Organic mixture and use thereof in photoelectric field

Abstract

Disclosed in the present invention is an organic mixture, containing a first luminous body E1 and a second luminous body E2. The first luminous body E1 and the second luminous body E2 are both fluorescent luminous bodies; the absorption spectrum of the second luminous body E2 at least partially overlaps the emission spectrum of the first luminous body E1; the full width at half maximum (FWHM) of the emission spectrum of the second luminous body E2 is less than or equal to 50 nm, and efficient fluorescence resonance energy transfer (FRET) is present between the first luminous body E1 and the second luminous body E2. Also disclosed in the present invention is a composition (printing ink) containing the first luminous body E1 and the second luminous body E2, thereby providing a technical option for printed OLEDs. Further disclosed in the present invention is a photovoltaic device, in particular an organic electroluminescent device which comprises a light-emitting layer containing the organic mixture. The organic electroluminescent device according to the present invention has a long device life and a narrow emission spectral line at the same time.

Description

Organic compounds and their applications in optoelectronics Technical Field

[0001] The present invention relates to the technical field of organic photoelectric materials and devices, and in particular to an organic mixture, a composition containing the same, a photoelectric device and applications thereof in the photoelectric field. Background Art

[0002] Organic semiconductor materials have great potential for applications in optoelectronic devices such as flat panel displays and lighting due to their diverse synthesis, relatively low manufacturing costs, and excellent optical and electrical properties.

[0003] To date, fluorescent and phosphorescent luminescent material systems have been developed. Organic light-emitting diodes using traditional fluorescent / phosphorescent materials exhibit broad emission spectra, with the full width at half maximum (FWHM) of bottom-emitting devices typically exceeding 30 nm. In recent years, multi-resonant TADF materials have been reported, particularly OLED luminescent materials based on BN fused-ring systems. When used as the luminescent layer in light-emitting devices, device efficiencies comparable to or exceeding those of traditional luminescent materials are achieved while offering narrower spectra, which facilitates achieving a wider display color gamut.

[0004] The efficiency and lifespan of OLED light-emitting devices depend largely on the properties of the luminescent materials. Currently, the most commonly used luminescent materials are multiply resonant TADF organic compounds containing BN fused ring systems. However, due to disadvantages such as their large structural conjugation, the lifespan of corresponding OLED devices is still lower than that of devices using traditional fluorescent materials as luminescent materials.

[0005] Therefore, existing OLED device technologies and related luminescent materials, especially solutions for blue light emitting materials, need to be improved and developed.

[0006] Summary of the Invention

[0007] Based on this, the object of the present invention is to provide an organic mixture, a composition, an optoelectronic device (especially an organic electroluminescent device) and applications thereof in the optoelectronic field.

[0008] The specific technical solutions are as follows:

[0009] An organic mixture comprises a first luminophore E1 and a second luminophore E2, wherein 1) the first luminophore E1 and the second luminophore E2 are both fluorescent luminophores; 2) the absorption spectrum of the second luminophore E2 and the emission spectrum of the first luminophore E1 at least partially overlap with each other; and 3) the full width at half maximum (FWHM) of the emission spectrum of the second luminophore E2 is less than or equal to 50 nm.

[0010] Preferably, the second luminophore E2 is selected from the structure shown in chemical formula (1) or (2):

[0011] Where: Ar 1 -Ar 3 The same or different aromatic or heteroaromatic groups are selected from 5 to 24 ring atoms; Ar 4 -Ar 5 The same or different aromatic or heteroaromatic groups are selected from empty or aromatic groups having 5 to 24 ring atoms; when Ar 4 -Ar 5 When not empty, X a and X b independently selected at each occurrence from N, C(R 9 ), or Si(R 9 );Y a and Y b independently selected at each occurrence from B, P=O, C(R 9 ) or Si(R 9 ); when Ar 4 or Ar 5 When it is empty, X b Selected from N, C(R 9 ) or Si(R 9 ), Y a Selected from B, P=O, C(R 9 ) or Si(R 9 ), X a and Y b In each occurrence, independently selected from N(R 9 )、C(R 9 R 10 )、Si(R 9 R 10 )、C=O、O、C=N(R 9 ), C=C(R 9 R 10 )、P(R 9 ), P(=O)R 9 , S, S=O or SO2; X 1 、X 2 R is independently selected from empty or a bridging group; 4 -R 10In each occurrence, the same or different radicals are independently selected from H, D, or a linear alkyl, haloalkyl, alkoxy, thioalkoxy radical having 1 to 20 C atoms, or a branched or cyclic alkyl, haloalkyl, alkoxy, thioalkoxy radical, silyl radical having 3 to 20 C atoms, or a keto radical having 1 to 20 C atoms, or an alkoxycarbonyl radical having 2 to 20 C atoms, or an aryloxycarbonyl radical having 7 to 20 C atoms, or a cyano radical (-CN), a carbamoyl radical (-C(=O)NH2), a haloformyl radical (-C(=O)-X wherein X represents a halogen atom), a formyl radical (-C (=O)-H), isocyanate group, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group, nitro group, CF3, Cl, Br, F, I, 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 an arylamine or heteroarylamine group having 5 to 40 ring atoms, a disubstituted unit at any position of the above groups or a combination of these groups, wherein one or more groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or the ring to which the groups are bonded.

[0012] Preferably, the first luminophore E1 is selected from chemical formula (1), chemical formula (2) or aromatic amine derivatives. Further, the first luminophore E1 is selected from chemical formula (1) or (2), chemical formula (1a)-(11), chemical formula (2a)-(2e) or any one of the following chemical formulas (3-1)-(3-17):

[0013] Where: R0-R3 are defined the same as R 4 ; Ar1-Ar4 may be the same or different and may be selected from aromatic or heteroaromatic groups having 5 to 60 ring atoms.

[0014] Preferably, the organic mixture further comprises a host material H, wherein the host material H is selected from the structure represented by chemical formula (4-1) or (4-2), and is preferably selected from anthracene derivatives;

[0015] Ar5 and Ar6 may be the same or different and may be selected from aromatic or heteroaromatic groups having 5 to 60 ring atoms.

[0016] The present invention further provides a composition comprising an organic mixture as described above, and at least one organic solvent.

[0017] The present invention also provides a photovoltaic device comprising the organic mixture as described above.

[0018] Preferably, the optoelectronic device is an organic electroluminescent device and comprises a substrate, an anode, a light-emitting layer and a cathode arranged in sequence, the light-emitting layer comprises at least one organic mixture as described above, or the light-emitting layer is prepared using the composition as described above.

[0019] Beneficial effects: According to the organic electroluminescent device of the present invention, its light-emitting layer contains two light-emitting bodies, a traditional fluorescent material (first light-emitting body E1) and a BN compound with a narrow emission spectrum (second light-emitting body E2); the traditional fluorescent material (first light-emitting body E1) has a long device life; the absorption spectrum of the second light-emitting body E2 at least partially overlaps with the emission spectrum of the first light-emitting body E1, thereby achieving resonant energy transfer between the first light-emitting body E1 and the second light-emitting body E2 (( Resonance energy transfer (FRET) is used to obtain the advantages of the first luminescent body E1 and the second luminescent body E2, while achieving a long device life and a narrow emission spectrum. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1: Absorption (Abs) and luminescence (PL) spectra of E2-1;

[0021] Figure 2: Absorption (Abs) and luminescence (PL) spectra of E2-2;

[0022] Figure 3: Absorption (Abs) and luminescence (PL) spectra of E2-3;

[0023] Figure 4: Absorption (Abs) and luminescence (PL) spectra of E2-4;

[0024] Figure 5: Absorption (Abs) and luminescence (PL) spectra of E2-5;

[0025] Figure 6: Absorption (Abs) and luminescence (PL) spectra of E2-9;

[0026] Figure 7: Absorption (Abs) and luminescence (PL) spectra of E1-2, and absorption (Abs) spectrum of E2-1;

[0027] Figure 8: Absorption (Abs) and luminescence (PL) spectra of E1-2, and absorption (Abs) spectrum of E2-2;

[0028] Figure 9: Absorption (Abs) and luminescence (PL) spectra of E1-2, and absorption (Abs) spectra of E2-3;

[0029] Figure 10: Absorption (Abs) and luminescence (PL) spectra of E1-2, and absorption (Abs) spectra of E2-4;

[0030] Figure 11: Absorption (Abs) and luminescence (PL) spectra of E1-2, and absorption (Abs) spectra of E2-5;

[0031] Figure 12: Absorption (Abs) and luminescence (PL) spectra of E1-2, and absorption (Abs) spectrum of E2-9. DETAILED DESCRIPTION

[0032] To facilitate understanding of the present invention, the present invention will be described more fully below with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the accompanying drawings. However, the present invention may be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and comprehensive understanding of the present disclosure.

[0033] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention pertains. The terms used herein in the specification of the present invention are for the purpose of describing specific embodiments only and are not intended to limit the present invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0034] In the description of the embodiments of the present invention, a numerical range represented by “~” refers to a range that includes the numerical values ​​described before and after “~” as the lower limit and the upper limit.

[0035] In the description of the embodiments of the present invention, a substituent may be further substituted by a substituent, and "substituted group a" may refer to group a being substituted by a substituent, and the substituent may be substituted by at least one further substituent or may be unsubstituted.

[0036] In this disclosure, the term "and / or" describes the relationship between associated objects, indicating that three possible relationships exist. For example, "A and / or B" can represent: A exists alone, A and B exist simultaneously, and B exists alone. A and B can be singular or plural. The character " / " generally indicates that the associated objects are in an "or" relationship.

[0037] In the present invention, "at least one" means one or more, and "plurality" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c" or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can each be single or plural.

[0038] It should be understood that in various embodiments of the present invention, the size of the serial numbers of the above-mentioned processes does not mean the order of execution. Some or all of the steps can be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present invention.

[0039] The terms used in the embodiments of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The singular forms "a", "an", "the" and "the" used in the embodiments of the present invention and the appended claims are also intended to include plural forms unless the context clearly indicates otherwise.

[0040] The term "OLED" is an abbreviation for "Organic Light Emitting Diode," which stands for organic electroluminescent diode, also known as organic electric laser display or organic light-emitting semiconductor (Organic Electroluminescence Display, OLED). OLED is a current-type organic light-emitting device that emits light through the injection and recombination of carriers, and the luminous intensity is proportional to the injected current. Under the action of the electric field, the holes generated by the anode and the electrons generated by the cathode will move, and are injected into the hole transport layer and the electron transport layer respectively, and migrate to the light-emitting layer. When the two meet in the light-emitting layer, energy excitons are generated, which excite the light-emitting molecules and ultimately produce visible light.

[0041] The term "TADF," short for "Thermally Activated Delayed Fluorescence," refers to thermally activated delayed fluorescence, which occurs when the triplet excited state and singlet excited state are close in energy, allowing the triplet excited state to transition to the singlet excited state through thermally activated reverse intersystem crossing (ISC). Conventional luminescence occurs as fluorescence and phosphorescence, respectively, where the exciton returns to the ground state via radiative emission from the singlet and triplet states. Furthermore, the energy difference between the lower singlet and triplet states is typically large, resulting in an inability to return the exciton to the singlet state once it reaches the triplet state through ISC.

[0042] In the present invention, main body material, matrix material, host material and matrix material have the same meaning and can be interchanged.

[0043] In the present invention, metal organic complex, metal organic complex and organometallic complex have the same meaning and can be used interchangeably.

[0044] In the present invention, composition, printing ink, ink and ink have the same meaning and can be interchanged.

[0045] In the embodiment of the present invention, the energy level structure of the organic material, the singlet energy level E S1 , triplet energy level E T1 , HOMO, and LUMO play a key role. The following is an introduction to the determination of these energy levels.

[0046] HOMO and LUMO energy levels can be measured by photoelectric effects, such as XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectroscopy), or by cyclic voltammetry (CV). Recently, quantum chemical methods, such as density functional theory (DFT), have also become effective methods for calculating molecular orbital energy levels.

[0047] The singlet energy level E of organic materials S1 The triplet energy level E can be determined by the luminescence spectrum. T1 It can be measured by low temperature time-resolved luminescence spectroscopy. S1 and E T1 It can also be obtained by quantum simulation calculation (such as by Time-dependent DFT), such as by the commercial software Gaussian 09W (Gaussian Inc.), and the specific simulation method can be found in WO2011141110 or described in the examples below. ST Defined as (E S1 -E T1 ).

[0048] It should be noted that HOMO, LUMO, E S1 、E T1 The absolute value of depends 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. S1 、E T1 The value is based on the simulation of Time-dependent DFT and does not affect the application of other measurement or calculation methods.

