TW201302812A - Polymer and optoelectronic device - Google Patents

Abstract

A polymer comprising a repeat unit of formula (X): wherein R10 in each occurrence represents H or a substituent; Sp2 represents a spacer group; t is 0 or 1; and POZ represents an optionally substituted, optionally fused phenoxazine group.

Description

Polymer and photovoltaic device

This invention relates to polymers, organic optoelectronic devices comprising such polymers, and methods of making such polymers and devices.

Electronic devices containing active organic materials are attracting more and more attention due to their use in devices such as organic light-emitting diodes, organic light-responsive devices (specifically, organic photovoltaic devices and organic light sensors). , organic transistor and memory array device. Devices containing organic materials offer a variety of benefits such as low weight, low power consumption and flexibility. Additionally, the use of soluble organic materials allows solution processing, such as inkjet printing or spin coating, to be used in the manufacture of the device.

The organic optoelectronic device can include a substrate carrying an anode, a cathode, and an organic semiconductor layer comprising a luminescent material between the anode and the cathode.

In the case where the device is an organic light-emitting device (OLED), the organic semiconductor layer is an organic light-emitting layer. During operation of the device, the holes are injected into the device via an anode (eg, indium tin oxide or ITO) and electrons are injected through the cathode. The holes in the highest occupied molecular orbital (HOMO) of light combine with the electrons in the lowest unoccupied molecular orbital (LUMO) to form excitons that release energy in the form of light. Suitable luminescent materials include small molecules, polymeric and dendritic materials. Suitable luminescent polymers for use in the luminescent layer include poly(arylene extended vinyl) (e.g., poly(p-phenylene vinyl)) and poly(aryl) (e.g., polyfluorene). Alternatively or additionally, the luminescent layer can comprise a host material and an emissive dopant (eg, a fluorescent or phosphorescent dopant).

The operation of the organic photovoltaic device or the photosensor necessitates reversing the above process, in which photons incident on the organic semiconductor layer generate excitons, which are separated into holes and electrons.

To facilitate the transfer of holes and electrons into the luminescent layer of the OLED (or in the case of a photovoltaic device or photosensor device, the transfer of separated charge towards the electrode), additional layers, such as an anode, may be provided between the anode and the cathode. An electron transport layer between the hole transport layer and/or the cathode and the light-emitting layer between the light-emitting layer.

One type of known hole transport material is electron-rich triphenylamine. WO 01/66618 discloses an organic light-emitting device in which a triphenylamine repeating unit of a hole transporting polymer is substituted with a pull-electron trifluoromethyl group to adjust the HOMO value of the repeating units.

Additionally or alternatively, a hole injection layer may be provided between the anode and the luminescent layer. The known hole injection layer comprises a conductive organic material such as poly(ethylene dioxythiophene) (PEDT), in particular a PEDT doped with a charge-balanced polyacid such as polysulfonated styrene (PSS), as in EP. And disclosed in 0901176; and conductive inorganic materials such as Vox, MoOx, and RuOx, as disclosed in Journal of Physics D: Applied Physics (1996), 29(11), 2750-2753.

Bardecker et al., Adv. Funct. Mater. 2008, 1,3964-3971 discloses an OLED having a self-assembled monolayer (SAM) on the surface of the ITO anode and a cross-linking 4,4',4"- over the SAM. A hole transport layer of tris(N-carbazolyl)triphenylamine bis(vinylbenzyl ether) or "BVB-TCTA". The device was formed using a SAM having a phosphonic acid group to bind to ITO.

Polymers and single layer devices comprising pendant tunnel transport groups are described in J. Mater. Chem., 2001, 11, 3023-3030, discloses a polyphenylene stretch vinyl derivative having a carbazole pendant group.

Adv. Mater. 2009, 21, 1972-1975 discloses polystyrene having a pendant hole transporting group bonded to the top of the ITO/PEDT:PSS anode/hole injection double layer.

Photocrosslinkable hole transport polymers comprising a triarylamine and an oxetane functionalized styrene copolymerized by free radical polymerization are disclosed in Macromolecules 2005, 38, 1640-1647.

Macromolecules 2009, 42, 4053-4062 discloses polyfluorenes having pendant charge transporting groups.

Chem. Mater. 2007, 19, 4827-4832 discloses an intermediate layer formed by crosslinking a non-conjugated backbone with a pendant benzocyclobutane (BCB) crosslinker and a hole transporting group.

WO 03/086026 discloses a hole transport polymer comprising a polyacrylate, polymethacrylate or polystyrene polymeric backbone and a pendant fused aromatic hole transport unit.

EP0712171, EP0850960, EP0851017, FR2736061, FR2785615, WO0002936, WO9965961 disclose a hole transport, electron transport and emission unit for use as an active pendant group. Examples of the disclosed active pendant groups include naphthylimine, carbazole, pyrazoline, benzoxazole, benzothiazole, anthracene, phenanthrene. The polymer backbone includes polyacrylate, polystyrene, polyethylene. Thermally induced and light-induced cross-linking units are also described.

The preparation and use of polymers having pendant active units are also set forth in the following references: J. Mat. Chem., 2007, 17, 4122-4135 describes tetrathiafulvalene (TTF) derivatives which are useful as pendant groups for electron donating polymers.

J. Mat. Chem, 1993, 3(1), 113-114 describes polymers containing pendant oligothiophenes which are useful as novel classes of electrochromic materials.

Macromolecules, 1995, 28, 723-729 describes the synthesis of polythiophenes, which are used as pendant groups for vinyl type electrochemically doped polymers.

Appl. Phys Lett., 2006, 88, 093505 describes tetraphenyldiamine as well as carbazole and triphenylamine derivatives for use in phosphorescent polymer LEDs. Proc. Of SPIE, Volume 6333 63330G-1 illustrates hole transport and emission of pendant polymers for use in OLEDs.

Synthetic Metals, 2008, 158, 670-675 describes the synthesis of novel hole transport molecular glasses with pendant carbazolyl moieties.

J. Mat. Chem., 2008, 18, 4495-4509 discloses crosslinkable hole transport materials for solution treated OLEDs.

In a first aspect, the invention provides a polymer comprising a repeating unit of formula (X): Wherein R ¹⁰ represents H or a substituent at each occurrence; Sp ² represents a spacer; t is 0 or 1; and POZ represents a phenoxazinyl group which is optionally substituted, optionally fused.

Optionally, the polymer comprises a repeating unit of formula (Xa): Wherein R ¹⁰ represents H or a substituent at each occurrence; Sp ² represents a spacer; t is 0 or 1; d is independently 0, 1, 2, 3 or 4 at each occurrence; R ⁸ is each When present, it represents a substituent; and the two substituents R ⁸ attached to the same benzene ring form a saturated or unsaturated ring.

Depending on the case, R ⁸ and R ¹⁰ are each independently selected from the group consisting of H; optionally substituted aryl; optionally substituted heteroaryl; and alkyl, optionally C _{1- a 20} alkyl group, wherein one or more non-adjacent C atoms in the alkyl group may be replaced by O, S, substituted N, -C=O and -COO-, -Si-, and one of the alkyl groups or Multiple H atoms can be replaced by F or aryl or heteroaryl groups. Preferred groups R ⁸ include a C _1-20 alkyl group and a phenyl group which may be unsubstituted or substituted with one or more C _1-20 alkyl groups. Preferred groups R ¹⁰ include H, C _1-20 alkyl and phenyl which may be unsubstituted or substituted by one or more C _1-20 alkyl groups.

Optionally, Sp ² comprises at least one non-cyclic atom that separates the phenoxazine unit from the polymer backbone.

