singlet emitter may be selected from monostyrylamine, distyrylamine, tristyrylamine, tetrastearylamine, styrylphosphine, styrylether and arylamine.

[0117] A monostyrylamine refers to a compound that contains an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine. A distyrylamine refers to a compound that contains two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A tristyrylamine refers to a compound that contains three unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A tetrastearylamine refers to a compound that contains 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 definitions of the corresponding phosphines and ethers are similar to those of amines. An arylamine or aromatic amine refers to a compound that contains three unsubstituted or substituted aromatic or heterocyclic ring systems directly linked to nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably selected from fused ring systems and preferably has at least 14 aromatic ring atoms. Preferred examples thereof include aromatic anthrylamine, aromatic anthryldiamine, aromatic pyrenamine, aromatic pyrenediamine, aromatic chrysenamine and aromatic chrysenediamine. An aromatic anthrylamine refers to a compound in which a diarylamine group is directly linked to anthracene, preferably at the 9 - position. An aromatic anthryldiamine refers to a compound in which two diarylamine groups are directly linked to anthracene, preferably at the 9,10 - positions. The definitions of aromatic pyrenamine, aromatic pyrenediamine, aromatic chrysenamine and aromatic chrysenediamine are similar, where the diarylamine group is preferably linked to the 1 - or 1,6 - positions of pyrene.

[0118] Examples of singlet emitters based on ethylenediamine and aromatic amines, which are also preferred examples, can be found in the following patent documents: WO 2006 / 000388, WO 2006 / 058737, WO 2006 / 000389, WO 2007 / 065549, WO 2007 / 115610, US 7250532 B2, DE 102005058557 A1, CN 1583691 A, JP 08053397 A, US 6251531B1, US 2006 / 210830 A, EP 1957606 A1 and US 2008 / 0113101 A1. The entire contents of the above-listed patent documents are hereby incorporated herein by reference.

[0119] An example of a singlet emitter based on stilbene and its derivatives is US 5121029.

[0120] Further preferred singlet emitters can be selected from indeno[1,2-b]fluorene-amine and indeno[1,2-b]fluorene-diamine, as disclosed in WO 2006 / 122630, benzo[def]indeno[1,2-b]fluorene-amine and benzo[def]indeno[1,2-b]fluorene-diamine, as disclosed in WO 2008 / 006449, dibenzo[def]indeno[1,2-b]fluorene-amine and dibenzo[def]indeno[1,2-b]fluorene-diamine, as disclosed in WO2007 / 140847.

[0121] Other materials that can be used as singlet emitters include polycyclic aromatic hydrocarbon compounds, especially derivatives of the following compounds: anthracene such as 9,10-bis(2-naphthylanthracene), naphthalene, tetraphene, xanthene, phenanthrene, pyrene (such as 2,5,8,11-tetra-t-butylperylene), indeno[1,2,3-cd]pyrene, phenylene such as (4,4'-bis(9-ethyl-3-carbazolylvinyl)-1,1'-biphenyl), diindeno[1,2,3-cd:1',2',3'-lm]pyrene, coronene, hexabenzocoronene, fluorene, spirobifluorene, arylpyrene (such as US20060222886), arylideneethylene (such as US5121029, US5130603), cyclopentadiene such as tetraphenylcyclopentadiene, rubrene, coumarin, rhodamine, quinacridone, pyran such as 4-(dicyanomethylene)-6-(4-dimethylaminostyryl-2-methyl)-4H-pyran (DCM), thiopyran, bis(azinyl)imine boron compounds (US 2007 / 0092753A1), bis(azinyl)methylene compounds, carbostyryl compounds, oxazinone, benzoxazole, benzothiazole, benzimidazole and pyrrolopyrrole dione. Examples of some singlet emitter materials can be found in the following patent documents: US20070252517 A1, US 4769292, US 6020078. The entire contents of the above-listed patent documents are hereby incorporated herein by reference.

