WO2016112761A1 - 含乙炔基交联基团的共轭聚合物、包含其的混合物、组合物、有机电子器件及其应用 - Google Patents
含乙炔基交联基团的共轭聚合物、包含其的混合物、组合物、有机电子器件及其应用 Download PDFInfo
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- WO2016112761A1 WO2016112761A1 PCT/CN2015/097192 CN2015097192W WO2016112761A1 WO 2016112761 A1 WO2016112761 A1 WO 2016112761A1 CN 2015097192 W CN2015097192 W CN 2015097192W WO 2016112761 A1 WO2016112761 A1 WO 2016112761A1
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- organic
- conjugated polymer
- acetylene
- crosslinking group
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Definitions
- the present invention relates to the field of polymeric optoelectronic materials, and in particular to a class of conjugated polymers containing acetylene crosslinking groups, mixtures, compositions, organic electronic devices and uses thereof.
- OLEDs organic light-emitting diodes
- organic photoelectric materials have similar solubility, that is, organic/polymer luminescent materials, hole injection/transport materials, electron injection/transport materials in toluene, chloroform, chlorobenzene, o-dichlorobenzene, o-xylene, tetrahydrofuran, etc.
- the solvent has good solubility, so when the solution processing method is used to prepare a multi-layer, complex OLED, there are problems such as interface miscibility and interface corrosion.
- the cross-linking group on the polymer can initiate a cross-linking group Perfluorocyclobutane (Adv.) under illumination, heating and the like.
- Perfluorocyclobutane Advanced under illumination, heating and the like.
- a conjugated polymer comprising an ethynyl crosslinking group, a mixture comprising the same, a composition, an organic electronic device, and uses thereof.
- the conjugated polymeric material can have a conjugated backbone structure and a functionalized side chain ethynyl crosslinking group. Since the polymer has a conjugated main chain structure, it imparts rich optical and electrical properties to the polymer.
- the conjugated polymer material can be crosslinked under heating to form an insoluble and infusible interpenetrating network polymer film, which has excellent solvent resistance and is suitable for fabricating complex multilayer organic electronic devices.
- the conjugated polymer can be applied to an optoelectronic device such as an organic light emitting diode, a polymer solar cell, an organic field effect transistor, a perovskite solar cell, and the like, and improves device performance.
- the conjugated polymer containing an ethynyl crosslinking group according to an aspect of the invention may have the following structure (chemical formula I):
- the conjugated polymer according to one aspect of the invention wherein Ar1 may be selected from the group consisting of polymer backbone structural units benzene, biphenyl, triphenyl, benzo, anthracene, fluorene Anthracene, carbazole, carbazole, dibenzothiazole, dithienocyclopentadiene, dithienothiole, thiophene, anthracene, naphthalene, benzodithiophene, benzofuran, benzothiophene, benzene And a selenophene compound or any combination thereof.
- Ar1 may be selected from the group consisting of polymer backbone structural units benzene, biphenyl, triphenyl, benzo, anthracene, fluorene Anthracene, carbazole, carbazole, dibenzothiazole, dithienocyclopentadiene, dithienothiole, thiophene, anthrac
- the conjugated polymer according to one aspect of the invention wherein Ar2 may be a hole transporting unit, and the hole transporting unit may be selected from the group consisting of aromatic amines, triphenylamines, naphthalenes. Amine, thiophene, carbazole, dibenzothiophene, dithienocyclopentadiene, dithienothiolan, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, anthracene Any one or combination of an azole or a carbazole compound.
- the conjugated polymer according to one aspect of the invention wherein Ar2 may be selected from an electron transport unit, and the electron transport unit may be selected from the group consisting of pyrazole, imidazole, and triazole. , oxazole, thiazole, oxadiazole, triazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxazine, oxadiazines, hydrazine, benzo Imidazole, oxazole, indoxazine, bisbenzoxazoles, isoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthalene, anthracene, pteridine, xanthene, acridine, phenazine Any one or a
- the conjugated polymer according to one aspect of the invention wherein R3 is selected from a linking group, and the linking group unit may be selected from the group consisting of 1 to 30 carbon atoms. Any one or combination of an alkyl group, an alkoxy group having 1 to 30 carbon atoms, an amino group, an alkenyl group, an alkynyl group, an aralkyl group, a heteroalkyl group, an aryl group, and a heteroaryl group.
- the present invention also relates to a mixture which may comprise the above-mentioned conjugated organic polymer, and at least another organic functional material, which may be selected from a hole injection material (HIM), a cavity Transmission material (HTM), electron transport material (ETM), electron injecting material (EIM), electron blocking material (EBM), hole blocking material (HBM), luminescent material (Emitter), host material (Host), and the like.
- HIM hole injection material
- HTM cavity Transmission material
- ETM electron transport material
- EIM electron injecting material
- EBM electron blocking material
- HBM hole blocking material
- Emitter luminescent material
- Hos host material
- the invention further relates to a composition useful as a printing ink, which may comprise a conjugated polymer or a mixture thereof according to one aspect of the invention, and at least one organic solvent.
- the invention further relates to an organic electronic device in which the conjugated organic polymer or composition thereof may be included, and uses thereof.
- the polymer material described in the present invention has the following advantages:
- a conjugated polymer containing an ethynyl crosslinking group imparts rich optical (photoluminescence, electroluminescence, photovoltaic effect, etc.) to the polymer ), electrical properties (semiconductor properties, carrier transport properties, etc.), acetylene crosslinking groups also have a crosslinkable function, which can form a three-dimensional insoluble and infusible interpenetrating network polymer film under heating conditions. Has excellent solvent resistance.
- the solution processing characteristics of the conjugated polymer can be utilized, and the polymer optoelectronic device can be prepared by solution processing such as inkjet printing, screen printing, spin coating, etc.;
- solution processing such as inkjet printing, screen printing, spin coating, etc.;
- the formation of an insoluble and infusible three-dimensional interpenetrating network polymer film has excellent solvent resistance and is advantageous for solution processing of a multilayer polymer photovoltaic device.
- the acetylene-containing crosslinking group-containing conjugated polymer described in one aspect of the present invention when heated, can initiate ethynyl crosslinking groups to each other as compared with a conventional crosslinkable photovoltaic material.
- a chemical reaction occurs to form a conjugated double bond of the SP 2 hybrid type, that is, the conjugated polymer chain is linked together by one or more conjugated double bonds to increase the carrier (hole or electron) conjugated polymer chain.
- the transfer between the chains and the chain is expected to improve the carrier transport characteristics of the conjugated polymer film.
- Example 1 is an absorbance curve of the crosslinked P1 film prepared in Example 1 and the uncrosslinked P1 film eluted with a tetrahydrofuran solution;
- Figure 2 is a 1 H NMR of the key intermediate hydrazine
- Figure 3 is a 1 H NMR of 2,7-dibromo-6,6,12,12-tetraoctylfluorene.
- a conjugated polymer comprising an ethynyl crosslinking group and uses thereof.
- the conjugated polymeric material has a conjugated backbone structure and a functionalized side chain ethynyl crosslinking group.
- the present invention provides a conjugated polymer containing an ethynyl crosslinking group having the following structure:
- 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 ⁇ 3000 g/mol, more preferably ⁇ 2000 g/mol, most preferably ⁇ 1500 g/mol.
- polymer ie, Polymer, as defined herein, includes homopolymers, copolymers, block copolymers. Also in the present invention, the 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.].
- conjugated polymer as defined herein is a polymer whose backbone is mainly composed of sp2 hybrid orbitals of C atoms, notable examples of which are: polyacetylene polyacetylene and Poly(phenylene vinylene), the C atom in its main chain may also be optionally substituted by other non-C atoms, and is still considered to be a conjugated polymer when the sp2 hybridization in the main chain is interrupted by some natural defects. . Further, in the present invention, the conjugated polymer may also include an aryl amine, an aryl phosphine and other heteroarmotics, and an organometallic complexes in the main chain. )Wait.
- polymers, polymers, and polymers have the same meaning and are interchangeable.
- the polymer according to one aspect of the invention has a molecular weight Mw ⁇ 10000 g/mol, more preferably ⁇ 50000 g/mol, more preferably ⁇ 100000 g/mol, most preferably ⁇ 200000 g / mol.
- the polymer according to one aspect of the invention wherein Ar1, Ar2, when multiple occurrences, may be independently or differently independently selected from any one of the following structural groups or Combination: a cyclic aromatic group including benzene, biphenyl, triphenyl, benzo, anthracene, anthracene and derivatives thereof; and an aromatic heterocyclic group including triphenylamine, dibenzothiophene, dibenzofuran , dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, oxazole, carbazole, pyridinium, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, Thiazole, oxadiazole, triazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, tri
- the Ar1, Ar2 cycloaromatic hydrocarbon group and the aromatic heterocyclic group may be further optionally substituted, and the substituent may be hydrogen, deuterium, alkyl, alkoxy, amino, alkenyl, alkynyl, Any one or combination of an aralkyl group, a heteroalkyl group, an aryl group, and a heteroaryl group.
- the conjugated polymer comprises at least one backbone structural unit.
- the main chain structural unit generally has a larger energy gap ⁇ -conjugated structural unit, also called a Backbone Unit, and may be selected from a monocyclic or polycyclic aryl or heteroaryl.
- the conjugated polymer may contain two or more main chain structural units.
- the content of the backbone structural unit may be ⁇ 40 mol%, more preferably ⁇ 50 mol%, still more preferably ⁇ 55 mol%, and most preferably ⁇ 60 mol%.
- Ar1 may be a polymer backbone structural unit selected from the group consisting of benzene, biphenyl, triphenyl, benzo, anthracene, fluorene Anthracene, carbazole, carbazole, dibenzothiazole, dithienocyclopentadiene, dithienothiole, thiophene, anthracene, naphthalene, benzodithiophene, benzofuran, benzothiophene, benzene And any one or a combination of selenophene and its derivatives.
- Ar1 may be a polymer backbone structural unit selected from the group consisting of benzene, biphenyl, triphenyl, benzo, anthracene, fluorene Anthracene, carbazole, carbazole, dibenzothiazole, dithienocyclopentadiene, dithienothiole, thiophene, anthracene, na
- the chain having the largest number of links or the chain having the largest number of repeating units in the polymer chain having a branched (side chain) structure is called a polymer main chain.
- the polymers of the present invention have hole transport properties.
- the polymer according to one aspect of the invention wherein Ar2 may be selected from the group consisting of a unit having a hole transporting property, and the preferred hole transporting unit may be selected from the group consisting of an aromatic amine, a triphenylamine, and a naphthalene.
- Ar2 may have the structure represented by Chemical Formula 1:
- Ar 1 , Ar 2 , Ar 3 can independently select the same or different forms when appearing multiple times
- Ar 1 is selected from a single bond or a mononuclear or polynuclear aryl or heteroaryl group, and this aryl or heteroaryl group may be optionally substituted with other side chains.
- Ar 2 selected from mononuclear or polynuclear aryl or heteroaryl, which may be optionally substituted by other side chains.
- Ar 3 selected from mononuclear or polynuclear aryl or heteroaryl, which may be optionally substituted by other side chains. Ar 3 may also be linked to other moieties in Chemical Formula 1 via a bridging group.
- n selected from 1, 2, 3, 4, or 5.
- Chemical Formula 2 The preferred structural unit represented by Chemical Formula 1 is Chemical Formula 2
- Ar 4 , Ar 6 ', Ar 7 , Ar 10 , Ar 11 , Ar 13 , Ar 14 are as defined in Ar 2 in Chemical Formula 1,
- Ar 5 , Ar 8 , Ar 9 , and Ar 12 are as defined in Ar 3 in Chemical Formula 1.
- Ar 1 -Ar 14 in Chemical Formula 1 and Chemical Formula 2 can be preferably selected from the group consisting of phenylene, naphthalene, anthracene, fluorene, spirobifluorene, and hydrazine. Any one or a combination of indenofuorene, phenanthrene, thiophene, pyrrole, carbazole, binaphthalene, dehydrophenanthrene, and the like.
- Ar2 may have the structure represented by Chemical Formula 3.
- Ar 15 and Ar 16 The same or different forms may be independently selected in multiple occurrences, and they may be selected from mononuclear or polynuclear aryl or heteroaryl, which may be optionally fused to their respective adjacent D 1 and D 2 .
- N1-n4 An integer from 0 to 4 can be selected independently.
- Preferred Ar 15 and Ar 16 in the material represented by Chemical Formula 3 are phenylene, naphthalene, anthracene, fluorene, spirobifluorene, (indenofuorene), phenanthrene. Any one or combination of thiophene, pyrrole, carbazole, binaphthalene, (dehydrophenanthrene).
- the cell having the hole transporting property may correspond to the hole transporting material HTM in the OLED.
- Suitable organic HTM materials may optionally include compounds having the following structural units: phthlocyanine, porphyrine, amine, aromatic amine, triarylamine, thiophene, and Fused thiophene (such as dithienothiophene and dibenzothiphene), pyrrole, aniline, carbazole, indolocarbazole, and their Any one or combination of derivatives.
- cyclic aromatic amine-derived compounds useful as HTM include, but are not limited to, the following general structures:
- each of Ar 1 to Ar 9 may be independently selected from a cyclic aromatic hydrocarbon group such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalene, phenanthrene, anthracene, pyrene, fluorene, fluorene, fluorene; Aromatic heterocyclic groups such as dibenzothiophene, dibenzofuran, furan, thiophene, benzofuran, benzothiophene, carbazole, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole , oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, hydrazine, benzimidazo
- Ar 1 to Ar 9 may be independently selected from the group consisting of:
- n is an integer from 1 to 20; X 1 to X 8 are CH or N; and Ar 1 is as defined above.
- cyclic aromatic amine-derived compounds can be found in US Pat. No. 3,567,450, US Pat. No. 4,724,432, US Pat. No. 5,061,569, US Pat.
- HTM Suitable non-limiting examples of HTM compounds are listed in the table below:
- the HTM described above can be incorporated into the polymer of the present invention by a hole transporting structural unit.
- the polymers of the present invention have electron transport properties.
- the polymer according to one aspect of the invention wherein Ar2 is selected from the group consisting of electron transporting characteristics, and the preferred electron transporting unit may be selected from the group consisting of pyrazole, imidazole, triazole, and evil.
- the unit having electron transport characteristics may correspond to the electron transport material ETM in the OLED.
- ETM is sometimes referred to as an n-type organic semiconductor material.
- suitable ETM materials are not particularly limited, and any metal complex or organic compound may be used as the ETM as long as they have electron transport properties.