Depending on the case, Sp ² contains an aryl group, optionally a phenyl group.

As the case may be, Sp ² contains an alkyl chain (optionally a C _1-20 alkyl chain), an alkoxy group or an ether group.

Optionally, the polymer comprises one or more other repeating units than the repeating unit of formula (X).

Optionally, one or more other repeating units include crosslinkable repeating units.

Optionally, one or more other repeating units comprise repeating units comprising a charge transport unit having a HOMO value that is different from the repeating unit of formula (X).

In a second aspect, the invention provides an organic electronic device comprising a polymer of a first aspect.

Optionally, the organic electronic device is an organic light-emitting device comprising an anode, a cathode, and a light-emitting layer between the anode and the cathode.

Optionally, the luminescent layer comprises a first aspect of the polymer.

Optionally, the luminescent layer further comprises an luminescent dopant.

Optionally, a charge transport layer is provided between the anode and the luminescent layer or between the cathode and the luminescent layer, the charge transport layer comprising a first aspect of the polymer. The charge transport layer is optionally a hole transport layer.

A composition comprising the polymer of the first aspect and at least one solvent can be provided, and the composition can be used to form a layer of an organic electronic device by depositing the composition from a solution stored in a solvent and evaporating the solvent. If the polymer of the first aspect comprises a crosslinkable repeating unit, the unit can be crosslinked. Another layer can then be deposited from the solution onto the crosslinked layer.

In a third aspect, the invention provides a polymer having a backbone and comprising first and second repeat units, wherein: the first repeat unit comprises a first backbone segment and hangs from the first backbone segment a first charge transporting group spaced apart from the first backbone segment by the first spacer, the first spacer comprising at least 4 non-ring atoms in a path connecting the first charge transport group to the polymer backbone And the second repeating unit comprises a second main chain segment and a crosslinkable group suspended from the second main chain segment and separated from the second main chain segment by the second spacer.

Depending on the situation, the main chain is substantially non-conjugated according to the third aspect.

Optionally, according to the third aspect, the first repeating unit has the formula (I): Wherein each R independently represents H or a substituent; Sp represents a first spacer; and CT represents a first charge transporting group.

Optionally, according to the third aspect, the second repeating unit has the formula (II): Wherein each R ¹ independently represents H or a substituent; Sp ¹ represents a second spacer; and XL represents a crosslinkable group.

Optionally, according to the third aspect, Sp ¹ comprises at least one non-ring atom of the interval XL and the second main chain segment.

Optionally, depending on the third aspect, the polymer contains one or more other repeating units.

Optionally, according to a third aspect, the polymer comprises one or more other repeating units, each of the one or more other repeating units comprising another charge transporting group than the first charge transporting group.

Depending on the situation, according to the third aspect, the other repeating units have the formula (XI): Wherein R ⁹ is H or a substituent which may be the same or different at each occurrence; a Sp ³ line spacer; w is 0 or 1; and CT 2 is the other charge transport group.

Optionally, according to the third aspect, the polymer comprises another repeating unit which is not substituted with a charge transporting group or a crosslinkable group.

Optionally, according to the third aspect, the further repeating unit is a styryl repeating unit, optionally via one or more selected from C _1-20 alkyl groups (wherein one or more non-adjacent C atoms of the alkyl group) Substituted by a substituent of O or S).

Optionally, according to the third aspect, R and R ¹ are each independently selected from the group consisting of: H; optionally substituted aryl; optionally substituted heteroaryl; and alkyl, Wherein one or more non-adjacent C atoms of the alkyl group may be replaced by O, S, substituted N, -C=O and -COO-, -Si-, and one or more H atoms of the alkyl group may pass through F Or an aryl or heteroaryl group.

Optionally, according to the third aspect, Sp comprises an alkyl chain (as appropriate, a C _4-20 alkyl chain), an alkoxy group or an ether group.

Optionally, according to the third aspect, Sp ¹ comprises an alkyl chain (as appropriate, a C _1-20 alkyl chain), an alkoxy group or an ether group.

Optionally, according to the third aspect, the first charge transporting group is a hole transporting group, an electron transporting group or a bipolar group.

Optionally, according to the third aspect, the crosslinkable group contains a polymerizable double bond, optionally substituted benzocyclobutane group or oxetane group.

Optionally, according to the third aspect, the first spacer comprises no more than 8 non-ring atoms spaced apart from the first charge transporting group and the first backbone segment.

Optionally, according to the third aspect, the second spacer comprises no more than 8 non-ring atoms of the crosslinkable group and the second backbone segment.

Optionally, according to the third aspect, the number of acyclic atoms of Sp plus the number of acyclic atoms of Sp1 does not exceed 10.

In addition to the repeating unit of formula (X), the polymer of the first aspect may comprise one or more repeating units which are illustrated in the third aspect of the invention and which differ from the repeating unit of formula (X).

In a fourth aspect, the invention provides a composition comprising a third aspect of a polymer and at least one solvent.

Optionally, according to the fourth aspect, the at least one solvent is selected from the group consisting of mono- or polyalkylated benzene.

In a fifth aspect, the present invention provides a method of forming a third aspect polymer by copolymerizing a first monomer to form a first repeating unit and copolymerizing a second monomer to form a second repeating unit.

In a sixth aspect, the invention provides an optoelectronic device comprising a layer comprising a polymer of a third aspect.

Optionally, according to the sixth aspect, the device is an organic light-emitting device.

Optionally, according to the sixth aspect, the layer is a hole transport layer.

In a seventh aspect, the present invention provides a method of forming an optoelectronic device, comprising the steps of: providing a first electrode; forming a charge transport layer by depositing a first aspect of the polymer over the first electrode; Crosslinking; depositing an organic semiconductor layer over the charge transport layer; and forming a second electrode over the organic semiconductor layer.

Optionally, according to the seventh aspect, the charge transport layer is a hole transport layer.

Optionally, according to the seventh aspect, a hole injection layer is deposited between the first electrode and the hole transport layer.

Optionally, according to the seventh aspect, the surface of the first electrode is modified by a self-assembled monolayer.

Optionally, according to the seventh aspect, the step of forming the charge transport layer comprises depositing a composition of the fourth aspect and evaporating at least one solvent.

Polymer backbone

The atoms that can be joined together to form a non-conjugated chain form the backbone of the polymer of the present invention.

The non-conjugated backbone can be formed by polymerizing a reactive monomer or a monomer comprising a reactive unsaturated group such as a carbon-carbon unsaturated bond, specifically a carbon-carbon double bond, to provide A backbone formed by a chain of carbon atoms.

Exemplary reactive monomers that form repeating units to form a non-conjugated backbone together include optionally substituted styrene, acrylates (including alkyl acrylates such as methacrylates), and vinyl groups. The monomers can be polymerized by methods known to those skilled in the art, such as free radical polymerization, ring opening metathesis polymerization (ROMP), and cationic or anionic polymerization.

The polymer backbone may further comprise a substituent selected from the group consisting of: an optionally substituted aryl; an optionally substituted heteroaryl; and an alkyl group wherein one or more non-adjacent C atoms of the alkyl group It may be replaced by O, S, substituted N, -C=O and -COO-, -Si-, and one or more H atoms of the alkyl group may be replaced by F or an aryl or heteroaryl group. The backbone substituent can be a solubilizing group such as an alkyl group.

Charge transport polymer side chain

Polymer backbone can carry (Ia) charge transport side chain: -Sp-CT (Ia)

Sp and charge transport group CT are set forth in more detail below.

