WO2017118137A1 - Dérivé de carbazole et polymère élevé, mélange, composition et dispositif électronique organique le comprenant et utilisation correspondante - Google Patents

Dérivé de carbazole et polymère élevé, mélange, composition et dispositif électronique organique le comprenant et utilisation correspondante Download PDF

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WO2017118137A1
WO2017118137A1 PCT/CN2016/101998 CN2016101998W WO2017118137A1 WO 2017118137 A1 WO2017118137 A1 WO 2017118137A1 CN 2016101998 W CN2016101998 W CN 2016101998W WO 2017118137 A1 WO2017118137 A1 WO 2017118137A1
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carbazole derivative
organic
aromatic
high polymer
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Chinese (zh)
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黄宏
潘君友
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广州华睿光电材料有限公司
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Priority to CN201680059919.5A priority Critical patent/CN108137558B/zh
Publication of WO2017118137A1 publication Critical patent/WO2017118137A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • 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

Definitions

  • the present invention relates to the field of organic electroluminescent materials, and more particularly to a carbazole derivative, a polymer, a mixture, a composition, an organic electronic device, and applications thereof.
  • organic electroluminescent materials have laid a solid foundation for the realization of large-area new display devices.
  • luminescent material systems based on fluorescence and phosphorescence have been developed so far, and organic light-emitting diodes using fluorescent materials have high reliability, but their internal electroluminescence under electrical excitation
  • the quantum efficiency is limited to 25% because the branch ratio of the singlet excited state and the triplet excited state of the exciton is 1:3.
  • organic light-emitting diodes using phosphorescent materials have achieved nearly 100% internal electroluminescence quantum efficiency.
  • the stability of phosphorescent OLEDs needs to be improved.
  • the stability of the OLED, in addition to the illuminant itself, the main material is the key.
  • carbazole derivatives Due to its high carrier transport capacity, photoelectric response properties and thermal stability, carbazole derivatives have become the focus of academic and industrial circles and are widely used in organic light-emitting diodes. Due to the certain activity of the 3,6-position of carbazole, most of the carbazole derivatives currently developed still have insufficient chemical/environmental stability, mainly due to the lone pair of nitrogen atoms in the structure of such materials. Conjugated to the benzene ring to form a CH bond with a high electron cloud density and high reactivity, resulting in poor chemical/environmental stability and short device life of this type of compound.
  • Ar 1 is an aromatic or 6 to 20 carbon atom heteroaromatic or non-aromatic ring system which is unsubstituted or substituted by one or more groups R 1 ;
  • Ar 2 is a heteroaromatic or non-aromatic ring system having 6 to 20 carbon atoms and 6 to 20 carbon atoms which are unsubstituted or substituted by one or more groups R 1 ;
  • Ar 3 is a heteroaromatic or non-aromatic ring system having 6 to 20 carbon atoms and 6 to 20 carbon atoms which are unsubstituted or substituted by one or more groups R 1 ;
  • Ar 4 is an aromatic or non-aromatic ring system having 6 to 40 carbon atoms or 6 to 40 carbon atoms which is unsubstituted or substituted by one or more groups R 1 ;
  • Ar 1 , Ar 2 and Ar 3 are the same or different, and the group R 1 may be the same or different when it occurs multiple times;
  • R is hydrogen, or R is an aromatic of 6 to 20 carbon atoms or a heteroaromatic or non-aromatic ring system of 2 to 20 carbon atoms which is unsubstituted or substituted by one or more groups R 0 , Or R is a linear alkane, an alkane ether, an alkane aromatic ring system, an alkane heteroaromatic or an alkane non-aromatic ring system of 1 to 20 carbon atoms, and the group R 0 may be the same or different when it occurs multiple times;
  • n 0, 1, 2, 3 or 4;
  • R 0 and R 1 in each occurrence the same or different selected from -H, -F, -Cl, -Br, -I, -D, -CN, -NO 2 , -CF 3 , -B (OR 2 ) 2 ,-Si(R 2 ) 3 , a linear alkane, an alkane ether, an alkane sulfide having 1 to 10 carbon atoms, a branched alkane, a cycloalkane or an alkane ether group having 3 to 10 carbon atoms;
  • the methylene group is an aromatic amine which is not replaced or substituted by one or more active R 2 or an aromatic group and a heteroaromatic ring, or a substituted or unsubstituted carbazole;
  • R 2 in each occurrence, the same or different selected from H, D, an aliphatic alkane having 1 to 10 carbon atoms, an aromatic hydrocarbon containing 5 to 10 ring atoms substituted or unsubstituted aromatic ring or aromatic Group.
  • a high polymer the compound corresponding to the repeating unit of the high polymer comprising the above carbazole derivative.
  • the organic functional material is selected from at least one of a hole injecting material, a hole transporting material, an electron transporting material, an electron injecting material, an electron blocking material, a hole blocking material, an illuminant, a host material, and an organic dye.
  • composition comprising the above carbazole derivative and at least one organic solvent
  • the composition includes the above high polymer and at least one organic solvent;
  • the composition comprises the above mixture and at least one organic solvent.
  • An organic electronic device comprising the above carbazole derivative, the above high polymer or a mixture thereof.
  • the above carbazole derivative comprises at least three aromatic ring or heteroaromatic ring conjugated units, which has good stability and can be used as an electrophosphorescent light-emitting host material.
  • the carbazole derivative can improve the luminous efficiency and lifetime of the electroluminescent device by blending with a suitable guest material; the carbazole derivative can also be used as a fluorescent host material or a luminescent material through a suitable fluorescent host material. Or the guest material is matched to facilitate the improvement of the efficiency and the lifetime of the electroluminescent device, and provides a solution for the light-emitting device with low manufacturing cost, high efficiency and long life.
  • the present invention provides a carbazole derivative, a high polymer, a mixture, a composition, an organic electronic device, and an application thereof, and the present invention will be further described in detail below in order to clarify and clarify the object, the technical solution and the effect of the present invention. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
  • composition and the printing ink, or ink have the same meaning and are interchangeable.
  • the subject material, the matrix material, the Host or the Matrix material have the same meaning, and they are interchangeable.
