[go: up one dir, main page]

WO2025092929A1 - 有机混合物及其在光电领域的应用 - Google Patents

有机混合物及其在光电领域的应用 Download PDF

Info

Publication number
WO2025092929A1
WO2025092929A1 PCT/CN2024/129071 CN2024129071W WO2025092929A1 WO 2025092929 A1 WO2025092929 A1 WO 2025092929A1 CN 2024129071 W CN2024129071 W CN 2024129071W WO 2025092929 A1 WO2025092929 A1 WO 2025092929A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
organic
atoms
aromatic
organic mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/CN2024/129071
Other languages
English (en)
French (fr)
Inventor
潘君友
刘彦峰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Brilliant Optoelectronic Technology Co Ltd
Original Assignee
Zhejiang Brilliant Optoelectronic Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang Brilliant Optoelectronic Technology Co Ltd filed Critical Zhejiang Brilliant Optoelectronic Technology Co Ltd
Publication of WO2025092929A1 publication Critical patent/WO2025092929A1/zh
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present invention relates to the technical field of organic optoelectronic materials and devices, and in particular to an organic mixture, a composition containing the organic mixture, an optoelectronic device and applications thereof in the optoelectronic field.
  • Organic semiconductor materials have great potential for applications in optoelectronic devices such as flat panel displays and lighting due to their versatility in synthesis, relatively low manufacturing costs, and excellent optical and electrical properties.
  • the device efficiency and life of OLED light-emitting devices depend largely on the performance of the light-emitting materials.
  • the commonly used light-emitting materials are a type of multi-resonance TADF organic compounds containing a BN fused ring system, but due to its disadvantages such as large structural conjugation, the corresponding OLED device life is still lower than that of devices using traditional fluorescent materials as light-emitting materials.
  • 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.
  • An organic mixture comprises a first luminescent body E1 and a second luminescent body E2, wherein 1) the first luminescent body E1 and the second luminescent body E2 are both fluorescent luminescent bodies; 2) the absorption spectrum of the second luminescent body E2 and the emission spectrum of the first luminescent body E1 at least partially overlap with each other; 3) the half maximum width (FWHM) of the emission spectrum of the second luminescent body E2 is less than or equal to 50nm.
  • the second luminophore E2 is selected from the structure shown in chemical formula (1) or (2):
  • Ar 1 -Ar 3 are the same or different and are selected from aromatic or heteroaromatic groups having 5 to 24 ring atoms;
  • the first luminophore E1 is selected from the group consisting of chemical formula (1), chemical formula (2) or aromatic amine derivatives. Further, the first luminophore E1 is selected from any one of chemical formula (1), chemical formula (2) or the following chemical formula (3):
  • R 0 -R 1 are defined as above for R 4 ;
  • Ar 1 -Ar 4 may be the same or different and may be selected from aromatic or heteroaromatic groups having 5 to 60 ring atoms.
  • 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;
  • Ar 5 and Ar 6 when present multiple times, may be identical or different and may be selected from aromatic or heteroaromatic groups having 5 to 60 ring atoms.
  • the present invention further provides a composition comprising an organic mixture as described above, and at least one organic solvent.
  • the present invention also provides a photovoltaic device comprising the organic mixture as described above.
  • 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.
  • the light-emitting layer thereof comprises two light-emitting bodies, a conventional fluorescent material (a first light-emitting body E1) and a BN compound having a narrow light-emitting spectrum (a second light-emitting body E2);
  • the conventional fluorescent material (the 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 light-emitting spectrum of the first light-emitting body E1, so that the resonance energy transfer between the first light-emitting body E1 and the second light-emitting body E2 can be realized (( resonance energy transfer, abbreviated as FRET), thereby obtaining the first luminescence
  • FRET resonance energy transfer
  • FIG9 Absorption (Abs) and luminescence (PL) spectra of E1-2, and absorption (Abs) spectrum of E2-2;
  • FIG12 Absorption (Abs) and luminescence (PL) spectra of E1-2, and absorption (Abs) spectra of E2-5;
  • FIG13 Absorption (Abs) and luminescence (PL) spectra of E1-3, and absorption (Abs) spectra of E2-5;
  • FIG. 14 Absorption (Abs) and luminescence (PL) spectra of E1-3, and absorption (Abs) spectrum of E2-9.
  • 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.
  • a substituent may be further substituted by a substituent
  • 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.
  • a and/or B can mean: A exists alone, A and B exist at the same time, and B exists alone.
  • a and B can be singular or plural.
  • the character "/" generally indicates that the objects before and after are in an "or" relationship.
  • At least one means one or more
  • plural 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.
  • at least one of a, b, or c or “at least one of a, b, and c” can all represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple, respectively.
  • 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, and 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.
  • OLED is an abbreviation of "Organic Light Emitting Diode”, which means organic electroluminescent diode, also known as organic electric laser display, organic light-emitting semiconductor (Organic Electroluminescence Display, OLED).
  • OLED is a current-type organic light-emitting device, which emits light through the injection and recombination of carriers, and the luminous intensity is proportional to the injected current.
  • 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.
  • energy excitons are generated, which excite the light-emitting molecules and finally produce visible light.
  • TADF is an abbreviation for "Thermally Activated Delayed Fluorescence", which stands for thermally activated delayed fluorescence. Its essence is that when the triplet excited state is close to the singlet excited state in energy, the triplet excited state can reverse intersystem crossing to the singlet excited state through thermal activation.
  • Traditional luminescence is fluorescence and phosphorescence, which are the exciton singlet state and triplet state returning to the ground state in the form of radiative luminescence.
  • the energy level difference between the lower singlet state and the lower triplet state is generally large, resulting in the exciton being unable to return to the singlet state once it reaches the triplet state from the singlet state through the intersystem crossing (ISC) process.
  • ISC intersystem crossing
  • main material, matrix material, host material and matrix material have the same meaning and can be interchangeable.
  • metal organic complex metal organic complex and organometallic complex have the same meaning and can be used interchangeably.
  • composition printing ink, ink and ink have the same meaning and can be interchangeable.
  • the energy level structure of the organic material the singlet energy level E S1 , the triplet energy level E T1 , HOMO, and LUMO play a key role.
  • the determination of these energy levels is introduced below.
  • 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 (hereafter referred to as CV).
  • photoelectric effects such as XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectroscopy) or by cyclic voltammetry (hereafter referred to as CV).
  • CV cyclic voltammetry
  • quantum chemical methods such as density functional theory (hereafter referred to as DFT) have also become effective methods for calculating molecular orbital energy levels.
  • DFT density functional theory
  • the singlet energy level E S1 of the organic material can be determined by luminescence spectroscopy, and the triplet energy level E T1 can be measured by low-temperature time-resolved luminescence spectroscopy.
  • E S1 and E T1 can also be obtained by quantum simulation calculation (such as by Time-dependent DFT), such as by commercial software Gaussian 09W (Gaussian Inc.), and the specific simulation method can be found in WO2011141110 or described in the examples below.
  • ⁇ E ST is defined as (E S1 -E T1 ).
  • the absolute values of HOMO, LUMO, E S1 , and E T1 depend on the measurement method or calculation method used. Even for the same method, different evaluation methods, such as the starting point and the peak point on the CV curve, may give different HOMO/LUMO values. Therefore, a reasonable and meaningful comparison should be made using the same measurement method and the same evaluation method.
  • the values of HOMO, LUMO, E S1 , and E T1 are based on the simulation of Time-dependent DFT, but do not affect the application of other measurement or calculation methods.
  • (HOMO-1) is defined as the second highest occupied orbital energy level
  • (HOMO-2) is the third highest occupied orbital energy level
  • (LUMO+1) is defined as the second lowest unoccupied orbital energy level
  • (LUMO+2) is the third lowest occupied orbital energy level, and so on.
  • the present invention provides an organic mixture, comprising a first luminescent body E1 and a second luminescent body E2, wherein 1) the first luminescent body E1 and the second luminescent body E2 are both fluorescent luminescent bodies; 2) the absorption spectrum of the second luminescent body E2 and the emission spectrum of the first luminescent body E1 at least partially overlap with each other; 3) the half maximum width (FWHM) of the emission spectrum of the second luminescent body E2 is less than or equal to 50nm.
  • FWHM half maximum width
  • the absorption spectrum of the second luminophore E2 is on the short-wavelength side of the emission spectrum of the first luminophore E1.
  • the absorption spectrum of the second light emitter E2 is on the long wavelength side of the light emission spectrum of the first light emitter E1.
  • 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, most preferably ⁇ 30 nm.
  • 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%.
  • PLQY fluorescence quantum efficiency
  • the second luminophore E2 is selected from the structure shown in chemical formula (1) or (2), more preferably chemical formula (1):
  • Ar 1 -Ar 3 are the same or different and are selected from aromatic or heteroaromatic groups having 5 to 24 ring atoms;
  • the second luminophore E2 is selected from the structure represented by the following chemical formula (1a) or (2a), more preferably chemical formula (1a):
  • Ar 1 to Ar 3 , Ar 4 to Ar 5 , X 1 , X 2 , and R 4 to R 8 have the same meanings as described above.
  • X1 and X2 are independently selected from O or S; in some more preferred embodiments, X1 and X2 are both O.
  • At least one of X 1 and X 2 is empty; particularly preferably, both are empty.
  • the second luminophore E2 is selected from the structure represented by the following chemical formula (1b) or (2b), and chemical formula (1b) is more preferred:
  • Ar 1 to Ar 3 , Ar 4 to Ar 5 , and R 4 to R 8 have the same meanings as described above.
  • At least one of X 1 and X 2 is a single bond; particularly preferably, both are single bonds.
  • the second luminophore E2 is selected from the structure represented by the following chemical formula (1c) or (2c), and chemical formula (1c) is more preferred:
  • Ar 1 to Ar 3 , Ar 4 to Ar 5 , and R 4 to R 8 have the same meanings as described above.
  • X 1 and X 2 when they appear each time, are identical or different di-bridging groups, and preferred di-bridging groups are:
  • R 4 , R 5 , R 6 and R 7 are defined the same as R 4 above; the dotted bond represents the bond to the adjacent structural unit.
  • 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.
  • aromatic or heteroaromatic ring systems include not only systems of aromatic or heteroaromatic radicals, but also systems in which a plurality of aromatic or heteroaromatic radicals may also be interrupted by short non-aromatic units ( ⁇ 10% non-H atoms, preferably less than 5% non-H atoms, such as C, N or O atoms).
  • systems such as 9,9′-spirobifluorene, 9,9-diarylfluorene, triarylamines, diaryl ethers, etc. are likewise considered to be aromatic ring systems for the purposes of the present invention.
  • any H atom on the first emitter E1 and the second emitter E2 is substituted by an R4 group, and R4 is defined as described above, preferably, (1) C1-C10 alkyl, particularly preferably 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, hexen
  • Aromatic and heteroaromatic ring systems are taken to mean, in addition to the aryl and heteroaryl radicals mentioned above, in particular biphenylene, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, tetrahydropyrene and cis- or trans-indenofluorene.
  • Ar 1 -Ar 5 are identical or different and are selected from aromatic or heteroaromatic groups having 5 to 20 ring atoms in each occurrence; 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.
  • the aromatic or heteroaromatic radicals of the present invention are substituted with one or two R4 radicals; they may be unsubstituted or substituted with one or two R4 radicals.
  • Preferred aromatic or heteroaromatic radicals are benzene, naphthalene, anthracene, phenanthrene, pyridine, pyrene or thiophene.
  • Ar 1 -Ar 5 are selected from the following structural formulas:
  • X 3 is CR 11 or N
  • Y 7 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 and R 15 are the same as defined above for R 4 .
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 , and Ar 5 are independently selected from one or a combination of the following chemical structures, and may be further substituted arbitrarily:
  • Ar 1 -Ar 5 are phenyl groups.
  • At least one of Ar 4 and Ar 5 is empty; particularly preferably, both are empty, and the second luminophore E2 is selected from the structure represented by the following chemical formula (1d) or (2d) or (1e) or (2e):
  • Ar 1 to Ar 3 , X a , Y b , and R 6 to R 8 have the same meanings as described above.
  • X a in formula (1d) and (1e) are the same or different and are independently selected from N(R 9 ), C(R 9 R 10 ), Si(R 9 R 10 ), O or S.
  • the second luminophore E2 comprises the structures shown in the following chemical formulas (1f)-(1i):
  • Yc may be the same or different and may be selected from O or S; Ar1 - Ar3 , Xa , R6 - R8 are as defined above.
  • Ar 2 and Ar 3 are preferably selected from the following structural units, and can be further Steps are replaced arbitrarily:
  • n1 is 1 or 2 or 3 or 4.
  • the second luminophore E2 is selected from the structures shown in the following chemical formulas (1j)-(11):
  • Yc is as defined above;
  • the second luminophore E2 is selected from the structures shown in the following chemical formulas (1o)-(1p):
  • R 22 and R 24 are the same or different each time they appear, and are 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; and most preferably selected from aromatic or heteroaromatic groups having 6 to 20 ring atoms.
  • R 22 and R 24 are the same or different each time they appear, and are independently selected from electron donating groups, aromatic groups consisting of benzene rings, or branched aliphatic groups with greater steric hindrance, and/or combinations of the above structures.
  • R 22 and R 24 are the same or different each time they appear, and are independently selected from the structures shown in the following chemical formulae (5-1) to (5-9):
  • * indicates the bonding position
  • triplet energy level (T1) and singlet energy level (S1), HOMO, LUMO and resonance factor intensity f play a key role in the energy level structure of organic materials.
  • T1 and S1 singlet energy level (S1), HOMO, LUMO and resonance factor intensity f play a key role in the energy level structure of organic materials.
  • S1 singlet energy level
  • HOMO HOMO
  • LUMO resonance factor intensity
  • 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 (hereafter referred to as CV).
  • photoelectric effects such as XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectroscopy) or by cyclic voltammetry (hereafter referred to as CV).
  • CV cyclic voltammetry
  • quantum chemical methods such as density functional theory (hereafter referred to as DFT) have also become effective methods for calculating molecular orbital energy levels.
  • DFT density functional theory
  • the triplet energy level T1 of organic materials can be measured by low-temperature time-resolved luminescence spectroscopy, or obtained by quantum simulation calculation (such as by Time-dependent DFT), such as by commercial software Gaussian 09W (Gaussian Inc.), and the specific simulation method is described below.
  • the singlet energy level S1 of organic materials can be determined by absorption spectrum or emission spectrum, or obtained by quantum simulation calculation (such as Time-dependent DFT); the resonance factor intensity f can also be obtained by quantum simulation calculation (such as Time-dependent DFT).
  • the absolute values of HOMO, LUMO, T1 and S1 depend on the measurement method or calculation method used. Even for the same method, different evaluation methods, such as the starting point and the peak point on the CV curve, may give different HOMO/LUMO values. Therefore, a reasonable and meaningful comparison should be made using the same measurement method and the same evaluation method.
  • the values of HOMO, LUMO, T1 and S1 are based on the simulation of Time-dependent DFT, but do not affect the application of other measurement or calculation methods.
  • 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, most preferably ⁇ 0.10 eV.
  • the second light-emitting body E2 and the first light-emitting body E1 are small molecules or polymers, preferably small molecules.
  • the organic mixture does not contain any resin.
  • R is selected from alkyl groups having 1 to 40 C atoms, preferably from the following groups: 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, cyclopenteny
  • Examples of the second luminous body E2 are given below (these can also be used as examples of the first luminous body E1), but are not limited to:
  • the first light-emitting body E1 is selected from the above-mentioned chemical formula (1) or (2), chemical formula (1a)-(1e) or chemical formula (2a)-(2e) or chemical formula (1f)-(1i) or chemical formula (1j)-(1l).
  • the first luminophore E1 is selected from a conventional fluorescent luminophore (i.e., a singlet luminophore); conventional singlet luminophores often have a longer conjugated ⁇ electron system.
  • a conventional fluorescent luminophore i.e., a singlet luminophore
  • conventional singlet luminophores often have a longer conjugated ⁇ electron system.
  • styrylamine and its derivatives disclosed in JP2913116B and WO2001021729A1 indenofluorene and its derivatives disclosed in WO2008/006449 and WO2007/140847
  • triarylamine derivatives of pyrene disclosed in US7233019 and KR2006-0006760.
  • the first luminophore E1 can be selected from monostyrylamine, distyrylamine, tristyrylamine, tetrastyrylamine, styrylphosphine, styrylether and aromatic amine.
  • 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 ring systems directly attached to the 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 are aromatic anthraceneamines, aromatic anthracene diamines, aromatic pyrene amines, aromatic pyrene diamines, aromatic chrysene amines and aromatic chrysene diamines.
  • An aromatic anthraceneamine is a compound wherein one diarylamine group is directly attached to anthracene, preferably at the 9 position.
  • An aromatic anthracenediamine is a compound wherein two diarylamine groups are directly attached to anthracene, preferably at the 9,10 positions.
  • Aromatic pyreneamines, aromatic pyrenediamines, aromatic chryseneamines and aromatic chrysenediamines are similarly defined, wherein the diarylamine groups are preferably attached to the 1 or 1,6 positions of the pyrene.
  • 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.
  • Further preferred traditional singlet emitters can be selected from fluorene-based fused ring systems, such as those disclosed in US2015333277A1, US2016099411A1, and US2016204355A1.
  • More preferred traditional singlet luminophores can be selected from derivatives of pyrene, 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.
  • polycyclic aromatic hydrocarbon compounds especially derivatives of the following compounds: anthracenes 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 rings such as (4,4'-bis(9-ethyl-3-carbazole vinyl)-1,1'-biphenyl), diindenopyrene, decacyclopentene, hexabenzophenone, fluorene, spirobifluorene, arylpyrene (such as US20060222886), arylenevinyl (such as US5121 029, US5130603), cyclopentadiene such as tetraphenylcyclopentadiene, rubrene,
  • anthracenes such as 9,10-d
  • the first luminophore E1 is not selected from thermally excited delayed fluorescence (TADF) compounds having a D-A structure, nor is it selected from compounds having aggregation induced emission (AIE) properties.
  • TADF thermally excited delayed fluorescence
  • AIE aggregation induced emission
  • the first light-emitting body E1 has S1-T1 ⁇ 0.25 eV, preferably ⁇ 0.3 eV.
  • R 0 -R 1 are as defined above for R 4 ;
  • the peak value ( ⁇ 2) of the absorption spectrum of the second luminescent body E2 is between the peak value ( ⁇ 1) of the emission spectrum of the first luminescent body E1 and the peak value ( ⁇ 3) of the absorption spectrum of the first luminescent body E1.
  • the luminescent spectrum of the organic mixture is completely derived from the second luminescent body E2, that is, complete energy transfer is achieved between the first luminescent body E1 and the second luminescent body E2.
  • the peak value ( ⁇ 1) of the light emission spectrum of the first light emitter E1 is between 400nm and 700nm, preferably between 410nm and 600nm, particularly preferably between 420nm and 500nm, and most preferably between 430nm and 460nm.
  • the peak value ( ⁇ 1) of the light emission spectrum of the first light emitting body E1 is between 440nm and 460nm.
  • the peak value ( ⁇ 4) of the light spectrum of the second light emitter E2 is between 400nm and 800nm.
  • the best range is between 450nm and 750nm, and the most preferred range is between 450nm and 700nm.
  • the peak value ( ⁇ 4) of the light emission spectrum of the second light emitting body E2 is between 455nm and 465nm.
  • the peak value ( ⁇ 4) of the light emission spectrum of the second light emitting body E2 is between 520nm and 535nm.
  • the peak value ( ⁇ 3) of the absorption spectrum of the first luminescent body E1 is between 350nm and 600nm, preferably between 400nm and 500nm, and most preferably between 420nm and 460nm.
  • the peak value ( ⁇ 3) of the absorption spectrum of the first luminescent body E1 is between 425nm and 445nm.
  • the peak value ( ⁇ 2) of the absorption spectrum of the second luminescent body E2 is between 350nm and 600nm, preferably between 400nm and 500nm, and most preferably between 440nm and 460nm.
  • the peak value ( ⁇ 2) of the absorption spectrum of the first luminescent body E2 is between 445nm and 455nm.
  • 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.
  • the organic mixture further comprises a host material H.
  • Suitable host material H can be selected from singlet host materials.
  • 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 emitter E1 and the second emitter E2.
  • 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, indolecarbazole, pyridineindole, pyrroledipyridine, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine,
  • the singlet host material may be selected from compounds comprising at least one of the following groups:
  • Each time Y occurs it is independently selected from C(R 101 ) 2 , NR 101 , O or S; each time X occurs, it is independently selected from CR 101 or N; each time R 101 occurs, it 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; n 2 is selected from an integer of 1 to 20.
  • the singlet host is selected from anthracene derivatives, such as CN102224614B, CN100471827C, CN1914293B, WO2015033559A1, US2014246657A1, Disclosed in patent documents such as WO2016117848A1, WO2016117861A1, WO2016171429A2, CN102369256B, and CN102428158B.
  • anthracene derivatives such as CN102224614B, CN100471827C, CN1914293B, WO2015033559A1, US2014246657A1
  • Disclosed in patent documents such as WO2016117848A1, WO2016117861A1, WO2016171429A2, CN102369256B, and CN102428158B.
  • the host material H is selected from the following chemical formula (4-1) or (4-2):
  • Ar 5 and Ar 6 are as defined above for Ar 1 .
  • Ar 5 and Ar 6 are selected from benzene, naphthalene, dibenzofuran, naphthobenzofuran, carbazole and combinations thereof.
  • singlet host materials that can be used as host material H are listed below:
  • 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.
  • the host material molecule contains at least one deuterium atom.
  • Another object of the present invention is to provide a material solution for printed OLEDs.
  • 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 present 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.
  • the solubility of the organic mixture according to the present invention in any one solvent of toluene, or xylene, or mesitylene, or cyclohexylbenzene, or methyl benzoate, or a mixed solvent of any two or more thereof at 25° C. is ⁇ 5 mg/mL, preferably ⁇ 10 mg/mL, more preferably ⁇ 15 mg/mL, more preferably ⁇ 20 mg/mL, and most preferably ⁇ 25 mg/mL.
  • the second luminophore E2 or the first luminophore E1 contains at least one cross-linkable group, as disclosed in the patent application with application number CN202110370910.9, the entire contents of which are hereby incorporated herein by reference.
  • the second luminophore E2 or the first luminophore E1 comprises at least two cross-linkable groups.
  • the second luminophore E2 or the first luminophore E1 comprises at least three cross-linkable groups.
  • the host material H comprises at least one cross-linkable group.
  • the host material H comprises at least two cross-linkable groups.
  • the host material H contains at least three cross-linkable groups.
  • the present invention also relates to a composition
  • a composition comprising an organic mixture as described above and at least one organic solvent.
  • the composition according to the present invention is a solution.
  • composition according to the present invention is a suspension.
  • composition in the embodiment of the present invention may include 0.01wt% to 20wt% of the organic mixture, preferably 0.1wt% to 20wt%, more preferably 0.2wt% to 20wt%, and most preferably 2wt% to 15wt%.
  • 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 esters or phosphate esters, or a combination of two or more organic solvents.
  • suitable and preferred organic solvents are aliphatic, alicyclic or aromatic hydrocarbons, amines, thiols, amides, nitriles, esters, ethers, polyethers, alcohols, diols or polyols.
  • alcohol represents an appropriate class of organic solvents.
  • Preferred alcohols include alkyl cyclohexanols, especially methylated aliphatic alcohols, naphthols, and the like.
  • the organic solvent may be used alone or as a combination of two or more organic solvents.
  • 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.
  • the composition according to the present invention wherein the organic solvent is selected from aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, alicyclic or olefinic compounds, or boric acid Ester or inorganic ester compound such as phosphate ester, or a combination of two or more solvents.
  • the organic solvent is selected from aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, alicyclic or olefinic compounds, or boric acid Ester or inorganic ester compound such as phosphate ester, or a combination of two or more solvents.
  • aromatic or heteroaromatic solvents 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
  • suitable and preferred organic solvents are aliphatic, alicyclic or aromatic hydrocarbons, amines, thiols, amides, nitriles, esters, ethers, polyethers.
  • the organic solvent may be a cycloalkane, such as decalin.
  • the composition according to the present invention contains 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.
  • the organic solvent particularly suitable for the present invention is a solvent having a Hansen solubility parameter in the following range:
  • ⁇ d (dispersion force) is in the range of 17.0 MPa 1/2 -23.2 MPa 1/2 , especially in the range of 18.5 MPa 1/2 -21.0 MPa 1/2 ;
  • ⁇ p (polar force) is in the range of 0.2 MPa 1/2 -12.5 MPa 1/2 , especially in the range of 2.0 MPa 1/2 -6.0 MPa 1/2 ;
  • ⁇ h (hydrogen bonding force) is in the range of 0.9 MPa 1/2 -14.2 MPa 1/2 , particularly in the range of 2.0 MPa 1/2 -6.0 MPa 1/2 .
  • the organic solvent should be selected considering its boiling point parameter.
  • the boiling point of the organic solvent is ⁇ 150°C; preferably ⁇ 180°C; more preferably ⁇ 200°C; more preferably ⁇ 250°C; most preferably ⁇ 275°C or ⁇ 300°C. Boiling points within these ranges are beneficial for preventing nozzle clogging of the inkjet print head.
  • the organic solvent can be evaporated from the solvent system to form a film containing a functional material.
  • composition according to the present invention :
  • the organic solvent should be selected considering its surface tension parameter.
  • the appropriate surface tension parameter is suitable for a specific substrate and a specific printing method.
  • the surface tension of the organic solvent at 25° C. is about 19 dyne/cm to 50 dyne/cm; more preferably, it is in the range of 22 dyne/cm to 35 dyne/cm; and most preferably, it is in the range of 25 dyne/cm to 33 dyne/cm.
  • 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; most preferably in the range of 25 dyne/cm to 33 dyne/cm.
  • the organic solvent should be selected in consideration of the viscosity parameter of the ink.
  • the viscosity can be adjusted by different methods, such as by the selection of a suitable organic solvent and the concentration of the functional material in the ink.
  • the viscosity of the organic solvent is less than 100 cps; more preferably less than 50 cps; and most preferably 1.5 cps to 20 cps.
  • the viscosity here refers to the viscosity at the ambient temperature during printing, generally 15°C-30°C, preferably 18°C-28°C, more preferably 20°C-25°C, and most preferably 23°C-25°C.
  • the composition thus formulated will be particularly suitable for inkjet printing.
  • 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.
  • the ink obtained from the organic solvent that satisfies the above-mentioned boiling point, surface tension parameters and viscosity parameters can form a functional material film with uniform thickness and composition properties.
  • the present invention further relates to an organic functional material film, which is prepared using the composition as described above.
  • the present invention also provides a method for preparing the organic functional material film, comprising the following steps:
  • 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, torsional roller printing, lithography, flexographic printing, rotary printing, spraying, brushing or pad printing, or slot extrusion coating;
  • 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, torsional roller printing, lithography, flexographic printing, rotary printing, spraying, brushing or pad printing, or slot extrusion coating;
  • the thickness of the organic functional material film is generally 5nm-20 ⁇ m, preferably 5nm-10 ⁇ m, more preferably 10nm-5 ⁇ m, and most preferably 10nm-1 ⁇ m.
  • the present invention also provides the application of the organic mixture and the organic functional material film in optoelectronic devices.
  • 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, or an organic laser.
  • OLED organic light emitting diode
  • OCV organic photovoltaic cell
  • OLED organic light emitting cell
  • OLED organic light emitting cell
  • OLED organic light emitting field effect transistor
  • the present invention provides a photoelectric device comprising the above-mentioned organic mixture or organic functional material film.
  • 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, a perovskite light emitting diode (PeLED), and a quantum dot light emitting diode (QD-LED), wherein a functional layer comprises one of the above 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).
  • 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.
  • the second light emitter E2 and the first light emitter E1 are small molecules or polymers, preferably small molecules.
  • the light-emitting layer does not contain any resin.
  • the organic electroluminescent device emits blue light.
  • the organic electroluminescent device is an OLED. Particularly preferably, the organic electroluminescent device is a top emission OLED.
  • the substrate can be opaque or transparent.
  • a transparent substrate can be used to make a transparent light-emitting device.
  • the substrate can be rigid or elastic.
  • the substrate can be plastic, metal, semiconductor wafer or glass. It is best that the substrate has a smooth surface. Substrates without surface defects are particularly ideal.
  • the substrate is flexible and can be selected from polymer films or plastics, and its glass transition temperature (Tg) is above 150°C, preferably above 200°C, more preferably above 250°C, and preferably above 300°C.
  • Tg glass transition temperature
  • suitable flexible substrates are polyethylene terephthalate (PET) and polyethylene glycol (2,6-naphthalene) (PEN).
  • the anode may include a conductive metal or metal oxide, or a conductive polymer.
  • the anode can easily inject holes into the hole injection layer (HIL) or the hole transport layer (HTL) or the light-emitting layer.
  • the absolute value of the difference between the work function of the anode and the HOMO energy level or valence band energy level of the light-emitting body in the light-emitting layer or the p-type semiconductor material serving as the HIL or HTL or the electron blocking layer (EBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV.
  • anode materials include, but are not limited to: Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), etc.
  • suitable anode materials are known, Those skilled in the art can easily choose to use.
  • the anode material can be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), etc.
  • the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.
  • the cathode may include a conductive metal or metal oxide.
  • the cathode can easily inject electrons into the EIL or ETL or directly into the light-emitting layer.
  • the absolute value of the 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 as the electron injection layer (EIL) or the electron transport layer (ETL) or the hole blocking layer (HBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV.
  • cathode materials examples include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2 /Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc.
  • the cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), etc.
  • the cathode has a transmittance of ⁇ 40% in the range of 400nm-680nm, preferably ⁇ 45%, more preferably ⁇ 50%, and most preferably ⁇ 60%.
  • Mg:Ag alloy of 10nm-20nm can be used as a transparent cathode, and the ratio of Mg:Ag can be from 2:8 to 0.5:9.5.
  • 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).
  • HIL hole injection layer
  • HTL hole transport layer
  • EBL electron blocking layer
  • EIL electron injection layer
  • ETL electron transport layer
  • HBL hole blocking layer
  • the organic electroluminescent device also includes a cathode capping layer (CPL for short).
  • CPL cathode capping layer
  • 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:
  • CPL materials More examples 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 by reference into this article.
  • the encapsulation layer is a thin film encapsulation (TFE).
  • the present invention further relates to a display panel, wherein at least one pixel comprises the above-mentioned organic electroluminescent device.
  • the mother liquor was concentrated with dichloromethane for three times and purified by column chromatography.
  • the eluent containing the product was concentrated to obtain 17.5 g of intermediate 1a in total, with a purity of 98% and a yield of 88%.
  • intermediate 1b In a dry reaction bottle, intermediate 1a (7.56 g, 41.3 mmol), compound 1-3 (11.89 g, 41.3 mmol), sodium tert-butoxide (11.89 g, 123.9 mmol), Pd 2 (dba) 3 (1.89 g, 2.1 mmol), XPhos (1.96 g, 4.1 mmol) were placed, and then 100 mL of 1,4-dioxane was added. The mixture was evacuated and nitrogen was filled for three cycles. The reaction was stirred at 100°C for 16 hours, cooled to room temperature, and the reaction solution was concentrated. After removing 1,4-dioxane, 150 mL of water was added.
