Organic Mixtures and Their Applications in Organic Electronic Devices

Abstract

An organic mixture is disclosed, as well as its application in organic electronic devices, particularly in organic light-emitting diodes. Also disclosed are organic electronic devices comprising the mixture, particularly organic light-emitting diodes, and their application in display and lighting technologies. Through device structure optimization, better device performance can be achieved; particularly for OLEDs, using the mixture as a host material in the light-emitting layer can significantly improve the luminous efficiency, enabling high-performance OLED devices and 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 relates to an organic 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] The organic electroluminescence phenomenon refers to the phenomenon of converting electrical energy into light energy using organic substances. An organic electroluminescent element utilizing the organic electroluminescence phenomenon generally has a structure including a positive electrode and a negative electrode and 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, 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 a 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 needs to be further improved. Therefore, developing high-efficiency and stable blue fluorescent materials is an urgent problem to be solved 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, WO04 / 018587). However, these compounds have poor thermal stability and are prone to decomposition, resulting in poor device lifetime, which is the most important 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 an organic 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) HOMO(H 2 ) ≥ HOMO(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 known as electric hole) injection material (HIM), hole transport material (HIM / HTM), hole blocking material (HBM), electron injection material (EIM), electron transport material (EIM / 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] Beneficial 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 aromatic 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 said transition excited state, S1 and T 1 has a ratio 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) HOMO(H 2 ) ≥ HOMO(H 1 ) + 0.10 eV

[0027] wherein, ΔE ST is E S1 -E T1 , E XIs 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 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 most preferred embodiments, E X -T 1 (H 2 ) ≥ 1.0 eV.

[0032] In some preferred embodiments, HOMO(H 2 ) ≥ HOMO(H 1 ) + 0.3 eV; in some preferred embodiments, HOMO(H 2 ) ≥ HOMO(H 1 ) + 0.2 eV; in some preferred embodiments, HOMO(H 2 ) ≥ HOMO(H 1 ) + 0.1 eV; in some preferred embodiments, HOMO(H 2 ) ≥ HOMO(H 1 ) + 0.05 eV; in some preferred embodiments, HOMO(H 2 ) ≥ HOMO(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.leV or |E X -S 1 (H 2 )|≤0.1eV; In some most preferred embodiments, |E X -S 1 (H 1 )|≤0.05eV or |E X -S 1 (H 2 )|≤0.05eV.

[0035] For the mixture satisfying the above 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 an energy much higher than that of 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, 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 2are each independently selected from substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 20 ring atoms, aryloxy or heteroaryloxy groups having 5 to 20 ring atoms, or combinations of these systems, where one or more of the groups may form monocyclic or polycyclic aliphatic or aromatic ring systems with each other and / or with the ring to which the groups are bonded.

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

[0040] In a 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 heteroatoms are 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 may 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 may 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, for example, 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, dibenzo[a,h]anthracene, 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] A mixture according to the present invention, the second organic compound H 2 contains an electron-donating group.

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

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

[0047] Examples of suitable electron-donating groups are shown in the following structures, but are not limited to, and they can be further arbitrarily substituted:

[0048]

[0049] Further electron-donating groups can be selected from structures containing the following groups, which can be further arbitrarily substituted:

[0050]

[0051] In some preferred embodiments, the second organic compound H 2 contains carbazole and its derivatives.

[0052] In some preferred embodiments, the second organic compound H 2 contains indolocarbazole and its derivatives.

[0053] In certain preferred embodiments, in the mixture, the first organic compound Hl contains an electron-withdrawing group.

[0054] In some preferred embodiments, the first organic compound H 1 contains two electron-withdrawing groups.

[0055] In some other preferred embodiments, the first organic compound H 1 contains three or more electron-withdrawing groups.

[0056] Suitable electron-withdrawing groups can be selected from one of F, cyano or the following groups:

[0057]

[0058] wherein, n 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 、M 3 each independently represents 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; R4 、 R 5 has the meanings shown above. When R are the same or different, they each 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.

