A mixture and its application in organic electronic devices

Abstract

The present invention discloses a mixture and its application in organic electronic devices, particularly in organic light-emitting diodes. The present invention also discloses an organic electronic device, particularly an organic light-emitting diode, comprising the mixture according to the present invention, 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 electronic materials and devices, and particularly to an organic mixture, a composition containing the same, an organic electronic device, and the application thereof in an organic electronic device. Background Art

[0002] Organic light-emitting diodes (OLEDs) have excellent properties such as light weight, active light emission, wide viewing angle, high contrast ratio, high luminous efficiency, low energy consumption, easy preparation of flexible and large-size panels, etc., and are regarded by the industry as the most promising next-generation display technology. In order to improve the luminous efficiency of organic light-emitting diodes and promote the large-scale industrialization process of organic light-emitting diodes, the key problems that need to be solved urgently for organic light-emitting diodes are luminous performance and lifespan.

[0003] To obtain high-performance organic light-emitting diodes, the host material is the key. At present, when preparing OLED light-emitting devices, a single host material is generally used in combination with a light-emitting body. However, the single host material will cause different carrier transport rates, resulting in serious roll-off of the device efficiency at high brightness, thereby shortening the lifespan of the device. Using a dual host material can weaken some problems brought by the single host. Especially through appropriate material combination, the selected dual host material can effectively form an exciplex, greatly improving the luminous efficiency and lifespan of the device. Kim et al. (see Kim et al., Adv. Func. Mater. 2013, DOI: 10.1002 / adfm.201300547, and Kim et al., Adv. Func. Mater. 2013, DOI: 10.1002 / adfm.201300187) achieved low roll-off and high-efficiency OLEDs by using a co-host that can form an exciplex and adding a metal complex as a phosphorescent light-emitting body.

[0004] In vapor deposition devices, by pre-forming a premix or an organic alloy of the dual host material, the vapor deposition process can be greatly simplified, and the lifespan of the device can be significantly improved (see patents US2016141505A1, WO2016060332A1, WO2016068450A1, WO2016068460A1, etc.).

[0005] At present, there is still a need to further improve materials, especially to find a host material system suitable for forming a co-host, especially a p-type host material with hole transport properties, which can be matched with an n-type host or a bipolar host to form a co-host, so that the organic electroluminescent element can have good efficiency and lifespan, be easily repeatable in the manufacture and operation of the device, and have simple material synthesis. However, the two host materials that can form a premix (Premix) need to have similarities in other physical properties in addition to meeting certain energy structure requirements, such as evaporation kinetics under vacuum, which brings great limitations to material design. This greatly hinders the design and performance improvement of the premix.

[0006] Furthermore, in printed OLEDs, functional materials, especially the light-emitting layer materials, must have good solubility and film-forming properties. Currently developed materials for vapor-deposited OLEDs often fail to meet these requirements. Summary of the Invention

[0007] Based on this, the object of the present invention is to provide a mixture and application thereof in organic electronic devices, in particular to provide a new solution for the design and development of premixes.

[0008] The specific technical solutions are as follows:

[0009] The present invention provides an organic mixture comprising compound 1 (H1) and compound 2 (H2), wherein compound 1 (H1) has a structure represented by general formula (I), and compound 2 (H2) has a structure represented by general formula (II):

[0010] BAB (I)

[0011] ABA (II)

[0012] In the above general formula, A and B are different groups, each selected from 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 A and B groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or the ring to which they are bonded. In general formula (I), the two B groups can be substituted with the same or different substituents; in general formula (II), the two A groups can be substituted with the same or different substituents, and one or more H groups in the above-mentioned A and B groups can be further substituted with D.

[0013] The present invention also provides another mixture, comprising at least one of the mixtures described above and at least one other organic functional material, and the at least one other organic functional material is 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.

[0014] The present invention also provides a composition, comprising at least one of the mixtures described above and at least one organic solvent.

[0015] The present invention also provides an application of the mixture or composition described above in an organic electronic device.

[0016] The present invention provides an organic electronic device, comprising at least one of the mixtures described above.

[0017] Advantageous effects: For the mixture according to the present invention, different molecules with similar molecular structures are mixed, which helps to maintain the amorphous morphology of the thin film, can adjust the energy level structure by the combination of different A and B groups, and at the same time facilitates maintaining the similarity of other physical properties of the two compounds, and is convenient for the design and preparation of a premix; in addition, through the combination of the n- and p-type groups of the present invention, it helps to separate and optimize the hole and electron transport channels in the thin film. The organic electroluminescent device prepared with such a mixture has high luminous efficiency and long device life. Detailed embodiments

[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 skilled 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, the matrix material, the Host material, and the Matrix material have the same meaning and can be interchanged.

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

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

[0023] The present invention provides an organic mixture comprising two organic compounds, wherein Compound 1 (H1) has a structure represented by General Formula (I), and Compound 2 (H2) has a structure represented by General Formula (II).

[0024] B - A - B (I)

[0025] A - B - A (II)

[0026] In the above general formulas, A and B are different groups, each selected from 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 A and B 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 of the H atoms in the various groups described above may further be substituted by D.

[0027] In some more preferred embodiments, A and B are different groups, each selected from a substituted or unsubstituted aromatic or heteroaromatic ring system having 9 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 9 to 40 ring atoms, or a combination of these systems, wherein one or more of the A and B 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 of the H atoms in the various A and B groups described above may further be substituted by D.

