CN110760056A

CN110760056A - Polymer containing condensed ring aromatic hydrocarbon group and application thereof in organic electronic device

Info

Publication number: CN110760056A
Application number: CN201911016609.7A
Authority: CN
Inventors: 温华文; 杨曦; 刘爱香; 潘君友; 谭甲辉
Original assignee: Guangzhou Hua Rui Photoelectric Material Co Ltd
Current assignee: Guangzhou Hua Rui Photoelectric Material Co Ltd
Priority date: 2018-12-18
Filing date: 2019-10-24
Publication date: 2020-02-07
Anticipated expiration: 2039-10-24
Also published as: CN110760056B

Abstract

The invention relates to the field of electroluminescent materials, in particular to a polymer containing condensed ring aromatic hydrocarbon groups, a mixture containing the polymer, a composition containing the polymer, an organic electronic device and application of the organic electronic device.

Description

Polymer containing condensed ring aromatic hydrocarbon group and application thereof in organic electronic device

The present application claims priority from the chinese patent application entitled "a polymer containing fused ring aromatic hydrocarbon groups and its use in organic electronic devices" filed by the chinese patent office on 2018, 12, month 18, and application No. 201811546381.8, the entire contents of which are incorporated herein by reference.

Technical Field

The invention relates to the field of electroluminescent materials, in particular to a polymer containing fused ring aromatic hydrocarbon groups, a mixture and a composition containing the polymer, and application of the polymer in an organic electronic device. The invention further relates to organic electronic devices comprising said polymers, in particular in organic electroluminescent devices, and to the use thereof.

Background

The organic photoelectric material has diversity in synthesis, relatively low manufacturing cost and excellent optical and electrical properties. Organic Light Emitting Diodes (OLEDs) have the advantages of wide viewing angle, fast response time, low operating voltage, thin panel thickness, etc., in the application of optoelectronic devices, such as flat panel displays and lighting, and thus have a wide potential for development.

The organic electroluminescence phenomenon refers to a phenomenon of converting electric energy into light energy using an organic substance. An organic electroluminescent element utilizing an organic electroluminescent phenomenon generally has a structure including a positive electrode and a negative electrode and an organic functional layer therebetween. In order to improve the efficiency and lifetime of the organic electroluminescent element, the organic functional layer has a multi-layer structure, each layer containing a different organic substance. Specifically, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like may be included. In such an organic electroluminescent element, when a voltage is applied between the two electrodes, holes are injected from the positive electrode into the organic functional layer, electrons are injected from the negative electrode into the organic functional layer, and when the injected holes and electrons meet, excitons are formed, and light is emitted when the excitons transition back to the ground state. The organic electroluminescent element has the characteristics of self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast and the like.

In order to realize an efficient organic electroluminescent device, development of a transport material is important in addition to development of a high-performance light emitting material. At present, most of transmission materials are micromolecular materials based on carbazole derivatives, and the defects of unbalanced hole and electron transmission still exist, so that the service life of devices using the compounds is short. Meanwhile, the preparation cost of the evaporation type OLED is high, the time is consumed, and the material utilization rate is not high; in contrast, solution processing OLEDs can be used to fabricate large-area, flexible devices by inexpensive solution processing methods such as inkjet printing and printing, and have a wide application prospect and commercial value.

In order to improve the efficiency and the lifetime of the organic electroluminescent device and solve the disadvantages of the evaporation type OLED material, a new type of transport material, especially a printing type transport material, needs to be developed.

Disclosure of Invention

In view of the above-mentioned deficiencies of the prior art, the present invention aims to provide a high polymer containing aromatic hydrocarbon groups with condensed rings, a mixture thereof, a composition, an organic electronic device and applications thereof, and aims to provide a new functional material, especially a hole transport material, which solves the problems of high cost, fast efficiency roll-off under high brightness and short lifetime of the existing electroluminescent devices.

The present invention relates to a polymer having a repeating unit represented by the general formula (1):

wherein:

a. b and c represent the mole percentage of the repeating units, a is more than 0, b is more than or equal to 0, c is more than or equal to 0, and a + b + c is 1;

A₂and A₃Each occurrence is independently selected from a substituted or unsubstituted aromatic or heteroaromatic group having from 5 to 60 ring atoms; orA non-aromatic ring system having 3 to 25 ring atoms which may be substituted or unsubstituted; or an aromatic amine group having 5 to 60 ring atoms which may be substituted or unsubstituted;

A₁is polycyclic aromatic hydrocarbon, and is independently selected from any one or the combination of the following structures in the general formulas (2-1) to (2-9) at each occurrence:

R₁～R₁₄each occurrence is independently selected from hydrogen, or D, or a straight chain alkyl, alkoxy or thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20C atoms, or an alkenyl group having 1 to 20C atoms, substituted or unsubstituted, or an alkynyl group having 1 to 20C atoms, substituted or unsubstituted, or a silyl group, or a ketone group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, a cyano group (-CN), a carbamoyl group (-C (═ O) NH₂) Haloformyl, formyl (-C (═ O) -H), isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxy, nitro, CF₃Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having from 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having from 5 to 60 ring atoms, or a combination of these systems, where two or more adjacent groups may optionally form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system with one another.

The invention further relates to a mixture comprising at least one polymer as described above, and at least one further organic functional material, which can be selected from the group consisting of Hole Injection Materials (HIM), Hole Transport Materials (HTM), p-dots, Electron Transport Materials (ETM), Electron Injection Materials (EIM), Electron Blocking Materials (EBM), Hole Blocking Materials (HBM), light emitting materials (Emitter), Host materials (Host) and organic dyes.

A composition comprising at least one polymer as described above or a mixture thereof, and at least one organic solvent.

An organic electronic device comprising a polymer or blend as described above.

The organic electronic device according to the above is an electroluminescent device comprising a hole transport layer or a light emitting layer, wherein the hole transport layer or the light emitting layer comprises a polymer or a mixture as described above.

Has the advantages that:

the conjugated structural unit of the polymer containing the aromatic hydrocarbon group with the condensed ring, which is protected by the invention, endows the compound with abundant optical (photoluminescence, electroluminescence, photovoltaic effect and the like) and electrical (semiconductor characteristics, carrier transmission characteristics and the like) performances, and improves the luminous efficiency and the service life of an electroluminescent device; the invention also relates to a polymer containing crosslinkable groups, which can generate chemical reaction under heating condition to form a three-dimensional insoluble infusible interpenetrating network polymer film with excellent solvent resistance. When the complex multilayer photoelectric device is prepared, the photoelectric device can be prepared by utilizing the solution processing characteristics through solution processing technologies such as ink-jet printing, silk-screen printing, spin coating and the like, and the intermolecular crosslinking can be realized to form an insoluble and infusible three-dimensional interpenetrating network polymer film, so that the complex multilayer photoelectric device has excellent solvent resistance.

Drawings

FIG. 1 is a block diagram of one embodiment of an OLED device. Wherein: reference numeral 101 denotes a substrate, 102 denotes an anode, 103 denotes a hole transport layer, 104 denotes a light-emitting layer, 105 denotes an electron transport layer, and 106 denotes a cathode.

Detailed Description

The invention provides a polymer based on aromatic hydrocarbon groups with condensed rings and application thereof in an organic electroluminescent device, and the invention is further detailed below in order to make the purposes, technical schemes and effects of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

In the present invention, "high polymer" and "polymer" have the same meaning.

In the present invention, "substituted" means substituted with a substituent by a hydrogen atom in a group.

In the present invention, the "number of ring atoms" represents the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, and a heterocyclic compound) in which atoms are bonded in a ring shape. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The "number of ring atoms" described below is the same unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.

In the present invention, "adjacent groups" means that these groups are bonded to the same carbon atom or bonded to adjacent carbon atoms. These definitions apply correspondingly to "adjacent substituents".

An aromatic group refers to a hydrocarbon group containing at least one aromatic ring. A heteroaromatic group refers to an aromatic hydrocarbon group that contains at least one heteroatom. The heteroatoms are preferably selected from Si, N, P, O, S and/or Ge, particularly preferably from Si, N, P, O and/or S. By fused ring aromatic group is meant that the rings of the aromatic group may have two or more rings in which two carbon atoms are shared by two adjacent rings, i.e., fused rings. The fused heterocyclic aromatic group means a fused ring aromatic hydrocarbon group containing at least one hetero atom. For the purposes of the present invention, aromatic or heteroaromatic radicals include not only aromatic ring systems but also non-aromatic ring systems. Thus, for example, systems such as pyridine, thiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, pyrazine, pyridazine, pyrimidine, triazine, carbene, and the like, are also considered aromatic or heterocyclic aromatic groups for the purposes of this invention. For the purposes of the present invention, fused-ring aromatic or fused-heterocyclic aromatic ring systems include not only systems of aromatic or heteroaromatic groups, but also systems in which a plurality of aromatic or heterocyclic aromatic groups may also be interrupted by short non-aromatic units (< 10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Thus, for example, systems such as 9,9' -spirobifluorene, 9, 9-diarylfluorene, triarylamines, diaryl ethers, etc., are also considered fused aromatic ring systems for the purposes of this invention.

Specifically, examples of the condensed ring aromatic group are: naphthalene, anthracene, fluoranthene, phenanthrene, triphenylene, perylene, tetracene, pyrene, benzopyrene, acenaphthene, fluorene, and derivatives thereof.

Specifically, examples of the fused heterocyclic aromatic group are: benzofuran, benzothiophene, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, quinoline, isoquinoline, phthalazine, quinoxaline, phenanthridine, primadine, quinazoline, quinazolinone, and derivatives thereof.