[0049] In the present invention, (HOMO-1) is defined as the second-highest occupied molecular orbital energy level, (HOMO-2) is the third-highest occupied molecular orbital energy level, and so on. (LUMO+1) is defined as the second-lowest unoccupied molecular orbital energy level, (LUMO+2) is the third-lowest occupied molecular orbital energy level, and so on.

[0050] The present invention provides an organic mixture comprising a first luminophore E1 and a second luminophore E2, wherein 1) the first luminophore E1 and the second luminophore E2 are both fluorescent luminophores; 2) the absorption spectrum of the second luminophore E2 and the emission spectrum of the first luminophore E1 at least partially overlap with each other; and 3) the full width at half maximum (FWHM) of the emission spectrum of the second luminophore E2 is less than or equal to 50 nm.

[0051] In some preferred embodiments, the full width at half maximum (FWHM) of the light emission spectrum of the second luminophore E2 is ≤45 nm, preferably ≤40 nm, more preferably ≤35 nm, and most preferably ≤30 nm.

[0052] In other preferred embodiments, the second luminophore E2 and / or the first luminophore E1 has a fluorescence quantum efficiency (PLQY) of ≥60%, preferably ≥65%, even better ≥70%, even better ≥80%, and most preferably ≥85%.

[0053] In some particularly preferred embodiments, the second luminophore E2 is selected from the structure shown in chemical formula (1) or (2), more preferably chemical formula (1):

[0054] Where: Ar 1 -Ar 3 The same or different aromatic or heteroaromatic groups are selected from 5 to 24 ring atoms; Ar 4 -Ar 5 The same or different aromatic or heteroaromatic groups are selected from empty or aromatic groups having 5 to 24 ring atoms; when Ar 4 -Ar 5 When not empty, X a and X b independently selected at each occurrence from N, C(R 9 ) or Si(R 9 ), Y a and Y b independently selected at each occurrence from B, P=O, C(R 9 ) or Si(R 9 ); when Ar 4 or Ar 5 When it is empty, X b Selected from N, C(R 9 ) or Si(R 9 ), Y a Selected from B, P=O, C(R 9 ) or Si(R 9 ), X a and Y b In each occurrence, independently selected from N(R 9 )、C(R 9 R 10)、Si(R 9 R 10 )、C=O、O、C=N(R 9 ), C=C(R 9 R 10 )、P(R 9 ), P(=O)R 9 , S, S=O or SO2; X 1 、X 2 R is independently selected from empty or a bridging group; 4 -R 10 and D, which may be identical or different on each occurrence, or a linear alkyl, haloalkyl, alkoxy, thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, haloalkyl, alkoxy, thioalkoxy group, silyl group having 3 to 20 C atoms, or a 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, or a cyano group (-CN), a carbamoyl group (-C(=O)NH2), a haloformyl group (-C(=O)-X wherein X represents a halogen atom) ), formyl group (-C(=O)-H), isocyanate group, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group, nitro group, CF3, Cl, Br, F, I, 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 an arylamine or heteroarylamine group having 5 to 40 ring atoms, a disubstituted unit at any position of the above groups or a combination of these groups, wherein one or more groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which the groups are bonded.

[0055] In some preferred embodiments, R 4 -R 10In each occurrence, the radicals may be identical or different and may be selected from H, D, or a linear alkyl, haloalkyl, alkoxy, thioalkoxy radical having 1 to 10 C atoms, or a branched or cyclic alkyl, haloalkyl, alkoxy, thioalkoxy radical, silyl radical having 3 to 10 C atoms, or a keto radical having 1 to 10 C atoms, or an alkoxycarbonyl radical having 2 to 10 C atoms, or an aryloxycarbonyl radical having 7 to 10 C atoms, or a cyano radical (-CN), a carbamoyl radical (-C(=O)NH2), a haloformyl radical (-C(=O)-X X represents a halogen atom), a formyl group (-C(=O)-H), an isocyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, 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 an arylamine or heteroarylamine group having 5 to 20 ring atoms, or a combination of these groups, 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 groups are bonded.

[0056] In some preferred embodiments, the second luminophore E2 is selected from the structure represented by the following chemical formula (1a) or (2a), more preferably chemical formula (1a):

[0057] Among them, Ar 1 -Ar 3 、Ar 4 -Ar 5 、X 1 、X 2 、R 4 -R 8 The definition of is as above.

[0058] In some preferred embodiments, X 1 and X 2 are independently selected from O or S; in some more preferred embodiments, X 1 and X 2 All are O.

[0059] In some preferred embodiments, X 1 、X 2 At least one is empty; particularly preferably, both are empty, and the second luminophore E2 is selected from the structure represented by the following chemical formula (1b) or (2b), more preferably chemical formula (1b):

[0060] Among them, Ar 1 -Ar 3 、Ar4 -Ar 5 、R 4 -R 8 The definition of is as above.

[0061] In some preferred embodiments, X 1 、X 2 At least one is a single bond; particularly preferably, both are single bonds. In this case, the second luminophore E2 is selected from the structure represented by the following chemical formula (1c) or (2c), more preferably chemical formula (1c):

[0062] Among them, Ar 1 -Ar 3 、Ar 4 -Ar 5 、R 4 -R 8 The definition of is as above.

[0063] In some preferred embodiments, X 1 、X 2 In each occurrence, the same or different two-bridge groups are present. Preferred two-bridge groups are:

[0064] Wherein: R4, R5, R6 and R7 are defined as above 4 ; Dashed bonds represent bonds to adjacent structural units.

[0065] For the purposes of the present invention, aromatic ring systems contain 5 to 10 carbon atoms in the ring system, and heteroaromatic ring systems contain 1 to 10 carbon atoms and at least one heteroatom in the ring system, provided that the total number of carbon atoms and heteroatoms is at least 4. The heteroatoms are preferably selected from Si, N, P, O, S and / or Ge, particularly preferably from Si, N, P, O and / or S. For the purposes of the present invention, aromatic or heteroaromatic ring systems include not only systems containing aromatic or heteroaromatic groups, but also systems in which multiple aromatic or heteroaromatic groups are 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, triarylamines, diaryl ethers, etc. are also considered aromatic ring systems for the purposes of this invention.

[0066] For the purpose of the present invention, any H atom on the first luminophore E1 and the second luminophore E2 is R 4 Group substitution, R 4The definition of is as described above, preferably, (1) C1-C10 alkyl, particularly preferably refers to the following groups: methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-methylheptyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclo hexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl and octynyl; (2) C1-C10-alkoxy, particularly preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy or 2-methylbutoxy; (3) C2-C10-aryl or heteroaryl, which may be monovalent or divalent depending on the application and may in each case also be replaced by the above-mentioned radicals R 4 Substituted and can be linked to the aromatic or heteroaromatic ring through any desired position, particularly preferably refers to the following groups: benzene, naphthalene, anthracene, pyrene, dihydropyrene, chrysene, fluoranthene, butane, Pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthimidazole, pyridimidazole, pyrazinimidazole, quinoxalinoimidazole, oxazole, benzoxazole, naphthioxazole, anthraquinoxazole, phenanthroquinoxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine , quinoxaline, pyrazine, anthracene, 1,5-naphthyridine, nitrogen carbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole. For the purposes of the present invention, aromatic and heteroaromatic ring systems are taken to mean, in particular, biphenylene, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, tetrahydropyrene and cis- or trans-indenofluorene, in addition to the aryl and heteroaryl radicals mentioned above.

[0067] In some preferred embodiments, in the second luminophore E2, Ar 1 -Ar 5The same or different in each occurrence are selected from aromatic or heteroaromatic groups having 5 to 20 ring atoms; preferably selected from aromatic or heteroaromatic groups having 5 to 18 ring atoms; more preferably selected from aromatic or heteroaromatic groups having 5 to 15 ring atoms; most preferably selected from aromatic or heteroaromatic groups having 5 to 10 ring atoms; they may be unsubstituted or substituted by one or two R 4 Preferred aryl or heteroaryl groups include benzene, naphthalene, anthracene, phenanthrene, pyridine, pyrene or thiophene.

[0068] In some preferred embodiments, Ar 1 -Ar 5 Selected from the following structural formula:

[0069] Where: X3 is CR 11 or N; Y7 is selected from NR 11 , CR 12 R 13 、SiR 14 R 15 , C(=O), S or O; R 11 、R 12 、R 13 、R 14 、R 15 The definition of R is the same as above 4 .

[0070] Further, Ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 Independently selected from one or a combination of the following chemical formulae, and may be further substituted arbitrarily:

[0071] In some particularly preferred embodiments, Ar 1 -Ar 5 It is phenyl.

[0072] In some preferred embodiments, Ar 4 、Ar 5 At least one is empty; particularly preferably, both are empty, and the second luminophore E2 is selected from the structure shown in the following chemical formula (1d) or (2d) or (1e) or (2e):

[0073] Among them, Ar 1 -Ar 3 、X a 、Y b 、R 6 -R 8 The definition of is as above.

[0074] Preferably, X in formula (1d) and (1e) a The same or different independently selected from N(R 9 ), C(R 9 R 10 )、Si(R 9 R 10 ), O or S.

[0075] Preferably, Y in formula (2d) and (2e) b The same or different are independently selected from C=O, O, S, P(=O)R 9 , S=O or SO2; particularly preferably selected from C=O.

[0076] In some other preferred embodiments, the second luminophore E2 comprises the structures shown in the following chemical formulas (1f) to (1i):

[0077] Among them, Y c which may be the same or different and are selected from O or S; Ar 1 -Ar 3 、X a 、R 6 -R 8 The definition of is as above.

[0078] In some particularly preferred embodiments, the above-mentioned Ar 2 、Ar 3 It is preferably selected from the following structural units and can be further substituted arbitrarily:

[0079] In certain preferred embodiments, according to the structural units of chemical formulae (1)-(1i) and (2)-(2e), wherein R 4 -R 8 When it occurs multiple times, it may contain the following structural units or their combinations, which may be the same or different:

[0080] Where n1 is 1 or 2 or 3 or 4.

[0081] In some particularly preferred embodiments, the second luminophore E2 is selected from the following structures:

[0082] Where: Y c The definition of R is as above; 21 、R 22 、R 23 、R 24 、R 25Each occurrence is the same or different and is independently selected from H, D, or a linear alkyl, alkoxy, thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy, thioalkoxy group, a silyl group having 3 to 20 C atoms, or a 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, or a cyano group (-CN), a carbamoyl group (-C(=O)NH2), a haloformyl group (-C(=O)-X wherein X represents a halogen atom), a formyl group (-C(=O)-H), Isocyanate group, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group, nitro group, 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 groups, wherein one or more groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring bonded to the group; m and n are independently selected from any integer from 0 to 4; o and q are independently selected from any integer from 0 to 5; p is independently selected from any integer from 0 to 3; "dashed line" indicates no or single bond.

[0083] Preferably, R 21 -R 25 It may be H, D, or a linear alkyl, alkoxy, or thioalkoxy group having 1 to 10 C atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group or silyl group having 3 to 10 C atoms, or a keto group having 1 to 10 C atoms, or an alkoxycarbonyl group having 2 to 10 C atoms, or an aryloxycarbonyl group having 7 to 10 C atoms, or a cyano group (-CN), a carbamoyl group (-C(=O)NH2), a haloformyl group (-C(=O)-X, etc. wherein X represents a halogen atom), a formyl group (—C(═O)—H), an isocyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, CF 3 , Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 20 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 20 ring atoms, or a combination of these groups, 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 groups are bonded.

[0084] In some preferred embodiments, the second luminophore E2 is selected from the structure represented by chemical formula (1m) or (1n):

[0085] where R21 、R 22 、R 23 、R 24 、R 25 and m, n, o, q, and p have the same meanings as described above.

[0086] In some preferred embodiments, the second luminophore E2 is selected from the structure represented by chemical formula (1o) or (1p):

[0087] where R 21 、R 22 、R 23 、R 24 、R 25 and m, o, and q have the same meanings as above.

[0088] In some preferred embodiments, for the chemical formulas (1m), (1n), (1o), and (1p), R 22 、R 24 Each occurrence is the same or different and is independently selected from aromatic or heteroaromatic groups having 5 to 40 ring atoms; preferably selected from aromatic or heteroaromatic groups having 6 to 40 ring atoms; more preferably selected from aromatic or heteroaromatic groups having 6 to 30 ring atoms; most preferably selected from aromatic or heteroaromatic groups having 6 to 20 ring atoms.

[0089] In other preferred embodiments, for the chemical formulas (1m), (1n), (1o), and (1p), R 22 、R 24 Each occurrence is identical or different and is independently selected from a straight-chain alkyl group having 1 to 20 C atoms or a keto group having 1 to 20 C atoms.