[0059] In some preferred embodiments, the first organic compound H 1 contains -F.

[0060] In some preferred embodiments, the first organic compound H 1 contains -CN.

[0061] In some more preferred embodiments, for the mixture, the first organic compound H 1 or the second organic compound H 2 is selected from the following structures:

[0062]

[0063] 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.

[0064] In some preferred embodiments, R 11 -R 28is 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, together with each other and / or with the ring to which they are bonded, a monocyclic or polycyclic aliphatic or aromatic ring system.

[0065] In some more preferred embodiments, said R 11 -R 28 are the same or different and are selected from one or more combinations of the structures shown in Table 1 below:

[0066] Table 1

[0067]

[0068] wherein Y is CR 701 or N; A is selected from O, S, CR 702 R 703 , NR 704 ; R 701 -R 704 when occurring multiple times are the same or different and can be a site for connection to other groups, is 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.

[0069] In some preferred embodiments, all of Y are CR 701 ;

[0070] In some other preferred embodiments, at least one of Y in each structure is N;

[0071] In some other more preferred embodiments, at least two of Y in each structure are N;

[0072] In some other more preferred embodiments, at least three of Y in each structure are N;

[0073] 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, 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. One or more H in the various groups described above may further be substituted by D.

[0074] In a particularly preferred embodiment, H 1 or H 2 is selected from the following structures:

[0075]

[0076] wherein, R 11 -R 20is 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.

[0077] 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, 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.

[0078] In a particularly preferred embodiment, R 11 , R 12 , R 14 , R 15 , R 16 , R 17 , R 19 , R 20 are selected from H, or D; R 13 , R 18A combination of one or more selected from the structures shown in Table 1.

[0079] In another more preferred embodiment, H 1 or H 2 is selected from the following structures:

[0080]

[0081] wherein R 21 -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, hydroxy, 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.

[0082] 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, 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 a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which they are bonded.

[0083] In a particularly preferred embodiment, R 21 , R 24 , R 25 , R 28 is selected from H, or D; R 22 , R 23 , R 26 , R 27 is selected from H, D or a combination of one or more of the structures shown in Table 1.

[0084] In some preferred embodiments, the R 11 -R 20 , R 21 -R 28 are the same or different and each independently selected from one of the structures shown below:

[0085]

[0086] In a particularly preferred embodiment, the mixture, wherein H 2 has the structure shown in Chemical Formula (I), wherein R 13 or R 18 comprises a combination of one or more of the electron-donating groups shown in Table 1.

[0087] In another particularly preferred embodiment, the mixture, wherein H 2 has the structure shown in Chemical Formula (II), wherein R 22 or R 23 or R 26 or R 27 comprises a combination of one or more of the electron-donating groups shown in Table 1.

[0088] In certain preferred embodiments, the mixture, wherein H 1 has the structure shown in Chemical Formula (I), wherein R 13 or R 18 is selected from the electron-withdrawing groups as described above.

[0089] In some other preferred embodiments, the mixture, wherein H 1 has the structure shown in Chemical Formula (II), wherein wherein R ２２ or R 23 or R ２6 or R 27 is selected from the electron-withdrawing groups as described above.

[0090] In certain preferred embodiments, the mixture wherein H 1 and H 2 form a type-I heterojunction structure.

[0091] 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 ranges from 3:7 to 7:3; a more preferred molar ratio ranges from 4:6 to 6:4.

[0092] In certain preferred embodiments, the mixture wherein H 1 and / or H 2 have 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 by quantum chemical simulations, as described in the following examples.

[0093] 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.

[0094] In a preferred embodiment, in the mixture according to the 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.

[0095] In a more preferred embodiment, for the mixture according to the invention, for H 1 and H 2 , at least one 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.

[0096] In a preferred embodiment, in the mixture material according to the invention, H 1 and H 2 are both a small molecule material.

[0097] An object of the present invention is to provide a material solution for vapor deposition type OLEDs.