The polymer side chain (Ia) can be attached to the polymer after the polymer backbone is formed. Alternatively, the monomer used to form the polymer backbone can be substituted with a side chain (Ia).

In one configuration, the charge transport side chains of the polymer can be the same. In another configuration, two or more different charge transport side chains can be provided. One or both of Sp and CT in different side chains may differ.

Polymers may carry side phenoxazine group, which may or may not by spacer group (e.g., set forth above, the spacer group Sp ²⁾ attached to the polymer backbone. The phenoxazine pendant group can be attached to the spacer via an aromatic carbon atom of the phenoxazine unit or via the N atom of the phenoxazine unit.

Crosslinking polymer side chains

The polymer backbone can carry a cross-linking chain of formula (IIa): -Sp ¹ -XL (IIa) wherein Sp ¹ is a spacer as set forth in more detail below, and XL is a crosslinkable group.

Exemplary crosslinkable groups XL include groups comprising a polymerizable double bond, such as a vinyl or acrylate group; optionally substituted benzocyclobutane (BCB) groups or oxetane groups.

After ring opening and subsequent cyclization without the formation of any by-products, the XL group may be crosslinkable under thermal conditions.

Charge transport group

One or more of the charge transporting groups of the polymer may each be a hole transporting group, an electron transporting group, or a bipolar group capable of transporting both holes and electrons.

The hole transport group can have low electron affinity (2 eV or lower) and low power The off potential (5.8 eV or lower, preferably 5.7 eV or lower, more preferably 5.6 eV or lower).

The electron transport group can have a high electron affinity (1.8 eV or higher, preferably 2 eV or higher, even more preferably 2.2 eV or higher) and a high ionization potential (5.8 eV or higher). Suitable electron transport groups include those disclosed, for example, in Shirota and Kageyama, Chem. Rev. 2007, 107, 953-1010.

Electron affinities and ionization potentials can be measured by cyclic voltammetry (CV).

One class of exemplary charge transporting groups are fused and thiophenes, each of which is optionally substituted with one or more substituents R3 as set forth below. Exemplary fused thiophenes include the following groups:

R ³ is H or a substituent at each occurrence, as explained in more detail below. Illustrative substituent R ³ includes optionally substituted alkyl, optionally substituted aryl or optionally substituted heteroaryl, preferably substituted alkyl, for example C _1-20 alkyl .

The thiophene can be substituted with one or more other substituents R ³ .

Another class of exemplary charge transporting groups are fused polycyclic aromatic compounds, for example, 3 to 7 fused benzene rings, each optionally having one or more substituents R ³ (eg, alkyl) as set forth below. Substituted, including, for example, pentacene, as appropriate.

Another class of exemplary charge transport groups are amine-containing hole transport groups, such as (hetero)arylamine groups of formula (III): Wherein Ar ¹ and Ar ² are independently selected, at each occurrence, from an optionally substituted aryl or heteroaryl group, m is greater than or equal to 1 (preferably 1 or 2), R ² is H, and x and y Each is independently 1, 2 or 3.

Any of the aryl or heteroaryl groups in the repeating unit of formula (III) may be bonded by a direct bond or a divalent linking atom or group.

The substituent R ^{2 is} preferably selected from the group consisting of an alkyl group (for example, a C _1-20 alkyl group), a branched chain of an Ar ³ or Ar ³ group, or a linear chain (for example, -(Ar ³ ) _r ), wherein Ar ^{3 is} present each time. When present, it is independently selected from aryl or heteroaryl and r is at least 1 (as appropriate, 1, 2 or 3).

Any of Ar ¹ , Ar ² and Ar ³ may be independently substituted with one or more substituents. Preferred substituents are selected from the group consisting of R ³ :alkyl (eg, C _1-20 alkyl), wherein one or more non-adjacent C atoms may be O, S, substituted N, C=O, and -COO-substitution, and one or more H atoms of the alkyl group may be substituted by F or, optionally, an aryl or heteroaryl group substituted with one or more groups R ⁴ , optionally via one or more groups R ^a substituted aryl or heteroaryl group, NR ⁵ ₂ , OR ⁵ , SR ⁵ , fluorine, nitro and cyano; wherein each R ^{4 is} independently alkyl (for example C _1-20 alkyl), wherein One or more non-adjacent C atoms may be replaced by O, S, substituted N, C=O and -COO-, and one or more H atoms of the alkyl group may be replaced by F, and each R ^{5 is} independent The group is selected from the group consisting of an alkyl group and, optionally, an aryl or heteroaryl group substituted with one or more alkyl groups.

If present, the substituted N or substituted C of R ³ , R ⁴ or a divalent linking group can each independently be NR ⁶ or CR ⁶ ₂ , wherein R ⁶ is alkyl or An aryl or heteroaryl group substituted. An optional substituent of the aryl or heteroaryl R ⁶ may be selected from R ⁴ or R ⁵ .

In a preferred configuration, R ² is Ar ³ and each of Ar ¹ , Ar ² and Ar ³ is independently and optionally substituted with one or more C _1-20 alkyl groups.

In another preferred configuration, an aryl or heteroaryl phenyl group of formula (III), each phenyl group being optionally substituted with one or more alkyl groups.

In another preferred configuration, Ar ¹ , Ar ² and Ar ³ -based phenyl groups, each of which may be substituted by one or more C _1-20 alkyl groups, and each of r, x and y is 1.

In another preferred configuration, Ar ¹ and Ar ² are phenyl groups, each of which may be substituted with one or more C _1-20 alkyl groups, and R is 3,5-diphenylbenzene, each of which Monophenyl can be substituted by one or more alkyl groups.

In still another preferred configuration, Ar ¹ , Ar ² and Ar ³ phenyl groups, each of which may be substituted by one or more C _1-20 alkyl groups, r=1 and Ar ¹ and Ar ² are Attached by O or S atoms, such as oxazole substituted with one or more alkyl groups.

In still another preferred configuration, Ar ¹ and Ar ² are phenyl groups, each of which may be substituted with one or more C _1-20 alkyl groups, R ² C _1-20 alkyl groups or one or more a C _1-20 alkyl substituted phenyl group; m, r, x and y each are 1 and Ar ¹ and Ar ² are linked by a direct bond, for example a carbazole substituted with one or more alkyl groups.

Exemplary charge transport amines include the following: Wherein * represents a charge transporting group and the polymer backbone or the attachment point Sp, R ³ and lines as set forth above. If * is not shown, the charge transport group can be attached via any aromatic ring atom of the charge transport group.

The spacer may be bonded to any of the above-mentioned charge transport groups, for example, to the aromatic C atom of the group of formula (III) or to the N atom.

After deposition from the solution, the side chains of the polymer can undergo a π-π stack, which can be used to increase the hole mobility of the hole transport layer.

Spacer

As compared to the absence of a polymer spacer, the spacer group Sp, Sp ^1, Sp ² and Sp ³ solubility increase of polymer. In addition, the spacer may contain a non-conjugated atom to separate and prevent conjugated charge transport groups from any unsaturated groups (eg, aromatic groups) that may be present in another portion of the backbone or side chain. . The spacer may contain a flexible chain in which the chain atom does not form part of the ring (eg, an alkyl group in which the carbon atom is not part of the ring), thereby providing sufficient flexibility for the charge transporting group and the crosslinking group. .

Exemplary spacers include: - a straight or branched alkyl group, such as a C _4-20 alkyl chain in the case of Sp and a C _1-20 alkyl chain in the case of Sp ¹ , Sp ² or Sp ³ And - an ether group or a polyether group, for example, a formula -(CH ₂ CH ₂ O)n- group, wherein n is at least 1.