[0090] In some preferred embodiments, for the chemical formulas (1m), (1n), (1o), and (1p), R 22 、R 24 Each occurrence is the same or different and is independently selected from an electron-donating group, an aromatic group consisting of a benzene ring, a branched aliphatic group with greater steric hindrance, and / or a combination of the above structures.

[0091] In some more preferred embodiments, for the chemical formulas (1m), (1n), (1o), and (1p), R 22 、R 24 Each occurrence is the same or different and is independently selected from the structures shown in the following chemical formulas (5-1) to (5-9):

[0092] Where * indicates the bonding position.

[0093] In the embodiment of the present invention, the triplet energy level (T1), the singlet energy level (S1), the HOMO, the LUMO, and the resonance factor strength f play a key role in the energy level structure of the organic material. The determination of these parameters is introduced below.

[0094] HOMO and LUMO energy levels can be measured by photoelectric effects, such as XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectroscopy), or by cyclic voltammetry (CV). Recently, quantum chemical methods, such as density functional theory (DFT), have also become effective methods for calculating molecular orbital energy levels.

[0095] The triplet energy level T1 of an organic material can be measured by low-temperature time-resolved luminescence spectroscopy or obtained by quantum simulation calculations (e.g., by time-dependent DFT), such as using the commercial software Gaussian 09W (Gaussian Inc.). The specific simulation method is described below. The singlet energy level S1 of an organic material can be determined by absorption or emission spectroscopy, or obtained by quantum simulation calculations (e.g., time-dependent DFT). The resonance factor intensity f can also be obtained by quantum simulation calculations (e.g., time-dependent DFT).

[0096] It should be noted that the absolute values ​​of HOMO, LUMO, T1, and S1 depend on the measurement 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 and evaluation methods. In the description of the embodiments of the present invention, the values ​​of HOMO, LUMO, T1, and S1 are based on time-dependent DFT simulations, but this does not affect the application of other measurement or calculation methods.

[0097] In certain preferred embodiments, the second luminophore E2 according to the present invention has (S1-T1)≤0.30 eV, preferably ≤0.25 eV, more preferably ≤0.20 eV, even more preferably ≤0.15 eV, and most preferably ≤0.10 eV.

[0098] In certain embodiments, in the organic mixture, the second luminophore E2 and the first luminophore E1 are small molecules or polymers, preferably small molecules.

[0099] In a preferred embodiment, the organic mixture does not contain any resin.

[0100] Furthermore, the H atoms or CH2 groups on individual aromatic or heteroaromatic rings of the present invention may be substituted by R groups. R is selected from alkyl groups having 1 to 40 C atoms, preferably from the group consisting of methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, ethylhexyl, trifluoromethyl, pentafluoroethyl, trifluoroethyl, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl and octynyl; and alkoxy groups having 1 to 40 C atoms, such as methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy or methylbutoxy.

[0101] Examples of the second luminous element E2 are given below (these can also be used as examples of the first luminous element E1), but are not limited to:

[0102] In some preferred embodiments, the first luminophore E1 is selected from the above chemical formula (1) or (2), chemical formula (1a)-(1e) or chemical formula (2a)-(2e) or chemical formula (1f)-(1i) or chemical formula (1j)-(1l).

[0103] In other preferred embodiments, the first luminophore E1 is selected from a conventional fluorescent luminophore (i.e., a singlet luminophore). Conventional singlet luminophores often have a long conjugated π-electron system. To date, many examples have been described, such as styrylamines and their derivatives disclosed in JP2913116B and WO2001021729A1, indenofluorenes and their derivatives disclosed in WO2008 / 006449 and WO2007 / 140847, and triarylamine derivatives of pyrene disclosed in US7233019 and KR2006-0006760.

[0104] In some preferred embodiments, the first luminophore E1 can be selected from monostyrylamine, distyrylamine, tertiary styrylamine, tetrastyrylamine, styrylphosphine, styryl ether and aromatic amine.

[0105] A monostyrylamine is a compound comprising an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine. A distyrylamine is a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A tert-styrylamine is a compound comprising three unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A tetrastyrylamine is a compound comprising four unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A preferred styrene is diphenylethylene, which may be further substituted. The corresponding phosphines and ethers are defined similarly to the amines. An arylamine or aromatic amine is a compound comprising three unsubstituted or substituted aromatic or heterocyclic rings directly attached 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 anthracenamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chryseneamines, and aromatic chrysenediamines. An aromatic anthracenamine is a compound in which one diarylamine group is directly attached to anthracene, preferably at the 9-position. An aromatic anthracenediamine is a compound in which two diarylamine groups are directly attached to anthracene, preferably at the 9- and 10-positions. Aromatic pyreneamines, aromatic pyrenediamines, aromatic chrysamines, and aromatic chrysenediamines are similarly defined, with the diarylamine groups preferably attached to the 1- or 1,6-positions of the pyrene group.

[0106] Examples of conventional singlet emitters based on vinylamines and aromatic amines, which are also preferred examples, can be found in the following patent documents: WO2006 / 000388, WO2006 / 058737, WO2006 / 000389, WO2007 / 065549, WO2007 / 115610, US7250532B2, DE102005058557A1, CN1583691A, JP08053397A, US6251531B1, US2006 / 210830A, EP1957606A1, and US2008 / 0113101A1. The entire contents of the above-mentioned patent documents are hereby incorporated herein by reference.

[0107] Examples of conventional singlet emitters based on stilbene and its derivatives are disclosed in US Pat. No. 5,121,029.

[0108] Further, preferred conventional singlet emitters can be selected from indenofluorene-amine and indenofluorene-diamine, as disclosed in WO2006 / 122630, benzoindenofluorene-amine and benzoindenofluorene-diamine, as disclosed in WO2008 / 006449, and dibenzoindenofluorene-amine and dibenzoindenofluorene-diamine, as disclosed in WO2007 / 140847.

[0109] Further preferred traditional singlet emitters can be selected from fluorene-based fused ring systems, such as those disclosed in US2015333277A1, US2016099411A1, and US2016204355A1.

[0110] More preferred traditional singlet emitters can be selected from pyrene derivatives, such as the structure disclosed in US2013175509A1; triarylamine derivatives of pyrene, such as the triarylamine derivatives of pyrene containing dibenzofuran units disclosed in CN102232068B; other triarylamine derivatives of pyrene with specific structures, such as those disclosed in CN105085334A and CN105037173A. Other materials that can be used as singlet emitters are polycyclic aromatic hydrocarbon compounds, especially derivatives of the following compounds: anthracene such as 9,10-di(2-naphthyl)anthracene, naphthalene, tetracene, xanthene, phenanthrene, pyrene (such as 2,5,8,11-tetra-t-butylperylene), indenopyrene, benzo-fused ring such as (4,4'-bis(9-ethyl-3-carbazolylvinyl)-1,1'-biphenyl), diindenopyrene, decacycloene, hexabenzophenone, fluorene, spirobifluorene, arylpyrene (such as US20060222886), arylenevinyl (such as US5121 029, US5130603), cyclopentadiene such as tetraphenylcyclopentadiene, rubrene, coumarin, rhodamine, quinacridone, pyran such as 4-(dicyanomethylene)-6-(4-(p-dimethylaminophenyl)-2-methyl)-4H-pyran (DCM), thiopyran, bis(azinyl)imine boron compounds (US2007 / 0092753A1), bis(azinyl)methylene compounds, carbostyryl compounds, oxazinones, benzoxazoles, benzothiazoles, benzimidazoles, and dione pyrrolopyrroles. Some conventional singlet emitter materials can be found in the following patent documents: US20070252517A1, US4769292, and US6020078. The entire contents of the above-listed patent documents are hereby incorporated herein by reference.

[0111] In certain embodiments, for stability considerations, the first luminophore E1 is not selected from thermally excited delayed fluorescence (TADF) compounds having a DA structure, nor is it selected from compounds having aggregation-induced emission (AIE) properties.

[0112] In a more preferred embodiment, the first light-emitting body E1 has S1-T1≥0.25eV, preferably ≥0.3eV.

[0113] In some preferred embodiments, the first luminophore E1 is selected from any one of the following chemical formulas (3-1) to (3-17):

[0114] Where: R0-R3 are defined as above4 ; Ar1-Ar4 may be the same or different and may be selected from aromatic or heteroaromatic groups having 5 to 60 ring atoms; preferably selected from aromatic or heteroaromatic groups having 6 to 40 ring atoms; more preferably selected from aromatic or heteroaromatic groups having 6 to 30 ring atoms; most preferably selected from aromatic or heteroaromatic groups having 6 to 20 ring atoms.

[0115] Some examples of suitable singlet emitters as the first emitter E1 are listed below:

[0116] According to the organic mixture of the present invention, the absorption spectrum of the second luminescent body E2 and the emission spectrum of the first luminescent body E1 have a large overlap, and relatively efficient energy transfer can be achieved between them.

[0117] In some preferred embodiments, the peak (λ2) of the absorption spectrum of the second luminophore E2 is on the short wavelength side of the peak (λ1) of the emission spectrum of the first luminophore E1, and there is a large overlap.

[0118] In other embodiments, the peak value (λ2) of the absorption spectrum of the second luminescent body E2 is on the long wavelength side of the peak value (λ1) of the emission spectrum of the first luminescent body E1, and there is a large overlap.

[0119] Preferably, the difference between λ1 and λ2 is ≤10 nm, more preferably ≤8 nm, more preferably ≤5 nm, particularly preferably ≤3 nm, and most preferably ≤2 nm.

[0120] In other preferred embodiments, the peak value (λ2) of the absorption spectrum of the second luminophore E2 is between the peak value (λ1) of the emission spectrum of the first luminophore E1 and the peak value (λ3) of the absorption spectrum of the first luminophore E1.

[0121] In some embodiments, the peak (λ1) of the light emission spectrum of the first light emitter E1 is between the peak (λ2) of the absorption spectrum of the second light emitter E2 and the peak (λ3) of the absorption spectrum of the first light emitter E1.

[0122] In some preferred embodiments, the luminescence spectrum of the organic mixture is completely derived from the second luminophore E2, that is, complete energy transfer is achieved between the first luminophore E1 and the second luminophore E2.

[0123] In some embodiments, the peak (λ1) of the light emission spectrum of the first light-emitting body E1 is between 400nm and 700nm, preferably between 410nm and 600nm, particularly preferably between 420nm and 500nm, and most preferably between 430nm and 460nm.

[0124] In a more preferred embodiment, the peak value (λ1) of the light emission spectrum of the first light-emitting body E1 is between 440 nm and 460 nm.

[0125] In some embodiments, the peak (λ4) of the light emission spectrum of the second light emitting body E2 is between 400 nm and 800 nm, preferably between 450 nm and 750 nm, and most preferably between 450 nm and 700 nm.

[0126] In a more preferred embodiment, the peak (λ4) of the light emission spectrum of the second light emitting body E2 is between 455 nm and 465 nm.

[0127] In another preferred embodiment, the peak (λ4) of the light emission spectrum of the second light emitting body E2 is between 520 nm and 535 nm.

[0128] In some embodiments, the peak (λ3) of the absorption spectrum of the first luminophore E1 is between 350 nm and 600 nm, preferably between 400 nm and 500 nm, and most preferably between 420 nm and 460 nm.

[0129] In a more preferred embodiment, the peak value (λ3) of the absorption spectrum of the first luminous body E1 is between 425nm and 445nm.

[0130] In some embodiments, the peak (λ2) of the absorption spectrum of the second luminophore E2 is between 350 nm and 600 nm, preferably between 400 nm and 500 nm, and most preferably between 440 nm and 460 nm.

[0131] In a more preferred embodiment, the peak value (λ2) of the absorption spectrum of the first luminophore E2 is between 445 nm and 455 nm.

[0132] In some preferred embodiments, in the organic mixture, the weight ratio between the first luminophore E1 and the second luminophore E2 is from 10:90 to 90:10, preferably from 20:80 to 80:20, more preferably from 70:30 to 30:70, particularly preferably from 60:40 to 40:60, and most preferably from 55:45 to 45:55.

[0133] In some preferred embodiments, the organic mixture further comprises a host material H. Suitable host material H can be selected from singlet host materials.

[0134] Examples of the singlet host material are not particularly limited, and any organic compound may be used as the host material of the present invention as long as its singlet energy level is higher than that of the first luminophore E1 and the second luminophore E2.