[0028] In some even more preferred embodiments, A and B are different groups, each selected from a substituted or unsubstituted aromatic or heteroaromatic ring system having 12 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 12 to 40 ring atoms, or a combination of these systems, wherein one or more of the A and B 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 of the H atoms in the various groups described above may further be substituted by D.

[0029] In some particularly preferred embodiments, A and B are different groups, each selected from a substituted or unsubstituted aromatic or heteroaromatic ring system having 14 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 14 to 40 ring atoms, or a combination of these systems, wherein one or more of the A and B 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 of the H atoms in the various groups described above may further be substituted by D.

[0030] In a more preferred embodiment, the aromatic ring system contains carbon atoms in the ring system, more preferably carbon atoms, and the heteroaromatic ring system contains a carbon atom, more preferably 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.

[0031] 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 ring species, 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.

[0032] Specifically, examples of aromatic groups are: benzene, naphthalene, anthracene, phenanthrene, dibenzo[a,h]anthracene, tetracene, pyrene, benzopyrene, triphenylene, acenaphthene, fluorene, spirofluorene, and their derivatives.

[0033] 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.

[0034] In certain embodiments, A and B can further be selected from one or more combinations of the following groups:

[0035]

[0036] wherein,

[0037] A 1 、A 2 、A 3 、A 4 、A 5 、A 6 、A 7 、A8 Each independently represents CR 3 or N;

[0038] Y 1 Selected from CR 4 R 5 、SiR 4 R 5 、NR 3 、C(=O), S or O;

[0039] R 3 、R 4 、R 5 is H, 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 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, a cyano group (-CN), a carbamoyl group (-C(=O)NH2), a halocarbonyl group (-C(=O)-X where X represents a halogen atom), a formyl group (-C(=O)-H), an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, a CF3 group, 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 groups, where one or more of the groups R 3 ,R 4 ,R 5 can form a monocyclic or polycyclic aliphatic or aromatic ring with each other and / or with the ring to which they are bonded.

[0040] In certain preferred embodiments, A and B can further be selected from one or more combinations of the following groups, where the H on the ring can be arbitrarily substituted:

[0041]

[0042] In certain embodiments, the B groups on the left and right sides in the general formula (I) can be substituted with different substituents.

[0043] In a preferred embodiment, the B groups on the left and right sides in the general formula (I) are substituted with the same substituents. In a particularly preferred embodiment, the general formula (I) has a symmetric structure centered on A.

[0044] In certain embodiments, the A groups on the left and right sides in the general formula (II) can be substituted with different substituents.

[0045] In a preferred embodiment, the A groups on the left and right sides in the general formula (II) are substituted with the same substituents. In a particularly preferred embodiment, the general formula (II) has a symmetric structure centered around B.

[0046] For the organic mixture according to the present invention, in the general formulas of H1 and H2, the A group is selected from groups having electron transport properties, and the B group is selected from groups having hole transport properties.

[0047] For the organic mixture according to the present invention, the A group contains one of the following structures:

[0048]

[0049] wherein m is any integer from 1 to 3; X 1 –X 8 is selected from CR 301 or N, and at least one is N; M 1 -M 3 is a single bond or C(R 301 )2 or O or S; R, R 1 , R 2 and R 301 can be independently selected from the following groups: hydrogen, deuterium, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl, and heteroaryl.

[0050] In some preferred embodiments, R, R 1 , R 2 and R 301 can be independently selected from H, or a straight-chain alkyl, alkoxy or thioalkoxy having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy 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)NH2), halocarbonyl (-C(=O)-X where X represents a halogen atom), formyl (-C(=O)-H), isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxyl, nitro, CF3, 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 groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which the group is bonded. One or more H in the above various groups can be further substituted by D.

[0051] In some more preferred embodiments, R, R1 , R 2 and R 301 may each independently be selected from H, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 10 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 10 carbon atoms, or a substituted or unsubstituted silyl group, or a substituted keto group having 1 to 10 carbon atoms, or an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 10 carbon atoms, cyano (-CN), carbamoyl (-C(=O)NH2), halocarbonyl (-C(=O)-X where X represents a halogen atom), formyl (-C(=O)-H), isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxyl, nitro, CF3, 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 groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which the groups are bonded. One or more H in the various groups described above may further be replaced by D.

[0052] In a preferred embodiment, R, R 1 , R 2 and R 301 are each independently preferably: methyl, isopropyl, tert-butyl, isobutyl, hexyl, octyl, 2-ethylhexyl, benzene, biphenyl, naphthalene, anthracene, phenanthrene, benzophenanthrene, pyrene, pyridine, pyrimidine, triazine, fluorene, thiophene, furan, thiazole, triphenylamine, triphenylphosphine oxide, tetraphenylsilicon, spirofluorene, spirosiliconfluorene and other groups; more preferably methyl, isopropyl, tert-butyl, isobutyl, benzene, biphenyl, naphthalene, anthracene, phenanthrene, benzophenanthrene fluorene, spirofluorene and other groups.