[0098] In a preferred embodiment, the mixture material according to the present invention is used in a vapor deposition type OLED device. For this purpose, in the mixture according to the present invention, H 1 and H 2 , having 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.

[0099] 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.

[0100] 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.

[0101] Another object of the present invention is to provide a material solution for printed OLEDs.

[0102] 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.

[0103] 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, in addition to molecular weight and sublimation temperature, can also be others, such as glass transition temperature, different molecular volumes, etc. For these purposes, preferred embodiments of the mixture according to the present invention are also:

[0104] 1) The difference in molecular weight between H 1 and H 2 ≥ 120 g / mol, preferably ≥ 140 g / mol, more preferably ≥ 160 g / mol, and most preferably ≥ 180 g / mol.

[0105] 2) H 1 and H2 The difference in sublimation temperature is ≤80 K, preferably ≤75 K, more preferably ≤70 K, and most preferably ≤60 K.

[0106] 3) H 1 and H 2 The difference in glass transition temperature is ≤45 K, preferably ≤40 K, more preferably ≤30 K, and most preferably ≤35 K.

[0107] 4) H 1 and H 2 The difference in molecular volume is ≥20%, preferably ≥30%, more preferably ≥40%, and most preferably ≥45%.

[0108] 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.

[0109] The term "small molecule" as defined herein refers to a molecule that is not a polymer, oligomer, dendrimer, or blend. In particular, small molecules do not have a repeating structure. The molecular weight of small molecules is ≤3000 g / mol, preferably ≤2000 g / mol, and most preferably ≤1500 g / mol.

[0110] Polymers, i.e., 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.].

[0111] A conjugated polymer is a polymer whose backbone is mainly composed of sp2 hybrid orbitals of carbon atoms. Well-known examples include polyacetylene and poly(phenylenevinylene). The carbon atoms in the backbone can also be replaced by other non-carbon atoms, and when the sp2 hybridization in the backbone is interrupted by some natural defects, it is still considered a conjugated polymer. In addition, in the present invention, conjugated polymers also include those containing aryl amines, aryl phosphines, other heteroaromatics, organometallic complexes, etc. in the backbone.

[0112] For the mixture according to the present invention, its specific H 1 Examples are as follows, but are not limited thereto:

[0113]

[0114]

[0115]

[0116]

[0117]

[0118] For a mixture according to the present invention, its specific H 2 Examples are as follows, but are not limited thereto:

[0119]

[0120]

[0121]

[0122] The present invention also provides a mixture, comprising at least one of the mixtures as 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 WO2011110277A1, and the entire content of these three patent documents is hereby incorporated herein by reference.

[0123] 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 . Such a possible advantage 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

[0124] In a preferentially 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%.

[0125] In certain embodiments, the mixture comprises an organic mixture according to the present invention and a TADF material.

[0126] Some more detailed descriptions (but not limited to this) of the singlet emitter and the TADF material are given below.

[0127] 1. Singlet Emitter

[0128] 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.

[0129] In a preferred embodiment, the singlet emitter can be selected from mono - styrylamine, di - styrylamine, tri - styrylamine, tetra - styrylamine, styrylphosphine, styrylether, and arylamine.

[0130] A mono - styrylamine refers to a compound that contains an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine. A di - styrylamine refers to a compound that contains two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A tri - styrylamine refers to a compound that contains three unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A tetra - styrylamine 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 pyrenylamine, aromatic pyrenyldiamine, aromatic chrysenylamine, and aromatic chrysenyldiamine. 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 pyrenylamine, aromatic pyrenyldiamine, aromatic chrysenylamine, and aromatic chrysenyldiamine are similar, where the diarylamine group is preferably linked to the 1 - or 1,6 - positions of pyrene.

[0131] 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.

[0132] An example of a singlet emitter based on stilbene and its derivatives is US 5121029.

