WO2013096921A1

WO2013096921A1 - Non-crosslinked polystyrene triscarbazole hole transport materials

Info

Publication number: WO2013096921A1
Application number: PCT/US2012/071511
Authority: WO
Inventors: Yadong Zhang; Seth Marder; Wojciech HASKE; Bernard Kippelen; Roland Martin
Original assignee: Georgia Tech Research Corporation; Solvay Sa
Priority date: 2011-12-22
Filing date: 2012-12-21
Publication date: 2013-06-27

Abstract

Provided herein are polymers that are highly processable in solution and have higher hole transporting properties than polymers such as PVK. These polymers can be used as either hosts or hole transporting layers in organic electronic devices. The materials can be blended with other polymers, including electron transport polymers, to modify matrix properties.

Description

NON-CROSSLINKED POLYSTYRENE TRISCARBAZOLE HOLE TRANSPORT

MATERIALS

BACKGROUND

The study of materials, processing, and organic light-emitting diodes (OLED) devices is a rapidly developing field. OLED devices are of interest partly because of their ability to be processed onto a variety of substrates, their potential for low cost fabrication, and the possibility for fabricating energy-efficient displays and/or solid-state lighting sources. Early OLED devices were based on fluorescent organic materials in which emission is only obtained from hole-electron recombination events that result in the formation of singlet excited states, placing limitations on the maximum efficiency of devices. Use of

phosphorescent transition-metal-based emitters, enabling emission from both singlet and triplet excited states, was first reported in 1995 and has since become popular. Continuing progress in increasing the performance and development of OLED devices has commonly been the result of new material and new complex architectures employing a variety of multilayers with different functions including: hole and electron injection and transport; hole, electron, and exciton blocking; and acting as a host for phosphorescent emitters.

The highest efficiency devices in the prior art are generally those fabricated using high-vacuum vapor deposition. This approach permits the fabrication of well-defined multilayers with relative ease. However, vacuum-processing is time-consuming and expensive, while fabrication on large-area substrates can also be problematic. In contrast, solution-based approaches have the potential to facilitate rapid and low-cost processing and can be extended to large area substrates, and to high-throughput reel-to-reel processing. At the same time, higher molecular- weight materials that are difficult to be vapor-deposited, such as polymers or oligomers, can show good morphological stability.

Therefore, a need exists for solution-processable hole transport materials suitable for fabricating emissive layer (as host) and hole-transport layer of OLED devices that are capable of achieving high external quantum efficiency. SUMMARY

Provided herein are polymers that are highly processable in solution and have improved hole transporting properties over polymers such as polyvinylcarbazole (PVK). Compositions comprising these polymers can be used as either hosts or hole transporting layers or hole injection layers in organic electronic devices. The host compositions can be blends with other materials, including electron transport small molecules or polymers, to modify matrix properties. Hole injection layers comprise the said polymers of the invention and soluble p-dopants. The polymers are more stable than PVK, both physically (high glass temperatures) and chemically (when accepting holes).

Embodiments described herein include, for example, compositions, articles, devices, and methods for making.

For example, provided is a solution-processable composition suitable for making electroluminescence devices, comprising at least one first polymer, said first polymer comprising at least one first polymer subunit represented by formula (I) or formula (II):

wherein Rl, R2, R3, R4, R5, R6, R7, R8, R9, RIO, Rl l, R12, R13, R14, R15, R16, R17 and R18 are each independently a hydrogen, a halogen, an optionally substituted alkyl, an optionally substituted aryl, an optionally substituted heteroalkyl, or an optionally substituted heteroaryl; wherein L is a linker group that comprises at least one carbon atom but does not comprise any 2-phenyl-5-phenyl-l,3,4-oxadiazole group; and wherein X, Y and Z are each independently H, alkyl, fluoroalkyl or fluoride. Also provided is an emissive layer deposited from a solution comprising the solution- processable composition discussed above, as well as an electroluminescence device comprising the emissive layer. In one embodiment, the electroluminescence device further comprises a hole transport layer fabricated also by solution deposition. In another embodiment, the emissive layer comprises Ir(ppy)3 as emitter, and the external quantum efficiency of the electroluminescence device at 1,000 cd/m is at least 5%, at least 10%, or at least 15%.

Moreover, also provided is a hole transport layer deposited from a solution comprising the solution-processable composition discussed above, as well as an

electroluminescence device comprising the hole transport layer. In one embodiment, the electroluminescence device further comprises an emissive layer comprising a bis(organo- sulfonyl)-biaryl host fabricated also by solution deposition. In another embodiment, the emissive layer comprises Ir(ppy)3 as emitter, and the external quantum efficiency of the electroluminescence device at 1,000 cd/m is at least 5%, at least 10%>, or at least 15%. In a further embodiment, the electroluminescence device comprises an emissive layer comprising FIrpic as emitter, and the external quantum efficiency of the electroluminescence device at 1,000 cd/m² is at least 5%, at least 10%, or at least 15%.

Furthermore, also provided is a method comprising: (i) providing a substrate comprising an anode layer and optionally comprising a hole injection layer; (ii) depositing a hole transport layer from a first solution onto the substrate; and (iii) depositing an emissive layer from a second solution onto the hole transport layer, wherein the second solution comprises the solution-processable composition discussed above. In one embodiment, the first solution comprises a crosslinking material that is crosslinked thermally or

photochemically before the deposition of the emissive layer.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows three embodiments of the polystyrene triscarbazole hole transporting polymer described herein. FIG. 2 shows performance of OLED devices comprising solution-processed electron transport/hole transport polymer hosts emissive layer (1 : 1 Polymer A:Polymer B blend and Ir(pppy)₃), with solution-processed p-TPDF hole transport layer (ITO/PEDOT:PSS/p-TPDF/ Polymer A:Polymer B:Ir(pppy)₃/BCP/LiF:Al:Ag).

FIG. 3 shows performance of OLED devices comprising solution-processed electron transport/hole transport polymer hosts emissive layer (3: 1 Polymer A:Polymer B blend and Ir(pppy)₃), with solution-processed p-TPDF hole transport layer (ITO/PEDOT:PSS/p-TPDF/ Polymer A:Polymer B:Ir(pppy)₃/BCP/LiF:Al:Ag).

FIG. 4 shows performance of OLED devices comprising solution-processed electron transport/hole transport polymer hosts emissive layer (1 :3 Polymer A:Polymer B blend and Ir(pppy) ), with solution-processed p-TPDF hole transport layer (ITO/PEDOT:PSS/p-TPDF/ Polymer A:Polymer B:Ir(pppy)₃/BCP/LiF:Al:Ag).

FIG. 5 shows performance of OLED devices comprising solution-processed electron transport/hole transport polymer hosts emissive layer (1 : 1 Polymer A:Polymer B blend and Ir(pppy) ), with solution-processed and crosslinked hole transport layer (Polymer 5.38) (ITO/Polymer 5.38/Polymer A:Polymer B:Ir(pppy)₃/BCP/LiF:Al:Ag). Polymer 5.38 is:

(target x = 0.9)

FIG. 6 shows performance of OLED devices comprising solution-processed electron transport/hole transport polymer hosts emissive layer (1 : 1 Polymer A:Polymer B blend and Ir(pppy)₃), with solution-processed and crosslinked hole transport layer (Polymer 5.40) (ITO/Polymer 5.40/Polymer A:Polymer B:Ir(pppy)₃/BCP/LiF:Al:Ag). Polymer 5.40 is:

(target x = 0.9)

FIG. 7 shows performance of OLED devices comprising solution-processed electron transport/hole transport polymer hosts emissive layer (1 : 1 Polymer A:Polymer B blend and Ir(pppy)₃), with solution-processed and crosslinked hole transport layer (Compound 5.42) (ITO/Compound 5.42/Polymer A:Polymer B:Ir(pppy)₃/BCP/LiF:Al:Ag). Compound 5.42 is:

FIG. 8 shows performance of OLED devices comprising Polymer A triscarbazole HTL and Compound D/Ir(ppy)₃ emissive layer (ITO/PEDOT:PSS/Polymer A/Compound D: Ir(ppy)₃ /BCP/LiF:Al:Ag). Compound D is:

FIG. 9 shows performance of OLED devices comprising Polymer A triscarbazole HTL and Compound D/Ir(ppy)₃ emissive layer (ITO/Mo0₃/Polymer A/Compound D:

Ir(PPy)3/BCP/LiF:Al:Ag).

FIG. 10 shows performance of OLED devices comprising Polymer A triscarbazole HTL and Compound D/Ir(ppy)₃ emissive layer (ITO/PEDOT:PSS/Polymer A/Compound D: Ir(ppy)₃/TAZ/LiF:Al:Ag).

FIG. 11 shows performance of OLED devices comprising Polymer A triscarbazole HTL and Compound D/FIrpic emissive layer (ITO/PEDOT:PSS/Polymer A/Compound D: FIrpic/TAZ/LiF:Al:Ag). FIG. 12 shows performance of OLED devices comprising Polymer A triscarbazole HTL and Compound D/FIrpic emissive layer (ITO/PEDOT:PSS/Polymer A/Compound D: FIrpic/BCP/LiF:Al:Ag).

FIG. 13 shows performance of OLED devices comprising Polymer A triscarbazole HTL and Compound D/FIrpic emissive layer (ITO/Polymer A/Compound D:FIrpic/BCP/ LiF:Al:Ag).

FIG. 14 shows performance of OLED devices comprising Polymer A triscarbazole HTL and Compound C/FIrpic emissive layer (ITO/Polymer A/Compound C:FIrpic/BCP/ LiF:Al:Ag). Compound C is:

FIG. 15 shows performance of OLED devices comprising Polymer A triscarbazole HTL and Compound C/Ir(ppy)₃ emissive layer (ITO/Polymer A/Compound C:Ir(ppy)₃/BCP/ LiF:Al:Ag).