Polymers, including homopolymers, copolymers, and mosaic copolymers. In the present invention, the polymer also includes dendrimers.

The conjugated polymer is a polymer, and the main chain of the conjugated polymer is mainly composed of sp2 hybridized orbitals of C atoms, such as: polyacetylene and poly (phenylene vinylene) in which the C atoms of the main chain may also be replaced by other non-C atoms and still be considered as conjugated polymers when sp2 hybridization in the main chain is interrupted by some natural defect.

wherein:

in one embodiment, a ═ 1; in one embodiment, a >0, b ≧ 0, z >0, and a + b + c ═ 1. In one embodiment, a >0, b >0, z ≧ 0, and a + b + c ≧ 1. In one embodiment, a >0, b >0, z >0, and a + b + c is 1.

A₂And A₃Each occurrence independently selected from the group consisting of substituted or unsubstituted cyclic 5 to 60An aromatic group or a heteroaromatic group; or a non-aromatic ring system having 3 to 25 ring atoms which may be substituted or unsubstituted; or an aromatic amine group having 5 to 60 ring atoms which may be substituted or unsubstituted;

In one embodiment, R₁～R₁₄Each occurrence is independently selected from hydrogen, or D, or a straight chain alkyl group having 1 to 20C atoms, a branched chain alkyl group having 3 to 20C atoms, or a cycloalkyl group having 3 to 20C atoms.

In a preferred embodiment, the polymer according to the invention, A₂And A₃Each occurrence independently selected from the group consisting of substituted or unsubstituted cyclic 5 to 40An aromatic group or a heteroaromatic group; or an aromatic amine group having 5 to 40 ring atoms which may be substituted or unsubstituted; more preferably, A₂And A₃Each occurrence is independently selected from substituted or unsubstituted aromatic or heteroaromatic groups having 10 to 30 ring atoms; or an aromatic amine group having 10 to 30 ring atoms which may be substituted or unsubstituted.

Further, polymers according to the invention, b>0, and A₂One or more combinations comprising the following structural groups:

wherein:

x is independently selected from CR at each occurrence₁₅Or N; preferably, X is, at each occurrence, independently selected from CR₁₅；

Each occurrence of Y is independently selected from CR₁₅R₁₆、SiR₁₅R₁₆、NR₁₅、C(＝O)、S、SO₂Or O; preferably, Y is independently selected from CR at each occurrence₁₅R₁₆Or NR₁₅；

Ar₁～Ar₃Each occurrence is independently selected from a substituted or unsubstituted aromatic or heteroaromatic group having from 5 to 60 ring atoms; or a non-aromatic ring system having 3 to 25 ring atoms which may be substituted or unsubstituted;

R₁₅and R₁₆Has the same meaning as R₁。

Specifically, A₂One or more combinations comprising the following structural groups:

wherein: the H atoms on the ring may be further substituted.

In a preferred embodiment, the polymers according to the invention, b>0, and A₂One or more groups comprising the structural groupsCombining:

wherein: x, Y has the meaning as defined above; and n is independently selected from integers of 1-3 at each occurrence.

In particular, b>0, and A₂One or more combinations comprising the following structural groups:

wherein: the H atoms of the ring may be further substituted, R₁₅、R₁₆The meaning is the same as above.

The polymer as described above may be selected from any one of the general formulae (3-1) to (3-8):

wherein: r₁～R₁₄X, Y, n has the meaning given above; a is>0，b>0, c is not less than 0, and a + b + c is 1.

In certain preferred embodiments, the polymer according to the invention, A₃Is a unit having hole-transporting properties, preferably selected from the group consisting of amines, triarylamines, phthalocyanines, thiophenes, pyrroles, carbazoles, indenocarbazoles, indolocarbazoles and isomers and derivatives thereof.

In certain preferred embodiments, the polymer according to the invention, c>0, and A₃Is a unit with hole transmission property, and is selected from one or the combination of the following groups:

wherein: x, Y, Ar₁～Ar₃The meaning is as described above.

In another embodiment, A₃Is a unit with electron-transport properties, preferably self-containedThere are pyridine, pyrimidine, pyrazine, phenazine, perylene, pyrene, imidazole, oxadiazole, triazine, triazole, phenazine and their isomer and derivative groups.

In a more preferred embodiment, c>0, and A₃Is a unit with electron transmission property, and is selected from one or the combination of the following groups:

preferably, A₃Selected from any of the following formulas:

The polymer as described above may be selected from any one of the general formulae (4-1) to (4-4):

wherein: r₁～R₁₄X, Y, n has the meaning given above; a is>0，b>0，c>0, and a + b + c is 1.

Further, it may be selected from any one of the general formulae (5-1) to (5-8):

The polymer according to the above further comprises at least one crosslinkable group Q, preferably the crosslinkable group Q is selected from linear or cyclic alkenyl, linear dienyl, alkynyl, alkenyloxy, dienyloxy, acrylic, glycidyloxy, epoxybutanyl, silyl, cyclobutanyl. The polymer containing the crosslinkable group has better solubility and film-forming property. The polymer can be subjected to cross-linking reaction of cross-linkable groups among molecules through heating treatment or ultraviolet irradiation, so that the polymer is cured to form a film, and the preparation of the multilayer film is facilitated. The crosslinking reaction temperature is generally above 100 ℃.

Specifically, the crosslinkable group Q is selected from one of the following structures:

wherein the dotted line represents the position where the crosslinking monomer is bonded to the functional group on the polymer, and t1 represent integers of 0 or more. R₂₀～R₂₂Has the same meaning as R₁；Ar₇Has the same meaning as Ar₁。

In the present invention, the "crosslinkable group Q" represents a functional group capable of forming an insoluble compound by a reaction. The crosslinkable groups can react to give correspondingly crosslinked compounds, or can react chemically in the layer to form an insoluble layer. Crosslinking can generally be initiated by heat or UV, microwave, X-ray or electron radiation, optionally under initiator.

In certain embodiments, the crosslinkable group Q is contained at A₃Or A₂Above, preferably in A₃The above. In one embodiment, A₃Contains crosslinkable group, and the crosslinkable group is vinyl.

In certain preferred embodiments, the mole percentage of repeating structural units comprising crosslinkable group Q is in the range of from 2% mol to 30% mol, preferably in the range of from 5% mol to 20% mol, most preferably in the range of from 5% mol to 15% mol.

The crosslinkable groups may be present in the polymer in various forms. Preferably, the crosslinkable group is present in a side chain of the polymer.

In certain embodiments, A₁Selected from any one of the following groups:

A₂selected from any one of the following groups:

A₃selected from any one of the following groups:

wherein,

x is selected from CR₁R₂Or N R₁₆；

R₁₆And R₂₀Has the same meaning as R₁；

R₁、R₂、R₈、R₉、R₁₀As defined above.

In certain embodiments, R₁、R₂、R₈、R₉、R₁₀Each independently a straight chain alkyl group having 1 to 20C atoms or a branched chain alkyl group having 1 to 20C atoms;

R₁₆is-Ph-R₂₀

R₂₀Selected from a straight chain alkyl group having 1 to 20C atoms, a branched alkyl group having 1 to 20C atoms, or an alkenyl group having 1 to 20C atoms, substituted or unsubstituted.

In certain embodiments, the polymers according to the invention have a molecular weight Mw of 10000 g/mol or more, preferably 50000 g/mol or more, more preferably 100000 g/mol or more, still more preferably 150000 g/mol or more, most preferably 200000 g/mol or more.

In some preferred embodiments, the polymer according to the present invention, wherein the molar fraction a satisfies the following relationship: 0< a.ltoreq.1, preferably 0.1. ltoreq. a.ltoreq.0.9, more preferably 0.3. ltoreq. a.ltoreq.0.7, most preferably 0.4. ltoreq. a.ltoreq.0.6.

In some preferred embodiments, the polymer according to the present invention, wherein the molar fraction b satisfies the following relationship: b is 0. ltoreq. b <1, preferably 0.1. ltoreq. b.ltoreq.0.7, more preferably 0.1. ltoreq. b.ltoreq.0.5, most preferably 0.2. ltoreq. b.ltoreq.0.5.

In some preferred embodiments, the polymer according to the present invention, wherein the molar fraction c satisfies the following relationship: c is 0. ltoreq. c <1, preferably 0.1. ltoreq. c.ltoreq.0.7, more preferably 0.1. ltoreq. c.ltoreq.0.5, most preferably 0.1. ltoreq. c.ltoreq.0.2.

In some preferred embodiments, the polymer according to the present invention, a + b + c, and a + b + c is 1.

In some preferred embodiments, the polymer according to the present invention, wherein the mole fractions a, b, c satisfy the following relationship: a is more than or equal to 0.4 and less than or equal to 0.6; b is more than or equal to 0.2 and less than or equal to 0.5; c is more than or equal to 0.1 and less than or equal to 0.2.

In some preferred embodiments, the polymer according to the present invention, wherein the mole fractions a, b, c satisfy the following relationship: a is more than or equal to 0.4 and less than or equal to 0.6, b is 0, and c is more than or equal to 0.4 and less than or equal to 0.6; or a is more than or equal to 0.4 and less than or equal to 0.6, c is more than or equal to 0, and b is more than or equal to 0.4 and less than or equal to 0.6.

In a more preferred embodiment, the polymer according to the invention is a conjugated polymer.

Examples of polymers according to the invention are listed below, but are not limited to:

wherein: the H atoms in the above structures may be further substituted.