[0135] Examples of organic compounds used as singlet host materials may be selected from aromatic hydrocarbon compounds containing rings, such as benzene, biphenyl, triphenylbenzene, triphenylene, naphthalene, anthracene, phenanthrene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; aromatic heterocyclic compounds, such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indole, carbazole, pyridine, indole, pyrrole, dipyridine, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, , indoleazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthalene, phthalide, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuran pyridine, furandipyridine, benzothiophene pyridine, thiophene dipyridine, benzoselenophene pyridine and selenophene dipyridine; containing groups having 2 to 10 ring atoms, which may be cyclic aromatic hydrocarbon groups or aromatic heterocyclic groups of the same or different types, and are linked to each other directly or through at least one of the following groups, such as oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, boron atoms, chain structural units and aliphatic ring groups.

[0136] In some preferred embodiments, the singlet host material may be selected from compounds comprising at least one of the following groups:

[0137] Each occurrence of Y is independently selected from C(R 101 )2、NR 101 , O or S, X each time occurs, is independently selected from CR 101 or N; R 101 Each occurrence is independently selected from the following groups: hydrogen, deuterium, halogen atoms (F, Cl, Br, I), cyano, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, heteroalkyl, aryl and heteroaryl, and n2 is selected from an integer from 1 to 20.

[0138] In some preferred embodiments, the singlet host is selected from anthracene derivatives, such as those disclosed in patent documents such as CN102224614B, CN100471827C, CN1914293B, WO2015033559A1, US2014246657A1, WO2016117848A1, WO2016117861A1, WO2016171429A2, CN102369256B, and CN102428158B.

[0139] In some preferred embodiments, the host material H is selected from the following chemical formula (4-1) or (4-2):

[0140] wherein Ar5 and Ar6 are as defined above for Ar1.

[0141] In some preferred embodiments, Ar5 and Ar6 are selected from benzene, naphthalene, dibenzofuran, naphthobenzofuran, carbazole and combinations thereof.

[0142] Some examples of singlet host materials that can serve as host material H are listed below:

[0143] In some more preferred embodiments, the anthracene-based singlet host material as the host material H is deuterated, that is, the host material molecule contains at least one deuterium atom. Such examples are disclosed in patent documents such as CN102369256B, CN102428158B, CN102639671B, and US2015021586A1. Specific examples include:

[0144] Another object of the present invention is to provide a material solution for printed OLEDs.

[0145] For this purpose, at least one of the first emitter E1 and the second emitter E2, and / or the host material H in the organic mixture according to the invention has a molecular weight of ≥700 g / mol, preferably ≥800 g / mol, very preferably ≥900 g / mol, more preferably ≥1000 g / mol and most preferably ≥1100 g / mol.

[0146] In certain embodiments, the organic mixture according to the present invention has a solubility of ≥5 mg / mL, preferably ≥10 mg / mL, more preferably ≥15 mg / mL, more preferably ≥20 mg / mL, and most preferably ≥25 mg / mL, in any one solvent of toluene, xylene, mesitylene, cyclohexylbenzene, or methyl benzoate, or a mixture of any two or more thereof at 25°C.

[0147] In other embodiments, in the organic mixture, the second luminophore E2 or the first luminophore E1 contains at least one cross-linkable group, as disclosed in patent application number CN202110370910.9, the entire contents of which are hereby incorporated herein by reference.

[0148] In some preferred embodiments, the second luminophore E2 or the first luminophore E1 comprises at least two cross-linkable groups.

[0149] In some other preferred embodiments, the second luminophore E2 or the first luminophore E1 comprises at least three cross-linkable groups.

[0150] In other embodiments, in the organic mixture, the host material H comprises at least one cross-linkable group.

[0151] In some preferred embodiments, the host material H comprises at least two cross-linkable groups.

[0152] In some other preferred embodiments, the host material H contains at least three cross-linkable groups.

[0153] The present invention also relates to a composition comprising an organic mixture as described above and at least one organic solvent.

[0154] In some preferred embodiments, the composition according to the present invention is a solution.

[0155] In other preferred embodiments, the composition according to the present invention is a suspension.

[0156] The composition in the embodiment of the present invention may include 0.01 wt % to 20 wt % of the organic mixture, preferably 0.1 wt % to 20 wt %, more preferably 0.2 wt % to 20 wt %, and most preferably 2 wt % to 15 wt %.

[0157] In some preferred embodiments, the organic solvent is selected from alcohols, esters, aromatic ketones or aromatic ethers, aliphatic ketones or aliphatic ethers, or inorganic ester compounds such as borate or phosphate esters, or a combination of two or more organic solvents.

[0158] In other embodiments, suitable and preferred organic solvents are aliphatic, cycloaliphatic or aromatic hydrocarbons, amines, thiols, amides, nitriles, esters, ethers, polyethers, alcohols, diols or polyols.

[0159] In other embodiments, alcohol represents an appropriate class of organic solvents. Preferred alcohols include alkylcyclohexanols, particularly methylated aliphatic alcohols, naphthols, and the like.

[0160] Other examples of suitable alcohol organic solvents include: dodecanol, phenyl tridecanol, benzyl alcohol, ethylene glycol, ethylene glycol methyl ether, glycerol, propylene glycol, propylene glycol ethyl ether and the like.

[0161] The organic solvent may be used alone or as a combination of two or more organic solvents.

[0162] Further, examples of organic solvents 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 combinations thereof.

[0163] In some preferred embodiments, according to the composition of the present invention, the organic solvent is selected from aromatic or heteroaromatic, esters, aromatic ketones or aromatic ethers, aliphatic ketones or aliphatic ethers, alicyclic or olefinic compounds, or inorganic ester compounds such as borate or phosphate esters, or a combination of two or more solvents.

[0164] Examples of aromatic or heteroaromatic solvents according to the present invention include, but are not limited to: 1-tetralone, 3-phenoxytoluene, acetophenone, 1-methoxynaphthalene, p-diisopropylbenzene, pentylbenzene, tetralin, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 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.

[0165] In other embodiments, suitable and preferred organic solvents are aliphatic, alicyclic or aromatic hydrocarbons, amines, thiols, amides, nitriles, esters, ethers, polyethers.

[0166] The organic solvent may be a cycloalkane, such as decalin.

[0167] In other preferred embodiments, the composition according to the present invention comprises at least 50 wt% of an alcohol solvent, preferably at least 80 wt% of an alcohol solvent, and particularly preferably at least 90 wt% of an alcohol solvent.

[0168] In some preferred embodiments, the organic solvent particularly suitable for the present invention is a solvent having a Hansen solubility parameter within the following range:

[0169] δ d (Dispersion force) at 17.0 MPa 1 / 2 -23.2MPa 1 / 2 range, especially at 18.5MPa 1 / 2 -21.0MPa 1 / 2 scope;

[0170] δ p (Polar force) at 0.2MPa 1 / 2 -12.5MPa 1 / 2 range, especially at 2.0MPa 1 / 2 -6.0MPa 1 / 2 scope;

[0171] δ h (Hydrogen bond force) at 0.9MPa 1 / 2 -14.2MPa 1 / 2 range, especially at 2.0MPa 1 / 2 -6.0MPa 1 / 2 range.

[0172] In the composition of the present invention, the organic solvent should be selected based on its boiling point. In the present 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 in inkjet printheads. The organic solvent can be evaporated from the solvent system to form a film containing the functional material.

[0173] In some preferred embodiments, the compositions according to the present invention:

[0174] 1) Its viscosity @25℃ is in the range of 1cps to 100cps, and / or

[0175] 2) Its surface tension @25℃ is in the range of 19 dyne / cm to 50 dyne / cm.

[0176] In the composition of the present invention, the organic solvent should be selected based on its surface tension. The appropriate surface tension parameter is tailored to the specific substrate and printing method. For example, for inkjet printing, in some preferred embodiments, 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.

[0177] In some preferred embodiments, the surface tension of the composition according to the present invention at 25°C is in the range of about 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.

[0178] In the composition of the present invention, the organic solvent should be selected taking into account the viscosity parameters of the ink. The viscosity can be adjusted by various methods, such as by selecting an appropriate organic solvent and the concentration of the functional material in the ink. In some preferred embodiments, the viscosity of the organic solvent is less than 100 cps; more preferably, less than 50 cps; and most preferably, between 1.5 cps and 20 cps. The viscosity here refers to the viscosity at the ambient temperature during printing, generally between 15°C and 30°C, preferably between 18°C ​​and 28°C, more preferably between 20°C and 25°C, and most preferably between 23°C and 25°C. The composition thus formulated is particularly suitable for inkjet printing.

[0179] In some preferred embodiments, the composition according to the present invention has a viscosity at 25°C in the range of about 1 cps to 100 cps; more preferably in the range of 1 cps to 50 cps; and most preferably in the range of 1.5 cps to 20 cps.

[0180] The ink obtained from the organic solvent that meets the above-mentioned boiling point, surface tension parameters and viscosity parameters can form a functional material film with uniform thickness and composition properties.

[0181] The present invention further relates to an organic functional material film, which is prepared using the composition as described above.

[0182] The present invention also provides a method for preparing the organic functional material thin film, comprising the following steps:

[0183] 1) preparing a composition according to the present invention;

[0184] 2) coating the composition on a substrate to form a thin film by printing or coating, wherein the printing or coating method is selected from inkjet printing, nozzle printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roller printing, rotary roller printing, offset printing, flexographic printing, rotary printing, spray coating, brush coating, pad printing, or slot die coating;

[0185] 3) The obtained film is heated at at least 50° C. to remove the organic solvent and solidify the film.

[0186] The thickness of the organic functional material film is generally 5 nm-20 μm, preferably 5 nm-10 μm, more preferably 10 nm-5 μm, and most preferably 10 nm-1 μm.

[0187] The present invention also provides the use of the organic mixture and the organic functional material film in optoelectronic devices.

[0188] In certain embodiments, the optoelectronic device may be selected from an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic light emitting field effect transistor (OLED), or an organic laser.

[0189] Furthermore, the present invention provides a photoelectric device comprising the above-mentioned organic mixture or organic functional material film.

[0190] Preferably, the optoelectronic device is an electroluminescent device, such as an organic light-emitting diode (OLED), an organic light-emitting cell (OLEEC), an organic light-emitting field-effect transistor (OLED), a perovskite light-emitting diode (PeLED), and a quantum dot light-emitting diode (QD-LED), wherein a functional layer comprises one of the aforementioned organic mixtures or organic functional material films. The functional layer can be selected from a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a light-emitting layer, or a cathode passivation layer (CPL).

[0191] In some preferred embodiments, the optoelectronic device is an organic electroluminescent device and comprises a substrate, an anode, a light-emitting layer and a cathode arranged in sequence, the light-emitting layer comprises at least one organic mixture as described above, or the light-emitting layer is prepared using the composition as described above.

[0192] In some embodiments, in the organic electroluminescent device, the second luminescent body E2 and the first luminescent body E1 are small molecules or polymers, preferably small molecules.

[0193] In some preferred embodiments, in the organic electroluminescent device, the light-emitting layer does not contain any resin.

[0194] In some preferred embodiments, the organic electroluminescent device emits blue light.

[0195] In some preferred embodiments, the organic electroluminescent device is an OLED. Particularly preferably, the organic electroluminescent device is a top emission OLED.

[0196] The substrate can be opaque or transparent. A transparent substrate can be used to make a transparent light-emitting device. For example, see Bulovic et al. Nature 1996, 380, p29, and Gu et al., Appl. Phys. Lett. 1996, 68, p2606. The substrate can be rigid or elastic. The substrate can be plastic, metal, semiconductor wafer or glass. It is best if the substrate has a smooth surface. Substrates without surface defects are particularly ideal. In some preferred embodiments, the substrate is flexible and can be selected from polymer films or plastics with a glass transition temperature (Tg) of above 150°C, preferably above 200°C, more preferably above 250°C, and most preferably above 300°C. Examples of suitable flexible substrates are polyethylene terephthalate (PET) and polyethylene glycol (2,6-naphthalene) (PEN).

[0197] The anode may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can readily inject holes into the hole injection layer (HIL), hole transport layer (HTL), or light-emitting layer. In some preferred embodiments, 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 material 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), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material can be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.

[0198] The cathode may comprise a conductive metal or metal oxide. The cathode can readily inject electrons into the EIL or ETL or directly into the light-emitting layer. In some preferred embodiments, the absolute difference between the work function of the cathode and the LUMO energy level or conduction band energy level of the luminophore 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 that can be used as cathodes in OLEDs may be used as cathode materials for the devices of the present invention. Examples of cathode materials include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF / Al, MgAg alloys, BaF2 / Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, and the like. The cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In some preferred embodiments, the cathode has a transmittance of ≥40% in the range of 400 nm to 680 nm, preferably ≥45%, more preferably ≥50%, and most preferably ≥60%. A Mg:Ag alloy of 10 nm to 20 nm in thickness can be used as the transparent cathode, with a Mg:Ag ratio ranging from 2:8 to 0.5:9.5.