[0133] 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[ghi]indeno[1,2-b]fluorene-amine and benzo[ghi]indeno[1,2-b]fluorene-diamine, as disclosed in WO2008 / 006449, dibenzo[ghi]indeno[1,2-b]fluorene-amine and dibenzo[ghi]indeno[1,2-b]fluorene-diamine, as disclosed in WO2007 / 140847.

[0134] 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-(p-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 pyrrolopyrrolidone. 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.

[0135] Some examples of suitable singlet emitters are listed below:

[0136]

[0137] 2. Thermally Activated Delayed Fluorescence (TADF) Materials

[0138] 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, enabling the internal quantum efficiency of the device to reach 100% due to the enhanced intersystem crossing by the strong spin-orbit coupling of heavy atom centers, the application of phosphorescent materials in OLEDs is limited by problems such as high cost, poor material stability, and severe efficiency roll-off of the device. 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 allows for the full utilization of 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, and the price is low without the need for precious metals, showing broad application prospects in the field of OLEDs.

[0139] 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.a1. 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. S0c, 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 the above-listed patents or article documents are hereby incorporated herein by reference.

[0140] Some examples of suitable TADF-emitting materials are listed below:

[0141]

[0142]

[0143] The organic functional material publications mentioned above are incorporated herein by reference for the purpose of disclosure.

[0144] The present invention also relates to another compound having a structure represented by the following chemical formula (I) or (II):

[0145]

[0146] Wherein: R 13 Contains an electron-withdrawing group as described above: R 22 Or R 23 Contains an electron-withdrawing group as described above; R 18 Contains an electron-donating group as described above; R 26 Or R 27 Contains an electron-donating group as described above, and the definitions of other symbols are as described above.

[0147] The present invention also provides a composition or ink solution for printed electronic devices.

[0148] 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.

[0149] The present invention also provides a composition comprising at least one mixture according to the present invention and at least one organic solvent.

[0150] In some embodiments, in the composition according to the present invention, the mixture serves as a singlet host material.

[0151] In a preferred embodiment, the composition according to the present invention comprises a guest material and a mixture according to the present invention.

[0152] 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.

[0153] In another preferred embodiment, a composition according to the present invention comprises a guest material, a thermally activated delayed fluorescence emitting material, and a mixture according to the present invention.

[0154] In some further preferred embodiments, a composition according to the present invention comprises a hole transporting material (HTM) and a mixture according to the present invention. More preferably, the HTM comprises a crosslinkable group.

[0155] In a preferred embodiment, the composition according to the present invention is a solution.

[0156] In another preferred embodiment, the composition according to the present invention is a suspension.

[0157] The composition in the examples 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.

[0158] 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 ester compounds such as borate esters or phosphate esters, or a mixture of two or more organic solvents.

[0159] In some 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.

[0160] 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.

[0161] In some other embodiments, suitable and preferred solvents are aliphatic, cycloaliphatic or aromatic hydrocarbons, amines, thiols, amides, nitriles, esters, ethers, polyethers, alcohols, diols or polyols.

[0162] In other embodiments, the alcohol represents a suitable class of solvents. Preferred alcohols include alkyl cyclohexanols, especially methylated aliphatic alcohols, naphthols, and the like.

[0163] The organic solvent described above may be a cycloalkane, such as decalin.

[0164] The organic solvent described above may be used alone or as a mixture of two or more organic solvents.

[0165] In certain 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 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.

[0166] 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:

[0167] 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 ;

[0168] 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 ;

[0169] 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 ;

[0170] A composition according to the present invention, wherein the organic solvent is selected considering its boiling point parameter. In the present invention, the boiling point of the organic solvent is ≥150 °C; preferably ≥180 °C; more preferably ≥200 °C; still 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 the functional material.

[0171] In some preferred embodiments, a composition according to the present invention:

[0172] 1) Its viscosity @25 °C is in the range of 1 cPs to 100 cPs, and / or

[0173] 2) Its surface tension @25 °C is in the range of 19 dyne / cm to 50 dyne / cm.

[0174] 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.