Spacer groups Sp, Sp ^1, Sp ² and Sp ³ independently can comprise ring atoms, for example, benzene, thus separating the charge-transporting group and the polymer backbone. For example, the phenyl group of the styrene monomer can form part of a spacer. However, Sp and, as the case may be, Sp ¹ , Sp ² and Sp ³ contain at least 4 spacer charge transport groups and acyclic atoms of the polymer backbone. In one configuration, the total number of non-cyclic atoms separating the charge transporting group and the crosslinkable group from the polymer backbone in Sp and Sp1 may be less than or equal to 10. In another configuration, Sp and/or Sp1 can have no more than 8 spacer charge transport groups and a non-cyclic atom of the crosslinkable group and the polymer backbone, respectively. For example, Sp may contain 6 acyclic atoms and Sp ¹ may contain 4 acyclic atoms. Up to 10 acyclic spacer atoms provide good polymer solubility without adversely affecting the semiconducting properties of the polymer due to the presence of non-semiconductor long spacers. Preferably, the non-cyclic atom of Sp and/or Sp1 is provided in a continuous chain, preferably a saturated chain.

Polymer repeating unit and composition

In one configuration, the polymer may be a polymer containing only repeating units of formula (I) and (II); a polymer containing only repeating units of formula (X); or only formula (X) and formula (II) The polymer of the repeating unit. In another configuration, the polymer may contain one or more other repeating units, such as repeating units having side chains different from the side chains of units (I) and (II), such as spacer co-repeat units. These other repeating units can be selected to modify the properties of the polymer, such as its electronic or physical properties (e.g., solubility of the polymer).

The polymer may contain more than one charge transport repeating unit. For example, the polymer may comprise a repeating unit of formula (I) or a repeating unit of formula (X) and one or more other repeating units containing different repeating units of charge transport. These other repeating units can provide different energy levels to allow for stepped charge transfer between the electrodes and the luminescent layer. For example, the polymer may comprise the formula (X) a hole transport repeating unit and another hole transport repeating unit having different hole transport units to provide a HOMO value different from the repeating unit of formula (X), such as the formula (I) as set forth above a repeat unit in which CT is not phenoxazine. The polymer may also comprise two different repeating units of formula (X) wherein the different repeating units differ in at least the HOMO values of the POZ groups of the individual repeating units due to the different substituents on the POZ group.

The polymer can be in any form of polymer, including random, block or stereoregular polymers, and the polymerization process employed can be selected accordingly.

If present, the crosslinkable repeating unit can be up to 20 mole percent, optionally in the range of from 0.5 mole percent to 20 mole percent, optionally in the range of from 1 mole percent to 15 mole percent, of the polymer. Provided in.

Exemplary polymers can include one or more charge transport repeat units, one or more crosslinkable repeat units, and one or more other repeat units selected from the group consisting of: charge transport repeat units:

Polymers comprising more than one charge transport repeat unit are explained below:

Crosslinkable repeating unit:

Other repeating units that do not provide any charge transport or cross-linking function are explained below: Where f is 1-5, as appropriate 1-3.

Crosslinked charge transport polymer: Wherein n+m represents the percentage of moles of repeating units in the polymer, and n+m=100. In other configurations, there may be other repeating units, in which case n+m is less than 100. Wherein n+m+p represents the percentage of moles of repeating units in the polymer, and n+m+p=100. In other configurations, there may be other repeating units, in which case n+m+p is less than 100.

The above exemplary polymers are not limited, and it will be appreciated that those skilled in the art will be aware of combinations of one or more of the charge transport repeating units and crosslinkable repeating units as set forth herein. For example, any of the benzocyclobutane crosslinkable repeat units explained above may comprise a crosslinkable group as set forth above. Another crosslinkable repeat unit of XL is substituted.

Charge transporting repeat units, repeating units and cross-linking repeating units each Jieke other by one or more substituents R ³ (e.g. one or more alkyl).

The presence of two different charge transport groups having different energy levels in the polymer allows for the stepwise injection of charge from the electrode into the luminescent layer via the charge transport layer containing the polymer between the electrode of the OLED and the luminescent layer.

FIG. 1 schematically illustrates an OLED of an embodiment of the present invention.

The OLED comprises a substrate 1; an anode 2 for injecting a hole into the device; a hole transport layer 3 comprising the polymer of the invention above the anode; a light-emitting layer 4 above the hole transport layer; and a cathode 5 above the light-emitting layer It is used to inject electrons into the device. Other charge transport layers, charge blocking layers, and/or charge injection layers may be provided between the anode and the cathode.

If the light is transmitted through the anode and the substrate, the substrate can be formed from a transparent material such as glass or transparent plastic, and the anode can be formed from a transparent conductive material. If the cathode 5 is transparent, the substrate and/or anode can be opaque.

anode

The anode 2 can be formed from any material suitable for injecting a hole. Suitable materials include metals, metal alloys, and conductive metal oxides. An exemplary transparent anode material is indium tin oxide. The anode surface can be modified by a self-assembled monolayer such as fluorinated phosphonic acid.

Hole injection layer

A conductive hole injection layer that can be formed from a conductive organic or inorganic material can be provided between the anode 2 and the hole transport layer 3. Doped organic hole injection material Examples include optionally substituted poly(vinyldioxythiophene) (PEDT), in particular doped with a charge-balancing polyacid (for example, polysulfostyrene as disclosed in EP 0901176 and EP 0947123 (PSS), polyacrylic acid or fluorinated sulfonic acid (e.g., Nafion®) PEDT; polyaniline as disclosed in U.S. Patent 5,723,873 and U.S. Patent 5,798,170; and optionally substituted polythiophene or poly(thienothiophene). Examples of conductive inorganic materials include transition metal oxides such as VOx, MoOx, and RuOx as disclosed in Journal of Physics D: Applied Physics (1996), 29(11), 2750-2753.

Charge transport layer

Another hole transport layer may be provided between the anode 2 and the light-emitting layer 4. Also, an electron transport layer can be provided between the cathode 5 and the light-emitting layer 4.

Similarly, an electron blocking layer may be provided between the anode 2 and the light-emitting layer 4, and a hole blocking layer may be provided between the cathode 5 and the light-emitting layer 4. The transport layer and the barrier layer can be used in combination. Looking at the HOMO and LUMO values of a single layer, it can transmit one of the holes and electrons, and block the other of the holes and electrons.

Luminous layer

Luminescent materials suitable for use in the luminescent layer include small molecules, polymeric and dendritic materials, and combinations thereof. Suitable luminescent polymers include conjugated polymers such as optionally substituted poly(aryl extended vinyl) (e.g., poly(p-phenylene vinyl)) and optionally substituted polyaryl groups, for example: poly茀, especially 2,7-linked 9,9-dialkyl polyfluorene or 2,7-linked 9,9-diarylpolyfluorene; polyspilen, especially 2,7-linked poly-9,9- Snail; 茚 茚 茀, especially 2,7- Agglomerated polyfluorene; a polyphenylene group, especially a poly-1,4-phenylene group substituted by an alkyl group or an alkoxy group. Such polymers are disclosed, for example, in Adv. Mater. 2000 12(23) 1737-1750 and references therein.

The polymer used as the luminescent material in the device of the present invention may comprise a repeating unit selected from optionally substituted amine repeating units and/or optionally substituted aryl or heteroaryl repeating units.

An exemplary amine repeat unit has the formula (IV): Wherein Ar ¹ and Ar ² are independently selected, at each occurrence, from an optionally substituted aryl or heteroaryl group, m is greater than or equal to 1 (preferably 1 or 2), and R ² is H or a substituent (compare Preferably, the base is substituted, and x and y are each independently 1, 2 or 3.