FIG. 16 shows performance of OLED devices comprising Polymer A triscarbazole HTL and CBP/Ir(ppy)₃ emissive layer (ITO/Polymer A/CBP:Ir(ppy)₃/BCP/LiF:Al:Ag).

FIG. 17 shows performance of OLED devices comprising Polymer A triscarbazole HTL and CBP/Ir(ppy)₃ emissive layer (ITO/PEDOT:PSS/Polymer A/CBP:Ir(ppy)₃/BCP/ LiF:Al:Ag).

FIG. 18 shows current density from hole only device comprising polymer A and current density from hole only device comprising polyvinylcarbazole.

FIG. 19 shows performance of OLED devices comprising Polymer A triscarbazole HTL and Compound G/Ir(ppy)₃ emissive layer (ITO/Polymer A/Compound G:

Ir(ppy)₃/BCP/LiF:Al:Ag). Compound G is:

FIG. 20 shows performance of OLED devices comprising Polymer A triscarbazole HTL and Compound G/Ir(ppy)₃ emissive layer (ITO/Mo0₃/Polymer A/Compound G:

Ir(ppy)₃/BCP/LiF:Al:Ag).

FIG. 21 shows performance of OLED devices comprising Polymer A triscarbazole HTL and Compound G/Ir(ppy)₃ emissive layer (ITO/PEDOT:PSS/Polymer A/Compound G: Ir(PPy)3/BCP/LiF:Al:Ag).

FIG. 22 shows performance of OLED devices comprising Polymer A triscarbazole HTL and Compound G/FIrpic emissive layer (ITO/Polymer A/Compound G:

FIrpic/BCP/LiF:Al:Ag).

FIG. 23 shows performance of OLED devices comprising Polymer A triscarbazole HTL and Compound G/FIrpic emissive layer (ITO/Mo0₃/Polymer A/Compound G:

FIrpic/BCP/LiF:Al:Ag).

FIG. 24 shows performance of OLED devices comprising Polymer A triscarbazole HTL and Compound G/FIrpic emissive layer (ITO/PEDOT:PSS/Polymer A/Compound G: FIrpic/BCP/LiF:Al:Ag).

FIG. 25 shows performance of OLED devices comprising Polymer A triscarbazole HTL and Compound E/FIrpic emissive layer (ITO/Polymer A/Compound E:FIrpic/BCP/ LiF:Al:Ag). Compound E is:

FIG. 26 shows performance of OLED devices comprising Polymer A triscarbazole HTL and Compound E/FIrpic emissive layer (ITO/PEDOT:PSS/Polymer A/Compound E: FIrpic/BCP/LiF:Al:Ag).

FIG. 27 shows performance of OLED devices comprising Polymer A triscarbazole HTL and Compound F/FIrpic emissive layer (ITO/Polymer A/Compound F:FIrpic/BCP/ LiF:Al:Ag). Compound F is:

DETAILED DESCRIPTION

INTRODUCTION

All references described herein are hereby incorporated by reference in their entirety. US provisional applications 61/579,402 and 61/579,418 filed December 22, 2011 are hereby incorporated by reference in their entirety.

Various terms are further described herein below:

"A", "an", and "the" refers to "at least one" or "one or more" unless specified otherwise.

"Optionally substituted" groups refers to, for example, functional groups that may be substituted or unsubstituted by additional functional groups. For example, when a group is unsubstituted by an additional group it can be referred to as the group name, for example alkyl or aryl. When a group is substituted with additional functional groups it may more generically be referred to as substituted alkyl or substituted aryl.

"Alkyl" refers to, for example, straight chain and branched alkyl groups having from 1 to 20 carbon atoms, or from 1 to 15 carbon atoms, or from 1 to 10, or from 1 to 5, or from 1 to 3 carbon atoms. This term is exemplified by groups such as for example methyl, ethyl, n- propyl, iso-propyl, n-butyl, t-butyl, n-pentyl, ethylhexyl, dodecyl, isopentyl, and the like.

"Aryl" refers to, for example, an aromatic carbocyclic group of from 6 to 14 carbon atoms having a single ring (e.g., phenyl) or multiple condensed rings (e.g., naphthyl or anthryl) which condensed rings may or may not be aromatic provided that the point of attachment is at an aromatic carbon atom. Preferred aryls include phenyl, naphthyl, and the like.

"Heteroalkyl" refers to, for example, an alkyl group wherein one or more carbon atom is substituted with a heteroatom. The heteroatom can be, for example, O, S, N, P, etc.

"Heteroaryl" refers to, for example, an aryl group wherein one or more carbon atom is substituted with a heteroatom. The heteroatom can be, for example, O, S, N, P, etc. One example of heteroaryl is carbazole. "Alkoxy" refers to, for example, the group "alkyl-O-" which includes, by way of example, methoxy, ethoxy, n-propyloxy, iso-propyloxy, n-butyloxy, t-butyloxy, n-pentyloxy, 1-ethylhex-l-yloxy, dodecyloxy, isopentyloxy, and the like.

"Aryloxy" refers, for example, to the group "aryl-O-" which includes, by way of example, phenoxy, naphthoxy, and the like.

"Alkylene" refers to, for example, straight chain and branched alkylene groups having from 1 to 20 carbon atoms, or from 1 to 15 carbon atoms, or from 1 to 10, or from 1 to 5, or from 1 to 3 carbon atoms. This term is exemplified by groups such as methylene, ethylene, n-propylene, z^'so-propylene, n-butylene, t-butylene, n-pentylene, ethylhexylene, dodecylene, isopentylene, and the like.

"Arylene" refers to, for example, an aromatic carbocyclic group of from 6 to 14 carbon atoms having a single ring (e.g., phenylene) or multiple condensed rings (e.g., naphthylene or anthrylene) which condensed rings may or may not be aromatic provided that the point of attachment is at an aromatic carbon atom. Preferred arylenes include phenylene, naphthylene, and the like.

"Heteroalkylene" refers to, for example, an alkylene group wherein one or more carbon atom is substituted with a heteroatom. The heteroatom can be, for example, O, S, N, P, etc.

"Heteroarylene" refers to, for example, an arylene group wherein one or more carbon atom is substituted with a heteroatom. The heteroatom can be, for example, O, S, N, P, etc.

"Oxyalkylene" refers to, for example, the group "-alkylene-O-", wherein the alkylene can be optionally substituted.

"Oxyarylene" refers to, for example, the group "-arylene-O-", wherein the arylene can be optionally substituted.

"Carbonyl alkylene" refers to, for example, the group "-alkylene-C(O)-" , wherein the alkylene can be optionally substituted.

"Carbonyl arylene" refers to, for example, the group "-arylene-C(O)-" , wherein the arylene can be optionally substituted.

"Carboxyl alkylene" refers to, for example, the group "-alkylene-C(0)-0-", wherein the alkylene can be optionally substituted. "Carboxyl arylene" refers to, for example, the group "-arylene-C(0)-0-", wherein the arylene can be optionally substituted.

"Ether" refers to, for example, the group -alkylene-O-alkylene-, -arylene-O-alkylene-, -arylene-O-arylene-, wherein the alkylene and arylene can be optionally substituted.

"Ester" refers to, for example, the group -alkylene-C(0)-0-alkylene-, -arylene-C(O)- O-alkylene-, -arylene-C(0)-0-arylene-, wherein the alkylene and arylene can be optionally substituted.

"Ketone" refers to, for example, the group -alkylene-C(0)-alkylene-, -arylene-C(O)- alkylene-, -arylene-C(0)-arylene-, wherein the alkylene and arylene can be optionally substituted.

"Triscarbazole" refers to, for example, three or more carbazole groups connected to each other through aryl carbon-nitrogen bond and/or aryl carbon-carbon bond.

Charge transport materials disclosed herein are semiconducting materials in which charges can migrate under the influence of an electric field. Charges can be introduced by doping with oxidizing or reducing agents, so that a fraction of the transport molecules or polymer repeat units is present as radical cations or anions. Charges can also be introduced by injection from another material under the influence of an electric field. Charge transport materials may be classified into hole transport materials and electron transport materials. In a hole transport material, electrons are removed, either by doping or injection, from a filled manifold of orbitals to give positively charged molecules or polymer repeat units. Transport takes place by electron-transfer between a molecule or polymer repeat unit and the corresponding radical cation; this can be regarded as movement of a positive charge (hole) in the opposite direction to this electronic motion. In an electron transport material, extra electrons are added, either by doping or injection; here the transport process includes electron-transfer from the radical anion of a molecule or polymer repeat unit to the corresponding neutral species.

FIRST POLYMER SUBUNIT

Polystyrenes comprising one or more carbazole groups are known in the art and described in, for example, Zhang et ah, Chem. Mater. 23:4002-2015 (2011), US 2002/0115810, WO 2010149618, WO 2010149620, WO 2010149622, JP-2002-302516A, and JP-2004-018787A, all of which are incorporated herein by reference in their entireties,

Many embodiments described herein relate to a solution-processable composition suitable for making electroluminescence devices. The solution-processable composition comprises at least one first polymer comprising a first polymer subunit represented by formula (I) or formula (II):

0 (ID

wherein Rl, R2, R3, R4, R5, R6, R7, R8, R9, R10, Rl l, R12, R13, R14, R15, R16, R17 and R18 are each independently a hydrogen, a halogen, an optionally substituted alkyl, an optionally substituted aryl, an optionally substituted heteroalkyl, or an optionally substituted heteroaryl; wherein L is a linker group that comprises at least one carbon atom but does not comprise any 2-phenyl-5-phenyl-l,3,4-oxadiazole group; and wherein X, Y and Z are each inde endently H, alkyl, fluoroalkyl or fluoride.