  • the mother liquor was concentrated with dichloromethane for three times and purified by column chromatography.
  • the eluent containing the product was concentrated to obtain 13.24 g of intermediate 1b in total, with a purity of 98% and a yield of 82%.
  • intermediate 2b The synthesis of intermediate 2b is similar to that of intermediate 1b, except that compound 2-1 is used instead of intermediate 1a.
  • intermediate 3b was similar to that of intermediate 1b, except that intermediate 3a was used instead of intermediate 1a.
  • the mother liquor was concentrated and extracted with dichloromethane three times, and then purified by column chromatography.
  • the eluent containing the product was concentrated to obtain 6.35 g of compound E1-3 with a purity of 99% and a yield of 78%.
  • compound E1-4 is similar to that of compound E1-3, except that intermediate 2b is used instead of intermediate 1b, and compound 2-4 is used instead of compound 1-4.
  • intermediate 4b In a 500mL three-necked flask, add intermediate 4a (30.0g, 55.0mmol), compound 4-3 (17.6g, 60.5mmol), cesium carbonate (26.5g, 82.5mmol), and DMF 300mL in sequence, and heat to reflux for reaction. Monitor the reaction by TLC, and stop the reaction after the raw materials are basically consumed. Use 300mL methanol and 100mL water to beat at room temperature for 2h to obtain intermediate 4b, which is about 29.2g after drying, and the yield is about 65.1%.
  • reaction system was extracted with ethyl acetate and saturated sodium chloride solution.
  • intermediate 8b In a 500mL three-necked flask, add intermediate 8a (18.14g, 30.6mmol), compound 6-3 (17.6g, 33.6mmol), 200mL toluene, sodium tert-butoxide (4.4g, 45.9mmol), Pd 2 (dba) 3 (280mg, 0.3mmol), TTBPH ⁇ BF 4 (174.0mg, 0.6mmol), vacuumize and replace with nitrogen three times, heat to 110°C for reaction, and track the reaction by TLC.
  • intermediate 9a In a 500mL three-necked flask, add intermediate 4a (30.0g, 55.0mmol), compound 9-1 (19.9g, 60.5mmol), cesium carbonate (26.5g, 82.5mmol), and DMF 300mL in sequence, and heat to reflux for reaction. Monitor the reaction by TLC, and stop the reaction after the raw materials are basically consumed. Use 300mL of methanol and 100mL of water to beat at room temperature for 2h to obtain intermediate 9a, which is about 30.3g after drying, and the yield is about 64.4%.
  • intermediate 10b In a 500mL three-necked flask, add intermediate 10a (32.8g, 55.0mmol), compound 9-1 (19.9g, 60.5mmol), cesium carbonate (26.5g, 82.5mmol), and DMF 300mL in sequence, and heat to reflux for reaction. Monitor the reaction by TLC, and stop the reaction after the raw materials are basically consumed. Use 300mL of methanol and 100mL of water to beat at room temperature for 2h to obtain intermediate 10b, which is about 35.2g after drying, and the yield is about 70.7%.
  • intermediate 11b In a 250mL three-necked flask, add intermediate 11a (14.4g, 30.6mmol), compound 11-2 (7.1g, 33.6mmol), 150mL of dioxane, 30mL of water, potassium carbonate (8.4g, 61.2mmol), Pd(PPh 3 ) 4 (346mg, 0.3mmol) in sequence, evacuate and replace with nitrogen three times, heat to 100°C for reaction, and track the reaction by TLC.
  • the energy levels of organic materials can be obtained by quantum calculation, for example, using TD-DFT (time-dependent density functional theory) through Gaussian 09W (Gaussian Inc.), and the specific simulation method can be found in WO2011141110.
  • TD-DFT time-dependent density functional theory
  • Gaussian 09W Gaussian Inc.
  • the specific simulation method can be found in WO2011141110.
  • the molecular geometry is optimized using the density functional theory method "Ground State/DFT/Default Spin/B3LYP” and the basis set "6-31G(d)” (Charge 0/Spin Singlet)
  • the energy structure of the organic molecule is calculated by the TD-DFT (time-dependent density functional theory) method "TD-SCF/DFT/Default Spin/B3PW91” and the basis set "6-31G(d)” (Charge 0/Spin Singlet).
  • the HOMO and LUMO energy levels are calculated according to the following calibration formula, and S1 and T1 are used directly.
  • HOMO(eV) ((HOMO(G) ⁇ 27.212)-0.9899)/1.1206
  • HOMO(G) and LUMO(G) are the direct calculation results of Gaussian 09W, and the unit is Hartree.
  • the HOMO energy level is the highest occupied molecular orbital energy of the organic molecule
  • the LUMO energy level is the lowest unoccupied molecular orbital energy of the organic molecule
  • ⁇ HOMO is the difference between the highest occupied molecular orbital energy and the second highest occupied molecular orbital energy of the organic molecule
  • the ES1 energy level is the lowest singlet excited state energy level of the organic molecule
  • the ET1 energy level is the lowest triplet excited state energy level of the organic molecule
  • the organic mixture of the present invention is prepared according to the following method: E1 and E2 in a certain mass ratio are dissolved in toluene to obtain a homogeneous solution, and the solvent is evaporated by vacuum drying to obtain a mixture solid; the above solid is further mechanically ground and mixed in a quartz mortar to obtain the organic mixture of the present invention.
  • polystyrene (PS) film The mixture formula and its photoluminescence properties in polystyrene (PS) film are shown in Table 2.
  • the preparation and characterization methods of the polystyrene doped film are as follows:
  • polystyrene (cas: 9003-53-6, average Mw ⁇ 280,000 by GPC, purchased from Sigma-Aldrich) is dissolved in toluene to form a 100 mg/mL solution
  • the comparative compound or the organic mixture according to the present invention is dissolved therein at a concentration of 3 mg/mL under oscillation conditions to form a homogeneous solution.
  • the above solution is spin-coated on glass at a speed of 1000 rpm for 30 seconds, and heated on a hot plate at 80°C for 5 minutes until it is completely solidified into a transparent film with a thickness of 2 ⁇ m; the emission spectrum of the above film under 360nm excitation in the wavelength range of 400nm-800nm is collected to obtain the emission peak wavelength and emission half-height width (FWHM) wavelength values.
  • the absorption spectrum peak is obtained by measuring the UV-visible absorption spectrum of the compound in toluene solution.
  • 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.
  • FWHM emission half-width
  • FIG7 shows the absorption (Abs) and luminescence (PL) spectra of E1-1, and the absorption (Abs) spectra of E2-1.
  • the absorption (Abs) spectra of E2-1 and the luminescence spectra of E1-1 have a large overlap.
  • FIG9 shows the absorption (Abs) and luminescence (PL) spectra of E1-2, and the absorption (Abs) spectra of E2-2.
  • the absorption (Abs) spectra of E2-2 and the luminescence spectra of E1-1 have a large overlap.
  • FIG10 shows the absorption (Abs) and luminescence (PL) spectra of E1-2, and the absorption (Abs) spectra of E2-3.
  • the absorption (Abs) spectra of E2-3 and the luminescence spectra of E1-2 have a large overlap.
  • FIG11 shows the absorption (Abs) and luminescence (PL) spectra of E1-2, and the absorption (Abs) spectra of E2-4.
  • the absorption (Abs) spectra of E2-4 and the luminescence spectra of E1-2 have a large overlap.
  • FIG12 shows the absorption (Abs) and luminescence (PL) spectra of E1-2, and the absorption (Abs) spectra of E2-5.
  • the absorption (Abs) spectra of E2-5 and the luminescence spectra of E1-2 have a large overlap.
  • FIG13 shows the absorption (Abs) and luminescence (PL) spectra of E1-3, and the absorption (Abs) spectra of E2-5.
  • the absorption (Abs) spectra of E2-5 and the luminescence spectra of E1-3 have a large overlap.
  • 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 HT-3 refers to the method described in patent WO2012034627; the synthesis of compound HT-4 refers to the method described in patent US20200144506; the synthesis of compound H1-2 refers to the method described in patent WO2010137285; the synthesis of compound H1-3 refers to the method described in patent US20220216410; the synthesis of compound H1-4 refers to the method described in patent WO2021107742; the synthesis of compound HB refers to the method described in patent WO2018074845; HAT-CN (HI), H1-1, ET and LiQ were purchased from Jilin Aolaide Optoelectronic Materials Co., Ltd.; other materials were synthesized according to the above method.
  • HAT-CN (HI) H1-1, ET and LiQ were purchased from Jilin Ao
  • ITO indium tin oxide
  • solvents such as one or more of chloroform, acetone or isopropyl alcohol
  • HI layer HAT-CN
  • HAT-CN HI layer with a thickness of 30 nm.
  • the HI layer is heated in sequence to form a 50 nm HT-1, followed by evaporation to form a 10 nm HT-2 layer on the HT-1 layer.
  • two evaporation sources are used to vaporize the materials at different rates to ensure that the weight ratio of BH: BD is 97:3 (here BH is H1-1, BD is shown in Table 3), forming a 25 nm light-emitting layer.
  • ET and LiQ are placed in different evaporation units and co-deposited at a ratio of 50 wt % to obtain a 30 nm electron transport layer, followed by deposition of 1 nm LiQ as an electron injection layer, and finally a 100 nm thick Al cathode is deposited on the electron injection layer.
  • the preparation process of the OLED devices OLEDA4 and OLEDA5 according to the present invention is as follows: a and c are the same as OLEDA1-OLEDA3,
  • ET and LiQ are placed in different evaporation units and co-deposited at a ratio of 50 weight % to obtain a 30nm electron transport layer, followed by deposition of 1nm LiQ as an electron injection layer, and finally a 100nm thick Al cathode is deposited on the electron injection layer.
  • the device performance of the above embodiments and comparative examples was tested, as shown in Table 3; the driving voltage was tested at a current density of 10 mA/ cm2 ; the device life of T95 refers to the time for the brightness to decay to 95% at a constant current density of 50 mA/ cm2 , with OLEDA1 as the benchmark (100%).
  • the lifespan of OLEDA4 and OLEDA5 is significantly improved, and the driving voltage has no significant difference, which indicates that the lifespan of the device can be improved by using the OLED device containing two luminous bodies of the present invention.
  • ITO indium tin oxide
  • solvents such as one or more of chloroform, acetone or isopropyl alcohol
  • HI layer HAT-CN
  • HAT-CN HI layer
  • the HI layer is heated in sequence to form a 50 nm HT-3, and then a 5 nm HT-4 is evaporated on the HT-3 layer.
  • two evaporation sources are used, and the materials are vaporized at different rates to ensure that the weight ratio of BH:BD is 97:3 (here BH is H1-2, and BD is shown in Table 4) to form a 20 nm light-emitting layer.
  • HB is evaporated on the light-emitting layer.
  • ET and LiQ are placed in different evaporation units, and they are co-deposited at a ratio of 50 weight % to obtain a 25 nm electron transport layer, followed by deposition of 2 nm LiQ as an electron injection layer, and finally a 100 nm thick Al cathode is deposited on the electron injection layer.
  • Packaging The device is packaged with UV-hardening resin and a glass cover in a nitrogen glove box.
  • the preparation process of the OLED devices OLEDB10-OLEDB23 according to the present invention is as follows:
  • a and c are the same as OLEDB1-OLEDB9;
  • HI layer HAT-CN
  • HAT-CN HI layer with a thickness of 10 nm.
  • the HI layer is heated in sequence to form a 50 nm HT-3, and then a 5 nm HT-4 is formed by evaporation on the HT-3 layer.
  • ET and LiQ are placed in different evaporation units, and they are co-deposited at a ratio of 50 weight % to obtain a 25 nm electron transport layer, followed by deposition of 2 nm LiQ as an electron injection layer, and finally a 100 nm thick Al cathode is deposited on the electron injection layer.
  • the device performances of the above embodiments and comparative examples were tested, as shown in Table 4; the EL peak, EL half-width and EQE were tested at a current density of 10 mA/cm 2 ; the device life of LT95 refers to the time for the brightness to decay to 95% at a constant current density of 50 mA/cm 2 , with OLED1 as the benchmark (100%).
  • comparative examples OLEDB1-OLEDB9 it is difficult for the device using a single BD to achieve both narrow emission linewidth and long device life: comparative examples OLEDB1-OLEDB4 can obtain a longer device life by using a single non-MR-TADF BD, but their spectrum half-peak widths are all above 30nm, and the color purity is significantly worse than that of comparative examples OLEDB5-OLEDB9 using MR-TADF BDs.
  • OLEDB10-OLEDB23 using the organic mixture according to the present invention as the guest comprehensively show a more ideal narrow emission spectrum, high device efficiency and long device life than using a single guest.
  • OLEDB10 using the organic mixture of the present invention has both a narrow spectrum close to OLEDB5 and an external quantum efficiency consistent with OLED1, and its device life is higher than OLEDB1 and significantly higher than OLEDB5.
  • OLEDB10 when OLEDB1 and OLEDB2 using a single E1 guest have similar EQE and lifetime, OLEDB10 exhibits higher device efficiency, narrower spectrum and longer device lifetime, which may be related to the fact that the E1-1 spectrum is bluer than that of E1-2, thus forming a more efficient excited state energy transfer between E1 and E2.
  • the consistency of the spectral half-width and the spectral half-width of a single E2 device is related to the degree of overlap of E1 luminescence and E2 absorption in the mixture, indicating that the realization of a narrow spectrum in the device using the organic mixture of the present invention is related to the energy transfer efficiency between E1 and E2; at the same time, the device lifespan of OLEDB14-OLEDB17 is increased compared to the devices using single E1 and E2.
  • OLEDB18-OLEDB21 have high comprehensive device performance at different E1:E2 doping ratios, which may be related to the good stability of E2 itself and the efficient excited state energy transfer mechanism between E1 and E2.
  • OLEDB18 with the highest E1 ratio also has a narrow spectrum close to that of single E2, indicating that due to the existence of an efficient energy transfer mechanism, a relatively ideal narrow emission spectrum can be obtained when the E2 ratio is low.
  • E2 ratio is higher than E1
  • a higher device life is also achieved, which may show that the combination of E1 and E2 in certain mixtures can better protect the relatively unstable MR-TADF guest and reduce the damage to its structure by the exciton energy.
  • OLEDB20 contains a higher proportion of E2 in the light-emitting layer than OLEDB18-OLEDB19, it still has a higher life than the other two.
  • the device performance improvement effect provided by the organic mixture of the present invention is unexpected and cannot be simply attributed to the averaging effect of the spectrum and life between the two different guests E1 and E2.
  • the active excited state energy transfer in the organic mixture according to the present invention provides an additional energy dissipation path, thereby protecting the relatively weak chemical bonds in the guest, and the dual guest structure according to the present invention further improves the carrier balance of the original device.
  • OLEDB22 and OLEDB23 also achieved certain lifetime gains compared to single-guest devices, and their spectral half-peak widths were consistent with those of OLEDB6 and OLEDB9 using a single E2 guest, respectively. This shows that in the organic mixture according to the present invention, the spectrum narrowing and device lifetime gain based on the efficient excited state energy transfer between E1 and E2 are universal.
  • the half-peak width of the electroluminescence spectrum of the light-emitting device in some embodiments may be higher/lower/equal to the half-peak width of the photoluminescence spectrum in the polystyrene film.
  • PEDOT:PSS solution was spin-coated on a glass substrate treated with oxygen plasma to obtain an 80 nm film, which was then annealed in air at 150°C for 20 min.
  • a 20 nm Poly-TFB film (CAS: 223569-31-1, purchased from Lumtec.Corp; 5 mg/mL toluene solution) was then spin-coated on the PEDOT:PSS layer and subsequently treated on a hot plate at 180°C for 60 min.
  • the light-emitting layer solution (see Table 5) was first spin-coated in a nitrogen glove box to obtain a 35 nm thin film, and then annealed at 120° C. for 10 minutes.
  • the device performance of the above embodiments and comparative examples was tested, as shown in Table 6; the driving voltage was tested at a current density of 10 mA/ cm2 ; the device life of T95 refers to the time for the device brightness to decay to 95% of the initial value at a constant current density of 20 mA/ cm2 , with P-OLED1 as the benchmark (100%).
  • PEDOT:PSS solution was spin-coated on a glass substrate treated with oxygen plasma to obtain an 80 nm film, which was then annealed in air at 150°C for 20 min.
  • a 20 nm Poly-TFB film (CAS: 223569-31-1, purchased from Lumtec.Corp; 5 mg/mL toluene solution) was then spin-coated on the PEDOT:PSS layer and subsequently treated on a hot plate at 180°C for 60 min.
  • the light-emitting layer solution (see Table 5) was first spin-coated in a nitrogen glove box to obtain a 35 nm thin film, and then annealed at 120° C. for 10 minutes.
  • the device performance of the above embodiments and comparative examples was tested, as shown in Table 7; the EL peak and half-peak width were tested under the condition of device brightness of 1000 nits; the device life of T95 refers to the time from the time when the constant current is continuously lit at an initial brightness of 1000 nits until the device brightness decays to 95% of the initial value, with P-OLEDB1 as the benchmark (100%).
  • the lifespans of the embodiments P-OLEDB7 to P-OLEDB14 are significantly improved; compared with the comparative examples P-OLEDB1 to P-OLEDB2, the spectra of the embodiments P-OLEDB7 to P-OLEDB14 are significantly narrowed, and the device lifespans are improved to a certain extent compared with the case of using a single object.
  • the above results show that for solution-processed OLEDs, using the dual luminophores of the present invention can also greatly improve the device lifespan while obtaining an ideal narrow emission spectrum.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