R ^{2 is} preferably a branched chain of an alkyl group (e.g., a C _1-20 alkyl group), an Ar ³ or Ar ³ group, or a linear chain (e.g., -(Ar ³ ) _r ), wherein Ar ³ is independently present at each occurrence. It is selected from an aryl or heteroaryl group, and r is at least 1 (as appropriate, 1, 2 or 3).

Any of Ar ¹ , Ar ² and Ar ³ may be independently substituted with one or more substituents. Preferred substituents are selected from the group consisting of R ³ :alkyl (eg, C _1-20 alkyl), wherein one or more non-adjacent C atoms may be O, S, substituted N, C=O, and -COO-substitution, and one or more H atoms of the alkyl group may be substituted by F or, optionally, an aryl or heteroaryl group substituted with one or more groups R ⁴ , optionally via one or more groups R ^{a 4-} substituted aryl or heteroaryl group, NR ⁵ ₂ , OR ⁵ , SR ⁵ and a fluorine, a nitro group and a cyano group; wherein each R ^{4 is} independently an alkyl group (for example, a C _1-20 alkyl group), wherein One or more non-adjacent C atoms may be replaced by O, S, substituted N, C=O and -COO-, and one or more H atoms of the alkyl group may be replaced by F, and each R ^{5 is} independent The group is selected from the group consisting of an alkyl group and, optionally, an aryl or heteroaryl group substituted with one or more alkyl groups.

Any of an aryl group or a heteroaryl group in the repeating unit of the formula (IV) may be bonded by a direct bond or a divalent linking atom or group. Preferred divalent linking atoms and groups include O, S; substituted N; and substituted C.

If present, the substituted N or substituted C of R ³ , R ⁴ or a divalent linking group can each independently be NR ⁶ or CR ⁶ ₂ , wherein R ⁶ is alkyl or An aryl or heteroaryl group substituted. An optional substituent of the aryl or heteroaryl R ⁶ may be selected from R ⁴ or R ⁵ .

In a preferred configuration, R ² is Ar ³ and each of Ar ¹ , Ar ² and Ar ³ is independently and optionally substituted with one or more C _1-20 alkyl groups.

A particularly good unit that conforms to formula (IV) includes units of formula 1-3: Wherein Ar ¹ and Ar ² are as defined above; and Ar ³ is optionally substituted aryl or heteroaryl. Preferred substituents for Ar ³ if present include substituents as set forth for Ar ¹ and Ar ² , specifically alkyl and alkoxy.

Ar ¹ , Ar ² and Ar ^{3 are} preferably phenyl groups, each of which may be independently substituted with one or more substituents as set forth above.

In another preferred embodiment, the aryl or heteroaryl phenyl of formula (IV), each phenyl is optionally substituted with one or more alkyl groups.

In another preferred configuration, Ar ¹ , Ar ² and Ar ³ are phenyl groups, each of which may be substituted with one or more C _1-20 alkyl groups, and r=1.

In another preferred configuration, Ar ¹ and Ar ² are phenyl groups, each of which may be substituted with one or more C _1-20 alkyl groups, and R is 3,5-diphenylbenzene, each of which Monophenyl can be substituted by one or more alkyl groups.

Exemplary extended (hetero)aryl repeating units include optionally substituted fluorene, phenyl extended and/or indenoindole repeating units.

Exemplary 茀 repeating units include repeating units of formula (V): Wherein R ⁶ and R ^{7 are} independently H or a substituent, and wherein R ⁶ and R ⁷ may be bonded to form a ring.

R ⁶ and R ⁷ are optionally selected from the group consisting of hydrogen; a linear or branched chain of an optionally substituted Ar ³ or Ar ³ group, wherein the Ar ³ is as described above; and optionally substituted An alkyl group (e.g., a C _1-20 alkyl group) wherein one or more non-adjacent C atoms of the alkyl group may be replaced by O, S, substituted N, C=O, and -COO-.

In the case where R ⁶ or R ⁷ comprises an alkyl group, the optional substituents of the alkyl group include F, CN, nitro and, optionally, aryl or heteroaryl substituted with one or more groups R ⁴ , wherein R ^{The 4} series is as explained above.

In the case where R ⁶ or R ⁷ contains an aryl or heteroaryl group, each aryl or heteroaryl group may be independently substituted. Preferred optional substituents for aryl or heteroaryl groups include one or more substituents R ³ .

In addition to the substituents R ⁶ and R ⁷ , the optional substituents of the indole unit are preferably selected from the group consisting of alkyl groups in which one or more non-adjacent C atoms may be via O, S, substituted N, C=O and -COO-substitution; optionally substituted aryl; optionally substituted heteroaryl; fluoro; cyano and nitro.

In a preferred configuration, at least one of R ⁶ and R ⁷ comprises optionally substituted C ₁ -C ₂₀ alkyl; or optionally substituted aryl, specifically one or more C _{1- 20} alkyl substituted phenyl.

The repeating unit of formula (V) can be linked via 2,7-.

An exemplary phenyl repeating unit includes a repeating unit of formula (VI): Wherein R ⁶ is as described above for formula (V), and p is 1, 2, 3 or 4, optionally 1 or 2. In one configuration, the repeating unit is a 1,4-phenylene repeating unit.

The repeating unit of formula (VI) may have the formula (VIa):

The luminescent layer may be comprised of a separate luminescent material or may comprise a combination of this material and one or more other materials. In particular, the luminescent material can be blended with the holes and/or electron transporting materials or can be covalently bonded to the holes and/or electron transporting materials as disclosed, for example, in WO 99/48160.

The luminescent copolymer may comprise at least one of a luminescent region and a hole transport region and an electron transport region, as disclosed in, for example, WO 00/55927 and US Pat. No. 6,353,083. If only one of the hole transmission area and the electron transmission area is provided, the electroluminescent area may also provide the other of the hole transmission function and the electron transmission function, for example, the amine of the formula (IV) as explained above. The unit can provide both hole transmission and illumination functions. A luminescent copolymer comprising one or both of a luminescent repeating unit and a hole transport repeating unit and an electron transport repeating unit may be in the polymer backbone (according to US Pat. No. 6,353,083) or on the polymer side depending from the polymer backbone These units are provided in the base.

Suitable luminescent materials can be emitted in the UV, visible and/or infrared regions of the electromagnetic spectrum. The OLED may contain one or more of red, green, and blue luminescent materials.

The blue luminescent material can have a photoluminescence spectrum having a peak wavelength in the range of less than or equal to 480 nm (eg, in the range of 400 nm to 480 nm).

Green luminescent materials can have peak wavelengths from 480 nm to 560 nm The photoluminescence spectrum inside the circle.

The red luminescent material may have a photoluminescence spectrum having a peak wavelength in the range of 560 nm or more to 630 nm.

More than one luminescent material can be used. For example, red, green, and blue luminescent materials can be used to obtain white emitted light.

The luminescent layer can comprise a host material and at least one luminescent dopant. The host material can be a material that illuminates itself in the absence of a dopant as set forth above. When the host material and dopant are used in the device, the individual dopants can illuminate. Alternatively, the host material and one or more dopants can illuminate. White light can be generated by emission from a plurality of light sources (e.g., emitted from both the host and one or more dopants or emitted from a plurality of dopants).

