An organic mixture and its use in organic electronic devices

Abstract

Disclosed is an organic mixture and its use in organic electronic devices, in particular in organic electroluminescent diodes. Further disclosed is an organic electronic device, in particular an organic electroluminescent diode, comprising a mixture according to the invention and its use in display and lighting technology. By device structure optimization, better device performance can be achieved, in particular 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] This invention relates to the field of organic electronic materials and devices, and in particular to an organic mixture, compositions comprising the mixture, organic electronic devices, and their applications in the field of organic electroluminescence. Background Technology

[0002] Organic light-emitting diodes (OLEDs) possess excellent properties such as light weight, active emission, wide viewing angle, high contrast, high luminous efficiency, low energy consumption, and ease of fabrication into flexible and large-size panels, making them the most promising next-generation display technology in the industry. To improve the luminous efficiency of OLEDs and advance their large-scale industrialization, the key issues that urgently need to be addressed are luminous performance and lifespan.

[0003] The host material is crucial for obtaining high-performance organic light-emitting diodes (OLEDs). Currently, OLED devices are generally fabricated using a single host material paired with an emitter. However, a single host material can cause variations in carrier transport rates, leading to a significant roll-off in device efficiency at high brightness, thus shortening device lifetime. Using dual host materials can mitigate some of the problems associated with single host materials. In particular, by using appropriate material combinations, the selected dual host materials can effectively form exciplexes, significantly improving the luminous efficiency and lifetime 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, high-efficiency OLEDs by utilizing a co-host that can form exciplexes, along with a metal complex as a phosphorescent emitter.

[0004] Furthermore, in vapor-deposited devices, pre-forming a blend of the two host materials can greatly simplify the vapor deposition process and significantly improve device lifespan (patents US2016141505A1, WO2016060332A1, WO2016068450A1, WO2016068460A1, etc.). However, vacuum vapor deposition is expensive and requires highly precise processing, such as the need for extremely precise shadow masks, which limits the application of organic light-emitting diodes (OLEDs) as large-area, low-cost display and lighting devices. In contrast, solution processing techniques such as inkjet printing and roll-to-roll printing offer significant advantages, including the elimination of precision shadow masks, greenhouse processes, high material utilization, and good scalability, making them promising technologies for fabricating organic optoelectronic devices, especially OLED displays. Suitable printing inks and materials are crucial for successful fabrication. Patent CN102498120A provides an effective method for preparing organic small-molecule functional materials suitable for solution processing. However, designing efficient co-substrate material systems remains a challenge for inkjet printing. For example, in typical co-substrate materials, the two components often have significantly different structures, resulting in varying solubility and film-forming properties in the same solvent, thus affecting process stability and device performance.

[0005] Therefore, new materials suitable for printing processes, especially the main material system, need to be developed. Summary of the Invention

[0006] Based on this, the purpose of the present invention is to provide an organic mixture and its application in organic electronic devices, and in particular to provide a new solution for the design and development of co-host materials.

[0007] The specific technical solution is as follows:

[0008] This invention provides an organic mixture comprising compound 1 (H1) and compound 2 (H2), wherein compound 1 (H1) has the structure shown in general formula (I) and compound 2 (H2) has the structure shown in general formula (II):

[0009] BAB (I)

[0010] AB (II)

[0011] In this system, A and B are each independently selected from substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 50 ring atoms, or aryloxy or heteroaryloxy groups having 5 to 50 ring atoms, or combinations thereof, wherein one or more A and B groups can form monocyclic or polycyclic aliphatic or aromatic ring systems with each other and / or with the rings they are bonded to; the two B groups of general formula (I) can be substituted with the same or different substituents; one or more H groups in the A and B groups described above can be further substituted with D.

[0012] The mixture according to the present invention further comprises at least one other organic functional material, which may be 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 excited delayed fluorescence materials, and organic dyes.

[0013] The present invention also provides a composition comprising at least one mixture as described above, and at least one organic solvent.

[0014] The present invention also provides the use of the mixture or composition described above in organic electronic devices.

[0015] The present invention provides an organic electronic device comprising at least one mixture as described above.

[0016] Beneficial effects: According to the mixture of the present invention, 1) since compounds 1 (H1) and 2 (H2) have structurally similar segments, they help maintain similar solubility and film-forming properties in the solvent, and help maintain the amorphous morphology of the film after film formation; 2) the energy level structure can be adjusted by using different combinations of A and B groups; 3) the combination of n and p type groups of the present invention helps to separate and optimize the transport channels of holes and electrons in the film. Organic electroluminescent devices prepared by such mixtures have high luminous efficiency and long device lifetime. Detailed Implementation

[0017] This invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of this invention.

[0018] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the specification of this invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0019] In this invention, the main material, matrix material, host material, and matrix material have the same meaning and can be used interchangeably.

[0020] In this invention, organometallic complexes, organometallic coordination compounds, and organometallic coordination compounds have the same meaning and can be used interchangeably.

[0021] In this invention, composition, printing ink, ink, and ink have the same meaning and can be used interchangeably.

[0022] This invention provides an organic mixture comprising compound 1 (H1) and compound 2 (H2), wherein compound 1 (H1) has the structure shown in general formula (I) and compound 2 (H2) has the structure shown in general formula (II):

[0023] BAB (I)

[0024] AB (II)

[0025] In the above general formula, A and B are each independently selected from substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 50 ring atoms, or aryloxy or heteroaryloxy groups having 5 to 50 ring atoms, or combinations of these systems, wherein one or more A groups and B groups can form monocyclic or polycyclic aliphatic or aromatic ring systems with each other and / or with the rings they are bonded to; the two groups B in general formula (I) can be substituted by the same or different substituents; one or more H groups in each of the A and B groups mentioned above can be further substituted by D.

[0026] In some embodiments, A and B are selected from the same group; in some preferred embodiments, A and B are selected from different groups.

[0027] In some preferred embodiments, A and B are distinct groups, each selected from substituted or unsubstituted aromatic or heteroaromatic ring systems having 9 to 50 ring atoms, or aryloxy or heteroaryloxy groups having 9 to 50 ring atoms, or combinations thereof, wherein one or more A and B groups may form monocyclic or polycyclic aliphatic or aromatic ring systems with each other and / or with the rings bonded to said groups. One or more H atoms in each of the A and B groups described above may further be substituted with D.

[0028] In some more preferred embodiments, A and B are distinct groups, each selected from substituted or unsubstituted aromatic or heteroaromatic ring systems having 12 to 40 ring atoms, or aryloxy or heteroaryloxy groups having 12 to 40 ring atoms, or combinations thereof, wherein one or more A and B groups may form monocyclic or polycyclic aliphatic or aromatic ring systems with each other and / or with the rings bonded to said groups. One or more H atoms in each of the A and B groups described above may further be substituted with D.