[0199] The OLED may further include other functional layers, such as a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL). Suitable materials for these functional layers are described in detail above and in WO2010135519A1, US20090134784A1, and WO2011110277A1, the entire contents of which are hereby incorporated by reference.

[0200] Furthermore, the organic electroluminescent device further includes a cathode capping layer (CPL for short).

[0201] In some preferred embodiments, the CPL is located between the second electrode and the color conversion layer.

[0202] In some other preferred embodiments, the CPL is located above the color conversion layer.

[0203] Materials used for CPL generally need to have a higher refractive index n, such as n≥1.95@460nm, n≥1.90@520nm, n≥1.85@620nm. Examples of materials used for CPL include:

[0204] More examples of further CPL materials can be found in the following patent documents: KR20140128653A, KR20140137231A, KR20140142021A, KR20140142923A, KR20140143618A, KR20140145370A, KR20150004099A, KR20150012835A, US9496520B2, US2015069350A1, CN10382 8485B, CN104380842B, CN105576143A, TW201506128A, CN103996794A, CN103996795A, CN104744450A, CN104752619A, CN101944570A, US2016308162A1, US9095033B2, US2014034942A1, WO2017014357A1; the above patent documents are hereby incorporated into this document for reference.

[0205] Preferably, in the above organic electroluminescent device, the encapsulation layer is a thin film encapsulation (TFE).

[0206] The present invention further relates to a display panel, wherein at least one pixel comprises the above-mentioned organic electroluminescent device.

[0207] Example

[0208] The present invention will be described below 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 concept of the present invention, those skilled in the art should realize that certain changes made to the various embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention.

[0209] 1. Synthesis of compounds

[0210] Compound E1-1:

[0211] The synthesis of compound E1-1 was carried out according to the method described in patent WO2015061198.

[0212] Compound E1-2:

[0213] The synthesis of compound E1-2 was carried out according to the method described in patent WO2008006449.

[0214] Compound E1-3:

[0215] The synthesis of compound E1-3 was carried out according to the method described in patent WO2019240251.

[0216] Compound E1-4:

[0217] The synthesis of compound E1-4 was carried out according to the method described in patent US20140309458.

[0218] Compound E1-5:

[0219] Synthesis of Intermediate 1a: To a 500 mL three-necked flask were added compound 1-1 (19.7 g, 100 mmol), compound 1-2 (35.2 g, 100 mmol), 300 mL of toluene, sodium tert-butoxide (14.4 g, 150 mmol), Pd2(dba)3 (916 mg, 1 mmol), and TTBPH·BF4 (580 mg, 2 mmol). The atmosphere was replaced with nitrogen by vacuum three times and the reaction was heated to 110°C. The reaction was monitored by TLC. After completion of the reaction, the system was cooled to room temperature and the solvent removed by rotary evaporation. The reaction mixture was extracted with ethyl acetate and saturated sodium chloride solution. The combined organic phases were dried, filtered, concentrated, and separated by silica gel chromatography using n-hexane:dichloromethane = 10:1 (volume ratio) as the eluent to afford Intermediate 2a, approximately 32.6 g after drying, with a yield of approximately 69.7%.

[0220] Synthesis of intermediate 2b: To a 500 mL three-necked flask, intermediate 1a (30.0 g, 64.0 mmol) was added. The mixture was evacuated and replaced with nitrogen three times, followed by the addition of 250 mL of THF solution. The mixture was cooled to -78°C using liquid nitrogen, followed by the addition of 28.2 mL of a 2.5 M n-butyllithium solution. After stirring for 1 h, triethyl borate (18.7 g, 128 mmol) was slowly added dropwise, and the mixture was gradually returned to room temperature and stirred overnight. After the reaction was complete, 10% dilute hydrochloric acid solution was added to quench the reaction, and the mixture was extracted with ethyl acetate and saturated sodium chloride solution. The organic phases were combined, dried, filtered, concentrated, and then slurried with n-hexane to obtain intermediate 1b, approximately 24.7 g after drying, with a yield of approximately 89.1%.

[0221] Synthesis of Intermediate 2a: Compound 2-1 (9.86 g, 50.0 mmol) and 60% sodium hydride powder (3.00 g, 75.0 mmol) were added to a 500 mL three-necked flask. The atmosphere was evacuated and replaced with nitrogen three times. 100 mL of DMF was then added and stirred at room temperature for half an hour. Compound 2-2 (11.0 g, 50.0 mmol) was then dissolved in 50 mL of DMF and slowly added to the three-necked flask via syringe. The temperature was raised to 110°C and the reaction was monitored by TLC. After the reaction was complete, the mixture was cooled to room temperature and the solvent was removed by rotary evaporation. The mixture was then extracted with ethyl acetate and saturated sodium chloride solution. The combined organic phases were dried, filtered, concentrated, and separated by silica gel chromatography using n-hexane:dichloromethane = 4:1 (volume ratio) as the eluent to obtain approximately 12.2 g of intermediate 2a after drying, with a yield of 61.5%.

[0222] Synthesis of Intermediate 3a: To a 500 mL three-necked flask were added Intermediate 1b (16.0 g, 36.8 mmol), Intermediate 2a (12.2 g, 30.7 mmol), and tetrakistriphenylphosphine palladium (355 mg, 0.307 mmol). The atmosphere was evacuated and replaced with nitrogen three times. Then, 31 mL of toluene and 31 mL of 2M potassium carbonate solution were added. The temperature was raised to 100°C, and the reaction was monitored by TLC. After the reaction was complete, the mixture was cooled to room temperature, and the solvent was removed from the reaction system by rotary evaporation. The mixture was then extracted with ethyl acetate and saturated sodium chloride solution. The combined organic phases were dried, filtered, and concentrated. The resulting mixture was then separated by silica gel chromatography using n-hexane:dichloromethane = 3:1 (volume ratio) as the eluent to afford approximately 18.0 g of Intermediate 3a, with a yield of 83.2%.

[0223] Synthesis of Intermediate 3b: To a 500 mL three-necked flask was added Intermediate 3a (18.0 g, 25.5 mmol). The atmosphere was evacuated and replaced with nitrogen three times. Then, 50 mL of triethyl phosphite was added and heated to reflux. The reaction was monitored by TLC. After completion of the reaction, the system was cooled to room temperature and the solvent removed by rotary evaporation. After concentration, the system was separated by silica gel chromatography using n-hexane:dichloromethane = 4:1 (volume ratio) as the eluent to afford Intermediate 3b, approximately 6.74 g after drying, for a yield of 39.2%.

[0224] Synthesis of Compound E1-5: To a 500 mL three-necked flask were added intermediate 3b (6.70 g, 9.94 mmol), compound 3-1 (2.04 g, 10.0 mmol), 100 mL of toluene, sodium tert-butoxide (1.44 g, 15.0 mmol), Pd2(dba)3 (91.6 mg, 0.1 mmol), and TTBPH·BF4 (58.0 mg, 0.2 mmol). The atmosphere was replaced with nitrogen by vacuum three times, and the reaction was heated to 110°C. The reaction was monitored by TLC. After the reaction was complete, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation. The mixture was extracted with ethyl acetate and saturated sodium chloride solution. The organic phases were combined, dried, filtered, concentrated, and separated by silica gel chromatography using n-hexane:dichloromethane = 4:1 (volume ratio) as the eluent to obtain approximately 6.81 g of compound E1-5 after drying, with a yield of approximately 91.3%.

[0225] Compound E1-6:

[0226] The synthesis of compound E1-6 was carried out according to the method described in patent WO2006098080.

[0227] Compound E1-7:

[0228] The synthesis of compound E1-7 was carried out according to the method described in patent WO2010083873.

[0229] Compound E1-8:

[0230] The synthesis of compound E1-8 was carried out according to the method described in patent WO2006122630.

[0231] Compound E1-9:

[0232] The synthesis of compound E1-9 was carried out according to the method described in patent KR2010003624.

[0233] Compound E2-1:

[0234] The synthesis of compound E2-1 was carried out according to the method described in patent CN117567491.

[0235] Compound E2-2:

[0236] Synthesis of Intermediate 4a: Compound 4-1 (28.8 g, 100.0 mmol), compound 4-2 (37.1 g, 110.0 mmol), 300 mL of toluene, sodium tert-butoxide (14.4 g, 150.0 mmol), Pd2(dba)3 (916 mg, 1.0 mmol), and Xantphos (1.1 g, 2.0 mmol) were added sequentially to a 500 mL three-necked flask. The atmosphere was evacuated and replaced with nitrogen three times. The reaction was heated to 110°C and monitored by TLC. After the reaction was complete, the mixture was cooled to room temperature and the solvent removed by rotary evaporation. The mixture was extracted with ethyl acetate and saturated sodium chloride solution. The organic phases were combined, dried, filtered, concentrated, and separated by silica gel chromatography using n-hexane:dichloromethane = 15:1 (volume ratio) as the eluent to obtain approximately 33.5 g of intermediate 4a after drying, with a yield of 61.5%.

[0237] Synthesis of Intermediate 4b: To a 500 mL three-necked flask, intermediate 4a (30.0 g, 55.0 mmol), compound 4-3 (17.6 g, 60.5 mmol), cesium carbonate (26.5 g, 82.5 mmol), and 300 mL of DMF were added in sequence and the mixture was heated to reflux. The reaction was monitored by TLC and stopped after the starting materials were substantially consumed. The mixture was slurried with 300 mL of methanol and 100 mL of water at room temperature for 2 h to obtain intermediate 4b, which was approximately 29.2 g after drying, with a yield of approximately 65.1%.

[0238] Synthesis of Intermediate 4c: To a 500 mL three-necked flask were added Intermediate 4b (25.0 g, 30.6 mmol), compound 4-4 (9.4 g, 33.6 mmol), 200 mL of toluene, sodium tert-butoxide (4.4 g, 45.9 mmol), Pd2(dba)3 (280 mg, 0.3 mmol), and TTBPH·BF4 (74.0 mg, 0.6 mmol). The atmosphere was evacuated and replaced with nitrogen three times. The reaction was heated to 110°C and monitored by TLC. After completion of the reaction, the system was cooled to room temperature and the solvent removed by rotary evaporation. The system was then extracted with ethyl acetate and saturated sodium chloride solution. The combined organic phases were dried, filtered, concentrated, and separated by silica gel chromatography using n-hexane:dichloromethane = 12:1 (volume ratio) as the eluent to afford Intermediate 4c, approximately 21.7 g after drying, for a yield of approximately 69.8%.

[0239] Synthesis of compound E2-2: Intermediate 4c (20.0 g, 19.7 mmol) and 200 mL of tert-butylbenzene were added to a 500 mL three-necked flask. The atmosphere was evacuated and replaced with nitrogen three times. 1.6 M tert-butyl lithium (25.8 mL, 43.34 mmol) was added dropwise at 0°C. After the addition was complete, the temperature was raised to 60°C for 1 h. Boron tribromide (5.6 mL, 59.1 mmol) was added dropwise at 0°C and the reaction was allowed to proceed at room temperature for 2 h. Diisopropylethylamine (25.8 mL, 147.7 mmol) was added dropwise at 0°C and the reaction was allowed to proceed at 120°C for 3 h. After the reaction was completed, the mixture was cooled to room temperature, and the solvent in the reaction system was removed by rotary evaporation. The mixture was extracted with ethyl acetate and saturated sodium chloride solution. The organic phases were combined, dried, filtered, concentrated, and recrystallized from toluene to obtain compound E2-2, approximately 2.9 g after drying, with a yield of approximately 14.9%.

[0240] Compound E2-3:

[0241] Synthesis of Intermediate 5a: Compound 5-1 (25.7 g, 100.0 mmol), compound 4-2 (37.1 g, 110.0 mmol), 300 ml of toluene, sodium tert-butoxide (14.4 g, 150.0 mmol), Pd2(dba)3 (916 mg, 1.0 mmol), and X-Phos (953 mg, 2.0 mmol) were added sequentially to a 500 mL three-necked flask. The atmosphere was evacuated and replaced with nitrogen three times. The reaction was heated to 110°C and monitored by TLC. After the reaction was complete, the mixture was cooled to room temperature and the solvent removed by rotary evaporation. The mixture was extracted with ethyl acetate and saturated sodium chloride solution. The organic phases were combined, dried, filtered, concentrated, and separated by silica gel chromatography using n-hexane:dichloromethane = 12:1 (volume ratio) as the eluent to obtain approximately 32.5 g of intermediate 5a after drying, with a yield of approximately 58.3%.