In a preferred embodiment, the polymer according to the invention is a conjugated polymer.

The polymers according to the invention can be used as functional materials in organic electronic devices. Organic functional materials can be classified into Hole Injection Materials (HIM), Hole Transport Materials (HTM), Electron Transport Materials (ETM), Electron Injection Materials (EIM), Electron Blocking Materials (EBM), Hole Blocking Materials (HBM), emitters (Emitter), and Host materials (Host). In a preferred embodiment, the polymers according to the invention can be used as host materials, or electron-transport materials, or hole-transport materials, or guest materials. In a more preferred embodiment, the polymers according to the invention are used as hole transport materials.

The invention also relates to a method for synthesizing a polymer according to the general formula (1), wherein a raw material containing a reactive group is used for reaction. The starting materials for these reactive groups comprise in each case at least two leaving groups, for example bromine, iodine, boric acid or boric acid esters. Suitable reactions for forming C-C linkages are well known to those skilled in the art and are described in the literature, particularly suitable and preferred coupling reaction methods are SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD-and ULLMAN.

The invention also relates to a method for synthesizing compounds according to the general formulae (2-1) to (2-9), the reactions used being well known to the person skilled in the art and described in the literature, the main starting materials being halogenated naphthalene derivatives. The synthesis of formula (2-1) can be obtained by the following reaction scheme, and other general structures are similar to that:

wherein: r is as defined for R₁。

In a preferred embodiment, the glass transition temperature (Tg) of the above-mentioned high polymer is not less than 100 ℃, preferably not less than 120 ℃, more preferably not less than 140 ℃, still more preferably not less than 160 ℃, most preferably not less than 180 ℃.

In a preferred embodiment, the molecular weight distribution (PDI) of the polymer is preferably in the range of 1 to 5; more preferably 1 to 4; more preferably 1 to 3, more preferably 1 to 2, and most preferably 1 to 1.5.

In a preferred embodiment, the weight average molecular weight (Mw) of the polymer is preferably in the range of 1 to 100 ten thousand; more preferably 5 to 50 ten thousand; more preferably 10 to 40 ten thousand, still more preferably 15 to 30 ten thousand, and most preferably 20 to 25 ten thousand.

The crosslinked polymers prepared according to the process of the invention are insoluble in all customary solvents, in which process the desired thickness of the functional layer can be obtained.

The invention also provides a mixture comprising at least one of the above polymers and at least one further organic functional material, which may be selected from Hole Injection Materials (HIM), Hole Transport Materials (HTM), p-dots, Electron Transport Materials (ETM), Electron Injection Materials (EIM), Electron Blocking Materials (EBM), Hole Blocking Materials (HBM), luminescent materials (Emitter), Host materials (Host) and organic dyes. Various organic functional materials are described in detail, for example, in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of this 3 patent document being hereby incorporated by reference.

In a preferred embodiment, the mixture of said one comprises at least one polymer according to the invention and a p-dock material, wherein the weight percentage of said p-dock material is 10 wt.% or less, preferably 9 wt.% or less, more preferably 7 wt.% or less, particularly preferably 6 wt.% or less, most preferably 5 wt.% or less.

In a preferred embodiment, the mixture comprises a polymer according to the invention and a fluorescent emitter (or singlet emitter). The polymers according to the invention can be used as hosts, where the fluorescent emitters are present in a proportion of < 15% by weight, preferably < 12% by weight, more preferably < 9% by weight, more preferably < 8% by weight, most preferably < 7% by weight.

In certain embodiments, the mixture comprises a polymer according to the present invention, and a TADF material.

In a further preferred embodiment, the mixture comprises a polymer according to the invention and a phosphorescent emitter (or triplet emitter). The polymers according to the invention can be used as hosts, where the phosphorescent emitters are present in a proportion of < 30% by weight, preferably < 25% by weight, more preferably < 20% by weight, most preferably < 18% by weight.

In further preferred embodiments, the mixture comprises a polymer according to the invention and an HTM material.

Some more details of singlet emitters, triplet emitters, p-dopants and TADF materials are described below (but not limited thereto).

1. Singlet state luminophor (Singlet Emitter)

Singlet emitters tend to have longer conjugated pi-electron systems. Hitherto, there have been many examples such as styrylamine and its derivatives disclosed in JP2913116B and WO2001021729a1, indenofluorene and its derivatives disclosed in WO2008/006449 and WO2007/140847, and triarylamine derivatives of pyrene disclosed in US7233019, KR 2006-0006760.

In a preferred embodiment, the singlet emitters may be selected from the group consisting of monostyrenes, distyrenes, tristyrenes, tetrastyrenes, styrylphosphines, styryl ethers, and arylamines.

A monostyrene amine is a compound comprising an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine. A distyrene amine refers to a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A tristyrenylamine refers to a compound comprising three unsubstituted or substituted styrene groups and at least one amine, preferably an aromatic amine. A tetrastyrene amine refers to a compound comprising four unsubstituted or substituted styrene groups and at least one amine, preferably an aromatic amine. One preferred styrene is stilbene, which may be further substituted. The corresponding phosphines and ethers are defined analogously to the amines. Arylamine or aromatic amine refers to a compound comprising three unsubstituted or substituted aromatic rings or heterocyclic systems directly linked to nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably a fused ring system and preferably has at least 14 aromatic ring atoms. Among them, preferred examples are aromatic anthracenamines, aromatic anthracenediamines, aromatic pyrenediamines, aromatic chrysenamines and aromatic chrysenediamines. An aromatic anthracylamine refers to a compound in which a diarylamine group is attached directly to the anthracene, preferably at the 9 position. An aromatic anthracenediamine refers to a compound in which two diarylamine groups are attached directly to the anthracene, preferably at the 9,10 positions. Aromatic pyrene amines, aromatic pyrene diamines, aromatic chrysene amines and aromatic chrysene diamines are similarly defined, wherein the diarylamine groups are preferably attached to the 1 or 1,6 position of pyrene.

Examples, also preferred, of singlet emitters based on vinylamines and arylamines can be found in WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549, WO 2007/115610, US 7250532B 2, DE 102005058557A 1, CN 1583691A, JP 08053397A, US 6251531B1, US 2006/210830A, EP 1957606A 1 and US 2008/0113101A 1 and the entire contents of the patent documents listed above are hereby incorporated by reference.

An example of singlet emitters based on stilbene and its derivatives is US 5121029.

Further preferred singlet emitters may be selected from indenofluorene-amines and indenofluorene-diamines, as disclosed in WO 2006/122630, benzindenofluorene-amines and benzindenofluorene-diamines, as disclosed in WO2008/006449, dibenzoindenofluorene-amines and dibenzoindenofluorene-diamines, as disclosed in WO 2007/140847.

Further preferred singlet emitters may be selected from fluorene based fused ring systems as disclosed in US2015333277a1, US2016099411a1, US2016204355a 1.

More preferred singlet emitters may be selected from pyrene derivatives, such as the structures disclosed in US2013175509a 1; triarylamine derivatives of pyrene, such as pyrene triarylamine derivatives containing dibenzofuran units as disclosed in CN 102232068B; other triarylamine derivatives of pyrene having specific structures are disclosed in CN105085334A, CN 105037173A. Other materials which can be used as singlet emitters are polycyclic aromatic compounds, in particular derivatives of anthracene, such as 9, 10-bis (2-naphthoanthracene), naphthalene, tetraphene, xanthene, phenanthrene, pyrene, such as 2,5,8, 11-tetra-t-butylperylene, indenopyrene, phenylene, such as (4,4 '-bis (9-ethyl-3-carbazolyl-vinyl) -1,1' -biphenyl, diindenopyrene, decacycloalkene, coronene, fluorene, spirobifluorene, arylpyrene, such as U.S. 20060222886, aryleneethene, such as U.S. Pat. No. 5121029, U.S. Pat. No. 5,8803, cyclopentadiene, such as tetraphenylcyclopentadiene, rubrene, coumarin, rhodamine, quinacridone, pyrans, such as 4 (dicyanomethylene) -6- (4-p-dimethylaminostyryl-2-methyl) -4H-pyran (DCM), thiopyran, bis (azinyl) iminoboron compounds (US 2007/0092753 a1), bis (azinyl) methylene compounds, carbostyryl compounds, oxazinones, benzoxazoles, benzothiazoles, benzimidazoles and pyrrolopyrrolediones. Some materials for singlet emitters can be found in US20070252517 a1, US4769292, US 6020078, US 2007/0252517 a1, US 2007/0252517 a 1. The entire contents of the above listed patent documents are hereby incorporated by reference.

Some examples of suitable singlet emitters are listed below:

2. thermally activated delayed fluorescence luminescent material (TADF):

the traditional organic fluorescent material can only emit light by utilizing 25% singlet excitons formed by electric excitation, and the internal quantum efficiency of the device is low (up to 25%). Although the phosphorescent material enhances intersystem crossing due to strong spin-orbit coupling of heavy atom centers, electric excitation can be effectively utilizedThe singlet excitons and the triplet excitons emit light, so that the internal quantum efficiency of the device reaches 100%. However, the application of the phosphorescent material in the OLED is limited by the problems of high price, poor material stability, serious efficiency roll-off of the device and the like. The thermally activated delayed fluorescence emitting material is a third generation organic emitting material developed after organic fluorescent materials and organic phosphorescent materials. Such materials typically have a small singlet-triplet energy level difference (Δ E)_st) The triplet excitons may be converted to singlet excitons by intersystem crossing to emit light. This can make full use of singlet excitons and triplet excitons formed upon electrical excitation. The quantum efficiency in the device can reach 100%. Meanwhile, the material has controllable structure, stable property, low price and no need of noble metal, and has wide application prospect in the field of OLED.