- Preferred organic ETM materials may be selected from the group consisting of tris(8-hydroxyquinoline)aluminum (AlQ3), phenazine, Phenanthroline, Anthracene, Phenanthrene, Fluorene, and Bifluorene, Spiro-bifluorene, Phenylene-vinylene, triazine, triazole, imidazole, pyrene, Perylene, Trans-Indenofluorene, cis-Indenon fluorene, Dibenzol-indenofluorene, Indenonaphthalene, Benzanthracene and their derivatives Any one or a combination thereof.
- AlQ3 tris(8-hydroxyquinoline)aluminum
- phenazine Phenanthroline
- Anthracene Phenanthrene
- Fluorene and Bifluorene
- Spiro-bifluorene Phenylene-vinylene
- the compound useful as ETM can be a molecule comprising at least one of the following groups:
- R 1 may be selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl, when they are aryl or heteroaryl group, which may be the same meaning Ar 1 in the above-described HTM, Ar 1 -Ar 5 may be the same meaning as Ar 1 HTM described, n being an integer from 0 to 20, X 1 -X 8 may be selected from From CR 1 or N.
- ETM compounds are listed in the table below:
- the ETM described above can be incorporated into the polymer of the present invention by an electron transporting structural unit.
- R3 is a linking group.
- R3 may be selected from alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, heteroalkyl, aryl and heteroaryl groups having from 2 to 30 carbon atoms.
- R 3 is a non-conjugated linking group, preferably selected from the group consisting of alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, heteroalkyl or combination.
- R3 is a conjugated linking group, preferably selected from the group consisting of C1-C30 alkyl, C1-C30 alkoxy, benzene, and hydrazine.
- Non-limiting examples of suitable linking groups R3 with crosslinkable groups are listed in the table below:
- the conjugated polymer of the present invention may have the following formula:
- the conjugated polymer as described above wherein at least one of Ar1, Ar2 and Ar2-1 is selected from the group consisting of hole transporting units, and at least one is selected from the group consisting of electron transporting units.
- Ar2-1 is selected from an electron transport unit, and Ar2 is selected from a hole transport unit;
- Ar1 is selected from a main chain structural unit having electron transporting property
- Ar2-1 is selected from a hole transporting unit
- Ar2 is selected from a hole transporting unit
- Ar2-1 is selected from the group consisting of a light-emitting unit (including a singlet emitter, a triple-single emitter), and Ar2 is selected from a hole transport unit;
- Ar2-1 is selected from a hole transport unit, and Ar2 is selected from an electron transport unit;
- the level of crosslinking groups can be y ⁇ 50 mol%, more preferably ⁇ 40 mol%, more preferably ⁇ 30 mol%, and most preferably ⁇ 20 mol%.
- Non-limiting examples of repeating units containing a crosslinking group are,
- a general synthesis method of a conjugated polymer containing an acetylene crosslinking group may be a synthesis of a monomer having a functionalized acetylene crosslinking group by a transition metal catalytic coupling (Suzuki Polymerization, Heck Polymerization, Sonogashira Polymerization,
- the conjugated polymer containing the alkynyl crosslinking group can be obtained by a polymerization method such as Still Polymerization), a Witting reaction, etc., by controlling the reaction time, the reaction temperature, the monomer ratio, the reaction pressure, the solubility, the amount of the catalyst, and the distribution.
- the ratio of body ratio and phase transfer catalyst can control the molecular weight and dispersion coefficient of the polymer.
- the synthetic route can be as shown in the following figure:
- a general synthesis method for a ternary (ternary or ternary or higher) conjugated polymer containing an ethynyl crosslinking group may be a synthesis of a monomer having a functionalized acetylene crosslinking group, a plurality of (three or three)
- the above-mentioned monomers can be obtained by a polymerization method such as Suzuki Polymerization (Heck Polymerization, Sonogashira Polymerization, Still Polymerization), Witting reaction, etc.
- the conjugated polymer of the linking group can control the molecular weight and the dispersion coefficient of the polymer by controlling the reaction time, the reaction temperature, the monomer ratio, the reaction pressure, the solubility, the amount of the catalyst, the ratio of the ligand, and the phase transfer catalyst.
- the synthetic route can be as shown below:
- certain specific chemical reagents, temperatures, etc. used in the polymer reaction process are sensitive to the cross-linking group ethynyl group, and the acetylene group can be chemically reacted.
- the temperature required for the polymerization exceeds 180 ° C, or even exceeds 280 ° C, and may exceed 380 ° C
- the crosslinking group of the side chain of the conjugated polymer is relatively active under high temperature conditions, and the acetylene crosslinking group is The polymerization reaction itself occurs, and the finally obtained polymer is insoluble and infusible, and does not have solution processing characteristics.
- the terminal hydrogen atom on the acetylene crosslinking group can be first protected to reduce the chemical reactivity.
- the most common protecting group for the acetylene terminal hydrogen atom of the crosslinking group may be trimethylsilyl (TMS).
- TMS trimethylsilyl
- the polymer precursor After obtaining a polymer precursor containing a trimethylsilyl group, the polymer precursor may be treated by an alkali solution. After the time, a conjugated polymer having an ethynyl crosslinking group of the target conjugated polymer can be obtained.
- TMS trimethylsilyl
- the synthetic route of the conjugated organic monomer containing an ethynyl crosslinking group can be as shown in the following figure, but is not limited to the synthesis of the target compound by the following route.
- the starting material A (commercial chemical reagent or chemical synthesis) can be obtained by electrophilic optional substitution reaction (such as chlorination, bromination, iodination, etc.) to obtain compound B, which can be used in the Pd-Cu cocatalyst.
- the Sonogashira coupling reaction with trimethylsilylacetylene is carried out to obtain Compound C.
- Compound C can remove the trimethylsilyl protecting functional group in an alkali solution to obtain the target compound D.
- conjugated polymer containing an ethynyl crosslinking group examples are listed below, but are not limited to these polymers, and the examples include
- the conjugated polymer of the ethynyl crosslinking group has a distinct feature that the ethynyl group is directly linked to the conjugated polymer backbone or linked by a conjugated aromatic ring or an aromatic heterocyclic ring.
- the invention further relates to a mixture which may comprise a polymer according to one aspect of the invention, and at least one other organic functional material.
- the organic functional material may include a hole (also called a hole) injection or transport material (HIM/HTM), a hole blocking material (HBM), an electron injection or transport material (EIM/ETM), and an electron blocking material ( EBM), organic matrix material (Host), singlet illuminant (fluorescent illuminant), heavy illuminant (phosphorescent illuminant), especially luminescent organic metal complex.
- HIM/HTM hole injection or transport material
- HBM hole blocking material
- EIM/ETM electron injection or transport material
- EBM electron blocking material
- organic matrix material Host
- Singlet illuminant fluorescent illuminant
- heavy illuminant phosphorescent illuminant
- Organic functional materials can be small molecules and polymeric materials. The following is a detailed description of the organic functional materials (but is not limited to this).
- Suitable organic HIM/HTM materials for use in one aspect of the invention may optionally comprise a compound having the following structural units: phthalocyanine, porphyrin, amine, aromatic amine, biphenyl triarylamine, thiophene, and thiophene such as dithiophene. And thiophene and thiophene, pyrrole, aniline, carbazole, azepine and aziridine, and their derivatives.
- HIMs also include fluorocarbon-containing polymers; conductively doped polymers; conductive polymers such as PEDOT/PSS; self-assembling monomers such as compounds containing phosphonic acid and sliane derivatives; metal oxides Any one or a combination of, for example, MoOx; a metal complex, and a crosslinking compound.
- metal complexes that can be used as HTM or HIM can include, but are not limited to, the following general structure:
- M can be a metal having an atomic weight greater than 40;
- (Y 1 -Y 2 ) is a two-dentate ligand, Y 1 and Y 2 are independently selected from C, N, O, P, and S; L is an ancillary ligand; m is an integer having a value from 1 The maximum coordination number of the metal to this point; m+n is the maximum coordination number of this metal.
- (Y 1 -Y 2 ) may be a 2-phenylpyridine derivative.
- (Y 1 -Y 2 ) may be a carbene ligand.
- M can be selected from the group consisting of Ir, Pt, Os, and Zn.
- the HOMO of the metal complex is greater than -5.5 eV (relative to the vacuum level).
- the ETM has been described above and is supplemented here.
- EIM/ETM material used in one aspect of the present invention are not particularly limited, and any metal complex or organic compound may be used as the EIM/ETM as long as they can transport electrons.
- Preferred organic EIM/ETM materials may be selected from the group consisting of tris(8-hydroxyquinoline)aluminum (AlQ 3 ), phenazine, phenanthroline, anthracene, phenanthrene, anthracene, diterpene, spirobifluorene, p-phenylacetylene, triazine Any one or combination of triazole, imidazole, hydrazine, hydrazine, ruthenium fluorene, hydrazine, dibenzo-indenoindole, indenylnaphthalene, benzindene and derivatives thereof.
- the hole blocking layer (HBL) used in one aspect of the invention is typically used to block cavities from adjacent functional layers, particularly luminescent layers. In contrast to a light-emitting device without a barrier layer, the presence of HBL typically results in an increase in luminous efficiency.
- the hole blocking material (HBM) of the hole blocking layer (HBL) needs to have a lower HOMO than an adjacent functional layer such as a light emitting layer.
- the HBM has a larger excited state level than the adjacent luminescent layer, For example, singlet or triplet, depending on the illuminant.
- the HBM has an electron transport function. EIM/ETM materials that typically have deep HOMO levels can be used as HBM.
- examples of the metal complex that can be used as the EIM/ETM may include, but are not limited to, the following general structure:
- (ON) or (NN) is a two-tooth ligand in which the metal is coordinated to O, N or N, N; L is an ancillary ligand; m is an integer from 1 to the maximum coordination of the metal number.
- an organic alkali metal compound can be used as the EIM.
- an organic alkali metal compound is understood to be a compound having at least one alkali metal, that is, lithium, sodium, potassium, rubidium, cesium, and further comprising at least one organic ligand.
- Non-limiting examples of suitable organic alkali metal compounds for use in one aspect of the invention may include the compounds described in US Pat. No. 7,767,317 B2, EP 1 941 562 B1 and EP 1 144 543 B1.
- Preferred organic alkali metal compounds may be compounds of the formula:
- R 1 has the meaning as defined above, the arc represents two or three atoms and a bond, so as to form a 5- or 6-membered ring with the metal M if necessary, wherein the atom may also be optionally substituted by one or more R 1 M is an alkali metal selected from the group consisting of lithium, sodium, potassium, rubidium, and cesium.
- the organic alkali metal compound may be in the form of a monomer, as described above, or in the form of an aggregate, for example, a two alkali metal ion and two ligands, 4 alkali metal ions and 4 ligands, 6 alkali metal ions and 6 ligands or in other forms.
- Preferred organic alkali metal compounds may be compounds of the formula:
- o each time it appears can be the same or different, is 0, 1, 2, 3 or 4;
- p each occurrence may be the same or different, is 0, 1, 2 or 3;
- the alkali metal M is selected from the group consisting of lithium, sodium, potassium, more preferably lithium or sodium, most preferably lithium.
- the organic alkali metal compound is electron-injected into the layer. More preferably, the electron injecting layer is composed of an organic alkali metal compound.
- the organoalkali metal compound is doped into other ETMs to form an electron transport layer or an electron injection layer. More preferably, it is an electron transport layer.
- Non-limiting examples of suitable organic alkali metal compounds are listed in the table below:
- the example of the triplet matrix material used in one aspect of the present invention is not particularly limited, and any metal complex or organic compound may be used as a matrix as long as its triplet energy ratio is an illuminant, particularly a triplet state.
- the illuminant or phosphorescent emitter is higher.
- metal complexes that can be used as the triplet host can include, but are not limited to, the following general structure:
- M may be a metal
- (Y 3 -Y 4 ) may be a two-dentate ligand, Y 3 and Y 4 may be independently selected from C, N, O, P, and S
- L may be an ancillary ligand; It can be an integer with a value from 1 to the maximum coordination number of the metal; m+n is the maximum coordination number of the metal.
- the metal complex that can be used as the triplet matrix has the following form:
- (O-N) may be a two-toothed ligand in which the metal coordinates with the O and N atoms.
- M can be selected from the group consisting of Ir and Pt.
- Non-limiting examples of the organic compound which can be used as the triplet substrate 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 diphenyl And thiophene, dibenzofuranophene, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole ,oxaazole,dioxazole,thiadiazole,pyridine,pyridazine,pyrimidine,pyrazine,triazine,oxazines,oxathiazines,oxadiazines,
- each Ar may be further optionally substituted, and the substituent may be any of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl. Kind or a combination thereof.
- the triplet matrix material can be selected from compounds comprising at least one of the following groups:
- R 1 -R 7 may be independently of one another selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl, when they are aryl Or a heteroaryl group, they may have the same meaning as Ar 1 and Ar 2 described above; n may be an integer from 0 to 20; X 1 -X 8 may be selected from CH or N; and X 9 may be selected from CR 1 R 2 or NR 1 .
- the example of the singlet matrix material used in one aspect of the present invention is not particularly limited, and any organic compound may be used as a matrix as long as it has a singlet energy ratio illuminant, particularly a singlet illuminant. Or the fluorescent illuminant is higher.
- Non-limiting examples of the organic compound used as the singlet matrix material may be selected from the group consisting of a cyclic aromatic compound such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalene, phenanthrene, anthracene, anthracene, quinone , anthracene, anthracene; aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, Pyrrolodipyridine, pyrazole, imidazole , triazole, isoxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyr
- the singlet matrix material can be selected from compounds comprising at least one of the following groups:
- R 1 may be independently of one another selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl;
- Ar 1 is aryl or hetero An aryl group having the same meaning as Ar 1 defined in the above HTM;
- n is an integer from 0 to 20; X 1 -X 8 is selected from CH or N; and X 9 and X 10 are selected from CR 1 R 2 or NR 1 .
- HBM Hole blocking material
- the hole blocking layer (HBL) used in one aspect of the invention is typically used to block cavities from adjacent functional layers, particularly luminescent layers. In contrast to an OLED without a barrier layer, the presence of HBL typically results in an increase in luminous efficiency.
- the hole blocking material (HBM) of the hole blocking layer (HBL) needs to have a lower HOMO than the adjacent functional layer, such as the luminescent layer. In a preferred embodiment, the HBM has a greater excitation than the adjacent luminescent layer.