[0242] Synthesis of Intermediate 5b: To a 500 mL three-necked flask were added Intermediate 5a (17.1 g, 30.6 mmol), compound 5-2 (17.3 g, 33.6 mmol), 200 mL of toluene, sodium tert-butoxide (4.4 g, 45.9 mmol), Pd2(dba)3 (280 mg, 0.3 mmol), and TTBPH·BF4 (174.0 mg, 0.6 mmol). The atmosphere was evacuated and replaced with nitrogen three times. The reaction was heated to 110°C and monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature and the solvent removed by rotary evaporation. The mixture was extracted with ethyl acetate and saturated sodium chloride solution. The combined organic phases were dried, filtered, concentrated, and separated by silica gel chromatography using n-hexane:dichloromethane = 8:1 (volume ratio) as the eluent to afford Intermediate 5b, approximately 19.6 g after drying, with a yield of approximately 61.9%.

[0243] Synthesis of Compound E2-3: Intermediate 5b (20.4 g, 19.7 mmol) and 200 mL of tert-butylbenzene were added to a 500 mL three-necked flask. The atmosphere was evacuated and replaced with nitrogen three times. 1.6 M tert-butyl lithium (25.8 mL, 43.34 mmol) was added dropwise at 0°C. After the addition was complete, the temperature was raised to 60°C for 1 h. Boron tribromide (5.6 mL, 59.1 mmol) was added dropwise at 0°C and the reaction was allowed to proceed at room temperature for 2 h. Diisopropylethylamine (25.8 mL, 147.7 mmol) was added dropwise at 0°C and the reaction was allowed to proceed at 120°C for 3 h. After the reaction was completed, the mixture was cooled to room temperature, and the solvent in the reaction system was removed by rotary evaporation. The mixture was extracted with ethyl acetate and saturated sodium chloride solution. The organic phases were combined, dried, filtered, concentrated, and recrystallized from toluene to obtain Compound E2-3, approximately 3.5 g after drying, with a yield of approximately 17.5%.

[0244] Compound E2-4:

[0245] Synthesis of intermediate 6a: Compound 6-2 (7.9 g, 30.6 mmol), compound 6-1 (14.3 g, 33.6 mmol), 150 mL of dioxane, 30 mL of water, potassium carbonate (8.4 g, 61.2 mmol), and Pd(PPh3)4 (346 mg, 0.3 mmol) were added sequentially to a 250 mL three-necked flask. The atmosphere was evacuated and replaced with nitrogen three times. The reaction was heated to 100°C and monitored by TLC. After the reaction was complete, the mixture was cooled to room temperature and the solvent in the reaction system was removed by rotary evaporation. The mixture was extracted with ethyl acetate and saturated sodium chloride solution. The organic phases were combined, dried, filtered, concentrated, and separated by silica gel chromatography using n-hexane as the eluent to obtain intermediate 6a, which was approximately 15.3 g after drying, with a yield of approximately 89.8%.

[0246] Synthesis of Intermediate 6b: To a 250 mL three-necked flask were added Intermediate 6a (14.2 g, 25.4 mmol), compound 4-2 (9.4 g, 27.9 mmol), 150 mL of toluene, sodium tert-butoxide (3.7 g, 38.1 mmol), Pd2(dba)3 (183 mg, 0.2 mmol), and X-Phos (190.6 mg, 0.4 mmol). The atmosphere was evacuated and replaced with nitrogen three times. The reaction was heated to 110°C and monitored by TLC. After the reaction was complete, the system was cooled to room temperature and the solvent removed by rotary evaporation. The system was then extracted with ethyl acetate and saturated sodium chloride solution. The combined organic phases were dried, filtered, concentrated, and separated by silica gel chromatography using n-hexane:dichloromethane = 10:1 (volume ratio) as the eluent to afford Intermediate 6b, approximately 14.6 g after drying, with a yield of approximately 66.6%.

[0247] Synthesis of Intermediate 6c: To a 250 mL three-necked flask were added Intermediate 6b (14.0 g, 16.2 mmol), compound 6-3 (9.4 g, 17.8 mmol), 150 mL of toluene, sodium tert-butoxide (2.3 g, 24.3 mmol), Pd2(dba)3 (183 mg, 0.2 mmol), and TTBPH·BF4 (116.0 mg, 0.4 mmol). The atmosphere was evacuated and replaced with nitrogen three times. The reaction was heated to 110°C and monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature and the solvent removed by rotary evaporation. The mixture was extracted with ethyl acetate and saturated sodium chloride solution. The combined organic phases were dried, filtered, concentrated, and separated by silica gel chromatography using n-hexane:dichloromethane = 7:1 (volume ratio) as the eluent to afford Intermediate 6c, approximately 16.0 g after drying, with a yield of approximately 73.3%.

[0248] Synthesis of Compound E2-4: Compound intermediate 6c (15.1 g, 11.2 mmol) and 200 mL of tert-butylbenzene were added to a 500 mL three-necked flask. The atmosphere was evacuated and replaced with nitrogen three times. 1.6 M tert-butyl lithium (14.7 mL, 24.7 mmol) was added dropwise at 0°C. After the addition was complete, the temperature was raised to 60°C for 1 h. Boron tribromide (3.2 mL, 33.6 mmol) was added dropwise at 0°C and the reaction was allowed to proceed at room temperature for 2 h. Diisopropylethylamine (14.7 mL, 84.1 mmol) was added dropwise at 0°C and the reaction was allowed to proceed at 120°C for 3 h. After the reaction was completed, the mixture was cooled to room temperature, and the solvent in the reaction system was removed by rotary evaporation. The mixture was extracted with ethyl acetate and saturated sodium chloride solution. The organic phases were combined, dried, filtered, concentrated, and recrystallized from toluene to obtain compound E2-4, approximately 3.6 g after drying, with a yield of approximately 24.2%.

[0249] Compound E2-5:

[0250] Synthesis of Intermediate 7b: To a 500 mL three-necked flask were added Intermediate 5a (17.1 g, 30.6 mmol), compound 6-3 (17.6 g, 33.6 mmol), 200 mL of toluene, sodium tert-butoxide (4.4 g, 45.9 mmol), Pd2(dba)3 (280 mg, 0.3 mmol), and TTBPH·BF4 (174.0 mg, 0.6 mmol). The atmosphere was evacuated and replaced with nitrogen three times. The reaction was heated to 110°C and monitored by TLC. After completion of the reaction, the system was cooled to room temperature and the solvent removed by rotary evaporation. The system was then extracted with ethyl acetate and saturated sodium chloride solution. The combined organic phases were dried, filtered, concentrated, and separated by silica gel chromatography using n-hexane:dichloromethane = 8:1 (volume ratio) as the eluent to afford Intermediate 7b, approximately 23.2 g after drying, with a yield of approximately 72.6%.

[0251] Synthesis of Compound E2-5: To a 500 mL three-necked flask, intermediate 7b (20.0 g, 19.7 mmol) and 200 mL of tert-butylbenzene were added. The mixture was evacuated and replaced with nitrogen three times. 1.6 M tert-butyllithium (25.8 mL, 43.34 mmol) was added dropwise at 0°C. After the addition was complete, the temperature was raised to 60°C for 1 h. Boron tribromide (5.6 mL, 59.1 mmol) was added dropwise at 0°C and the reaction was allowed to proceed at room temperature for 2 h. Diisopropylethylamine (25.8 mL, 147.7 mmol) was added dropwise at 0°C and the reaction was allowed to proceed at 120°C for 3 h. After the reaction was completed, the mixture was cooled to room temperature, and the solvent in the reaction system was removed by rotary evaporation. The mixture was extracted with ethyl acetate and saturated sodium chloride solution. The organic phases were combined, dried, filtered, concentrated, and recrystallized from toluene to obtain compound E2-5, approximately 4.3 g after drying, with a yield of approximately 21.1%.

[0252] Compound E2-6:

[0253] Synthesis of Intermediate 8a: Compound 5-1 (25.6 g, 100.0 mmol), compound 8-1 (40.8 g, 110.0 mmol), 300 ml of toluene, sodium tert-butoxide (14.4 g, 150.0 mmol), Pd2(dba)3 (916 mg, 1.0 mmol), and X-Phos (953 mg, 2.0 mmol) were added sequentially to a 500 mL three-necked flask. The atmosphere was evacuated and replaced with nitrogen three times. The reaction was heated to 110°C and monitored by TLC. After the reaction was complete, the mixture was cooled to room temperature and the solvent was removed by rotary evaporation. The mixture was extracted with ethyl acetate and saturated sodium chloride solution. The organic phases were combined, dried, filtered, concentrated, and separated by silica gel chromatography using n-hexane:dichloromethane = 10:1 (volume ratio) as the eluent to obtain approximately 40.1 g of intermediate 8a after drying, with a yield of approximately 67.7%.

[0254] Synthesis of Intermediate 8b: To a 500 mL three-necked flask were added Intermediate 8a (18.14 g, 30.6 mmol), compound 6-3 (17.6 g, 33.6 mmol), 200 mL of toluene, sodium tert-butoxide (4.4 g, 45.9 mmol), Pd2(dba)3 (280 mg, 0.3 mmol), and TTBPH·BF4 (174.0 mg, 0.6 mmol). The atmosphere was evacuated and replaced with nitrogen three times. The reaction was heated to 110°C and monitored by TLC. After completion of the reaction, the system was cooled to room temperature and the solvent removed by rotary evaporation. The system was then extracted with ethyl acetate and saturated sodium chloride solution. The combined organic phases were dried, filtered, concentrated, and separated by silica gel chromatography using n-hexane:dichloromethane = 6:1 (volume ratio) as the eluent to afford Intermediate 8b, approximately 24.5 g after drying, with a yield of approximately 73.9%.

[0255] Synthesis of Compound E2-6: Intermediate 8b (21.3 g, 19.7 mmol) and 200 mL of tert-butylbenzene were added to a 500 mL three-necked flask. The atmosphere was evacuated and replaced with nitrogen three times. 1.6 M tert-butyllithium (25.8 mL, 43.34 mmol) was added dropwise at 0°C. After the addition was complete, the temperature was raised to 60°C for 1 h. Boron tribromide (5.6 mL, 59.1 mmol) was added dropwise at 0°C and the reaction was allowed to proceed at room temperature for 2 h. Diisopropylethylamine (25.8 mL, 147.7 mmol) was added dropwise at 0°C and the reaction was allowed to proceed at 120°C for 3 h. After the reaction was completed, the mixture was cooled to room temperature, and the solvent in the reaction system was removed by rotary evaporation. The mixture was extracted with ethyl acetate and saturated sodium chloride solution. The organic phases were combined, dried, filtered, concentrated, and recrystallized from toluene to obtain Compound E2-6, approximately 2.4 g after drying, with a yield of approximately 11.7%.

[0256] Compound E2-7:

[0257] Synthesis of Intermediate 9a: In a 500 mL three-necked flask, intermediate 4a (30.0 g, 55.0 mmol), compound 9-1 (19.9 g, 60.5 mmol), cesium carbonate (26.5 g, 82.5 mmol), and 300 mL of DMF were added in sequence and the mixture was heated to reflux. The reaction was monitored by TLC and stopped after the starting materials were substantially consumed. The mixture was slurried with 300 mL of methanol and 100 mL of water at room temperature for 2 h to obtain intermediate 9a, which was approximately 30.3 g after drying, with a yield of approximately 64.4%.

[0258] Synthesis of Intermediate 9b: To a 500 mL three-necked flask were added Intermediate 9a (26.1 g, 30.6 mmol), compound 4-4 (9.4 g, 33.6 mmol), 200 mL of toluene, sodium tert-butoxide (4.4 g, 45.9 mmol), Pd2(dba)3 (280 mg, 0.3 mmol), and TTBPH·BF4 (174.0 mg, 0.6 mmol). The atmosphere was evacuated and replaced with nitrogen three times. The reaction was heated to 110°C and monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature and the solvent removed by rotary evaporation. The mixture was extracted with ethyl acetate and saturated sodium chloride solution. The combined organic phases were dried, filtered, concentrated, and separated by silica gel chromatography using n-hexane:dichloromethane = 12:1 (volume ratio) as the eluent to afford Intermediate 9b, approximately 21.3 g after drying, with a yield of approximately 66.1%.

[0259] Synthesis of Compound E2-7: Intermediate 9b (20.7 g, 19.7 mmol) and 200 mL of tert-butylbenzene were added to a 500 mL three-necked flask. The atmosphere was evacuated and replaced with nitrogen three times. 1.6 M tert-butyllithium (25.8 mL, 43.34 mmol) was added dropwise at 0°C. After the addition was complete, the temperature was raised to 60°C for 1 h. Boron tribromide (5.6 mL, 59.1 mmol) was added dropwise at 0°C and the reaction was allowed to proceed at room temperature for 2 h. Diisopropylethylamine (25.8 mL, 147.7 mmol) was added dropwise at 0°C and the reaction was allowed to proceed at 120°C for 3 h. After the reaction was completed, the mixture was cooled to room temperature, and the solvent in the reaction system was removed by rotary evaporation. The mixture was extracted with ethyl acetate and saturated sodium chloride solution. The organic phases were combined, dried, filtered, concentrated, and recrystallized from toluene to obtain Compound E2-7, approximately 3.3 g after drying, with a yield of approximately 16.6%.