[0053] The organic mixture according to the present invention contains a structure shown below in the B group:

[0054]

[0055] wherein Y represents an aromatic group or heteroaromatic group having 5 to 40 carbon atoms; Z 1 , Z 2 , Z 3 are each independently selected from a single bond, N(R 302 ), C(R 302 )2, Si(R 302 )2, O, S, C=N(R 302 ), C=C(R 302 )2 and P(R 302 ); R0, R1, R2 and R 302Independently selected from alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl, and heteroaryl, respectively.

[0056] In a preferred embodiment, the B group contains one of the following formulas:

[0057]

[0058] Wherein, Z 2 , Z 3 , and the meanings of R0 are as described above.

[0059] In a more preferred embodiment, the B group contains one of the following formulas:

[0060]

[0061] Wherein, the meanings of R0 and R 302 are as described above.

[0062] For the organic mixture according to the present invention, one of the A group and the B group may also be selected from groups having the following structures:

[0063]

[0064] Furthermore, for the organic mixture according to the present invention, one or a combination of the following structural units may be included in the A group or the B group, and they may be further substituted:

[0065]

[0066]

[0067] Where n is 1 or 2 or 3 or 4.

[0068] In the examples of the present invention, the energy level structure of the organic material, the triplet energy level E T , HOMO, and LUMO play a key role. The determination of these energy levels is introduced below.

[0069] The HOMO and LUMO energy levels can be measured by the photoelectric effect, such as XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV). Recently, quantum chemical methods, such as density functional theory (hereinafter referred to as DFT), have also become effective methods for calculating the energy levels of molecular orbitals.

[0070] The triplet energy level E TIt can be measured by time-resolved luminescence spectroscopy at low temperature, or obtained by quantum simulation calculations (such as through Time-dependent DFT), e.g., using commercial software Gaussian 03W (Gaussian Inc.); the singlet energy level E of the organic material S It can also be obtained by or through quantum simulation calculations (such as through Time-dependent DFT). For specific simulation methods, reference can be made to WO2011141110 or as described in the following examples.

[0071] It should be noted that the absolute values of HOMO, LUMO, E S 、E T depend on the measurement method or calculation method used. Even for the same method, different evaluation methods, such as the starting point and peak point on the CV curve, can give different HOMO / LUMO values. Therefore, reasonable and meaningful comparisons should be made using the same measurement method and the same evaluation method. In the description of the embodiments of the present invention, the values of HOMO, LUMO, E T are based on simulations by Time-dependent DFT, but this does not affect the application of other measurement or calculation methods.

[0072] In the invention, (HOMO-1) is defined as the second highest occupied orbital energy level, (HOMO-2) as the third highest occupied orbital energy level, and so on. (LUMO+1) is defined as the second lowest unoccupied orbital energy level, (LUMO+2) as the third lowest occupied orbital energy level, and so on.

[0073] For an organic compound, its ΔE ST is defined as the difference between the singlet and triplet energy levels, i.e., E S -E T , its ΔLUMO is defined as (LUMO+1)-LUMO, and its ΔHOMO is defined as HOMO-(HOMO-1).

[0074] Preferably, for the organic mixture according to the present invention, the compound 1 (H1) and the compound 2 (H2) need to satisfy certain restrictions on the energy level structure.

[0075] In certain embodiments, the difference in LUMO and / or HOMO between H1 and H2 ≤ 0.3 eV, i.e., |HOMO(H1)-HOMO(H2)| ≤ 0.3 eV and / or |LUMO(H1)-LUMO(H2)| ≤ 0.3 eV.

[0076] In some preferred embodiments, the difference between the LUMO and / or HOMO of H1 and H2 is ≤ 0.2 eV, i.e., |HOMO(H1) - HOMO(H2)| ≤ 0.2 eV and / or |LUMO(H1) - LUMO(H2)| ≤ 0.2 eV.

[0077] In some preferred embodiments, the difference between the LUMO and / or HOMO of H1 and H2 is ≤ 0.1 eV, i.e., |HOMO(H1) - HOMO(H2)| ≤ 0.1 eV and / or |LUMO(H1) - LUMO(H2)| ≤ 0.1 eV.

[0078] In some preferred embodiments, the difference between the LUMO and / or HOMO of H1 and H2 is ≤ 0.05 eV, i.e., |HOMO(H1) - HOMO(H2)| ≤ 0.05 eV and / or |LUMO(H1) - LUMO(H2)| ≤ 0.05 eV.

[0079] For the organic mixture according to the present invention, ΔE of H1 or H2 ST ≤ 0.3 eV.

[0080] In some preferred embodiments, ΔE of H1 or H2 ST ≤ 0.2 eV.

[0081] In some preferred embodiments, ΔE of H1 or H2 ST ≤ 0.1 eV.

[0082] In some preferred embodiments, ΔE of H1 or H2 ST ≤ 0.05 eV.

[0083] In some preferred embodiments, ΔE of H1 or H2 ST ≤ 0.01 eV.

[0084] In certain preferred embodiments, for H1 or H2, ΔHOMO ≥ 0.2 eV, preferably ≥ 0.25 eV, more preferably ≥ 0.3 eV, particularly preferably ≥ 0.35 eV, and most preferably ≥ 0.4 eV.

[0085] In some other preferred embodiments, for H1 or H2, ΔLUMO ≥ 0.2 eV, preferably ≥ 0.25 eV, more preferably ≥ 0.3 eV, particularly preferably ≥ 0.35 eV, and most preferably ≥ 0.4 eV.