[0029] In some particularly preferred embodiments, A and B are distinct groups, each selected from substituted or unsubstituted aromatic or heteroaromatic ring systems having 14 to 450 ring atoms, or aryloxy or heteroaryloxy groups having 14 to 50 ring atoms, or combinations of these groups, wherein one or more A and B groups may form monocyclic or polycyclic aliphatic or aromatic ring systems with each other and / or with the rings bonded to said groups. One or more H atoms in each of the A and B groups described above may further be substituted with D.

[0030] In a preferred embodiment, the aromatic ring system includes... One carbon atom, even better is One carbon atom, the heteroaromatic ring system contains [a certain number of carbon atoms], the ring system contains [a certain number of carbon atoms]. One carbon atom, even better is The device comprises 1 carbon atom and at least 1 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 from Si, N, P, O and / or S, and even more particularly preferably from N, O or S.

[0031] The aromatic ring systems or aromatic groups described above refer to hydrocarbon groups containing at least one aromatic ring, including monocyclic groups and polycyclic ring systems. The heterocyclic ring systems or heteroaromatic groups described above refer to hydrocarbon groups (containing heteroatoms) containing at least one heteroaromatic ring, including monocyclic groups and polycyclic ring systems. These polycyclic rings may have two or more rings, wherein two carbon atoms are shared by two adjacent rings, i.e., fused rings. At least one of these polycyclic ring types is aromatic or heteroaromatic. For the purposes of this invention, aromatic or heteroaromatic ring systems not only include systems containing aromatic or heteroaromatic groups, but also systems in which multiple aryl or heteroaromatic groups can 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). Therefore, systems such as 9,9'-spirodifluorene, 9,9-diarylfluorene, triarylamines, and diaryl ethers are also considered aromatic ring systems for this purpose of the invention.

[0032] Specifically, examples of aromatic groups include: benzene, naphthalene, anthracene, phenanthrene, dinaphthalene, tetraphenylene, pyrene, benzo[a]pyrene, triphenylene, acenaphthene, fluorene, spirofluorene and their derivatives.

[0033] Specifically, examples of heteroaromatic groups include: furan, benzofuran, dibenzofuran, thiophene, benzothiophene, dibenzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazolium, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furanolopyrrole, furanolofuran, thienofuran, benzoisoxazole, benzoisothiazazole, pyridine, pyrazine, pyrimidine, triazine, quinoline, isoquinoline, o-diazonine, quinoxaline, phenanthridine, primidine, quinazoline, quinazoline, and their derivatives.

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

[0035]

[0036] in,

[0037] A 1 A 2 A 3 A 4 A 5 A 6 A 7 A 8 CR are represented independently. 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 5It is H, D, or a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, or a silyl group, or a substituted ketone group having 1 to 20 carbon atoms, or an alkoxycarbonyl group having 2 to 20 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, a cyano group (-CN), a carbamoyl group (-C(=O)NH2), a halogen Formyl group (-C(=O)-X where X represents a halogen atom), formyl group (-C(=O)-H), isocyanate group, isocyanate group, thiocyanate group or isothiocyanate group, hydroxy group, nitro group, CF3 group, Cl, Br, F, crosslinkable group or substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or combination of these groups, wherein one or more R 3 R 4 R 5 Groups can form monocyclic or polycyclic aliphatic or aromatic rings with each other and / or with the rings they are bonded to.

[0040] In some preferred embodiments, A and B may further be selected to include one or more combinations of the following groups, wherein the H on the ring can be arbitrarily substituted:

[0041]

[0042] In some embodiments, the two B groups in general formula (I) may be replaced by different substituents.

[0043] In a preferred embodiment, the two B groups in general formula (I) are substituted with the same substituents.

[0044] In a particularly preferred embodiment, general formula (I) has a symmetrical structure centered on A.

[0045] In some embodiments, the A groups on the left and right sides of general formula (II) can be replaced by different substituents.

[0046] In a preferred embodiment, the left segment BA or the right segment AB in formula (II) and formula (I) have exactly the same structure.

[0047] In some embodiments, in the general formula (I) of compound 1 (H1) and the general formula (II) of compound 2 (H2), the A group and the B group are independently selected from groups having electron transport properties or groups having hole transport properties.

[0048] In some preferred embodiments, in general formula (I) of compound 1 (H1) and general formula (II) of compound 2 (H2), group A is selected from groups having electron transport properties and group B is selected from groups having hole transport properties.

[0049] In some other preferred embodiments, in general formula (I) of compound 1 (H1) and general formula (II) of compound 2 (H2), the B group is selected from groups having electron transport properties and the A group is selected from groups having hole transport properties.

[0050] In some preferred embodiments, the group having electron transport properties comprises one or more combinations of the following structures:

[0051]

[0052] Where m is any integer from 1 to 3; X 1 –X 8 Selected from CR 301 Or N, and at least one of them is N; M 1 -M 3 For single bonds or C(R) 301 )2 or O or S; R, R 1 R 2 R 301 It can be independently selected from the following groups: hydrogen, deuterium, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl, and heteroaryl.

[0053] In some preferred embodiments, R, R 1 R 2 R 301 It may be independently selected from H, or a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, or a substituted or unsubstituted silyl group, or a substituted ketone group having 1 to 20 carbon atoms, or an alkoxycarbonyl group having 2 to 20 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, cyano (-CN), carbamoyl (-C(=O)NH2), or haloformyl (-C(=O)). -X (where X represents a halogen atom), formyl (-C(=O)-H), isocyanate, isocyanate, thiocyanate or isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F, crosslinkable groups, or 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 bonded to said groups. One or more H atoms in the various groups described above may further be substituted with D.

[0054] In some preferred embodiments, R, R 1 R 2 R 301 It may be independently 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 ketone 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), or haloformyl (-C(=O)). -X (where X represents a halogen atom), formyl (-C(=O)-H), isocyanate, isocyanate, thiocyanate or isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F, crosslinkable groups, or substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 20 ring atoms, or aryloxy or heteroaryloxy groups having 5 to 20 ring atoms, or combinations of these systems, wherein one or more groups may form monocyclic or polycyclic aliphatic or aromatic ring systems with each other and / or with the rings bonded to said groups. One or more H atoms in the various groups described above may further be substituted with D.