TADF materials need to have a small singlet-triplet level difference, preferably Δ Est <0.3eV, less preferably Δ Est <0.25eV, more preferably Δ Est <0.20eV, and most preferably Δ Est <0.1 eV. In a preferred embodiment, the TADF material has a relatively small Δ Est, and in another preferred embodiment, the TADF has a good fluorescence quantum efficiency. Some TADF luminescent materials may be found in 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. appl.phys.lett, 101,2012,093306, Adachi, chem.comm.comm, 48,2012,11392, Adachi, et. nature. natronics, 6,2012,253, Adachi, et. nature,492,2012,234, Adachi, am.j.am, Adachi, et. adochi, et. nature, adochi, et. phytol.73, adochi, et. phyton.8, Adachi, adachi.73, et. phytol.73, Adachi, et. phyton.73, et. phytol.35, Adachi, et. phytol.8, Adachi, adachi.t.t.t.

Some examples of suitable TADF phosphors are listed below:

3. triplet Emitter (Triplet Emitter)

Triplet emitters are also known as phosphorescent emitters. In a preferred embodiment, the triplet emitter is a metal complex of the general formula M (L) n, where M is a metal atom, L, which may be the same or different at each occurrence, is an organic ligand which is bonded or coordinately bound to the metal atom M via one or more positions, and n is an integer from 1 to 6. Preferably, the triplet emitter comprises a chelating ligand, i.e. a ligand, which coordinates to the metal via at least two binding sites, particularly preferably the triplet emitter comprises two or three identical or different bidentate or polydentate ligands. Chelating ligands are advantageous for increasing the stability of the metal complex. In a preferred embodiment, the metal complexes which can be used as triplet emitters are of the form:

the metal atom M is selected from the transition metals or the lanthanides or actinides, preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Re, Cu, Ag, Ni, Co, W or Eu, particularly preferably Ir, Au, Pt, W or Os.

Ar¹,Ar²May be the same or different at each occurrence and is a cyclic group wherein Ar¹Contains at least one donor atom, i.e. an atom having a lone pair of electrons, such as nitrogen, which is coordinately bound to the metal via its cyclic group; wherein Ar is²Contains at least one carbon atom through which the cyclic group is attached to the metal; ar (Ar)₁And Ar₂Linked together by covalent bonds, may each carry one or more substituent groups, which may in turn be substitutedAre connected together; l', which may be the same or different at each occurrence, is a bidentate chelating ancillary ligand, preferably a monoanionic bidentate chelating ligand; q1 may be 0,1,2 or 3, preferably 2 or 3; q2 may be 0,1,2 or 3, preferably 1 or 0. Examples of organic ligands may be selected from phenylpyridine derivatives or 7, 8-benzoquinoline derivatives. All of these organic ligands may be substituted, for example, with alkyl or fluorine or silicon. The ancillary ligand may preferably be selected from acetone acetate or picric acid.

Examples of materials and their use for some triplet emitters can be found in patent documents and literature, WO200070655, WO200141512, WO200202714, WO200215645, WO2005033244, WO2005019373, US20050258742, US20070087219, US20070252517, US2008027220, WO2009146770, US20090061681, US20090061681, WO2009118087, WO2010015307, WO2010054731, WO2011157339, WO2012007087, WO 2012012012012012018, WO2013107487, WO2013094620, WO2013174471, WO 2014031977, WO 2014112450, WO2014007565, WO 2014024131, Baldo et al Nature (2000),750, Adachi et al.Appl. Phys.Lett. (2001),1622, Kido et al.Phyt. Phyt., Lett. (2001), Synrather et al.1994, American et al., Meth.1974, Meth., Meth.1978, and Met.1978 (Met et al). The entire contents of the above listed patent documents and literature are hereby incorporated by reference. Some examples of suitable triplet emitters are listed in the following table:

4、p-dopant

p-dopant refers to a P-type dopant used for doping a hole transport material, examples of such materials are not particularly limited, and any organic compound may be used as the P-type dopant, as long as they are strong electron acceptors, taking the hole transport material NPB (N, N '-di (1-naphthyl) -N, N' -diphenyl-1, 1 '-biphenyl-4, 4' -diamine) and the P-type dopant F4TCNQ (2,3,5, 6-tetrafluorotetracyano-1, 4-benzoquinodimethane) as an example, since the HOMO energy level of NPB is close to the LUMO energy level of F4TCNQ, electrons of the HOMO energy level of NPB can transition to the LUMO energy level of F4TCNQ, the free holes are formed in the hole transport layer to improve the conductivity of the hole transport layer, and the doping bends the band so that holes have a chance to be injected in a tunneling manner.

Strong electron acceptors such as Tetracyanoquinodimethane (TCNQ) or 2,3,5, 6-tetrafluorotetracyano-1, 4-quinodimethane (F4TCNQ) are known. Reference is made to the articles M.Pfeiffer, A.Beyer, T.Fritz, K.Leo, App.Phys.Lett.,73(22), 3202-. Due to the drawbacks of TCNQ and F4TCNQ in specific applications (too small molecular weight and too volatile), some more preferred P-type dopant materials (disclosed in DE102013205093a1, WO2009003455a1, CN101330129B, etc.) can be selected from the following:

wherein: A. e, G is independently selected from the following general structures:

R¹～R⁸at each occurrence, independently H, D, F, Cl, CN, NO₂、CF₃Perfluoroalkyl, sulfone, crosslinkable groups or substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 40 ring atoms or aryloxy or heteroaryloxy groups having 5 to 40 ring atoms or combinations of these systems, where one or more radicals R¹～R⁸The rings which may be bonded to each other and/or to said groups form a mono-or polycyclic aliphatic or aromatic ring system;

M¹-M¹²independently is N or CR⁹,R⁹Is the same as R¹～R⁸；

In the general formula T-1, n is an integer of 1-4;

ar is selected from substituted or unsubstituted aromatic or heteroaromatic ring systems having from 5 to 40 carbon atoms, or aryloxy or heteroaryloxy groups having from 5 to 40 carbon atoms, or combinations of these systems, wherein one or more of the groups may form a mono-or polycyclic aliphatic or aromatic ring system with each other and/or with the ring to which said group is bonded.

Some examples of P-dopants are disclosed in TW200629362A, EP2690662A, CN101346830A, DE102013205093A, etc., and specific examples of P-dopants are:

the invention also relates to a composition comprising at least one polymer or mixture as described above, and at least one organic solvent; the at least one organic solvent is selected from aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, alicyclic or olefinic compound, or boric acid ester or phosphoric acid ester compound, or a mixture of two or more solvents.

In a preferred embodiment, a composition according to the invention is characterized in that said at least one organic solvent is chosen from aromatic or heteroaromatic-based solvents.

Examples of aromatic or heteroaromatic-based solvents suitable for the present invention include, but are not limited to, p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisoprene, dipentylbenzene, tripentylbenzene, pentyltoluene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3, 4-tetramethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, cyclohexylbenzene, benzylbutylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisoprene, 1-methylnaphthalene, 1,2, 4-trichlorobenzene, 4-difluorodiphenylmethane, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α -dichlorodiphenylmethane, 4- (3-phenylpropyl) pyridine, 1, 2-dimethylquinoline, 2-benzoic acid, 2-isopropylquinoline, 2-benzoic acid, 2-ethyl benzoate, and the like;

examples of aromatic ketone-based solvents suitable for the present invention are, but not limited to: 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, and the like;

examples of aromatic ether-based solvents suitable for the present invention are, but not limited to: 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethylacetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxan, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylphenetole, 1, 3-dipropoxybenzene, 1,2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidylphenyl ether, dibenzyl ether, 4-t-butylanisole, trans-p-propenylanisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, methyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether;

in some preferred embodiments, the at least one organic solvent may be selected from: aliphatic ketones such as 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2, 5-hexanedione, 2,6, 8-trimethyl-4-nonanone, fenchylone, phorone, isophorone, di-n-amyl ketone, etc.; or aliphatic ethers such as amyl ether, hexyl ether, dioctyl ether, ethylene glycol 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.

In other preferred embodiments, the at least one organic solvent may be selected from ester-based solvents: alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkyl lactones, alkyl oleates, and the like. Octyl octanoate, diethyl sebacate, diallyl phthalate, isononyl isononanoate are particularly preferred.

The solvents mentioned may be used alone or as a mixture of two or more organic solvents.

In certain preferred embodiments, a composition according to the present invention comprises at least one organometallic complex or polymer or mixture as described above and at least one organic solvent, and may further comprise another organic solvent. Examples of another organic solvent include (but are not limited to): methanol, ethanol, 2-methoxyethanol, methylene chloride, 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, indene, and/or mixtures thereof.

In some preferred embodiments, particularly suitable solvents for the present invention are those having Hansen (Hansen) solubility parameters within the following ranges:

δ_d(dispersion force) of 17.0 to 23.2MPa^1/2In particular in the range of 18.5 to 21.0MPa^1/2A range of (d);

δ_p(polar force) is 0.2 to 12.5MPa^1/2In particular in the range of 2.0 to 6.0MPa^1/2A range of (d);

δ_h(hydrogen bonding force) of 0.9 to 14.2MPa^1/2In particular in the range of 2.0 to 6.0MPa^1/2The range of (1).