(2-phenyl-5-phenyl-l ,3,4-oxadiazole)

In some embodiments, the first polymer subunit of the solution-processable composition is represented by formula (III), formula (IV), or formula (V):

In some embodiments, Rl, R2, R3, R4, R5, R6, R7, R8, R9, RIO, Rl 1, R12, R13, R14, R15, R16, R17 and R18 are each a hydrogen. In other embodiments, at least one of Rl, R2, R3, R4, R5, R6, R7, R8, R9, RIO, Rl l, R12, R13, R14, R15, R16, R17 and R18 is an optionally substituted carbazole group. In further embodiments, at least four of Rl, R2, R3, R4, R5, R6, R7, R8, R9, RIO, Rl l, R12, R13, R14, R15, R16, R17 and R18 are optionally substituted carbazole groups.

When Rl, R2, R3, R4, R5, R6, R7, R8, R9, RIO, Rl l, R12, R13, R14, R15, and R16 are each a hydrogen, the first polymer subunit can be represented by, for example, formula (VI):

When at least four of Rl, R2, R3, R4, R5, R6, R7, R8, R9, RIO, Rl 1, R12, R13, R14, R15, and R16 are carbazole groups, the first polymer subunit can be represented by, for example, formula (VII):

(vii)

Optionally, one or more carbazole groups of formula (VI) and (VII) can be further substituted with at least one hydrogen, halogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroalkyl, and/or optionally substituted heteroaryl.

The first polymer subunit can comprise, for example, one or more moieties such as electron transporters, solubilizing groups, and/or compatibilizing groups. In one

embodiment, the first polymer subunit comprises no oxadiazole group.

Specific examples of the first polymer subunit include the following:

In one embodiment, the first polymer subunit comprises at least one of X, Y, or Z which is F or fluoroalkyl. In a particular embodiment, the solution-processable composition comprises at least one first non-fluorinated polymer and at least one second fluorinated polymer comprising subunits represented by formula (I) or formula (II). Fluorinated polymer backbone structure can enable, for example, orthogonal solution processing of the emissive layer on top.

LINKER GROUP

Linker groups are known in the art and described in, for example, WO 2009080799, WO 2010149618, WO 2010149620, and WO 2010149622, all of which are incorporated herein by reference in their entireties.

The linker group can be, for example, an optionally substituted alkylene, an optionally substituted arylene, an optionally substituted heteroalkylene, or an optionally substituted heteroarylene.

More specifically, the linker group can be, for example, an alkylene, an oxyalkylene, an oligo-oxyalkylene, an oxyarylene, a carbonyl alkylene, a carbonyl arylene, a carboxyl alkylene, a carboxyl arylene, an ether, an ester, or a ketone.

In some embodiments, the linker group is resistant to oxidative, reductive, or thermal destruction under normal operating conditions of OLED devices.

In some embodiments, the linker group does not comprise any 2-phenyl-5-phenyl- 1,3,4-oxadiazole group. In other embodiments, the linker group comprises no oxadiazole group. FIRST POLYMER

The first polymer described herein is solution-processable and possesses good hole transport ability.

The weight average molecular weight (Mw) of the first polymer can be, for example, 5,000 Da or more, or 10,000 Da or more, or 15,000 Da or more, or 20,000 Da or more, or 25,000 Da or more, or 50,000 Da or more, or 100,000 Da or more, or 200,000 Da or more.

The glass transition temperature (Tg) of the first polymer can be, for example, 150°C or more, or 175°C or more, or 200°C or more, or 225°C or more, or 250°C or more, or 275°C or more, or 300°C or more.

The first polymer can be, for example, a homopolymer. The first polymer also be a copolymer such as a block copolymer or an alternating copolymer. The copolymer can be, for example, a copolymer comprising in the polymer backbone a second polymer subunit. The second polymer subunit can comprise, for example, one or more moieties such as electron transporters, solubilizing groups, compatibilizing groups, and crosslinking groups.

In some embodiments, the first polymer does not comprise any 2-phenyl-5-phenyl- 1,3,4-oxadiazole group. In other embodiment, the first polymer comprises no oxadiazole group.

The first polymer can be adapted to, for example, transport holes. The first polymer can also be adapted to, for example, transport electrons in addition to holes.

The first polymer described herein can have, for example, higher hole mobility than PVK. The first polymer described herein can have, for example, a reversible first oxidation step. Examples of the first polymer include, but are not limited to, Polymer A shown below.

Polymers described herein can be unexpectedly effective as hole transporting material, and can be used to make organic electronic devices such as, for example, highly efficient and stable OLED devices. Moreover, polymers described herein can have unexpectedly superior physical properties, such as high solubility and processability, and/or high resistance to crystallization and/or thermal degradation during normal OLED operation.

Further, polymers described herein can be readily soluble in common organic solvents. These polymers can be readily processed to form compositions useful in many organic electronic devices, including but are not limited to, active electronic components, passive electronic components, electroluminescent devices (e.g., OLED), photovoltaic cells, light-emitting diodes, field-effect transistors, phototransistors, radio-frequency ID tags, semiconductor devices, photoconductive diodes, metal-semiconductor junctions (e.g., Schottky barrier diodes), p-n junction diodes, p-n-p-n switching devices, photo-detectors, optical sensors, photo-transducers, bipolar junction transistors (BJTs), heterojunction bipolar transistors, switching transistors, charge-transfer devices, thin-film transistors, organic radiation detectors, infra-red emitters, tunable micro-cavities for variable output wavelength, telecommunications devices and applications, optical computing devices, optical memory devices, chemical detectors, combinations thereof, and the like.

EMISSIVE LAYER COMPRISING FIRST POLYMER

Many embodiments described herein also relate to an emissive layer. The emissive transport layer can comprise, for example, the solution-processable composition comprising the first polymer described herein.

The solution-processable composition can further comprise, for example, a second active material, which can be a small molecule or a polymer. While the first polymer can be adapted to, for example, transport holes, the second material can be adapted to, for example, transport electrons. The second material can comprise, for example, at least one oxadiazole, triazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine or tetrazine group. Examples of the second polymer include, but are not limited to, Polymer B shown below.

(Polymer B)

In addition to the polymer host, the solution-processable composition can further comprise, for example, at least one organometallic complex as phosphorescent guest emitter. The organometallic complex can comprise, for example, at least one metal of Ir, Rd, Pd, Pt, Os, and Re. Particular examples of the organometallic emitter include tris(2- phenylpyridinato-N,C) ruthenium, bis(2-phenylpyridinato-N,C ) palladium, bis(2- phenylpyridinato-N,C ) platinum, tris(2-phenylpyridinato-N,C) osmium, tris(2- phenylpyridinato-N,C) rhenium, octaethyl platinum porphyrin, octaphenyl platinum porphyrin, octaethyl palladium porphyrin, octaphenyl palladium porphyrin, iridium(III)

2 2 bis[(4,6-difluorophenyl)-pyridinato-N,C ] picolinate (FIrpic), tris-(2-phenylpyridinato-N,C ) iridium (Ir(ppy)3), green material bis-(2-phenylpyridinato-N,C ) iridium(acetylacetonate) (Ir(ppy)2(acac)), and red material 2,3,7,8,1 2,13,17,18-octaethyl-21H,23H-porphine platinum(II) (PtOEP), as well as other materials known in the art of OLED.

The emissive layer can be fabricated from a solution of the solution-processable composition described herein. The solution can comprise, for example, an organic solvent such as chlorobenzene. The solution can comprise, for example, between 0.1-50 wt.% of the polymer, or between 0.2-25 wt.% of the polymer, or between 0.5-10 wt.% of the polymer, or between 1-5 wt.% of the polymer.

The emissive layer can be fabricated by methods known in the art. Examples include spin coating from solution and vacuum vapor deposition. If the emissive layer is a film deposited from a solution, following solution processing, the film can be dried on a hotplate. The emissive layer can be fabricated on top of a hole transport layer, on top of a hole injection layer, or directly on top of an anode layer.

In a preferred embodiment, the emissive layer is solution deposited on top of a hole transport layer. Said underlying hole transport layer can be deposited from, for example, a solution of a crosslinking material. The crosslinking material can be, for example, a crosslinking polystyrene comprising at least one optionally substituted triscarbazole group and at least one crosslinking side group, such as Polymer 5.40 and Polymer 5.38. The crosslinking material can also be, for example, a crosslinking small molecule compound comprising at least one optionally substituted triscarbazole group and at least two

crosslinking groups, such as Compound 5.42. Other crosslinking materials suitable for hole transport layer are known in the art and include, for example, p-TPDF shown below.

-TPDF, m:n=4: l).

The underlying hole transport layer described here can be thermally or

photochemically crosslinked following its own solution-deposition and before the solution- deposition of the emissive layer. The crosslinking of the underlying hole transport layer can result in the formation of new covalent bonds leading to the insolubilization of the hole transport layer, which would improve the ability of the hole transport layer to resist against potential degradation caused by solution-processing of the subsequent emissive layer.

HOLE TRANSPORT LAYER COMPRISING FIRST POLYMER

Many embodiments described herein also relate to a hole transport layer fabricated from the solution-processable composition comprising the first polymer. Depending on the linking position of the carbazole units, the HOMO energy level can be manipulated over a large range of typically -5.8eV to -5.2eV, thus facilitating the injection of positive charge carriers. Cf. Brunner et al., J. Am. Chem. Soc. 726:6035-6042 (2004) and Jiang et al., J. Mater. Chem. 27:4918-26 (2011), both of which are incorporated herein by reference in their entireties. The solution-processable composition can further comprise, for example, a second polymer. More particularly, the first polymer can be non-fluorinated and the second polymer can be fluorinated, such as to enable vertical phase segregation during layer processing. The resulting demixing can be attractive to install a vertical compositional gradient of different hole transport functional groups or to create a partially fluorinated surface resistant to solution processing on top of the hole transport layer.