[0122] Examples of some suitable singlet emitters are listed in the following table:

[0123]

[0124] 2. Thermally Activated Delayed Fluorescence (TADF) Materials

[0125] Traditional organic fluorescent materials can only utilize 25% of the singlet excitons formed by electrical excitation for luminescence, resulting in a relatively low internal quantum efficiency of the device (up to 25%). Although phosphorescent materials can effectively utilize both singlet and triplet excitons formed by electrical excitation for luminescence, with an internal quantum efficiency of the device reaching 100%, due to the strong spin-orbit coupling of the heavy atom center enhancing intersystem crossing. However, problems such as the high cost of phosphorescent materials, poor material stability, and severe device efficiency roll-off limit their application in OLEDs. Thermally activated delayed fluorescence materials are the third generation of organic light-emitting materials developed after organic fluorescent materials and organic phosphorescent materials. Such materials generally have a small singlet-triplet energy level difference (ΔEst), and triplet excitons can be converted into singlet excitons for luminescence through reverse intersystem crossing. This can make full use of both singlet and triplet excitons formed under electrical excitation. The internal quantum efficiency of the device can reach 100%. At the same time, the material structure is controllable, the properties are stable, the price is low without the need for precious metals, and it has broad application prospects in the field of OLEDs.

[0126] TADF materials need to have a small singlet-triplet energy level difference, preferably ΔEst < 0.3 eV, second preferably ΔEst < 0.2 eV, and most preferably ΔEst < 0.1 eV. In a preferred embodiment, the TADF material has a relatively small ΔEst. In another preferred embodiment, the TADF has a good fluorescence quantum efficiency. Some TADF-emitting 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. Nature, 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 content of the above-listed patents or article documents is hereby incorporated herein by reference.

[0127] Examples of some suitable TADF-emitting materials are listed below:

[0128]

[0129]

[0130] The organic functional material publications mentioned above are incorporated herein by reference for the purpose of disclosure.

[0131] The present invention also provides a material or ink solution for printed electronic devices.

[0132] In certain embodiments, the mixture according to the present invention has a solubility in toluene of ≥10 mg / ml, preferably ≥15 mg / ml, and most preferably ≥20 mg / ml at 25°C.

[0133] The present invention also provides a composition comprising at least one mixture according to the present invention and at least one organic solvent.

[0134] In some embodiments, in the composition according to the present invention, the mixture serves as a singlet host material.

[0135] In a preferred embodiment, the composition according to the present invention comprises a guest material and a mixture according to the present invention.

[0136] In another preferred embodiment, the composition according to the present invention comprises a thermally activated delayed fluorescence (TADF) emitting material and a mixture according to the present invention.

[0137] In another preferred embodiment, a composition according to the present invention comprises a guest material, a thermally activated delayed fluorescence (TADF) emitting material, and a mixture according to the present invention.

[0138] In other preferred embodiments, a composition according to the present invention comprises a hole transport material (HTM) and a mixture according to the present invention. More preferably, the HTM contains a crosslinkable group.

[0139] In a preferred embodiment, the composition according to the present invention is a solution.

[0140] In another preferred embodiment, the composition according to the present invention is a suspension.

[0141] The composition in the embodiments of the present invention may include 0.01 to 20 wt% of the mixture, preferably 0.1 to 15 wt%, more preferably 0.2 to 10 wt%, and most preferably 0.25 to 5 wt% of the mixture.

[0142] In some preferred embodiments, a composition according to the present invention, wherein the organic solvent is selected from aromatic or heteroaromatic, esters, aromatic ketones or aromatic ethers, aliphatic ketones or aliphatic ethers, cycloaliphatic or olefinic compounds, or inorganic esters such as borate esters or phosphate esters, or a mixture of two or more organic solvents.

[0143] In other preferred embodiments, a composition according to the present invention, which comprises at least 50 wt% of an aromatic or heteroaromatic solvent; preferably at least 80 wt% of an aromatic or heteroaromatic solvent; particularly preferably at least 90 wt% of an aromatic or heteroaromatic solvent.