The compositions according to the invention, in which the organic solvent is selected taking into account its boiling point parameter. In the invention, the boiling point of the organic solvent is more than or equal to 150 ℃; preferably equal to or more than 180 ℃; more preferably more than or equal to 200 ℃; more preferably more than or equal to 250 ℃; most preferably more than or equal to 275 ℃ or more than or equal to 300 ℃. Boiling points in these ranges are beneficial for preventing nozzle clogging in inkjet print heads. The organic solvent may be evaporated from the solvent system to form a thin film comprising the functional material.

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

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

The compositions of the embodiments of the present invention may contain from 0.01 to 10 wt%, preferably from 0.1 to 15 wt%, more preferably from 0.2 to 5 wt%, most preferably from 0.25 to 3 wt% of a polymer or mixture according to the present invention.

The invention also relates to the use of said composition as a coating or printing ink for the production of organic electronic devices, particularly preferably by a printing or coating production process.

Suitable printing or coating techniques include, but are not limited to, ink jet printing, spray printing (Nozleprinting), letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roll printing, twist roll printing, lithographic printing, flexographic printing, rotary printing, spray coating, brush or pad printing, slot die coating, and the like. Gravure printing, jet printing and ink jet printing are preferred. The solution or suspension may additionally include one or more components such as surface active compounds, lubricants, wetting agents, dispersants, hydrophobing agents, binders, and the like, for adjusting viscosity, film forming properties, enhancing adhesion, and the like. For details on the printing technology and its requirements concerning the solutions, such as solvent and concentration, viscosity, etc., reference is made to the Handbook of Print Media, technology and production Methods, published by Helmut Kipphan, ISBN 3-540-67326-1.

The present invention also provides the use of a polymer, mixture or composition as described above in an Organic electronic device, which may be selected from, but is not limited to, Organic Light Emitting Diodes (OLEDs), Organic photovoltaic cells (OPVs), Organic light Emitting cells (OLEECs), Organic Field Effect Transistors (OFETs), Organic light Emitting field effect transistors (effets), Organic lasers, Organic spintronic devices, Organic sensors and Organic Plasmon Emitting diodes (Organic plasma Emitting diodes), etc., particularly preferably OLEDs. In the embodiment of the present invention, the organic compound or the high polymer is preferably used for a light emitting layer of an OLED device.

The invention further relates to an organic electronic device comprising at least one polymer or mixture as described above. Generally, such organic electronic devices comprise at least a cathode, an anode and a functional layer located between the cathode and the anode, wherein the functional layer comprises at least one polymer or mixture as described above. The Organic electronic device can be selected from, but not limited to, Organic Light Emitting Diodes (OLEDs), Organic photovoltaic cells (OPVs), Organic light Emitting cells (OLEECs), Organic Field Effect Transistors (OFETs), Organic light Emitting field effect transistors (fets), Organic lasers, Organic spintronic devices, Organic sensors, Organic Plasmon Emitting diodes (Organic Plasmon Emitting diodes), and the like, and particularly preferred are Organic electroluminescent devices such as OLEDs, OLEECs, Organic light Emitting field effect transistors.

In certain preferred embodiments, the electroluminescent device, the hole transport layer or the light-emitting layer, comprises a polymer or mixture as described above.

In certain preferred embodiments, the electroluminescent device, the hole transport layer or the light-emitting layer thereof, comprises a polymer as described above, or comprises a polymer as described above and a p-dopant material, or comprises a polymer as described above and a phosphorescent emitter, or comprises an organic compound as described above and a fluorescent emitter, or comprises an organic compound as described above and a TADF material.

The invention further comprises a process for the preparation of a functional layer comprising the polymer according to the invention in an organic electronic device, comprising at least the following steps:

the first step is as follows: dissolving the polymer in an organic solvent or a mixed solvent to prepare a solution;

the second step is that: applying the solution to a functional layer of a device by Printing or coating, wherein the Printing or coating can be selected from, but is not limited to, ink jet Printing, jet Printing (Nozzle Printing), letterpress Printing, screen Printing, dip coating, spin coating, doctor blade coating, roll Printing, twist roll Printing, offset Printing, flexographic Printing, rotary Printing, spray coating, brush coating or pad Printing, slit die coating, and the like;

the third step: the obtained film is subjected to heat treatment at a temperature of at least 100 ℃, and ultraviolet light can be optionally added to carry out crosslinking reaction, so that the film is cured.

Optional steps are as follows: and cleaning the film after crosslinking and curing by using an organic solvent to remove residual compounds which are not crosslinked and cured.

In certain embodiments, the resulting crosslinked cured film (after solvent washing) has a thickness of at least 50%, preferably at least 60%, more preferably at least 70%, and most preferably at least 85% of the film prior to crosslinking and curing.

As shown in fig. 1, the light emitting device, particularly an OLED, includes a substrate 101, an anode 102, at least one light emitting layer 104, and a cathode 105.

In one embodiment, a hole transport layer 103 is further disposed between the anode 102 and the light emitting layer 104, and an electron transport layer 105 is further disposed between the light emitting layer 104 and the cathode 106.

The substrate may be opaque or transparent. A transparent substrate may be used to fabricate a transparent light emitting device. See, for example, Bulovic et al Nature 1996,380, p29, and Gu et al, appl.Phys.Lett.1996,68, p 2606. The substrate may be rigid or elastic. The substrate may be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. A substrate free of surface defects is a particularly desirable choice. In a preferred embodiment, the substrate is flexible, and may be selected from a polymer film or plastic, having a glass transition temperature Tg of 150 ℃ or higher, preferably over 200 ℃, more preferably over 250 ℃, and most preferably over 300 ℃. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).

The anode may 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 an emission layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light emitting layer or the p-type semiconductor material acting as a HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. Examples of anode materials include, but are not limited to: al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is pattern structured. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.

The cathode may comprise a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the light emitting layer. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO level or conduction band level of the emitter in the light-emitting layer or of the n-type semiconductor material as Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. In principle, all materials which can be used as cathodes in OLEDs are possible as cathode materials for the device according to the invention. Examples of cathode materials include, but are not limited to: al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF₂Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.

The OLED may also comprise further 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), a Hole Blocking Layer (HBL). Suitable materials for use in these functional layers are described in detail above and in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of these 3 patent documents being hereby incorporated by reference.

The light-emitting device according to the present invention emits light at a wavelength of 300 to 1200nm, preferably 350 to 1000nm, and more preferably 400 to 900 nm.

The invention also relates to the use of the electroluminescent device according to the invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.

The present invention will be described in connection with preferred embodiments, but the present invention is not limited to the following embodiments, and it should be understood that the appended claims outline the scope of the present invention and those skilled in the art, guided by the inventive concept, will appreciate that certain changes may be made to the embodiments of the invention, which are intended to be covered by the spirit and scope of the appended claims.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

1. Synthesis of polymers

Example 1: synthesis of Polymer P1

Synthesis of Compound 3

31.40g (0.1mol) of Compound 1 and 24.39g (0.2mol) of Compound 2 were placed in a 250ml three-necked round-bottomed flask, 250ml of toluene was added thereto, and the mixture was dissolved by stirring, and 50ml of water and 21.2g of Na were added thereto successively₂CO₃(0.2mol), stirred until all the solid had dissolved, 0.5ml of Aliquat336 and 75mg of Pd (PPh) were added₃)₄Introducing nitrogen for protection for 10min, heating to reflux (92-100 ℃), refluxing for 20min, closing the nitrogen to keep the system sealed, refluxing for reaction overnight, cooling, extracting the reaction solution with toluene, combining organic phases, washing with NaCl saturated solution and water in sequence, evaporating to remove the solvent, and drying to obtain 26.18g of compound 3 with the yield of 85%.

Synthesis of Compound 4

A250 ml three-necked round-bottomed flask was charged with mechanical stirring, 15.42g (0.05mol) of Compound 3 was added, 250ml of pyridine was added and dissolved by stirring, and 30ml of water and 39.51g of potassium permanganate (KMnO) were further added successively₄) (0.25mol), heating and refluxing (about 105 ℃ C. and 110 ℃ C.) to react for 2h,after refluxing for 30min, 60ml of water and 15.59 of potassium permanganate (KMnO) are added₄) (0.1mol) was repeated four times. After every 6h of reflux, 60ml of water were added with cooling and repeated four times. Filtering while hot after the reaction, washing filter cake with boiled water, combining filtrates, evaporating to remove solvent to about 100ml, adding 50ml concentrated hydrochloric acid, cooling, filtering, washing with cold water, and vacuum drying to obtain 11.05g of compound 4 with yield of 60%.

Synthesis of Compound 5

100ml of concentrated sulfuric acid was added to a 500ml three-necked round-bottomed flask, 3.68g of Compound 4(0.01mol) was slowly added with stirring, and after 0.5 hour of reaction at room temperature, 5 to 10 drops of fuming sulfuric acid were added, and after 6 hours of reaction, the reaction solution was poured into an ice-water mixture while stirring with a glass rod. The mixture was filtered with suction, washed with a large amount of water and dried to give 2.29g of Compound 5 as a dark red solid in 69% yield.

Synthesis of Compound 6

6.65g of compound 5(0.02mol) was added to a 500ml three-necked round-bottomed flask, 300ml of diethylene glycol and 4ml of hydrazine hydrate (85%) were slowly added thereto while stirring, and 28.10g of KOH (0.5mol) which had been ground into a fine powder was added thereto, and after protection with nitrogen gas for 10 minutes, the mixture was heated to reflux (195 ℃) and reacted for 48 hours, and then cooled and poured into a crushed ice/concentrated hydrochloric acid (v: v ═ 8:1) mixture while stirring with a glass rod. The mixture was filtered by suction, washed with water and dried to give 2.74g of Compound 6 in 45% yield.