  • metal organic complexes, metal organic complexes, and organometallic complexes have the same meaning and are interchangeable.
  • Ar 1 is an aromatic or 6 to 20 carbon atom heteroaromatic or non-aromatic ring system which is unsubstituted or substituted by one or more groups R 1 ;
  • Ar 2 is an aromatic or 6 to 20 carbon atom heteroaromatic or non-aromatic ring system which is unsubstituted or substituted by one or more groups R 1 and has 6 to 20 carbon atoms.
  • Ar 3 is an aromatic or 6 to 20 carbon atom heteroaromatic or non-aromatic ring system which is unsubstituted or substituted by one or more groups R 1 and has 6 to 20 carbon atoms.
  • Ar 4 is an aromatic or non-aromatic ring system having 6 to 40 carbon atoms and 2 to 40 carbon atoms which are unsubstituted or substituted by one or more groups R 1 .
  • Ar 1 , Ar 2 and Ar 3 are the same or different, and the groups R 1 may be the same or different when they occur multiple times.
  • R may be the same or different when it occurs multiple times.
  • R is hydrogen, or R is an aromatic of 6 to 20 carbon atoms or a heteroaromatic or non-aromatic ring system of 2 to 20 carbon atoms which is unsubstituted or substituted by one or more groups R 0 ,
  • R is a linear alkane, an alkane ether, an alkane aromatic ring system, an alkane heteroaromatic or an alkane non-aromatic ring system of 1 to 20 carbon atoms, and the group R 0 may be the same or different when it occurs multiple times.
  • n 0, 1, 2, 3 or 4.
  • R 0 and R 1 in each occurrence the same or different selected from -H, -F, -Cl, -Br, -I, -D, -CN, -NO 2 , -CF 3 , -B (OR 2 ) 2 ,-Si(R 2 ) 3 , a linear alkane, an alkane ether, an alkane sulfide having 1 to 10 carbon atoms, a branched alkane, a cycloalkane or an alkane ether group having 3 to 10 carbon atoms.
  • the methylene group is an aromatic amine which is not replaced or substituted by one or more active R 2 or an aromatic group and a heteroaromatic ring, or a substituted or unsubstituted carbazole.
  • R 2 in each occurrence, the same or different selected from H, D, an aliphatic alkane having 1 to 10 carbon atoms, an aromatic hydrocarbon containing 5 to 10 ring atoms substituted or unsubstituted aromatic ring or aromatic Group.
  • Ar 1 -Ar 4 , and at least one R may have the same or different ones selected from unsubstituted or substituted by R 1 in each occurrence.
  • the aromatic ring system contains 5 to 18 carbon atoms in the ring system.
  • the heteroaromatic ring system contains 2 to 18 carbon atoms and at least one hetero atom in the ring system. Further, the total number of carbon atoms and hetero atoms in the heteroaromatic ring is at least 4.
  • the aromatic ring system contains from 5 to 16 carbon atoms in the ring system
  • the heteroaromatic ring system contains from 2 to 16 carbon atoms and at least one hetero atom in the ring system.
  • the aromatic ring system contains 5 to 13 carbon atoms in the ring system
  • the heteroaromatic ring system contains 2 to 13 carbon atoms and at least one hetero atom in the ring system.
  • the hetero atom is selected from the group consisting of Si, N, P, O, S, and/or Ge. Further, the hetero atom is selected from the group consisting of Si, N, P, O, and/or S.
  • An aromatic ring system or aromatic group refers to a hydrocarbon group containing at least one aromatic ring, including a monocyclic group and a polycyclic ring system.
  • a heteroaromatic or heteroaromatic group refers to a hydrocarbyl group (containing heteroatoms) comprising at least one heteroaromatic ring, including monocyclic groups and polycyclic ring systems. These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, a fused ring. At least one of these rings of the polycyclic ring is aromatic or heteroaromatic.
  • aromatic or heteroaromatic ring systems include not only aromatic or heteroaromatic systems, but also multiple aryl or heteroaryl groups may also be interrupted by short non-aromatic units ( ⁇ 10%).
  • Non-H atoms preferably less than 5% of non-H atoms, such as C, N or O atoms).
  • systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, etc., are also considered to be aromatic ring systems for the purposes of the present invention.
  • examples of the aromatic group are: benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, anthracene, benzofluorene, triphenylene, anthracene, anthracene, and derivatives thereof.
  • heteroaromatic groups are: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, anthracene, anthracene Oxazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrol, furanfuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, Pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-diazine, quinoxaline, phenanthridine, carbaidine, quinazoline, quinazolinone, and derivatives thereof.
  • At least one of Ar 1 -Ar 4 comprises a non-aromatic ring system having from 2 to 20 carbon atoms which is unsubstituted or substituted with R 1 .
  • non-aromatic ring systems contain from 1 to 10, preferably from 1 to 6 carbon atoms in the ring system, and include not only saturated but also partially unsaturated cyclic systems which may be unsubstituted or grouped. Single or multiple R 1 substitutions.
  • the groups R 1 may be the same or different in each occurrence, and may also contain one or more heteroatoms, specifically, R 1 is Si, N, P, O, S and/or Ge, further, R 1 It is Si, N, P, O and/or S.
  • These examples may be cyclohexyl- or piperidine-like systems or ring-like octadiene ring systems.
  • the term also applies to fused non-aromatic ring systems.
  • the H atom or the bridging group CH 2 group on NH may be substituted by an R 1 group, and R 1 may be selected from (1) a C1 to C10 alkyl group, for example, may be a group as follows : 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-ethylhexyl, trifluoromethyl, pentafluoromethyl, 2,2,2-trifluoroethyl, ethylene Base, propenyl, butenyl, pentenyl, cyclopentenyl, ethylene Base, propenyl
  • aromatic and heteroaromatic ring systems are considered to be especially in addition to the above-mentioned aryl and heteroaryl groups, but also to biphenylene, benzene terphenyl, anthracene, spirobifluorene, dihydrogen. Phenanthrene, tetrahydroanthracene and cis or trans fluorene.
  • Ar 1 , Ar 2 and Ar 3 may be the same or different, each is selected from the group consisting of aromatic and heteroaromatic groups having 2 to 10 carbon atoms. Or non-aromatic ring systems which may be unsubstituted or substituted by one or more R 1 groups.