- the state energy level, such as the singlet or triplet state, depends on the illuminant. In another preferred embodiment, the HBM has an electron transport function.
- the HBM used contains the same molecules as the matrix material in the luminescent layer.
- the HBM can be selected from compounds comprising at least one of the following groups:
- Singlet emitters used in one aspect of the invention tend to have longer conjugated pi-electron systems.
- there have been many examples such as, but not limited to, any one or a combination of styrylamine and its derivatives, and any one of indenofluorene and its derivatives. Or a combination thereof.
- the singlet emitter can be selected from the group consisting of monostyrylamines, distyrylamines, tristyrylamines, tetrastyrylamines. Any one or combination of styryl phosphines, styryl ethers, and arylamines.
- the monostyrylamine refers to a compound comprising an optionally substituted or optionally substituted styryl group and at least one amine, most preferably an aromatic amine.
- the distyrylamine refers to a compound comprising two unsubstituted or optionally substituted styryl groups and at least one amine, most preferably an aromatic amine.
- Ternary styrylamine refers to a compound comprising three unsubstituted or optionally substituted styryl groups and at least one amine, most preferably an aromatic amine.
- Tetrastyrylamine refers to a compound comprising four unsubstituted or optionally substituted styryl groups and at least one amine, most preferably an aromatic amine.
- a preferred styrene is stilbene, which may be further optionally 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 optionally substituted aromatic ring or heterocyclic systems directly bonded to the nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably selected from the group consisting of fused ring systems, and most preferably 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.
- Aromatic decylamine refers to a compound in which a diarylamino group is directly attached to the oxime, most preferably at the position of 9.
- Aromatic quinone diamine refers to a compound in which two diarylamino groups are directly attached to the oxime, most 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 most preferably bonded to the 1 or 1 and 6 positions of hydrazine.
- Non-limiting examples of singlet emitters based on vinylamines and arylamines are also preferred examples and can be found in the following patent documents: WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549 , WO 2007/115610, US Pat. No. 7,250,532 B2, DE 102005058557 A1, CN 1583691 A, JP 08053397 A, US Pat. No. 6251531 B1, US 2006/210830 A, EP 1957606 A1 and US 2008/0113101 A1.
- a non-limiting example of a singlet emitter based on distyrylbenzene and its derivatives is US 5121029.
- Further preferred singlet emitters may be selected from the group consisting of anthraquinone-amine and anthraquinone-diamine, benzoindenofluorene-amine and benzoindenofluorene-diamine ), dibenzoindenofluorene-amine and dibenzoindenofluorene-diamine.
- polycyclic aromatic hydrocarbon compounds particularly derivatives of compounds such as 9,10-bis(2-naphthoquinone) (9,10-di(2) -naphthylanthracene)), naphthalene, tetraphenyl, xanthene, phenanthrene, perylene such as 2,5,8,11-tetra-t-butylperylene, indenoperylene, phenylenes
- arylpyrene eg US20060222886
- arylenevinylene eg US5121029, US5130603
- cyclopentadiene such as tetraphenylcyclopen
- Non-limiting examples of some suitable singlet emitters are listed in the table below:
- the triplet emitters used in one aspect of the invention are also referred to as phosphorescent emitters.
- the triplet emitter may be a metal complex having the formula M(L)n, wherein M may be a metal atom, and each time L may be the same or different, it is an organic A ligand which may be bonded to the metal atom M by one or more position linkages or coordination, n may be an integer greater than 1, more preferably 1, 2, 3, 4, 5 or 6.
- these metal complexes may be coupled to a polymer by one or more positions, most preferably by an organic ligand.
- the metal atom M may be selected from transition metal elements or lanthanides or actinides, preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy Re, Cu or Ag, particularly preferably Os, Ir, Ru, Rh, Re, Pd, Pt.
- the triplet emitter comprises a chelating ligand, ie a ligand, coordinated to the metal by at least two bonding sites, it is particularly preferred to consider 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.
- Non-limiting examples of organic ligands may be selected from the group consisting of phenylpyridine derivatives, 7,8-benzoquinoline derivatives, 2 (2-thienyl) pyridine derivative, 2 (1-naphthyl) pyridine derivative, or 2 phenylquinoline derivative Things. All of these organic ligands may be optionally substituted, for example by fluorine or trifluoromethyl.
- the ancillary ligand may preferably be selected from the group consisting of acetoacetate or picric acid.
- the metal complex that can be used as the triplet emitter can have the following form:
- M is a metal selected from the group consisting of 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 Most 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;
- Non-limiting examples of the extreme application of materials for some triplet emitters can be found in the following patent documents and documents: WO 200070655, WO 200141512, WO 200202714, WO 200215645, EP 1191613, EP 1191612, EP 1191614, WO 2005033244, WO 2005019373 , US 2005/0258742, WO 2009146770, WO 2010015307, WO 2010031485, WO 2010054731, WO 2010054728, WO 2010086089, WO 2010099852, WO 2010102709, US 20070087219 A1, US 20090061681 A1, US 20010053462 A1, Baldo, Thompson et al.
- triplet emitters Some non-limiting examples of suitable triplet emitters are listed in the table below:
- the organic functional materials described above including HIM, HTM, ETM, EIM, Host, fluorescent emitters, phosphorescent emitters, may all be in the form of a polymer.
- the polymer suitable for the present invention is a conjugated polymer.
- the conjugated polymer can have the general formula:
- A can be independent when it appears multiple times
- B a ⁇ -conjugated structural unit having a large energy gap, also called a Backbone Unit, selected from a monocyclic or polycyclic aryl or heteroaryl group, and a preferred unit form is benzene, diphenylene.
- a ⁇ -conjugated structural unit having a small energy gap may be selected from hole injection or transport materials (HIM/HTM) containing the above-described functions according to different functional requirements. , hole blocking material (HBM), electron injecting or transporting material (EIM/ETM), electron blocking material (EBM), organic matrix material (Host), singlet illuminant (fluorescent illuminant), heavy illuminant ( Any one or combination of structural units of the phosphorescent emitter.
- HBM hole blocking material
- EIM/ETM electron injecting or transporting material
- EBM electron blocking material
- organic matrix material Host
- singlet illuminant fluorescent illuminant
- heavy illuminant Any one or combination of structural units of the phosphorescent emitter.
- Non-limiting examples of luminescent polymers are disclosed in the following patent applications: WO2007043495, WO2006118345, WO2006114364, WO2006062226, WO2006052457, WO2005104264, WO2005056633, WO2005033174, WO2004113412, WO2004041901, WO2003099901, WO2003051092, WO2003020790, WO2003020790, US2020040076853, US2020040002576, US2007208567, US2005962631, EP201345477, EP2001344788, DE102004020298.
- polymers suitable for the present invention may be non-conjugated polymers. This can be that all functional groups are on the side chain and the backbone is a non-conjugated polymer.
- Some non-limiting examples of such non-conjugated polymers useful as phosphorescent or phosphorescent materials are disclosed in the patent applications of U.S. Patent Nos. 7,250,226, B2, JP 2007 059 939 A, JP 2007 211 243 A2, and JP 2007 1975 074 A2, some of which are incorporated herein by reference.
- Non-limiting examples of non-conjugated polymers can be found in the patent applications of JP2005108556, JP2005285661 and JP2003338375.
- non-conjugated polymer may also be a polymer, and the functional units conjugated to the main chain are linked by non-conjugated linking units.
- Non-limiting examples of such polymers are in DE102009023154.4 and DE102009023156.0. There is publicity in it.
- the invention further relates to a composition which may comprise a conjugated organic polymer and at least one organic solvent according to one aspect of the invention.
- 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, tetrahydronaphthalene, naphthalene Alkanes,
- the composition according to one aspect of the invention is a solution.
- composition according to one aspect of the invention is a suspension.
- composition in the examples of the invention may comprise from 0.01 to 20% by weight of the organic mixture, more preferably from 0.1 to 15% by weight, more preferably from 0.2 to 10% by weight, most preferably from 0.25 to 5% by weight of the organic mixture.
- the invention further relates to the use of the composition as a coating or printing ink in the preparation of an organic electronic device, particularly preferably by a printing or coating process.
- suitable printing or coating techniques may include, but are not limited to, inkjet printing, letterpress printing, screen printing, dip coating, spin coating, blade coating, roller printing, torsion roller printing, lithography, and softness.
- Preferred are inkjet printing, screen printing and gravure 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 the use of a polymer as described above, that is, the polymer is applied to an organic electronic device, which may be selected from, but not limited to, an organic light emitting diode (OLED). ), organic photovoltaic cells (OPV), organic light-emitting cells (OLEEC), organic field effect transistors (OFETs), organic light-emitting field effect transistors, organic lasers, organic spintronic devices, organic sensors and organic plasmon emitting diodes ( Organic Plasmon Emitting Diode), especially OLED.
- OLED organic light emitting diode
- OLED organic light emitting diode
- OLED organic photovoltaic cells
- OLED organic light-emitting cells
- OFETs organic field effect transistors
- organic light-emitting field effect transistors organic lasers
- organic spintronic devices organic spintronic devices
- organic sensors and organic plasmon emitting diodes Organic Plasmon Emitting Diode
- the invention further relates to an organic electronic device which can comprise at least one polymer as described above.
- an organic electronic device may comprise at least a cathode, an anode and a functional layer between the cathode and the anode, wherein the functional layer may comprise at least one polymer as described above.
- the organic electronic device described above is an electroluminescent device, which may include a substrate, an anode, at least one luminescent layer, and a cathode.
- the organic electronic device described above may be an OLED.
- the substrate can be opaque or transparent. Transparent substrates can be used to make transparent light-emitting components. 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. Most preferably, the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice.
- the substrate is flexible and may be selected from polymeric films or plastics having a glass transition temperature Tg of 150 ° C or higher, more preferably more than 200 ° C, more preferably more than 250 ° C, most preferably More than 300 ° C.
- suitable flexible substrates are poly(ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).
- the anode can include 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 energy level of the illuminant in the luminescent layer or the p-type semiconductor material as the HIL or HTL or electron blocking layer (EBL) may be less than 0.5 eV, more preferably less than 0.3 eV, most preferably less than 0.2 eV.
- Non-limiting examples of anode materials can 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 suitable physical vapor deposition, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
- the anode can be 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 or conductance 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
- EIL electron injection layer
- ETL electron transport layer
- HBL hole blocking layer
- the absolute value of the difference in band level can be less than 0.5 eV, more 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 may 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, and the like. Any one or a combination thereof.
- 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. Any one of (HBL) or a combination thereof. Materials suitable for use in these functional layers are described in detail in WO2010135519A1, US20090134784A1 and WO2011110277A1.
- the light emitting layer thereof may be by printing the group of the present invention.
- the compound is prepared.
- the light-emitting device may have an emission wavelength of between 300 and 1000 nm, more preferably between 350 and 900 nm, and even more preferably between 400 and 800 nm.
- the invention further relates to the use of an organic electronic device according to one aspect of 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 one aspect of the invention, including, but not limited to, a display device, a lighting device, a light source, a sensor, and the like.
- a 250 ml three-neck round bottom flask was mechanically stirred, 12.92 g (0.05 mol) of 2,5-diphenyl-p-xylene was added, 250 ml of pyridine was added, stirred to dissolve, and then 30 ml of water and 39.51 g of potassium permanganate were added ( KMnO 4 ) (0.25 mol), heated under reflux (about 105-110 ° C) for 2 h, after each reflux for 30 min, 60 ml of water and 15.59 potassium permanganate (KMnO 4 ) (0.1 mol) were added, and the mixture was repeated four times. After each reflux for 6 hours, 60 ml of water was added and cooled four times.
- the rotor was placed in a 250 ml long-necked three-neck round bottom flask with a high vacuum piston in the middle and a plug on both sides.
- the flask was evacuated with an oil pump while heating the flask with a fan.
- 4.31 g of 2,8-dibromo-6,6,12,12-tetraoctylindole (5 mmol) was dissolved in 120 ml of THF and added to the flask with a syringe, stirred at -78 ° C for 20 min and then placed in a flask with a syringe.
- the temperature of the reaction liquid was raised to 70 ° C, and the reaction was carried out for 6 hours under argon gas protection.
- the degree of the reaction was monitored by thin layer chromatography, and after the completion of the reaction, the reaction solution was cooled to room temperature, and impurities such as solid salts were removed by suction filtration.
- the crude product was separated and purified by column chromatography (silica gel column eluting eluting with petroleum ether), and then recrystallized from methanol to give a white solid, which was filtered and dried in vacuo to yield 9.58 g.
- the reaction was carried out under the conditions of argon gas protection at 110 ° C for 24 hours, followed by refluxing with 50 ⁇ L of bromobenzene for 2 hours, and refluxing with 20 mg of phenylboronic acid for 2 hours. After the reaction was cooled to room temperature, the reaction solution was added dropwise to methanol for precipitation. The obtained flocculent precipitate was filtered, and the obtained polymer was redissolved in about 30 mL of tetrahydrofuran under vacuum drying. The obtained tetrahydrofuran solution was filtered through a PTFE filter head having a pore size of 0.45 ⁇ m, concentrated under reduced pressure, and then dropped dropwise.
- polymer P2 prepared in example 1 as hole transporting material in organic/polymer electroluminescent device O/PLEDs (ITO anode/hole transport layer/light emitting layer/electron transport layer/aluminum cathode)
- the ITO conductive glass a sheet resistance of about 20 ohms/cm 2 was pre-cut into 15 mm ⁇ 15 mm square pieces. Ultrasonic cleaning with acetone, micro-scale semiconductor special detergent, deionized water and isopropyl alcohol in sequence, nitrogen whistle and placed in a constant temperature oven for use. Prior to use, the ITO glass sheets were bombarded with plasma for 10 minutes in an oxygen plasma etch oven.
- PEDOT PSS aqueous dispersion (about 1%)
- Clevios TM PEDOT: PSS Al4083 as a buffer layer with a high speed spin coating machine (KW-4A), the thickness is determined by the solution concentration and rotation speed, using a surface profiler (Tritek Alpha- Tencor-500 type) measured monitoring.
- the film thickness of PEDOT:PSS on the ITO substrate was 80 nm.
- the polymer P2 synthesized in Example 1 was dissolved in a toluene solution at a concentration of 5 mg/ml, and the polymer P2 was spin-coated on a PEDOT:PSS film to a thickness of 20 nm, and heated on a hot plate to 200 ° C for 30 minutes to form a polymer. A cross-linking reaction occurs in P2.
- the polymer P2 film was then rinsed with toluene to a thickness of 18-19 nm, indicating that the crosslinking reaction was effective and the polymer P2 film was cured more completely.