In the case of a fluorescent dopant, the singlet excited state energy level (S ₁ ) of the host material should be higher than that of the fluorescent dopant so that singlet excitons can be transferred from the host material to the phosphorescent dopant. In the agent. Similarly, in the case of a phosphorescent dopant, the triplet excited state energy level (T ₁ ) of the host material should be higher than that of the phosphorescent dopant so that the triplet excitons can be transferred from the host material to the fluorescent light emitting dopant. In the agent.

Exemplary phosphorescent dopants include metal complexes comprising a substituted formula (VII) as appropriate: ML ¹ _q L ² _r L ³ _s (VII) wherein M is a metal; L ¹ , L ² And each of L ³ is a coordinating group; q is an integer; r and s are each independently 0 or an integer; and the sum of (aq) + (br) + (cs) is equal to the available coordination on M The number of sites, where a is the number of coordination sites on L ¹ , b is the number of coordination sites on L ² and c is the number of coordination sites on L ³ .

Heavy element M induces strong spin-orbital coupling to allow rapid intersystem crossing and emission from triplet or higher states (phosphorescence). Suitable heavy metals M include d-region metals, in particular those in columns 2 and 3, ie elements 39 to 48 and 72 to 80, in particular ruthenium, rhodium, palladium, iridium, osmium, iridium, Platinum and gold. Yu Youjia.

Exemplary ligands L ¹ , L ² and L ³ include a carbon or nitrogen donor, such as a porphyrin or a bidentate ligand of formula (VIII): Wherein Ar ⁴ and Ar ⁵ may be the same or different and independently selected from optionally substituted aryl or heteroaryl; X ¹ and Y ¹ may be the same or different and independently selected from carbon or nitrogen; and Ar ⁴ and Ar ⁵ can be thick together. A ligand in which X ¹ is carbon and Y ¹ is nitrogen is particularly preferred.

Examples of bidentate ligands are as follows:

Each of Ar ⁴ and Ar ⁵ can carry one or more substituents. Two or more of the substituents may be joined to form a ring, such as an aromatic ring.

Other ligands suitable for the elements of zone d include diketonates, in particular acetamidine pyruvate (acac); triarylphosphines and pyridine, each of which may be substituted.

Exemplary substituents include the group R ³ as set forth above for formula (IV). Particularly preferred substituents include fluoro or trifluoromethyl, which can be used to effect blue shifting of the complex, as disclosed in, for example, WO 02/45466, WO 02/44189, US 2002-117662, and US 2002-182441; An alkyl or alkoxy group, for example a C _1-20 alkyl or alkoxy group, as disclosed in JP 2002-324679; a carbazole which can be used to assist in hole transport when a complex is used as an emissive material To the complex, for example as disclosed in WO 02/81448; bromine, chlorine or iodine, which can be used to functionalize ligands for the attachment of other groups, for example as disclosed in WO 02/68435 and EP 1245659 And a dendron which can be used to obtain or enhance the solution treatability of the metal complex, as disclosed, for example, in WO 02/66552.

The luminescent dendrimer typically comprises a luminescent core bonded to one or more dendritic groups, wherein each dendritic group comprises a branching point and two or more dendritic branches. Preferably, the dendritic group is at least partially conjugated, and at least one of the branching point and the dendritic branch comprises an aryl or heteroaryl group, such as a phenyl group. In one configuration, both the branch point group and the branch group are phenyl groups, and each phenyl group can be independently substituted with one or more substituents (eg, alkyl or alkoxy groups).

The dendritic group may have the formula (IX) substituted as appropriate Wherein BP represents a branch point attached to the core, and G ₁ represents a first generation branch group.

The dendritic group can be a first, second, third or higher generation dendritic group. G ₁ may be substituted by two or more second-generation branching groups G _{2 ,} etc., as in the formula (IXa), as the case may be substituted: Where u is 0 or 1; if u is 0, then v is 0, or if u is 1, v can be 0 or 1; BP represents the branch point attached to the core, and G ₁ , G ₂ and G ₃ Represents the first, second and third generation dendritic group branching groups.

BP and/or any group G may be substituted with one or more substituents (eg, one or more C _1-20 alkyl or alkoxy groups).

If used, the luminescent dopant can be about 0.05% relative to its host material. The ear is present in an amount up to about 20 mol%, optionally from about 0.1 mol% to 10 mol%.

The luminescent dopant can be physically mixed with the host material, or it can be chemically bonded to the host material in the same manner as described above for the combination of luminescent dopant and charge transport material.

The luminescent layer can be patterned or unpatterned. For example, a device comprising an unpatterned layer can be used as the illumination source. White light emitting devices are particularly suitable for this purpose. The device comprising the patterned layer can be, for example, an active matrix display or a passive matrix display. In the case of an active matrix display, the patterned electroluminescent layer is typically used in combination with a patterned anode layer and an unpatterned cathode. In the case of a passive matrix display, the anode layer is formed by parallel strips of anode material, and the parallel strips of electroluminescent material and cathode material are disposed perpendicular to the anode material, wherein the strips of electroluminescent material and cathode material are typically It is isolated by a strip of insulating material ("cathode isolation strip") formed by photolithography.

The luminescent layer may comprise a polymer comprising repeating units of formula (X) as set forth above. The polymer comprising the repeating unit of formula (X) may comprise a luminescent repeating unit. Alternatively, the polymer can be a body that is blended with a fluorescent or phosphorescent dopant, such as a metal complex as set forth above.

cathode

The cathode 5 is selected from materials having a work function that allows electrons to be injected into the light-emitting layer 4. Other factors influence the choice of cathode, such as the possibility of adverse interactions between the cathode and the luminescent layer material. The cathode may be composed of a single material such as an aluminum layer. Alternatively, it may comprise a plurality of metals, for example, a low work function Bilayers of materials and high work function materials such as calcium and aluminum, as disclosed in WO 98/10621; elements 钡, such as WO 98/57381, Appl. Phys. Lett. 2002, 81(4), 634 and WO A thin layer of a metal compound (particularly an oxide or fluoride of an alkali or alkaline earth metal), such as lithium fluoride, as disclosed in WO 00/48258; Barium fluoride, as disclosed in Appl. Phys. Lett. 2001, 79 (5), 2001; and cerium oxide. To effectively inject electrons into the device, the work function of the cathode is preferably below 3.5 eV, more preferably below 3.2 eV, and optimally below 3 eV. The work function of metals can be found, for example, in Michaelson, J. Appl. Phys. 48 (11), 4729, 1977.

The cathode can be opaque or transparent. Transparent cathodes are particularly advantageous for active matrix devices because the emission through the transparent anode in such devices is at least partially blocked by the drive circuitry underlying the emitting pixels. The transparent cathode will contain a layer of electron injecting material that is sufficiently thin to be transparent. Typically, the lateral conductivity of this layer will be lower due to its thinner. In this case, the electron injecting material layer is used in combination with a thicker transparent conductive material layer such as indium tin oxide.

It should be understood that the transparent cathode device need not have a transparent anode (unless, of course, a device that is completely transparent is desired), and thus a layer of reflective material such as an aluminum layer may be substituted or supplemented with a transparent anode for the bottom emitting device. Examples of transparent cathode devices are disclosed, for example, in GB 2348316.

Solution treatment

The polymer is preferably soluble to allow it to be deposited from a composition comprising a solvent solution. The polymer is preferably soluble in common organic solvents and may be included, for example, including alkylated benzenes (e.g., xylene and toluene) and chlorinated solvents (e.g., trichloro). In the composition of methane). Exemplary deposition methods include spin coating, dip coating, knife coating, ink jet printing, roll printing, and screen printing.

Exemplary solvents for the polymers of the present invention include organic solvents such as mono or polyalkyl benzenes such as toluene and xylene, and chlorinated solvents.