[0055] In a preferred embodiment, R, R 1 R 2 R 301 The following groups are preferred individually: methyl, isopropyl, tert-butyl, isobutyl, hexyl, octyl, 2-ethylhexyl, benzene, biphenyl, naphthalene, anthracene, phenanthrene, benzo[a]phenanthrene, pyrene, pyrimidine, pyrimidine, triazine, fluorene, thiofluorene, silylfluorene, carbazole, thiophene, furan, thiazole, triphenylamine, triphenylphosphine oxide, tetraphenylsilane, spirofluorene, spirosilylfluorene, etc.; more preferred are methyl, isopropyl, tert-butyl, isobutyl, benzene, biphenyl, naphthalene, anthracene, phenanthrene, benzo[a]phenanthrenefluorene, spirofluorene, etc.

[0056] In some other preferred embodiments, the group having hole transport properties comprises one or more combinations of the structures shown below:

[0057]

[0058] Wherein, Y represents an aromatic group or heteroaromatic group with 5 to 40 carbon atoms; Z 1 Z 2 Z 3 Selected independently from single bonds, N(R) 302 ), C(R 302 )2、Si(R 302 )2、O、S、C=N(R 302 ), C = C(R)302 )2 or P(R 302 R0, R1, R2 and R 302 Each of the following is independently selected from alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl, and heteroaryl groups.

[0059] In a more preferred embodiment, the base A having hole transport properties is selected from one of the following formulas:

[0060]

[0061] Among them, Z 2 Z 3 The meanings of R0 are as described above.

[0062] In a more preferred embodiment, the group having hole transport properties is selected from one of the following formulas:

[0063]

[0064] Among them, R0 and R 302 The meaning of is as described above.

[0065] In other facility designs, group A or group B may also include a group having the following structure:

[0066]

[0067] Furthermore, in an organic mixture according to the invention, group A or group B comprises one or a combination of the following structural units, which may be further substituted:

[0068]

[0069] Where n is 1, 2, 3, or 4.

[0070] In this embodiment of the invention, the energy level structure of the organic material, the triplet energy level E T HOMO and LUMO play a crucial role. The determination of these energy levels will be introduced below.

[0071] HOMO and LUMO energy levels can be measured using the photoelectric effect, such as XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectroscopy), or cyclic voltammetry (CV). Recently, quantum chemical methods, such as density functional theory (DFT), have also become effective methods for calculating molecular orbital energy levels.

[0072] triplet energy level E of organic materials TIt can be measured by low-temperature time-resolved emission spectroscopy or obtained through quantum simulation calculations (such as time-dependent DFT), such as using commercial software Gaussian 03W (Gaussian Inc.); singlet energy levels E of organic materials S It can also be obtained through quantum simulation calculations (such as through Time-dependent DFT). Specific simulation methods can be found in WO2011141110 or as described below in the embodiments.

[0073] It should be noted that HOMO, LUMO, and E S E T The absolute value depends on the measurement or calculation method used. Even for the same method, different evaluation methods, such as those at the starting point and peak point on the CV curve, can give different HOMO / LUMO values. Therefore, a reasonable and meaningful comparison should be made using the same measurement method and the same evaluation method. In the description of the embodiments of this invention, HOMO, LUMO, and E are used... T The value is based on a simulation of the Time-dependent DFT, but does not affect the application of other measurement or calculation methods.

[0074] In this 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.

[0075] For an organic compound, its ΔE ST Defined as the energy difference between singlet and triplet states, i.e., E S -E T Its ΔLUMO is defined as (LUMO+1)-LUMO, and its ΔHOMO is defined as HOMO-(HOMO-1).

[0076] Preferably, an organic mixture according to the present invention, compounds 1 (H1) and 2 (H2), needs to satisfy certain energy level structure restrictions.

[0077] In some embodiments, the difference between the LUMO and / or HOMO of H1 and H2 is ≤0.3eV, i.e., |HOMO(H1)-HOMO(H2)|≤0.3eV and / or |LUMO(H1)-LUMO(H2)|≤0.3eV.

[0078] In some preferred embodiments, the difference between the LUMO and / or HOMO of H1 and H2 is ≤0.2eV, i.e., |HOMO(H1)-HOMO(H2)|≤0.2eV and / or |LUMO(H1)-LUMO(H2)|≤0.2eV.

[0079] In some preferred embodiments, the difference between the LUMO and / or HOMO of H1 and H2 is ≤0.1eV, i.e., |HOMO(H1)-HOMO(H2)|≤0.1eV and / or |LUMO(H1)-LUMO(H2)|≤0.1eV.

[0080] 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.

[0081] According to the present invention, in an organic mixture, the ΔE of H1 or H2 is... ST ≤0.3eV.

[0082] In some preferred embodiments, the ΔE of H1 or H2 ST ≤0.2eV.

[0083] In some preferred embodiments, the ΔE of H1 or H2 ST ≤0.1eV.

[0084] In some preferred embodiments, the ΔE of H1 or H2 ST ≤0.05eV.

[0085] In some preferred embodiments, the ΔE of H1 or H2 ST ≤0.01eV.

[0086] In some preferred embodiments, H1 or H2 has a ΔHOMO ≥ 0.2 eV, preferably ≥ 0.25 eV, more preferably ≥ 0.3 eV, particularly preferably ≥ 0.35 eV, and most preferably ≥ 0.4 eV.

[0087] In other preferred embodiments, H1 or H2 has a ΔLUMO ≥ 0.2 eV, preferably ≥ 0.25 eV, more preferably ≥ 0.3 eV, particularly preferably ≥ 0.35 eV, and most preferably ≥ 0.4 eV.

[0088] In some embodiments, the organic mixture wherein H1 and H2 form a type II heterojunction structure.

[0089] In a preferred embodiment, the organic mixture has a minimum value of min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1)) ≤ min(E). T (H1),E T (H2)).

[0090] In a preferred embodiment, the organic mixture has a minimum value of min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1)) ≤ min(E). T (H1),E T (H2))-0.05eV.

[0091] In a more preferred embodiment, the organic mixture has a minimum value of min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1)) ≤ min(E). T (H1),E T (H2))-0.1eV.

[0092] In a very preferred embodiment, the organic mixture has a min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1)) ≤ min(E T (H1),E T (H2))-0.15eV.

[0093] In a most preferred embodiment, the organic mixture has a minimum value of min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1)) ≤ min(E). T (H1),E T (H2))-0.2eV.

[0094] In other embodiments, the organic mixture wherein H1 and H2 form a type I heterojunction structure.

[0095] According to the present invention, in an organic mixture, the mass ratio of H1 or H2 is 1:9 to 9:1.

[0096] In some preferred embodiments, the mass ratio of H1 or H2 is 3:7 to 7:3.

[0097] In some preferred embodiments, the mass ratio of H1 or H2 is 4:6 to 6:4.

[0098] In some preferred embodiments, the mass ratio of H1 to H2 is 5:5.