The hole transport layer can be fabricated from a solution comprising the solution- processable polymer compositions described herein. The solution can further comprise, for example, an organic solvent such as chlorobenzene.

The solution can comprise, for example, between 0.1-50 wt.% of the polymer, or between 0.2-25 wt.% of the polymer, or between 0.5-10 wt.% of the polymer, or between 1-5 wt.% of the polymer.

The hole transport layer can be fabricated by methods known in the art. Examples include spin coating from solution and vacuum vapor deposition. If the hole transport layer is a film deposited from a solution, following solution processing, the film can be dried on a hotplate.

HOLE-INJECTION LAYER COMPRISING FIRST POLYMER

A hole injection layer can be formed from the solution-processable composition comprising the first polymer described herein modified by soluble molecular p-dopants known in the art. Examples of particularly useful dopants are dithiolene complexes of Cr(VI) and Mo(VI) described in Qi et al, J. Am. Chem. Soc. 131 : 12530-12531 (2009), incorporated herein by reference in its entirely. Other examples are described in WO 2008/061517, incorporated herein by reference in its entirety. Particularly useful are "Mo(tfd)3" and "Cr(tfd)3" as dopants:

ELECTROLUMINESCENCE DEVICES

Electroluminescence devices such as OLED are well known in the art. The electroluminescence device can comprise, for example, an anode layer, a cathode layer, an emissive layer comprising the first polymer described herein, and a hole transport layer comprising at least one crosslinked material comprising one or more triscarbazole groups. The electroluminescence device can also comprise, for example, an anode, a cathode, an emissive layer, and a hole transport layer comprising the first polymer described herein. The electroluminescence device can also comprise, for example, an anode, a cathode, an emissive layer, a hole transport layer and a hole injection layer comprising the first polymer described herein, p-doped by a suitable molecular dopant.

The electroluminescence device may optionally comprise an electron transport layer. The thickness of the anode layer, the cathode layer, the emissive layer, the hole transport layer, and the electron transport layer can be, for example, about 0.001-1000 μιη, about 0.005-100 μιη, or about 0.01-10 μιη, or about 0.02-1 μιη.

Many suitable materials for anode in electroluminescence devices are known in the art and include, for example, ITO, which can be applied by vacuum deposition in a layer over an inert and transparent substrate such as glass. Other examples include metal oxide with high work function, such as zinc oxide and indium zinc oxide.

Many suitable materials for cathode in electroluminescence devices are known in the art and include, for example, a combination of LiF as electron injecting material coated with a vacuum deposited layer of Al. Other suitable electron injecting materials include alkali metal salts such as CsOH, CS₂CO₃, L1₂CO₃.

Many suitable materials for electron transport layer in electroluminescence devices are known in the art and include, for example, 2,9-Dimethyl-4,7-diphenyl-l,10- phenanthroline (BCP) and 3-(4-Biphenyl)-4-phenyl-5-tert-butylphenyl-l,2,4-triazole (TAZ), as well as those described in WO 2009080796, WO 2009080797, and Kulkarni et al, Chem. Mater. 16(23)"4556-4573 (2004), all of which are incorporated herein by reference in their entireties.

When the solution-processable composition comprising the first polymer described herein is used in the hole transport layer, materials different from said solution-processable composition can be used for the emissive layer. Many suitable materials for the emissive layer of electroluminescence devices are known in the art. Suitable host materials include, for example, 4,4'-Bis(carbazol-9-yl)biphenyl (CBP) and ambipolar materials described in WO 2010149618, WO 2010149620, and WO 2010149622, all of which are incorporated herein by reference in their entireties. Other examples of suitable host material include Compound C, Compound D, Compound E, Compound F and Compound G. In one embodiment, said emissive layer comprises a polar bis(organo-sulfonyl)-biaryl host fabricated also by solution deposition.

(Compound E)

pound F)

(Compound G)

Suitable guest materials include, for example, Iridium complexes such as Tris(2- phenylpyridine)iridium(III) (Ir(ppy)₃), Tris(5-phenyl-10,10-dimethyl-4-aza- tricycloundeca- 2,4,6-triene)Iridium(III) (Ir(pppy)₃) and Bis(3,5-difluoro-2-(2-pyridyl)phenyl-(2- carboxypyridyl)iridium (III) (Fir(pic)), as well as Platinum complexes such as platinum(II)[2- (4',6'-difluorophenyl)pyridinato-N,C )](2,4-pentanedionato) (F-Pt) and those described in WO 2011000873, which is incorporated herein by reference in its entirety.

In some embodiments, both the emissive layer and the hole transport layer of the electroluminescence device are fabricated by solution-processing, such as spin-coating. In other embodiments, the electroluminescence device comprises a solution-deposited hole transport layer and a vapor-deposited emissive layer.

In some embodiments, the electroluminescence device comprises an emissive layer comprising the solution processable material described herein as host, as well as a green emitter (e.g., Ir(ppy)3, etc.). The external quantum efficiency of such electroluminescence device at 1,000 cd/m can be, for example, at least 5%, or at least 8%, or at least 10%, or at least 12%, or at least 15%, or at least 18%, or at least 20%, or at least 25%.

In some embodiments, the electroluminescence device comprises an emissive layer comprising the solution processable material described herein as host, as well as a blue emitter (e.g., FIrpic, etc.). The external quantum efficiency of such electroluminescence device at 1,000 cd/m can be, for example, at least 5%, or at least 8%, or at least 10%>, or at least 12%, or at least 15%, or at least 18%, or at least 20%, or at least 25%.

In other embodiments, the electroluminescence device comprises a hole transport layer comprising the solution processable material described herein, as well as an emissive layer comprising a green emitter (e.g., Ir(ppy)3, etc.). The external quantum efficiency of such electroluminescence device at 1,000 cd/m can be, for example, at least 5%, or at least 8%, or at least 10%, or at least 12%, or at least 15%, or at least 18%, or at least 20%, or at least 25%.

In other embodiments, the electroluminescence device comprises a hole transport layer comprising the solution processable material described herein, as well as an emissive layer comprising a blue emitter (e.g., FIrpic, etc.). The external quantum efficiency of such 2

electroluminescence device at 1,000 cd/m can be, for example, at least 5%, or at least 8%, or at least 10%, or at least 12%, or at least 15%, or at least 18%, or at least 20%, or at least 25%.

In some embodiments, the electroluminescence device is fabricated by the following methods: (i) providing a substrate comprising an anode layer and optionally comprising a hole injection layer; (ii) depositing a hole transport layer from a first solution onto the substrate; and (iii) depositing an emissive layer from a second solution onto the hole transport layer, wherein the second solution comprises the solution-processable composition described herein. Optionally, the first solution comprises a crosslinking material that is crosslinked thermally or photochemically to form a crosslinked hole transport layer before the deposition of the emissive layer.

PCT/US2011/066597 (WO 2012/088316) describes devices. In one embodiment, the polymer described therein and labeled as YZ-IV-17 (pages 21, 34, 35) is excluded from compounds, compositions, devices, and methods as described and claimed herein.

ADDITIONAL EMBODIMENTS OF FIGURE 1

A polystyrene polymer with a multicarbazole pendant group like structure I, where P is the polymer backbone and R can be other carbazole units. Each carbazole ring can be further substituted with halogens, alkyl, heteroalkyl groups (e.g., functional groups), aryl, or heteroaryl groups. Examples are a "triscarbazole" such as structure II or a

"heptakiscarbazole" such as structure III. The multicarbazole pendant groups can sometimes be referred to as "dendrimers," where, for example, structure II would be a second generation dendrimer and structure III would be a third generation dendrimer. Each carbazole substituent may be substituted in the ortho, either meta, and/or para position relative to the nitrogen of the parent carbazole. Each dendrimer generation maybe have different ortho, meta, and/or para substitutions relative to the nitrogens of their parent compared to the substitution pattern of carbazoles in previous generations (e.g., the second generation carbazoles are substituted para to the first carbazole's nitrogen and the third generation's carbazoles are substituted meta to the second generation's nitrogens). Multicarbazole pendant groups may be attached to each subunit of the polystyrene or may be attached to less than each subunit. The fraction of multicarbazole pendant groups can be varied in the polymer to effect properties such as hole transport ability, processibility, mechanical stability, etc. The polystyrene may also contain other groups such as electron transporters, solubilizing groups, compatibilizing groups, crosslinker groups, etc. The styrene polymers may also be a

copolymer with other backbone subunits.

WORKING EXAMPLES

1. Material Synthesis

(6-( 9H-ca rbazol- 9-y I )- 9-(4- vin yl b en zy I )- 9H-3 ,9'-bicarbazole)

Triscarbazole monomer (6-(9H-carbazol-9-yl)-9-(4-vinylbenzyl)-9H-3,9'-bicarbazole):

To a solution of Triscarbazole (3.0 g, 6.03 mmol) and l-(chloromethyl)-4-vinylbenzene (1.5 g, 9.83 mmol) in DMF (40.0 ml) was added K₂CO₃ (10 g, 72.36 mmol) at room temperature under stirring. The reaction was carried out at room temperature for 52 h. Water (200.0 ml) was added. The white solid product was obtained by filtration, washed with water and methanol. After dry, the crude product was purified by silica gel column chromatography using dichloromethane/hexanes (6:4) as eluent. After removal of solvent, the white solid product was obtained and collected from hexanes by filtration. After vacuum dry, the product was collected as a white solid in 3.55 g (95.9%) yield.