  • the specific aromatic or heteroaryl group may be benzene, naphthalene, anthracene, phenanthrene, pyridine, perylene or thiophene.
  • Ar 1 , Ar 2 and Ar 3 are the same or differently selected from one of the following structural groups:
  • X 1 is CR 3 or N;
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 may also be selected from a combination of the above corresponding groups, wherein one or more of the groups R 3 , R 4 , R 5 , R 6 , R 7 , R 8 may form a monocyclic or polycyclic aliphatic or aromatic ring to each other and/or to the ring to which the group is bonded.
  • Ar 1 , Ar 2 and Ar 3 are the same or different ones selected from the group consisting of the following structural groups:
  • Ar 1 , Ar 2 and Ar 3 are identical or differently selected from the structural groups in which the above-mentioned structural group is substituted by one or more groups R 1 .
  • n 0, 1, 2, 3 or 4.
  • carbazole derivative according to the present invention is selected from one of the following structural formulae:
  • the carbazole derivative may also be a structural group obtained by further substituting the above structural formula.
  • the carbazole derivative according to the present invention can be used as a light-emitting layer host material in an electroluminescent device.
  • the carbazole derivative has a higher triplet energy level (T 1 ), generally reaching T 1 ⁇ 2.10 eV, further reaching T 1 ⁇ 2.40 eV, and further reaching T 1 ⁇ 2.60 eV, and further reaching T 1 ⁇ 2.70 eV, and further up to T 1 ⁇ 2.80 eV.
  • the carbazole derivative according to the invention has a triplet energy level T 1 ⁇ 2.2 eV. At this time, this organic compound can be preferentially used as a phosphorescent host material.
  • the compound according to the invention may be applied to a luminescent layer fluorescent host material or luminescent material in an electroluminescent device.
  • the carbazole derivative has a higher singlet energy level (S 1 ) and a lower triplet energy level (T 1 ), generally S 1 ⁇ 2.80 eV, T 1 ⁇ 2.10 eV, further, S 1 ⁇ 2.90 eV, T 1 ⁇ 2.00 eV, further S 1 ⁇ 2.90 eV, T 1 ⁇ 1.90 eV, and further S 1 ⁇ 2.90 eV, T 1 ⁇ 1.8 eV.
  • the difference ⁇ E(S 1 -T 1 ) between the singlet energy level (S 1 ) and the triplet energy level (T 1 ) of the carbazole derivative is relatively large, and such a compound can be used as a luminescence.
  • the fluorescent host material of the layer The general ⁇ E(S 1 -T 1 ) ⁇ 0.60eV, further ⁇ E(S 1 -T 1 ) ⁇ 0.80eV, further ⁇ E(S 1 -T 1 ) ⁇ 1.0eV, further ⁇ E(S 1 -T 1 ) ⁇ 1.1eV.
  • the carbazole derivative according to the invention has a smaller ⁇ E(S 1 -T 1 ), a general ⁇ E(S 1 -T 1 ) ⁇ 0.30 eV, and further ⁇ E (S 1 -T 1 ) ⁇ 0.25eV, further ⁇ E(S 1 -T 1 ) ⁇ 0.20eV, further ⁇ E(S 1 -T 1 ) ⁇ 0.15eV, further ⁇ E(S 1 -T 1 ) ⁇ 0.10eV.
  • An electron donating group is included, and/or at least one R or Ar 4 contains an electron withdrawing group.
  • the electron donating group is selected from one of the following groups D1 to D10:
  • the electron withdrawing group is selected from the group consisting of F, a cyano group, or an electron withdrawing group selected from the group consisting of:
  • a is 1, 2, 3 or 4;
  • X 2 to X 9 are selected from CR or N, and at least one is N;
  • the carbazole derivative according to the invention is a small molecule material.
  • small molecule refers to a molecule that is not a polymer, oligomer, dendrimer, or blend. In particular, there are no repeating structures in small molecules.
  • the molecular weight of the small molecule is ⁇ 4000 g/mol, further the molecular weight is ⁇ 3000 g/mol, further the molecular weight is ⁇ 2000 g/mol, and further the molecular weight is ⁇ 1500 g/mol.
  • the polymer that is, the polymer, includes a homopolymer, a copolymer, and a block copolymer. Further in the present invention, the high polymer also includes a dendrimer.
  • a dendrimer For the synthesis and application of the tree, see [Dendrimers and Dendrons, Wiley-VCH Verlag GmbH & Co. KGaA, 2002, Ed. George R. Newkome, Charles N. Moorefield, Fritz Vogtle.].
  • the conjugated polymer is a high polymer, and its backbone backbone is mainly composed of sp 2 hybrid orbitals of C atoms. Famous examples are: polyacetylene polyacetylene and poly(phenylene vinylene).
  • the C atom on the chain can also be substituted by other non-C atoms, and is still considered a conjugated polymer when the sp 2 hybrid on the backbone is interrupted by some natural defects.
  • the conjugated high polymer also includes an aryl amine, an aryl phosphine and other heteroarmotics, and an organometallic complexes in the main chain. )Wait.
  • the solubility of the organic small molecule compound is ensured by the substituent R on the units of the formulae (1) to (38) and optionally on the unit additionally present, and by adjusting the position of the bond between the core structure and the substituent. .
  • substituents can also promote solubility if other substituents are present.
  • the structural units of the general formulae (1) to (38) are suitable for various functions in organic small molecule compounds depending on the substitution pattern. Therefore, they are preferably used as the main skeleton of the small molecule compound or as an illuminant.
  • examples of the units of the general formulae (1) to (38) may be the following structures. Further these structures can be substituted at all possible points of substitution.
  • the above carbazole derivative comprises at least three aromatic ring or heteroaromatic ring conjugated units, which has good stability and can be used as an electrophosphorescent light-emitting host material.
  • the carbazole derivative can improve the luminous efficiency and lifetime of the electroluminescent device by blending with a suitable guest material; the carbazole derivative can also be used as a fluorescent host material or a luminescent material through a suitable fluorescent host material. Or the guest material is matched to facilitate the improvement of the efficiency and the lifetime of the electroluminescent device, and provides a solution for the light-emitting device with low manufacturing cost, high efficiency and long life.