本发明公开一种有机混合物，包含第一发光体E1和第二发光体E2，第一发光体E1和第二发光体E2都是荧光发光体；第二发光体E2的吸收谱和第一发光体E1的发光谱至少部分相互重叠；第二发光体E2的发光谱的半峰宽(FWHM)小于或等于50nm，并且第一发光体E1和第二发光体E2之间具有较有效的共振能量转移(FRET)。本发明还公开了一种包含第一发光体E1和第二发光体E2的组合物(印刷油墨)，从而为印刷OLED提供了一种技术选项。本发明进一步公开了一种光电器件，特别是有机电致发光器件，其发光层包含所述的有机混合物，按照本发明的有机电致发光器件同时具有长的器件寿命和较窄的发光谱线。

Description

有机混合物及其在光电领域的应用 技术领域
本发明涉及有机光电材料及器件技术领域，特别是涉及一种有机混合物，包含其的组合物、光电器件及其在光电领域的应用。
背景技术
有机半导体材料在合成上具有多样性，制造成本相对较低，以及具有优良的光学与电学性能，因此有机发光二极管(OLED)在光电器件(例如平板显示器和照明)的应用方面具有很大的潜力。
目前为止，基于荧光和磷光的发光材料体系已被开发出来，使用传统荧光/磷光材料的有机发光二极管具有较宽的发射光谱，底发射器件半高全宽(FWHM)通常超过30nm。近年来，多重共振TADF材料陆续被报道出来，特别是基于BN稠环体系的OLED发光材料，以其作为发光层制备发光器件，器件效率与采用传统发光材料相近或更优的同时，其光谱更窄，这有利于获得更高的显示色域。
OLED发光器件的器件效率及寿命在很大程度上取决于发光材料的性能。当前常用的发光材料为一类含BN稠环体系的多重共振TADF有机化合物，但由于其结构共轭较大等缺点，目前相应的OLED器件寿命仍然低于用传统荧光材料作为发光材料的器件。
因此，现有的OLED器件技术及与之相关的发光材料，特别是蓝光发光材料的解决方案还有待于改进和发展。
发明内容
基于此，本发明的目的是提供一种有机混合物、组合物、光电器件(特别是有机电致发光器件)及其在光电领域中的应用。
具体技术方案如下：
一种有机混合物，包含一种第一发光体E1和一种第二发光体E2，1)所述第一发光体E1和所述第二发光体E2都是荧光发光体；2)所述第二发光体E2的吸收谱和所述第一发光体E1的发光谱至少部分相互重叠；3)所述第二发光体E2的发光谱的半峰宽(FWHM)小于或等于50nm。
优选的，所述第二发光体E2选自化学式(1)或(2)所示的结构：
其中：Ar1-Ar3相同或不同的选自具有5～24个环原子的芳香族或杂芳香族；Ar4-Ar5相同或不同的选自空或具有5～24个环原子的芳香族或杂芳香族；当Ar4-Ar5不为空时，Xa和Xb在每次出现时独立选自N、C(R9)或Si(R9)；Ya和Yb在每次出现时独立选自B、P＝O、C(R9)或Si(R9)；当Ar4或Ar5为空时，Xb选自N、C(R9)或Si(R9)，Ya选自B、P＝O、C(R9)或Si(R9)，Xa和Yb在每次出现时独立选自N(R9)、C(R9R10)、Si(R9R10)、C＝O、O、C＝N(R9)、C＝C(R9R10)、P(R9)、P(＝O)R9、S、S＝O或SO2；X1、X2独立选自空或一个桥接基团；R4-R10在每次出现时，相同或不同的选自H、D，或者具有1～20 个C原子的直链的烷基、卤代烷基、烷氧基、硫代烷氧基基团，或者具有3～20个C原子的支链或环状的烷基、卤代烷基、烷氧基、硫代烷氧基基团、甲硅烷基基团，或者具有1～20个C原子的酮基基团，或者具有2～20个C原子的烷氧基羰基基团，或者具有7～20个C原子的芳氧基羰基基团，或者氰基基团(-CN)、氨基甲酰基基团(-C(＝O)NH2)、卤甲酰基基团(-C(＝O)-X其中X代表卤素原子)、甲酰基基团(-C(＝O)-H)、异氰基基团、异氰酸酯基团、硫氰酸酯基团、异硫氰酸酯基团、羟基基团、硝基基团、CF3、Cl、Br、F、I、可交联的基团，或者具有5～40个环原子的取代或未取代的芳族或杂芳族环系，或者具有5～40个环原子的芳氧基或杂芳氧基基团，或者具有5～40个环原子的芳胺基或杂芳胺基基团，以上基团任意位置的二取代单元或这些基团的组合，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。
优选的，所述第一发光体E1选自化学式(1)、化学式(2)或芳胺类衍生物。进一步的，所述第一发光体E1选自化学式(1)、化学式(2)或如下化学式(3)中的任何一个：
其中：R0-R1的定义同上述R4；Ar1-Ar4可相同或不同的选自具有5～60个环原子的芳香族或杂芳香族。
优选的，所述有机混合物还包含一种主体材料H，所述主体材料H选自化学式(4-1)或(4-2)所示的结构，优先选自蒽的衍生物；
其中，Ar5和Ar6在多次出现时可相同或不同的选自具有5～60个环原子的芳香族或杂芳香族。
本发明进一步提供一种组合物，包含一种如上所述的有机混合物，和至少一种有机溶剂。
本发明还提供一种光电器件，包含一种如上所述的有机混合物。
优选的，所述光电器件是有机电致发光器件，且包含依次设置的一基板、一阳极、一发光层和一阴极，所述发光层包含至少一种如上所述的有机混合物，或所述发光层采用如上所述的组合物制备所得。
有益效果：按照本发明的有机电致发光器件，其发光层包含两种发光体，传统的荧光材料(第一发光体E1)和具有窄发光谱的BN化合物(第二发光体E2)；传统的荧光材料(第一发光体E1)具有较长的器件寿命；第二发光体E2的吸收谱与第一发光体E1的发光谱至少部分相互重叠，这样可以实现第一发光体E1和第二发光体E2之间的共振能量转移((resonance energy transfer，简写FRET)，从而得到第一发光 体E1和第二发光体E2的优点，同时实现长器件寿命和窄发光谱线。
附图说明
图1：E2-1的吸收(Abs)和发光(PL)谱线图；
图2：E2-2的吸收(Abs)和发光(PL)谱线图；
图3：E2-3的吸收(Abs)和发光(PL)谱线图；
图4：E2-4的吸收(Abs)和发光(PL)谱线图；
图5：E2-5的吸收(Abs)和发光(PL)谱线图；
图6：E2-9的吸收(Abs)和发光(PL)谱线图；
图7：E1-1的吸收(Abs)和发光(PL)谱线图，及E2-1的吸收(Abs)谱线图；
图8：E1-2的吸收(Abs)和发光(PL)谱线图，及E2-1的吸收(Abs)谱线图；
图9：E1-2的吸收(Abs)和发光(PL)谱线图，及E2-2的吸收(Abs)谱线图；
图10：E1-2的吸收(Abs)和发光(PL)谱线图，及E2-3的吸收(Abs)谱线图；
图11：E1-2的吸收(Abs)和发光(PL)谱线图，及E2-4的吸收(Abs)谱线图；
图12：E1-2的吸收(Abs)和发光(PL)谱线图，及E2-5的吸收(Abs)谱线图；
图13：E1-3的吸收(Abs)和发光(PL)谱线图，及E2-5的吸收(Abs)谱线图；
图14：E1-3的吸收(Abs)和发光(PL)谱线图，及E2-9的吸收(Abs)谱线图。
具体实施方式
为了便于理解本发明，下面将参照相关附图对本发明进行更全面的描述。附图中给出了本发明的较佳实施例。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反的，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。本文所使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。
在本发明实施例的描述中，使用“～”所表示的数值范围是指包含“～”前后所记载的数值作为下限值和上限值的范围。
在本发明实施例的描述中，取代基可以进一步的被取代基取代，“取代的基团a”可以指基团a经取代基取代，该取代基可以经至少一个进一步的取代基取代或者未经取代。
本发明中，术语“和/或”，描述关联对象的关联关系，表示可以存在三种关系，
例如，A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B的情况。其中A，B可以是单数或者复数。字符“/”一般表示前后关联对象是一种“或”的关系。
本发明中，“至少一个”是指一个或者多个，“多个”是指两个或两个以上。“以下至少一项(个)”或其类似表达，是指的这些项中的任意组合，包括单项(个)或复数项(个)的任意组合。例如，“a，b，或c中的至少一项(个)”，或，“a，b，和c中的至少一项(个)”，均可以表示：a，b，c，a-b(即a和b)，a-c，b-c，或a-b-c，其中a，b，c分别可以是单个，也可以是多个。
应理解，在本发明的各种实施例中，上述各过程的序号的大小并不意味着执行顺序的先后，部分或全部步骤可以并行执行或先后执行，各过程的执行顺序应以其功能和内在逻辑确定，而不应对本发明实施例的实施过程构成任何限定。
在本发明实施例中使用的术语是仅仅出于描述特定实施例的目的，而非旨在限制本发明。在本发明实施例和所附权利要求书中所使用的单数形式的“一种”、“所述”和“该”也旨在包括多数形式，除非上下文清楚地表示其他含义。
术语“OLED”为“Organic Light Emitting Diode”的缩写，表示有机电致发光二极管，又称为有机电激光显示、有机发光半导体(Organic Electroluminescence Display，OLED)。OLED属于一种电流型的有机发光器件，是通过载流子的注入和复合而致发光的现象，发光强度与注入的电流成正比。OLED在电场的作用下，阳极产生的空穴和阴极产生的电子就会发生移动，分别向空穴传输层和电子传输层注入，迁移到发光层。当二者在发光层相遇时，产生能量激子，从而激发发光分子最终产生可见光。
术语“TADF”为“Thermally Activated Delayed Fluorescence”的缩写，表示热活化延迟荧光，其本质是三重态激发态与单重态激发态能量接近时，三重态激发态可以通过热活化反向系间窜越至单重态激发态。传统的发光是荧光和磷光，分别是激子单线态和三线态以辐射发光形式回到基态。而且一般较低单线态和较低三线态之间的能级差比较大，导致激子一旦从单线态通过系间窜越ISC过程到达三线态后就不能再回到单线态了。
在本发明中，主体材料、基质材料、Host材料和Matrix材料具有相同的含义，可以互换。
在本发明中，金属有机络合物、金属有机配合物和有机金属配合物具有相同的含义，可以互换。
在本发明中，组合物、印刷油墨、油墨和墨水具有相同的含义，可以互换。
在本发明实施例中，有机材料的能级结构，单线态能级ES1、三线态能级ET1、HOMO、LUMO起着关键的作用。下面对这些能级的确定做介绍。
HOMO和LUMO能级可以通过光电效应进行测量，例如XPS(X射线光电子光谱法)和UPS(紫外光电子能谱)或通过循环伏安法(以下简称CV)。最近，量子化学方法，例如密度泛函理论(以下简称DFT)，也成为行之有效的计算分子轨道能级的方法。
有机材料的单线态能级ES1可通过发光光谱来确定，三线态能级ET1可通过低温时间分辨发光光谱来测量。ES1和ET1还可以或通过量子模拟计算(如通过Time-dependent DFT)得到，如通过商业软件Gaussian 09W(Gaussian Inc.)，具体的模拟方法可参见WO2011141110或如下在实施例中所述。ΔEST定义为(ES1-ET1)。
应该注意，HOMO、LUMO、ES1、ET1的绝对值取决于所用的测量方法或计算方法，甚至对于相同的方法，不同评价的方法，例如在CV曲线上起始点和峰点可给出不同的HOMO/LUMO值。因此，合理有意义的比较应该用相同的测量方法和相同的评价方法进行。本发明实施例的描述中，HOMO、LUMO、ES1、ET1的值是基于Time-dependent DFT的模拟，但不影响其他测量或计算方法的应用。
在发明中，(HOMO-1)定义为第二高的占有轨道能级，(HOMO-2)为第三高的占有轨道能级，以此类推。(LUMO+1)定义为第二低的未占有轨道能级，(LUMO+2)为第三低的占有轨道能级，以此类推。
本发明提供一种有机混合物，包含一种第一发光体E1和一种第二发光体E2，1)第一发光体E1和第二发光体E2都是荧光发光体；2)第二发光体E2的吸收谱和第一发光体E1的发光谱至少部分相互重叠；3)第二发光体E2的发光谱的半峰宽(FWHM)小于或等于50nm。
在一个优选的实施例中，第二发光体E2的吸收谱在第一发光体E1的发光谱的短波长的一侧。
在另一些实施例中，第二发光体E2的吸收谱在第一发光体E1的发光谱的长波长的一侧。
在一些优选的实施例中，第二发光体E2的发光谱的半峰宽(FWHM)≤45nm，较好是≤40nm，更好是≤35nm，最好是≤30nm。
在另一些优选的实施例中，第二发光体E2和/或第一发光体E1，其荧光量子效率(PLQY)≥60％，较好是≥65％，更好是≥70％，更更好是≥80％，最好是≥85％。
在一些特别优选的实施例中，第二发光体E2选自化学式(1)或(2)所示的结构，更优选化学式(1)：
其中：Ar1-Ar3相同或不同的选自具有5～24个环原子的芳香族或杂芳香族；Ar4-Ar5相同或不同的选自空或具有5～24个环原子的芳香族或杂芳香族；当Ar4-Ar5不为空时，Xa和Xb在每次出现时独立选自N、C(R9)或Si(R9)，Ya和Yb在每次出现时独立选自B、P＝O、C(R9)或Si(R9)；当Ar4或Ar5为空时，Xb选自N、C(R9)或Si(R9)，Ya选自B、P＝O、C(R9)或Si(R9)，Xa和Yb在每次出现时独立选自N(R9)、C(R9R10)、Si(R9R10)、C＝O、O、C＝N(R9)、C＝C(R9R10)、P(R9)、P(＝O)R9、S、S＝O或SO2；X1、X2独立选自空或一个桥接基团；R4-R10在每次出现时，可相同或不同的选自H、D，或者具有1～20个C原子的直链的烷基、卤代烷基、烷氧基、硫代烷氧基基团，或者具有3～20个C原子的支链或环状的烷基、卤代烷基、烷氧基、硫代烷氧基基团、甲硅烷基基团，或者具有1～20个C原子的酮基基团，或者具有2～20个C原子的烷氧基羰基基团，或者具有7～20个C原子的芳氧基羰基基团，或者氰基基团(-CN)、氨基甲酰基基团(-C(＝O)NH2)、卤甲酰基基团(-C(＝O)-X其中X代表卤素原子)、甲酰基基团(-C(＝O)-H)、异氰基基团、异氰酸酯基团、硫氰酸酯基团、异硫氰酸酯基团、羟基基团、硝基基团、CF3、Cl、Br、F、I、可交联的基团，或者具有5～40个环原子的取代或未取代的芳族或杂芳族环系，或者具有5～40个环原子的芳氧基或杂芳氧基基团，或者具有5～40个环原子的芳胺基或杂芳胺基基团，以上基团任意位置的二取代单元或这些基团的组合，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。
在一些较为优选的实施例中，R4-R10在每次出现时，可相同或不同的选自H、D，或者具有1～10个C原子的直链的烷基、卤代烷基、烷氧基、硫代烷氧基基团，或者具有3～10个C原子的支链或环状的烷基、卤代烷基、烷氧基、硫代烷氧基基团、甲硅烷基基团，或者具有1～10个C原子的酮基基团，或者具有2～10个C原子的烷氧基羰基基团，或者具有7～10个C原子的芳氧基羰基基团，或者氰基基团(-CN)、氨基甲酰基基团(-C(＝O)NH2)、卤甲酰基基团(-C(＝O)-X其中X代表卤素原子)、甲酰基基团(-C(＝O)-H)、异氰基基团、异氰酸酯基团、硫氰酸酯基团、异硫氰酸酯基团、羟基基团、硝基基团、CF3、Cl、Br、F、可交联的基团，或者具有5～20个环原子的取代或未取代的芳族或杂芳族环系，或者具有5～20个环原子的芳氧基或杂芳氧基基团，或者具有5～20个环原子的芳胺基或杂芳胺基基团，或这些基团的组合，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。
在一些优选的实施例中，第二发光体E2选自包含如下化学式(1a)或(2a)所示的结构，更优选化学式(1a)：
其中，Ar1-Ar3、Ar4-Ar5、X1、X2、R4-R8的定义如上所述。
在某些较为优选的实施例中，X1和X2独立选自O或S；在一些更优选的实施例中，X1和X2均为O。
在某些较为优选的实施例中，X1、X2至少有一个是空；特别优选的是两个都为空，这时第二发光体E2选自包含如下化学式(1b)或(2b)所示的结构，更优选化学式(1b)：
其中，Ar1-Ar3、Ar4-Ar5、R4-R8的定义如上所述。
在某些较为优选的实施例中，X1、X2至少有一个是单键；特别优选的是两个都为单键，这时第二发光体E2选自包含如下化学式(1c)或(2c)所示的结构，更优选化学式(1c)：
其中，Ar1-Ar3、Ar4-Ar5、R4-R8的定义如上所述。
在某些较为优选的实施例中，X1、X2在每一次出现时，相同或不同的是二桥联基，优选的二桥联基有：