Synthesis of Compound 7

A250 ml long neck three neck round bottom flask was charged with a rotor, 1.52g of Compound 6(5mmol) was added, the middle was charged with a high vacuum piston (paraffin seal), reverse neck stoppers were added on both sides, and the flask was evacuated with an oil pump while the flask was heated with a blower. 100ml of dry THF was added to the flask by syringe. 3.8ml of 2.87M n-butyllithium (11mmol) was added dropwise to the flask at-78 ℃ with stirring using a syringe, and the mixture was reacted with l h under a nitrogen atmosphere. The system is heated to room temperature for reaction for 30min, then cooled to-78 ℃, 2.10g of 1-bromooctane (11mmol) is added by a syringe, the reaction is carried out at-78 ℃ for 1h, and then the reaction is heated to room temperature for reaction for 4 h. 1.9ml of 2.87M n-butyllithium (5.5mmol) are added dropwise and the reaction is carried out under nitrogen atmosphere l h. The system was warmed to room temperature for reaction for 30min, then cooled to-78 deg.C, and 1.05g of 1-bromooctane (5.5mmol) was added via syringe, and the reaction was slowly returned to room temperature overnight. To the flask was added about 30ml of water to effect reactionQuenching, extracting reaction liquid with petroleum ether, combining organic phases, and adding anhydrous Na₂SO₄Drying, evaporating to remove solvent, and purifying by column chromatography to obtain 2.17g of compound 7 with a yield of 68%.

Synthesis of Compound 8

1.34g of potassium tert-butoxide (12mmol) are added portionwise under nitrogen to 6.41g of compound 7(10mmol) in anhydrous diethyl ether (80mL), stirred under nitrogen for 2.5 hours, added under nitrogen to 4mL (13mol) of nonanoyl chloride in anhydrous diethyl ether (80mL), stirred at room temperature for 2 hours, quenched with 40mL of water, washed several times with saturated aqueous sodium bicarbonate and water, the organic phase is separated and chromatographed to give 7.26g of compound 8 in 93% yield.

Synthesis of Compound 9

A solution of diisobutylaluminum hydride in dichloromethane (1M,15mL,15mmol) was added dropwise to a solution of compound 8(10mmol) in anhydrous dichloromethane (80mL) at room temperature (80mL), stirring was continued for 4 hours, then cooled to 10 ℃ in an ice bath, an aqueous solution of citric acid (1M,17mL) was added with stirring, then 30mL of dilute hydrochloric acid was added, the aqueous phase was extracted with dichloromethane, the organic phases were combined, and column chromatography gave 6.73g of compound 9, 86% yield.

Synthesis of Compound 10

Dissolving 7.83g of compound 9(10mmol) in 80mL of glacial acetic acid, slowly adding 1mL of concentrated sulfuric acid, stirring and refluxing for reaction for 1 hour under the protection of nitrogen, cooling to room temperature, adding 100mL of water, extracting with diethyl ether for multiple times, extracting the organic phase with aqueous sodium carbonate solution and water for multiple times, drying the organic phase, and performing column chromatography to obtain 5.73g of compound 10 with the yield of 75%.

Synthesis of monomer a

Dissolving 7.65g of compound 10(10mmol) in 100mL of dichloromethane under ice bath, slowly dropwise adding 1.17mL of liquid bromine (23mmol) in dichloromethane, slowly returning to room temperature after dropwise adding, continuously stirring for reacting overnight, adding aqueous sodium sulfite to terminate the reaction, extracting the organic phase with aqueous sodium carbonate solution and water for multiple times, drying the organic phase, and separating by column chromatography to obtain 5.72g of monomer a with a yield of 62%.

Synthesis of Polymer P1

Into a 25mL two-necked round-bottomed flask, 923mg (1.0mmol) of monomer a, 442mg (0.8mmol) of monomer b, 105mg (0.2mmol) of monomer c, and 20mg of Pd (PPh) were charged₃)₄20mL of degassed toluene and 2mL of a 20% aqueous tetraethylammonium hydroxide solution were uniformly stirred, and then introduced with argon for 15 minutes. The reaction is carried out for 24 hours under the condition of argon protection and 110 ℃, 500 mu L of bromobenzene is sequentially added for reflux reaction for 2 hours, 200mg of phenylboronic acid is sequentially added for reflux reaction for 2 hours, and after the reaction is finished and cooled to room temperature, the reaction liquid is dropwise added into methanol for precipitation. The flocculent precipitate obtained was filtered and after vacuum drying the polymer obtained was soxhlet extracted with acetone to remove unreacted monomers and the remaining solid was vacuum dried to give 0.94g of product in 89% yield.

Example 2: synthesis of Polymer P2

Into a 25mL two-necked round-bottomed flask, 923mg (1.0mmol) of monomer a, 521mg (1.0mmol) of monomer d, and 20mg of Pd (PPh)₃)₄20mL of degassed toluene and 2mL of a 20% aqueous tetraethylammonium hydroxide solution were uniformly stirred, and then introduced with argon for 15 minutes. The reaction is carried out for 24 hours under the condition of argon protection and 110 ℃,200 mu L of bromobenzene is sequentially added for reflux reaction for 2 hours, 200mg of phenylboronic acid is sequentially added for reflux reaction for 2 hours, and after the reaction is finished and cooled to room temperature, the reaction liquid is dropwise added into methanol for precipitation. The resulting flocculent precipitate was filtered and dried under vacuum and the resulting polymer was soxhlet extracted with acetone to remove unreacted monomers and the remaining solid was dried under vacuum to give 0.63g of product in 61% yield.

Example 3: synthesis of Polymer P3

In a 25mL two-necked round-bottomed flask, 923mg (1.0mmol) of monomer a, 516mg (0.8mmol) of monomer e, 105mg (0.2mmol) of monomer c, 20mg of Pd (PPh)₃)₄20mL of degassed toluene and 2mL of 20 mass percent tetraethylammonium hydroxide aqueous solution are uniformly stirred and introducedArgon gas for 15 minutes. The reaction is carried out for 24 hours under the condition of argon protection and 110 ℃,200 mu L of bromobenzene is sequentially added for reflux reaction for 2 hours, 200mg of phenylboronic acid is sequentially added for reflux reaction for 2 hours, and after the reaction is finished and cooled to room temperature, the reaction liquid is dropwise added into methanol for precipitation. The resulting flocculent precipitate was filtered and dried under vacuum and the resulting polymer was soxhlet extracted with acetone to remove unreacted monomers and the remaining solid was dried under vacuum to give 0.79g of product in 70% yield.

Example 4: synthesis of Polymer P4

Synthesis of Compound 12

31.40g (0.1mol) of Compound 11 and 24.39g (0.2mol) of Compound 2 were placed in a 250ml three-necked round-bottomed flask, 250ml of toluene was added thereto, and the mixture was dissolved by stirring, and 50ml of water and 21.2g of Na were added thereto successively₂CO₃(0.2mol), stirred until all the solid had dissolved, 0.5ml of Aliquat336 and 75mg of Pd (PPh) were added₃)₄Introducing nitrogen for protection for 10min, heating to reflux (92-100 ℃), refluxing for 20min, closing the nitrogen to keep the system sealed, refluxing for reaction overnight, cooling, extracting the reaction solution with toluene, combining organic phases, washing with NaCl saturated solution and water in sequence, evaporating to remove the solvent, and drying to obtain 22.79g of the compound 12 with the yield of 74%.

Synthesis of Compound 13

A250 ml three-necked round-bottomed flask was charged with mechanical stirring, 15.42g (0.05mol) of Compound 12 was added, 250ml of pyridine was added and dissolved by stirring, and 30ml of water and 39.51g of potassium permanganate (KMnO) were further added successively₄) (0.25mol), heating and refluxing (about 105-110 ℃) to react for 2h, cooling after refluxing for 30min, adding 60ml of water and 15.59 potassium permanganate (KMnO)₄) (0.1mol) was repeated four times. After every 6h of reflux, 60ml of water were added with cooling and repeated four times. Filtering when the reaction is finished, washing filter cake with boiled water, mixing filtrates, evaporating to remove solvent to about 100ml, adding 50ml concentrated hydrochloric acid, cooling, filtering, washing with cold water, and vacuum-filteringDrying afforded 12.88g of Compound 13, in 70% yield.

Synthesis of Compound 14

100ml of concentrated sulfuric acid was added to a 500ml three-necked round-bottomed flask, 3.68g of Compound 13(0.01mol) was slowly added with stirring, and after 0.5 hour of reaction at room temperature, 5 to 10 drops of fuming sulfuric acid were added, and after 6 hours of reaction, the reaction solution was poured into an ice-water mixture while stirring with a glass rod. The mixture was filtered with suction, washed with a large amount of water and dried to give 2.65g of compound 14 as a dark red solid in 72% yield.

Synthesis of Compound 15

6.65g of compound 14(0.02mol) was added to a 500ml three-necked round-bottomed flask, 300ml of diethylene glycol and 4ml of hydrazine hydrate (85%) were slowly added with stirring, 28.10g of KOH (0.5mol) which had been ground to a fine powder was added thereto, and after protection with nitrogen gas for 10 minutes, the mixture was heated to reflux (195 ℃) and reacted for 48 hours, and then cooled and poured into a crushed ice/concentrated hydrochloric acid (v: v ═ 8:1) mixture while stirring with a glass rod. The mixture was filtered by suction, washed with water and dried to give 3.46g of compound 15, 57% yield.