  • the present invention also relates to a high polymer in which at least one compound corresponding to the repeating unit contains any of the structures represented by the general formulae (1) to (8).
  • the high polymer in certain embodiments is a non-conjugated high polymer in which the structural unit represented by the general formulae (1) to (8) is located on the side chain of the high polymer. In another embodiment, the high polymer is a conjugated high polymer.
  • the invention relates to a mixture comprising the above-mentioned carbazole derivative and an organic functional material.
  • the mixture includes the above high polymer and an organic functional material.
  • Organic functional materials are selected from the group consisting of holes (also known as holes) injection or transport materials (HIM/HTM), hole blocking materials (HBM), electron injecting or transporting materials (EIM/ETM), electron blocking materials (EBM), organic At least one of a host material, a singlet illuminant (fluorescent illuminant), a heavy illuminator (phosphorescent illuminant), an organic thermal excitation delayed fluorescent material (TADF material), particularly a luminescent organic metal complex .
  • Various organic functional materials are described in detail in, for example, WO2010135519A1, US20090134784A1, and WO2011110277A1, the entire disclosure of which is hereby incorporated by reference.
  • the organic functional material may be a small molecule and a high polymer material.
  • the mixture comprises a carbazole derivative or polymer according to the invention, and a phosphorescent emitter.
  • the carbazole derivative or polymer according to the present invention may be used as a host, wherein the phosphorescent emitter accounts for ⁇ 30% by weight, further ⁇ 25% by weight, and further ⁇ 20% by weight in the mixture.
  • the mixture comprises a carbazole derivative or polymer according to the invention, and a fluorescent illuminant.
  • the carbazole derivative or polymer according to the present invention can be used as a fluorescent host material, wherein the fluorescent illuminant accounts for ⁇ 15% by weight, further ⁇ 10% by weight, and further ⁇ 8% by weight in the mixture.
  • the mixture comprises a carbazole derivative or polymer according to the invention, and a fluorescent host material.
  • the carbazole derivative or polymer according to the invention may be used as a fluorescent luminescent material, the carbazole derivative or polymer in the mixture by weight percentage ⁇ 15% by weight, further ⁇ 10% by weight, further ⁇ 8% by weight .
  • the mixture comprises a carbazole derivative or polymer according to the invention, a phosphorescent emitter and a host material.
  • the carbazole derivative or polymer according to the present invention may be used as an auxiliary luminescent material, and the weight ratio of the carbazole derivative or polymer to the phosphorescent emitter may be from 1:2 to 2:1.
  • the carbazole derivative according to the present invention, the polymer or a T 1 higher than the phosphorescent emitter may be used as auxiliary luminescent material, and the weight ratio of the carbazole derivative or polymer to the phosphorescent emitter may be from 1:2 to 2:1.
  • the carbazole derivative according to the present invention, the polymer or a T 1 higher than the phosphorescent emitter may be used as auxiliary luminescent material, and the weight ratio of the carbazole derivative or polymer to the phosphorescent emitter may be from 1:2 to 2:1.
  • the carbazole derivative according to the present invention, the polymer or a T 1 higher than the phosphorescent emitter
  • the mixture comprises a carbazole derivative or polymer according to the invention, and a TADF material.
  • the carbazole derivative or polymer according to the present invention may be used as the TADF host material, wherein the TADF material accounts for ⁇ 15% by weight, further ⁇ 10% by weight, and further ⁇ 8% by weight in the mixture.
  • the subject material, the phosphorescent material and the fluorescent host material, the fluorescent material and the TADF material are described in some detail below (but are not limited thereto).
  • the example of the triplet host material is not particularly limited, and any metal complex or organic compound may be used as the host as long as its triplet energy is higher than that of the illuminant, particularly the triplet illuminant or the phosphorescent illuminant.
  • metal complexes that can be used as the triplet host include, but are not limited to, the following general structure:
  • M is a metal
  • (Y 3 -Y 4 ) is a bidentate ligand, Y 3 and Y 4 are independently selected from C, N, O, P, and S
  • L is an ancillary ligand
  • m is an integer , the value from 1 to the maximum coordination number of this metal
  • m + n is the maximum coordination number of this metal.
  • the metal complex that can be used as the triplet host has the following form:
  • (O-N) is a two-tooth ligand in which the metal is coordinated to the O and N atoms.
  • M can be selected from Ir and Pt.
  • Examples of the organic compound which can be used as the host of the triplet state are selected from compounds containing a cyclic aromatic hydrocarbon group such as benzene, biphenyl, triphenyl, benzo, anthracene; compounds containing an aromatic heterocyclic group such as dibenzothiophene, Dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, carbazole, pyridinium, pyrrole dipyridine, pyrazole, imidazole, three Azole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, thiazide, dioxazin, hydrazine Anthracen
  • the triplet host material can be selected from compounds comprising at least one of the following groups:
  • R 1 to R 7 may be independently selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl, when they are aromatic Or a heteroaryl group, which has the same meaning as Ar 1 and Ar 2 described above; n is an integer from 0 to 20; X 1 -X 8 is selected from CH or N; and X 9 is selected from CR 1 R 2 or NR. 1 .
  • the triplet emitter is a metal complex of the formula M(L)n, wherein M is a metal atom, and each occurrence of L may be the same or different and is an organic ligand. It is bonded to the metal atom M by one or more positional bonding or coordination, and n is an integer greater than 1, preferably 1, 2, 3, 4, 5 or 6. Alternatively, these metal complexes are coupled to a polymer by one or more positions, preferably by an organic ligand.
  • the metal atom M is selected from a transition metal element or a lanthanide or a lanthanide element, preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy , Re, Cu or Ag, especially preferred Os, Ir, Ru, Rh, Re, Pd or Pt.
  • the triplet emitter comprises a chelating ligand, ie a ligand, coordinated to the metal by at least two bonding sites, with particular preference being given to the triplet emitter comprising two or three identical or different pairs Tooth or multidentate ligand.
  • Chelating ligands are beneficial for increasing the stability of metal complexes.