- the fluorescent conjugated polymer P-PPV (P-PPV is a green-emitting material) or MEH-PPV (MEH-PPV is an orange-red material) is weighed in a clean bottle and transferred to a special glove box for nitrogen protection film formation. Dissolved in toluene and filtered through a 0.45 micron filter. The fluorescent polymer was spin-coated on the hole transport layer polymer P2 film, and the polymer light-emitting layer had an optimum thickness of 80 nm. The film thickness was measured using an Alpha-Tencor-500 surface profiler. Subsequently, about 2 to 5 nm of CsF was obtained as a electron injection/transport layer on the vacuum evaporation condition.
- Aluminum (100 nm) was vacuum evaporated on the electron transport layer as a cathode.
- the area of the light-emitting region of the device having a mask on the ITO interactive cover was determined to be 0.04 square centimeters. All preparations were carried out in a glove box providing a nitrogen atmosphere.
- the current-voltage characteristics, luminous intensity and external quantum efficiency of the device were measured by a Keithley 236 current-voltage-measurement system and a calibrated silicon photodiode.
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Abstract
本发明提供含乙炔基交联基团的共轭聚合物、包含其的混合物、组合物、有机电子器件及其应用。所述共轭聚合物材料具有共轭的主链结构及功能化的侧链乙炔基交联基团。所述共轭聚合物材料在加热的条件下交联生成不溶不熔的互穿网络聚合物薄膜,具有优异的抗溶剂性能,适于制作复杂的多层有机电子器件。所述共轭聚合物能够应用于有机场效应晶体管、有机发光二极管、聚合物太阳电池、钙钛矿太阳电池等光电器件中,并改善器件性能。
Description
本发明涉及聚合物光电材料领域,具体涉及一类含乙炔基交联基团的共轭聚合物、包含其的混合物、组合物、有机电子器件及其应用。
自有机发光二极管(OLEDs)发明以来,由于有机/聚合物半导体材料在合成上具有多样性、制造成本相对较低和优良的光学与电学性能,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。
为了实现高效的OLED器件,电子和空穴分别从阴极和阳极高效的注入是其中的关键。因此,高效的OLED器件都是采用多层器件结构,即除了发光层外,还含有一层或多层空穴传输/注入层或电子传输/注入层。因此,除了开发优异的发光材料,开发优异的电子传输/注入材料和空穴传输/注入材料也是实现高效OLED的关键(J Mater Chem,2008,18:4495-4509.;Acc Chem Res,2005,38:632-643.;Adv Mater,2007,19:810-814)。
对小分子真空蒸镀OLEDs而已,很容易通过真空蒸镀方法获得多层、复杂的高效OLEDs器件,但是由于真空蒸镀方法具有价格昂贵、耗时、浪费材料、难以实现大面积应用等缺点。相比而言,溶液加工型OLEDs由于能够通过低廉的喷墨打印、印刷等溶液加工方法制备大面积、柔性器件等优点,具有广泛的应用前景和商业价值。由于一般有机光电材料具有相似的溶解性,即有机/聚合物发光材料、空穴注入/传输材料、电子注入/传输材料在甲苯、氯仿、氯苯、邻二氯苯、邻二甲苯、四氢呋喃等溶剂中具有良好的溶解性,因此在溶液加工方法制备多层、复杂的OLED时,存在界面混溶、界面侵蚀等问题。例如溶液加工聚合物或小分子发光层时,所使用的溶剂会溶解下面的空穴传输层,造成界面混溶、界面侵蚀等问题(J Mater Chem,2008,18:4495-4509.;Chem Soc Rev,2010,39:2500-2521)。
采用常规的交联基团如Perfluorocyclobutane,Styrene,Oxetane,Siloxane,Acrylate,Benzocyclobutene修饰共轭聚合物时,聚合物上的交联基团在光照、加热等条件可引发交联基团Perfluorocyclobutane(Adv.Funct.Mater.,2002,12,745),Styrene(Adv.Mater.,2007,19,300),Oxetane(Nature,2003,421,829.),Siloxane(Acc.Chem.Res.,2005,38,632),Acrylate(Chem.Mater.,2003,15,1491),Benzocyclobutene(Chem.Mater.,2007,19,4827.)发生交联反应,形成不溶不熔的互穿网络聚合物膜,具有优异的抗溶剂性能,可以避免界面混溶、界面侵蚀等问题(TW201406810A,US7592414B2)。
但是基于这些交联基团的交联聚合物的溶液加工OLED的性能还有待提高。
因此新的高性能的可交联的聚合物电荷传输材料急需要开发出来。
发明内容
本发明的一个方面中,提供含乙炔基交联基团的共轭聚合物、包含其的混合物、组合物、有机电子器件及其应用。所述共轭聚合物材料可以具有共轭的主链结构及功能化的侧链乙炔基交联基团。由于所述聚合物具有共轭的主链结构,赋予聚合物丰富的光学、电学性能。所述共轭聚合物材料在加热的条件下可以交联生成不溶不熔的互穿网络聚合物薄膜,具有优异的抗溶剂性能,适于制作复杂的多层有机电子器件。所述共轭聚合物能够应用于有机发光二极管、聚合物太阳电池、有机场效应晶体管、钙钛矿太阳电池等光电器件中,并改善器件性能。
按照本发明的一个方面中所述的含乙炔基交联基团的共轭聚合物,可以具有如下结构(化学式I):
其中,x,y为摩尔百分比(mol%),x+y=1,Ar1和Ar2在多次出现时可相同或者不同地独立选自芳基或杂芳基团,R3是一连接基团。
在一个优选的实施例中,按照本发明的一个方面中所述的共轭聚合物,其中Ar1可以选自聚合物主链结构单元苯、联苯、三苯基、苯并、芴、吲哚芴、咔唑、吲哚咔唑、二苯并噻咯、二噻吩并环戊二烯、二噻吩并噻咯、噻吩、蒽、萘、苯并二噻吩、苯并呋喃、苯并噻吩、苯并硒吩类化合物中的任一种或其组合。
在另一个优选的实施例中,按照本发明的一个方面中所述的共轭聚合物,其中Ar2可以是空穴传输单元,所述的空穴传输单元可选自芳香胺、三苯胺、萘胺、噻吩、咔唑、二苯并噻吩、二噻吩并环戊二烯、二噻吩并噻咯、二苯并硒吩、呋喃、噻吩、苯并呋喃、苯并噻吩、苯并硒吩、咔唑、吲哚咔唑类化合物中的任一种或其组合。
在另一个优选的实施例中,按照本发明的一个方面中所述的共轭聚合物,其中Ar2可以选自电子传输单元,所述的电子传输单元可选自吡唑、咪唑、***类、恶唑、噻唑、恶二唑、恶***、二恶唑、噻二唑、吡啶、哒嗪、嘧啶、吡嗪、三嗪类、恶嗪,恶噻嗪、oxadiazines、吲哚、苯并咪唑、吲唑、indoxazine、bisbenzoxazoles、异恶唑、苯并噻唑、喹啉、异喹啉、cinnoline、喹唑啉、喹喔啉、萘、酞、蝶啶、氧杂蒽、吖啶、吩嗪、吩噻嗪、phenoxazines、benzofuropyridine、furodipyridine、benzothienopyridine、thienodipyridine、benzoselenophenopyridine和selenophenodipyridine类化合物中的任一种或其组合。
在另一个优选的实施例中,按照本发明的一个方面中所述的共轭聚合物,其中R3选自连接基团,所述的连接基团单元可选自具有1-30个碳原子的烷基、具有1-30个碳原子的烷氧基、氨基、烯基、炔基、芳烷基、杂烷基、芳基和杂芳基中的任一种或其组合。
本发明还涉及一种混合物,其可以包含有以上所述的共轭有机聚合物,及至少另一种有机功能材料,所述的有机功能材料可选自空穴注入材料(HIM),空穴传输材料(HTM),电子传输材料(ETM),电子注入材料(EIM),电子阻挡材料(EBM),空穴阻挡材料(HBM),发光材料(Emitter),主体材料(Host)等。
本发明还涉及一种能用作印刷油墨的组合物,其可以包含有按照本发明的一个方面中所述的共轭聚合物或其混合物,及至少一种有机溶剂。
本发明进一步涉及一种有机电子器件,其中可以包含有所述共轭有机聚合物或其组合物,及其应用。
与现有技术相比,本发明中所述的聚合物材料具有以下优点:
(1)本发明的一个方面中所述的含乙炔基交联基团的共轭聚合物,共轭的主链结构赋予聚合物具有丰富的光学(光致发光、电致发光、光伏效应等)、电学(半导体特性、载流子传输特性等)等性能,乙炔基交联基团还具有可交联的功能,在加热条件下可形成三维的不溶不熔的互穿网络聚合物薄膜,具有优异的抗溶剂性能。在制备复杂多层光电器件时即可利用共轭聚合物的溶液加工特性,通过喷墨打印、丝网印刷、旋涂等溶液加工工艺制备聚合物光电器件;又可利用交联的方式使之形成不溶不熔的三维互穿网络聚合物薄膜,具有优异的抗溶剂性能,有利于进行多层聚合物光电器件的溶液加工。
(2)和传统的可交联光电材料相比,本发明的一个方面中所述的含乙炔基交联基团的共轭聚合物,在加热的条件下可引发乙炔基交联基团相互发生化学反应生成SP2杂化型的共轭双键,即共轭聚合物链通过一个或者多个共轭双键链接在一起,可增加载流子(空穴或者电子)共轭聚合物链与链之间的传递,有望提高共轭聚合物薄膜的载流子传输特性。
图1为实施例1所制备的经交联处理的P1膜、未经交联处理的P1膜经四氢呋喃溶液洗脱处理后的吸光度曲线图;
图2为关键中间体吲哚芴的1H NMR;
图3为分2,7-二溴-6,6,12,12-四辛基吲哚芴的1H NMR。
本发明的一个方面中提供一种含乙炔基交联基团的共轭有聚合物及其应用。所述共轭聚合物材料具有共轭的主链结构及功能化的侧链乙炔基交联基团。为使本发明的目的、技术方案及效果更加清楚、明确,以下对本发明进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
本发明提供一种含乙炔基交联基团的共轭聚合物,具有如下结构:
其中,x,y为mol%,x+y=1,Ar1和Ar2在多次出现时可相同或者不同地独立选自芳基或杂芳基团,R3是一连接基团。
本文中所定义的术语“小分子”是指不是聚合物,低聚物,树枝状聚合物,或共混物的分子。特别是,小分子中没有重复结构。小分子的分子量≤3000克/摩尔,较优选是≤2000克/摩尔,最优选是≤1500克/摩尔。
本文中所定义的术语聚合物,即Polymer,包括均聚物(homopolymer),共聚物(copolymer),镶嵌共聚物(block copolymer)。另外在本发明中,聚合物也包括树状物(dendrimer),有关树状物的合成及应用请参见[Dendrimers and Dendrons,Wiley-VCH Verlag GmbH&Co.KGaA,2002,Ed.George R.Newkome,Charles N.Moorefield,Fritz Vogtle.]。
本文中所定义的术语共轭聚合物(conjugated polymer)是一聚合物,它的主链(backbone)主要是由C原子的sp2杂化轨道构成,著名的非限制性例子有:聚乙炔polyacetylene和poly(phenylene vinylene),其主链上的C原子的也可以被其它非C原子任选取代,而且当主链上的sp2杂化被一些自然的缺陷打断时,仍然被认为是共轭聚合物。另外在本发明中共轭聚合物也可以包括主链上包含有芳基胺(aryl amine)、芳基磷化氢(aryl phosphine)及其他杂环芳烃(heteroarmotics)、有机金属络合物(organometallic complexes)等。
在本发明中,聚合物,聚合物,Polymer具有相同的含义,可以互换。
在某些实施例中,按照本发明的一个方面中所述的聚合物,其分子量Mw≥10000克/摩尔,较优选是≥50000克/摩尔,更优选是≥100000克/摩尔,最优选是≥200000克/摩尔。
在某些优选的实施例中,按照本发明的一个方面中所述的聚合物,其中Ar1、Ar2在多次出现时可相同或者不同地独立选自如下结构基团中的任一种或其组合:环芳香基团,包括苯、联苯、三苯基、苯并、芴、吲哚芴及其衍生物;和芳香杂环基团,包括三苯胺、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、pyrrolodipyridine、吡唑、咪唑、***类、恶唑、噻唑、恶二唑、恶***、二恶唑、噻二唑、吡啶、哒嗪、嘧啶、吡嗪、三嗪类、恶嗪,恶噻嗪、oxadiazines、吲哚、苯并咪唑、吲唑、indoxazine、bisbenzoxazoles、异恶唑、苯并噻唑、喹啉、异喹啉、cinnoline、喹唑啉、喹喔啉、萘、酞、蝶啶、氧杂蒽、吖啶、吩嗪、吩噻嗪、phenoxazines、benzofuropyridine、furodipyridine、benzothienopyridine、thienodipyridine、benzoselenophenopyridine和selenophenodipyridine等。
在某些实施例中Ar1、Ar2环芳香烃基团和芳香杂环基团可以进一步被任选取代,取代基可选为氢、氘,烷基、烷氧基、氨基、烯基、炔基、芳烷基、杂烷基、芳基和杂芳基中的任一种或其组合。
一般地,共轭聚合物包含有至少一个主链结构单元。主链结构单元一般具有较大的能隙的π-共轭结构单元,也称骨干单元(Backbone Unit),可选自单环或多环芳基(aryl)或杂芳基(heteroaryl)。本发明中,共轭聚合物可以包含两个或以上的主链结构单元。一般的,主链结构单元的含量可以是≥40mol%,较优选是≥50mol%,更优选是≥55mol%,最优选是≥60mol%。
在一个优选的实施例中,按照本发明的一个方面中所述的聚合物,其中Ar1可以是聚合物主链结构单元,选自苯、联苯、三苯基、苯并、芴、吲哚芴、咔唑、吲哚咔唑、二苯并噻咯、二噻吩并环戊二烯、二噻吩并噻咯、噻吩、蒽、萘、苯并二噻吩、苯并呋喃、苯并噻吩、苯并硒吩及其衍生物中的任一种或其组合。
聚合物主链,在有支链(侧链)结构的高分子链中链节数最多的链或者重复单元数最多的链,称为聚合物主链。
在某些实施例中,本发明的聚合物具有空穴传输特性。
在一个优选的实施例中,按照本发明的一个方面中所述的聚合物,其中Ar2可以选自具有空穴传输特性的单元,优选的空穴传输单元可选自芳香胺、三苯胺、萘胺、噻吩、咔唑、二苯并噻吩、二噻吩并环戊二烯、二噻吩并噻咯、二苯并硒吩、呋喃、噻吩、苯并呋喃、苯并噻吩、苯并硒吩、咔唑、吲哚咔唑及其衍生物中的任一种或其组合。
在另一个优选的实施例中,Ar2可以具有化学式1表示的结构:
其中Ar1,Ar2,Ar3在多次出现时可独立选择相同或不同的形式
Ar1:选自一单键或者单核或多核芳基或杂芳基,此芳基或杂芳基可以被其他侧链任选取代的。
Ar2:选自单核或多核芳基或杂芳基,此芳基或杂芳基可以是被其他侧链任选取代的。
Ar3:选自单核或多核芳基或杂芳基,此芳基或杂芳基可以是被其他侧链任选取代的。Ar3也可以通过一桥接基团与化学式1中的其他部分相联接。
n:选自1,2,3,4,或5。
优选的化学式1所表示的结构单元为化学式2
其中
Ar4,Ar6’,Ar7,Ar10,Ar11,Ar13,Ar14的定义如化学式1中的Ar2,
Ar5,Ar8,Ar9,Ar12的定义如化学式1中的Ar3。
在化学式1和化学式2中的Ar1-Ar14可以从如下基团中优先选择:苯(phenylene),萘(naphthalene),蒽(anthracene),芴(fluorene),螺双芴(spirobifluorene),吲哚芴(indenofuorene),菲(phenanthrene),噻吩(thiophene),吡咯(pyrrole),咔唑(carbazole),联萘(binaphthalene),dehydrophenanthrene等中的任一种或其组合。
按照化学式1和化学式2所表示的结构单元中特别优选的选择列于表1,其中的每个化合物都可以被一个或多个取代基任选取代,R为一取代基。
表1
在另一个优选的实施例中,Ar2可以具有化学式3表示的结构
其中
D1和D2:在多次出现时可独立选择相同或不同的形式,它们可以选自如下功能基团中的任一种或其组合:噻吩(thiophene),硒酚(selenophene),噻吩酮[2,3b]噻吩(thieno[2,3b]thiophene),噻吩酮[3,2b]噻吩(thieno[3,2b]thiophene),二噻吩并噻吩(dithienothiophene),吡咯(pyrrole)和苯胺(aniline),所有这些功能基团都可非强制性的被如下基团任选取代:卤素,-CN,-NC,-NCO,-NCS,-OCN,SCN,C(=O)NR0R00,-C(=O)X,-C(=O)R0,-NH2,-NR0R00,SH,SR0,-SO3H,-SO2R0,-OH,-NO2,-CF3,-SF5,有1-40个C原子的甲硅烷基(silyl)或二价碳基(carbyl)或烃基(hydrocarbyl);其中R0,R00为一取代基.