1H NMR (400 MHz, CDC1₃) δ 8.25 (s, 2 H), 8.17 (d, J= 8.0 Hz, 4 H), 7.63 (d, J= 1.2

Hz, 4 H), 7.44-7.37 (m, 10 H), 7.30-7.26 (m, 6 H), 6.72 (dd, J = 17.6 Hz, J₂ = 10.8 Hz, 1 H,

C=C-H), 5.76 (d, J = 17.6 Hz, 1 H, C=C-H), 5.68 (s, 2 H, NCH₂), 5.27 (d, J = 10.8 Hz, 1 H,

C=C-H) ppm. ¹³C NMR (100 MHz, CDCI3) δ 141.76, 140.34, 137.32, 136.16, 135.99,

129.79, 126.86, 126.79, 126.16, 125.84, 123.62, 123.10, 120.26, 119.83, 119.64, 114.33, 110.33, 109.71, 46.96 ppm. MS-EI (m/z): [M]⁺ calcd for C₄₅H₃₁N₃, 613.3, 614.3, 615.3, 616.3, found 613.2, 614.2, 615.2, 616.2. Anal. Calcd for C₄₅H₃₁N₃: C, 88.06; H, 5.09; N, 6.85. Found: C, 87.15; H, 5.03; N, 6.50.

Poly(6-(9H-carbazol-9-yl)-9-(4- vinylbenzyl)-9 - -3,9'-bicarbazole)

Poly(triscarbazole) (Polymer A, Poly(6-(9H-carbazol-9-yl)-9-(4-vinylbenzyl)-9H-3,9'- bicarbazole)): A Schlenk flask was charged with tris-carbazole monomer 6-(9H-carbazol-9- yl)-9-(4-vinylbenzyl)-9H-3,9'-bicarbazole (1.0 g, 1.6 mmol), AIBN (7.0 mg, 0.042 mmol) and dry THF (20.0 ml). The polymerization mixture was purged with nitrogen (removal of oxygen), securely sealed under nitrogen, and heated to 60°C. The polymerization was carried out at 60°C with stirring for 7 days. After cooling to room temperature, the polymer was precipitated with acetone. The white polymer precipitate was collected by filtration, dissolved in dichloromethane, and precipitated with acetone again. This dissolution/precipitation procedure was repeated three more times. The collected polymer was dried under vacuum. After vacuum dry, the polymer as white solid in 0.93 g (93.0 %) was obtained.

^!Η-ΝΜΚ(400 MHz, CDCI₃) δ: 8.09 (m, br, 10 H), 7.16 (m, br, 16 H), 5.28 (m, br, 2 H), 1.25-0.75 (m, br, 3 H) ppm. Anal. Calcd for C₄₅H₃₁N₃: C, 88.06; H, 5.09; N, 6.85. Found: C, 87.58; H, 5.04; N, 6.68. GPC (CHC1₃): M_w = 29000, M_n = 14000, PDI = 2.0. DSC: T_g = 296 °C. TGA: T_d = 412 °C

S3.1 : Synthesized according to Maegawa, Y.; Goto, Y.; Inagaki, S.; Shimada, T.

Tetrahedron. Letters 2006, 47, 6957-6960. 1H NMR was consistent with the literature.

S3.2: To a solution of S3.1 (10.0 g, 23.87 mmol) and 11-bromo-l-undecanol (7.0 g, 28 mmol) in N,N-dimethyformamide (100.0 mL) was added K₂CO₃ (32.0 g, 230 mmol). The reaction was stirred at room temperature for 24 h. Deionized water (300 mL) was added. The precipitate was filtered. The crude product was purified by column chromatography (silica gel; hexanes:ethyl acetate = 7:3). 12.4 g (87.9 %) of a white product was obtained. 1H NMR (500 MHz, CDCI3) : δ 8.32 (d, J = 1.5 Hz, 2H), 7.71 (dd, J/ = 1.5 Hz, J₂ = 8.5 Hz, 2H), 7.16 (dd, J = 1.5 Hz, J₂ = 8.5 Hz, 2H), 4.21 (t, J= 6.8 Hz, 2 H), 3.64 (m, 2 H), 3.41 (s, 1 H), 1.81 (m, 4 H), 1.54 (m, 4 H), 1.30 (m, 10 H). ¹³C{1H} (75 MHz, CDC1₃): 139.50, 134.48, 129.35, 123.96, 110.91, 81.77, 63.08, 43.24, 32.77, 29.48, 29.41, 29.39, 29.35, 29.30, 28.80, 27.18, 25.69. MS (EI) m/z : 588.9 [M+]. Anal, calcd. for C₂₃H₂₉I₂NO: C, 46.88; H, 4.96; N, 2.38. Found: C, 46.76; H, 5.10; N,

S3.3: To a solution of S3.2 (8.0 g, 14 mmol), 9H-carbazole (6.8 g, 41 mmol) in dimethylsulfoxide (50.0 mL) were added Cu powder (10.0 g, 160 mmol) and Na₂C03 (30.0 g, 280 mmol). The reaction was stirred at 180 °C for 12 h. Insoluble inorganic salts were removed by filtration and washed with THF. After removal of THF, water (250 mL) was added. The precipitate was collected by filtration and purified by column chromatography (silica gel; toluene:ethyl acetate = 7:3). 8.1 g (91.0 %) of product was obtained as white solid. 1H (300MHz, CDC1₃): δ 8.24-8.13 (m, 5H), 7.71-7.63 (m, 4H), 7.43-7.22 (m, 13H), 4.49 (t, J = 6.98 Hz, 2H), 3.62 (t, J= 6.34 Hz, 2H), 2.05 (p, J= 7.28 Hz, 2H), 1.77-1.23 (m, 18H), 1.18 (s, 1H). ¹³C{1H} (75 MHz, CDCI₃): 5142.09, 140.42, 129.54, 126.19, 126.08, 123.62, 123.35, 123.33, 120.51, 120.07, 119.85, 110.34, 109.97, 63.31, 43.94, 33.02, 29.82, 29.79, 29.71, 29.66, 29.43, 27.66, 25.98. MS (EI) m/z : 667.4 [M+]. Anal, calcd. for C₄₇H₄₅N₃0: C, 84.52; H, 6.79; N, 6.29. Found: C, 84.37; H, 6.74; N, 6.29. )₂

S5.1 : In a round bottom flask, 4-bromobenzocyclobutene (1.509 g, 8.244 mmol) was dissolved in anhydrous diethyl ether (10.0 mL) under nitrogen atmosphere and the resulting solution was cooled at -78°C (dry-ice/acetone bath). To the cooled solution, 1.7M tert- butyllithium in pentane (6.0 mL, 10 mmol) was added dropwise. To the resulting pale yellow solution was then added 5.70 mL of trimethyl borate (0.80 M solution of in diethyl ether) and the reaction was stirred overnight. The solution was diluted through the addition of 10 mL of diethyl ether and the reaction was quenched by the addition of a dilute HC1 (aq) solution. The resulting solution was then washed twice with deionized water (2 x 15 mL) and dried over magnesium sulfate. The solvent was removed in vacuo to yield a viscous yellow oil (0.643 g, crude yield = 53.05%).¹H (300 MHz, CDCI3): δ 6.89 (d, J = 7.7 Hz, 1H), 6.68-6.62 (m, 1H), 6.60-6.57 (m, 1H), 5.71 (br, 1H), 4.62 (br, 1H), 3.09 (s, 4H). [Intermediate was found to be consistent with a literature example of the target prepared by an alternate method (Yang, j.- X.; Ma, K.-Y.; Zhu, F.-H.; Chen, W.; Li, B.; Zhang, L.; Xie, R.-G. J. Chem. Res. 2005, 3,

184-186.)].

S5.2: S5.1 (0.623 g, 4.21 mmol), deionized water (18.0 mL), and of 30% aq. hydrogen peroxide (0.88 mL) were mixed in a round bottom flask and the reaction was stirred at room temperature for 24 hours. It was observed that the starting material was only partially dissolved and 5mL of acetone were added to promote further dissolution and the reaction was allowed to proceed at room temperature for an additional 48 hours. The organic layer was then extracted with diethyl ether (30 mL), washed with deionized water (30 mL), and dried over magnesium sulfate. Solvent was removed in vacuo to yield a brown oil that was purified by column chromatography (silica gel ; hexanes:ethyl acetate 90: 10) to yield a yellow solid (0.194 g, 38.2%).1H (300 MHz, CDC1₃): δ 6.90 (d, J = 7.8 Hz, 1H), 6.65 (dd, J = 7.8 Hz, J₂ = 2.1 Hz, 1H), 6.59 (d, J= 2.1Hz, 1H), 4.69 (s, 1H), 3.09 (s, 4H). Anal, calcd. for C₈H₈0: C, 79.97; H, 6.71. Found: C, 79.74; H, 6.77. [Intermediate was found to be consistent with a literature example of the target prepared by an alternate method (Tan, L.-S.; Venkatasubramanian, N. Synth. Commun. 25, 2189-2195.)].