  • Examples of the organic ligand may be selected from a phenylpyridine derivative, a 7,8-benzoquinoline derivative, a 2(2-thienyl)pyridine derivative, a 2(1-naphthyl)pyridine derivative, or a 2 benzene.
  • a quinolinol derivative All of these organic ligands may be substituted, for example by fluorine or trifluoromethyl.
  • the ancillary ligand may preferably be selected from the group consisting of acetone acetate or picric acid.
  • the metal complex that can be used as the triplet emitter has the following form:
  • M is a metal selected from transition metal elements or lanthanides or actinides
  • Ar 1 may be the same or different at each occurrence, and is a cyclic group containing at least one donor atom, that is, an atom having a lone pair of electrons, such as nitrogen or phosphorus, through which a cyclic group is coordinated to a metal.
  • Ar 2 may be the same or different each time it appears, is a cyclic group containing at least one C atom through which a cyclic group is attached to the metal; Ar 1 and Ar 2 are bonded by a covalent bond Together, each may carry one or more substituent groups which may also be joined together by a substituent group; each occurrence of L may be the same or different and is an ancillary ligand, preferably a bidentate chelate ligand Preferred is a monoanionic bidentate chelate ligand; m is 1, 2 or 3, preferably 2 or 3, particularly preferably 3; n is 0, 1, or 2, preferably 0 or 1, Particularly preferred is 0.
  • Triplet emitters are also known as phosphorescent emitters.
  • the triplet emitter is a metal complex of the formula M(L)n, wherein M is a metal atom, and each occurrence of L may be the same or different and is an organic ligand. It is bonded to the metal atom M by one or more positional bonding or coordination, and n is an integer greater than 1, preferably 1, 2, 3, 4, 5 or 6.
  • these metal complexes are coupled to a polymer by one or more positions, preferably by an organic ligand.
  • the metal atom M is selected from a transition metal element or a lanthanide or a lanthanide element, preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy, Re , Cu or Ag, particularly preferred Os, Ir, Ru, Rh, Re, Pd or Pt.
  • the triplet emitter comprises a chelating ligand, ie, a ligand, coordinated to the metal by at least two bonding sites, and it is particularly preferred that the triplet emitter comprises two or three identical or different pairs Tooth or multidentate ligand.
  • Chelating ligands are beneficial for increasing the stability of metal complexes.
  • Examples of the organic ligand may be selected from a phenylpyridine derivative, a 7,8-benzoquinoline derivative, a 2(2-thienyl)pyridine derivative, a 2(1-naphthyl)pyridine derivative, or a 2 benzene.
  • a quinolinol derivative All of these organic ligands may be substituted, for example by fluorine or trifluoromethyl.
  • the ancillary ligand may preferably be selected from the group consisting of acetone acetate or picric acid.
  • the metal complex that can be used as the triplet emitter has the following form:
  • M is a metal selected from transition metal elements or lanthanides or actinides
  • Ar1 may be the same or different at each occurrence, and is a cyclic group containing at least one donor atom, that is, an atom having a lone pair of electrons, such as nitrogen or phosphorus, through which a cyclic group is coordinated to a metal.
  • Ar2 may be the same or different at each occurrence, and is a cyclic group containing at least one C atom through which a cyclic group is bonded to a metal; Ar1 and Ar2 are linked by a covalent bond, respectively Carrying one or more substituent groups, which may also be linked together by a substituent group; each occurrence of L may be the same or different and is an ancillary ligand, preferably a bidentate chelate ligand, preferably a monoanionic bidentate chelate ligand; m is 1, 2 or 3, preferably 2 or 3, particularly preferably 3; n is 0, 1, or 2, preferably 0 or 1, particularly preferably 0;
  • triplet emitters Some examples of suitable triplet emitters are listed in the table below:
  • the example of the singlet host material is not particularly limited, and any organic compound may be used as the host as long as its singlet energy is higher than that of the illuminant, particularly the singlet illuminant or the luminescent illuminant.
  • Examples of the organic compound used as the singlet host material may be selected from the group consisting of a cyclic aromatic compound such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, anthracene, phenanthrene, anthracene, anthracene, fluorene, fluorene, fluorene, An aromatic heterocyclic compound such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, oxazole, carbazole, pyridine Anthraquinone, pyrrole dipyridine, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, triazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrim
  • the singlet host material can be selected from compounds comprising at least one of the following groups:
  • R1 may be independently selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl;
  • Ar1 is aryl or hetero An aryl group having the same meaning as Ar1 defined in the above HTM;
  • n is an integer from 0 to 20;
  • X1 to X8 are selected from CH or N; and
  • X9 and X10 are selected from CR1R2 or NR1.
  • Singlet emitters tend to have longer conjugated pi-electron systems.
  • styrylamine and its derivatives disclosed in JP 2913116 B and WO 2001021729 A1
  • indenoindenes and derivatives thereof disclosed in WO 2008/006449 and WO 2007/140847.
  • the singlet emitter can be selected from the group consisting of monostyrylamine, dibasic styrylamine, ternary styrylamine, quaternary styrylamine, styrene phosphine, styrene ether and aromatic amine.
  • a monostyrylamine refers to a compound comprising an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine.
  • a dibasic styrylamine refers to a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • a ternary styrylamine refers to a compound comprising three unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • a quaternary styrylamine refers to a compound comprising four unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • a preferred styrene is stilbene, which may be further substituted.
  • the corresponding phosphines and ethers are defined similarly to amines.
  • An arylamine or an aromatic amine refers to a compound comprising three unsubstituted or substituted aromatic ring or heterocyclic systems directly bonded to a nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably selected from the fused ring system and preferably has at least 14 aromatic ring atoms.
  • Preferred examples thereof are aromatic decylamine, aromatic quinone diamine, aromatic decylamine, aromatic quinone diamine, aromatic thiamine and aromatic quinone diamine.
  • An aromatic amide refers to a compound in which a diaryl arylamine group is attached directly to the oxime, preferably at the position of 9.
  • An aromatic quinone diamine refers to a compound, two of which The diarylamine groups are attached directly to the oxime, preferably at the 9,10 position.