Ar15和Ar16:在多次出现时可独立选择相同或不同的形式,它们可选自单核或多核芳基或杂芳基(heteroaryl),它们可非强制性地稠合到各自临近的D1和D2.
n1-n4:可独立选择一个0到4的整数。
化学式3所表示的材料中优选的Ar15和Ar16为苯(phenylene),萘(naphthalene),蒽(anthracene),芴(fluorene),螺双芴(spirobifluorene),(indenofuorene),菲(phenanthrene),噻吩(thiophene),吡咯(pyrrole),咔唑(carbazole),联萘(binaphthalene),(dehydrophenanthrene)中的任一种或其组合。
具有空穴传输特性的单元可以对应于OLED中的空穴传输材料HTM。合适的有机HTM材料可选包含有如下结构单元的化合物:酞菁(phthlocyanine)、卟啉(porphyrine)、胺(amine)、芳香胺、联苯类三芳胺(triarylamine)、噻吩(thiophene)、并噻吩(fused thiophene)(如二噻吩并噻吩(dithienothiophene)和并噻吩(dibenzothiphene))、吡咯(pyrrole)、苯胺(aniline)、咔唑(carbazole)、氮茚并氮芴(indolocarbazole),及它们的衍生物中的任一种或其组合。
可用作HTM的环芳香胺衍生化合物的例子包括(但不限于)如下的一般结构:
其中,每个Ar1到Ar9可独立选自环芳香烃基团,如苯、联苯、三苯基、苯并、萘、蒽、phenalene、菲、芴、芘、屈、苝、薁;和芳香杂环基团,如二苯并噻吩、二苯并呋喃、呋喃、噻吩、苯并呋喃、苯并噻吩、咔唑、吡唑、咪唑、三氮唑、异恶唑、噻唑、恶二唑、oxatriazole、二恶唑、噻二唑、吡啶、哒嗪、嘧啶、吡嗪、三嗪、恶嗪、oxathiazine、oxadiazine、吲哚、苯并咪唑、吲唑、indoxazine、苯并恶唑、benzisoxazole、苯并噻唑、喹啉、异喹啉、邻二氮(杂)萘、喹唑啉、喹喔啉、萘、酞、蝶啶、氧杂蒽、吖啶、吩嗪、吩噻嗪、吩恶嗪、dibenzoselenophene、benzoselenophene、benzofuropyridine、indolocarbazole、pyridylindole、pyrrolodipyridine、furodipyridine、benzothienopyridine、thienodipyridine、benzoselenophenopyridine和selenophenodipyridine;包含有2至10环结构的基团,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。其中,每个Ar可以进一步被任选取代,取代基可选为氢、烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基和杂芳基。
在一个方面,Ar1到Ar9可独立选自包含如下组的基团:
其中,n是1到20的整数;X1到X8是CH或N;Ar1如以上所定义。环芳香胺衍生化合物的另外的非限制性例子可参见US3567450、US4720432、US5061569、US3615404和US5061569。
在下面的表中列出合适的可作为HTM化合物的非限制性例子:
以上所述的HTM都可以一空穴传输结构单元结合到本发明的聚合物中。
在某些实施例中,本发明的聚合物具有电子传输特性。
在一个优选的实施例中,按照本发明的一个方面中所述的聚合物,其中Ar2选自具有电子传输特性的单元,优选的电子传输单元可选自吡唑、咪唑、***类、恶唑、噻唑、恶二唑、恶***、二恶唑、噻二唑、吡啶、哒嗪、嘧啶、吡嗪、三嗪类、恶嗪,恶噻嗪、oxadiazines、吲哚、苯并咪唑、吲唑、indoxazine、bisbenzoxazoles、异恶唑、苯并噻唑、喹啉、异喹啉、cinnoline、喹唑啉、喹喔啉、萘、酞、蝶啶、氧杂蒽、吖啶、吩嗪、吩噻嗪、phenoxazines、benzofuropyridine、furodipyridine、benzothienopyridine、thienodipyridine、benzoselenophenopyridine和selenophenodipyridine及其衍生物中的任一种或其组合。
具有电子传输特性的单元可以对应于OLED中电子传输材料ETM。ETM有时也称n型有机半导体材料。原则上,合适的ETM材料的例子并不受特别的限制,任何金属络合物或有机化合物都可能被用作为ETM,只要它们具有电子传输特性。优选的有机ETM材料可选自三(8-羟基喹啉)铝(AlQ3)、吩嗪(Phenazine)、菲罗啉(Phenanthroline)、蒽(Anthracene)、菲(Phenanthrene)、芴(Fluorene)、二芴(Bifluorene)、螺二芴(Spiro-bifluorene)、对苯乙炔(Phenylene-vinylene)、三嗪(triazine)、***(triazole)、咪唑(imidazole)、芘(Pyrene)、苝(Perylene)、反茚并芴(trans-Indenofluorene)、顺茚并(cis-Indenonfluorene)、二苯并-茚并芴(Dibenzol-indenofluorene)、茚并萘(Indenonaphthalene)、苯并蒽(benzanthracene)及它们的衍生物中的任一种或其组合。
另一方面,可用作ETM的化合物可以是至少包含一个以下基团的分子:
其中,R1可选自如下的基团:氢、烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基和杂芳基,当它们是芳基或杂芳基时,它们可以与上述HTM中的Ar1意义相同,Ar1-Ar5可以与在HTM中所描述的Ar1意义相同,n是一个从0到20的整数,X1-X8可以选自CR1或N。
在下面的表中列出合适的可作ETM化合物的非限制性例子:
以上所述的ETM都可以电子传输结构单元结合到本发明的聚合物中。
按照本发明的一个方面中所述的具有结构式化学式I的含乙炔基交联基团的共轭聚合物,其中R3是一个连接基团。在一个优选的实施例中,R3可以选自具有2-30个碳原子的烷基、烷氧基、氨基、烯基、炔基、芳烷基、杂烷基、芳基和杂芳基。
在某些实施例中,R3是一个非共轭连接基团,优选的选自烷基、烷氧基、氨基、烯基、炔基、芳烷基、杂烷基中的任一种或其组合。
在某些优选的实施例中,R3是一个共轭连接基团,优选的选自C1-C30的烷基、C1-C30的烷氧基、苯、联
苯、三苯基、苯并、噻吩、蒽、萘、苯并二噻吩、芳香胺、三苯胺、萘胺、噻吩、咔唑、二苯并噻吩、二噻吩并环戊二烯、二噻吩并噻咯、二苯并硒吩、呋喃、噻吩、苯并呋喃、苯并噻吩、苯并硒吩、咔唑、呋喃等中的任一种或其组合。
在下面的表中列出合适的带有可交联基团的连接基团R3的非限制性例子:
在一个优选的实施例中,本发明的共轭聚合物,可以具有如下通式:
其中,x,y,z为mol%,且大于0,x+y+z=1,Ar2-1和前面所述的Ar2的含义相同。
在一个较为优选的实施例中,如上所述的共轭聚合物,其中Ar1,Ar2和Ar2-1中至少有一个选自空穴传输单元,及至少有一个选自电子传输单元。
一些较为优选的组合非限制性例子有:
1)Ar2-1选自电子传输单元,Ar2选自空穴传输单元;
2)Ar1选自具有电子传输特性的主链结构单元,Ar2-1选自空穴传输单元,Ar2选自空穴传输单元;
3)Ar2-1选自发光单元(包括单重态发光体,三单重态发光体),Ar2选自空穴传输单元;
4)Ar2-1选自空穴传输单元,Ar2选自电子传输单元;
在某些优选的实施例中,交联基团的含量可以是y≤50mol%,较优选是≤40mol%,更优选是≤30mol%,最优选是≤20mol%。
含有交联基团的重复单元的非限制性例子有,
含乙炔基交联基团的共轭聚合物通用合成方法可以是先合成带有功能化的乙炔基交联基团的单体,通过过渡金属催化偶联(Suzuki Polymerization,Heck Polymerization,Sonogashira Polymerization,Still Polymerization)、Witting反应等聚合方法得到所述的含炔基交联基团的共轭聚合物,可以通过控制反应时间、反应温度、单体配比、反应压强、溶度、催化剂用量、配体比例、相转移催化剂等参数可以控制聚合物的分子量以及分散系数,合成路线可以如下图所示:
含乙炔基交联基团的多元(三元或者三元以上)共轭聚合物通用合成方法可以是先合成带有功能化的乙炔基交联基团的单体,多种(三种或者三种以上)单体通过过渡金属催化偶联(Suzuki Polymerization,Heck Polymerization,Sonogashira Polymerization,Still Polymerization)、Witting反应等聚合方法可以得到所述的含炔基交
联基团的共轭聚合物,通过控制反应时间、反应温度、单体配比、反应压强、溶度、催化剂用量、配体比例、相转移催化剂等参数可以控制聚合物的分子量以及分散系数,合成路线可以如下图所示:
对于有些特殊的聚合物反应,在聚合物反应过程所使用的某些特定化学试剂、温度等对交联基团乙炔基比较敏感,可使乙炔基团发生化学反应。例如,若聚合反应所需要的温度超过180℃,甚至超过280℃,可能超过380℃时,共轭聚合物侧链的交联基团在高温条件下,比较活泼,乙炔基交联基团就自身发生聚合反应,最终得到的聚合物不溶不熔,不具备溶液加工特性。以在特殊聚合反应条件下,可以先将乙炔交联基团的上的末端氢原子保护,使之化学反应活性降低。交联基团乙炔基末端氢原子最常见的保护基团可以为三甲基硅基(TMS),得到含三甲基硅基的聚合物前驱体后,聚合物前驱体可以通过碱溶液处理一定时间后即可得到目标共轭聚合物含乙炔基交联基团的共轭聚合物。优化后的共轭聚合物合成路线如下图所示:
含乙炔基交联基团的共轭有机单体的合成路线可以如下图所示,但不局限于采用以下路线合成目标化合物。初始原料A(商业化化学试剂或者通过化学方法合成)可以通过亲电任选取代反应(如氯化、溴化、碘化等卤化反应)得到化合物B,化合物B可以在Pd-Cu共催化剂的作用下与三甲基硅基乙炔发生Sonogashira偶联反应得到化合物C,化合物C可以在碱溶液中脱去三甲基硅基保护官能团,得到目标化合物D。
为了便于对本发明涉及的含乙炔基交联基团的共轭聚合物的理解,以下列举含乙炔基交联基团的共轭聚合物的例子,但不局限于这些聚合物,所列举的含乙炔基交联基团的共轭聚合物具有一个明显的特点,即乙炔基基团与共轭聚合物主链是直接相连或者通过共轭的芳香环或者芳香杂环链接在一起。
本发明还涉及一种混合物,其可以包括一种按照本发明的一个方面中所述的聚合物,及至少另一种有机功能材料。所述的有机功能材料,可以包括空穴(也称电洞)注入或传输材料(HIM/HTM),空穴阻挡材料(HBM),电子注入或传输材料(EIM/ETM),电子阻挡材料(EBM),有机基质材料(Host),单重态发光体(荧光发光体),重态发光体(磷光发光体),特别是发光有机金属络合物。各种有机功能材料的非限制性示例例如在WO2010135519A1,
US20090134784A1和WO 2011110277A1中的描述。有机功能材料可以是小分子和聚合物材料。下面对有机功能材料作一些较详细的描述(但不限于此)。
1.HIM/HTM
HTM前面已有所述,这里做些补充说明。
本发明的一个方面中所使用的合适的有机HIM/HTM材料可选包含有如下结构单元的化合物:酞菁,卟啉,胺,芳香胺,联苯类三芳胺,噻吩,并噻吩如二噻吩并噻吩和并噻吩,吡咯,苯胺,咔唑,氮茚并氮芴,及它们的衍生物。另外的合适的HIM也包括含有氟烃的聚合物;含有导电掺杂的聚合物;导电聚合物,如PEDOT/PSS;自组装单体,如含有膦酸和sliane衍生物的化合物;金属氧化物,如MoOx;金属络合物,和交联化合物等中的任一种或其组合。
其他可用作HTM或HIM的金属络合物的例子可以包括(但不限于)如下的一般结构:
M可以是金属,有大于40的原子量;
(Y1-Y2)是一两齿配体,Y1和Y2独立地选自C,N,O,P,和S;L是一个辅助配体;m是一整数,其值从1到此金属的最大配位数;m+n是此金属的最大配位数。
在一个实施例中,(Y1-Y2)可以是一2-苯基吡啶衍生物.