[0175] 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; better in the range of 22 dyne / cm to 35 dyne / cm; best in the range of 25 dyne / cm to 33 dyne / cm.

[0176] A composition according to the present invention, wherein the organic solvent is selected considering the viscosity parameter of the ink. The viscosity can be adjusted by different methods, such as by selecting a suitable organic solvent and the concentration of the functional material 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.

[0177] 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; better in the range of 1 cps to 50 cps; best in the range of 1.5 cps to 20 cps.

[0178] The ink obtained from the organic solvent satisfying the above boiling point, surface tension parameter and viscosity parameter can form a functional material film with uniform thickness and compositional properties.

[0179] Another object of the present invention is to provide the application of the above organic mixture and its composition in organic electronic devices.

[0180] 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.

[0181] Another object of the present invention is to provide a preparation method of the above electronic device.

[0182] The specific technical solution includes the following steps:

[0183] The above mixture is used to form a functional layer on a substrate by evaporation coating, or together with at least one other organic functional material by co-evaporation coating to form a functional layer on a substrate, 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, knife coating, roller printing, reverse roller printing, lithographic printing, flexographic printing, rotary printing, spraying, brush coating or pad printing, slot die coating, etc.

[0184] The present invention also relates to the use of the composition as a printing ink in the preparation of organic electronic devices, and particularly preferably by a preparation method of printing or coating.

[0185] Among them, suitable printing or coating techniques include (but are not limited to) inkjet printing, letterpress printing, screen printing, dip coating, spin coating, blade coating, roller printing, reverse roller printing, lithography, flexography, rotary printing, spraying, brush coating or pad printing, slot die extrusion coating, etc. The preferred ones are gravure printing, screen printing and inkjet printing. Gravure printing and inkjet printing will be applied in the embodiments 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.

[0186] In the preparation method as described above, the formed functional layer has a thickness of 5 nm to 1000 nm.

[0187] The present invention further relates to an organic electronic device, which at least comprises a mixture or a polymer according to the present invention, or at least comprises a functional layer prepared using the composition according to the present invention. Generally, such an organic electronic device at least comprises a cathode, an anode and a functional layer located between the cathode and the anode, wherein at least one of the above-mentioned mixtures is included in the functional layer.

[0188] In a more preferred embodiment, the above-mentioned organic electronic device is an organic electroluminescent device, especially an OLED, which includes a substrate, an anode, at least one light-emitting layer, and a cathode. In some preferred embodiments, the light-emitting layer contains at least one of the above-mentioned mixtures.

[0189] The substrate can be opaque or transparent. A transparent substrate can be used to fabricate a transparent light-emitting device. 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 above 150 °C, preferably above 200 °C, more preferably above 250 °C, and most preferably above 300 °C. Examples of suitable flexible substrates include poly(ethylene terephthalate) (PET) and poly(ethylene 2,6-naphthalate) (PEN).

[0190] The anode can include a conductive metal, metal oxide, or 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 lumophore 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 some 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.

[0191] 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 level or conduction band level of the lumophore 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.

[0192] 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.

[0193] 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.

[0194] 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.

[0195] 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.

[0196] 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.

[0197] 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.

[0198] 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, those skilled in the art should realize that certain changes made to the embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention.

[0199] Synthesis Example 1: Synthesis of Compound H1-1

[0200]

[0201] (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, dissolved by stirring with 100 ml of toluene and 25 ml of ethanol, 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. It was cooled to room temperature, and the reaction solution was washed three times with 100 ml of saturated brine, dried over anhydrous sodium sulfate, filtered, and then the solvent was evaporated off. The residue was purified by column chromatography with DCM / PE (1:10) to obtain the white solid compound H1-1 (6.68 g, yield 79.5%). MS (ASAP) = 420.2.