其中：R4、R5、R6及R7的定义同上述R4；虚线键表示与相邻的结构单元键合的键。
对于本发明的目的，芳香环系在环系中包含5～10个碳原子，杂芳香环系在环系中包含1～10个碳原子和至少一个杂原子，条件是碳原子和杂原子的总数至少为4。杂原子优选选自Si、N、P、O、S和/或Ge，特别优选选自Si、N、P、O和/或S。对于本发明的目的，芳香族或杂芳香族环系不仅包括芳香基或杂芳香基的体系，而且，其中多个芳基或杂芳基也可以被短的非芳族单元间断(<10％的非H原子，优选小于5％的非H原子，比如C、N或O原子)。因此，比如9,9′-螺二芴，9,9-二芳基芴，三芳胺，二芳基醚等体系，对于该发明目的同样认为是芳香族环系。
对于本发明的目的，其中第一发光体E1和第二发光体E2上的任一H原子以被R4基团取代，R4的定义如上所述，优选于，(1)C1-C10烷基，特别优选是指如下的基团：甲基、乙基、正丙基、异丙基、环丙基、正丁基、异丁基、仲丁基、叔丁基、环丁基、2-甲基丁基、正戊基、正己基、环己基、正庚基、环庚基、正辛基、环辛基、2-甲基庚基、三氟甲基、五氟乙基、2,2,2-三氟乙基、乙烯基、丙烯基、丁烯基、戊烯基、环戊烯基、己烯基、环己烯基、庚烯基、环庚烯基、辛烯基、环辛烯基、乙炔基、丙炔基、丁炔基、戊炔基、己炔基和辛炔基；(2)C1-C10烷氧基，特别优选的是指甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基、叔丁氧基或者2-甲基丁氧基；(3)C2-C10芳基或杂芳基，取决于用途其可以是一价或二价的，在每一情况下也可以被上述提及的基团R4取代并可以通过任何希望的位置与芳香族或杂芳香环连接，特别优选的是指以下的基团：苯、萘、蒽、嵌二萘、二氢芘、屈、萤蒽、丁省、戊省、苯并芘、呋喃、苯并呋喃、异苯并呋喃、二苯并呋喃、噻吩、苯并噻吩、异苯并噻吩、硫芴、吡咯、吲哚、异吲哚、咔唑、吡啶、喹啉、异喹啉、吖啶、菲啶、苯并-5,6-喹啉、苯并-6,7-喹啉、苯并-7,8-喹啉、吩噻嗪、吩恶嗪、吡唑、吲唑、咪唑、苯并咪唑、萘并咪唑、菲并咪唑、吡啶并咪唑、吡嗪并咪唑、喹喔啉并咪唑、恶唑、苯并恶唑、萘并恶唑、蒽并恶唑、菲并恶唑、异恶唑、1,2-噻唑、1,3-噻唑、苯并噻唑、哒嗪、苯并哒嗪、嘧啶、苯并嘧啶、喹喔啉、吡嗪、二氮蒽、1,5-二氮杂萘、氮咔唑、苯并咔啉、菲咯啉、1,2,3-三唑、1,2,4-三唑、苯并三唑、1,2,3-恶二唑、1,2,4-恶二唑、1,2,5-恶二唑、1,3,4-恶二唑、1,2,3-噻二唑、1,2,4-噻二唑、1,2,5-噻二唑、1,3,4-噻二唑、1,3,5-三嗪、1,2,4-三嗪、1,2,3-三嗪、四唑、1,2,4,5-四嗪、1,2,3,4-四嗪、1,2,3,5-四嗪、嘌呤、蝶啶、中氮茚和苯并噻二唑。用于本发明的目的，芳香和杂芳族环系认为特别是除上述提及的芳基和杂芳基之外，还指亚联苯基、亚三联苯、芴、螺二芴、二氢菲、四氢芘和顺式或者反式茚并芴。
在某些优选的实施例中，第二发光体E2中，Ar1-Ar5相同或不同的在每一次出现中选自具有5～20个环原子的芳香或杂芳族；较好的选自具有5～18个环原子的芳香或杂芳族；更好的选自具有5～15个环原子的芳香或杂芳族；最好的选自具有5～10个环原 子的芳香或杂芳族；它们可以未被取代或者被一个或二个R4基团取代。优选的芳基或者杂芳基有苯、萘、蒽、菲、吡啶、嵌二萘或噻吩。
在某些较为优选的实施例中，Ar1-Ar5选自如下结构式：
其中：X3是CR11或N；Y7选自NR11、CR12R13、SiR14R15、C(＝O)、S或O；R11、R12、R13、R14、R15的定义同上述R4。
进一步，Ar1、Ar2、Ar3、Ar4、Ar5独立选自如下化学结构式之一或其组合，且可进一步被任意取代：
在一些特别优选的实施例中，Ar1-Ar5为苯基。
在某些较为优选的实施例中，Ar4、Ar5至少有一个是空；特别优选的是两个都为空，这时第二发光体E2选自包含如下化学式(1d)或(2d)或(1e)或(2e)所示的结构：
其中，Ar1-Ar3、Xa、Yb、R6-R8的定义如上所述。
优先的，化学式(1d)和(1e)中的Xa相同或不同的彼此独立地选自N(R9)、C(R9R10)、Si(R9R10)、O或S。
优先的，化学式(2d)和(2e)中的Yb相同或不同的彼此独立地选自C＝O、O、S、P(＝O)R9、S＝O或SO2；特别优先的选自C＝O。
在另一些较为优选的实施例中，第二发光体E2包含如下化学式(1f)-(1i)所示的结构：
其中，Yc可相同或不同的选自O或S；Ar1-Ar3、Xa、R6-R8的定义如上所述。
在一些特别优选的实施例中，上述的Ar2、Ar3优先选自如下结构单元，且可进一 步被任意取代：
在某些优选的实施例中，按照化学式(1)-(1i)、化学式(2)-(2e)的结构单元中，其中R4-R8在多次出现时，可相同或不同的包含以下结构单元或它们中的组合：
其中n1是1或2或3或4。
在一些特别优选的实施例中，第二发光体E2选自如下化学式(1j)-(1l)所示的结构：
其中：Yc的定义如上述；R21、R22、R23、R24、R25每次出现时相同或不同，分别独立地选自D，或者具有1～20个C原子的直链的烷基、烷氧基、硫代烷氧基基团，或者具有3～20个C原子的支链或环状的烷基、烷氧基、硫代烷氧基基团、甲硅烷基基团，或者具有1～20个C原子的酮基基团，或者具有2～20个C原子的烷氧基羰基基团，或者具有7～20个C原子的芳氧基羰基基团，或者氰基基团(-CN)、氨基甲酰基基团(-C(＝O)NH2)、卤甲酰基基团(-C(＝O)-X其中X代表卤素原子)、甲酰基基团(-C(＝O)-H)、异氰基基团、异氰酸酯基团、硫氰酸酯基团、异硫氰酸酯基团、羟基基团、硝基基团、CF3、Cl、Br、F、可交联的基团，或者具有5～40个环原子的取代或未取代的芳族或杂芳族环系，或者具有5～40个环原子的芳氧基或杂芳氧基基团，或这些基团的组合，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系；m、n分别独立选自0～4的任一整数；o、q分别独立选自0～5的任一整数；p独立选自0～3的任一整数；“虚线”表示无或者单键。
优选的，R21-R25可以是D，或者具有1～10个C原子的直链的烷基、烷氧基、硫代烷氧基基团，或者具有3～10个C原子的支链或环状的烷基、烷氧基、硫代烷氧基基团、甲硅烷基基团，或者具有1～10个C原子的酮基基团，或者具有2～10个C原子的烷氧基羰基基团，或者具有7～10个C原子的芳氧基羰基基团，或者氰基基团(-CN)、氨基甲酰基基团(-C(＝O)NH2)、卤甲酰基基团(-C(＝O)-X其中X代表卤素原子)、甲酰基基团(-C(＝O)-H)、异氰基基团、异氰酸酯基团、硫氰酸酯基团、异硫氰酸酯基团、羟基基团、硝基基团、CF3、Cl、Br、F、可交联的基团，或者具有5～20个环原子的取代或未取代 的芳族或杂芳族环系，或者具有5～20个环原子的芳氧基或杂芳氧基基团，或这些基团的组合，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。
在一些较为优选的实施例中，第二发光体E2选自如下化学式(1m)-(1n)所示的结构：
其中R21、R22、R23、R24、R25和m、n、o、q、p的含义如上述。
在一些优选的实施例中，第二发光体E2选自如下化学式(1o)-(1p)所示的结构：
其中R21、R22、R23、R24、R25和m、o、q的含义如上述。
在一些优选的实施例中，对于化学式(1m)、(1n)、(1o)、(1p)，R22、R24每次出现时相同或不同，分别独立地选自具有5～40个环原子的芳香族或杂芳香族；较好是选自具有6～40个环原子的芳香族或杂芳香族；更好选自具有6～30个环原子的芳香族或杂芳香族；最好是选自具有6～20个环原子的芳香族或杂芳香族。
在另一些优选的实施例中，对于化学式(1m)、(1n)、(1o)、(1p)，R22、R24每次出现时相同或不同，分别独立地选自具有1～20个C原子的直链的烷基，或者具有1～20个C原子的酮基基团。
在一些优选的实施例中，对于化学式(1m)、(1n)、(1o)、(1p)，R22、R24每次出现时相同或不同，分别独立地选自给电子基团、由苯环构成的芳香族基团、或具有较大位阻的支化脂肪族基团，和/或上述结构的组合。
在一些更为优选的实施例中，对于化学式(1m)、(1n)、(1o)、(1p)，R22、R24每次出现时相同或不同，分别独立地选自如下化学式(5-1)-(5-9)所示的结构：

其中，*表示键合的位置。
在本发明实施例中，对于有机材料的能级结构，三线态能级(T1)及单线态能级(S1)、HOMO、LUMO和谐振因子强度f起着关键的作用。以下对这些参数的确定作一介绍。
HOMO和LUMO能级可以通过光电效应进行测量，例如XPS(X射线光电子光谱法)和UPS(紫外光电子能谱)或通过循环伏安法(以下简称CV)。最近，量子化学方法，例如密度泛函理论(以下简称DFT)，也成为行之有效的计算分子轨道能级的方法。
有机材料的三线态能级T1可通过低温时间分辨发光光谱来测量，或通过量子模拟计算(如通过Time-dependent DFT)得到，如通过商业软件Gaussian 09W(Gaussian Inc.)，具体的模拟方法如下面所述。有机材料的单线态能级S1，可通过吸收光谱，或发射光谱来确定，也可通过量子模拟计算(如Time-dependent DFT)得到；谐振因子强度f也可通过量子模拟计算(如Time-dependent DFT)得到。
应该注意，HOMO、LUMO、T1及S1的绝对值取决于所用的测量方法或计算方法，甚至对于相同的方法，不同评价的方法，例如在CV曲线上起始点和峰点可给出不同的HOMO/LUMO值。因此，合理有意义的比较应该用相同的测量方法和相同的评价方法进行。本发明实施例的描述中，HOMO、LUMO、T1及S1的值是基于Time-dependent DFT的模拟，但不影响其他测量或计算方法的应用。
在某些优选的实施例中，按照本发明的第二发光体E2，其(S1-T1)≤0.30eV，较好是≤0.25eV，更好是≤0.20eV，更更好是≤0.15eV，最好是≤0.10eV。
在某些实施例中，所述的有机混合物，其中第二发光体E2和第一发光体E1是小分子或高聚物，优选小分子。
在优选的实施例中，所述的有机混合物，其中不包含任何树脂。
此外，本发明中单独的芳环或杂芳环上的H原子或CH2基团可被基团R取代。R选自具有1～40个C原子的烷基基团，优先选自以下的基团：甲基，乙基，正丙基，异丙基，环丙基，正丁基，异丁基，仲丁基，叔丁基，环丁基，甲基丁基，正戊基，仲戊基，环戊基，正己基，环己基，正庚基，环庚基，正辛基，环辛基，乙基己基，三氟甲基，五氟乙基，三氟乙基，乙烯基，丙烯基，丁烯基，戊烯基，环戊烯基，己烯基，环己烯基，庚烯基，环庚烯基，辛烯基，环辛烯基，乙炔基，丙炔基，丁炔基，戊炔基，己炔基和辛炔基；具有1～40个C原子的烷氧基基团，如甲氧基，三氟甲氧基，乙氧基，正丙氧基，异丙氧基，正丁氧基，异丁氧基，仲丁氧基，叔丁氧基或甲基丁氧基。
下面给出第二发光体E2的例子(这些也可作为第一发光体E1的例子)，但不限于：