在另一个实施例中,(Y1-Y2)可以是一卡宾配体.
在另一个实施例中,M可以选自Ir,Pt,Os,和Zn.
在另一个方面,金属络合物的HOMO大于-5.5eV(相对于真空能级).
2.EIM/ETM/HBM
ETM前面已有说明,在此做补充说明。
本发明的一个方面中所使用的EIM/ETM材料的例子并不受特别的限制,任何金属络合物或有机化合物都可能被用作为EIM/ETM,只要它们可以传输电子。优选的有机EIM/ETM材料可选自三(8-羟基喹啉)铝(AlQ3),吩嗪,菲罗啉,蒽,菲,芴,二芴,螺二芴,对苯乙炔,三嗪,***,咪唑,芘,苝,反茚并芴,顺茚并,二苯并-茚并芴,茚并萘,苯并蒽及它们的衍生物中的任一种或其组合。
本发明的一个方面中所使用的空穴阻挡层(HBL)通常用来阻挡来自相邻功能层,特别是发光层的空穴。对比一个没有阻挡层的发光器件,HBL的存在通常会导致发光效率的提高。空穴阻挡层(HBL)的空穴阻挡材料(HBM)需要有比相邻功能层,如发光层更低的HOMO。在一个优选的实施方案中,HBM有比相邻发光层更大的激发态能级,
如单重态或三重态,取决于发光体.在另一个优选的实施方案中,HBM有电子传输功能.。通常具有深的HOMO能级的EIM/ETM材料可以做为HBM。
另一方面,可用作EIM/ETM的金属络合物的例子可以包括(但不限于)如下的一般结构:
(O-N)或(N-N)是一两齿配体,其中金属与O,N或N,N配位;L是一个辅助配体;m是一整数,其值从1到此金属的最大配位数。
在另一个优选的实施方案中,有机碱金属化合物可用作EIM。在本发明中,有机碱金属化合物可以理解为如下的化合物,其中至少有一个碱金属,即锂,钠,钾,铷,铯,并进一步包含至少一个有机配体。
本发明的一个方面中所使用的合适的有机碱金属化合物的非限制性例子可以包括US 7767317B2,EP 1941562B1和EP 1144543B1中所描述的化合物。
优选的有机碱金属化合物可以是下列化学式的化合物:
其中R1的含义如上所述,弧线代表两个或三个原子及键接,以便必要时与金属M形成5元或六元环,其中原子也可以由一个或多个R1任选取代,M为碱金属,选自锂,钠,钾,铷,铯。
有机碱金属化合物可以有单体的形式,如以上所述的,或有聚集体的形式,例如,两碱金属离子与两个配体,4碱金属离子和4配体,6碱金属离子和6配体或在其他的形式。
优选的有机碱金属化合物可以是下列化学式的化合物:
其中使用的符号有上述定义相同,另外:
o,每次出现时可以是相同或不同,是0,1,2,3或4;
p,每次出现时可以是相同或不同,是0,1,2或3;
在一个优选的实施方案中,碱金属M选自锂,钠,钾,更优选是锂或钠,最优选是锂。
在一个优选的实施方案中,有机碱金属化合物电子注入层中.更优选地,电子注入层由有机碱金属化合物组成。
在另一个优选的实施方案中,有机碱金属化合物掺杂到其他ETM中形成电子传输层或电子注入层中.更优选地,是电子传输层。
在下面的表中列出合适的有机碱金属化合物的非限制性例子:
3.三重态基质材料(Triplet Host):
本发明的一个方面中所使用的三重态基质材料的例子并不受特别的限制,任何金属络合物或有机化合物都可能被用作为基质,只要其三重态能量比发光体,特别是三重态发光体或磷光发光体更高。
可用作三重态基质(Host)的金属络合物的例子可以包括(但不限于)如下的一般结构:
M可以是金属;(Y3-Y4)可以是一两齿配体,Y3和Y4可以独立地选自C,N,O,P,和S;L可以是一个辅助配体;m可以是一整数,其值从1到此金属的最大配位数;m+n是此金属的最大配位数。
在一个优选的实施方案中,可用作三重态基质的金属络合物有如下形式:
(O-N)可以是一两齿配体,其中金属与O和N原子配位.
在某一个实施方案中,M可选自Ir和Pt.
可作为三重态基质的有机化合物的非限制性例子选自包含有环芳香烃基的化合物,如苯,联苯,三苯基,苯并,芴;包含有芳香杂环基的化合物,如二苯并噻吩,二苯并呋喃,dibenzoselenophene,呋喃,噻吩,苯并呋喃,苯并噻吩,benzoselenophene,咔唑,indolocarbazole,pyridylindole,pyrrolodipyridine,吡唑,咪唑,***类,恶唑,噻唑,恶二唑,oxatriazole,二恶唑,噻二唑,吡啶,哒嗪,嘧啶,吡嗪,三嗪类,oxazines,oxathiazines,oxadiazines,吲哚,苯并咪唑,吲唑,indoxazine,bisbenzoxazoles,benzisoxazole,苯并噻唑,喹啉,异喹啉,cinnoline,喹唑啉,喹喔啉,萘,酞,蝶啶,氧杂蒽,吖啶,吩嗪,吩噻嗪,phenoxazines,benzofuropyridine,furodipyridine,benzothienopyridine,thienodipyridine,benzoselenophenopyridine和selenophenodipyridine;包含有2至10环结构的基团,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。其中,每个Ar可以进一步被任选取代,取代基可选为氢,烷基,烷氧基,氨基,烯,炔,芳烷基,杂烷基,芳基和杂芳基中的任一种或其组合。
在一个优选的实施方案中,三重态基质材料可选自包含至少一个以下基团的化合物:
R1-R7可相互独立地选自如下的基团:氢,烷基,烷氧基,氨基,烯,炔,芳烷基,杂烷基,芳基和杂芳基,当它们是芳基或杂芳基时,它们可以与上述的Ar1和Ar2意义相同;n可以是一个从0到20的整数;X1-X8可以选自CH或N;X9可以选自CR1R2或NR1。
在下面的表中列出合适的三重态基质材料的非限制性例子:
4.单重态基质材料(Singlet Host):
本发明的一个方面中所使用的单重态基质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基质,只要其单重态能量比发光体,特别是单重态发光体或荧光发光体更高。
作为单重态基质材料使用的有机化合物的非限制性例子可选自含有环芳香烃化合物,如苯,联苯,三苯基,苯并,萘,蒽,phenalene,菲,芴,芘,屈,苝,薁;芳香杂环化合物,如二苯并噻吩,二苯并呋喃,dibenzoselenophene,呋喃,噻吩,苯并呋喃,苯并噻吩,benzoselenophene,咔唑,indolocarbazole,pyridylindole,Pyrrolodipyridine,吡唑,咪唑,三氮唑,异恶唑,噻唑,恶二唑,oxatriazole,二恶唑,噻二唑,吡啶,哒嗪,嘧啶,吡嗪,三嗪,恶嗪,oxathiazine,oxadiazine,吲哚,苯并咪唑,吲唑,indoxazine,苯并恶唑,benzisoxazole,苯并噻唑,喹啉,异喹啉,cinnoline,喹唑啉,喹喔啉,萘,酞,蝶啶,氧杂蒽,吖啶,吩嗪,吩噻嗪,吩恶嗪,benzofuropyridine,furodipyridine,benzothienopyridine,thienodipyridine,benzoselenophenopyridine和selenophenodipyridine;包含有2至10环结构的基团,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。
在一个优选的实施方案中,单重态基质材料可选自包含至少一个以下基团的化合物:
R1可相互独立地选自如下的基团:氢,烷基,烷氧基,氨基,烯,炔,芳烷基,杂烷基,芳基和杂芳基;Ar1是芳基或杂芳基,它与上述的HTM中定义的Ar1意义相同;
n是一个从0到20的整数;X1-X8选自CH或N;X9和X10选自CR1R2或NR1。
在下面的表中列出合适的单重态基质材料的非限制性例子:
5.空穴阻挡材料(HBM)
本发明的一个方面中所使用的空穴阻挡层(HBL)通常用来阻挡来自相邻功能层,特别是发光层的空穴。对比一个没有阻挡层的OLED,HBL的存在通常会导致发光效率的提高。空穴阻挡层(HBL)的空穴阻挡材料(HBM)需要有比相邻功能层,如发光层更低的HOMO.在一个优选的实施方案中,HBM有比相邻发光层更大的激发态能级,如单重态或三重态,取决于发光体.在另一个优选的实施方案中,HBM有电子传输功能.
在一个实施方案中,所用HBM含有与发光层中基质材料相同的分子。
在另一个优选的实施方案中,HBM可选自包含至少一个以下基团的化合物:
n可以是一个从0到20的整数;L可以是一个辅助配体;m可以是一个从1到3的整数.
6.单重态发光体(Singlet Emitter)
本发明的一个方面中所使用的单重态发光体往往有较长的共轭π电子***。迄今,已有许多例子,例如但不限于,苯乙烯胺(styrylamine)及其衍生物中的任一种或其组合,和茚并芴(indenofluorene)及其衍生物中的任一种
或其组合.
在一个优选的实施方案中,单重态发光体可选自一元苯乙烯胺(monostyrylamines),二元苯乙烯胺(distyrylamines),三元苯乙烯胺(tristyrylamines),四元苯乙烯胺(tetrastyrylamines),苯乙烯膦(styrylphosphines),苯乙烯醚(styryl ethers)和芳胺(arylamines)中的任一种或其组合。
一元苯乙烯胺是指一化合物,它包含无任选取代或任选取代的苯乙烯基组和至少一个胺,最优选是芳香胺。二元苯乙烯胺是指一化合物,它包含二个无任选取代或任选取代的苯乙烯基组和至少一个胺,最优选是芳香胺。三元苯乙烯胺是指一化合物,它包含三个无任选取代或任选取代的苯乙烯基组和至少一个胺,最优选是芳香胺。四元苯乙烯胺是指一化合物,它包含四个无任选取代或任选取代的苯乙烯基组和至少一个胺,最优选是芳香胺。优选的苯乙烯是二苯乙烯,其可能会进一步被任选取代。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任选取代或任选取代的芳香环或杂环***。这些芳香族或杂环的环***中至少有一个优选选自稠环***,并最优选有至少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。芳香蒽胺是指一化合物,其中一个二元芳基氨基团(diarylamino)直接联到蒽上,最优选是在9的位置上。芳香蒽二胺是指一化合物,其中二个二元芳基氨基团(diarylamino)直接联到蒽上,最优选是在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,其中二元芳基氨基团最优选联到芘的1或1,6位置上.
基于乙烯胺及芳胺的单重态发光体的非限制性例子,也是优选的例子,可在下述专利文件中找到:WO 2006/000388,WO 2006/058737,WO 2006/000389,WO 2007/065549,WO 2007/115610,US 7250532B2,DE 102005058557 A1,CN 1583691 A,JP 08053397 A,US 6251531 B1,US 2006/210830 A,EP 1957606 A1和US 2008/0113101 A1。
基于均二苯乙烯(distyrylbenzene)及其衍生物的单重态发光体的非限制性例子有US 5121029.