[0260] Compound E2-8:

[0261] Synthesis of Intermediate 10a: Compound 4-1 (28.8 g, 100.0 mmol), compound 10-1 (42.8 g, 110.0 mmol), 300 mL of toluene, sodium tert-butoxide (14.4 g, 150.0 mmol), Pd2(dba)3 (916 mg, 1.0 mmol), and Xantphos (1.1 g, 2.0 mmol) were added sequentially to a 500 mL three-necked flask. The atmosphere was evacuated and replaced with nitrogen three times. The reaction was heated to 110°C and monitored by TLC. After the reaction was complete, the mixture was cooled to room temperature and the solvent removed by rotary evaporation. The mixture was extracted with ethyl acetate and saturated sodium chloride solution. The organic phases were combined, dried, filtered, concentrated, and separated by silica gel chromatography using n-hexane:dichloromethane = 15:1 (volume ratio) as the eluent to obtain approximately 38.5 g of Intermediate 10a after drying, with a yield of approximately 64.6%.

[0262] Synthesis of Intermediate 10b: To a 500 mL three-necked flask, intermediate 10a (32.8 g, 55.0 mmol), compound 9-1 (19.9 g, 60.5 mmol), cesium carbonate (26.5 g, 82.5 mmol), and 300 mL of DMF were added sequentially and heated to reflux. The reaction was monitored by TLC and stopped when the starting materials were substantially consumed. The product was slurried with 300 mL of methanol and 100 mL of water at room temperature for 2 h to obtain intermediate 10b, which was approximately 35.2 g after drying, with a yield of approximately 70.7%.

[0263] Synthesis of Intermediate 10c: To a 500 mL three-necked flask were added Intermediate 10b (27.7 g, 30.6 mmol), compound 4-4 (9.4 g, 33.6 mmol), 200 mL of toluene, sodium tert-butoxide (4.4 g, 45.9 mmol), Pd2(dba)3 (280 mg, 0.3 mmol), and TTBPH·BF4 (174.0 mg, 0.6 mmol). The atmosphere was evacuated and replaced with nitrogen three times. The reaction was heated to 110°C and monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature and the solvent removed by rotary evaporation. The reaction mixture was extracted with ethyl acetate and saturated sodium chloride solution. The combined organic phases were dried, filtered, concentrated, and separated by silica gel chromatography using n-hexane:dichloromethane = 12:1 (volume ratio) as the eluent to afford Intermediate 10c, approximately 23.0 g after drying, with a yield of approximately 68.1%.

[0264] Synthesis of Compound E2-8: Intermediate 10c (21.7 g, 19.7 mmol) and 200 mL of tert-butylbenzene were added to a 500 mL three-necked flask. The atmosphere was evacuated and replaced with nitrogen three times. 1.6 M tert-butyllithium (25.8 mL, 43.34 mmol) was added dropwise at 0°C. After the addition was complete, the temperature was raised to 60°C for 1 h. Boron tribromide (5.6 mL, 59.1 mmol) was added dropwise at 0°C and the reaction was allowed to proceed at room temperature for 2 h. Diisopropylethylamine (25.8 mL, 147.7 mmol) was added dropwise at 0°C and the reaction was allowed to proceed at 120°C for 3 h. After the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed from the reaction system by rotary evaporation. The mixture was extracted with ethyl acetate and saturated sodium chloride solution. The organic phases were combined, dried, filtered, concentrated, and recrystallized from toluene to obtain Compound E2-8, approximately 2.1 g after drying, with a yield of approximately 10.6%.

[0265] Compound E2-9:

[0266] Synthesis of Intermediate 11a: Compound 11-1 (13.4 g, 55.0 mmol), compound 4-4 (19.9 g, 60.5 mmol), cesium carbonate (26.5 g, 82.5 mmol), and 300 mL of DMF were added sequentially to a 500 mL three-necked flask and heated to 100°C. The reaction was monitored by TLC and stopped when the starting materials were essentially consumed. The product was slurried with 300 mL of methanol and 100 mL of water at room temperature for 2 h to obtain Intermediate 11a, which was approximately 25.5 g after drying, with a yield of approximately 92.2%.

[0267] Synthesis of Intermediate 11b: To a 250 mL three-necked flask were added Intermediate 11a (14.4 g, 30.6 mmol), Compound 11-2 (7.1 g, 33.6 mmol), 150 mL of dioxane, 30 mL of water, potassium carbonate (8.4 g, 61.2 mmol), and Pd(PPh3)4 (346 mg, 0.3 mmol). The mixture was evacuated and replaced with nitrogen three times. The reaction was heated to 100°C and monitored by TLC. After the reaction was complete, the mixture was cooled to room temperature and the solvent removed by rotary evaporation. The mixture was extracted with ethyl acetate and saturated sodium chloride solution. The organic phases were combined, dried, filtered, concentrated, and separated by silica gel chromatography using n-hexane:dichloromethane = 10:1 (volume ratio) as the eluent to afford Intermediate 11b, approximately 15.1 g after drying, with a yield of approximately 83.7%.

[0268] Synthesis of Intermediate 11c: To a 250 mL three-necked flask were added Intermediate 11b (15.0 g, 25.4 mmol), compound 4-2 (9.4 g, 27.9 mmol), 150 mL of toluene, sodium tert-butoxide (3.7 g, 38.1 mmol), Pd2(dba)3 (183 mg, 0.2 mmol), and TTBPH·BF4 (116.0 mg, 0.4 mmol). The atmosphere was evacuated and replaced with nitrogen three times. The reaction was heated to 110°C and monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature and the solvent removed by rotary evaporation. The mixture was extracted with ethyl acetate and saturated sodium chloride solution. The combined organic phases were dried, filtered, concentrated, and separated by silica gel chromatography using n-hexane:dichloromethane = 8:1 (volume ratio) as the eluent to afford Intermediate 11c, approximately 14.3 g after drying, for a yield of approximately 63.5%.

[0269] Synthesis of compound E2-9: Intermediate 11c (10.0 g, 11.2 mmol) and 200 mL of tert-butylbenzene were added to a 500 mL three-necked flask. The atmosphere was evacuated and replaced with nitrogen three times. 1.6 M tert-butyl lithium (14.7 mL, 24.7 mmol) was added dropwise at 0°C. After the addition was complete, the temperature was raised to 60°C for 1 h. Boron tribromide (3.2 mL, 33.6 mmol) was added dropwise at 0°C and the reaction was allowed to proceed at room temperature for 2 h. Diisopropylethylamine (14.7 mL, 84.1 mmol) was added dropwise at 0°C and the reaction was allowed to proceed at 120°C for 3 h. After the reaction was completed, the mixture was cooled to room temperature, and the solvent in the reaction system was removed by rotary evaporation. The mixture was extracted with ethyl acetate and saturated sodium chloride solution. The organic phases were combined, dried, filtered, concentrated, and recrystallized from toluene to obtain compound E2-9, approximately 2.1 g after drying, with a yield of approximately 21.8%.

[0270] 2. Energy level structure of compound E1

[0271] The energy levels of organic materials can be calculated through quantum calculations, such as using TD-DFT (time-dependent density functional theory) with Gaussian 09W (Gaussian Inc.). For detailed simulation methods, see WO2011141110. The molecular geometry is first optimized using the semi-empirical method "Ground State / Semi-empirical / Default Spin / AM1" (Charge 0 / Spin Singlet). The energy structure of the organic molecule is then calculated using TD-DFT (time-dependent density functional theory) using the basis set "TD-SCF / DFT / Default Spin / B3PW91" and "6-31G(d)" (Charge 0 / Spin Singlet). The HOMO and LUMO energy levels are calculated using the following calibration formulas, with S1 and T1 used directly.

[0272] HOMO(eV)=((HOMO(G)×27.212)-0.9899) / 1.1206

[0273] LUMO(eV)=((LUMO(G)×27.212)-2.0041) / 1.385

[0274] The HOMO(G) and LUMO(G) are the direct calculation results of Gaussian 09W, and the unit is Hartree.

[0275] The results are shown in Table 1:

[0276] Table 1

[0277] Where: HOMO energy level is the highest occupied molecular orbital energy of an organic molecule, LUMO energy level is the lowest unoccupied molecular orbital energy of an organic molecule; ΔHOMO is the difference between the highest occupied molecular orbital energy and the second highest occupied molecular orbital energy of an organic molecule (ΔHOMO = HOMO - (HOMO - 1)); E S1 The energy level is the lowest singlet excited state energy level of the organic molecule, E T1 The energy level is the lowest triplet excited state energy level of organic molecules ， ΔE ST The difference between the lowest singlet excited state energy level and the lowest triplet excited state energy level of the organic molecule (ΔE ST =E S1 -E T1 ).

[0278] 3. Optical properties of mixtures

[0279] The organic mixture of the present invention was prepared by the following method: E1 and E2 in a certain mass ratio were dissolved in toluene to obtain a homogeneous solution, and the solvent was evaporated by vacuum drying to obtain a mixture solid; the solid was further mechanically ground and mixed in a quartz mortar to obtain the organic mixture of the present invention.

[0280] The mixture formulation and its photoluminescence properties in polystyrene (PS) films are shown in Table 2. The preparation and characterization methods of the polystyrene doped film are as follows:

[0281] Polystyrene (CAS: 9003-53-6, average Mw ~280,000 by GPC, purchased from Sigma-Aldrich) was dissolved in toluene to form a 100 mg / mL solution. A comparative example compound or an organic mixture according to the present invention was then dissolved in the solution at a concentration of 3 mg / mL under shaking until a homogeneous solution formed. The solution was spin-coated onto glass at 1000 rpm for 30 seconds and heated on an 80°C hot plate for 5 minutes until fully solidified into a 2 μm thick transparent film. The emission spectrum of the film was collected over a wavelength range of 400 nm to 800 nm under 360 nm excitation to obtain the emission peak wavelength and full width at half maximum (FWHM) wavelength. The absorption spectrum peak was determined by measuring the UV-visible absorption spectrum of the compound in toluene solution.

[0282] Table 2

[0283] Figures 1 to 6 show the absorption (Abs) and luminescence (PL) spectra of E2-1, E2-2, E2-3, E2-4, E2-5, and E2-9, respectively. It can be seen that the emission half-width (FWHM) of E2-1, E2-2, E2-3, E2-4, E2-5, and E2-9 are 25nm, 21nm, 21nm, 23nm, 20nm, and 23nm, respectively.

[0284] FIG7 shows the absorption (Abs) and luminescence (PL) spectra of E1-2, and the absorption (Abs) spectrum of E2-1. The absorption (Abs) spectrum of E2-1 and the luminescence spectrum of E1-1 have a large overlap.

[0285] FIG8 shows the absorption (Abs) and luminescence (PL) spectra of E1-2, as well as the absorption (Abs) spectrum of E2-2. The absorption (Abs) spectrum of E2-2 and the luminescence spectrum of E1-1 have a large overlap.

[0286] FIG9 shows the absorption (Abs) and luminescence (PL) spectra of E1-2, and the absorption (Abs) spectrum of E2-3. The absorption (Abs) spectrum of E2-3 and the luminescence spectrum of E1-1 have a large overlap.

[0287] FIG10 shows the absorption (Abs) and luminescence (PL) spectra of E1-2, and the absorption (Abs) spectrum of E2-4. The absorption (Abs) spectrum of E2-4 has a large overlap with the luminescence spectrum of E1-1.

[0288] FIG11 shows the absorption (Abs) and luminescence (PL) spectra of E1-2, and the absorption (Abs) spectrum of E2-5. The absorption (Abs) spectrum of E2-5 and the PL spectrum of E1-1 have a large overlap.

[0289] FIG12 shows the absorption (Abs) and luminescence (PL) spectra of E1-2, and the absorption (Abs) spectrum of E2-9. The absorption (Abs) spectrum of E2-9 and the luminescence spectrum of E1-1 have a large overlap.

[0290] 4. Preparation and characterization of evaporation-type OLED devices

[0291] The materials used in the device embodiments of the present invention are as follows:

[0292] Among them, the synthesis of compound HT-1 refers to the method described in patent CN110416418; the synthesis of compound HT-2 refers to the method described in patent WO2016060332; the synthesis of compound H1-2 refers to the method described in patent WO2010137285; H1-1, HAT-CN, ET and LiQ were purchased from Jilin Aolide Optoelectronic Materials Co., Ltd.; other materials were synthesized according to the above methods.