[0099] In a preferred embodiment, in the mixture according to the 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.

[0100] Furthermore, in an organic mixture according to the present invention, the physical properties of H1 and H2 need to meet certain requirements.

[0101] In a preferred embodiment, the organic mixture according to the invention, wherein the glass transition temperature T of H1 and / or H2 is... g ≥100℃, in a preferred embodiment, T g ≥120℃, in a preferred embodiment, T g ≥140℃, in a more preferred embodiment, T g ≥160℃, in a most preferred embodiment, T g ≥180℃.

[0102] For the first objective of this invention, it is to provide a common substrate material solution for vapor-deposited OLEDs. For this objective, the following preferred embodiments are available.

[0103] In a preferred embodiment, the organic mixture wherein 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; and most preferably, the difference in molecular weight does not exceed 60 Dalton.

[0104] In another preferred embodiment, the organic mixture wherein 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; and more preferably, the difference in sublimation temperature does not exceed 10 K.

[0105] In a preferred embodiment, the molecular weight of H1 and / or H2 in the mixture according to the invention is ≤1000 mol / kg, preferably ≤900 mol / kg, very preferably ≤850 mol / kg, more preferably ≤800 mol / kg, and most preferably ≤750 mol / kg.

[0106] According to the present invention, specific examples of the mixture are as follows (but not limited thereto), wherein n-1 (chemical formulas 1-1 to 55-1 below, where n represents an integer from 1 to 55) and n (chemical formulas 1 to 55 below) can be mixed to form the mixture, and n and n-2 (chemical formulas 51-2 to 55-2 below, where n represents an integer from 1 to 55) can be mixed to form the mixture:

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117] The present invention also relates to a method for synthesizing organic compounds according to general formula (I) or (II), wherein a reaction is carried out using a starting material containing an active group. These active starting materials contain at least one leaving group, such as bromine, iodine, boric acid, or borate ester. Suitable reactions for forming CC linkages are well known to those skilled in the art and described in the literature; particularly suitable and preferred coupling reactions are the SUZUKI, STILLE, and HECK coupling reactions.

[0118] Furthermore, the organic mixture according to the present invention also comprises at least one other organic functional material, which may be selected from hole injection materials (HIM), hole transport materials (HTM), hole blocking materials (HBM), electron injection materials (EIM), electron transport materials (ETM), electron blocking materials (EBM), organic matrix materials (Host), singlet emitters (fluorescent emitters), triplet emitters (phosphorescent emitters), thermally excited delayed fluorescence materials (TADF materials), and organic dyes. For example, various organic functional materials are described in detail in WO2010135519A1, US20090134784A1, and WO 2011110277A1, the entire contents of which are hereby incorporated herein by reference.

[0119] In a preferred embodiment, the other organic functional material is selected from fluorescent guest materials. Here, the organic mixture (H1+H2) according to the invention can be used as the host, and the guest material has a weight percentage of ≤10wt%, preferably ≤9wt%, more preferably ≤7wt%, even more preferably ≤6wt%, and most preferably ≤5wt%.

[0120] In a preferred embodiment, the other organic functional material is selected from phosphorescent guest materials. Here, the organic mixture (H1+H2) according to the invention can be used as the main body, and the guest weight percentage is ≤15wt%, preferably ≤12wt%, more preferably ≤9wt%, even more preferably ≤8wt%, and most preferably ≤7wt%.

[0121] In some embodiments, the other organic functional material is selected from TADF materials.

[0122] In other embodiments, the other organic functional material is selected from HTM materials.

[0123] The following provides a more detailed description (but is not limited to) of phosphorescent guest materials, singlet luminescent materials (i.e., fluorescent guest materials) and TADF materials.

[0124] 1. Triplet Emitter or Phosphorescent Guest Material

[0125] Triplet emitters are also known as 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 (which may appear the same or different times) is an organic ligand that is bonded or coordinated to the metal atom M through one or more sites, and n is an integer between 1 and 6. Preferably, the triplet emitter contains chelating ligands, i.e., ligands that coordinate with the metal through at least two binding sites. Particularly preferred is that the triplet emitter contains two or three identical or different bidentate or polydentate ligands. Chelating ligands are beneficial for 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:

[0126]

[0127] The metal atom M is selected from transition metals, lanthanides, or actinides, with preference given to Ir, Pt, Pd, Au, Rh, Ru, Os, Re, Cu, Ag, Ni, Co, W, or Eu, and especially Ir, Au, Pt, W, or Os.

[0128] Ar1 and Ar2, which may appear the same or different each time, are cyclic groups. Ar1 contains at least one donor atom, i.e., an atom with a lone pair of electrons, such as nitrogen, which is coordinated to the metal through its cyclic group. Ar2 contains at least one carbon atom, which is also coordinated to the metal through its cyclic group. Ar1 and Ar2 are covalently linked together and may each carry one or more substituents, and they may also be linked together through substituents. L', which may appear the same or different each time, is a bidentate auxiliary ligand, preferably a monoanionic bidentate ligand. q1 can be 0, 1, 2, or 3, preferably 2 or 3. q2 can be 0, 1, 2, or 3, preferably 1 or 0. Examples of organic ligands may be phenylpyridine derivatives or 7,8-benzoquinoline derivatives. All these organic ligands may be substituted, for example, with alkyl chains or fluorinated or silicon-containing compounds. The auxiliary ligand may preferably be selected from acetone acetate or picric acid.

[0129] Examples of materials and applications of some triplet luminescent materials can be found in the following patent documents and literature: WO200070655, WO200141512, WO200202714, WO200215645, WO2005033244, WO2005019373, US20050258742, US20070087219, US20070252517, US200802722 0,WO2009146770,US20090061681,US20090061681,WO2009118087,WO2010015307,WO201005473 1,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 patent documents and literature listed above are incorporated herein by reference. Examples of suitable triplet luminescent materials are listed in the table below:

[0130]

[0131] 2. Singlet Emitter

[0132] Singlet luminescent organisms often have a long conjugated π-electron system. Numerous examples exist to date, such as styreneamines and their derivatives disclosed in JP2913116B and WO2001021729A1, and indofluorenes and their derivatives disclosed in WO2008 / 006449 and WO2007 / 140847.

[0133] In a preferred embodiment, the singlet emitter may be selected from monostyreneamine, distyreneamine, tristyreneamine, tetrastyreneamine, styrenephosphine, styrene ether, and aromatic amine.