The luminescent layer can be deposited by any method including vacuum evaporation and solution deposition from a solvent.

Coating (eg spin coating) is particularly suitable for devices that do not require patterning of the luminescent layer, such as for lighting applications or simple monochrome segmented displays, for example.

Printing (eg inkjet printing) is particularly suitable for high information capacity displays, in particular full color displays. By providing a patterned layer on the first electrode and defining a hole for printing one color (in the case of a monochrome device) or multiple colors (in the case of a multi-color, in particular a full-color device) The device performs inkjet printing. The patterned layer is typically patterned to define a photoresist layer of the aperture, as set forth, for example, in EP 0880303.

The hole transport layer, the luminescent layer, and, if present, the hole injection layer can be printed into a single aperture.

As an alternative to the holes, the ink can be printed into the channels defined within the patterned layer. In particular, the photoresist can be patterned to form channels that, unlike the holes, extend over a plurality of pixels, and the ends of the channels can be closed or open.

Instance

Charge transporting monomers and crosslinking monomers can be prepared by methods known to those skilled in the art. The following examples illustrate certain features of the invention. It is intended to illustrate and not to limit the invention.

Intermediate (I)

Add n-butyllithium (11 ml, 1.0 eq, 2.5 M in hexane) to bromostyrene (5 g, 0.03 mol) in THF (100 ml) at -78 ° C under nitrogen. In the solution. After stirring at this temperature for 1 hr, 1,4-dibromobutane (58 g, 0.3 mol) was quickly added and the reaction mixture was warmed to ambient temperature overnight. Water (100 ml) was then added and the solvent was removed under reduced pressure. With DCM (3 × 50 ml) the organic phase was extracted, washed with water, dried (MgSO ₄₎ and concentrated in vacuo. The resulting yellow oil was treated with 3,5-di-tert-butyl-catechol (1%) and excess dibromobutane was removed via distillation (99 ° C, about 10 mbar pressure). The orange residue was filtered <RTI ID=0.0>(2 </RTI> EtOAc (EtOAc)

¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 7.34 (2H, d, Ar H ), 7.14 (2H, d, Ar H ), 6.38 (1H, dd, = C H2 ), 5.71 (1H, d, C H =), 5.20 (1H, d), 3.42 (2H, t, ArC H ₂ ), 2.64 (2H, t, Br-C H ₂ ), 1.89 (2H, m, C H ₂ CH ₂ ) , 1.78 (2H, m, CH ₂ C H ₂ ); MS: M ⁺ 238 (100%).

Intermediate (II)

The solution of phenoxazine (35 g, 19 mmol) in DMF (50 ml) was added dropwise to NaH (8.4 g, 21 mmol, 60% in mineral oil) at 0 ° C under nitrogen. In a suspension in DMF (250 ml) to maintain an internal temperature of <5 °C. After stirring for 1 hr, (I) (45.7 mL, 19 mmol)EtOAc. The (100 ml) of water was added to the reaction mixture, and washed with toluene (3 × 50ml) The organic phase was extracted, washed with water, dried (MgSO ₄₎ and concentrated under reduced pressure. The obtained crude material was dissolved in toluene, filtered (florisil / ruthenium dioxide), concentrated, and the obtained oil was recrystallized (IPA / toluene) to give the product as a white solid (53 g, 81%).

MS: M ⁺ 341 (100%).

Intermediate (III)

The first portion of a solution of styrene (I) (9.8 g, 41 mmol) in THF (15 ml) was added dropwise to magnesium turnings (magnesium turning, 1.32 g, 55 mmol) and iodine crystals under nitrogen. In a suspension in THF (26 ml). The mixture was heated to initiate the reaction, and (I) was continued to be added dropwise to maintain a gentle reflux. After the addition was completed, the reaction mixture was heated to 60 ° C for 1 hr 30 min, allowed to cool to room temperature, and added dropwise to benzocyclobutyl bromide (BCBBr) (5 g, 27 mmol), PdCl ₂ (dppf) (1.11 g, 0.05 eq) and dppf (1.51 g, 0.1 eq) in THF (50 ml). Then washed with water (500 ml) was quenched, the mixture was cooled to room temperature and extracted with toluene (3 × 50 ml), and the organic phase was washed with water, dried (MgSO ₄₎ and concentrated under reduced pressure. By column chromatography (SiO _2, hexanes) to give the crude material of the product as a clear oil (1.3 g, 18%).

MS: M ⁺ 262 (100%) Polymer example 1

The synthesis of Polymer Example 1 is as follows:

A suspension of (II) (7.37 g, 21 mmol) and (III) (0.63 g, 2.4 mmol) in 20 ml of heptanone (degassed with nitrogen for 30 min before use) was heated to 40 °C. Azobisisobutyronitrile (AIBN) (35.4 mg, 1.0 mol%) was added and the reaction mixture was heated at 60 °C for 24 hr. The reaction mixture was diluted with toluene (30 ml) and added dropwise to diethyl ether (500 ml) to precipitate a polymer. The obtained polymer was redissolved in toluene (20 ml) and precipitated again in diethyl ether (400 ml) to give a product.

Mw 95,000, Mp 85,000, PD 2.01.

Polymer example 2

A suspension of (II) (8.0 g, 23 mmol) in 20 ml of heptanone (degassed with nitrogen for 30 min before use) was heated to 40 °C. Azobisisobutyronitrile (AIBN) (38.5 mg, 1.0 mol%) was added and the reaction mixture was heated at 60 °C for 24 hr. The reaction mixture was diluted with toluene (30 ml) and added dropwise to Diethyl ether (500 ml) was used to precipitate the polymer. The obtained polymer was redissolved in toluene (20 ml), and again precipitated in diethyl ether (400 ml) to give a homopolymer.

Mw 81,000, Mp 72,000, PD 1.94.

Example 3

It has been found that a charge transport polymer (Example 2) containing a spacer of at least 4 carbon atoms between the non-conjugated backbone and the hole transport unit is soluble in o-xylene as its cross-linking counterpart (example) 1) General. In the absence of a spacer (Example 3), it was found that the polymer was extremely insoluble in o-xylene and its solubility in anisole was limited even after prolonged heating. Similar results were observed for PVK. In contrast, a corresponding cross-linked derivative (Example 4) having a spacer having 4 carbon atoms between the cross-linking group and the polymer main chain was found to be soluble.

Device example 1

A device having the following structure was prepared: an ITO/HIL/HTL/EL/cathode in which an ITO-based indium tin oxide anode; a HIL-based hole injection layer containing a hole injecting material available from Plextronics; and an HTL-based hole transport layer. It comprises the hole transport polymer of Example 1; an EL-based light-emitting layer comprising a poly And a cathode cathode comprising a fluoride layer, an aluminum layer, and a silver layer.

Although the present invention has been described in terms of the specific embodiments thereof, it will be understood that those skilled in the art will be able to understand various modifications, changes and/or combinations of the features disclosed herein without departing from the scope of the following claims. The scope of the invention is described.

1‧‧‧Substrate

2‧‧‧Anode

3‧‧‧ hole transport layer

4‧‧‧Lighting layer

5‧‧‧ cathode

The invention will now be described in more detail with reference to the accompanying drawings in which: FIG. 1 illustrates an organic light-emitting device in accordance with an embodiment of the invention.