5.34: S5.2 (0.157 g, 1.31 mmol) was dissolved in N,N-dimethylformamide (20 mL) under nitrogen atmosphere, l-bromo-4-vinylbenzene (0.204 g, 1.34 mmol) was added dropwise and the resulting solution was cooled to 0 °C. NaH (0.095 g, 3.96 mmol) was then added over a five minute period, producing an intense yellow solution, which was stirred at room temperature overnight. The reaction was quenched by the addition of a saturated aq. NaCl solution (10 mL). The organic layer was extracted with diethyl ether (2 x 50 mL), washed with deionized water (40 mL), and dried over magnesium sulfate. Solvent was removed at reduced pressure to yield an off-white solid that was purified by column chromatography (silica gel; diethyl ether:hexanes 50:50) to yield a white solid (0.240 g, 77.4%). 1H (300 MHz, CDC1₃ ): δ 7.42 (d, J = 8.4 Hz, 2H), 7.38 (d, J = 8.4 Hz, 2H), 6.94 (d, J = 8.1 Hz, 1H) 6.81 (dd, J = 8.0 Hz, J₂ = 2.1 Hz, 1H) 6.72 (dd, J = 17.4 Hz, J₂ = 11.1 Hz, 1H), 6.72 (d, J = 2.1 Hz, 1H), 5.75 (dt, J, = 17.7 Hz, J₂ = 0.9 Hz, 1H), 5.25 (dt, J, = 10.8 Hz, J₂ = 0.9 Hz, 1H), 5.017 (s, 2H), 3.10 (s, 4H). ¹³C{1H} (75 MHz, DMSO- ¾: δ 146.71, 137.96, 137.41, 136.70, 127.86, 126.61, 123.72, 114.48, 114.22, 110.0, 70.32, 29.24, 28.98. MS (EI) m/z = 236.2 [M+]. Anal, calcd. for Ci₇Hi₆0: C, 86.40; H, 6.82. Found: C, 86.68; H, 6.95.

S5.3: Triethylamine (3.266 g, 32.3 mmol), 3-ethyl-3-hydroxymethyl oxetane (3.018 g, 26.0 mmol), and toluene (30.0 mL) were combined under nitrogen atmosphere and cooled to 0 °C over an ice-water bath. Mesyl chloride (3.243 g, 28.3 mmol) was added to the reaction mixture dropwise over the period of 1 h while maintain the mixture at 0 °C. After 3 h, the reaction was filtered to remove the insoluble salt by-product. The organic phase was concentrated in vacuo to afford a clear lightly yellow colored oil (5.192 g). The product was not purified. 1H (300 MHz, CDC1₅): δ 4.47-4.42 (m, 4H), 4.38-4.36 (m, 2H), 3.06 (s, 3H), 1.80 (q, J= 7.5 Hz, 2H), 0.93 (t, J= 7.5 Hz, 3H). [Intermediate was prepared according to the patent literature (Hirotsu, K.; Takebayashi, K.; Kaneko, T. Patent JP 1999030490919991027, 2001; Hirotsu, K.; Murakami, T. Patent JP6137420070605, 2007.)].

S5.4: Under nitrogen atmosphere, LiCl (1.207 g, 28.5 mmol) and anhydrous THF (20 mL) were combined and heated to 50 °C. S5.3 (5.192 g) was added into the heated solution dropwise over a period of 1 h. After 5 h, heating was stopped and toluene (50 mL) was added to the reaction flask. The organic layer was extracted with deionized water (3 x 30 mL) and the organic layer solvents were removed in vacuo to give a faintly yellow clear oil (2.105 g). The product was used without further purified. 1H (300 MHz, CDCI3): δ 4.41 (s, 3H), 3.79 (s, 2H), 1.83 (q, J = 7.5 Hz, 2H), 0.89 (t, J = 7.5 Hz, 3H). [Intermediate was prepared according to the patent literature (Hirotsu, K.; Takebayashi, K.; Kaneko, T. Patent JP 1999030490919991027, 2001; Hirotsu, K.; Murakami, T. Patent JP6137420070605,

2007.)].

5.36: 3-ethyl-3-((6-(4-vinylbenzyloxy)hexyloxy)methyl)oxetane (3.5 g, 14.9 mmol) was dissolved in anhydrous N,N-dimethylformamide (50 mL) under a nitrogen atmosphere and NaH (0.724 g, 30.1 mmol) was added to the reaction in small portions. After three freeze- pump-thaw cycles the reaction mixture was heated to 50 °C and S5.4 (2.105 g, 15.6 mmol) was added to the reaction dropwise. The reaction was then heated to 90 °C. After 19 h, the reaction was diluted with ethyl acetate (100 mL) and then washed with deionized water (3 x 200 mL) to remove the DMF. The organic phase was dried over MgS0₄ and solvents were removed in vacuo to produce a brown colored oil. The oil was purified by column chromatography (silica gel, hexanes:ethyl acetate = 6:4) and concentrated to afford a lightly yellow oil (1.579 g, 31.8%). 1H (300 MHz, CDC/₅): δ 7.41-7.37 (m, 2H), 7.30-7.27 (m, 2H), 6.71 (dd, J = 17.6, J₂ = 10.9 Hz, 1H), 5.74 (dd, J = 17.6, J₂ = 0.9 Hz, 1H), 5.23 (dd, J = 10.9, J2 = 0.9 Hz, 1H), 4.58-4.31 (m, 6H), 3.51 (s, 2H), 3.45 (dt, J = 6.7, J? = 3.8 Hz, 4H), 1.75 (q, J = 7.5 Hz, 2H), 1.67-1.54 (m, 4H), 1.44-1.33 (m, 4H), 0.90 (t, J = 7.45 Hz, 3H). [Product was found to be consistent with a literature example of the target prepared by an alternate method (Bacher, E.; Bayerl, M. S.; Rudati, P.; Reckefuss, N.; Muller, C. D.; Meerholz, K.; Nuyken, O. Macr -1647)].

S5.6: Toluene (50 mL) was used to dissolve S3.3 (2.352 g, 3.52 mmol) in a flask. 50% aqueous sodium hydroxide (98.081 g) and tetrabutylammonium bromide (0.171 g, 0.53 mmol) were added to the flask. Under vigorous stirring, 4-vinylbenzyl chloride (0.601 g, 3.94 mmol) was added and the reaction was heated over an oil bath (50 °C). After one week, TLC analyses showed starting material was still present. Deionized water (100 mL) was added to the flask and diethyl ether was used to extract the product (3 x 100 mL). The ethereal layers were combined and solvents were removed in vacuo to give a yellow/orange crude product. The crude product was purified by silica gel column chromatography (hexanes/ethyl acetate -

(8:2)) to give a white powder (1.156 g, 54%). 1H (300 MHz, CDC1₃): 58.19 (ddd, J = 8.7, J_? = 2.2 Hz, J3 = 1.3 Hz, 5H), 7.67 (d, J = 0.99 Hz, 4H), 7.48-7.17 (m, 17H), 6.80-6.61 (m, 1H ), 5.81-5.65 (m, 1H), 5.29-5.16 (m, 1H), 4.57-4.41 (m, 4H), 3.44 (m, 2H), 2.04 (p, J = 7.1 Hz, 2H), 1.70-1.22 (m, 16H). ¹³C (75 MHz, CDC1₃): δ 142.1, 140.4, 138.6, 137.1, 136.8, 129.5, 128.1, 126.4, 126.2, 126.1, 123.6, 123.3m 120.5, 120.1, 119.9, 114.0, 110.4, 110.0, 72.3, 70.7, 43.9, 30.0, 29.8, 29.7, 29.4, 27.7, 26.5. MS (FAB) m/z = 783.3 [M+]. Anal, calcd. for C₅₆H₅₃N₃0: C, 85.79; H, 6.81; N, 5.36. Found: C, 85.90; H, 6.72; N, 5.36.

(target x = 0.9)

5.38 (Polymer 5.38): S5.6 (0.649 g, 0.828 mmol), 5.34 (0.0197 g, 0.0834 mmol), and AIBN (0.0070 mg) where dissolved in 8.0 mL anhydrous THF in a Schlenk tube. Freeze-pump-thaw (3 x) was performed and the tube was sealed under static nitrogen afterward. The reaction mixture was then stirred at 60 °C for 2 weeks. The reaction mixture was concentrated in vacuo, yielding a pale yellow oily solid that was dissolved in chloroform and precipitated into acetone to yield a white solid (0.555g, 82.8%). 1H (300MHz, CDC1₅): δ 8.24-7.95 (br m, 5H), 7.68-7.09 (br m, 14H), 7.09-6.01 (br m, 0.4H), 4.53-4.02 (br m, 4H), 3.50-3.14 (br m, 2H), 3.00-2.87 (br m, 0.4H), 2.06-1.73 (br m, 3H), 1.52-0.84 (br m, 15H). Gel Permeation Chromatography (chloroform): M_w = 24,000; M_n = 10,200; PDI = 2.35. Anal, calcd. for copolymer: C, 85.80; H, N, 5.14.

(target x = 0.9)

5.40 (Polymer 5.40): S5.6 (0.373 g, 0.48 mmol), AIBN (0.0027 g, 0.016 mmol) and anhydrous tetrahydrofuran (4.0 mL) were combined in a Schlenk tube under nitrogen atmosphere. In a separate flask, 5.36 (0.01662 g, 0.05 mmol) was dissolved in anhydrous tetrahydrofuran (1.0 mL). The 5.36 solution (1.0 mL) was added to the reaction flask to give a 5.0 mL reaction volume. The mixture was subjected to freeze-pump-thaw (3 x) then placed under static nitrogen atmosphere and heated over an oil bath (60 °C). After 7 days, the solution was concentrated in vacuo and precipitated into acetone. The isolated polymer was re-precipitated into acetone (3 x) and then dried to produce a white powder (0.223 g, 57.0%).

1H (300 MHz, CDC1₅): δ 8.26-8.00 (br m, 5H), 7.69-7.11 (br m, 14H), 7.08-6.18 (br m, 5H), 4.55-4.12 (br m, 4H), 3.57-3.26 (br m, 2.2H), 2.10-0.78 (br m, 18H). Gel Permeation Chromatography (chloroform): M_w = 25,700; M_n = 7,400; PDI = 3.45. Anal, calcd. for copolymer: C, 84.80; H, 7.10; N, 5.36. Found: C, 84.40; H, 6.86; N, 5.27.

S5.7: Synthesized according to Mariampillai, B.; Alberico, D.; Bidau, V.; Lautens, M. J. Am. Chem. Soc. 2006, 128, 14436- with the literature.