[0144] Examples of aromatic or heteroaromatic solvents according to the present invention include, but are not limited to: 1-tetralone, 3-phenoxytoluene, acetophenone, 1-methoxynaphthalene, p-diisopropylbenzene, pentylbenzene, tetralin, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylcumene, dipentylbenzene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, 1-methylnaphthalene, 1,2,4-trichlorobenzene, 1,3-dipropoxybenzene, 4,4-difluorodiphenylmethane, diphenyl ether, 1,2-dimethoxy-4-(1-propenyl)benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether, N-methyldiphenylamine, 4-isopropylbiphenyl, α,α-dichlorodiphenylmethane, 4-(3-phenylpropyl)pyridine, benzyl benzoate, 1,1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, dibenzyl ether, etc.

[0145] In other embodiments, suitable and preferred organic solvents are aliphatic, cycloaliphatic or aromatic hydrocarbons, amines, thiols, amides, nitriles, esters, ethers, polyethers, alcohols, diols or polyols.

[0146] In other embodiments, the alcohol represents a suitable class of organic solvents. Preferred alcohols include alkyl cyclohexanols, especially methylated aliphatic alcohols, naphthols, etc.

[0147] The organic solvent may be a cycloalkane, such as decalin.

[0148] The organic solvent may be used alone or as a mixture of two or more organic solvents.

[0149] In some embodiments, the composition according to the present invention comprises a mixture as described above and at least one organic solvent, and may further comprise another organic solvent. Examples of the 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, tetralin, decalin, indene and / or mixtures thereof.

[0150] In some preferred embodiments, the organic solvent particularly suitable for the present invention is a solvent having a Hansen solubility parameter in the following ranges:

[0151] δ d (Dispersion force) ranges from 17.0 to 23.2 MPa 1 / 2 especially in the range of 18.5 to 21.0 MPa 1 / 2 ;

[0152] δ p (Polar force) ranges from 0.2 to 12.5 MPa 1 / 2 especially in the range of 2.0 to 6.0 MPa 1 / 2 ;

[0153] δ h (Hydrogen bond force) ranges from 0.9 to 14.2 MPa 1 / 2 especially in the range of 2.0 to 6.0 MPa 1 / 2 ;

[0154] For the composition according to the present invention, the boiling point parameter of the organic solvent needs to be considered when selecting. In the present invention, the boiling point of the organic solvent ≥ 150 °C; preferably ≥ 180 °C; more preferably ≥ 200 °C; even more preferably ≥ 250 °C; most preferably ≥ 275 °C or ≥ 300 °C. The boiling points within these ranges are beneficial for preventing nozzle clogging of the inkjet print head. The organic solvent can evaporate from the solvent system to form a thin film containing functional materials.

[0155] In some preferred embodiments, a composition according to the present invention

[0156] 1) its viscosity @ 25 °C ranges from 1 cPs to 100 cPs, and / or

[0157] 2) its surface tension @ 25 °C ranges from 19 dyne / cm to 50 dyne / cm.

[0158] A composition according to the present invention, wherein the organic solvent is selected considering its surface tension parameter. Suitable ink surface tension parameters are suitable for a specific substrate and a specific printing method. For example, for inkjet printing, in a preferred embodiment, the surface tension of the organic solvent at 25 °C is about in the range of 19 dyne / cm to 50 dyne / cm; more preferably in the range of 22 dyne / cm to 35 dyne / cm; most preferably in the range of 25 dyne / cm to 33 dyne / cm.

[0159] In a preferred embodiment, the surface tension of the ink according to the present invention at 25 °C is about in the range of 19 dyne / cm to 50 dyne / cm; more preferably in the range of 22 dyne / cm to 35 dyne / cm; most preferably in the range of 25 dyne / cm to 33 dyne / cm.

[0160] A composition according to the present invention, wherein the organic solvent is selected considering its viscosity parameter of the ink. The viscosity can be adjusted by different methods, such as by the selection of a suitable organic solvent and the concentration of the functional materials in the ink. In a preferred embodiment, the viscosity of the organic solvent is less than 100 cps; more preferably less than 50 cps; most preferably 1.5 to 20 cps. The viscosity here refers to the viscosity at the ambient temperature during printing, generally 15 - 30 °C, preferably 18 - 28 °C, more preferably 20 - 25 °C, most preferably 23 - 25 °C. The composition formulated in this way will be particularly suitable for inkjet printing.