[0202] Synthesis Examples 2-7: Synthesis of Compounds H1-2 to H1-7

[0203] The synthesis of compounds H1-2 to H1-7 was carried out using the same synthetic technical route as that of compound H1-1. The proportions of the raw materials used were similar, and the intermediates could all be purchased from the commercial market. The required target products were obtained by one-step SUZUKI coupling reaction according to the following intermediates:

[0204]

[0205]

[0206] Synthesis Examples 8-18: Synthesis of Compounds H2-1 to H2-11

[0207] The synthesis of compounds H2-1 to H2-11 was carried out using the same synthetic technical route as that of compound H1-1. Both intermediate A and intermediate B could be purchased from the commercial market. The required target products were obtained by one-step SUZUKI coupling reaction according to the following intermediates:

[0208]

[0209]

[0210] 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 found in WO2011141110. First, use the semi-empirical method "Ground State / Semi-empirical / Default Spin / AM1" (Charge 0 / Spin Singlet) to optimize the molecular geometry. 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" and the basis set "6-31G(d)" (Charge 0 / Spin Singlet). The HOMO and LUMO energy levels are calculated according to the following calibration formula, and S1 and T1 are used directly.

[0211] HOMO (eV) = ((HOMO(G) × 27.212) - 0.9899) / 1.1206

[0212] LUMO (eV) = ((LUMO(G) × 27.212) - 2.0041) / 1.385

[0213] Where HOMO(G) and LUMO(G) are the direct calculation results of Gaussian 09W, in Hartree units. The results are shown in Table 2 below:

[0214] Table 2

[0215]

[0216]

[0217] Comparative Synthesis Example 1: Synthesis of Comparative Compound D1

[0218]

[0219] 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, and then add Pd(pph 3 ) 4(1.13 mg, 1 mmol), 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 D1 (7.12 g, yield 78%). MS (ASAP) = 456.2.

[0220] Comparative Synthesis Example 2: Synthesis of Comparative Compound D2

[0221]

[0222] (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, dissolved by stirring 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%). MS (ASAP) = 546.2.

[0223] The mixtures of the Examples were mixed in the following manner:

[0224]

[0225]

[0226] Equivalent amounts of the two compounds were heated to complete melting under vacuum, stirred and mixed, then cooled to room temperature and ground.

[0227] The mixtures of H1-1 to H1-7 as H1 were also obtained in a similar manner.

[0228] Preparation and Characterization of OLED Devices:

[0229] Materials Used for Each Layer of OLED Devices:

[0230] HIL: A triarylamine derivative;

[0231] HTL: A triarylamine derivative;

[0232] Host: Mixtures 1 - 11, Comparative Compounds D1 - D2;

[0233] Dopant: An aromatic amine derivative K1.

[0234]

[0235] The preparation steps of the OLED device with ITO / HIL(50nm) / HTL(35nm) / Host: 3% Dopant(25nm) / ETL(28nm) / LiQ(1nm) / Al(150nm) / cathode are as follows:

[0236] a. Cleaning of the conductive glass substrate: When used for the first time, it can be cleaned with various solvents, such as chloroform, ketone, isopropanol, and then treated with ultraviolet ozone plasma.

[0237] b. HIL(50nm), HTL(35nm), EML(25nm), ETL(28nm): Thermally evaporated in a high vacuum (1×10 -6 mbar). The mixed host is obtained by co-evaporating two hosts.

[0238] c. Cathode: LiQ / Al(1nm / 150nm) is thermally evaporated in a high vacuum (1×10 -6 mbar);

[0239] d. Encapsulation: The device is encapsulated with ultraviolet curable resin in a nitrogen glove box.

[0240] 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 are shown in Table 3 below:

[0241] Table 3

[0242]

[0243]

[0244] Similar results are obtained by substituting the following guest materials K2 and K3 for K1, and higher luminous efficiency can be obtained using the mixtures according to the present invention as the host.

[0245]

[0246] 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-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope described in this specification.

[0247] The above-described embodiments merely 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 still be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the present invention patent shall 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 as claimed in claim 1 or 2 and at least one organic solvent.

4. An organic electronic device comprising at least one mixture as claimed in 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 a mixture as claimed in any one of claims 1 or 2.

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