进一步的优选的单重态发光体可选自茚并芴-胺和茚并芴-二胺,苯并茚并芴-胺(benzoindenofluorene-amine)和苯并茚并芴-二胺(benzoindenofluorene-diamine),二苯并茚并芴-胺(dibenzoindenofluorene-amine)和二苯并茚并芴-二胺(dibenzoindenofluorene-diamine),。
其他可用作单重态发光体的材料包括但不限于多环芳烃化合物,特别是如下化合物的衍生物:蒽如9,10-二(2-萘并蒽)(9,10-di(2-naphthylanthracene)),萘,四苯,氧杂蒽,菲(phenanthrene),芘(perylene)如2,5,8,11-tetra-t-butylperylene,茚并芘(indenoperylene),苯撑(phenylenes)如(4,4’-(bis(9-ethyl-3-carbazovinylene)-1,1’-biphenyl),periflanthene,十环烯(decacyclene),六苯并苯(coronene),芴,螺二芴(spirofluorene),芳基芘(arylpyrene)(如US20060222886),亚芳香基乙烯(arylenevinylene)(如US5121029,US5130603),环戊二烯如四苯基环戊二烯(tetraphenylcyclopentadiene),红荧烯(rubrene),香豆素(coumarine),若丹明(rhodamine),喹吖啶酮(quinacridone),吡喃(pyrane)如4(dicyanoethylene)-6-(4-dimethylaminostyryl-2-methyl)-4H-pyrane(DCM),噻喃(thiapyran),bis(azinyl)imine-boron化
合物(US 2007/0092753 A1),bis(azinyl)methene化合物,carbostyryl化合物,噁嗪酮(oxazone),苯并恶唑(benzoxazole),苯并噻唑(benzothiazole),苯并咪唑(benzimidazole)及diketopyrrolopyrrole中的任一种或其组合。一些单重态发光体的材料的非限制性的例子可在下述专利文件中找到:US 20070252517 A1,US 4769292,US 6020078,US 2007/0252517 A1,US 2007/0252517 A1。
在下面的表中列出一些合适的单重态发光体的非限制性例子:
7.三重态发光体(Triplet Emitter)
本发明的一个方面中所使用的三重态发光体也称磷光发光体。在一个优选的实施方案中,三重态发光体可以是有通式M(L)n的金属络合物,其中M可以是一金属原子,L每次出现时可以是相同或不同,是一有机配体,它可以通过一个或多个位置键接或配位连接到金属原子M上,n可以是一个大于1的整数,较优选选是1,2,3,4,5或6。可选地,这些金属络合物可以通过一个或多个位置联接到一个聚合物上,最优选是通过有机配体。
在一个优选的实施方案中,金属原子M可以选自过渡金属元素或镧系元素或锕系元素,优选Ir,Pt,Pd,Au,Rh,Ru,Os,Sm,Eu,Gd,Tb,Dy,Re,Cu或Ag,特别优选Os,Ir,Ru,Rh,Re,Pd,Pt。
优选地,三重态发光体包含有螯合配体,即配体,通过至少两个结合点与金属配位,特别优选考虑的是三重态发光体包含有两个或三个相同或不同的双齿或多齿配体。螯合配体有利于提高金属络合物的稳定性。
有机配体的非限制性例子可选自苯基吡啶(phenylpyridine)衍生物,7,8-苯并喹啉(7,8-benzoquinoline)衍生物,
2(2-噻吩基)吡啶(2(2-thienyl)pyridine)衍生物,2(1-萘基)吡啶(2(1-naphthyl)pyridine)衍生物,或2苯基喹啉(2phenylquinoline)衍生物。所有这些有机配体都可能被任选取代,例如被含氟或三氟甲基任选取代。辅助配体可优选选自乙酸丙酮(acetylacetonate)或苦味酸。
在一个优选的实施方案中,可用作三重态发光体的金属络合物可以有如下形式:
其中M是一金属,选自过渡金属元素或镧系元素或锕系元素;
Ar1每次出现时可以是相同或不同,是一个环状基团,其中至少包含有一个施主原子,即有一孤对电子的原子,如氮或磷,通过它环状基团与金属配位连接;Ar2每次出现时可以是相同或不同,是一个环状基团,其中至少包含有一个C原子,通过它环状基团与金属连接;Ar1和Ar2由共价键联接在一起,可各自携带一个或多个取代基团,它们也可再通过取代基团联接在一起;L每次出现时可以是相同或不同,是一个辅助配体,优选自双齿螯合配体,最优选是单阴离子双齿螯合配体;m是1,2或3,优选地是2或3,特别优选地是3;n是0,1,或2,优选地是0或1,特别优选地是0;
一些三重态发光体的材料极其应用的非限制性例子可在下述专利文件和文献中找到:WO 200070655,WO 200141512,WO 200202714,WO 200215645,EP 1191613,EP 1191612,EP 1191614,WO 2005033244,WO 2005019373,US 2005/0258742,WO 2009146770,WO 2010015307,WO 2010031485,WO 2010054731,WO 2010054728,WO 2010086089,WO 2010099852,WO 2010102709,US 20070087219 A1,US 20090061681 A1,US 20010053462 A1,Baldo,Thompson et al.Nature 403,(2000),750-753,US 20090061681 A1,US 20090061681 A1,Adachi et al.Appl.Phys.Lett.78(2001),1622-1624,J.Kido et al.Appl.Phys.Lett.65(1994),2124,Kido et al.Chem.Lett.657,1990,US 2007/0252517 A1,Johnson et al.,JACS 105,1983,1795,Wrighton,JACS 96,1974,998,Ma et al.,Synth.Metals 94,1998,245,US 6824895,US 7029766,US 6835469,US 6830828,US 20010053462 A1,WO 2007095118 A1,US 2012004407A1,WO 2012007088A1,WO2012007087A1,WO 2012007086A1,US 2008027220A1,WO 2011157339A1,CN 102282150A,WO 2009118087A1。
在下面的表中列出一些合适的三重态发光体的非限制性例子:
8.聚合物
在某些实施例中,以上所述的有机功能材料,包括HIM,HTM,ETM,EIM,Host,荧光发光体,磷光发光体都可以是聚合物的形式。
在一个优选的实施例中,适合于本发明的聚合物是共轭聚合物。一般地,共轭聚合物可以有如下通式:
其中B,A在多次出现时可独
立选择相同或不同的结构单元
B:具有较大的能隙的π-共轭结构单元,也称骨干单元(Backbone Unit),选自单环或多环芳基或杂芳基,优选的单元形式为苯,联二亚苯(Biphenylene),萘,蒽,菲,二氢菲,9,10-二氢菲,芴,二芴,螺二芴,对苯乙炔,反茚并芴,顺茚并,二苯并-茚并芴,茚并萘及它们的衍生物中的任一种或其组合。
A:具有较小能隙的π-共轭结构单元,也称功能单元(Functional Unit),按照不同的功能要求,可选自包含有以上所述的空穴注入或传输材料(HIM/HTM),空穴阻挡材料(HBM),电子注入或传输材料(EIM/ETM),电子阻挡材料(EBM),有机基质材料(Host),单重态发光体(荧光发光体),重态发光体(磷光发光体)的结构单元中的任一种或其组合。
x,y:>0,且x+y=1;
发光聚合物的非限制性例子在如下的专利申请中公开:WO2007043495,WO2006118345,WO2006114364,WO2006062226,WO2006052457,WO2005104264,WO2005056633,WO2005033174,WO2004113412,
WO2004041901,WO2003099901,WO2003051092,WO2003020790,WO2003020790,US2020040076853,US2020040002576,US2007208567,US2005962631,EP201345477,EP2001344788,DE102004020298。
在另一个实施例中,适合于本发明的聚合物可以是非共轭聚合物。这可以是所有功能基团都在侧链上,而主链是非共轭的聚合物。一些用作磷光主体或磷光发光材料的这类非共轭聚合物的非限制性示例可参见在US 7250226 B2,JP2007059939A,JP2007211243A2和JP2007197574A2等专利申请中的公开,一些用作荧光发光材料的这类非共轭聚合物的非限制性示例可参见在JP2005108556,JP2005285661和JP2003338375等专利申请中的公开。另外,非共轭聚合物也可以是一种聚合物,主链上共轭的功能单元通过非共轭的链接单元链接起来,这种聚合物的非限制性例子在DE102009023154.4和DE102009023156.0中有公开。
本发明还涉及一种组合物,其可以包含有一种按照本发明的一个方面中所述的共轭有机聚合物及至少一种有机溶剂。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。
在一个优选的实施方案中,按照本发明的一个方面中所述的组合物是一溶液。
在另一个优选的实施方案中,按照本发明的一个方面中所述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0.01至20wt%的有机混合物,较优选的是0.1至15wt%,更优选的是0.2至10wt%,最优选的是0.25至5wt%的有机混合物。
本发明还涉及所述组合物作为涂料或印刷油墨在制备有机电子器件时的用途,特别优选的是通过打印或涂布的制备方法。
其中,适合的打印或涂布技术可以包括(但不限于)喷墨打印,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,狭缝型挤压式涂布等。首选的是喷墨印刷,丝网印刷及凹版印刷。溶液或悬浮液可以另外包括一个或多个组份例如表面活性化合物,润滑剂,润湿剂,分散剂,疏水剂,粘接剂等,用于调节粘度,成膜性能,提高附着性等。有关打印技术,及其对有关溶液的相关要求,如溶剂及浓度,粘度等,的详细信息请参见Helmut Kipphan主编的《印刷媒体手册:技术和生产方法》(Handbook of Print Media:Technologies and Production Methods),ISBN 3-540-67326-1。
基于上述聚合物,本发明还提供一种如上所述的聚合物的应用,即将所述聚合物应用于有机电子器件,所述的有机电子器件可选自,但不限于,有机发光二极管(OLED)、有机光伏电池(OPV)、有机发光电池(OLEEC)、有机场效应管(OFET)、有机发光场效应管、有机激光器,有机自旋电子器件,有机传感器及有机等离激元发射二极管(Organic Plasmon Emitting Diode),特别是OLED。在一个特别优选的实施例中,按照本发明的一个方面中所述的聚合物用于有机电子器件的电荷传输层,特别是空穴传输层。
本发明进一步涉及一种有机电子器件,其可以至少包含一种如上所述的聚合物。一般地,此种有机电子器件可以至少包含阴极,阳极及位于阴极和阳极之间的功能层,其中所述的功能层中可以至少包含一种如上所述的聚合物。
在一个优选的实施例中,以上所述的有机电子器件是一种电致发光器件,其中可以包括基片,阳极,至少一个发光层,和阴极。在一个特别优选的实施例中,以上所述的有机电子器件可以是OLED。
基片可以是不透明或透明。透明的基板可以用来制造透明的发光元器件。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。最优选是基片有平滑的表面。无表面缺陷的基板是特别理想的选择。在一个优选的实施例中,基片是柔性的,可选自聚合物薄膜或塑料,其玻璃化温度Tg为150℃以上,较优选是超过200℃,更优选是超过250℃,最优选是超过300℃。合适的柔性基板的非限制性例子有聚(对苯二甲酸乙二醇酯)(PET)和聚乙二醇(2,6-萘)(PEN)。
阳极可包括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。在一个实施例中,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可以小于0.5eV,较优选是小于0.3eV,最优选是小于0.2eV。阳极材料的非限制性例子可以包括但不限于: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,阳极可以是图案结构化的。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。
阴极可包括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。在一个实施例中,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可以小于0.5eV,较优选是小于0.3eV,最优选是小于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。阴极材料的例子可以包括但不限于:Al、Au、Ag、Ca、Ba、Mg、LiF/Al、MgAg合金、BaF2/Al、Cu、Fe、Co、Ni、Mn、Pd、Pt、ITO等中的任一种或其组合。阴极材料可以使用任何合适的技术沉积,如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。
OLED还可以包含其他功能层,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)中的任一种或其组合。适合用于这些功能层中的材料在WO2010135519A1、US20090134784A1和WO2011110277A1中有详细的描述。
在一个优选的实施例中,按照本发明的一个方面中所述的发光器件中,其发光层可以是通过打印本发明的组
合物制备而成。
按照本发明的一个方面中所述的发光器件,其发光波长可以在300到1000nm之间,较优选的是在350到900nm之间,更优选的是在400到800nm之间。
本发明还涉及按照本发明的一个方面中所述的有机电子器件在各种电子设备中的应用,包括,但不限于,显示设备,照明设备,光源,传感器等等。
本发明还涉及包含有按照本发明的一个方面中所述的有机电子器件的电子设备,包括,但不限于,显示设备,照明设备,光源,传感器等等。
下面将结合优选实施例对本发明进行了说明,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。
具体实施例
实施例1
2,5一二苯基对二甲苯(3)的合成:
在250ml三口圆底烧瓶中加入26.40g(0.1mol)2,5-二溴对二甲苯和24.39g(0.2mmol)苯硼酸,加入250ml甲苯,搅拌使其溶解,再依次加入50ml水和21.2g Na2CO3(0.2mol),搅拌至固体全部溶解,加入0.5ml Aliquat 336和75mg三苯基膦四合钯催化剂(0)(PPh3)4Pd,通氮气保护10min后加热至回流(92-100℃),回流20min后关闭氮气保持***密封,回流反应过夜,冷却后用甲苯萃取反应液(50mlx4),合并有机相,依次用NaCl饱和溶液和水洗涤,蒸除溶剂干燥得白色晶体22.48g,理论值25.84g,产率约为87%。M.P.180-181℃(lit.180℃),1H NMR(CDCl3,400MHz,ppm):δ7.44-7.30(m,10H),7.14(s,2H),2.26(s,6H).
2,5-二苯基对二甲酸(4)的合成:
250ml三口圆底烧瓶中加机械搅拌,加入12.92g(0.05mol)2,5-二苯基对二甲苯,加入250ml吡啶,搅拌使其溶解,再依次加入30ml水和39.51g高锰酸钾(KMnO4)(0.25mol),加热回流(约105-110℃)反应2h后,每回流30min后冷却加入60ml水和15.59高锰酸钾(KMnO4)(0.1mol),共重复四次。再每回流6h后冷却加入60ml水,重复四次。反应完毕趁热过滤,滤饼用开水冲洗(1000mlx4),合并滤液,蒸除溶剂至约100ml时加入50ml浓盐酸,冷却过滤,冷水洗涤,真空干燥得白色固体9.21g,理论值15.92g,产率约为57.9%。M.P.281-282℃(lit.282℃),1H NMR(DMSO-d6,400MHz,ppm):δ7.67(s,2H),7.46-7.38(m,10H).
6,12-吲哚芴二酮(5)的合成
向500ml三口圆底烧瓶中加入100ml浓硫酸,搅拌下缓慢加入3.18g 2,5-二苯基对二甲酸(0.01mol),室温反应0.5h后加入5-10滴发烟硫酸,反应6h后将反应液倒入冰水混合液中,同时用玻璃棒搅拌。抽滤混合液,大量水洗涤,干燥得暗红色固体1.95g,理论值2.82g,产率约69%。M.P.>300℃(lit.>300℃),1H NMR(CDCl3,400MHz,ppm):δ7.79(s,2H),7.68(d,J=7.36Hz,2H),7.57-7.51(m,4H),7.37-7.29(m,2H).
吲哚芴(6)的合成
向500ml三口圆底烧瓶中加入5.64g 6,22-吲哚芴二酮(0.02mol),搅拌下依次缓慢加入300ml一缩二乙二醇和4ml水合肼(85%),再加入经研磨成细粉的28.10g KOH(0.5mol),通氮气保护10min后加热至回流(195℃),反应48h后冷却倒入碎冰/浓盐酸(v:v=8:1)混合液中,同时用玻璃棒搅拌。抽滤混合液,水洗涤,干燥得土黄灰色固体2.29g,理论值5.09g,产率45%。M.P.300-301℃(lit.300-302℃),1H NMR(DMSO-d6,400MHz,ppm):δ8.09(s,2H),7.93(d,J=7.4Hz,2H),7.59(d,J=7.4Hz,2H),7.39(t,J=7.4Hz,2H),7.31(t,J=7.4Hz,2H),3.99(s,4H).
6,6,12,12-四辛基吲哚芴(7)的合成
在250ml长颈三口圆底烧瓶中加入转子,加入1.27g吲哚芴(6),中间加高真空活塞(石蜡封口),两边加反口胶塞,在用风机加热***同时用油泵将烧瓶抽真空。用注射器将100ml干燥的THF加入烧瓶。在-78℃下边搅拌边用注射器向烧瓶中滴加6ml 2.87M正丁基锂(17.22mmol),在氮气保护下反应l h。将***升至室温反应30min后再降至-78℃,用注射器加入3.82g的1-溴辛烷(n-C8H17Br,20mmol),在-78℃下反应1h后自然升至室温反应过夜。向烧瓶中加入约30ml水使反应淬灭,反应液用石油醚萃取(50mlx4),合并有机相后用无水Na2SO4干燥,蒸除溶剂后柱层析提纯(100-200目硅胶/石油醚)。在甲醇中重结晶得米黄色晶体1.68g,理论值3.52g,产率约47.7%。1H NMR(CDCl3,400MHz,ppm):δ7.72(d,J=6.8Hz,2H),7.58(s,2H),7.33-7.24(m,6H),1.99(t,J=8.0Hz,8H),1.12-0.98(m,24H),0.76-0.59(m,20H);13C NMR(CDCl3,100MHz,ppm):δ151.08,149.92,141.48,140.50,126.59,122.81,119.30,113.81,54.66,40.67,31.50,29.69,23.67,22.51,13.96.