[0161] In a preferred embodiment, the composition according to the present invention has a viscosity at 25 °C of about in the range of 1 cps to 100 cps; more preferably in the range of 1 cps to 50 cps; most preferably in the range of 1.5 cps to 20 cps.

[0162] An ink obtained with an organic solvent satisfying the above boiling point, surface tension parameter and viscosity parameter can form a functional material thin film having a uniform thickness and compositional properties.

[0163] Another object of the present invention is to provide the use of the above organic mixture and its composition in an organic electronic device.

[0164] The organic electronic device can be selected from an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting electrochemical cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, an organic laser, an organic spintronic device, an organic sensor and an organic plasmon emitting diode.

[0165] Another object of the present invention is to provide a method for preparing the above electronic device.

[0166] The specific technical solution includes the following steps:

[0167] The above mixture is used to form a functional layer on a substrate by vapor deposition, or is used together with at least one other organic functional material to form a functional layer on a substrate by co-vapor deposition, or the above composition is coated on a substrate by printing or coating methods to form a functional layer, where the printing or coating methods can be selected from (but not limited to) inkjet printing, nozzle printing, letterpress printing, screen printing, dip coating, spin coating, blade coating, roller printing, reverse roller printing, lithographic printing, flexographic printing, rotary printing, spraying, brushing or pad printing, slot die coating, etc.

[0168] The present invention also relates to the use of the above composition as a printing ink in the preparation of organic electronic devices, and particularly preferably by a preparation method of printing or coating.

[0169] Among them, suitable printing or coating techniques include (but not limited to) inkjet printing, letterpress printing, screen printing, dip coating, spin coating, blade coating, roller printing, reverse roller printing, lithographic printing, flexographic printing, rotary printing, spraying, brushing or pad printing, slot die coating, etc. The preferred ones are gravure printing, screen printing and inkjet printing. Gravure printing and inkjet printing will be applied in the examples of the present invention. The solution or suspension may additionally include one or more components such as surface active compounds, lubricants, wetting agents, dispersants, water repellents, adhesives, etc., for adjusting viscosity, film-forming properties, improving adhesion, etc. For detailed information on printing techniques and their related requirements for relevant solutions, such as solvents and concentrations, viscosities, etc., please refer to "Handbook of Print Media: Technologies and Production Methods" edited by Helmut Kipphan, ISBN 3-540-67326-1.

[0170] For the preparation method as described above, the formed functional layer has a thickness of 5 nm to 1000 nm.

[0171] The present invention further relates to an organic electronic device, which at least contains a mixture or polymer according to the present invention, or at least contains a functional layer prepared using the composition according to the present invention. Generally, such an organic electronic device at least contains a cathode, an anode and a functional layer located between the cathode and the anode, where at least one of the above mixtures is included in the functional layer.

[0172] In a more preferred embodiment, the above-described organic electronic device is an organic electroluminescent device, particularly an OLED, which includes a substrate, an anode, at least one light-emitting layer, and a cathode. In certain preferred embodiments, the light-emitting layer contains at least one of the above-described mixtures.

[0173] The substrate can be opaque or transparent. A transparent substrate can be used to fabricate a transparent light-emitting component. See, for example, Bulovic et al., Nature 1996, 380, p29, and Gu et al., Appl. Phys. Lett. 1996, 68, p2606. The substrate can be rigid or flexible. The substrate can be plastic, metal, semiconductor wafer, or glass. Preferably, the substrate has a smooth surface. A substrate without surface defects is a particularly desirable choice. In a preferred embodiment, the substrate is flexible and can be selected from polymer films or plastics with a glass transition temperature Tg of 150 °C or higher, preferably exceeding 200 °C, more preferably exceeding 250 °C, and most preferably exceeding 300 °C. Examples of suitable flexible substrates include poly(ethylene terephthalate) (PET) and poly(ethylene 2,6-naphthalate) (PEN).