[0086] In certain embodiments, for the organic mixture described, H1 and H2 form a type-II heterojunction structure.

[0087] In a preferred embodiment, for the organic mixture, min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1)) ≤ min(E T (H1), E T (H2));

[0088] In a more preferred embodiment, for the organic mixture, min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1)) ≤ min(E T (H1), E T (H2)) - 0.05 eV;

[0089] In a still more preferred embodiment, for the organic mixture, min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1)) ≤ min(E T (H1), E T (H2)) - 0.1 eV;

[0090] In a very preferred embodiment, for the organic mixture, min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1)) ≤ min(E T (H1), E T (H2)) - 0.15 eV;

[0091] In a most preferred embodiment, for the organic mixture, min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1)) ≤ min(E T (H1), E T (H2)) - 0.2 eV;

[0092] In other embodiments, for the mixture, H1 and H2 form a type-I heterojunction structure.

[0093] For the organic mixture according to the present invention, the mass ratio of H1 to H2 is from 1:9 to 9:1.

[0094] In some preferred embodiments, the mass ratio of H1 to H2 is from 2:8 to 8:2.

[0095] In some preferred embodiments, the mass ratio of H1 to H2 is from 3:7 to 7:3.

[0096] In some preferred embodiments, the mass ratio of H1 to H2 is from 4:6 to 6:4.

[0097] In some preferred embodiments, the mass ratio of H1 to H2 is 5:5.

[0098] In a more preferred embodiment, in the mixture according to the present invention, H1 and / or H2 are at least 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.

[0099] In another more preferred embodiment, in the mixture according to the present invention, H2 is at least 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.

[0100] Furthermore, for the organic mixture, H1 and H2 need to meet certain requirements in terms of physical properties.

[0101] In a preferred embodiment, for the organic mixture, the difference in molecular weight between H1 and H2 does not exceed 120 Dalton; preferably the difference in molecular weight does not exceed 80 Dalton; more preferably the difference in molecular weight does not exceed 60 Dalton; most preferably the difference in molecular weight does not exceed 30 Dalton.

[0102] In another preferred embodiment, for the organic mixture, the difference in sublimation temperature between H1 and H2 does not exceed 30 K; preferably the difference in sublimation temperature does not exceed 20 K; more preferably the difference in sublimation temperature does not exceed 10 K.

[0103] In a preferred embodiment, the organic mixture according to the present invention is used for vapor-deposited OLED devices. For this purpose, for H1 and H2 in the mixture according to the present invention, the molecular weight ≤ 1000 mol / kg, preferably ≤ 900 mol / kg, very preferably ≤ 850 mol / kg, more preferably ≤ 800 mol / kg, and most preferably ≤ 750 mol / kg.

[0104] In a preferred embodiment, for the organic mixture according to the present invention, the glass transition temperature T of H1 and / or H2 g ≥ 100 °C, in a preferred embodiment, the T of H1 and / or H2 g ≥ 120 °C, in a more preferred embodiment, the T of H1 and / or H2 g ≥ 140 °C, in a still more preferred embodiment, the T of H1 and / or H2 g ≥ 160 °C, in a most preferred embodiment, the T of H1 and / or H2 g ≥ 180 °C.

[0105] Examples of the mixture according to the present invention are as follows (but are not limited thereto), where n-1 (as shown in Chemical Formulas 1-1 to 52-1 below, n represents an integer from 1 to 52), and n-2 (as shown in Chemical Formulas 1-2 to 52-2 below, n represents an integer from 1 to 52) can be correspondingly mixed to form the said mixture:

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115] The present invention also relates to a method for synthesizing an organic compound according to General Formula (I) or (II), in which a raw material containing an active group is used for the reaction. These active raw materials contain at least one leaving group, for example, bromine, iodine, boric acid or borate ester. Appropriate reactions for forming C-C bonds are well-known to those skilled in the art and are described in the literature. Particularly appropriate and preferred coupling reactions are SUZUKI, STILLE and HECK coupling reactions.

[0116] Furthermore, the organic mixture according to the present invention further contains 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. For example, various organic functional materials are described in detail in WO2010135519A1, US20090134784A1 and WO 2011110277A1. The entire contents of these 3 patent documents are hereby incorporated herein by reference.

[0117] In a preferred embodiment, the other organic functional material is selected from fluorescent guest materials. Here, the organic mixture (H1 + H2) according to the present invention can be used as the host, and the weight percentage of the guest is ≤ 10 wt%, preferably ≤ 9 wt%, more preferably ≤ 7 wt%, even more preferably ≤ 6 wt%, and most preferably ≤ 5 wt%.

[0118] In a more preferred embodiment, the other organic functional material is selected from phosphorescent guest materials. Here, the organic mixture (H1 + H2) according to the present invention can be used as the host, and the weight percentage of the guest is ≤ 15 wt%, preferably ≤ 12 wt%, more preferably ≤ 9 wt%, even more preferably ≤ 8 wt%, and most preferably ≤ 7 wt%.

[0119] In some embodiments, the other organic functional material is selected from TADF materials.

[0120] In other embodiments, the other organic functional material is selected from HTM materials.