[0134] A monostyrene amine refers to a compound comprising an unsubstituted or substituted styrene group and at least one amine, preferably an aromatic amine. A distyrene amine refers to a compound comprising two unsubstituted or substituted styrene groups and at least one amine, preferably an aromatic amine. A tristyrene amine refers to a compound comprising three unsubstituted or substituted styrene groups and at least one amine, preferably an aromatic amine. A tetrastyrene amine refers to a compound comprising four unsubstituted or substituted styrene 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 for amines. An aryl amine or aromatic amine refers to a compound comprising three unsubstituted or substituted aromatic or heterocyclic systems directly linked to nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably a fused ring system and preferably has at least 14 aromatic ring atoms. Preferred examples include aromatic anthracene amines, aromatic anthracene diamines, aromatic pyrene amines, aromatic pyrene diamines, aromatic drosamines, and aromatic drosamines. An aromatic anthracene amine refers to a compound in which one diarylamine group is directly attached to anthracene, preferably at the 9-position. An aromatic anthracene diamine refers to a compound in which two diarylamine groups are directly attached to anthracene, preferably at the 9 or 10 positions. Aromatic pyrene amines, aromatic pyrene diamines, aromatic trehalamines, and aromatic trehaline diamines are similarly defined, wherein the diarylamine group is preferably attached to the 1 or 1,6 position of pyrene.

[0135] Examples, and preferred examples, of singlet luminescent materials based on ethyleneamine and aromatic amines 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 patent documents listed above are hereby incorporated herein by reference.

[0136] Examples of singlet luminescent organisms based on isostyrene and its derivatives include US 5121029.

[0137] Further preferred singlet luminescent materials may be indene-fluorene-amine and indene-fluorene-diamine, as disclosed in WO 2006 / 122630, benzo[a]indene-fluorene-amine and benzo[a]indene-fluorene-diamine, as disclosed in WO 2008 / 006449, and dibenzo[a]indene-fluorene-amine and dibenzo[a]indene-fluorene-diamine, as disclosed in WO2007 / 140847.

[0138] Other materials that can be used as singlet luminescent materials are polycyclic aromatic hydrocarbons, particularly derivatives of the following compounds: anthracene such as 9,10-di(2-naphthoanthracene), naphthalene, tetraphenyl, oxanthracene, phenanthrene, pyrene (such as 2,5,8,11-tetra-t-butylperylene), indene, phenylene such as (4,4'-bis(9-ethyl-3-carbazovinyl)-1,1'-biphenyl), diindene, decacyclicene, hexabenzobenzene, fluorene, spirodifluorene, Arylpyrene (e.g., US20060222886), arylethylene (e.g., US5121029, US5130603), cyclopentadiene such as tetraphenylcyclopentadiene, rubrene, coumarin, rhodamine, quinacridone, pyran such as 4(dicyanomethylene)-6-(4-p-dimethylaminostyryl-2-methyl)-4H-pyran (DCM), thiaran, bis(acrazinyl)imineborone compounds (US 2007 / 0092753A1), bis(acrazinyl)methylene compounds, carbostyryl compounds, oxazinones, benzoxazole, benzothiazole, benzimidazole, and pyrrolopyrroledione. Materials for some singlet luminescent 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 aforementioned patent documents are hereby incorporated herein by reference.

[0139] Below are some examples of suitable singlet luminescent organisms:

[0140]

[0141] 3. Thermally Excited Delayed Fluorescence (TADF) Materials

[0142] Traditional organic fluorescent materials can only utilize 25% of singlet excitons formed by electrical excitation to emit light, resulting in low internal quantum efficiency (maximum 25%). While phosphorescent materials, due to the strong spin-orbit coupling at the heavy atom centers enhancing intersystem crossing, can effectively utilize singlet and triplet excitons formed by electrical excitation to emit light, achieving an internal quantum efficiency of 100%, their high cost, poor material stability, and severe efficiency roll-off limit their application in OLEDs. Thermally activated delayed fluorescence (TERF) materials are the third generation of organic light-emitting materials developed after organic fluorescent and organic phosphorescent materials. These materials generally possess a small singlet-triplet energy level difference (ΔEst), allowing triplet excitons to transform into singlet excitons through anti-intersystem crossing. This fully utilizes singlet and triplet excitons formed under electrical excitation, achieving an internal quantum efficiency of 100%. Furthermore, the material structure is controllable, its properties are stable, and it is inexpensive, requiring no precious metals, making it a promising candidate for OLED applications.

[0143] TADF materials need to have a small singlet-triplet energy level difference, preferably ΔEst < 0.3 eV, second best ΔEst < 0.2 eV, and most preferably ΔEst < 0.1 eV. In one 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 luminescent materials can be found in the following patent documents: CN103483332(A), TW201309696(A), TW201309778(A), TW201343874(A), TW201350558(A), US20120217869(A1), WO2013133359(A1), WO2013154064(A1), Adachi, et al. Adv. Mater.,21,2009,4802,Adachi,et.al.Appl.Phys.Lett.,98,2011,083302,Adachi,et.al.Appl.Phys.Lett.,101,2012,093306,Adachi,et.al.Chem.Commun.,48,2012,11392,Adachi,et.al.Nature Photonics, 6, 2012, 253, Adachi, et.al. 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.Mate r.,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 patents or articles listed above are hereby incorporated herein by reference.

[0144] Below are some examples of suitable TADF luminescent materials:

[0145]

[0146] The above-mentioned publications on organic functional materials are incorporated herein by reference for the purpose of disclosure.

[0147] Another objective of this invention is to provide a material solution for printed OLEDs.

[0148] For this purpose, at least one of H1 and H2 in the mixture according to the invention 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.

[0149] In some embodiments, the mixture according to the invention has a solubility in toluene of ≥10 mg / ml, preferably ≥15 mg / ml, and most preferably ≥20 mg / ml at 25°C.

[0150] The present invention also provides a composition comprising at least one mixture described herein and at least one organic solvent.

[0151] In some embodiments, the composition according to the invention uses the mixture as a singlet host material.

[0152] In some embodiments, the composition according to the invention uses the mixture as a triplet host material.

[0153] In a preferred embodiment, the composition according to the invention comprises a guest material and a mixture according to the invention.

[0154] In another preferred embodiment, the composition according to the invention comprises a guest material, a thermally activated delayed fluorescence luminescent material, and a mixture according to the invention.

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

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

[0157] The compositions 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 an organic compound.

[0158] In some preferred embodiments, the solvent in the composition according to the invention is selected from aromatic or heteroaromatic compounds, esters, aromatic ketones or aromatic ethers, aliphatic ketones or aliphatic ethers, alicyclic or olefinic compounds, or inorganic esters such as borate esters or phosphate esters, or mixtures of two or more solvents.