[0174] The anode can include a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into the hole injection layer (HIL), hole transport layer (HTL), or light-emitting layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the light-emitting body in the light-emitting layer or the p-type semiconductor material serving as the HIL, HTL, or electron blocking layer (EBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. Examples of anode materials include, but are not limited to: Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), etc. Other suitable anode materials are known and can be easily selected and used by those of ordinary skill in the art. The anode material can be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), etc. In certain embodiments, the anode is pattern-structured. Patterned ITO conductive substrates are commercially available and can be used to fabricate the devices according to the present invention.

[0175] The cathode may include a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the light-emitting layer. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO energy level or the conduction band energy level of the light-emitting body in the light-emitting layer or the n-type semiconductor material serving as the electron injection layer (EIL) or electron transport layer (ETL) or hole blocking layer (HBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. In principle, all materials that can be used as the cathode of an OLED may be used as the cathode material of the device of the present invention. Examples of cathode materials include, but are not limited to: Al, Au, Ag, Ca, Ba, Mg, LiF / Al, MgAg alloy, BaF2 / Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc. The cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), etc.

[0176] The OLED may also include other functional layers, such as a hole injection layer (HIL) or hole transport layer (HTL), an electron blocking layer (EBL), an electron injection layer (EIL) or electron transport layer (ETL), and a hole blocking layer (HBL). Materials suitable for use in these functional layers are described in detail in WO2010135519A1, US20090134784A1, and WO2011110277A1, and the entire contents of these three patent documents are hereby incorporated herein by reference.

[0177] In a preferred embodiment, in the light-emitting device according to the present invention, the light-emitting layer is formed by vacuum evaporation, and the evaporation source contains a mixture according to the present invention.

[0178] In another preferred embodiment, in the light-emitting device according to the present invention, the light-emitting layer is prepared by printing a composition according to the present invention.

[0179] The electroluminescent device according to the present invention has a light-emitting wavelength between 300 and 1000 nm, preferably between 350 and 900 nm, and more preferably between 400 and 800 nm.

[0180] The present invention also relates to the application of the organic electronic device according to the present invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, and the like.

[0181] The present invention also relates to an electronic device including the organic electronic device according to the present invention, including, but not limited to, display devices, lighting devices, light sources, sensors, and the like.

[0182] The present invention will be described below in conjunction with preferred embodiments. However, the present invention is not limited to the following embodiments. It should be understood that the appended claims define the scope of the present invention. Under the guidance of the inventive concept of the present invention, those skilled in the art should realize that certain changes made to the various embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention.

[0183] Synthesis Example 1: Synthesis of Compound H1-1

[0184]

[0185] (10-(2-Benzofuran)anthracene-9-boronic acid (7.76 g, 20 mmol), bromobenzene (3.1 g, 20 mmol) and a 2.00 mol / L sodium carbonate solution (4.12 g, 40 mmol) were added to a three-necked flask, stirred and dissolved with 100 ml of toluene, protected by nitrogen, and then Pd(pph 3 ) 4 (1.13 mg, 1 mmol) was added. The reaction solution was stirred and refluxed for 12 hours. TLC and MS showed that the reaction was complete, mainly the target product. After cooling, the reaction solution was washed three times with 100 ml of saturated brine, dried over anhydrous sodium sulfate, and then the solvent was evaporated off. The residue was purified by column chromatography with DCM / PE (1:10) to obtain white solid Compound H1-1 (6.7 g, yield 80%).

[0186] Synthesis Examples 2-18: Synthesis of Compounds H2-1 to H2-17.