1‧‧‧Substrate

2‧‧‧Anode

3‧‧‧ hole transport layer

4‧‧‧Lighting layer

5‧‧‧ cathode

Claims (47)

A polymer comprising a repeating unit of formula (X): Wherein R ¹⁰ each represents H or a substituent at each occurrence; Sp ² represents a spacer; t is 0 or 1; and POZ represents a optionally substituted, optionally fused, phenoxazine group. A polymer according to claim 1, which has the formula (Xa): Wherein d is independently 0, 1, 2, 3 or 4 at each occurrence; R ⁸ represents a substituent at each occurrence; and two substituents R ⁸ attached to the same phenyl ring may form saturated or not Saturated ring. The polymer of claim 1 or 2, wherein R ⁸ and R ¹⁰ are each independently selected from the group consisting of: H; optionally substituted aryl; optionally substituted heteroaryl; An alkyl group, wherein one or more non-adjacent C atoms of the alkyl group may be replaced by O, S, substituted N, -C=O and -COO-, -Si-, and one or more H of the alkyl group The atom can be replaced by an F or aryl or heteroaryl group. The polymer of claim 1 or 2, wherein Sp ² comprises at least one non-cyclic atom of the interstitial phenoxazine unit and the polymer backbone. The polymer of claim 1 or 2, wherein Sp ² comprises an aryl group, optionally a phenyl group. The polymer of claim 1 or 2, wherein Sp ² comprises an alkyl chain, optionally a C _1-20 alkyl chain; an alkoxy group or an ether group. The polymer of claim 1 or 2, wherein the polymer comprises one or more other repeating units than the repeating unit of formula (X). The polymer of claim 7, wherein the one or more other repeating units comprise crosslinkable repeating units. The polymer of claim 7, wherein the one or more other repeating units comprise repeating units comprising a charge transport unit having a HOMO value different from the repeating unit of formula (X). An organic electronic device comprising the polymer of any one of claims 1 to 9. The organic electronic device of claim 10, wherein the organic electronic device comprises an organic light-emitting device comprising an anode, a cathode, and a light-emitting layer between the anode and the cathode. The organic light-emitting device of claim 11, wherein the light-emitting layer comprises the polymer of any one of claims 1 to 9. The organic light-emitting device of claim 12, wherein the light-emitting layer further comprises an illuminating dopant. The organic light-emitting device of claim 11, wherein a charge transport layer is provided between the anode and the light-emitting layer or between the cathode and the light-emitting layer, the charge transport layer comprising the polymer according to any one of claims 1 to 9. . A composition comprising the polymer of any one of claims 1 to 9 and at least one solvent. The composition of claim 15 wherein the at least one solvent is selected from the group consisting of mono- or polyalkylated benzene. A method of forming an organic light-emitting device according to any one of claims 10 to 14, comprising the step of depositing a polymer according to any one of claims 1 to 9 on one of an anode and a cathode. Forming a charge transport layer or a light emitting layer comprising the polymer; and depositing the other of the anode and the cathode on the charge transport layer or the light emitting layer. The method of claim 17, wherein the charge transport layer or the light-emitting layer is formed by depositing the composition of claim 15 or 16 and evaporating the at least one solvent. a polymer having a backbone and comprising first and second repeat units, wherein: the first repeat unit comprises a first backbone segment and hangs from the first backbone segment and is coupled by a first spacer The first main chain segment is spaced apart by a first charge transporting group, the first spacer is connected to the first charge transport The group and the polymer backbone comprise at least 4 non-ring atoms in the path; and the second repeat unit comprises a second backbone segment and hangs from the second backbone segment and is coupled to the second spacer The second backbone segment is spaced apart from crosslinkable groups. The polymer of claim 19, wherein the backbone is substantially non-conjugated. The polymer of claim 19 or 20, wherein the first repeating unit has the formula (I): Wherein each R independently represents H or a substituent; Sp represents the first spacer; and CT represents the first charge transport group. The polymer of claim 19 or 20, wherein the second repeating unit has the formula (II): Wherein each R ¹ independently represents H or a substituent; Sp ¹ represents the second spacer; and XL represents the crosslinkable group. The polymer of claim 22, wherein Sp ¹ comprises at least one spacer XL and a non-cyclic atom of the second backbone segment. The polymer of claim 19 or 20, wherein the polymer comprises one or more other repeating units. The polymer of claim 24, wherein the polymer comprises one or more other repeating units, each of the one or more other repeating units comprising another charge transporting group different from the first charge transporting group group. The polymer of claim 25, wherein the other repeating units have the formula (XI): Wherein R ⁹ is H or a substituent which may be the same or different at each occurrence; a Sp 3 line spacer; w is 0 or 1; and CT 2 is the other charge transport group. The polymer of claim 24, wherein the polymer comprises another repeating unit that is not substituted with a charge transporting group or a crosslinkable group. The polymer of claim 27, wherein the other repeating unit is a styryl repeating unit, optionally substituted with one or more substituents selected from C _1-20 alkyl groups, in the C _1-20 alkane One or more non-adjacent C atoms of the alkyl groups may be replaced by O or S. The polymer of claim 19 or 20, wherein R and R ¹ are each independently selected from the group consisting of: H; optionally substituted aryl; optionally substituted heteroaryl; and alkane a group wherein one or more non-adjacent C atoms of the alkyl group may be replaced by O, S, substituted N, -C=O and -COO-, -Si-, and one or more H atoms of the alkyl group It can be replaced by F or an aryl or heteroaryl group. The polymer of claim 19 or 20, wherein Sp comprises an alkyl chain, optionally a C _4-20 alkyl chain; an alkoxy group or an ether group. The polymer of claim 19 or 20, wherein Sp ¹ comprises an alkyl chain, optionally a C _1-20 alkyl chain; an alkoxy group or an ether group. The polymer of claim 19 or 20, wherein the first charge transporting group is a hole transporting group, an electron transporting group or a bipolar group. The polymer of claim 19 or 20, wherein the crosslinkable group comprises a polymerizable double bond, optionally substituted benzocyclobutane group or oxetane group. The polymer of claim 19 or 20, wherein the first spacer comprises no more than 8 non-cyclic atoms separating the first charge transport group from the first backbone segment. The polymer of claim 19 or 20, wherein the second spacer comprises no more than 8 non-cyclic atoms separating the crosslinkable group from the second backbone segment. The polymer of claim 19 or 20, wherein the number of such acyclic atoms in Sp plus the number of such acyclic atoms in Sp ¹ does not exceed 10. A composition comprising the polymer of any one of claims 19 to 36 and at least one solvent. The composition of claim 37, wherein the at least one solvent is selected from the group consisting of single or multiple Alkylation of benzene. A method of forming a polymer according to any one of claims 19 to 36, wherein the first monomer is copolymerized to form the first repeating unit and the second monomer is copolymerized to form the second repeating unit. Implementation. An optoelectronic device comprising a layer comprising the polymer of any one of claims 19 to 36. The optoelectronic device of claim 40, wherein the device is an organic light emitting device. The photovoltaic device of claim 40 or 41, wherein the layer is a hole transport layer. A method of forming an optoelectronic device, comprising the steps of: providing a first electrode; forming a charge transport layer by depositing a polymer according to any one of claims 19 to 36 on the first electrode; making the crosslinkable The group is crosslinked; an organic semiconductor layer is deposited on the charge transport layer; and a second electrode is formed on the organic semiconductor layer. The method of claim 43, wherein the charge transport layer is a hole transport layer. The method of claim 44, wherein a hole injection layer is deposited between the first electrode and the hole transport layer. The method of claim 44 or 45, wherein the surface of the first electrode is modified by a self-assembled monolayer. The method of any one of claims 43 to 45, wherein the step of forming the charge transport layer comprises depositing the composition of claim 37 or 38 and evaporating the at least one solvent.