  • the definitions of aromatic decylamine, aromatic quinone diamine, aromatic thiamine and aromatic quinone diamine are similar, wherein the diaryl aryl group is preferably bonded to the 1 or 1,6 position of hydrazine.
  • Examples of singlet emitters based on vinylamines and arylamines are also preferred examples and can be found in the following patent documents: WO2006/000388, WO2006/058737, WO2006/000389, WO2007/065549, WO2007/115610, US 7250532 B2, DE 102005058557 A1, CN 1583691 A, JP 08053397 A, US Pat. No. 6,251,531 B1, US 2006/210830 A, EP 1 957 606 A1 and US 2008/0113101 A1, the entire contents of each of which is hereby incorporated by reference.
  • Further preferred singlet emitters are selected from the group consisting of an indeno-amine and an indeno-diamine, as disclosed in WO2006/122630, benzoindolo-amine and benzoindeno-diamine, Dibenzoindolo-amine and dibenzoindenoindole-diamine as disclosed in WO 2008/006449, as disclosed in WO 2007/140847.
  • polycyclic aromatic hydrocarbon compounds in particular derivatives of the following compounds: for example, 9,10-bis(2-naphthoquinone), naphthalene, tetraphenyl, xanthene, phenanthrene , ⁇ (such as 2,5,8,11-tetra-t-butyl fluorene), anthracene, phenylene such as (4,4'-bis(9-ethyl-3-carbazolevinyl)-1 , 1 '-biphenyl), indenyl hydrazine, decacycloolefin, hexacene benzene, anthracene, spirobifluorene, aryl hydrazine (such as US20060222886), arylene vinyl (such as US5121029, US5130603), cyclopentane Alkene such as tetraphenylcyclopentadiene, rub
  • the thermally activated delayed fluorescent luminescent material is a third generation organic luminescent material developed after organic fluorescent materials and organic phosphorescent materials.
  • Such materials generally have a small singlet-triplet energy level difference ( ⁇ Est), and triplet excitons can be converted into singlet exciton luminescence by anti-intersystem crossing. This can make full use of the singlet excitons and triplet excitons formed under electrical excitation.
  • the quantum efficiency in the device can reach 100%.
  • the material structure is controllable, the property is stable, the price is cheap, no precious metal is needed, and the application prospect in the OLED field is broad.
  • the TADF material needs to have a small singlet-triplet energy level difference, preferably ⁇ Est ⁇ 0.3 eV, and secondly ⁇ Est ⁇ 0.2 eV, preferably ⁇ Est ⁇ 0.1 eV.
  • the TADF material has a relatively small ⁇ Est, and in another preferred embodiment, the TADF has a better fluorescence quantum efficiency.
  • TADF luminescent materials can be found in the following patent documents: CN103483332(A), TW201309696(A), TW201309778(A), TW201343874(A), TW201350558(A), US20120217869(A1), WO2013133359(A1), WO2013154064( A1), Adachi, et.al. Adv. Mater., 21, 2009, 4802, Adachi, et. al. Appl. Phys. Lett., 98, 2011, 083302, Adachi, et. al. Appl. Phys. Lett ., 101, 2012, 093306, Adachi, et. al. Chem.
  • TADF luminescent materials are listed in the table below:
  • Another object of the invention is to provide a material solution for printing OLEDs.
  • the carbazole derivative according to the invention has a molecular weight of ⁇ 700 g/mol, a further molecular weight ⁇ 900 g/mol, a further molecular weight ⁇ 900 g/mol, and further a molecular weight ⁇ 1000 g/mol. Further molecular weight ⁇ 1100g / mol.
  • the carbazole derivative according to the invention has a solubility in toluene of > 10 mg/ml at 25 ° C, a further solubility of ⁇ 15 mg/ml, and further a solubility of ⁇ 20 mg/ml.
  • the invention still further relates to a composition or ink comprising a carbazole derivative as described above and at least one organic solvent.
  • the composition is a high polymer as described above and at least one organic solvent.
  • the composition comprises the above mixture and at least one organic solvent.
  • the viscosity and surface tension of the ink are important parameters when used in the printing process. Suitable surface tension parameters for the ink are suitable for the particular substrate and the particular printing method.
  • the ink according to the present invention has a surface tension at an operating temperature or at 25 ° C in the range of from about 19 dyne/cm to 50 dyne/cm. Further, the surface tension is in the range of 22 dyne/cm to 35 dyne/cm. Further, the surface tension is in the range of 25 dyne/cm to 33 dyne/cm.
  • the ink according to the present invention has a viscosity at an operating temperature or 25 ° C ranging from about 1 cps to 100 cps. Further, the viscosity is in the range of 1 cps to 50 cps. Further, the viscosity is in the range of 1.5 cps to 20 cps. Further, the viscosity is in the range of 4.0 cps to 20 cps.
  • the composition so formulated will facilitate ink jet printing.
  • the viscosity can be adjusted by different methods, such as by selection of a suitable solvent and concentration of the functional material in the ink.
  • the ink containing the metal organic complex or polymer according to the present invention can facilitate the adjustment of the printing ink to an appropriate range in accordance with the printing method used.
  • the composition according to the invention comprises a functional material in a weight ratio ranging from 0.3% to 30% by weight, preferably from 0.5% to 20% by weight, more preferably from 0.5% to 15% by weight, even more preferably. In the range of 0.5% to 10% by weight, The most preferred range is from 1% to 5% by weight.
  • the at least one organic solvent is selected from the group consisting of aromatic or heteroaromatic based solvents, particularly aliphatic chain/ring substituted aromatic solvents, or aromatic ketones, in accordance with the inks of the present invention.
  • Solvent, or aromatic ether solvent is selected from the group consisting of aromatic or heteroaromatic based solvents, particularly aliphatic chain/ring substituted aromatic solvents, or aromatic ketones, in accordance with the inks of the present invention.
  • Solvent, or aromatic ether solvent is selected from the group consisting of aromatic or heteroaromatic based solvents, particularly aliphatic chain/ring substituted aromatic solvents, or aromatic ketones, in accordance with the inks of the present invention.