S5.8: S5.7 (2.415, 9.14 mmol), 3,6-bis(carbazol-9-yl)carbazole (3.507 g, 7.03 mmol), 18- crown-6 ether (0.059 g, 0.21 mmol), copper powder (5.849 g, 92.0 mmol), and o- dichlorobenzene (75 mL) combined in flask under nitrogen atmosphere. Postassium carbonate (11.532 g, 83.4 mmol) was added and reaction heated to 180 °C for 24 h. After cooling, solids were filtered and washed and the filtrate solvents were removed in vacuo. The crude was purified by column chromatography (silica gel; hexanes:ethyl acetate = 8:2) to afford an off-white powder after recrystallization from hot dichloromethane/methanol (3.199 g, 71.7%). 1H (300 MHz, CDC1₅): δ 8.27-8.26 (m, 2H), 8.16 (dt, J = 7.7 Hz, 4H), 7.75-7.70 (m, 2H), 7.64-7.59 (m, 2H), 7.42-7.37 (m, 8H), 7.31-7.26 (m, 4H), 6.88 (d, J = 2.2 Hz, 2H), 6.66 (t, J = 2.2 Hz, 1H), 3.92 (s, 6H). ¹³C{1H} (75 MHz, CDC1₅): δ 162.1, 141.8, 140.6, 138.8, 130.5, 126.3, 125.9, 124.0, 123.2, 120.2, 1 19.7, 111.5, 109.7, 105.5, 100.3, 55.7. MS (EI) m/z = 633.2 [M+]. Anal, calcd. for C44H31N3O2: C, 83.39; H, 4.93; N, 6.63. Found: C, 82.42; H, 4.71; N, 6.49.

S5.9: S5.8 (4.011 g, 6.33 mmol) was dissolved in anhydrous dichloromethane (40 mL) under nitrogen atmosphere and cooled to -78 °C (dry-ice/acetone bath). Boron tribromide (50 mL, 1.0 M in DCM) added dropwise to cooled solution and cooling bath removed. After ~4 h, mixture was added into ice-water (150 mL) with stirring. The biphasic mixture was separated and the aqueous phase was extracted with dichloromethane (2 x 100 mL). The combined organic phase was dried over magnesium sulfate, filtered, and solvents removed in vacuo. The crude was purified by column chromatography (silica gel; toluene = 100%) and recrystallized from acetone/methanol to afford an grayish white powder (1.551 g, 40.6%). 1H

(300 MHz, DMS(W_tf): δ 9.91 (s, 2H), 8.66 (d, J = 1.9 Hz, 2H), 8.27-8.21 (m, 4H), 7.82-7.75 (m, 2H), 7.72-7.66 (m, 2H), 7.46-7.36 (m, 8H), 7.30-7.22 (m, 4H), 6.66 (d, J = 2.1 Hz, 2H), 6.51 (t, J = 2.1 Hz, 1H). ¹³C{1H} (75 MHz, DMSO-^): δ 160.3, 141.5, 140.2, 138.3, 129.9, 126.6, 126.4, 124.0, 122.9, 120.9, 120.7, 120.2, 112.1, 110.2, 105.1, 102.8. MS (EI) m/z = 605.2 [M+]605.2. Anal, calcd. for C₄2H₂₇N₃02: C, 83.29; H, 4.49; N, 6.94. Found: C, 82.64; H, 4.29; N, 6.81.

5.42 (Compound 5.42): S5.9 (1.002 g, 1.65 mmol), DMF (25 mL), and potassium carbonate (2.775 g, 20.1 mmol) combined in a flask. l-(chloromethyl)-4-vinylbenzene (0.607 g, 3.98 mmol) added dropwise to mixture. After 24h, deionized water (100 mL) added to flask and white precipitate formed. The crude material was isolated by filtration and purified by column chromatography (silica gel ; hexanes: ethyl acetate = 8:2). The resulting oil was precipitated into methanol, collected by filtration, and dried to afford a white powder (0.559 g, 40.5%). 1H (300 MHz, DMSO-^): δ 8.64 (d, J = 1.5 Hz, 2H), 8.23 (d, J = 7.7 Hz, 4H), 7.58-7.31 (m, 20H), 7.26 (t, J = 7.4 Hz, 4H), 6.99 (d, J = 2.2 Hz, 2H), 6.91 (t, J = 2.0 Hz, 1H), 6.71 (dd, J = 17.7, 11.0 Hz, 2H), 5.83-5.77 (d, J = 17.6 Hz, 2H), 5.25 (s, 4H), 5.18 (d, J = 10.9 Hz, 2H). ¹³C{1H} (75 MHz, DMSO-^): δ 162.1, 160.8, 141.4, 140.0, 137.2, 136.9, 136.7, 130.0, 128.4, 128.2, 126.8, 126.6, 124.1, 122.9, 120.9, 120.2, 115.0, 110.1, 105.9, 69.8. MS (EI) m/z = 837.2 [M+]. Anal, calcd. for C₆₀H₄3N₃O₂: C, 86.00; H, 5.17; N, 5.01. Found: C, 85.76; H, 5.14; N, 5.08.

2. Device Fabrication - Polymer A as Emissive Layer Host

EML Exam le 1 :

Indium tin oxide (ITO)-coated glass slides (Colorado Concept Coatings LLC) with a sheet resistivity of -15 Ω/sq were used as substrates for the OLEDs fabrication. The ITO substrates were masked with kapton tape and the exposed ITO was etched in acid vapor (1 :3 by volume, ΕΓΝ0₃: HC1) for 5 min at 60 °C. The substrates were cleaned in an ultrasonic bath in the following solutions: detergent water, distilled water, acetone, and isopropanol for 20 min in each step. At the end the substrates were blown dry with nitrogen. Subsequently, ITO substrates were 0₂ plasma treated for 2 min.

Immediately after 0₂ plasma treatment of the ITO slides, PEDOT:PSS AI4083 (Clevios) was spin-coated at 5000 rpm, acceleration - 928 rpm/s for 60 sec. Subsequently, the films were heated on a hot plate at 140°C for 15 min. PEDOT:PSS was deposited in air. p-TPDF was processed in the glove box under nitrogen. 10 mg of p-TPDF was dissolved in 1ml of anhydrous chlorobenzene (Aldrich). The hole-transport layer was spin- coated onto ITO at 1500 rpm, acceleration 1,000 rpm/sec for 60 sec. The films were then heated at 80 °C for 15 minutes to remove solvent and subsequently exposed to 365 nm UV light for 10 min to photo cross-link the p-TPDF film.

The following blends were used as the emissive layer:

a) Polymer blend composed of 1 : 1 wt. ratio of Polymer A and Polymer B was processed in the glove box under nitrogen. 5 mg of Polymer A and 5 mg of Polymer B was dissolved together in 1ml of anhydrous chlorobenzene (Aldrich). 6 wt. % of Ir(pppy)₃ was added to the polymer mixture. ~30 nm thick films of the blend were spin-coated at 2000 rpm, acceleration 1,000 rpm/sec for 60 sec. The films were then heated at 80 °C for 30 minutes to remove solvent.

b) Polymer blend composed of 3: 1 wt. ratio of Polymer A and Polymer B was processed in the glove box under nitrogen. 7.5 mg of Polymer A and 2.5 mg of Polymer B was dissolved together in 1ml of anhydrous chlorobenzene (Aldrich). 6 wt. % of Ir(pppy)₃ was added to the polymer mixture. ~30 nm thick films of the blend were spin-coated at 2000 rpm, acceleration 1,000 rpm/sec for 60 sec. The films were then heated at 80 °C for 30 minutes to remove solvent.

c) Polymer blend composed of 1 :3 wt. ratio of Polymer A and Polymer B was processed in the glove box under nitrogen. 2.5 mg of Polymer A and 7.5 mg of Polymer B was dissolved together in 1ml of anhydrous chlorobenzene (Aldrich). 6 wt. % of Ir(pppy)₃ was added to the polymer mixture. ~30 nm thick films of the blend were spin-coated at 2000 rpm, acceleration 1,000 rpm/sec for 60 sec. The films were then heated at 80 °C for 30 minutes to remove solvent.

The electron transport layer, BCP (Aldrich), the electron-injection layer, LiF (Aldrich), aluminum and silver were thermally evaporated at 1 A/s, 0.2 A/s, 2 A/s and 2 A/s respectively. The pressure in the vacuum chamber was l x lO^"7 Torr. The active area of the tested devices was about 0.1 cm . The devices were tested in a glove box under nitrogen.

OLED devices comprising the triscarbazole polymer as the host material for the emissive layer exhibited good efficiency. As shown in Figures 2-4, higher fractions of the hole transport polymer having a triscarbazole pendant group in the polymer blend increased the efficiency of the device. In another experiment, the OLED efficiency exhibited weak dependence on the concentration of the emitter. In addition, the current densities of the OLED devices were modified by varying the temperature (e.g., RT, 75 °C, 120 °C, and 150 °C) and time of film annealing after spin deposition.

EML Example 2: 6

Indium tin oxide (ITO)-coated glass slides (Colorado Concept Coatings LLC) with a sheet resistivity of -15 Ω/sq were used as substrates for the OLEDs fabrication. The ITO substrates were masked with kapton tape and the exposed ITO was etched in acid vapor (1 :3 by volume, HNO₃: HC1) for 5 min at 60 °C. The substrates were cleaned in an ultrasonic bath in the following solutions: detergent water, distilled water, acetone, and isopropanol for 20 min in each step. At the end the substrates were blown dry with nitrogen. Subsequently, ITO substrates were 0₂ plasma treated for 2 min.