[0121] Some more detailed descriptions (but not limited to this) of phosphorescent guest materials, singlet emitters (i.e., fluorescent guest materials), and TADF materials are given below.

[0122] 1. Triplet Emitter or Phosphorescent Guest Material

[0123] Triplet emitters are also called phosphorescent emitters. In a preferred embodiment, the triplet emitter is a metal complex having the general formula M(L)n, where M is a metal atom, L may be the same or different each time it appears, and is an organic ligand that is bonded or coordinated to the metal atom M through one or more positions, and n is an integer between 1 and 6. Preferably, the triplet emitter contains a chelating ligand, that is, a ligand that coordinates to the metal through at least two binding points. Particularly preferred is that the triplet emitter contains two or three identical or different bidentate or multidentate ligands. Chelating ligands are beneficial to improving the stability of the metal complex. In a preferred embodiment, the metal complex that can be used as a triplet emitter has the following form:

[0124]

[0125] The metal atom M is selected from transition metal elements, lanthanide elements, or actinide elements. Preferably, Ir, Pt, Pd, Au, Rh, Ru, Os, Re, Cu, Ag, Ni, Co, W, or Eu is selected, and particularly preferably Ir, Au, Pt, W, or Os is selected.

[0126] Ar1 and Ar2, each occurrence of which may be the same or different, is a cyclic group, wherein Ar1 contains at least one donor atom, i.e., an atom with a lone pair of electrons such as nitrogen, through which the cyclic group is coordinately linked to the metal; wherein Ar2 contains at least one carbon atom, through which the cyclic group is linked to the metal; Ar1 and Ar2 are linked together by a covalent bond, and each may carry one or more substituents, and they may also be linked together through the substituents; L’, each occurrence of which may be the same or different, is a bidentate chelating auxiliary ligand, preferably a monoanionic bidentate chelating ligand; q1 may be 0, 1, 2 or 3. Preferably, it is 2 or 3; q2 may be 0, 1, 2 or 3, preferably 1 or 0. Examples of the organic ligand may be selected from phenylpyridine derivatives or 7,8-benzoquinoline derivatives. All of these organic ligands may be substituted, for example, by an alkyl chain or a fluorine- or silicon-containing substituent. The auxiliary ligand may preferably be selected from acetylacetone or picric acid.

[0127] Examples of materials and their applications of some triplet emitters can be found in the following patent documents and literature: WO200070655, WO200141512, WO200202714, WO200215645, WO2005033244, WO2005019373, US20050258742, US20070087219, US20070252517, US2008027220, WO2009146770, US20090061681, US20090061681, WO2009118087, WO2010015307, WO2010054731, WO2011157339, WO2012007087, WO201200708, WO2013107487, WO2013094620, WO2013174471, WO 2014031977, WO 2014112450, WO2014007565, WO 2014024131, Baldo et al. Nature (2000), 750, Adachi et al. Appl. Phys. Lett. (2001), 1622, Kido et al. Appl. Phys. Lett. (1994), 2124, Wrighton et al. J. Am. Chem. Soc. (1974), 998, Ma et al. Synth. Metals (1998), 245. The entire contents of the above-listed patent documents and literature are hereby incorporated herein by reference. Some examples of suitable triplet emitters are listed below:

[0128]

[0129] 2. Singlet Emitter

[0130] 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.

[0131] In a preferred embodiment, the singlet emitter may be selected from monostyrylamine, distyrylamine, tristyrylamine, tetrastearylamine, styrylphosphine, styrylether, and arylamine.

[0132] 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 rings or heterocyclic 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, and the diarylamine group is preferably linked to the 1 - or 1,6 - positions of pyrene.

[0133] 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.

[0134] An example of a singlet emitter based on stilbene and its derivatives is US 5121029.

[0135] 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.

[0136] 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, tetracene, 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 pyrrolopyrrole dione. Examples of some singlet emitter materials can be found in the following patent documents: US20070252517 A1, US 4769292, US 6020078, US 2007 / 0252517 A1, US 2007 / 0252517 A1. The entire contents of the above-listed patent documents are hereby incorporated herein by reference.

[0137] Examples of some suitable singlet emitters are listed below:

[0138]

[0139] 3. Thermally activated delayed fluorescence emitting materials (TADF materials)

[0140] 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 the heavy atom center, the high cost of phosphorescent materials, poor material stability, and severe efficiency roll-off of the device limit their application in OLEDs. Thermally activated delayed fluorescence emitting 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 fully utilize 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, and the price is cheap without the need for precious metals, showing broad application prospects in the field of OLEDs.

[0141] 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, and 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 contents of the above-listed patents or article documents are hereby incorporated herein by reference.

[0142] Some examples of suitable TADF-emitting materials are listed below:

[0143]

[0144] The organic functional material publications mentioned above are incorporated into this application by reference for the purpose of disclosure.

[0145] Another object of the present invention is to provide a material solution for printed OLEDs.

[0146] For this purpose, for H1 and H2 in the mixture according to the present invention, at least one of them has a molecular weight ≥ 700 mol / kg, preferably ≥ 900 mol / kg, very preferably ≥ 900 mol / kg, more preferably ≥ 1000 mol / kg, and most preferably ≥ 1100 mol / kg.

[0147] In certain embodiments, for the mixture according to the present invention, at 25 °C, its solubility in toluene is ≥ 10 mg / ml, preferably ≥ 15 mg / ml, and most preferably ≥ 20 mg / ml.