在一些较为优选的实施例中，第一发光体E1选自上述的化学式(1)或(2)、化学式(1a)-(1e)或化学式(2a)-(2e)或化学式(1f)-(1i)或化学式(1j)-(1l)。
在另一些较为优选的实施例中，第一发光体E1选自传统的荧光发光体(即单重态发光体)；传统的单重态发光体往往有较长的共轭π电子系统。迄今，已有许多例子，例如在JP2913116B和WO2001021729A1中公开的苯乙烯胺及其衍生物，在WO2008/006449和WO2007/140847中公开的茚并芴及其衍生物及在US7233019、KR2006-0006760中公开的芘的三芳胺衍生物。
在一些优选的实施例中，第一发光体E1可选自一元苯乙烯胺，二元苯乙烯胺，三元苯乙烯胺，四元苯乙烯胺，苯乙烯膦，苯乙烯醚和芳胺。
一个一元苯乙烯胺是指一化合物，它包含一个无取代或取代的苯乙烯基组和至少一个胺，最好是芳香胺。一个二元苯乙烯胺是指一化合物，它包含二个无取代或取代的苯乙烯基组和至少一个胺，最好是芳香胺。一个三元苯乙烯胺是指一化合物，它包含三个无取代或取代的苯乙烯基组和至少一个胺，最好是芳香胺。一个四元苯乙烯胺是指一化合物，它包含四个无取代或取代的苯乙烯基组和至少一个胺，最好是芳香胺。一个优选的苯乙烯是二苯乙烯，其可能会进一步被取代。相应的膦类和醚类的定义与胺类相似。芳基胺或芳香胺是指一种化合物，包含三个直接联接氮的无取代或取代的芳香环或杂环系统。这些芳香族或杂环的环系统中至少有一个优先选于稠环系统，并最好有至少14个芳香环原子。其中优选的例子有芳香蒽胺，芳香蒽二胺，芳香芘胺，芳香芘二胺，芳香屈胺和芳香屈二胺。一个芳香蒽胺是指一化合物，其中一个二元芳基胺基团直接联到蒽上，最好是在9的位置上。一个芳香蒽二胺是指一化合物，其中二个二元芳基胺基团直接联到蒽上，最好是在9,10的位置上。芳香芘胺，芳香芘二胺，芳香屈胺和芳香屈二胺的定义类似，其中二元芳基胺基团最好联到芘的1或1,6位置上。
基于乙烯胺及芳胺的传统的单重态发光体的例子，也是优选的例子，可在下述专利文件中找到：WO2006/000388、WO2006/058737、WO2006/000389、WO2007/065549、WO2007/115610、US7250532B2、DE102005058557A1、CN1583691A、JP08053397A、US6251531B1、US2006/210830A、EP1957606A1和US2008/0113101A1。特此上述列出的专利文件中的全部内容并入本文作为参考。
基于均二苯乙烯极其衍生物的传统的单重态发光体的例子有US5121029。
进一步的，优选的传统的单重态发光体可选于茚并芴-胺和茚并芴-二胺，如WO2006/122630所公开的，苯并茚并芴-胺和苯并茚并芴-二胺，如WO2008/006449所公开的，二苯并茚并芴-胺和二苯并茚并芴-二胺，如WO2007/140847所公开的。
进一步优选的传统的单重态发光体可选于基于芴的稠环体系，如US2015333277A1、US2016099411A1、US2016204355A1所公开的。
更加优选的传统的单重态发光体可选于芘的衍生物，如US2013175509A1所公开的结构；芘的三芳胺衍生物，如CN102232068B所公开的含有二苯并呋喃单元的芘的三芳胺衍生物；其它具有特定结构的芘的三芳胺衍生物，如CN105085334A、CN105037173A所公开的。其他可用作单重态发光体的材料有多环芳烃化合物，特别是如下化合物的衍生物：蒽如9,10-二(2-萘基)蒽，萘，并四苯，氧杂蒽，菲，芘(如2,5,8,11-四-t-丁基苝)，茚并芘，苯并稠环如(4,4’-双(9-乙基-3-咔唑乙烯基)-1,1’-联苯)，二茚并芘，十环烯，六苯并苯，芴，螺二芴，芳基芘(如US20060222886)，亚芳香基乙烯(如US5121029，US5130603)，环戊二烯如四苯基环戊二烯，红荧烯，香豆素，若丹明，喹吖啶酮，吡喃如4(二氰基亚甲基)-6-(4-对二甲氨基苯乙烯基-2-甲基)-4H-吡喃(DCM)，噻喃，双(吖嗪基)亚胺硼化合物(US2007/0092753A1)，双(吖嗪基)亚甲基化合物，carbostyryl化合物，噁嗪酮，苯并恶唑，苯并噻唑，苯并咪唑及吡咯并吡咯二酮。一些传统的单重态发光体的材料可在下述专利文件中找到：US20070252517A1、US4769292、US6020078。特此将上述列出的专利文件中的全部内容并入本文作为参考。
在某些实施例中，出于对稳定性的考虑，第一发光体E1不选自具有D-A结构的热激发延迟荧光(TADF)化合物，也不选自具有聚集诱导发光(AIE)特性的化合物。
在一个较为优选的实施例中，第一发光体E1，其S1-T1≥0.25eV，较好是≥0.3eV。
在一些较为优选的实施例中，第一发光体E1选自如下化学式(3)：
其中：R0-R1的定义如上述的R4；
Ar1-Ar4可相同或不同的选自具有5～60个环原子的芳香族或杂芳香族；较好是选自具有6～40个环原子的芳香族或杂芳香族；更好选自具有6～30个环原子的芳香族或杂芳香族；最好是选自具有6～20个环原子的芳香族或杂芳香族。
在一些更为优选的实施例中，第一发光体E1选自如下化学式(3a)-(3c)：
其中，R0-R9的定义如上述的R4；a、b分别独立选自0～2的任一整数。
下面列出一些合适的作为第一发光体E1的传统的单重态发光体的例子：


按照本发明的有机混合物，第二发光体E2的吸收光谱和第一发光体E1的发射光谱有较大的重叠，相互之间可以实现较为高效的能量转移。
在一些优选的实施例中，第二发光体E2的吸收谱的峰值(λ2)在第一发光体E1的发光谱的峰值(λ1)的短波长的一侧，且有较大的重叠。
在另一些实施例中，第二发光体E2的吸收谱的峰值(λ2)在第一发光体E1的发光谱的峰值(λ1)的长波长的一侧，且有较大的重叠。
优选的，λ1和λ2之间差值≤10nm，较好是≤8nm，更好是≤5nm，特别好是≤3nm，最好是≤2nm。
在另一些优选的实施例中，第二发光体E2的吸收谱的峰值(λ2)在第一发光体E1的发光谱的峰值(λ1)和第一发光体E1的吸收谱的峰值(λ3)之间。
在某些实施例中，第一发光体E1的发光谱的峰值(λ1)在第二发光体E2的吸收谱的峰值(λ2)和第一发光体E1的吸收谱的峰值(λ3)之间。
在某些优选的实施例中，所述有机混合物，其发光光谱完全来自第二发光体E2，即第一发光体E1和第二发光体E2之间实现完全的能量转移。
在某些实施例中，第一发光体E1发光谱的峰值(λ1)在400nm～700nm之间，较好是在410nm～600nm之间，特别好是在420nm～500nm之间，最好是在430nm～460nm之间。
在一个较为优选的实施例中，第一发光体E1发光谱的峰值(λ1)在440nm～460nm之间。
在某些实施例中，第二发光体E2发光谱的峰值(λ4)在400nm～800nm之间，较 好是在450nm～750nm之间，最好是在450nm～700nm之间。
在一个较为优选的实施例中，第二发光体E2发光谱的峰值(λ4)在455nm～465nm之间。
在另一个较为优选的实施例中，第二发光体E2发光谱的峰值(λ4)在520nm～535nm之间。
在某些实施例中，第一发光体E1吸收谱的峰值(λ3)在350nm～600nm之间，较好是在400nm～500nm之间，最好是在420nm～460nm之间。
在一个较为优选的实施例中，第一发光体E1吸收谱的峰值(λ3)在425nm～445nm之间。
在某些实施例中，第二发光体E2吸收谱的峰值(λ2)在350nm～600nm之间，较好是在400nm～500nm之间，最好是在440nm～460nm之间。
在一个较为优选的实施例中，第一发光体E2吸收谱的峰值(λ2)在445nm～455nm之间。
在一些优选的实施例中，所述有机混合物中，第一发光体E1和第二发光体E2之间的重量比为从10：90到90：10，较好是从20：80到80：20，更好是从70：30到30：70，特别好是从60：40到40：60，最好是55：45到45：55。
在一些较为优选的实施例中，所述有机混合物还包括一种主体材料H。合适的主体材料H可以选自单重态主体材料。
单重态主体材料的例子并不受特别的限制，任何有机化合物都可能被用作为本发明的主体材料，只要其单重态能级比第一发光体E1和第二发光体E2更高。
作为单重态主体材料使用的有机化合物的例子可选自含有环芳香烃化合物，如苯、联苯、三苯基苯、苯并菲、萘、蒽、萉、菲、芴、芘、屈、苝、薁；芳香杂环化合物，如二苯并噻吩、二苯并呋喃、二苯并硒吩、呋喃、噻吩、苯并呋喃、苯并噻吩、苯并硒吩、咔唑、吲哚咔唑、吡啶吲哚、吡咯二吡啶、吡唑、咪唑、三氮唑、异恶唑、噻唑、恶二唑、恶三唑、二恶唑、噻二唑、吡啶、哒嗪、嘧啶、吡嗪、三嗪、恶嗪、恶噻嗪、恶二嗪、吲哚、苯并咪唑、吲唑、吲哚嗪、苯并恶唑、苯异恶唑、苯并噻唑、喹啉、异喹啉、噌啉、喹唑啉、喹喔啉、萘、酞、蝶啶、氧杂蒽、吖啶、吩嗪、吩噻嗪、吩恶嗪、苯并呋喃吡啶、呋喃二吡啶、苯并噻吩吡啶、噻吩二吡啶、苯并硒吩吡啶和硒吩二吡啶；包含有2～10环原子的基团，它们可以是相同或不同类型的环芳香烃基团或芳香杂环基团，并彼此直接或通过至少一个以下的基团连结在一起，如氧原子、氮原子、硫原子、硅原子、磷原子、硼原子、链结构单元和脂肪环基团。
在一些优选的实施例中，单重态主体材料可选于包含至少一个以下基团的化合物：
Y每次出现时，独立选自C(R101)2、NR101、O或S，X每次出现时，独立选自CR101或N；R101每次出现时，独立选自如下的基团：氢、氘、卤原子(F，Cl，Br，I)、氰基、烷基、烷氧基、氨基、烯基、炔基、芳烷基、杂烷基、芳基和杂芳基，n2选自1～20的整数。
在一些优选的实施例中，单重态主体选自蒽的衍生物，如CN102224614B、CN100471827C、CN1914293B、WO2015033559A1、US2014246657A1、 WO2016117848A1、WO2016117861A1、WO2016171429A2、CN102369256B、CN102428158B等专利文献中所公开的。
在一些优选先的实施例中，主体材料H选自如下化学式(4-1)或(4-2)的结构：
其中Ar5和Ar6的定义如上所述的Ar1。
在一些较为优选的实施例中，Ar5和Ar6选自苯、萘、二苯并呋喃、萘并苯并呋喃、咔唑及其组合。
下面列出一些可以作为主体材料H的单重态主体材料的例子：
在一些更加优选的实施例中，作为主体材料H的蒽基单重态主体材料是氘代的，即主体材料分子中含有至少一个以上的氘原子，这样的例子在CN102369256B、CN102428158B、CN102639671B、US2015021586A1等专利文献中所公开，具体的例子有：
本发明的另一个目的是为印刷OLED提供材料解决方案。
用于这个目的，按照本发明的有机混合物中的第一发光体E1和第二发光体E2，和/或主体材料H，至少有一个，其分子量≥700g/mol，优选≥800g/mol，很优选≥900g/mol，更优选≥1000g/mol，最优选≥1100g/mol。
在某些实施例中，按照本发明的有机混合物，在25℃时，在甲苯、或二甲苯、或均三甲苯、或环己基苯、或苯甲酸甲酯任一种溶剂或任意两者及以上的混合溶剂中的溶解度≥5mg/mL，优选≥10mg/mL，较优选≥15mg/mL，更优选≥20mg/mL，最优选≥25mg/mL。
在另一些实施例中，所述有机混合物中，第二发光体E2或第一发光体E1包含至少一个可交联基团，如在申请号为CN202110370910.9的专利申请中所公开的，特此将其全部内容并入本文作为参考。
在一些较为优选的实施例中，第二发光体E2或第一发光体E1包含至少两个可交联基团。
在另一些较为优选的实施例中，第二发光体E2或第一发光体E1包含至少三个可交联基团。
在另一些实施例中，所述有机混合物中，主体材料H包含至少一个可交联基团。
在一些较为优选的实施例中，主体材料H包含至少两个可交联基团。
在另一些较为优选的实施例中，主体材料H包含至少三个可交联基团。
本发明还涉及一种组合物，包含一种如上所述的有机混合物和至少一种有机溶剂。
在一些优选的实施例中，按照本发明的组合物是一溶液。
在另一些优选的实施例中，按照本发明的组合物是一悬浮液。
本发明实施例中的组合物中可以包括0.01wt％至20wt％的所述的有机混合物，较好的是0.1wt％至20wt％，更好的是0.2wt％至20wt％，最好的是2wt％至15wt％。
在一些优选的实施例中，所述有机溶剂选自醇、酯、芳族酮或芳族醚、脂肪族酮或脂肪族醚、或硼酸酯或磷酸酯等无机酯类化合物，或两种及两种以上有机溶剂的组合物。
在另一些实施例中，适当的和优选的有机溶剂是脂肪族、脂环族或芳烃族、胺、硫醇、酰胺、腈、酯、醚、聚醚、醇、二醇或多元醇。
在另一些实施例中，醇代表适当类别的有机溶剂。优选的醇包括烷基环己醇，特别是甲基化的脂肪族醇、萘酚等。
另外适当的醇类有机溶剂的例子有：十二醇、苯基十三醇、苯甲醇、乙二醇、乙二醇甲醚、丙三醇、丙二醇、丙二醇乙醚等。
所述有机溶剂可以是单独使用，也可以是作为两种或多种有机溶剂的组合物使用。
进一步，有机溶剂的例子，包括(但不限于)：甲醇、乙醇、2-甲氧基乙醇、二氯甲烷、三氯甲烷、氯苯、邻二氯苯、四氢呋喃、苯甲醚、吗啉、甲苯、邻二甲苯、间二甲苯、对二甲苯、1,4-二氧杂环己烷、丙酮、甲基乙基酮、1,2-二氯乙烷、3-苯氧基甲苯、1,1,1-三氯乙烷、1,1,2,2-四氯乙烷、醋酸乙酯、醋酸丁酯、二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、四氢萘、萘烷、茚和/或它们的组合物。
在一些优选的实施例中，按照本发明的组合物，其中所述有机溶剂选自芳族或杂芳族、酯、芳族酮或芳族醚、脂肪族酮或脂肪族醚、脂环族或烯烃类化合物、或硼酸 酯或磷酸酯等无机酯类化合物、或两种及两种以上溶剂的组合物。
按照本发明的基于芳族或杂芳族溶剂的例子有，但不限于：1-四氢萘酮、3-苯氧基甲苯、苯乙酮、1-甲氧基萘、对二异丙基苯、戊苯、四氢萘、环己基苯、氯萘、1,4-二甲基萘、3-异丙基联苯、对甲基异丙苯、二戊苯、邻二乙苯、间二乙苯、对二乙苯、1,2,3,4-四甲苯、1,2,3,5-四甲苯、1,2,4,5-四甲苯、丁苯、十二烷基苯、1-甲基萘、1,2,4-三氯苯、1,3-二丙氧基苯、4,4-二氟二苯甲烷、二苯醚、1,2-二甲氧基-4-(1-丙烯基)苯、二苯甲烷、2-苯基吡啶、3-苯基吡啶、2-苯氧基甲醚、2-苯氧基四氢呋喃、乙基-2-萘基醚、N-甲基二苯胺、4-异丙基联苯、α，α-二氯二苯甲烷、4-(3-苯基丙基)吡啶、苯甲酸苄酯、1,1-双(3,4-二甲基苯基)乙烷、2-异丙基萘、二苄醚等。
在另一些实施例中，适当的和优选的有机溶剂是脂肪族、脂环族或芳烃族、胺、硫醇、酰胺、腈、酯、醚、聚醚。
所述有机溶剂可以是环烷烃，例如十氢化萘。
在另一些优选的实施例中，按照本发明的组合物，其中包含至少50wt％的醇类溶剂；优选至少80wt％的醇类溶剂；特别优选至少90wt％的醇类溶剂。
一些优选的实施例中，特别适合本发明的有机溶剂是汉森(Hansen)溶解度参数在以下范围内的溶剂：
δd(色散力)在17.0MPa1/2-23.2MPa1/2的范围，尤其是在18.5MPa1/2-21.0MPa1/2的范围；
δp(极性力)在0.2MPa1/2-12.5MPa1/2的范围，尤其是在2.0MPa1/2-6.0MPa1/2的范围；
δh(氢键力)在0.9MPa1/2-14.2MPa1/2的范围，尤其是在2.0MPa1/2-6.0MPa1/2的范围。
按照本发明的组合物，其中有机溶剂在选取时需考虑其沸点参数。本发明中，所述的有机溶剂的沸点≥150℃；优选为≥180℃；较优选为≥200℃；更优为≥250℃；最优为≥275℃或≥300℃。这些范围内的沸点对防止喷墨印刷头的喷嘴堵塞是有益的。所述的有机溶剂可从溶剂体系中蒸发，以形成包含功能材料薄膜。
在一些优选的实施例中，按照本发明的组合物：
1)其粘度@25℃，在1cps到100cps范围，和/或
2)其表面张力@25℃，在19dyne/cm到50dyne/cm范围。
按照本发明的组合物，其中有机溶剂在选取时需考虑其表面张力参数。合适的表面张力参数适合于特定的基板和特定的印刷方法。例如对喷墨印刷，在一些优选的实施例中，所述有机溶剂在25℃下的表面张力约在19dyne/cm到50dyne/cm范围；更优是在22dyne/cm到35dyne/cm范围；最优是在25dyne/cm到33dyne/cm范围。
在一些优选的实施例中，按照本发明的组合物在25℃下的表面张力约在19dyne/cm到50dyne/cm范围；更好是在22dyne/cm到35dyne/cm范围；最好是在25dyne/cm到33dyne/cm范围。
按照本发明的组合物，其中有机溶剂在选取时需考虑其油墨的粘度参数。粘度可以通过不同的方法调节，如通过合适的有机溶剂的选取和油墨中功能材料的浓度。在一些优选的实施例中，所述有机溶剂的粘度低于100cps；更优为低于50cps；最优为为1.5cps到20cps。这里的粘度是指在印刷时的环境温度下的粘度，一般在15℃-30℃，较好的是18℃-28℃，更好是20℃-25℃，最好是23℃-25℃。如此配制的组合物将特别适合于喷墨印刷。
在一些优选的实施例中，按照本发明的组合物，在25℃下的粘度约在1cps到100cps范围；更好是在1cps到50cps范围；最好是在1.5cps到20cps范围。
满足上述沸点及表面张力参数及粘度参数的有机溶剂获得的油墨能够形成具有均匀厚度及组成性质的功能材料薄膜。
本发明进一步涉及一种有机功能材料薄膜，所述有机功能材料薄膜利用一种如上所述的组合物制备而成。
本发明还提供一种所述有机功能材料薄膜的制备方法，包含如下步骤：
1)制备一种按照本发明的组合物；
2)用印刷或涂布的方法将所述的组合物涂布于一基板上形成一薄膜，其中印刷或涂布的方法选自喷墨打印、喷印(Nozzle Printing)、活版印刷、丝网印刷、浸涂、旋转涂布、刮刀涂布、辊筒印花、扭转辊印刷、平版印刷、柔版印刷、轮转印刷、喷涂、刷涂或移印、或狭缝型挤压式涂布；
3)将所得的薄膜在至少50℃加热，除去有机溶剂，固化薄膜。
所述有机功能材料薄膜厚度一般为5nm-20μm，较好为5nm-10μm，更好为10nm-5μm，最好为10nm-1μm。
本发明还提供上述有机混合物及有机功能材料薄膜在光电器件中的应用。
在某些实施例中，所述光电器件可选自有机发光二极管(OLED)、有机光伏电池(OPV)、有机发光电池(OLEEC)、有机发光场效应管、或有机激光器。
更进一步，本发明提供一种光电器件，包含一种上述的有机混合物或有机功能材料薄膜。
优先的，所述光电器件是电致发光器件，如有机发光二极管(OLED)、有机发光电池(OLEEC)、有机发光场效应管、钙钛矿发光二极管(PeLED)、及量子点发光二极管(QD-LED)，其中一功能层中包含一种上述的有机混合物或有机功能材料薄膜。所述的功能层可以选自空穴注入层、空穴传输层、电子注入层、电子传输层、发光层或阴极钝化层(CPL)。
在一些优选的实施例中，所述光电器件是有机电致发光器件，且包含依次设置的一基板、一阳极、一发光层和一阴极，所述发光层包含至少一种如上所述的有机混合物，或所述发光层采用如上所述的组合物制备所得。
在某些实施例中，所述有机电致发光器件中，所述第二发光体E2和所述第一发光体E1是小分子或高聚物，优选小分子。
在一些优选的实施例中，所述有机电致发光器件中，所述发光层中不包含任何树脂。
在一些优选的实施例中，所述有机电致发光器件发射蓝光。
在一些优选的实施例中，所述有机电致发光器件是OLED。特别优先的，所述的有机电致发光器件是顶发射(Top Emission)OLED。
所述基板可以是不透明或透明。一个透明的基板可以用来制造一个透明的发光元器件。例如可参见，Bulovic等Nature 1996,380,p29，和Gu等，Appl.Phys.Lett.1996,68,p2606。基片可以是刚性的或弹性的。基片可以是塑料、金属、半导体晶片或玻璃。最好是基片有一个平滑的表面。无表面缺陷的基板是特别理想的选择。在一些优选的实施例中，基片是柔性的，可选于聚合物薄膜或塑料，其玻璃化温度(Tg)为150℃以上，较好是超过200℃，更好是超过250℃，最好是超过300℃。合适的柔性基板的例子有聚对苯二甲酸乙二醇酯(PET)和聚乙二醇(2,6-萘)(PEN)。
所述阳极可包括一导电金属或金属氧化物，或导电聚合物。阳极可以容易地注入空穴到空穴注入层(HIL)或空穴传输层(HTL)或发光层中。在一些优选的实施例中，阳极的功函数和发光层中的发光体或作为HIL或HTL或电子阻挡层(EBL)的p型半导体材料的HOMO能级或价带能级的差的绝对值小于0.5eV，较好是小于0.3eV，最好是小于0.2eV。阳极材料的例子包括但不限于：Al、Cu、Au、Ag、Mg、Fe、Co、Ni、Mn、Pd、Pt、ITO、铝掺杂氧化锌(AZO)等。其他合适的阳极材料是已知的， 本领域普通技术人员可容易地选择使用。阳极材料可以使用任何合适的技术沉积，如一合适的物理气相沉积法，包括射频磁控溅射，真空热蒸发，电子束(e-beam)等。在某些实施例中，阳极是图案结构化的。图案化的ITO导电基板可在市场上买到，并且可以用来制备根据本发明的器件。
所述阴极可包括一导电金属或金属氧化物。阴极可以容易地注入电子到EIL或ETL或直接到发光层中。在一些优选的实施例中，阴极的功函数和发光层中发光体或作为电子注入层(EIL)或电子传输层(ETL)或空穴阻挡层(HBL)的n型半导体材料的LUMO能级或导带能级的差的绝对值小于0.5eV，较好是小于0.3eV，最好是小于0.2eV。原则上，所有可用作OLED的阴极的材料都可能作为本发明器件的阴极材料。阴极材料的例子包括但不限于：Al、Au、Ag、Ca、Ba、Mg、LiF/Al、MgAg合金、BaF2/Al、Cu、Fe、Co、Ni、Mn、Pd、Pt、ITO等。阴极材料可以使用任何合适的技术沉积，如一合适的物理气相沉积法，包括射频磁控溅射，真空热蒸发，电子束(e-beam)等。在一些优选的实施例中，所述的阴极在400nm-680nm范围的透光度≥40％，较好是≥45％，更好是≥50％，最好是≥60％。通常是10nm-20nm的Mg：Ag合金可以用来做透明阴极，Mg：Ag的比例可以从2：8到0.5：9.5。
所述OLED还可以进一步包含其他功能层，如空穴注入层(HIL)、空穴传输层(HTL)、电子阻挡层(EBL)、电子注入层(EIL)、电子传输层(ETL)、空穴阻挡层(HBL)。适合用于这些功能层中的材料在上面及在WO2010135519A1、US20090134784A1和WO2011110277A1中有详细的描述，特此将此3篇专利文件中的全部内容并入本文作为参考。
进一步，所述有机电致发光器件还包括一个阴极覆盖层(Capping layer，简称CPL)。
用于CPL的材料一般需要有较高的折射率n，如n≥1.95@460nm，n≥1.90@520nm，n≥1.85@620nm。用于CPL材料的例子有：
更多的进一步的CPL材料的例子可以在如下的专利文献中找到：KR20140128653A，KR20140137231A，KR20140142021A，KR20140142923A，KR20140143618A，KR20140145370A，KR20150004099A，KR20150012835A，US9496520B2，US2015069350A1，CN103828485B，CN104380842B，CN105576143A，TW201506128A，CN103996794A，CN103996795A，CN104744450A，CN104752619A，CN101944570A，US2016308162A1，US9095033B2，US2014034942A1，WO2017014357A1；特将以上专利文献并入此文作为参考。
优先的，上述的有机电致发光器件，其中所述封装层是薄膜封装(TFE)。
本发明进一步涉及一显示面板，其中至少有一个像素包含上述的有机电致发光器件。
实施例
下面将结合优选实施例对本发明进行说明，但本发明并不局限于下述实施例，应当理解，所附权利要求概括了本发明的范围。在本发明构思的引导下本领域的技术人员应意识到，对本发明的各实施例所进行的一定的改变，都将被本发明的权利要求书的精神和范围所覆盖。
1、化合物的合成
化合物E1-1：
化合物E1-1的合成参照专利WO2013077405所描述的方法。
化合物E1-2：
化合物E1-2的合成参照专利WO2016042781A1所描述的方法。
化合物E1-3：
中间体1a的合成：在一个干燥的反应瓶里放置化合物1-1(20g，109.9mmol)，化合物1-2(13.41g，109.9mmol)，碳酸钾(45.50g，329.7mmol)，四三苯基磷钯(6.35g，5.5mmol)，然后加入1,4-二氧六环400mL和水40mL，抽真空充氮气循环三次，90℃搅拌反应16小时，冷却到室温，浓缩反应液，除去1,4-二氧六环后加入600mL的水中，用二氯甲烷萃取三次浓缩母液后用柱层析提纯，淋洗剂为二氯甲烷：正己烷＝3：10，浓缩含有产品的淋洗剂得中间体1a共17.5g，纯度98％，产率88％。
中间体3a的合成与中间体1a的合成相似，区别仅在于使用化合物2-2替代化合物1-2；
中间体3a的合成所使用原料及产率如下：