[0187] The synthesis of Compounds H2-1 to H2-17 was carried out using the same synthetic technical route as that of Compound H1-1 and was obtained by a one-step coupling reaction according to the following intermediates:

[0188]

[0189]

[0190]

[0191] The energy levels of organic compound materials can be obtained through quantum calculations. For example, using TD-DFT (Time-Dependent Density Functional Theory) through Gaussian09W (Gaussian Inc.). The specific simulation method can be referred to WO2011141110. First, the molecular geometry is optimized using the semi-empirical method "Ground State / Semi-empirical / Default Spin / AM1" (Charge 0 / Spin Singlet). Then, the energy structure of the organic molecule is calculated by the TD-DFT (Time-Dependent Density Functional Theory) method "TD-SCF / DFT / Default Spin / B3PW91" with the basis set "6-31G(d)" (Charge 0 / Spin Singlet). The HOMO and LUMO energy levels are calculated according to the following calibration formulas, and S1 and T1 are used directly.

[0192] HOMO(eV) = ((HOMO(G) × 27.212) - 0.9899) / 1.1206

[0193] LUMO(eV) = ((LUMO(G) × 27.212) - 2.0041) / 1.385

[0194] Where HOMO(G) and LUMO(G) are the direct calculation results of Gaussian 09W, in Hartree. The results are shown in Table 2 below:

[0195] Table 2

[0196]

[0197] Comparative Synthesis Example 1: Synthesis of Comparative Compound D1

[0198]

[0199] Add [1,1'-biphenyl]-2-boronic acid (3.96 g, 20 mmol), 9-bromo-10-(2-naphthyl)anthracene (7.66 g, 20 mmol) and a 2.00 mol / L sodium carbonate (4.12 g, 40 mmol) solution to a three-necked flask, stir and dissolve with 100 ml of toluene, protect with nitrogen, then add Pd(pph 3 ) 4 (1.13 mg, 1 mmol). Stir the reaction solution and reflux for 12 hours. TLC and MS show that the reaction is complete, mainly the target product. Cool, wash the reaction solution three times with 100 ml of saturated brine, dry over anhydrous sodium sulfate, then evaporate to remove the solvent. The residue is purified by column chromatography with DCM / PE (1:10) to obtain the white solid compound D1 (7.12 g, yield 78%).

[0200] Comparative Synthesis Example 2: Synthesis of Comparative Compound D2

[0201]

[0202] (10-([1,1'-Biphenyl]-2-yl)anthracene-9-boronic acid (7.48 g, 20 mmol), 2-bromobenzo[b]naphtho[2,3-d]furan (5.94 g, 20 mmol) and a solution of 2.00 mol / L sodium carbonate (4.12 g, 40 mmol) were added to a three-necked flask, stirred and dissolved with 100 ml of toluene, protected by nitrogen, and then Pd(pph 3 ) 4 (1.13 mg, 1 mmol) was added. The reaction solution was stirred and refluxed for 12 hours. TLC and MS showed that the reaction was complete, mainly the target product. After cooling, the reaction solution was washed three times with 100 ml of saturated brine, dried over anhydrous sodium sulfate, and then the solvent was evaporated off. The residue was purified by column chromatography with DCM / PE (1:10) to obtain white solid compound D2 (8.73 g, yield 80%).

[0203] The example mixtures were mixed in the following manner:

[0204] Mixture Compound Compound Ratio Mixture 1 H1-1 H2-1 1:1 Mixture 2 H1-1 H2-2 1:1 Mixture 3 H1-1 H2-3 1:1 Mixture 4 H1-1 H2-4 1:1 Mixture 5 H1-1 H2-5 1:1 Mixture 6 H1-1 H2-6 1:1 Mixture 7 H1-1 H2-7 1:1 Mixture 8 H1-1 H2-8 1:1 Mixture 9 H1-1 H2-9 1:1 Mixture 10 H1-1 H2-10 1:1 Mixture 11 H1-1 H2-11 1:1 Mixture 12 H1-1 H2-12 1:1 Mixture 13 H1-1 H2-13 1:1 Mixture 14 H1-1 H2-14 1:1 Mixture 15 H1-1 H2-15 1:1 Mixture 16 H1-1 H2-16 1:1 Mixture 17 H1-1 H2-17 1:1

[0205] Equivalent amounts of the two compounds were heated to complete melting under vacuum, stirred and mixed, then cooled to room temperature and ground.