Synthesis of Compound 16

A250 ml long neck three neck round bottom flask was charged with a rotator, 1.52g of compound 15(5mmol) was added, the middle was charged with a high vacuum piston (paraffin seal), reverse neck stoppers were added on both sides, and the flask was evacuated with an oil pump while the flask was heated with a blower. 100ml of dry THF was added to the flask by syringe. 3.8ml of 2.87M n-butyllithium (11mmol) was added dropwise to the flask at-78 ℃ with stirring using a syringe, and the mixture was reacted with l h under a nitrogen atmosphere. The system is heated to room temperature for reaction for 30min, then cooled to-78 ℃, 2.10g of 1-bromooctane (11mmol) is added by a syringe, the reaction is carried out at-78 ℃ for 1h, and then the reaction is heated to room temperature for reaction for 4 h. 1.9ml of 2.87M n-butyllithium (5.5mmol) are added dropwise and the reaction is carried out under nitrogen atmosphere l h. The system was warmed to room temperature for reaction for 30min, then cooled to-78 deg.C, and 1.05g of 1-bromooctane (5.5mmol) was added via syringe, and the reaction was slowly returned to room temperature overnight. The reaction was quenched by adding about 30ml of water to the flask, the reaction solution was extracted with petroleum ether, and the organic phases were combined and then extracted with anhydrous Na₂SO₄Drying, evaporating to remove solvent, and purifying by column chromatography to obtain 2.24g of compound 16 with a yield of 70%.

Synthesis of Compound 17

1.34g of potassium tert-butoxide (12mmol) are added portionwise under nitrogen to 6.41g of compound 16(10mmol) in anhydrous diethyl ether (80mL), stirred under nitrogen for 2.5 hours, added under nitrogen to 4mL (13mol) of nonanoyl chloride in anhydrous diethyl ether (80mL), stirred at room temperature for 2 hours, quenched with 40mL of water, washed several times with saturated aqueous sodium bicarbonate and water, the organic phase is separated and chromatographed to give 6.64g of compound 17 in 85% yield.

Synthesis of Compound 18

A solution of diisobutylaluminum hydride in dichloromethane (1M,15mL,15mmol) was added dropwise to a solution of compound 17(10mmol) in anhydrous dichloromethane (80mL) at room temperature (80mL) and stirred for 4 hours, then cooled to below 10 ℃ in an ice bath, an aqueous solution of citric acid (1M,17mL) was added with stirring, then 30mL of dilute hydrochloric acid was added, the aqueous phase was extracted with dichloromethane, the organic phases were combined and subjected to column chromatography to give 6.11g of compound 18 in 78% yield.

Synthesis of Compound 19

Dissolving 7.83g of compound 18(10mmol) in 80mL of glacial acetic acid, slowly adding 1mL of concentrated sulfuric acid, stirring and refluxing for reaction for 1 hour under the protection of nitrogen, cooling to room temperature, adding 100mL of water, extracting with diethyl ether for multiple times, extracting the organic phase with aqueous sodium carbonate solution and water for multiple times, drying the organic phase, and separating by column chromatography to obtain 5.73g of compound 19 with a yield of 75%.

Synthesis of monomer f

Dissolving 7.65g of compound 19(10mmol) in 100mL of dichloromethane in ice bath, slowly dropwise adding 1.17mL of liquid bromine (23mmol) in dichloromethane, slowly returning to room temperature after dropwise adding, continuously stirring for reaction overnight, adding aqueous sodium sulfite solution to terminate the reaction, extracting the organic phase with aqueous sodium carbonate solution and water for multiple times, drying the organic phase, and separating by column chromatography to obtain 5.63g of monomer f with the yield of 61%.

Synthesis of Polymer P4

Into a 25mL two-necked round-bottomed flask were charged 923mg (1.0mmol) of monomer f, 442mg (0.8mmol) of monomer b, 105mg (0.2mmol) of monomer c, and 20mg of Pd (PPh)₃)₄20mL of degassed toluene and 2mL of a 20% aqueous tetraethylammonium hydroxide solution were uniformly stirred, and then introduced with argon for 15 minutes. Is reacted inReacting for 24 hours under the condition of 110 ℃ under the protection of argon, sequentially adding 500 mu L of bromobenzene for reflux reaction for 2 hours, and 200mg of phenylboronic acid for reflux reaction for 2 hours, cooling to room temperature after the reaction is finished, and dropwise adding the reaction solution into methanol for precipitation. The resulting flocculent precipitate was filtered and dried under vacuum and the resulting polymer was soxhlet extracted with acetone to remove unreacted monomers and the remaining solid was dried under vacuum to give 0.80g of product in 76% yield.

Example 5: synthesis of Polymer P5

Into a 25mL two-necked round-bottomed flask, 923mg (1.0mmol) of monomer f, 521mg (1.0mmol) of monomer d, 20mg of Pd (PPh)₃)₄20mL of degassed toluene and 2mL of a 20% aqueous tetraethylammonium hydroxide solution were uniformly stirred, and then introduced with argon for 15 minutes. The reaction is carried out for 24 hours under the condition of argon protection and 110 ℃,200 mu L of bromobenzene is sequentially added for reflux reaction for 2 hours, 200mg of phenylboronic acid is sequentially added for reflux reaction for 2 hours, and after the reaction is finished and cooled to room temperature, the reaction liquid is dropwise added into methanol for precipitation. The resulting flocculent precipitate was filtered and dried under vacuum and the resulting polymer was soxhlet extracted with acetone to remove unreacted monomers and the remaining solid was dried under vacuum to give 0.56g of product in 54% yield.

Example 6: synthesis of Polymer P6

In a 25mL two-necked round-bottomed flask, 923mg (1.0mmol) of monomer f, 516mg (0.8mmol) of monomer e, 105mg (0.2mmol) of monomer c, 20mg of Pd (PPh)₃)₄20mL of degassed toluene and 2mL of a 20% aqueous tetraethylammonium hydroxide solution were uniformly stirred, and then introduced with argon for 15 minutes. The reaction is carried out for 24 hours under the condition of argon protection and 110 ℃,200 mu L of bromobenzene is sequentially added for reflux reaction for 2 hours, 200mg of phenylboronic acid is sequentially added for reflux reaction for 2 hours, and after the reaction is finished and cooled to room temperature, the reaction liquid is dropwise added into methanol for precipitation. Filtering the obtained flocculent precipitate, and vacuum dryingThe polymer obtained thereafter was subjected to soxhlet extraction with acetone to remove unreacted monomers, and the remaining solid was dried under vacuum to obtain 0.90g of a product in 80% yield.

Example 7: synthesis of Polymer P7

In a 25mL two-necked round-bottomed flask, 923mg (1.0mmol) of monomer a, 454mg (0.8mmol) of monomer g, 119mg (0.2mmol) of monomer h, 20mg of Pd (PPh)₃)₄20mL of degassed toluene and 2mL of a 20% aqueous tetraethylammonium hydroxide solution were uniformly stirred, and then introduced with argon for 15 minutes. The reaction is carried out for 24 hours under the condition of argon protection and 110 ℃,200 mu L of bromobenzene is sequentially added for reflux reaction for 2 hours, 200mg of phenylboronic acid is sequentially added for reflux reaction for 2 hours, and after the reaction is finished and cooled to room temperature, the reaction liquid is dropwise added into methanol for precipitation. The resulting flocculent precipitate was filtered and dried under vacuum and the resulting polymer was soxhlet extracted with acetone to remove unreacted monomers and the remaining solid was dried under vacuum to give 0.65g of product in 60% yield.

Example 8: synthesis of Polymer P8

Into a 25mL two-necked round-bottomed flask, 923mg (1.0mmol) of monomer a, 532mg (1.0mmol) of monomer i, 20mg of Pd (PPh)₃)₄20mL of degassed toluene and 2mL of a 20% aqueous tetraethylammonium hydroxide solution were uniformly stirred, and then introduced with argon for 15 minutes. The reaction is carried out for 24 hours under the condition of argon protection and 110 ℃,200 mu L of bromobenzene is sequentially added for reflux reaction for 2 hours, 200mg of phenylboronic acid is sequentially added for reflux reaction for 2 hours, and after the reaction is finished and cooled to room temperature, the reaction liquid is dropwise added into methanol for precipitation. The resulting flocculent precipitate was filtered and dried under vacuum and the resulting polymer was soxhlet extracted with acetone to remove unreacted monomers and the remaining solid was dried under vacuum to give 0.55g of product in 53% yield.

Preparation and characterization of OLED devices

The device structure of the OLED device (OLED-Ref) is as follows: ITO/PEDOT PSS (60nm)/HTM (20nm)/EML (40nm)/ET Liq (5:5,25 nm)/cathode; the OLED device (OLED-Ref) is prepared by the following steps:

1) cleaning of an ITO transparent electrode (anode) glass substrate: carrying out ultrasonic treatment for 30 minutes by using an aqueous solution of 5% Decon90 cleaning solution, then carrying out ultrasonic cleaning for several times by using deionized water, then carrying out ultrasonic cleaning by using isopropanol, and carrying out nitrogen blow-drying; processing for 5 minutes under oxygen plasma to clean the ITO surface and improve the work function of an ITO electrode;

2) preparation of HIL and HTL by spin coating PEDOT: PSS (Clevios) on a glass substrate treated with oxygen plasma^TMPEDOT, PSS Al4083), obtaining a 60nm film, and annealing in air at 150 ℃ for 20 minutes after the spin coating is finished; then spin-coated on a PEDOT: PSS layer to obtain a 20nm Poly-TFB film (CAS:223569-31-1, available from Lumtec. Corp.; 5mg/mL toluene solution), followed by treatment at 180 ℃ for 60 minutes in a nitrogen atmosphere;

3) the luminescent layer is prepared by dissolving BH and BD in toluene according to a weight ratio of 93:7, wherein the concentration of the solution is 20mg/mL, spin-coating the solution in a nitrogen glove box to obtain a 40nm film, and then annealing at 120 ℃ for 10 minutes.