[0159] In other preferred embodiments, the composition according to the invention contains 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-tetrahydronaphthylone, 3-phenoxytoluene, acetophenone, 1-methoxynaphthyl, p-diisopropylbenzene, pentanylbenzene, tetrahydronaphthyl, cyclohexylbenzene, chloronaphthyl, 1,4-dimethylnaphthyl, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butanediol, dodecylbenzene, 1-methylnaphthyl, 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 other embodiments, suitable and preferred solvents are aliphatic, alicyclic or aromatic, 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 alkylcyclohexanols, particularly methylated aliphatic alcohols, naphthols, etc.

[0163] The solvent may be a cycloalkane, such as decahydronaphthalene.

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

[0165] In some embodiments, the composition according to the invention comprises an organic functional compound as described above and at least one organic solvent, and may further comprise another organic solvent, examples of which include (but are not limited to): methanol, ethanol, 2-methoxyethanol, dichloromethane, trichloromethane, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4-dioxane, acetone, methyl ethyl ketone, 1,2-dichloroethane, 3-phenoxytoluene, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene, naphthane, indene, and / or mixtures thereof.

[0166] In some preferred embodiments, solvents particularly suitable for the present invention are those with Hansen solubility parameters within the following ranges:

[0167] δ d (Dispersion force) in the range of 17.0–23.2 MPa 1 / 2 The range, especially in the range of 18.5–21.0 MPa 1 / 2 Scope;

[0168] δ p (Polar force) in the range of 0.2–12.5 MPa 1 / 2 The range, especially 2.0–6.0 MPa 1 / 2 Scope;

[0169] δ h (Hydrogen bond strength) ranges from 0.9 to 14.2 MPa 1 / 2 The range, especially 2.0–6.0 MPa 1 / 2 The range.

[0170] In the compositions of the present invention, the boiling point of the organic solvent is taken into consideration when selecting it. In this invention, the boiling point of the organic solvent is ≥150°C; preferably ≥180°C; more preferably ≥200°C; even more preferably ≥250°C; and most preferably ≥275°C or ≥300°C. Boiling points within these ranges are beneficial for preventing nozzle clogging of the inkjet printhead. The organic solvent can evaporate from the solvent system to form a thin film containing functional materials.

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

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

[0173] 2) Its surface tension at 25℃ ranges from 19 dyne / cm to 50 dyne / cm.

[0174] In the compositions according to the present invention, the surface tension parameter of the organic solvent must be considered when selecting it. Suitable ink surface tension parameters are appropriate 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 approximately in the range of 19 dyne / cm to 50 dyne / cm; more preferably in the range of 22 dyne / cm to 35 dyne / cm; and most preferably in the range of 25 dyne / cm to 33 dyne / cm.

[0175] In a preferred embodiment, the ink according to the invention has a surface tension of about 19 dyne / cm to 50 dyne / cm at 25°C; more preferably, it is in the range of 22 dyne / cm to 35 dyne / cm; and most preferably, it is in the range of 25 dyne / cm to 33 dyne / cm.

[0176] According to the composition of the present invention, the organic solvent is selected with consideration for the viscosity parameters of the ink. Viscosity can be adjusted by various methods, such as by selecting a suitable organic solvent and the concentration of 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; and most preferably 1.5 to 20 cps. Viscosity here refers to viscosity at the ambient temperature during printing, generally between 15 and 30°C, preferably 18 to 28°C, more preferably 20 to 25°C, and most preferably 23 to 25°C. The composition thus formulated will be particularly suitable for inkjet printing.

[0177] In a preferred embodiment, the composition according to the invention has a viscosity at 25°C ranging from about 1 cps to 100 cps; more preferably from 1 cps to 50 cps; and most preferably from 1.5 cps to 20 cps.

[0178] Inks obtained from organic solvents that meet the above-mentioned boiling point, surface tension, and viscosity parameters can form functional material films with uniform thickness and compositional properties.

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

[0180] The organic electronic device may be selected from organic light-emitting diodes (OLEDs), organic photovoltaic cells (OPVs), organic light-emitting cells (OLEECs), organic field-effect transistors (OFETs), organic light-emitting field-effect transistors, organic lasers, organic spintronic devices, organic sensors, and organic plasmon emitting diodes.

[0181] Another object of the present invention is to provide a method for preparing the above-mentioned electronic device.

[0182] The specific technical solution is as follows:

[0183] A preparation method involves forming a functional layer on a substrate by co-evaporation of the above-mentioned organic compound H1 and organic compound H2, or forming a functional layer on a substrate by evaporation of the mixture as a premix, or forming a functional layer by printing or coating the above-mentioned composition on a substrate. The printing or coating method may be selected from (but is not limited to) inkjet printing, nozzle printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roller printing, torsional roller printing, offset printing, flexographic printing, rotary printing, spraying, brushing, pad printing, slot extrusion 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, particularly preferably by a preparation method of printing or coating.

[0185] Suitable printing or coating technologies include (but are not limited to) inkjet printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roller printing, torsional roller printing, offset printing, flexographic printing, rotary printing, spraying, brushing or pad printing, slot extrusion coating, etc. Gravure printing, screen printing, and inkjet printing are preferred. Gravure printing and inkjet printing will be used in embodiments of the present invention. The solution or suspension may additionally include one or more components such as surfactants, lubricants, wetting agents, dispersants, hydrophobic agents, binders, etc., to adjust viscosity, film-forming properties, improve adhesion, etc. For detailed information on printing technologies and their related requirements for solutions, such as solvent and concentration, viscosity, etc., please refer to "Handbook of Print Media: Technologies and Production Methods" edited by Helmut Kipphan, ISBN 3-540-67326-1.

[0186] The functional layer formed by the preparation method described above has a thickness of 5nm-1000nm.

[0187] The present invention further relates to an organic electronic device comprising at least one organic mixture according to the present invention, or at least one functional layer prepared using a composition according to the present invention. Generally, such an organic electronic device comprises at least a cathode, an anode, and a functional layer located between the cathode and the anode, wherein the functional layer comprises at least one organic mixture as described above.

[0188] In a more preferred embodiment, the organic electronic device described above 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.

[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 particularly desirable. In a preferred embodiment, the substrate is flexible and can be a polymer film or plastic with a glass transition temperature (Tg) of 150°C or higher, preferably 200°C or higher, more preferably 250°C or higher, and most preferably 300°C or higher. Examples of suitable flexible substrates include polyethylene terephthalate (PET) and polyethylene glycol (2,6-naphthalene) (PEN).

[0190] The anode may comprise a conductive metal or metal oxide, or a conductive polymer. Holes can be readily injected 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 level or valence band level of the light emitter 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 readily selected by those skilled 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 patterned. Patterned ITO conductive substrates are commercially available and can be used to fabricate devices according to the present invention.