  • Solvent, or aromatic ether solvent is selected from the group consisting of aromatic or heteroaromatic based solvents, particularly aliphatic chain/ring substituted aromatic solvents, or aromatic ketones, in accordance with the inks of the present invention.
  • Solvent, or aromatic ether solvent is selected from the
  • solvents suitable for the present invention are, but are not limited to, aromatic or heteroaromatic based solvents: p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethyl Naphthalene, 3-isopropylbiphenyl, p-methyl cumene, dipentylbenzene, triphenylbenzene, pentyltoluene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethyl Benzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, two Hexylbenzene, di
  • the at least one solvent may be selected from the group consisting of: an aliphatic ketone, for example, 2-nonanone, 3-fluorenone, 5-nonanone, 2-nonanone, 2, 5 -hexanedione, 2,6,8-trimethyl-4-indolone, phorone, di-n-pentyl ketone, etc.; or an aliphatic ether, for example, pentyl ether, hexyl ether, dioctyl ether, ethylene Dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether , tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and the like.
  • an aliphatic ketone for example, 2-nonan
  • the printing ink further comprises another organic solvent.
  • another organic solvent include, but are not limited to, methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, Toluene, o-xylene, m-xylene, p-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1,1 , 1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene , decalin, hydrazine and/or mixtures thereof.
  • the composition according to the invention is a solution.
  • composition according to the invention is a suspension.
  • composition in the examples of the present invention may comprise from 0.010% by weight to 20% by weight of the carbazole derivative according to the invention or a mixture thereof, further from 0.1 to 15% by weight, further further from 0.2 to 10% by weight, further It is 0.25 to 5 wt% of an organic compound or a mixture thereof.
  • the invention relates to the use of the composition as a coating or printing ink in the preparation of an organic electronic device, particular preference being given to a preparation process by printing or coating.
  • suitable printing or coating techniques include, but are not limited to, inkjet printing, Nozzle Printing, typography, screen printing, dip coating, spin coating, blade coating, roller printing, torsion rolls. Printing, lithography, flexographic printing, rotary printing, spraying, brushing or pad printing, slit-type extrusion coating, etc. Preferred are gravure, inkjet and inkjet printing.
  • the solution or suspension may additionally comprise one or more components such as surface active compounds, lubricants, wetting agents, dispersing agents, hydrophobic agents, binders and the like for adjusting viscosity, film forming properties, adhesion, and the like.
  • the present invention also provides an application of the carbazole derivative as described above, that is, the carbazole derivative is applied to an organic electronic device, and the organic electronic device can be selected from, but not limited to, organic light emission.
  • Diodes OLEDs
  • OLEDs Organic Photovoltaic Cells
  • OLEDs Organic Light Emitting Cells
  • OFETs Organic Field Effect Transistors
  • Organic Light Emitting Fields Organic Lasers, Organic Spintronics, Organic Sensors and Organic Plasmons Organic Plasmon Emitting Diode, etc., especially OLED.
  • the organic compound is preferably used in a light-emitting layer of an OLED device.
  • the invention further relates to an organic electronic device comprising at least one carbazole derivative, polymer or mixture as described above.
  • an organic electronic device comprises at least one cathode, an anode and a functional layer between the cathode and the anode, wherein the functional layer contains at least one organic compound or polymer as described above.
  • the organic electronic device may be selected from, but not limited to, an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, and an organic Lasers, organic spintronic devices, organic sensors and organic plasmon emitting diodes (Organic Plasmon Emitting Diode), etc., particularly preferred are organic electroluminescent devices such as OLED, OLEEC, organic light-emitting field effect transistors.
  • the electroluminescent device has a light-emitting layer comprising at least one of the carbazole derivatives or at least one of the high polymers.
  • the luminescent layer of the electroluminescent device comprises one of said carbazole derivatives and a phosphorescent illuminant, a fluorescent illuminant or a host material.
  • the luminescent layer luminescent layer of the electroluminescent device comprises one of said high polymer and a host material and a phosphorescent illuminant, a fluorescent illuminant or a host material.
  • the light-emitting layer of the electroluminescent device comprises one of the above-mentioned carbazole derivatives, a phosphorescent emitter and a host material.
  • the luminescent layer of the electroluminescent device comprises a high polymer, a phosphorescent illuminant and a host Body material.
  • a substrate an anode, at least one light-emitting layer, and a cathode are included.
  • the substrate can be opaque or transparent.
  • a transparent substrate can be used to make a transparent light-emitting component. See, for example, Bulovic et al. Nature 1996, 380, p29, and Gu et al, Appl. Phys. Lett. 1996, 68, p2606.
  • the substrate can be rigid or elastic.
  • the substrate can be plastic, metal, semiconductor wafer or glass.
  • the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice.
  • the substrate is flexible, optionally in the form of a polymer film or plastic, having a glass transition temperature Tg of 150 ° C or higher, preferably more than 200 ° C, more preferably more than 250 ° C, preferably More than 300 ° C. Examples of suitable flexible substrates are poly(ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).
  • PET poly(ethylene terephthalate)
  • PEN polyethylene glycol (2,6-na
  • the anode can comprise a conductive metal or metal oxide, or a conductive polymer.
  • the anode can easily inject holes into a hole injection layer (HIL) or a hole transport layer (HTL) or a light-emitting layer.
  • HIL hole injection layer
  • HTL hole transport layer
  • the absolute value of the difference between the work function of the anode and the HOMO level or the valence band level of the illuminant in the luminescent layer or the p-type semiconductor material as the HIL or HTL or electron blocking layer (EBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV.
  • anode material examples include, but are not limited to, Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like.
  • suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art.
  • the anode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
  • the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices in accordance with the present invention.
  • the cathode can include a conductive metal or metal oxide.
  • the cathode can easily inject electrons into the EIL or ETL or directly into the luminescent layer.
  • the work function of the cathode and the LUMO level of the illuminant or the n-type semiconductor material as an electron injection layer (EIL) or electron transport layer (ETL) or hole blocking layer (HBL) in the luminescent layer or
  • EIL electron injection layer
  • ETL electron transport layer
  • HBL hole blocking layer
  • the absolute value of the difference in conduction band energy levels is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV.