[0148] The present invention also provides a composition comprising at least one mixture according to the present invention and at least one organic solvent.

[0149] In some embodiments, for the composition according to the present invention, the mixture serves as a singlet host material.

[0150] In some embodiments, for the composition according to the present invention, the mixture serves as a triplet 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 guest material, a thermally activated delayed fluorescence emitting material, and a mixture according to the present invention.

[0153] In a preferred embodiment, the composition according to the present invention is a solution.

[0154] In another preferred embodiment, the composition according to the present invention is a suspension.

[0155] The composition in the embodiments of the present invention may include 0.01 to 20 wt% of an organic compound, preferably 0.1 to 15 wt%, more preferably 0.2 to 10 wt%, and most preferably 0.25 to 5 wt% of the organic compound.

[0156] In some preferred embodiments, the composition according to the invention, wherein the 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 solvents.

[0157] In other preferred embodiments, the composition according to the invention, which contains at least 50 wt% of aromatic or heteroaromatic solvent; preferably at least 80 wt% of aromatic or heteroaromatic solvent; particularly preferably at least 90 wt% of aromatic or heteroaromatic solvent.

[0158] Examples of aromatic or heteroaromatic solvents according to the 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.

[0159] In other embodiments, suitable and preferred solvents are aliphatic, cycloaliphatic or aromatic hydrocarbons, amines, thiols, amides, nitriles, esters, ethers, polyethers, alcohols, diols or polyols.

[0160] In other embodiments, the alcohol represents a suitable class of solvents. Preferred alcohols include alkyl cyclohexanols, especially methylated aliphatic alcohols, naphthols, etc.

[0161] The solvent may be a cycloalkane, such as decalin.

[0162] The solvent may be used alone or as a mixture of two or more organic solvents.

[0163] In some embodiments, the composition according to the present invention comprises an organic functional compound 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 their mixtures.

[0164] In some preferred embodiments, the solvents particularly suitable for the present invention are solvents having Hansen solubility parameters in the following ranges:

[0165] δ d (dispersion force) ranges from 17.0 to 23.2 MPa 1 / 2 and particularly in the range from 18.5 to 21.0 MPa 1 / 2 ;

[0166] δ p (polar force) ranges from 0.2 to 12.5 MPa 1 / 2 and particularly in the range from 2.0 to 6.0 MPa 1 / 2 ;

[0167] δ h (hydrogen bond force) ranges from 0.9 to 14.2 MPa 1 / 2 and particularly in the range from 2.0 to 6.0 MPa 1 / 2 ;

[0168] For the composition according to the present invention, the organic solvent is selected considering its boiling point parameter. In the present invention, the boiling point of the organic solvent ≥ 150 °C; preferably ≥ 180 °C; more preferably ≥ 200 °C; still more preferably ≥ 250 °C; most preferably ≥ 275 °C or ≥ 300 °C. Boiling points within these ranges are beneficial for preventing nozzle blockage of the inkjet print head. The organic solvent can evaporate from the solvent system to form a thin film containing the functional material.

[0169] In some preferred embodiments, the composition according to the present invention

[0170] 1) has a viscosity @ 25 °C in the range of 1 cPs to 100 cPs, and / or

[0171] 2) has a surface tension @ 25 °C in the range of 19 dyne / cm to 50 dyne / cm.

[0172] 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.

[0173] 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; 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.

[0174] 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.

[0175] 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; preferably in the range of 1 cps to 50 cps; most preferably in the range of 1.5 cps to 20 cps.

[0176] The ink obtained with an 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.

[0177] Another object of the present invention is to provide the application of the above mixture in an organic electronic device.

[0178] 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.

[0179] Another object of the present invention is to provide a method for preparing the above electronic device.

[0180] The specific technical solution is as follows: A preparation method, in which the above-mentioned organic compound H1 and organic compound H2 are used to form a functional layer on a substrate by co-evaporation, or the above-mentioned mixture is used as Premix to form a functional layer on a substrate by co-evaporation, or the above-mentioned 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, brush coating or pad printing, slot die coating, etc.

[0181] The present invention also relates to the use of the above-mentioned composition as a printing ink in the preparation of organic electronic devices, and particularly preferably by a preparation method of printing or coating.

[0182] 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, brush coating 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.

[0183] For the preparation method as described above, the formed functional layer has a thickness of 5 nm - 1000 nm.

[0184] The present invention further relates to an organic electronic device, which at least contains an organic mixture 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 the functional layer at least contains an organic mixture as described above.

[0185] In a more preferred embodiment, the above-described organic electronic device is an electroluminescent device, particularly an organic light-emitting diode (OLED), which includes a substrate, an anode, at least one light-emitting layer, and a cathode.

[0186] 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 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).

[0187] 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 a preferred embodiment, the absolute value of the difference between the work function of the anode and the HOMO energy level or valence band energy level of the light-emitting body in the light-emitting layer or the p-type semiconductor material serving as the HIL or HTL 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.

[0188] 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 a preferred 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 substance 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.

[0189] 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.

[0190] 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 (Premix) according to the present invention.

[0191] 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.

[0192] 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.

[0193] 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.

[0194] 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.

[0195] 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.