中间体1b的合成：在一个干燥的反应瓶里放置中间体1a(7.56g，41.3mmol)，化合物1-3(11.89g，41.3mmol)，叔丁醇钠(11.89g，123.9mmol)，Pd2(dba)3(1.89g，2.1mmol)，XPhos(1.96g，4.1mmol)，然后加入1,4-二氧六环100mL，抽真空充氮气循环三次，100℃搅拌反应16小时，冷却到室温，浓缩反应液，除去1,4-二氧六环后加入150mL的水中，用二氯甲烷萃取三次浓缩母液后用柱层析提纯，淋洗剂为二氯甲烷：正己烷＝1：10，浓缩含有产品的淋洗剂得中间体1b共13.24g，纯度98％，产率82％。
中间体2b的合成与中间体1b的合成类似，区别仅在于使用化合物2-1替代中间体1a。
中间体3b的合成与中间体1b的合成类似，区别仅在于使用中间体3a替代中间体1a。
中间体2b及中间体3b的合成所使用原料及产率如下：

化合物E1-3的合成：在一个干燥的反应瓶里放置化合物1-4(3.00g，8.3mmol)，中间体1b(9.74g，24.9mmol)，叔丁醇钠(3.19g，33.2mmol)，Pd2(dba)3(380mg，0.4mmol)，PtBu3·HBF4(230mg，0.8mmol)然后加入甲苯60mL，抽真空充氮气循环三次，120℃搅拌反应16小时，冷却到室温，浓缩反应液后加入100mL的水中，用二氯甲烷萃取三次浓缩母液后用柱层析提纯，淋洗剂为二氯甲烷：正己烷＝1：8，浓缩含有产品的淋洗剂得化合物E1-3共6.35g，纯度99％，产率78％。
化合物E1-4～化合物E1-6：
化合物E1-4的合成与化合物E1-3的合成相似，区别仅在于采用中间体2b替代中间体1b，用化合物2-4替代化合物1-4。
化合物E1-5的合成与化合物E1-3的合成相似，区别仅在于采用中间体3b替代中间体1b，用化合物2-4替代化合物1-4。
化合物E1-6的合成与化合物E1-3的合成相似，区别仅在于采用中间体2b替代中间体1b。
化合物E1-4～化合物E1-6的合成所使用原料及产率如下：
化合物E2-1：
化合物E2-1的合成参照专利CN117567491所描述的方法。
化合物E2-2：
中间体4a的合成：在500mL的三口烧瓶中依次加入将化合物4-1(28.8g，100.0mmol)，化合物4-2(37.1g，110.0mmol)，甲苯300mL，叔丁醇钠(14.4g，150.0mmol)，Pd2(dba)3(916mg，1.0mmol)，Xantphos(1.1g，2.0mmol)，抽真空氮气置换三次，加热到110℃反应，TLC跟踪反应。待反应完全，冷却到室温，旋蒸除去反应体系中的溶剂，用乙酸乙酯和饱和氯化钠溶液萃取，合并有机相干燥、过滤浓缩后用正己烷：二氯甲烷＝15：1(体积比)做淋洗剂通过硅胶层析柱分离得到中间体4a，干燥后约33.5g，产率为61.5％。
中间体4b的合成：在500mL的三口烧瓶中依次加入将中间体4a(30.0g，55.0mmol)，化合物4-3(17.6g，60.5mmol)，碳酸铯(26.5g，82.5mmol)，DMF 300mL，升温至回流反应。TLC监测反应，待原料基本消耗完全后停止反应。用300mL甲醇和100mL水室温打浆2h，得到中间体4b，干燥后约29.2g，产率约为65.1％。
中间体4c的合成：在500mL的三口烧瓶中依次加入将中间体4b(25.0g，30.6mmol)，化合物4-4(9.4g，33.6mmol)，甲苯200mL，叔丁醇钠(4.4g，45.9mmol)，Pd2(dba)3(280mg，0.3mmol)，TTBPH·BF4(174.0mg，0.6mmol)，抽真空氮气置换三次，加热到110℃反应，TLC跟踪反应。待反应完全，冷却到室温，旋蒸除去反应体系中的溶剂，用乙酸乙酯和饱和氯化钠溶液萃取，合并有机相干燥、过滤浓缩后用正己烷：二氯甲烷＝12：1(体积比)做淋洗剂通过硅胶层析柱分离得到中间体4c，干燥后约21.7g，产率约为69.8％。
化合物E2-2的合成：在500mL的三口烧瓶中加入将中间体4c(20.0g，19.7mmol)，叔丁基苯200mL，抽真空氮气置换三次，0℃滴加1.6M叔丁基锂(25.8mL，43.34mmol)，滴加完毕后升温至60℃反应1h，0℃滴加三溴化硼(5.6mL，59.1mmol)，室温反应2h，0℃滴加二异丙基乙胺(25.8mL，147.7mmol)，升温至120℃反应3h。反应结束，冷却到室温，旋蒸除去反应体系中的溶剂，用乙酸乙酯和饱和氯化钠溶液萃取，合并有机相干燥、过滤浓缩后用甲苯重结晶得到化合物E2-2，干燥后约2.9g，产率约为14.9％。
化合物E2-3：
中间体5a的合成：在500mL的三口烧瓶中依次加入将化合物5-1(25.7g，100.0mmol)，化合物4-2(37.1g，110.0mmol)，甲苯300mL，叔丁醇钠(14.4g，150.0mmol)，Pd2(dba)3(916mg，1.0mmol)，X-Phos(953mg，2.0mmol)，抽真空氮气置换三次，加热到110℃反应，TLC跟踪反应。待反应完全，冷却到室温，旋蒸除去反应体系中的溶剂，用乙酸乙酯和饱和氯化钠溶液萃取，合并有机相干燥、过滤浓缩后用正己烷：二氯甲烷＝12：1(体积比)做淋洗剂通过硅胶层析柱分离得到中间体5a，干燥后约32.5g，产率约为58.3％。
中间体5b的合成：在500mL的三口烧瓶中依次加入将中间体5a(17.1g，30.6mmol)，化合物5-2(17.3g，33.6mmol)，甲苯200mL，叔丁醇钠(4.4g，45.9mmol)，Pd2(dba)3(280mg，0.3mmol)，TTBPH·BF4(174.0mg，0.6mmol)，抽真空氮气置换三次，加热到110℃反应，TLC跟踪反应。待反应完全，冷却到室温，旋蒸除去反应体系中的溶剂，用乙酸乙酯和饱和氯化钠溶液萃取，合并有机相干燥、过滤浓缩后用正己烷：二氯甲烷＝8：1(体积比)做淋洗剂通过硅胶层析柱分离得到中间体5b，干燥后约19.6g，产率约为61.9％。
化合物E2-3的合成：在500mL的三口烧瓶中加入将中间体5b(20.4g，19.7mmol)，叔丁基苯200mL，抽真空氮气置换三次，0℃滴加1.6M叔丁基锂(25.8mL，43.34mmol)，滴加完毕后升温至60℃反应1h，0℃滴加三溴化硼(5.6mL，59.1mmol)，室温反应2h，0℃滴加二异丙基乙胺(25.8mL，147.7mmol)，升温至120℃反应3h。反应结束，冷却到室温，旋蒸除去反应体系中的溶剂，用乙酸乙酯和饱和氯化钠溶液萃取，合并有机相干燥、过滤浓缩后用甲苯重结晶得到化合物E2-3，干燥后约3.5g，产率约为17.5％。
化合物E2-4：
中间体6a的合成：在250mL的三口烧瓶中依次加入将化合物6-2(7.9g，30.6mmol)，化合物6-1(14.3g，33.6mmol)，二氧六环150mL，水30mL，碳酸钾(8.4g，61.2mmol)，Pd(PPh3)4(346mg，0.3mmol)，抽真空氮气置换三次，加热到100℃ 反应，TLC跟踪反应。待反应完全，冷却到室温，旋蒸除去反应体系中的溶剂，用乙酸乙酯和饱和氯化钠溶液萃取，合并有机相干燥、过滤浓缩后用正己烷做淋洗剂通过硅胶层析柱分离得到中间体6a，干燥后约15.3g，产率约为89.8％。
中间体6b的合成：在250mL的三口烧瓶中依次加入将中间体6a(14.2g，25.4mmol)，化合物4-2(9.4g，27.9mmol)，甲苯150mL，叔丁醇钠(3.7g，38.1mmol)，Pd2(dba)3(183mg，0.2mmol)，X-Phos(190.6mg，0.4mmol)，抽真空氮气置换三次，加热到110℃反应，TLC跟踪反应。待反应完全，冷却到室温，旋蒸除去反应体系中的溶剂，用乙酸乙酯和饱和氯化钠溶液萃取，合并有机相干燥、过滤浓缩后用正己烷：二氯甲烷＝10：1(体积比)做淋洗剂通过硅胶层析柱分离得到中间体6b，干燥后约14.6g，产率约为66.6％。
中间体6c的合成：在250mL的三口烧瓶中依次加入将化合物6b(14.0g，16.2mmol)，化合物6-3(9.4g，17.8mmol)，甲苯150mL，叔丁醇钠(2.3g，24.3mmol)，Pd2(dba)3(183mg，0.2mmol)，TTBPH·BF4(116.0mg，0.4mmol)，抽真空氮气置换三次，加热到110℃反应，TLC跟踪反应。待反应完全，冷却到室温，旋蒸除去反应体系中的溶剂，用乙酸乙酯和饱和氯化钠溶液萃取，合并有机相干燥、过滤浓缩后用正己烷：二氯甲烷＝7：1(体积比)做淋洗剂通过硅胶层析柱分离得到中间体6c，干燥后约16.0g，产率约为73.3％。
化合物E2-4的合成：在500mL的三口烧瓶中加入将化合物中间体6c(15.1g，11.2mmol)，叔丁基苯200mL，抽真空氮气置换三次，0℃滴加1.6M叔丁基锂(14.7mL，24.7mmol)，滴加完毕后升温至60℃反应1h，0℃滴加三溴化硼(3.2mL，33.6mmol)，室温反应2h，0℃滴加二异丙基乙胺(14.7mL，84.1mmol)，升温至120℃反应3h。反应结束，冷却到室温，旋蒸除去反应体系中的溶剂，用乙酸乙酯和饱和氯化 钠溶液萃取，合并有机相干燥、过滤浓缩后用甲苯重结晶得到化合物E2-4，干燥后约3.6g，产率约为24.2％。
化合物E2-5：
中间体7b的合成：在500mL的三口烧瓶中依次加入将中间体5a(17.1g，30.6mmol)，化合物6-3(17.6g，33.6mmol)，甲苯200mL，叔丁醇钠(4.4g，45.9mmol)，Pd2(dba)3(280mg，0.3mmol)，TTBPH·BF4(174.0mg，0.6mmol)，抽真空氮气置换三次，加热到110℃反应，TLC跟踪反应。待反应完全，冷却到室温，旋蒸除去反应体系中的溶剂，用乙酸乙酯和饱和氯化钠溶液萃取，合并有机相干燥、过滤浓缩后用正己烷：二氯甲烷＝8：1(体积比)做淋洗剂通过硅胶层析柱分离得到中间体7b，干燥后约23.2g，产率约为72.6％。
化合物E2-5的合成：在500mL的三口烧瓶中加入将中间体7b(20.0g，19.7mmol)，叔丁基苯200mL，抽真空氮气置换三次，0℃滴加1.6M叔丁基锂(25.8mL，43.34mmol)，滴加完毕后升温至60℃反应1h，0℃滴加三溴化硼(5.6mL，59.1mmol)，室温反应2h，0℃滴加二异丙基乙胺(25.8mL，147.7mmol)，升温至120℃反应3h。反应结束，冷却到室温，旋蒸除去反应体系中的溶剂，用乙酸乙酯和饱和氯化钠溶液萃取，合并有机相干燥、过滤浓缩后用甲苯重结晶得到化合物E2-5，干燥后约4.3g，产率约为21.1％。
化合物E2-6：
中间体8a的合成：在500mL的三口烧瓶中依次加入将化合物5-1(25.6g，100.0mmol)，化合物8-1(40.8g，110.0mmol)，甲苯300mL，叔丁醇钠(14.4g，150.0mmol)，Pd2(dba)3(916mg，1.0mmol)，X-Phos(953mg，2.0mmol)，抽真空氮气置换三次，加热到110℃反应，TLC跟踪反应。待反应完全，冷却到室温，旋蒸除去反应体系中的溶剂，用乙酸乙酯和饱和氯化钠溶液萃取，合并有机相干燥、过滤浓缩后用正己烷：二氯甲烷＝10：1(体积比)做淋洗剂通过硅胶层析柱分离得到中间体8a，干燥后约40.1g，产率约为67.7％。
中间体8b的合成：在500mL的三口烧瓶中依次加入将中间体8a(18.14g，30.6mmol)，化合物6-3(17.6g，33.6mmol)，甲苯200mL，叔丁醇钠(4.4g，45.9mmol)，Pd2(dba)3(280mg，0.3mmol)，TTBPH·BF4(174.0mg，0.6mmol)，抽真空氮气置换三次，加热到110℃反应，TLC跟踪反应。待反应完全，冷却到室温，旋蒸除去反应体系中的溶剂，用乙酸乙酯和饱和氯化钠溶液萃取，合并有机相干燥、过滤浓缩后用正己烷：二氯甲烷＝6：1(体积比)做淋洗剂通过硅胶层析柱分离得到中间体8b，干燥后约24.5g，产率约为73.9％。
化合物E2-6的合成：在500mL的三口烧瓶中加入将中间体8b(21.3g，19.7mmol)，叔丁基苯200mL，抽真空氮气置换三次，0℃滴加1.6M叔丁基锂(25.8mL，43.34mmol)，滴加完毕后升温至60℃反应1h，0℃滴加三溴化硼(5.6mL，59.1mmol)，室温反应2h，0℃滴加二异丙基乙胺(25.8mL，147.7mmol)，升温至120℃反应3h。反应结束，冷却到室温，旋蒸除去反应体系中的溶剂，用乙酸乙酯和饱和氯化钠溶液萃取，合并有机相干燥、过滤浓缩后用甲苯重结晶得到化合物E2-6，干燥后约2.4g，产率约为11.7％。
化合物E2-7：
中间体9a的合成：在500mL的三口烧瓶中依次加入将中间体4a(30.0g，55.0mmol)，化合物9-1(19.9g，60.5mmol)，碳酸铯(26.5g，82.5mmol)，DMF 300mL，升温至回流反应。TLC监测反应，待原料基本消耗完全后停止反应。用300mL甲醇和100mL水室温打浆2h，得到中间体9a，干燥后约30.3g，产率约为64.4％。
中间体9b的合成：在500mL的三口烧瓶中依次加入将中间体9a(26.1g，30.6mmol)，化合物4-4(9.4g，33.6mmol)，甲苯200mL，叔丁醇钠(4.4g，45.9mmol)，Pd2(dba)3(280mg，0.3mmol)，TTBPH·BF4(174.0mg，0.6mmol)，抽真空氮气置换三次，加热到110℃反应，TLC跟踪反应。待反应完全，冷却到室温，旋蒸除去反应体系中的溶剂，用乙酸乙酯和饱和氯化钠溶液萃取，合并有机相干燥、过滤浓缩后用正己烷：二氯甲烷＝12：1(体积比)做淋洗剂通过硅胶层析柱分离得到中间体9b，干燥后约21.3g，产率约为66.1％。
化合物E2-7的合成：在500mL的三口烧瓶中加入将中间体9b(20.7g，19.7mmol)，叔丁基苯200mL，抽真空氮气置换三次，0℃滴加1.6M叔丁基锂(25.8mL，43.34mmol)，滴加完毕后升温至60℃反应1h，0℃滴加三溴化硼(5.6mL，59.1mmol)，室温反应2h，0℃滴加二异丙基乙胺(25.8mL，147.7mmol)，升温至120℃反应3h。反应结束，冷却到室温，旋蒸除去反应体系中的溶剂，用乙酸乙酯和饱和氯化钠溶液萃取，合并有机相干燥、过滤浓缩后用甲苯重结晶得到化合物E2-7，干燥后约3.3g，产率约为16.6％。
化合物E2-8：
中间体10a的合成：在500mL的三口烧瓶中依次加入将化合物4-1(28.8g，100.0mmol)，化合物10-1(42.8g，110.0mmol)，甲苯300mL，叔丁醇钠(14.4g，150.0mmol)，Pd2(dba)3(916mg，1.0mmol)，Xantphos(1.1g，2.0mmol)，抽真空氮气置换三次，加热到110℃反应，TLC跟踪反应。待反应完全，冷却到室温，旋蒸除去反应体系中的溶剂，用乙酸乙酯和饱和氯化钠溶液萃取，合并有机相干燥、过滤浓缩后用正己烷：二氯甲烷＝15：1(体积比)做淋洗剂通过硅胶层析柱分离得到中间体10a，干燥后约38.5g，产率约为64.6％。
中间体10b的合成：在500mL的三口烧瓶中依次加入将中间体10a(32.8g，55.0mmol)，化合物9-1(19.9g，60.5mmol)，碳酸铯(26.5g，82.5mmol)，DMF 300mL，升温至回流反应。TLC监测反应，待原料基本消耗完全后停止反应。用300mL甲醇和100mL水室温打浆2h，得到中间体10b，干燥后约35.2g，产率约为70.7％。
中间体10c的合成：在500mL的三口烧瓶中依次加入将中间体10b(27.7g，30.6mmol)，化合物4-4(9.4g，33.6mmol)，甲苯200mL，叔丁醇钠(4.4g，45.9mmol)，Pd2(dba)3(280mg，0.3mmol)，TTBPH·BF4(174.0mg，0.6mmol)，抽真空氮气置换三次，加热到110℃反应，TLC跟踪反应。待反应完全，冷却到室温，旋蒸除去反应体系中的溶剂，用乙酸乙酯和饱和氯化钠溶液萃取，合并有机相干燥、过滤浓缩后用正己烷：二氯甲烷＝12：1(体积比)做淋洗剂通过硅胶层析柱分离得到中间体10c，干燥后约23.0g，产率约为68.1％。
化合物E2-8的合成：在500mL的三口烧瓶中加入将中间体10c(21.7g，19.7mmol)，叔丁基苯200mL，抽真空氮气置换三次，0℃滴加1.6M叔丁基锂(25.8mL，43.34mmol)，滴加完毕后升温至60℃反应1h，0℃滴加三溴化硼(5.6mL，59.1mmol)，室温反应2h，0℃滴加二异丙基乙胺(25.8mL，147.7mmol)，升温至120℃反应3h。反应结束，冷却到室温，旋蒸除去反应体系中的溶剂，用乙酸乙酯和饱和氯化钠溶液萃取，合并有机相干燥、过滤浓缩后用甲苯重结晶得到化合物E2-8，干燥后约2.1g，产率约为10.6％。
化合物E2-9：
中间体11a的合成：在500mL的三口烧瓶中依次加入将化合物11-1(13.4g，55.0mmol)，化合物4-4(19.9g，60.5mmol)，碳酸铯(26.5g，82.5mmol)，DMF 300mL，升温至100℃。TLC监测反应，待原料基本消耗完全后停止反应。用300mL甲醇和100mL水室温打浆2h，得到中间体11a，干燥后约25.5g，产率约为92.2％。
中间体11b的合成：在250mL的三口烧瓶中依次加入中间体11a(14.4g，30.6mmol)，化合物11-2(7.1g，33.6mmol)，二氧六环150mL，水30mL，碳酸钾(8.4g，61.2mmol)，Pd(PPh3)4(346mg，0.3mmol)，抽真空氮气置换三次，加热到100℃反应，TLC跟踪反应。待反应完全，冷却到室温，旋蒸除去反应体系中的溶剂，用乙酸乙酯和饱和氯化钠溶液萃取，合并有机相干燥、过滤浓缩后用正己烷：二氯甲烷＝10：1(体积比)做淋洗剂通过硅胶层析柱分离得到中间体11b，干燥后约15.1g，产率约为83.7％。
中间体11c的合成：在250mL的三口烧瓶中依次加入将中间体11b(15.0g，25.4mmol)，化合物4-2(9.4g，27.9mmol)，甲苯150mL，叔丁醇钠(3.7g，38.1mmol)，Pd2(dba)3(183mg，0.2mmol)，TTBPH·BF4(116.0mg，0.4mmol)，抽真空氮气置换三次，加热到110℃反应，TLC跟踪反应。待反应完全，冷却到室温，旋蒸除去反应体系中的溶剂，用乙酸乙酯和饱和氯化钠溶液萃取，合并有机相干燥、过滤浓缩后用正己烷：二氯甲烷＝8：1(体积比)做淋洗剂通过硅胶层析柱分离得到中间体11c，干燥后约14.3g，产率约为63.5％。
化合物E2-9的合成：在500mL的三口烧瓶中加入将中间体11c(10.0g，11.2mmol)，叔丁基苯200mL，抽真空氮气置换三次，0℃滴加1.6M叔丁基锂(14.7mL，24.7mmol)，滴加完毕后升温至60℃反应1h，0℃滴加三溴化硼(3.2mL，33.6mmol)，室温反应2h，0℃滴加二异丙基乙胺(14.7mL，84.1mmol)，升温至120℃反应3h。反应结束，冷却到室温，旋蒸除去反应体系中的溶剂，用乙酸乙酯和饱和氯化钠溶液萃取，合并有机相干燥、过滤浓缩后用甲苯重结晶得到化合物E2-9，干燥后约2.1g，产率约为21.8％。
2、化合物E1的能级结构
有机材料的能级可通过量子计算得到，比如利用TD-DFT(含时密度泛函理论)通过Gaussian 09W(Gaussian Inc.)，具体的模拟方法可参见WO2011141110。首先用密度泛函理论方法“Ground State/DFT/Default Spin/B3LYP”与基组“6-31G(d)”(Charge 0/Spin Singlet)来优化分子几何结构，然后有机分子的能量结构由TD-DFT(含时密度泛函理论)方法算得“TD-SCF/DFT/Default Spin/B3PW91”与基组“6-31G(d)”(Charge 0/Spin Singlet)。HOMO和LUMO能级按照下面的校准公式计算，S1和T1直接使用。
HOMO(eV)＝((HOMO(G)×27.212)-0.9899)/1.1206
LUMO(eV)＝((LUMO(G)×27.212)-2.0041)/1.385
其中HOMO(G)和LUMO(G)是Gaussian 09W的直接计算结果，单位为Hartree。
结果如表1所示：
表1
其中：HOMO能级为有机分子的最高已占据分子轨道能量，LUMO能级为有机分子的最低未占据分子轨道能量；ΔHOMO为有机分子的最高已占据分子轨道能量与次高已占据分子轨道能量的差值(ΔHOMO＝HOMO-(HOMO-1))；ES1能级为有机分子的最低单重激发态能级，ET1能级为有机分子的最低三重激发态能级，ΔEST为有机分子的最低单重激发态能级与最低三重激发态能级的差值(ΔEST＝ES1-ET1)。
3、混合物光学性能
按照以下方法制备本发明所述的有机混合物：将一定质量比的E1与E2共同溶解于甲苯中得到均相溶液，通过真空干燥挥发溶剂得到混合物固体；将上述固体进一步在石英研钵中机械研磨混合均匀，得到按照本发明所述的有机混合物。
混合物配方和其在聚苯乙烯(PS)薄膜中的光致发光性质如表2所示。聚苯乙烯掺杂膜的制备和表征方法如下：
将聚苯乙烯(cas：9003-53-6，average Mw～280,000by GPC，购买自sigma-aldrich)溶于甲苯形成100mg/mL的溶液后，在振荡条件下以3mg/mL的浓度在其中溶解对比例化合物或按照本发明的有机混合物至形成均相溶液。将上述溶液以1000rpm转速在玻璃上旋涂30s，在80℃的热台上加热5min至完全固化为2μm厚度的透明薄膜；采集上述薄膜在360nm激发下，400nm-800nm波长范围的发射光谱，得到发射峰波长和发射半高宽(FWHM)波长数值。吸收光谱峰值由测量化合物在甲苯溶液中的紫外-可见吸收光谱得到。
表2


图1-图6依次显示了E2-1、E2-2、E2-3、E2-4、E2-5、E2-9的吸收(Abs)和发光(PL)谱线，可知E2-1、E2-2、E2-3、E2-4、E2-5、E2-9的发射半高宽(FWHM)分别对应是25nm、21nm、21nm、23nm、20nm、23nm。
图7显示了E1-1的吸收(Abs)和发光(PL)谱线，及E2-1吸收(Abs)谱线，E2-1吸收(Abs)谱线和E1-1的发光谱线有较大的重叠。
图8显示了E1-2的吸收(Abs)和发光(PL)谱线，及E2-1吸收(Abs)谱线，E2-1吸收(Abs)谱线和E1-2的发光谱线有一定的重叠。
图9显示了E1-2的吸收(Abs)和发光(PL)谱线，及E2-2吸收(Abs)谱线，E2-2吸收(Abs)谱线和E1-1的发光谱线有较大的重叠。
图10显示了E1-2的吸收(Abs)和发光(PL)谱线，及E2-3吸收(Abs)谱线，E2-3吸收(Abs)谱线和E1-2的发光谱线有较大的重叠。
图11显示了E1-2的吸收(Abs)和发光(PL)谱线，及E2-4吸收(Abs)谱线，E2-4吸收(Abs)谱线和E1-2的发光谱线有较大的重叠。
图12显示了E1-2的吸收(Abs)和发光(PL)谱线，及E2-5吸收(Abs)谱线，E2-5吸收(Abs)谱线和E1-2的发光谱线有较大的重叠。
图13显示了E1-3的吸收(Abs)和发光(PL)谱线，及E2-5吸收(Abs)谱线，E2-5吸收(Abs)谱线和E1-3的发光谱线有很大的重叠。
图14显示了E1-3的吸收(Abs)和发光(PL)谱线，及E2-9吸收(Abs)谱线，E2-9吸收(Abs)谱线和E1-3的发光谱线有很大的重叠。
本发明发光器件实施例中使用的材料如下：