  • all materials which can be used as cathodes for OLEDs are possible as cathode materials for the devices of the invention.
  • cathode material examples include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF 2 /Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, and the like.
  • the cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
  • 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.
  • 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 light-emitting layer is prepared by the composition according to the invention.
  • a light-emitting device has an emission wavelength of between 300 and 1000 nm, preferably between 350 and 900 nm. More preferably, it is between 400 and 800 nm.
  • the invention further relates to the use of oxazole derivatives according to the invention in various electronic devices, including, but not limited to, display devices, illumination devices, light sources, sensors and the like.
  • the invention further relates to an electronic device comprising an organic electronic device according to the invention, including, but not limited to, a display device, a lighting device, a light source, a sensor and the like.
  • the synthesis procedure was similar to that of Example 1. Into a 250 ml three-necked flask was added 3.19 g, 10 mmol of phenanthroline and oxazole, 4.3 g, and 11 mmol of 2-(3-bromophenyl)-4,6-diphenyl-1,3. , 5-triazine, 6.9 g, 50 mmol potassium carbonate, 0.26 g, 1 mmol 18-crown-6, 3.0 g, 15 mmol copper iodide and 150 ml o-dichlorobenzene, reacted in a N 2 atmosphere at 160 ° C, TLC tracking The progress of the reaction, until the reaction is over, is lowered to room temperature.
  • the energy level of the organic compound material can be obtained by quantum calculation, for example, by 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
  • the semi-empirical method “Ground State/Semi-empirical/Default Spin/AM1” (Charge 0/Spin Singlet) is used to optimize the molecular geometry, and then the energy structure of the organic molecule is determined by TD-DFT (time-dependent density functional theory) method.
  • TD-SCF/DFT/Default Spin/B3PW91 and the base group "6-31G(d)” (Charge 0/Spin Singlet).
  • the HOMO and LUMO levels are calculated according to the following calibration formula, and S 1 , T 1 and the resonance factor f(S 1 ) are used directly.
  • HOMO(eV) ((HOMO(G) ⁇ 27.212)-0.9899)/1.1206
  • HOMO (G) and LUMO (G) are direct calculation results of Gaussian 09W, the unit is Hartree.
  • the calculation results of the materials prepared in Examples 1 to 6 are shown in Table 1:
  • the materials (1) and materials (2) can be applied to the green phosphorescent host material, and the materials (3) to (6) can be used for the blue fluorescent host material or the luminescent material to satisfy various conditions of the luminescent layer material.
  • the host material of the currently used carbazole material architecture is labeled with Ref 1 :
  • ITO/HATCN (10 nm) / NPB (35 nm) / TCTA (5 nm) / (1) ⁇ (2): 5% Ir (ppy) 3 / B3PYMPM (40 nm) / LiF (1 nm) / Al (150 nm), OLED
  • the preparation steps of the device are as follows:
  • a, cleaning of the conductive glass substrate when used for the first time, can be washed with a variety of solvents, such as chloroform, ketone, isopropyl alcohol, and then UV ozone plasma treatment;
  • cathode LiF / Al (1nm / 150nm) in a high vacuum (1 ⁇ 10 -6 mbar) in the thermal evaporation;
  • the device is encapsulated in a nitrogen glove box with an ultraviolet curable resin.
  • the current-voltage (J-V) characteristics of each OLED device are characterized by characterization equipment while recording important parameters such as efficiency, lifetime and external quantum efficiency.
  • the luminous efficiency and lifetime of OLED1 are more than three times that of OLED Ref1 (corresponding material (Ref1)), and the luminous efficiency of OLED2 (corresponding material (2)) is four times that of OLED Ref1.
  • the life is 5 More than double, especially the maximum external quantum efficiency of OLED 2 is over 19%. It can be seen that the OLED device prepared by using the organic mixture of the invention has greatly improved luminous efficiency and lifetime, and the external quantum efficiency is also significantly improved.

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Abstract

La présente invention concerne un dérivé de carbazole et une utilisation correspondante. Le dérivé de carbazole présente une structure générale représentée par l'une quelconque des formules (1) à (8), la formule (1) étant décrite dans ce qui suit : Ar1, Ar2 et Ar3 <sb /> représentent, indépendamment, un système aromatique comprenant 6-20 atomes de carbone ou un système cyclique hétéroaromatique ou non aromatique comprenant 2-20 atomes de carbone, le système étant non substitué ou substitué par un ou plusieurs groupes R1 ; et Ar4 représente un système aromatique comprenant 6-40 atomes de carbone ou un système cyclique hétéroaromatique ou non aromatique comprenant 2-40 atomes de carbone, le système étant non substitué ou substitué par un ou plusieurs groupes R1.
PCT/CN2016/101998 2016-01-07 2016-10-13 Dérivé de carbazole et polymère élevé, mélange, composition et dispositif électronique organique le comprenant et utilisation correspondante WO2017118137A1 (fr)

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WO2023003468A1 (fr) 2021-07-23 2023-01-26 Rijksuniversiteit Groningen Nouveaux inhibiteurs de l'histone désacétylase (hdac), procédés, compositions et utilisations s'y rapportant

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CN109575002A (zh) * 2017-12-14 2019-04-05 广州华睿光电材料有限公司 有机化合物及其应用
WO2020091522A1 (fr) * 2018-11-02 2020-05-07 주식회사 엘지화학 Composé et dispositif électroluminescent organique le comprenant
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CN112533912B (zh) * 2018-11-02 2024-01-02 株式会社Lg化学 化合物及包含其的有机发光器件
CN110669048A (zh) * 2018-12-06 2020-01-10 广州华睿光电材料有限公司 基于含氮稠环的有机化合物及其应用
CN114685483A (zh) * 2020-12-28 2022-07-01 宁波卢米蓝新材料有限公司 一种有机电致发光化合物及其应用
CN114685483B (zh) * 2020-12-28 2023-07-04 宁波卢米蓝新材料有限公司 一种有机电致发光化合物及其应用
WO2023003468A1 (fr) 2021-07-23 2023-01-26 Rijksuniversiteit Groningen Nouveaux inhibiteurs de l'histone désacétylase (hdac), procédés, compositions et utilisations s'y rapportant

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