4) The preparation of the electron transport layer comprises putting the spin-coated device into a vacuum evaporation chamber, putting ET and LiQ into different evaporation units, co-depositing at a ratio of 50 wt% respectively, and forming an electron transport layer with a thickness of 25nm on the luminescent layer

5) And (3) preparing a cathode, namely evaporating 2nm barium and 100nm aluminum on the electron transport layer in sequence to finish the light-emitting device.

6) All devices were encapsulated in a nitrogen glove box with uv cured resin plus glass cover plate.

The current-voltage and emission (IVL) characteristics of the blue device were characterized by characterization equipment, while recording important parameters such as efficiency, lifetime and drive voltage. The performance of the blue OLED devices is summarized in the table. The efficiency and lifetime are relative comparative values.

The preparation methods of OLED-1 to OLED-8 are the same as OLED-Ref, except that the HIL functional layer employs the corresponding polymers in Table 1.

The polymers according to the invention provide a significant improvement in efficiency when used in HTL's over other comparative device performance. This is probably because the polymer having a condensed ring structure according to the present invention has a better intramolecular conjugation effect.

It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.

Preparation and characterization of OFET devices

Fabricating a top-gate Organic Field Effect Transistor (OFET) on a glass substrate with gold source-drain electrodes: polymer P8 was dissolved in an organic solvent dichlorobenzene solution (5mg/mL), spin-coated on top, annealed at 150 ℃ for 5 minutes in air after spin-coating was complete, followed by spin-coating a fluoropolymer dielectric material (C.) (

Merck, germany). Finally, a gold gate electrode is deposited. Characterization was performed under air using an Agilent4155C semiconductor parametric analyzer. Charge carrier mobility (μ) in the saturation region was calculated_sat) The following formula is used:

wherein W is the channel width, L is the channel length, C_iIs an insulating layer capacitor, V_gIs the gate voltage, V₀Is the turn-on voltage, mu_satIs the saturation region carrier mobility.

Polymer and method of making same	Charge carrier mobility (cm)²V^-1s^-1)
		P8	1.13 ⅹ 10^-3

Claims

1. A polymer containing a condensed ring aromatic hydrocarbon group having a repeating unit represented by the general formula (1):

wherein:

a. b and c each represents A₁、A₂And A₃Mole percent of a>0, b is more than or equal to 0, c is more than or equal to 0, and a + b + c is 1;

A₂and A₃Each occurrence is independently selected from a substituted or unsubstituted aromatic or heteroaromatic group having from 5 to 60 ring atoms; or a substituted or unsubstituted non-aromatic ring system having 3 to 25 ring atoms; or a substituted or unsubstituted aromatic amine group having 5 to 60 ring atoms;

R₁～R₁₄each occurrence is independently selected from hydrogen, or D, or a straight chain alkyl, alkoxy or thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20C atoms, or 1 to 20 substituted or unsubstitutedAlkylene having C atoms, or alkynylene having 1 to 20C atoms which may be substituted or unsubstituted, or silyl, or keto having 1 to 20C atoms, or alkoxycarbonyl having 2 to 20C atoms, or aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxy, nitro, CF₃Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having from 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having from 5 to 60 ring atoms, or a combination of these systems, where two or more adjacent groups may optionally form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system with one another.

2. The polymer of claim 1, wherein b is>0, and A₂One or more combinations comprising the following structural groups:

wherein: x is independently selected from CR at each occurrence₁₅Or N;

each occurrence of Y is independently selected from CR₁₅R₁₆、SiR₁₅R₁₆、NR₁₅、C(＝O)、S、SO₂Or O;

R₁₅and R₁₆Each occurrence is independently selected from hydrogen, or D, or a straight chain alkyl, alkoxy or thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20C atoms, or an alkylene group having 1 to 20C atoms, which may be substituted or unsubstituted, or an alkynyl group having 1 to 20C atoms, which may be substituted or unsubstituted, or a silyl groupA group, or a keto group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate, a thiocyanate or isothiocyanate, a hydroxyl group, a nitro group, a CF₃Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having from 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having from 5 to 60 ring atoms, or a combination of these systems, where two or more adjacent groups may optionally form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system with one another.

3. The polymer of claim 2, wherein b is>0, and A₂One or more combinations comprising the following structural groups:

wherein: and n is independently selected from integers of 1-3 at each occurrence.

4. The polymer of claim 3, wherein the polymer is selected from any one of the general formulas (3-1) to (3-8):

5. the polymer of any of claims 1-4, wherein: c. C>0, and A₃Is a unit with hole transmission property, and is selected from one or the combination of the following groups:

wherein:

x is independently selected from CR at each occurrence₁₅Or N;

R₁₅and R₁₆Each occurrence is independently selected from hydrogen, or D, or a straight chain alkyl, alkoxy or thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20C atoms, or an alkylene group having 1 to 20C atoms, which is substituted or unsubstituted, or an alkynyl group having 1 to 20C atoms, which is substituted or unsubstituted, or a silyl group, or a ketone group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate, a thiocyanate or isothiocyanate, a hydroxyl group, a nitro group, a CF, a hydroxyl group, a cyano group, a hydroxyl group, a carboxyl group, a cyano group, a carbamoyl group, a₃Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having from 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having from 5 to 60 ring atoms, or a combination of these systems, where two or more adjacent groups may optionally form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system with one another.

6. The polymer of any of claims 1-4, wherein: c. C>0，A₃Is a unit with electron transmission property, and is selected from one or the combination of the following groups:

wherein: the H atoms on the ring may be further substituted;

n1 represents an integer of 1 to 20;

Z₁-Z₈at each occurrence, is independently selected from CR₁₈Or N;

M₁、M₂、M₃each independently represents NR₁₈、CR₁₈R₁₉、SiR₁₈R₁₉、O、C＝NR₁₈、C＝CR₁₈R₁₉、PR₁₈、P(＝O)R₁₉、S、S＝O、SO₂Or none;

R₁₇～R₁₉each occurrence is independently selected from hydrogen, or D, or a straight chain alkyl, alkoxy or thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20C atoms, or an alkylene group having 1 to 20C atoms, which is substituted or unsubstituted, or an alkynyl group having 1 to 20C atoms, which is substituted or unsubstituted, or a silyl group, or a ketone group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate, a thiocyanate or isothiocyanate, a hydroxyl group, a nitro group, a CF, a hydroxyl group, a cyano group, a hydroxyl group, a carboxyl group, a cyano group, a carbamoyl group, a₃Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having from 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having from 5 to 60 ring atoms, or a combination of these systems, where two or more adjacent groups may optionally form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system with one another;

Ar₄～Ar₆each occurrence is independently selected from a substituted or unsubstituted aromatic or heteroaromatic group having from 5 to 60 ring atoms; or a non-aromatic ring system having 3 to 25 ring atoms which may be substituted or unsubstituted.

7. The polymer of claim 1, wherein a >0, b >0, c >0, wherein,

A₂selected from any of the following formulas:

A₃selected from any of the following formulas:

wherein: x is independently selected from CR at each occurrence₁₅Or N;

R₁₅and R₁₆Each occurrence is independently selected from hydrogen, or D, or a straight chain alkyl, alkoxy or thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20C atoms, or an alkylene group having 1 to 20C atoms, which is substituted or unsubstituted, or an alkynyl group having 1 to 20C atoms, which is substituted or unsubstituted, or a silyl group, or a ketone group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate, a thiocyanate or isothiocyanate, a hydroxyl group, a nitro group, a CF, a hydroxyl group, a cyano group, a hydroxyl group, a carboxyl group, a cyano group, a carbamoyl group, a₃Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having from 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having from 5 to 60 ring atoms, or a combination of these systems, where two or more adjacent groups may optionally form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system with one another;

and n is independently selected from integers of 1-3 at each occurrence.

8. The polymer of claim 1, wherein A is₃And A₂At least one of which contains a crosslinkable group; the crosslinkable group is selected from linear or cyclic alkenyl, linear dienyl, alkynyl, alkenyloxy, dienyloxy, acrylic, glycidoxy, epoxybutyl, silyl, cyclobutylalkyl.

9. The polymer of claim 8, wherein A is₃Contains crosslinkable group, and the crosslinkable group is vinyl.

10. The polymer according to claim 1, characterized in that it is selected from the compounds having the following structure:

11. a mixture comprising at least one polymer according to any of claims 1 to 10 and at least one further organic functional material selected from one or more of hole injecting materials, hole transporting materials, p-dots, electron transporting materials, electron injecting materials, electron blocking materials, hole blocking materials, light emitting materials, host materials and organic dyes.

12. A composition comprising at least one polymer according to any one of claims 1 to 10 or a mixture according to claim 11, and at least one organic solvent.

13. An organic electronic device comprising a polymer as claimed in any of claims 1 to 10 or a mixture as claimed in claim 11.