[0191] The cathode may comprise a conductive metal or metal oxide. Electrons can be readily injected 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 level or conduction band level of the luminescent material in the light-emitting layer or the n-type semiconductor material serving as the electron injection layer (EIL), 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 suitable for use as cathodes in OLEDs can be used as cathode materials for the devices of this 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] OLEDs 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, the entire contents of which are hereby incorporated herein by reference.

[0193] In a preferred embodiment, the light-emitting layer of the light-emitting device according to the present invention is formed by vacuum co-deposition of H1 and H2.

[0194] In a preferred embodiment, the light-emitting device according to the present invention has a light-emitting layer formed by vacuum evaporation of a premix of H1 and H2, wherein the evaporation source comprises a mixture according to the present invention.

[0195] In another preferred embodiment, the light-emitting layer of the light-emitting device according to the invention is prepared by printing the composition according to the invention.

[0196] The electroluminescent device according to the present invention has an emission wavelength between 300 and 1000 nm, preferably between 350 and 900 nm, and more preferably between 400 and 800 nm.

[0197] The present invention also relates to the application of the organic electronic device according to the invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.

[0198] The present invention also relates to electronic devices comprising organic electronic devices according to the present invention, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.

[0199] The present invention will now be described in conjunction with preferred embodiments, but the present invention is not limited to the following embodiments. It should be understood that the appended claims summarize the scope of the present invention. Under the guidance of the inventive concept, those skilled in the art should realize that any changes made to the various embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention.

[0200] Example 1: Synthesis of the compound

[0201] Synthesis of compounds 33-1, 33 and 33-2:

[0202]

[0203]

[0204] A solution of Boronicacid, B-[3-(12-phenylindolo[2,3-a]carbazol-11(12H)-yl)phenyl] (9.0 g, 20 mmol), 2,4-dichloro-6-phenyl-1,3,5-triazine (2.2 g, 10 mmol), and 2.00 mol / L sodium carbonate (4.12 g, 40 mmol) was added to a three-necked flask and dissolved with 100 mL of toluene under nitrogen protection. Then, Pd(pph3)4 (1.13 g, 1 mmol) was added, and the reaction mixture was stirred and refluxed for 12 hours. TLC and MS showed that the reaction was complete, with the target product being the main component. After cooling, the reaction mixture was washed three times with 150 mL of saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated. The residue was purified by DCM / PE (1:4) column chromatography to give approximately 7.3 g of a white solid compound 33-1, with a yield of 75%.

[0205] 33-2 was synthesized using a similar method, with a yield of 63%.

[0206]

[0207] Compound Boronicacid, B-[3-(12-phenylindolo[2,3-a]carbazol-11(12H)-yl)phenyl] (4.5 g, 10 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (2.6 g, 10 mmol), and a 2.00 mol / L sodium carbonate solution (2.10 g, 20 mmol) were added to a three-necked flask and dissolved with 100 mL of toluene under nitrogen protection. Then, Pd(pph3)4 (0.57 g, 0.5 mmol) was added, and the reaction mixture was stirred and refluxed for 12 hours. TLC and MS showed that the reaction was complete, with the target product being the main component. After cooling, the reaction mixture was washed three times with 150 mL of saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated. The residue was purified by DCM / PE (1:4) column chromatography to give approximately 4.8 g of a white solid compound 33, with a yield of 81%.

[0208] Other compounds can be synthesized using similar methods, summarized as follows:

[0209]

[0210] Example 2: Energy level structure of the compound

[0211] The energy levels of organic compound materials can be obtained through quantum computing, such as using TD-DFT (time-dependent density functional theory) with Gaussian09W (Gaussian Inc.). For specific simulation methods, please refer to WO2011141110. First, the molecular geometry is optimized using the semi-empirical method "Ground State / Semi-empirical / Default Spin / AM1" (Charge 0 / Spin Singlet). Then, the energy structure of the organic molecule is calculated using TD-DFT (time-dependent density functional theory) to obtain "TD-SCF / DFT / Default Spin / B3PW91" and the basis set "6-31G(d)" (Charge 0 / Spin Singlet). HOMO and LUMO energy levels are calculated according to the calibration formula below; S1 and T1 are used directly.

[0212] HOMO(eV)=((HOMO(G)×27.212)-0.9899) / 1.1206

[0213] LUMO(eV)=((LUMO(G)×27.212)-2.0041) / 1.385

[0214] HOMO(G) and LUMO(G) are direct calculations using Gaussian 09W, expressed in Hartree units. The results are shown in Table 1 below.

[0215] Table 1

[0216]

[0217] Example 3 Preparation of the mixture

[0218] Mixtures 1-13 according to the present invention are mixed in the manner described below for the combination of compounds.

[0219]

[0220]

[0221] Mixing method of mixture 1: Take H1 and H2 in a mass ratio of 1:1 under a vacuum degree of less than 10. -3 In the Torr chamber, the mixture is heated to a molten state for thorough mixing, then cooled to room temperature, and the resulting solid mixture is ground.

[0222] The mixing methods of mixtures 2-13 and 1b-13b are the same as those of mixture 1.

[0223] Example 4 Preparation of the composition

[0224] The composition is prepared as follows:

[0225] Place a stir bar in the vial, clean it thoroughly, and transfer it to a glove box. Prepare 9.8 g of 3-phenoxytoluene solvent in the vial. Weigh 0.2 g of mixtures 1-13 and 1b-13b in the glove box and add them to the solvent system in the vial, stirring to mix. Stir at 60℃-80℃ until the organic mixture is completely dissolved, then cool to room temperature. Filter the resulting organic mixture solution through a 0.2 μm PTFE membrane, seal, and store.

[0226] The viscosity of the organic composition was measured using a DV-I Prime Brookfield rheometer; the surface tension of the organic composition was measured using a SITA bubble pressure tensiometer.

[0227] The above tests showed that the viscosity of the obtained compositions was in the range of 2.7±0.4cPs-6.7±0.4cPs, and the surface tension was in the range of 27.0±0.5dyne / cm-37.1±0.5dyne / cm.

[0228] In further experiments, mixtures 1-13 and 1b-13b were used to prepare compositions in the following solvents: 1-tetrahydronaphthone, tetrahydronaphthalene, 1-methoxynaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-p-methylisopropylbenzene, isopropylbiphenyl, dipentylbenzene, 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, and dibenzyl ether. The resulting compositions all had viscosities in the range of 2-15 cPs. The viscosity could be further adjusted by combining solvents and other methods to meet the needs of technologies such as inkjet printing.

[0229] The above composition, plus 5wt%-10wt% of a guest component, can be used as a printing ink for the light-emitting layer in an OLED.