2,7-二溴-6,6,12,12-四辛基吲哚芴(8)的合成
在250ml三口圆底烧瓶中加入转子和7.03g 6,6,12,12-四辛基吲哚芴(10mmol),加入100ml CCl4,搅拌使其溶解,加入40g Al2O3/CuBr(0.25mol),回流反应18h。将反应物过滤,滤液用水洗涤,用无水Na2SO4干燥。蒸出溶剂,所得固体在甲醇中重结晶,得白色晶体3.73g,理论值8.61g,产率约为43.3%。1H NMR(CDCl3,400MHz,ppm):δ7.57(d,J=8.4Hz,2H),7.52(s,2H),7.45(s,2H),7.44(d,J=8.4Hz,2H),1.97(t,J=8.2Hz,8H),1.11-0.96(m,24H),0.75-0.58(m,20H);13C NMR(CDCl3,100MHz,ppm):δ153.12,149.68,140.12,139.72,129.69,125.97,120.73,120.63,113.84,55.13,40.60,31.58,29.71,23.76,22.62,14.11。
2,8-双(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-二基)-6,6,12,12一四辛基吲哚芴(DBO-IF)的合成
在250ml长颈三口圆底烧瓶中加入转子,中间加高真空活塞,两边加翻口塞。在用风机加热***同时用油泵将烧瓶抽真空。将4.31g 2,8-二溴-6,6,12,12一四辛基吲哚芴(5mmol)溶于120mlTHF中用注射器加入烧瓶,在-78℃下搅拌20min后再用注射器向烧瓶中滴加6ml2.87M正丁基锂(17.22mmol),在氮气保护下反应2h再用注射器加入5ml 2-异丙基-4,4,5,5-四甲基-1,3,2-二氧杂硼烷,在-78℃下反应2h后自然升至室温反应过夜。向烧瓶中加入约30ml水使反应淬灭,反应液用***萃取(50mLx4),合并有机相后用无水Na2SO4,干燥,蒸除溶剂后柱层析提纯(100-200目
硅胶/石油醚:乙酸乙酯v:v=9:1),得白色晶体1.18g,理论值4.78g,产率约为24.7%。1H NMR(CDCl3,400MHz,ppm):δ7.75(d,J=7.7Hz,2H),7.71(d,J=7.3Hz,2H),7.70(s,2H),7.59(s,2H)4.19(t,J=5.3Hz,8H),2.08(t,J=5.3Hz,4H),2.01(q,J=6.4Hz,8H),1.07-0.96(m,24H),0.68(t,J=7.0Hz,12H),0.58(t,J=6.7Hz,8H);13C NMR(CDCl3,100MHz,ppm):δ150.49,150.15,143.94,140.83,132.35,127.75,118.59,114.17,61.99,54.58,40.64,31.51,29.71,27.42,23.65,22.52,13.96。
4-溴三苯胺的合成
向500ml三口圆底烧瓶中加入49g三苯胺(0.2mol),搅拌下依次缓慢加入300ml N,N-二甲基甲酰胺,再分批缓慢加入经研磨成细粉的N-溴代丁二酰亚胺34.10g(0.2mol),通氮气保护后在室温避光下反应48h后冷却倒入碎冰中,用二氯甲烷萃取三次,合并有机相,水洗3次,浓缩,采用200-300目硅胶柱进行分离,淋洗剂为石油醚。得到58g,理产率90%。
4-三甲基硅基乙炔基三苯胺的合成
在500mL的两颈圆底烧瓶中,一次加入4-溴三苯胺(12.00g,40.00mmol),CuI(0.052g,0.28mmol),(Ph3P)2PdCl2(0.475g,0.68mmol),200mL脱气甲苯、60mL脱气二异丙胺,搅拌使其中固体溶解、混合均匀。在氩气保护、室温条件下逐滴滴加三甲基乙炔基硅(4.32g,44.0mmol)的二异丙胺溶液(30mL)。滴加完毕,反应液温度升至70℃,氩气保护条件下反应6小时。用薄层色谱监测反应程度,反应结束后将反应液冷却至室温,抽滤除去固体盐等杂质。粗产物用柱色谱(硅胶柱,淋洗剂为石油醚)进行分离提纯,进一步采用甲醇重结晶得到白色固体、过滤、真空干燥得到9.58克,产率为70%。
4,4-二溴-4’-三甲基硅基乙炔基三苯胺的合成
向500ml三口圆底烧瓶中加入6g 4-三甲基硅基乙炔基三苯胺(0.02mol),搅拌下依次缓慢加入300ml N,N-二甲基甲酰胺,再分批缓慢加入经研磨成细粉的N-溴代丁二酰亚胺6.810g(0.04mol),通氮气保护后在室温避光下反应48h后冷却倒入碎冰中,用二氯甲烷萃取三次,合并有机相,水洗3次,浓缩,采用200-300目硅胶柱进行分离,淋洗剂为石油醚。得到5.6g,理产率90%。
聚合物P1的合成
在25mL的两颈圆底烧瓶中,加入195mg(0.5mmol)单体4,4-二溴-4’-三甲基硅基乙炔基三苯胺,418mg(0.5mmol)单体2,8-双(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-二基)-6,6,12,12一四辛基吲哚芴,10mg Pd(PPh3)4,10mL脱气甲苯、4mL脱气四氢呋喃和2mL质量分数20%的氢氧化四乙基铵水溶液,均匀搅拌,通氩气15分钟。反应在氩气保护110℃条件下反应24小时,依次加入50μL溴苯回流反应2小时、20mg苯硼酸回流反应2小时,反应完冷却至室温后,将反应液逐滴滴加到甲醇中沉淀。得到的絮状沉淀物过滤,真空干燥后所得聚合物重新溶于约30mL四氢呋喃中,所得四氢呋喃溶液用孔径为0.45μm的聚四氟乙烯(PTFE)滤头过滤,减压蒸馏浓缩后
逐滴滴加到甲醇中沉淀,真空干燥、得到浅黄色固体392mg,产率74%。GPC(四氢呋喃,聚苯乙烯标准样品)Mn=21 000g mol-1,PDI=1.8。
聚合物P2的合成
往聚合物P1(392mg)的四氢呋喃(200mL)溶液中加入15mL 20wt%的氢氧化钾水溶液,随后加入20mL甲醇稀释反应液。在氩气保护、常温条件下均匀搅拌反应1小时。反应结束后将反应液倒入冰水中,经三氯甲烷萃取,油层分别用水、饱和氯化钠水溶液洗涤,浓缩得到粗产物。粗产物用柱色谱(硅胶柱,淋洗剂为石油醚)进行分离提纯,进一步采用甲醇重结晶得到白色固体、过滤、真空干燥得到352mg,产率为80%。GPC(四氢呋喃,聚苯乙烯标准样品)Mn=21 000g mol-1,PDI=1.8。
实施例2
实施例1所制备的聚合物P2作为空穴传输材料在有机/聚合物电致发光器件O/PLEDs(ITO阳极/空穴传输层/发光层/电子传输层/铝阴极)中的应用
将ITO导电玻璃、约20欧/平方厘米得方块电阻预切成15毫米×15毫米方片。依次用丙酮、微米级半导体专用洗涤剂、去离子水、异丙醇超声清洗,氮气吹哨后置于恒温烘箱备用。使用前,ITO玻璃片在氧等离子体刻蚀仪中以等离子体轰击10分钟。PEDOT:PSS水分散液(约1%)CleviosTM PEDOT:PSS Al4083作为缓冲层以匀胶机(KW-4A)高速旋涂,厚度由溶液浓度和转速决定,用表面轮廓仪(Tritek公司Alpha-Tencor-500型)实测监控。成膜后,于恒温真空烘箱中驱除残余溶剂。在ITO基片上PEDOT:PSS的膜厚为80纳米。实施例1所合成的聚合物P2溶于甲苯溶液浓度为5mg/ml,在PEDOT:PSS膜上旋涂聚合物P2,厚度为20纳米,于加热板上加热至200℃反应30min,使聚合物P2发生交联反应。之后将聚合物P2膜用甲苯冲洗,测得厚度为18-19纳米,表明交联反应有效,聚合物P2膜固化比较完全。将荧光共轭聚合物P-PPV(P-PPV为发绿光材料)或MEH-PPV(MEH-PPV为发橙红光材料)于干净瓶中称量后,转入氮气保护成膜专用手套箱,在甲苯中溶解,以0.45微米滤膜过滤。在空穴传输层聚合物P2膜上旋涂荧光聚合物,聚合物发光层最佳厚度为80纳米。膜厚用Alpha-Tencor-500表面轮廓仪测定。随后在真空蒸镀条件上得到约2-5nm CsF作为电子注入/传输层上。在电子传输层上真空蒸镀铝(100纳米)作阴极。器件的发光区域有掩膜于ITO交互盖的区域确定为0.04平方厘米。所有制备过程均在提供氮气氛围的手套箱内进行。器件的电流-电压特性,发光强度和外量子效率由Keithley236电流电压-测量***及一个经校正的硅光二极管测得。
Claims (14)
- 根据权利要求1所述的含乙炔基交联基团的共轭聚合物,其特征在于,Ar1、Ar2在多次出现时可相同或者不同地独立选自如下结构基团中的任一种或其组合:环芳香基团,包括苯、联苯、三苯基、苯并、芴、吲哚芴类化合物中的任一种或其组合;和芳香杂环基团,包括三苯胺、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、pyrrolodipyridine、吡唑、咪唑、***类、恶唑、噻唑、恶二唑、恶***、二恶唑、噻二唑、吡啶、哒嗪、嘧啶、吡嗪、三嗪类、恶嗪,恶噻嗪、oxadiazines、吲哚、苯并咪唑、吲唑、indoxazine、bisbenzoxazoles、异恶唑、苯并噻唑、喹啉、异喹啉、cinnoline、喹唑啉、喹喔啉、萘、酞、蝶啶、氧杂蒽、吖啶、吩嗪、吩噻嗪、phenoxazines、benzofuropyridine、furodipyridine、benzothienopyridine、thienodipyridine、benzoselenophenopyridine和selenophenodipyridine中的任一种或其组合。
- 根据权利要求1-2中任一个所述的含乙炔基交联基团的共轭聚合物,其特征在于,所述环芳香烃基团和芳香杂环基团进一步被任选取代,取代基选自氢、氘,烷基、烷氧基、氨基、烯基、炔基、芳烷基、杂烷基、芳基和杂芳基中的任一种或其组合。
- 根据权利要求1-3中任一个所述的含乙炔基交联基团的共轭聚合物,其特征在于,所述Ar1为聚合物主链结构单元,所述的聚合物主链结构单元可以选自苯、联苯、三苯基、苯并、芴、吲哚芴、咔唑、吲哚咔唑、二苯并噻咯、二噻吩并环戊二烯、二噻吩并噻咯、噻吩、蒽、萘、苯并二噻吩、苯并呋喃、苯并噻吩、苯并硒吩类化合物中的任一种或其组合。
- 根据权利要求1-4中任一个所述的含乙炔基交联基团的共轭聚合物,其特征在于,所述Ar2为空穴传输单元,所述空穴传输单元选自芳香胺、三苯胺、萘胺、噻吩、咔唑、二苯并噻吩、二噻吩并环戊二烯、二噻吩并噻咯、二苯并硒吩、呋喃、噻吩、苯并呋喃、苯并噻吩、苯并硒吩、咔唑、吲哚咔唑及其衍生物中的任一种或其组合。
- 根据权利要求1-5中任一个所述的含乙炔基交联基团的共轭聚合物,其特征在于,所述Ar2选自电子传输 单元,所述电子传输单元选自吡唑、咪唑、***类、恶唑、噻唑、恶二唑、恶***、二恶唑、噻二唑、吡啶、哒嗪、嘧啶、吡嗪、三嗪类、恶嗪,恶噻嗪、oxadiazines、吲哚、苯并咪唑、吲唑、indoxazine、bisbenzoxazoles、异恶唑、苯并噻唑、喹啉、异喹啉、cinnoline、喹唑啉、喹喔啉、萘、酞、蝶啶、氧杂蒽、吖啶、吩嗪、吩噻嗪、phenoxazines、benzofuropyridine、furodipyridine、benzothienopyridine、thienodipyridine、benzoselenophenopyridine和selenophenodipyridine类化合物中的任一种或其组合。
- 根据权利要求1-6中任一个所述的含乙炔基交联基团的共轭聚合物,其特征在于,所述R3选自具有1-30个碳原子的烷基、具有1-30个碳原子的烷氧基、氨基、烯基、炔基、芳烷基、杂烷基、芳基和杂芳基中的任一种或其组合。
- 根据权利要求8所述的含乙炔基交联基团的共轭聚合物,其中Ar1,Ar2和Ar2-1中至少有一个选自空穴传输单元,及至少有一个选自电子传输单元。
- 一种混合物,其特征在于,包括如权利要求1至9任一项所述的含乙炔基交联基团的共轭聚合物,及至少一种有机功能材料,所述有机功能材料选自空穴注入材料,空穴传输材料,电子传输材料,电子注入材料,电子阻挡材料,空穴阻挡材料,发光材料,主体材料中的任一种或其组合。
- 一种组合物,其特征在于,包括如权利要求1至9任一项所述的含乙炔基交联基团的共轭聚合物或其混合物,及至少一种有机溶剂。
- 根据权利要求1至9任一项所述的含乙炔基交联基团的共轭聚合物或其混合物在有机电子器件中的应用。
- 一种有机电子器件,其特征在于,包括如权利要求1-9任一项所述的含乙炔基交联基团的共轭聚合物或其混合物。
- 根据权利要求14所述的有机电子器件,其特征在于,所述有机电子器件选自有机发光二极管、有机光伏电池、有机发光电池、有机场效应管、有机发光场效应管、有机激光器、有机自旋电子器件、有机传感器、有机等离激元发射二极管及钙钛矿太阳能电池。
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CN107108862B (zh) | 2019-08-02 |
US10364316B2 (en) | 2019-07-30 |
EP3246347A4 (en) | 2018-08-22 |
EP3246347A1 (en) | 2017-11-22 |
CN107108862A (zh) | 2017-08-29 |
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