[0196] Synthesis of Compounds in Example 1

[0197] Synthesis of Compounds 1-1 and 1-2:

[0198]

[0199] Add (4-(9-phenyl-9H-carbazol-3-yl)phenyl)boronic acid (7.2 g, 20 mmol), 2,4-dichloro-6-phenyl-1,3,5-triazine (2.2 g, 10 mmol) and a 2.00 mol / L sodium carbonate solution (4.12 g, 40 mmol) into a three-necked flask, stir and dissolve with 100 ml of toluene, protect with nitrogen, then add Pd(pph3)4 (1.13 g, 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 150 ml of saturated brine, dry with anhydrous sodium sulfate, then evaporate to remove the solvent, and purify the residue by column chromatography with DCM / PE (1:4) to obtain about 6.4 g of white solid compound 1-1 with a yield of 80%.

[0200]

[0201] Add 4'-(4-boronic acid phenyl)-2,2':6',2”-terpyridine (7.0 g, 20 mmol), 3,6-dibromo-9-phenylcarbazole (4.0 g, 10 mmol) and a 2.00 mol / L sodium carbonate solution (4.12 g, 40 mmol) into a three-necked flask, stir and dissolve with 100 ml of toluene, protect with nitrogen, then add Pd(pph3)4 (1.13 g, 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 150 ml of saturated brine, dry with anhydrous sodium sulfate, then evaporate to remove the solvent, and purify the residue by column chromatography with DCM / PE (1:4) to obtain about 6.9 g of white solid compound 1-2 with a yield of 80%.

[0202] Other compounds can be synthesized in a similar manner and are summarized as follows:

[0203]

[0204] Energy level structure of the compound in Example 2

[0205] The energy levels of the organic compound material can be obtained by quantum calculation. For example, using TD-DFT (Time-Dependent Density Functional Theory) through Gaussian09W (Gaussian Inc.). The specific simulation method can be referred to WO2011141110. First, optimize the molecular geometry structure with the semi-empirical method "Ground State / Semi-empirical / Default Spin / AM1" (Charge 0 / Spin Singlet), and then calculate the energy structure of the organic molecule 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.

[0206] HOMO (eV) = ((HOMO(G) × 27.212) - 0.9899) / 1.1206

[0207] LUMO (eV) = ((LUMO(G) × 27.212) - 2.0041) / 1.385

[0208] Where HOMO(G) and LUMO(G) are the direct calculation results of Gaussian 09W, and the unit is Hartree. The results are shown in Table 1 below:

[0209] Table 1

[0210]

[0211] Preparation of the mixture in Example 3

[0212] The mixtures 1 - 13 of the present invention are mixed according to the following compound combination methods.

[0213]

[0214]

[0215] Mixing method of mixture1: Take H1 and H2 with a mass ratio of 1:1 in a cavity with a vacuum degree less than 10 -3 Torr, heat up to the molten state for sufficient mixing, then cool down to room temperature, and grind the mixed solid.

[0216] The mixing methods of mixtures 2 - 13 and comparative mixtures 1 - 2 are the same as that of mixture 1.

[0217] Among them, the structural formulas of compounds A, B, C, and D are as follows;

[0218]

[0219] Preparation of the composition of Example 4

[0220] The preparation method of the composition is as follows:

[0221] Place a magnetic stir bar in a vial, clean it and transfer it to a glove box. Prepare 9.8 g of 3-phenoxytoluene solvent in the vial. Weigh 0.2 g of each of Mixtures 1 - 13 in the glove box and add them to the solvent system in the vial, then stir and mix. Stir at a temperature of 60 °C - 80 °C until the organic mixture is completely dissolved, and then cool to room temperature. Filter the obtained organic mixture solution through a 0.2-μm PTFE membrane, seal and store it.

[0222] The viscosity of the organic composition was measured by a DV-I Prime Brookfield rheometer; the surface tension of the organic composition was measured by a SITA bubble pressure tensiometer.

[0223] Through the above tests, the viscosities of the obtained compositions were all in the range of 2.7 ± 0.5 cPs - 6.9 ± 0.4 cPs, and the surface tensions were in the range of 28.0 ± 0.5 dyne / cm - 39.0 ± 0.5 dyne / cm.

[0224] In further experiments, Compositions were prepared from Mixtures 1 - 13 in the following solvents: 1-tetralone, tetralin, 1-methoxynaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-p-cymene, isopropylbiphenyl, diamylbenzene, o-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, dodecylbenzene, 4-isopropylbiphenyl, benzyl benzoate, 1,1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, dibenzyl ether. The viscosities of the obtained compositions were all in the range of 2 - 15 cPs, and the viscosity could be further adjusted by a combined solvent and other methods to meet the requirements of technologies such as inkjet printing.

[0225] The above composition, plus 5 wt% - 10 wt% of the guest, can be used as the printing ink for the light-emitting layer in OLEDs. The obtained composition can be used for the preparation of printed OLEDs.

[0226] Preparation and Characterization of OLED Devices in Example 5: OLED1 - OLED13, Comparative OLEDs

[0227] Using Mixture 1 - Mixture 13 and Comparative Mixture 1 - Comparative Mixture 2 as the host materials respectively, the complexes of Ir in the following structural formula as the luminescent materials (GD is the green light guest, RD is the red light guest), HATCN as the hole injection material, SFNFB as the hole transport material, NaTzF2 as the electron transport material, and Liq as the electron injection material, an electroluminescent device with the device structure of ITO / HATCN / SFNFB / host material:guest (10%) / NaTzF2:Liq / Liq / Al is constructed.