[0230] Example 5: Fabrication and characterization of OLED devices: OLED1-13, OLED1b-13b and contrast OLEDS

[0231]

[0232] The above materials are GD (green light guest), RD (red light guest), GH (green light host), and RH (red light host). Their synthesis methods are all existing technologies, which can be found in the references in the existing technologies and will not be repeated here.

[0233] The fabrication steps for OLED devices with an ITO / HIL / HTL / EML / Al structure are as follows:

[0234] 1) Cleaning of ITO transparent electrode (anode) glass substrate: Ultrasonic treatment with 5% Decon90 cleaning solution for 30 minutes, followed by ultrasonic cleaning with deionized water several times, then ultrasonic cleaning with isopropanol, and drying with nitrogen; treatment under oxygen plasma for 5 minutes to clean the ITO surface and improve the work function of the ITO electrode.

[0235] 2) Preparation of HIL and HTL: PEDOT:PSS (Clevios) was spin-coated onto a glass substrate treated with oxygen plasma. TM PEDOT:PSS Al4083 was used to obtain an 80 nm thin film. After spin coating, the film was annealed in air at 150 °C for 20 minutes. Then, a 20 nm Poly-TFB thin film (CAS: 223569-31-1, purchased from Lumtec Corp.; 5 mg / mL toluene solution) was obtained by spin coating on the PEDOT:PSS layer. Subsequently, the film was treated on a hot plate at 180 °C for 60 minutes.

[0236] 3) Preparation of the light-emitting layer: The above composition (containing 5 wt% of the guest, see Table 1) was spin-coated in a nitrogen glove box to obtain an 80 nm thin film, and then annealed at 120 °C for 10 minutes;

[0237] 4) Cathode fabrication: The spin-coated device is placed in a vacuum evaporation chamber, and 2nm barium and 100nm aluminum are deposited sequentially to complete the light-emitting device;

[0238] 5) All devices are encapsulated in a nitrogen glove box using UV-cured resin and a glass cover.

[0239] The current-voltage (JV) characteristics of each OLED device were characterized using a characterization device, and important parameters such as efficiency, lifetime, and current efficiency were recorded. Table 2 shows the data for all devices, with relative values ​​for green light compared to the control device OLED1, and relative values ​​for red light compared to the control device OLED2. Testing revealed that the luminous efficiency and lifetime of OLEDs 1-13 and OLEDs 1b-13b were significantly improved compared to controls OLED1 and OLED2. This demonstrates that the solution-processed OLED devices prepared using the organic mixture of this invention exhibit significantly improved luminous efficiency and lifetime, as well as a marked improvement in external quantum efficiency.

[0240] It should be understood that the application of the present invention is not limited to the examples above. Those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims.

[0241] Table 2

[0242]

[0243]

[0244] The mixture described above can also be formed by co-evaporation and used in vapor-deposited OLED devices.

[0245] The technical features of the above embodiments can be combined in any way. For the sake of brevity, 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, they should be considered to be within the scope of this specification.

[0246] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. An organic mixture consisting of compound 1 and compound 2, characterized in that, Compound 1 has the structure of general formula (I) and compound 2 has the structure of general formula (II): wherein A and B are each independently selected from an aromatic or heteroaromatic ring system having 5 to 50 ring atoms, an aryloxy or heteroaryloxy group having 5 to 50 ring atoms, or a combination of these systems; the difference in LUMO and / or HOMO of compound 1 and compound 2 is less than or equal to 0.3 eV; the structure of general formula (I) is centred on A and has a symmetrical structure, and the structure of general formula (II) and the left-hand fragment B-A or the right-hand fragment A-B in the structure of general formula (I) are identical; A is selected from the following groups having electron-transporting properties: B is selected from the group consisting of groups having hole transporting properties, ； or, A is selected from the following groups having electron-transporting properties: B is selected from the group consisting of: wherein n is 1 or 2 or 3 or 4.

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

3. The organic mixture of claim 1, wherein, The organic mixture further comprises at least one further organic functional material selected from a hole injection material, an electron 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 or an organic dye.

4. An organic mixture consisting of Compound 1 and Compound 2, characterized in that, Compound 1 has the structure of general formula (I) and compound 2 has the structure of general formula (II): wherein A and B are each independently selected from an aromatic or heteroaromatic ring system having 5 to 50 ring atoms, an aryloxy or heteroaryloxy group having 5 to 50 ring atoms, or a combination of these systems; the difference in LUMO and / or HOMO of compound 1 and compound 2 is less than or equal to 0.3 eV; the structure of general formula (I) is centred on A and has a symmetrical structure, and the structure of general formula (II) and the left-hand fragment B-A or the right-hand fragment A-B in the structure of general formula (I) are identical; A is selected from the following groups having electron-transporting properties: wherein m is an integer from 1 to 3; X 1 - X 8 is selected from CR 301 or N, and at least one is N; R, R 301 may each independently be selected from 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 silyl group, it being also possible for one or more H in each of the aforementioned groups to be further replaced by D, B is selected from the following groups having hole-transporting properties: wherein Y represents an aromatic group or an aromatic hetero group having 5 to 40 carbon atoms; Z 1 , Z 2 , Z 3 each independently represents a single bond, N(R), C(R)2, Si(R)2, O, S, C=N(R), C=C(R)2, or P(R); R, R 1 , R 2 each independently represents an alkyl group, an alkoxy group, an amino group; or, A is selected from the following groups having electron-transporting properties: wherein m is an integer from 1 to 3; X 1 - X 8 is selected from CR 301 or N, and at least one is N; R, R 301 may each independently be selected from 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 silyl group, a hydroxyl group, one or more H in the various groups mentioned above can also be further replaced by D; B is selected from the following groups: 。 5. The organic mixture according to claim 4, characterized in that, The organic mixture further comprises at least one further organic functional material selected from a hole injection material, an electron 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 or an organic dye.

6. A composition comprising at least one organic mixture according to any one of claims 1 to 5 and at least one organic solvent.

7. An organic electronic device comprising at least one organic mixture according to any one of claims 1 to 5.

8. Organic electronic device according to claim 7, characterized in that The organic electronic device is selected from an organic light emitting diode, an organic photovoltaic cell, an organic photovoltaic cell, an organic field effect transistor, an organic light emitting field effect transistor, an organic laser, an organic spintronics device, an organic sensor or an organic plasmonic emitter diode.

9. Organic electronic device according to claim 7, characterized in that The organic electronic device comprises at least one light emitting layer, which comprises at least one organic mixture according to any one of claims 1 to 5.

10. Organic electronic device according to claim 9, characterized in that The organic mixture is a host material.

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