其中，化合物HT-1的合成参照专利CN110416418所描述的方法；化合物HT-2的合成参照专利WO2016060332所描述的方法；化合物HT-3的合成参照专利WO2012034627所描述的方法；化合物HT-4的合成参照专利US20200144506所描述的方法；化合物H1-2的合成参照专利WO2010137285所描述的方法；化合物H1-3的合成参照专利US20220216410所描述的方法；化合物H1-4的合成参照专利WO2021107742所描述的方法；化合物HB的合成参照专利WO2018074845所描述的方法；HAT-CN(HI)、H1-1、ET和LiQ采购自吉林奥来德光电材料股份有限公司；其他材料参照前述方法合成。
4、蒸镀型OLED器件的制备及表征
在一种方案中，蒸镀型OLED器件结构为HI(30nm)/HT-1(50nm)/HT-2(10nm)/BH：BD＝97：3(25nm)/ET：LiQ＝50：50(30nm)/LiQ(1nm)/Al(100nm)。
器件实施例OLEDA1-OLEDA3(对比实施例)的制备过程如下：
a、ITO(铟锡氧化物)导电玻璃基片的清洗：使用各种溶剂(例如氯仿、丙酮或异丙醇中的一种或几种)清洗，然后进行紫外臭氧处理。
b、蒸镀：将ITO基片移入真空气相沉积设备中，在高真空(1×10-6毫巴)下，采用电阻加热蒸发源形成厚度为30nm的HI层(HAT-CN)，在HI层上依次加热形成50nm的HT-1，紧接着在HT-1层上蒸镀形成10nm的HT-2层。随后使用两个蒸发源，材料按不同速率气化，保证BH：BD的重量比在97：3(这里BH是H1-1，BD见表3)，形成25nm的发光层。ET和LiQ置于不同的蒸发单元，使其分别以50重量％的比例进行共沉积，得到30nm的电子传输层，随后沉积1nm的LiQ作为电子注入层，最后在所述电子注入层上沉积厚度为100nm的Al阴极。
c、封装：器件在氮气手套箱中用紫外线硬化树脂加玻璃盖板封装。
按照本发明的OLED器件OLEDA4、OLEDA5的制备过程如下：a和c同OLEDA1-OLEDA3，
b、蒸镀：将ITO基片移入真空气相沉积设备中，在高真空(1×10-6毫巴)下，采用电阻加热蒸发源形成厚度为30nm的HI层(HAT-CN)，在HI层上依次加热形成 50nm的HT-1，紧接着在HT-1层上蒸镀形成10nm的HT-2层。随后使用三个蒸发源，材料按不同速率气化，保证BH：BD1：BD2的重量比在97：1.5：1.5(这里BH是H1-1，BD1和BD2见表3)，形成25nm的发光层。ET和LiQ置于不同的蒸发单元，使其分别以50重量％的比例进行共沉积，得到30nm的电子传输层，随后沉积1nm的LiQ作为电子注入层，最后在所述电子注入层上沉积厚度为100nm的Al阴极。
对上述实施例和对比例的器件性能进行测试，具体如表3所示；其中驱动电压是在10mA/cm2电流密度下进行测试；T95的器件寿命是指在恒定电流密度50mA/cm2亮度衰减至95％的时间，以OLEDA1为基准(100％)。
表3
和对比例OLEDA1，OLEDA2，OLEDA3相比，OLEDA4和OLEDA5的寿命有明显的提升，驱动电压无明显差异。说明利用本发明的含有两种发光体的OLED器件，可以提升器件的寿命。
在另一种方案中，蒸镀型OLED器件结构为HI(10nm)/HT-3(50nm)/HT-4(5nm)/BH:BD＝97:3(20nm)/HB(5nm)/ET:LiQ＝50:50(25nm)/LiQ(2nm)/Al(100nm)。
器件实施例OLEDB1-OLEDB9(对比实施例)的制备过程如下：
a、ITO(铟锡氧化物)导电玻璃基片的清洗：使用各种溶剂(例如氯仿、丙酮或异丙醇中的一种或几种)清洗，然后进行紫外臭氧处理。
b、蒸镀：将ITO基片移入真空气相沉积设备中，在高真空(1×10-6毫巴)下，采用电阻加热蒸发源形成厚度为10nm的HI层(HAT-CN)，在HI层上依次加热形成50nm的HT-3，紧接着在HT-3层上蒸镀形成5nm的HT-4。随后使用两个蒸发源，材料按不同速率气化，保证BH：BD的重量比在97：3(这里BH是H1-2，BD见表4)，形成20nm的发光层。随后，在发光层上蒸镀形成5nm的HB。ET和LiQ置于不同的蒸发单元，使其分别以50重量％的比例进行共沉积，得到25nm的电子传输层，随后沉积2nm的LiQ作为电子注入层，最后在所述电子注入层上沉积厚度为100nm的Al阴极。
c、封装：器件在氮气手套箱中用紫外线硬化树脂加玻璃盖板封装。
按照本发明的OLED器件OLEDB10-OLEDB23的制备过程如下：
a和c同OLEDB1-OLEDB9；
b、蒸镀：将ITO基片移入真空气相沉积设备中，在高真空(1×10-6毫巴)下，采用电阻加热蒸发源形成厚度为10nm的HI层(HAT-CN)，在HI层上依次加热形成50nm的HT-3，紧接着在HT-3层上蒸镀形成5nm的HT-4。随后使用三个蒸发源，材料按不同速率气化，保证BH：BD1：BD2的重量比在97：x：3-x(这里BH是H1-2，BD1和BD2材料选择及比例见表4)，形成20nm的发光层。随后，在发光层上蒸镀形成5nm的HB。ET和LiQ置于不同的蒸发单元，使其分别以50重量％的比例进行共沉积，得到25nm的电子传输层，随后沉积2nm的LiQ作为电子注入层，最后在所述电子注入层上沉积厚度为100nm的Al阴极。
对上述实施例和对比例的器件性能进行测试，具体如表4所示；其中EL峰值、EL半峰宽和EQE是在10mA/cm2电流密度下进行测试；LT95的器件寿命是指在恒定电流密度50mA/cm2亮度衰减至95％的时间，以OLED1为基准(100％)。
表4
在对比例OLEDB1-OLEDB9中，采用单一BD的器件难以兼得窄发射线宽和长器件寿命：对比例OLEDB1-OLEDB4使用单一的非MR-TADF类BD可以获得较长的器件寿命，但其光谱半峰宽均在30nm以上，色纯度显著差于采用MR-TADF类BD的对比例OLEDB5-OLEDB9。同时，对比例OLEDB5-OLEDB9尽管具有较理想的窄发射光谱(半峰宽均<25nm，OLEDB6半峰宽最窄，仅18nm)，但其器件寿命显著低于OLEDB1-OLEDB3。
作为对比，采用按照本发明的有机混合物作为客体的实施例OLEDB10-OLEDB23综合表现出比采用单一客体更理想的窄发射光谱、高器件效率和长器件寿命。对比OLEDB1、OLEDB5和OLEDB10，采用本发明有机混合物的OLEDB10同时兼具接近于OLEDB5的窄光谱和与OLED1一致的外量子效率，同时其器件寿命高于OLEDB1，显著高于OLEDB5。
对比OLEDB1、OLEDB2、OLEDB10和OLEDB11，在使用单一E1客体的OLEDB1和OLEDB2具有相似EQE和寿命的情况下，OLEDB10表现出更高的器件效率、更窄的光谱和更长的器件寿命，这可能与E1-1光谱相比E1-2偏蓝，从而在E1和E2之间形成了更有效的激发态能量转移有关。
对比OLEDB14-OLEDB17，光谱半峰宽与单一E2器件光谱半峰宽的一致性和混合物中E1发光和E2吸收的重叠程度相关，显示采用本发明的有机混合物的器件中窄光谱的实现与E1-E2之间的能量转移效率有关；同时，OLEDB14-OLEDB17的器件寿命相比使用单一E1和E2的器件均有增益。
OLEDB18-OLEDB21在不同的E1：E2掺杂比例下都具有较高的综合器件性能，这可能与E2本身具有较好的稳定性，以及E1和E2之间存在高效的激发态能量转移机制有关。其中E1比例最高的OLEDB18也具有比较接近单一E2的窄光谱，显示由于存在具有高效的能量转移机制，在E2比例较低时也能得到比较理想的窄发射光谱。另一方面，在OLEDB21中，尽管E2比例高于E1，同样取得了较高的器件寿命，这可能显示某些混合物中E1和E2的组合能够较好地保护相对不稳定的MR-TADF客体，减小激子能量对其结构的破坏。同时，尽管OLEDB20相比于OLEDB18-OLEDB19在发光层中含有更高比例的E2，其仍然具有比另外两者更高的寿命。综上，按照本发明的有机混合物所提供的器件性能改进效果是出乎意料的，不能被简单归于E1、E2两种不同客体之间光谱和寿命的平均化效应。可能的解释是按照本发明的有机混合物中活跃的激发态能量转移提供了额外的能量耗散路径，从而保护了客体中相对较弱的化学键，以及按照本发明的双客体构造进一步改善了原有器件的载流子平衡。
另外，OLEDB22和OLEDB23相比于单客体器件也取得了一定的寿命增益，同时其光谱半峰宽分别与采用单一E2客体的OLEDB6和OLEDB9一致。这显示在按照本发明的有机混合物中，基于E1和E2间有效激发态能量转移的光谱窄化和器件寿命增益具有一定的普遍性。
需要说明的是，由于存在主客体相容性的差异和底发射器件中弱微腔效应的影响，一些实施例中发光器件的电致发光光谱半峰宽可能高于/低于/等于聚苯乙烯薄膜中的光致发光光谱半峰宽。
5、溶液的配置
按照表5，将发光层的组分以20mg/mL的浓度倒入甲苯，加热搅拌，使得溶质充分溶解，过滤得到溶液1-溶液18。
表5
6、溶液加工型P-OLED器件制备
在一种方案中，具体步骤如下：
1)ITO透明电极(阳极)玻璃衬底的清洗：使用5％Decon90清洗液的水溶液超声处理30分钟，之后去离子水超声清洗数次，然后异丙醇超声清洗，氮气吹干；在氧气等离子下处理5分钟，以清洁ITO表面并提升ITO电极的功函。
2)空穴传输层制备：在经过氧气等离子体处理过的玻璃衬底上旋涂PEDOT：PSS溶液，得到80nm的薄膜，旋涂完成后在空气中150℃退火20分钟，然后在PEDOT：PSS层上旋涂得到20nm的Poly-TFB薄膜(CAS：223569-31-1，购自Lumtec.Corp；5mg/mL甲苯溶液)，随后在180℃的热板上处理60分钟。
3)发光层制备：先将发光层溶液(见表5)在氮气手套箱中旋涂得到35nm薄膜，然后在120℃退火10分钟。
4)电子传输层的制备：将基片移入真空气相沉积设备中，在高真空(1×10-6毫巴)下，ET和LiQ置于不同的蒸发单元，使其分别以50重量％的比例进行共沉积，得到30nm的电子传输层。
5)阴极制备：将旋涂完成的器件放入真空蒸镀腔体，依次蒸镀2nm钡和100nm铝，完成发光器件。
6)所有器件在氮气手套箱中采用紫外固化树脂加玻璃盖板封装。
对上述实施例和对比例的器件性能进行测试，具体如表6所示；其中驱动电压是在10mA/cm2电流密度下进行测试；T95的器件寿命是指在恒定电流密度20mA/cm2下器件亮度衰减至初始值95％的时间，以P-OLED1为基准(100％)。
表6
和对比例P-OLEDA1，P-OLEDA2，P-OLEDA3相比，P-OLEDA4和P-OLEDA5的驱动电压没有显著差异，同时寿命有明显的提升，说明对于溶液加工OLED，利用本发明的双发光体，也可以较大提升器件的寿命。
在另一种方案中，具体步骤如下：
1)ITO透明电极(阳极)玻璃衬底的清洗：使用5％Decon90清洗液的水溶液超声处理30分钟，之后去离子水超声清洗数次，然后异丙醇超声清洗，氮气吹干；在氧气等离子下处理5分钟，以清洁ITO表面并提升ITO电极的功函。
2)空穴传输层制备：在经过氧气等离子体处理过的玻璃衬底上旋涂PEDOT：PSS溶液，得到80nm的薄膜，旋涂完成后在空气中150℃退火20分钟，然后在PEDOT：PSS层上旋涂得到20nm的Poly-TFB薄膜(CAS：223569-31-1，购自Lumtec.Corp；5mg/mL甲苯溶液)，随后在180℃的热板上处理60分钟。
3)发光层制备：先将发光层溶液(见表5)在氮气手套箱中旋涂得到35nm薄膜，然后在120℃退火10分钟。
4)电子传输层的制备：将基片移入真空气相沉积设备中，在高真空(1×10-6毫巴)下，ET和LiQ置于不同的蒸发单元，使其分别以25：75重量％的比例进行共沉积，得到30nm的电子传输层。
5)阴极制备：将旋涂完成的器件放入真空蒸镀腔体，依次蒸镀1nm镱和100nm银，完成发光器件。
6)所有器件在氮气手套箱中采用紫外固化树脂加玻璃盖板封装。
对上述实施例和对比例的器件性能进行测试，具体如表7所示；EL峰值和半峰宽均在器件亮度为1000nits条件下进行测试；T95的器件寿命是指在初始亮度1000nits下，恒电流持续点亮至器件亮度衰减至初始值95％的时间，以P-OLEDB1为基准(100％)。
表7
和对比例P-OLEDB1～P-OLEDB6相比，实施例P-OLEDB7～P-OLEDB14的寿命有明显的提升；与对比例P-OLEDB1～P-OLEDB2对比，实施例P-OLEDB7～P-OLEDB14的光谱有明显的窄化，同时器件寿命相比采用单一客体的情况均有一定的提升。上述结果说明对于溶液加工OLED，利用本发明的双发光体，也可以在取得理想的窄发射光谱的同时，较大地提升器件的寿命。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (10)

  1. 一种有机混合物，包含一种第一发光体E1和一种第二发光体E2，其特征在于，1)所述第一发光体E1和所述第二发光体E2都是荧光发光体；2)所述第二发光体E2的吸收谱和所述第一发光体E1的发光谱至少部分相互重叠；3)所述第二发光体E2的发光谱的半峰宽小于或等于50nm。
  2. 根据权利要求1所述的有机混合物，其特征在于，所述第二发光体E2选自化学式(1)或(2)所示的结构：
    其中：
    Ar1-Ar3相同或不同的选自具有5～24个环原子的芳香族或杂芳香族；
    Ar4-Ar5相同或不同的选自空或具有5～24个环原子的芳香族或杂芳香族；
    当Ar4-Ar5不为空时，Xa和Xb在每次出现时独立选自N、C(R9)或Si(R9)，Ya和Yb在每次出现时独立选自B、P＝O、C(R9)或Si(R9)；
    当Ar4或Ar5为空时，Xb选自N、C(R9)或Si(R9)，Ya选自B、P＝O、C(R9)或Si(R9)，Xa和Yb在每次出现时独立选自N(R9)、C(R9R10)、Si(R9R10)、C＝O、O、C＝N(R9)、C＝C(R9R10)、P(R9)、P(＝O)R9、S、S＝O或SO2；
    X1、X2独立选自空或一个桥接基团；
    R4-R10在每次出现时，可相同或不同的选自H、D，或者具有1～20个C原子的直链的烷基、卤代烷基、烷氧基、硫代烷氧基基团，或者具有3～20个C原子的支链或环状的烷基、卤代烷基、烷氧基、硫代烷氧基基团、甲硅烷基基团，或者具有1～20个C原子的酮基基团，或者具有2～20个C原子的烷氧基羰基基团，或者具有7～20个C原子的芳氧基羰基基团，或者氰基基团、氨基甲酰基基团、卤甲酰基基团、甲酰基基团、异氰基基团、异氰酸酯基团、硫氰酸酯基团、异硫氰酸酯基团、羟基基团、硝基基团、CF3、Cl、Br、F、I、可交联的基团，或者具有5～40个环原子的取代或未取代的芳族或杂芳族环系，或者具有5～40个环原子的芳氧基或杂芳氧基基团，或者具有5～40个环原子的芳胺基或杂芳胺基基团，以上基团任意位置的二取代单元或这些基团的组合，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。
  3. 根据权利要求1或2所述的有机混合物，其特征在于，所述第二发光体E2选自如下化学式(1a)-(1e)或(2a)-(2e)所示的结构：

  4. 根据权利要求1至3任意一项所述的有机混合物，其特征在于，所述第二发光体E2包含如下化学式(1f)-(1i)所示的结构：
    其中，Yc可相同或不同的选自O或S。
  5. 根据权利要求1至4任意一项所述的有机混合物，其特征在于，所述第二发光体E2选自如下化学式(1j)-(1l)所示的结构：
    其中：R21、R22、R23、R24、R25每次出现时相同或不同，分别独立地选自D，或者具有1～20个C原子的直链的烷基、烷氧基、硫代烷氧基基团，或者具有3～20个C原子的支链或环状的烷基、烷氧基、硫代烷氧基基团、甲硅烷基基团，或者具有1～20个C原子的酮基基团，或者具有2～20个C原子的烷氧基羰基基团，或者具有7～20个C原子的芳氧基羰基基团，或者氰基基团、氨基甲酰基基团、卤甲酰基基团、甲酰基基团、异氰基基团、异氰酸酯基团、硫氰酸酯基团、异硫氰酸酯基团、羟基基团、硝基基团、CF3、Cl、Br、F、可交联的基团，或者具有5～40个环原子的取代或未取代的芳族或杂芳族环系，或者具有5～40个环原子的芳氧基或杂芳氧基基团，或这些基团的组合，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系；m、n分别独立选自0～4的任一整数；o、q分别独立选自0～5的任一整数；p独立选自0～3的任一整数；“虚线”表示无或者单键。
  6. 根据权利要求1至5任意一项所述的有机混合物，其特征在于，所述第一发光体E1选自化学式(1)或(2)、化学式(1a)-(1l)、化学式(2a)-(2e)或如下化学式(3)中的任何一个：
    其中：
    R0-R1的定义同权利要求2中的R4；
    Ar1-Ar4可相同或不同的选自具有5～60个环原子的芳香族或杂芳香族。
  7. 根据权利要求1至6任意一项所述的有机混合物，其特征在于，所述有机混合物还包含一种主体材料H，所述主体材料H选自化学式(4-1)或(4-2)所示的结构：
    其中，Ar5和Ar6的定义同权利要求6中的Ar1。
  8. 一种组合物，包含一种如权利要求1至7任意一项所述的有机混合物，和至少一种有机溶剂。
  9. 一种光电器件，包含一种如权利要求1至7任意一项所述的有机混合物。
  10. 根据权利要求9所述的光电器件，其特征在于，所述光电器件是有机电致发 光器件，且包含依次设置的一基板、一阳极、一发光层和一阴极，所述发光层包含至少一种如权利要求1至7任意一项所述的有机混合物，或所述发光层采用如权利要求8所述的组合物制备所得。
PCT/CN2024/129071 2023-11-01 2024-10-31 有机混合物及其在光电领域的应用 Pending WO2025092929A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202311439799 2023-11-01
CN202311439799.X 2023-11-01

Publications (1)

Publication Number Publication Date
WO2025092929A1 true WO2025092929A1 (zh) 2025-05-08

Family

ID=95582680

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/CN2024/129071 Pending WO2025092929A1 (zh) 2023-11-01 2024-10-31 有机混合物及其在光电领域的应用
PCT/CN2024/129075 Pending WO2025092930A1 (zh) 2023-11-01 2024-10-31 有机混合物及其在光电领域的应用

Family Applications After (1)

Application Number Title Priority Date Filing Date
PCT/CN2024/129075 Pending WO2025092930A1 (zh) 2023-11-01 2024-10-31 有机混合物及其在光电领域的应用

Country Status (1)

Country Link
WO (2) WO2025092929A1 (zh)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080113101A1 (en) * 2006-11-09 2008-05-15 Idemitsu Kosan Co., Ltd. Organic-electroluminescence-material-containing solution, method for forming thin film of organic electroluminescence material, thin film of organic electroluminescence material and organic electroluminescence device
CN109608342A (zh) * 2017-12-25 2019-04-12 广州华睿光电材料有限公司 芳香胺衍生物、聚合物、混合物、组合物和有机电子器件
CN113045443A (zh) * 2021-04-30 2021-06-29 江西冠能光电材料有限公司 一种二芳环酰胺化合物及其应用
WO2021230658A1 (ko) * 2020-05-12 2021-11-18 머티어리얼사이언스 주식회사 유기 전계 발광 소자
WO2022078432A1 (zh) * 2020-10-14 2022-04-21 浙江光昊光电科技有限公司 组合物及其在光电领域的应用
US20230255112A1 (en) * 2020-10-14 2023-08-10 Zhejiang Brilliant Optoelectronic Technology Co., Ltd. Organic compounds and applications thereof in optoelectronic field

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018181188A1 (ja) * 2017-03-31 2018-10-04 出光興産株式会社 有機エレクトロルミネッセンス素子および電子機器
CN111029477B (zh) * 2019-12-10 2022-10-18 昆山国显光电有限公司 一种有机电致发光器件、显示面板及显示装置
KR20220098515A (ko) * 2021-01-04 2022-07-12 경희대학교 산학협력단 지연 형광 화합물 및 이를 포함하는 유기 발광 소자
JPWO2022196612A1 (zh) * 2021-03-15 2022-09-22

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080113101A1 (en) * 2006-11-09 2008-05-15 Idemitsu Kosan Co., Ltd. Organic-electroluminescence-material-containing solution, method for forming thin film of organic electroluminescence material, thin film of organic electroluminescence material and organic electroluminescence device
CN109608342A (zh) * 2017-12-25 2019-04-12 广州华睿光电材料有限公司 芳香胺衍生物、聚合物、混合物、组合物和有机电子器件
WO2021230658A1 (ko) * 2020-05-12 2021-11-18 머티어리얼사이언스 주식회사 유기 전계 발광 소자
WO2022078432A1 (zh) * 2020-10-14 2022-04-21 浙江光昊光电科技有限公司 组合物及其在光电领域的应用
US20230255112A1 (en) * 2020-10-14 2023-08-10 Zhejiang Brilliant Optoelectronic Technology Co., Ltd. Organic compounds and applications thereof in optoelectronic field
CN113045443A (zh) * 2021-04-30 2021-06-29 江西冠能光电材料有限公司 一种二芳环酰胺化合物及其应用

Also Published As

Publication number Publication date
WO2025092930A1 (zh) 2025-05-08

Similar Documents

Publication Publication Date Title
CN109790460B (zh) 含硼有机化合物及应用、有机混合物、有机电子器件
CN111278838B (zh) 含硼杂环化合物、高聚物、混合物、组合物及其用途
CN110698351B (zh) 电子器件的材料
WO2017092495A1 (zh) 热激发延迟荧光材料、高聚物、混合物、组合物以及有机电子器件
TW201726589A (zh) 用於電子裝置之化合物
CN109638171B (zh) 有机混合物、高聚物、组合物及其用途
CN118126004A (zh) 用于电子器件的基于螺二芴衍生物的材料
CN108137622B (zh) 含硅的有机化合物及其应用
TW201038576A (en) Materials for organic electroluminescent devices
TW201042001A (en) Organic electronic device
US10510967B2 (en) Organic compound, and mixture, formulation and organic device comprising the same
TW201833100A (zh) 具有受體基團與供體基團之化合物
CN109608342B (zh) 芳香胺衍生物、聚合物、混合物、组合物和有机电子器件
TW201629007A (zh) 電子裝置用材料
CN110325524A (zh) 用于有机电子器件的材料
CN109790087B (zh) 氘代稠环化合物、高聚物、混合物、组合物以及有机电子器件
CN109705100B (zh) 含萘咔唑类有机光化合物、混合物、组合物及其用途
WO2019114668A1 (zh) 一种过渡金属配合物材料及其在电子器件的应用
WO2018108110A1 (zh) 金属有机配合物及其应用、混合物、有机电子器件
CN109790193B (zh) 过渡金属配合物及其应用、混合物、有机电子器件
TW201936579A (zh) 用於電子裝置之材料
US11674080B2 (en) Transition metal complex, polymer, mixture, formulation and use thereof
WO2022213996A1 (zh) 化合物及其在光电领域的应用
CN116635365A (zh) 用于电子器件的材料
WO2022078429A1 (zh) 一种发光器件以及其在显示中的应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24884927

Country of ref document: EP

Kind code of ref document: A1