[0228]

[0229] The above materials HATCN, SFNFB, GD (Ir(p - ppy)3), RD, NaTzF2, and Liq are all commercially available. For example, from Jilin OLED Material Tech Co., Ltd (www.jl - oled.com), or their synthesis methods are all prior arts. For details, refer to the references in the prior arts and will not be elaborated here.

[0230] The preparation process of the above - mentioned OLED device will be described in detail through specific examples below. The structure of the OLED device is: ITO / HATCN / SFNFB / host material:guest (10%) / NaTzF2:Liq / Liq / Al. The preparation steps are as follows:

[0231] a. Cleaning of the ITO (indium tin oxide) conductive glass substrate: Clean it with various solvents (such as one or several of chloroform, acetone, or isopropyl alcohol), and then perform ultraviolet ozone treatment;

[0232] b. HATCN (30 nm), SFNFB (50 nm), host material:guest (40 nm), NaTzF2:Liq (30 nm), Liq (1 nm), and Al (100 nm) are thermally evaporated in a high vacuum (1×10 -6 mbar);

[0233] c. Encapsulation: The device is encapsulated with ultraviolet - curable resin in a nitrogen glove box.

[0234] The other steps of OLED6b and 13b are the same as above, except that the two hosts are co - evaporated from two separate sources instead of being evaporated as a mixture.

[0235] 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 green light OLED device are shown in Table 2 below, where the lifetime is relative to the comparative device OLED1:

[0236] Table 2

[0237]

[0238] The experimental results of the red OLED device are shown in Table 3 below. The lifetime is relative to the comparative device OLED5:

[0239] Table 3

[0240]

[0241]

[0242] 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.

[0243] 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 still be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the invention patent should be subject to the appended claims.

Claims

1. An organic mixture comprising compound 1 and compound 2, characterized in that, Compound 1 has the structure shown in general formula (I), and compound 2 has the structure shown in general formula (II): B—A—B (I) A—B—A (II) wherein A and B are different groups, the A group is selected from the structures having electron transport properties shown below, wherein, m is any integer from 1 to 3; X 1 -X 8 is selected from CR 301 or N, and at least one is N; M 1 -M 3 is a single bond or C(R 301 )2 or O or S; R, R 1 , R 2 and R 301 are selected from the following groups: hydrogen, deuterium, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl, and the B group is selected from the structures with hole transport properties shown below, Among them, Y represents an aromatic group or heteroaromatic group having 5 to 40 carbon atoms; Z 1 , Z 2 , Z 3 are each independently selected from a single bond, N(R 302 ), C(R 302 )2, Si(R 302 )2, O, S, C═N(R 302 ), C═C(R 302 )2, and P(R 302 ); R0, R1, R2, and R 302 are each independently selected from the following groups: alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl, and heteroaryl; alternatively, the A group is selected from the structures having electron transport properties shown below, wherein, m is any integer from 1 to 3; X 1 -X 8 is selected from CR 301 or N, and at least one of them is N; M 1 -M 3 is a single bond or C(R 301 )2 or O or S; R, R 1 , R 2 and R 301 are selected from the following groups: hydrogen, deuterium, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl, while the B group is selected from the structures shown below: alternatively, the A group is selected from the structures shown below: meanwhile the B group is selected from the structures having hole transport properties shown below, wherein, Y represents an aromatic group or heteroaromatic group having 5 to 40 carbon atoms; Z 1 , Z 2 , Z 3 are each independently selected from a single bond, N(R 302 ), C(R 302 )2, Si(R 302 )2, O, S, C═N(R 302 ), C═C(R 302 )2, and P(R 302 ); R0, R1, R2, and R 302 are each independently selected from the following groups: alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl, and heteroaryl.

2. The organic mixture according to claim 1, characterized in that, one or more H in the A and B groups are further replaced by D.

3. The organic mixture according to claim 1, characterized in that, 1) The difference between the LUMO and / or HOMO of Compound 1 and Compound 2 is less than or equal to 0.3 eV; or 2) ΔE of Compound 1 or Compound 2 ST is less than or equal to 0.3 eV.

4. The organic mixture according to claim 1, characterized in that, The organic mixture contains at least one other organic functional material, and the at least one other organic functional material is selected from hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, organic matrix materials, singlet emitters, triplet emitters, thermally activated delayed fluorescence materials.

5. A composition, characterized in that, It contains at least one organic mixture as described in any one of claims 1-4, and at least one organic solvent.

6. An organic electronic device, comprising at least one organic mixture as described in any one of claims 1-4.

7. The organic electronic device according to claim 6, wherein, The organic electronic device is selected from organic light-emitting diodes, organic photovoltaic cells, organic light-emitting cells, organic field-effect transistors, organic light-emitting field-effect transistors, organic lasers, organic spintronic devices, organic sensors, and organic plasmon-emitting diodes.

8. The organic electronic device according to claim 6, wherein The organic electronic device comprises a light-emitting layer, and the light-emitting layer contains at least one organic mixture as described in any one of claims 1-4.

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