[0206] Preparation and Characterization of OLED Devices:

[0207] Materials used for each layer of the OLED device;

[0208] HIL: A triarylamine derivative;

[0209] HTL: A triarylamine derivative;

[0210] Host: Mixtures 1 - 17, Comparative Compounds D1 - D2;

[0211] Dopant: An aromatic amine derivative K1.

[0212]

[0213] The preparation steps of the OLED device with ITO / HIL (50 nm) / HTL (35 nm) / Host: 3% Dopant (25 nm) / ETL (28 nm) / LiQ (1 nm) / Al (150 nm) / cathode are as follows:

[0214] a. Cleaning of the conductive glass substrate: When used for the first time, it can be cleaned with various solvents, such as chloroform, ketone, and isopropyl alcohol, and then treated with ultraviolet ozone plasma.

[0215] b. HIL (50 nm), HTL (35 nm), EML (25 nm), ETL (28 nm): Thermally evaporated in a high vacuum (1 × 10 -6 mbar).

[0216] c. Cathode: LiQ / Al (1 nm / 150 nm) thermally evaporated in a high vacuum (1 × 10 -6 mbar);

[0217] d. Encapsulation: The device is encapsulated with ultraviolet-curing resin in a nitrogen glove box.

[0218] The current-voltage (J-V) characteristics of each OLED device are characterized by a characterization device, and important parameters such as efficiency, lifetime, and external quantum efficiency are recorded simultaneously. The experimental results of the efficiency are shown in Table 3 below (taking Example 2 as 100%):

[0219] Table 3

[0220] Example Matrix material Voltage (V) Efficiency (cd / A) Example 1 Mixture 1 3.5 110％ Example 2 Mixture 2 3.5 103％ Example 3 Mixture 3 3.6 120％ Example 4 Mixture 4 3.6 125％ Example 5 Mixture 5 3.6 115％ Example 6 Mixture 6 3.6 130％ Example 7 Mixture 7 3.5 104％ Example 8 Mixture 8 3.7 128％ Example 9 Mixture 9 3.7 135％ Example 10 Mixture 10 3.7 130％ Example 11 Mixture 11 3.6 141％ Example 12 Mixture 12 3.6 124％ Example 13 Mixture 13 3.6 138％ Example 14 Mixture 14 3.5 134％ Example 15 Mixture 15 3.6 127％ Example 16 Mixture 16 3.5 136％ Example 17 Mixture 17 3.6 138％ Comparative Example 1 Comparative Compound D1 3.7 95％ Comparative Example 2 Comparative Compound D2 3.7 100％

[0221] When the following guests K2 and K3 are used to replace K1, similar results are also obtained. A higher luminescence efficiency can be obtained using the mixture according to the present invention as the host.

[0222]

[0223] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as falling within the scope described in this specification.

[0224] The above-described embodiments only represent several implementation manners of the present invention. The description is relatively specific and detailed, but it should not be construed as a limitation on the scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the present invention patent should be subject to the appended claims.

Claims

1. A mixture comprising a first organic compound H 1 and a second organic compound H 2 , It is characterized in that The first organic compound H 1 Selected from: Second organic compound H 2 Selected from the following structures:

2. The mixture according to claim 1, It is characterized in that the mixture further comprises at least one other organic functional material selected from a hole injection material, a hole transport material, a hole blocking material, an electron injection material, an electron transport material, an electron blocking material, an organic matrix material, a singlet emitter, a triplet emitter, a thermally activated delayed fluorescence material, and an organic dye.

3. A composition comprising at least one mixture according to any one of claims 1 or 2 and at least one organic solvent.

4. An organic electronic device comprising at least one mixture according to any one of claims 1 or 2.

5. The organic electronic device according to claim 4, It is characterized in that the organic electronic device is an organic electroluminescent device and comprises a light emitting layer, and the light emitting layer comprises at least one mixture according to any one of claims 1 or 2.

Images