[0293] The structure of the evaporation-type OLED device is HI (10 nm) / HT-1 (50 nm) / HT-2 (10 nm) / H1-1:BD=97:3 (20 nm) / ET:LiQ=50:50 (25 nm) / LiQ (2 nm) / Al (100 nm).

[0294] The preparation process of device examples OLED1-OLED4 (comparative examples) is as follows:

[0295] a. Cleaning of ITO (Indium Tin Oxide) conductive glass substrates: Use various solvents (such as one or more of chloroform, acetone or isopropyl alcohol) to clean, and then perform ultraviolet ozone treatment.

[0296] b. Evaporation: Move the ITO substrate into the vacuum vapor deposition equipment and place it in a high vacuum (1×10 -6At 100 mbar, a resistive heating evaporation source was used to form a 10nm thick HI layer (HAT-CN). A 50nm HT-1 layer was then formed on the HI layer by heating, followed by a 10nm HT-2 layer formed by evaporation on the HT-1 layer. Subsequently, two evaporation sources were used to vaporize the materials at different rates to ensure a BH:BD weight ratio of 97:3 (here, BH is H1-1, and BD is shown in Table 2), forming a 20nm light-emitting layer. ET and LiQ were placed in different evaporation units and co-deposited at a ratio of 50 wt%, respectively, to obtain a 25nm electron transport layer. Subsequently, 2nm of LiQ was deposited as an electron injection layer, and finally a 100nm thick Al cathode was deposited on the electron injection layer.

[0297] c. Packaging: The device is packaged with UV-curable resin and a glass cover in a nitrogen glove box.

[0298] The preparation process of the OLED devices OLED5-OLED10 according to the present invention is as follows: a and c are the same as OLED1-OLED4,

[0299] b. Evaporation: Move the ITO substrate into the vacuum vapor deposition equipment and place it in a high vacuum (1×10 -6 At 100 mbar, a resistive heating evaporation source was used to form a 10nm thick HI layer (HAT-CN). HT-1 was then heated on the HI layer to form a 50nm thick layer. Compound 1 was then evaporated on the HT-1 layer to form a 10nm thick HT-2 layer. Three evaporation sources were then used to vaporize the materials at varying rates, ensuring a BH:BD1:BD2 weight ratio of 97:x:3-x (here, BH is H1-1; the material selection and ratios of BD1 and BD2 are shown in Table 2), forming a 20nm thick light-emitting layer. ET and LiQ were co-deposited in separate evaporation units at a 50wt% ratio, respectively, to form a 25nm thick electron transport layer. Subsequently, 2nm of LiQ was deposited as an electron injection layer. Finally, a 100nm thick Al cathode was deposited on the electron injection layer.

[0300] The device performance of the above embodiment and comparative example was tested, as shown in Table 3. The EL peak value, half-maximum width and EQE were measured at 10 mA / cm 2 The device life of LT95 is tested at a constant current density of 50mA / cm 2 The time it takes for the device's brightness to decay to 95% under EQE and LT95 conditions is given relative to OLED1 (100%).

[0301] Table 3

[0302] In Comparative Examples OLED1-OLED4, devices using a single BD struggle to achieve both a narrow emission linewidth and a long device lifespan. Comparative Examples OLED1-OLED2, using a single non-boron-nitride compound BD, achieve a longer device lifespan, but their spectral half-maximum widths (WFHM) are all above 30nm, and their color purity is significantly lower than that of Comparative Examples OLED3-OLED4, which use boron-nitride compound BDs. Furthermore, despite having relatively narrow emission spectra (WFHM <25nm, with OLED3 having the narrowest WFHM at 19nm), Comparative Examples OLED3-OLED4 exhibit significantly shorter device lifespans than OLED1-OLED2.

[0303] In contrast, examples OLED5-OLED10, which employ the organic mixture according to the present invention as a guest, exhibit a more ideally narrow emission spectrum, high device efficiency, and long device lifetime compared to devices employing a single guest. Comparing OLED1 and OLED3, which employ a single guest, with OLED5-OLED8 having different dual-guest doping ratios, OLED5-OLED8 employing the organic mixture according to the present invention exhibit a narrower spectrum similar to that of OLED3 while also achieving a longer device lifetime than the comparative example using a single BD. Furthermore, their EQE approaches the higher of the single-BD devices.

[0304] Comparing OLED1-OLED4 with OLED7, OLED9 and OLED10 having the same dual guest doping ratio (1:1), it can also be seen that the devices using the organic mixture of the present invention have a narrow spectrum close to that of a single boron nitrogen guest and high efficiency of a single non-boron nitrogen guest, as well as a device lifespan that is longer than both.

[0305] It should be noted that due to the differences in host-guest compatibility and the influence of the weak microcavity effect in the bottom-emitting device, the half-peak width of the electroluminescence spectrum of the light-emitting device in some embodiments may be higher than / lower than / equal to the half-peak width of the photoluminescence spectrum in the polystyrene film.

[0306] 5. Solution preparation

[0307] According to Table 4, the components of the light-emitting layer were poured into toluene at a concentration of 20 mg / mL, heated and stirred to fully dissolve the solute, and filtered to obtain solutions 1 to 5.

[0308] Table 4

[0309] 6. Preparation of solution-processed P-OLED devices

[0310] The specific steps are as follows:

[0311] 1) Cleaning of the ITO transparent electrode (anode) glass substrate: ultrasonic treatment with an aqueous solution of 5% Decon90 cleaning solution for 30 minutes, followed by ultrasonic cleaning with deionized water several times, then ultrasonic cleaning with isopropyl alcohol, 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.

[0312] 2) Hole Transport Layer Preparation: A PEDOT:PSS solution was spin-coated onto an oxygen plasma-treated glass substrate to obtain an 80 nm thin film. The film was then annealed in air at 150°C for 20 min. A 20 nm thick poly-TFB film (CAS: 223569-31-1, Lumtec Corp; 5 mg / mL toluene solution) was then spin-coated onto the PEDOT:PSS layer and subsequently treated on a hot plate at 180°C for 60 min.

[0313] 3) Preparation of the light-emitting layer: The light-emitting layer solution (see Table 3) was first spin-coated in a nitrogen glove box to obtain a 35 nm thin film, which was then annealed at 120° C. for 10 minutes.

[0314] 4) Preparation of electron transport layer: The substrate was moved into a vacuum vapor deposition device and placed in a high vacuum (1×10 -6 mbar), ET and LiQ were placed in different evaporation units and co-deposited at a ratio of 50 wt % to obtain a 30 nm electron transport layer.

[0315] 5) Cathode preparation: The spin-coated device is placed in a vacuum evaporation chamber, and 2 nm of barium and 100 nm of aluminum are evaporated in sequence to complete the light-emitting device.

[0316] 6) All devices were encapsulated with UV-curable resin and glass cover in a nitrogen glove box.

[0317] The device performance of the above embodiments and comparative examples was tested, as shown in Table 5. EQE is the external quantum efficiency of the device at a brightness of 1000 nits, with P-OLED1 as a reference (100%). The EL peak and half-value width are both tested at a device brightness of 1000 nits. The device lifespan T95 refers to the time it takes for the device to decay to 95% of its initial value after continuous constant current illumination at an initial brightness of 1000 nits, with P-OLED1 as a reference (100%).

[0318] Table 5

[0319] Compared with the comparative examples P-OLED1 to P-OLED3, the lifespans of the examples P-OLED4 to P-OLED5 are all improved to a certain extent; in particular, compared with P-OLED2 to P-OLED3 using a single E2 guest, P-OLED4 to P-OLED5 using the organic mixture according to the present invention have significantly improved EQE and lifespan.

[0320] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned 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.

[0321] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.

Claims

1. An organic mixture comprising a first luminophore E1 and a second luminophore E2, characterized in that: 1) The first luminous body E1 and the second luminous body E2 are both fluorescent luminous bodies; 2) The absorption spectrum of the second luminophore E2 and the luminescence spectrum of the first luminophore E1 at least partially overlap with each other; 3) The half-peak width of the luminescence spectrum of the second luminophore E2 is less than or equal to 50 nm.

2. The organic mixture according to claim 1, characterized in that The second luminophore E2 is selected from the structure shown in chemical formula (1) or (2): in: Ar 1 -Ar 3 The same or different ones are selected from aromatic or heteroaromatic groups having 5 to 24 ring atoms; Ar 4 -Ar 5 The same or different ones are selected from aromatic or heteroaromatic groups with 5 to 24 ring atoms; When Ar 4 -Ar 5 When not empty, X a and X b independently selected at each occurrence from N, C(R 9 ) or Si(R 9 ), Y a and Y b independently selected at each occurrence from B, P=O, C(R 9 ) or Si(R 9 ); When Ar 4 or Ar 5 When it is empty, X b Selected from N, C (R 9 ) or Si(R 9 ), Y a Selected from B, P=O, C(R 9 ) or Si(R 9 ), X a and Y b In each occurrence, independently selected from N(R 9 )、C(R 9 R 10 )、Si(R 9 R 10 )、C=O、O、C=N(R 9 )、C=C(R 9 R 10 )、P(R 9 )、P(=O)R 9 , S, S=O or SO2; X 1 , X 2 are independently selected from empty or a bridging group; R 4 -R 10 at each occurrence, which may be identical or different, is selected from H, D, or a linear alkyl, haloalkyl, alkoxy, thioalkoxy radical having 1 to 20 C atoms, or a branched or cyclic alkyl, haloalkyl, alkoxy, thioalkoxy radical, silyl radical having 3 to 20 C atoms, or a keto radical having 1 to 20 C atoms, or an alkoxycarbonyl radical having 2 to 20 C atoms, or an aryloxycarbonyl radical having 7 to 20 C atoms, or a cyano radical, a carbamoyl radical, a haloformyl radical, a formyl radical, an isocyano radical , isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group, nitro group, CF3, Cl, Br, F, I, a cross-linkable 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 an arylamine or heteroarylamine group having 5 to 40 ring atoms, a disubstituted unit at any position of the above groups or a combination of these groups, wherein one or more groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring bonded to the group.

3. The organic mixture according to claim 1 or 2, characterized in that The second luminophore E2 is selected from the following chemical formulas (1a)-(1e) or (2a)-(2e):

4. The organic mixture according to any one of claims 1 to 3, characterized in that The second luminophore E2 comprises the structures shown in the following chemical formulas (1f)-(1i): Among them, Y c They may be the same or different and may be selected from O or S.

5. The organic mixture according to any one of claims 1 to 4, characterized in that Ar 1 ,Ar 2 ,Ar 3 ,Ar 4 ,Ar 5 Each of the following structural formulas is independently selected from one or a combination thereof:

6. The organic mixture according to any one of claims 1 to 5, characterized in that The second luminophore E2 is selected from the structures shown in the following chemical formulas (1j)-(1l): Where: R 21 , R 22 , R 23 , R 24 , R 25 are identical or different on each occurrence and are independently selected from H, D, or a linear alkyl, alkoxy, thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy, thioalkoxy group, silyl group having 3 to 20 C atoms, or a 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, or a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, Isothiocyanate group, hydroxyl group, nitro group, CF3, Cl, Br, F, cross-linkable 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 a combination of these groups, wherein one or more groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring bonded to the group; m, n are independently selected from any integer of 0 to 4; o, q are independently selected from any integer of 0 to 5; p is independently selected from any integer of 0 to 3; "dashed line" indicates no or single bond.

7. The organic mixture according to any one of claims 1 to 6, characterized in that The first luminophore E1 is selected from any one of chemical formula (1) or (2), chemical formula (1a)-(11), chemical formula (2a)-(2e) or the following chemical formula (3-1)-(3-17): in: R0-R3 are defined as R in claim 2 4 ; Ar1-Ar4 may be the same or different and may be selected from aromatic or heteroaromatic groups having 5 to 60 ring atoms.

8. The organic mixture according to any one of claims 1 to 7, characterized in that The organic mixture further comprises a host material H, wherein the host material H is selected from the structure shown in chemical formula (4-1) or (4-2): Wherein, Ar5 and Ar6 may be the same or different and may be selected from aromatic or heteroaromatic groups having 5 to 60 ring atoms.

9. A composition comprising an organic mixture as claimed in any one of claims 1 to 8, and at least one organic solvent.

10. An optoelectronic device comprising an organic mixture according to any one of claims 1 to 8.

11. The optoelectronic device according to claim 10, characterized in that: The optoelectronic device is an organic electroluminescent device, and comprises a substrate, an anode, a light-emitting layer and a cathode arranged in sequence, the light-emitting layer comprises at least one organic mixture as described in any one of claims 1 to 8, or the light-emitting layer is prepared using the composition as described in claim 9.

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