Polymer 5.38 was processed in the glove box under nitrogen. 10 mg of Polymer 5.38 was dissolved in 1ml of anhydrous chlorobenzene (Aldrich). 35 nm thick films of the hole- transport material were spin-coated at 1000 rpm, acceleration 1540 rpm/sec for 60 sec. The films were then dried on a hot plate at 110 °C for 30 minutes followed by thermal curing at 300 °C for 10 min. A watch glass was used during the curing process over the samples in order to avoid excessive heat loses.

Emissive layer, consisting of a polymer blend and emitter was prepared in the following way in the glove box: 10 mg of Polymer A in 1 ml chlorobenzene, 10 mg of Polymer B in 1 ml of chlorobenzene and 10 mg of Ir(pppy)₃ (Solvay) in 1 ml of chlorobenzne. The solutions of the polymers were then mixed together (1ml of each) to which 128 μΐ of Ir(pppy)₃ was added. The mixture was spin-coated at 2000 rpm, 1000 rpm / sec, 60 sec and dried on hot plate at 120 °C for 10-15 min.

The electron transport layer, BCP (Aldrich), the electron-injection layer, LiF (Aldrich), aluminum and silver were thermally evaporated at 1 A/s, 0.2 A/s, 2 A/s and 2 A/s respectively. The pressure in the vacuum chamber was l x lO^"7 Torr. The active area of the tested devices was about 0.1 cm . The devices were tested in a glove box under nitrogen. The performance of the device is shown in Figure 5. EML Exam le 3 :

Polymer 5.40 was processed in the glove box under nitrogen. 5 mg of TAG (DPI- TPFPB) (Aldrich) was dissolve in 10 ml of anhydrous chlorobenzene (Aldrich) then 10 mg of Polymer 5.40 was dissolved in 1ml of previously prepared TAG solution. Around 35 nm thick films of the hole-transport material were spin-coated at 1000 rpm, acceleration 1540 rpm/sec for 60 sec. The films were then dried on a hot plate at 110 °C for 30 minutes followed by thermal curing at 200 °C for 30 min. A watch glass was used during the curing process over the samples in order to avoid excessive heat loses.

Emissive layer, consisting of a polymer blend and emitter was prepared in the following way in the glove box: 10 mg of Polymer A in 1 ml chlorobenzene, 10 mg of Polymer B in 1 ml of chlorobenzene and 10 mg of Ir(pppy)₃ (Solvay) in 1 ml of

chlorobenzne. The solutions of the polymers were then mixed together (1ml of each) to which 128 μΐ of Ir(pppy)₃ was added. The mixture was spin-coated at 2000 rpm, 1000 rpm / sec, 60 sec and dried on hot plate at 120 °C for 10-15 min.

The electron transport layer, BCP (Aldrich), the electron-injection layer, LiF

(Aldrich), aluminum and silver were thermally evaporated at 1 A/s, 0.2 A/s, 2 A/s and 2 A/s respectively. The pressure in the vacuum chamber was 1 x 10^~7 Torr. The active area of the tested devices was about 0.1 cm . The devices were tested in a glove box under nitrogen. The performance of the device is shown in Figure 6.

EML Exam le 4:

Indium tin oxide (ITO)-coated glass slides (Colorado Concept Coatings LLC) with a sheet resistivity of -15 Ω/sq were used as substrates for the OLEDs fabrication. The ITO substrates were masked with kapton tape and the exposed ITO was etched in acid vapor (1 :3 by volume, FINOs: HC1) for 5 min at 60 °C. The substrates were cleaned in an ultrasonic bath in the following solutions: detergent water, distilled water, acetone, and isopropanol for 20 min in each step. At the end the substrates were blown dry with nitrogen. Subsequently, ITO substrates were 0₂ plasma treated for 2 min.

Compound 5.42 was processed in the glove box under nitrogen. 10 mg of Compound 5.42 was dissolved in 1ml of anhydrous chlorobenzene (Aldrich). 35 nm thick films of the hole-transport material were spin-coated at 1000 rpm, acceleration 1540 rpm/sec for 60 sec. The films were then dried on a hot plate at 110 °C for 30 minutes followed by thermal curing at 200 °C for 30 min. A watch glass was used during the curing process over the samples in order to avoid excessive heat loses.

Emissive layer, consisting of a polymer blend and emitter was prepared in the following way in the glove box: 10 mg of Polymer A in 1 ml chlorobenzene, 10 mg of Polymer B in 1 ml of chlorobenzene and 10 mg of Ir(pppy)₃ (Solvay) in 1 ml of chlorobenzne. The solutions of the polymers were then mixed together (1ml of each) to which 128 μΐ of Ir(pppy)₃ was added. The mixture was spin-coated at 2000 rpm, 1000 rpm / sec, 60 sec and dried on hot plate at 120 °C for 10-15 min. The electron transport layer, BCP (Aldrich), the electron-injection layer, LiF (Aldrich), aluminum and silver were thermally evaporated at 1 A/s, 0.2 A/s, 2 A/s and 2 A/s respectively. The pressure in the vacuum chamber was l x lO^"7 Torr. The active area of the tested devices was about 0.1 cm . The devices were tested in a glove box under nitrogen. The performance of the device is shown in Figure 7.

3. Device Fabrication - Polymer A in Hole-Transport Layer

HTL Exam le 1 :

Immediately after 0₂ plasma treatment of the ITO slides, PEDOT:PSS AI4083 (Clevios) was spin-coated at 5000 rpm, acceleration - 928 rpm/s for 60 sec. Subsequently, the films were heated on a hot plate at 140°C for 15 min. PEDOT:PSS was deposited in air.

Polymer A was processed in the glove box under nitrogen. 10 mg of Polymer A was dissolved in 1ml of anhydrous chlorobenzene (Aldrich). 35 nm thick films of the hole- transport material were spin-coated at 1500 rpm, acceleration 1,000 rpm/sec for 60 sec. The films were then heated on a hot plate at 120 °C for 20 minutes.

(Compound D)

Emissive layer, consisting of a host - Compound D and an emitter - Ir(ppy)₃ (Lumtec) was deposited by co-evaporation of the two components at 0.94 A/s and 0.06 A/s

respectively. The electron transport layer, BCP (Aldrich), the electron-injection layer, LiF (Aldrich), aluminum and silver were thermally evaporated at 1 A/s, 0.2 A/s, 2 A/s and 2 A/s respectively. The pressure in the vacuum chamber was 1 x 10^"7 Torr. The active area of the tested devices was about 0.1 cm . The devices were tested in a glove box under nitrogen.

The performance of the device is shown in Figure 8.

HTL Example 2:

Indium tin oxide (ITO)-coated glass slides (Colorado Concept Coatings LLC) with a sheet resistivity of -15 Ω/sq were used as substrates for the OLEDs fabrication. The ITO substrates were masked with kapton tape and the exposed ITO was etched in acid vapor (1 :3 by volume, FIN0₃: HC1) for 5 min at 60 °C. The substrates were cleaned in an ultrasonic bath in the following solutions: detergent water, distilled water, acetone, and isopropanol for 20 min in each step. At the end the substrates were blown dry with nitrogen. Subsequently, ITO substrates were 0₂ plasma treated for 2 min.

The hole injection layer, M0O3 (Aldrich) was thermally evaporated at 0.2 A/s. The pressure in the vacuum chamber was 1 x 10^"7 Torr.

Emissive layer, consisting of a host - Compound D and an emitter - Ir(ppy)₃ (Lumtec) was deposited by co-evaporation of the two components at 0.94 A/s and 0.06 A/s respectively. The electron transport layer, BCP (Aldrich), the electron-injection layer, LiF (Aldrich), aluminum and silver were thermally evaporated at 1 A/s, 0.2 A/s, 2 A/s and 2 A/s respectively. The pressure in the vacuum chamber was l x lO^"7 Torr. The active area of the tested devices was about 0.1 cm . The devices were tested in a glove box under nitrogen.

The performance of the device is shown in Figure 9.

HTL Exam le 3 :

Indium tin oxide (ITO)-coated glass slides (Colorado Concept Coatings LLC) with a sheet resistivity of -15 Ω/sq were used as substrates for the OLEDs fabrication. The ITO substrates were masked with kapton tape and the exposed ITO was etched in acid vapor (1 :3 by volume, FfN0₃: HC1) for 5 min at 60 °C. The substrates were cleaned in an ultrasonic bath in the following solutions: detergent water, distilled water, acetone, and isopropanol for 20 min in each step. At the end the substrates were blown dry with nitrogen. Subsequently, ITO substrates were 0₂ plasma treated for 2 min.

Polymer A was processed in the glove box under nitrogen. 10 mg of Polymer A was dissolved in 1ml of anhydrous chlorobenzene (Aldrich). 35 nm thick films of the hole- transport material were spin-coated at 1500 rpm, acceleration 1 ,000 rpm/sec for 60 sec. The films were then heated on a hot plate at 120 °C for 20 minutes.

Emissive layer, consisting of a host - Compound D and an emitter - Ir(ppy)₃ (Lumtec) was deposited by co-evaporation of the two components at 0.94 A/s and 0.06 A/s respectively. The electron transport layer, TAZ (Lumtec), the electron-injection layer, LiF (Aldrich), aluminum and silver were thermally evaporated at 1 A/s, 0.2 A/s, 2 A/s and 2 A/s respectively. The pressure in the vacuum chamber was l x lO^"7 Torr. The active area of the tested devices was about 0.1 cm . The devices were tested in a glove box under nitrogen.

The performance of the device is shown in Figure 10.

HTL Exam le 4:

Emissive layer, consisting of a host - Compound D and an emitter - FIrpic (Lumtec) was deposited by co-evaporation of the two components at 0.88 A/s and 0.12 A/s respectively. The electron transport layer, TAZ (Lumtec), the electron-injection layer, LiF (Aldrich), aluminum and silver were thermally evaporated at 1 A/s, 0.2 A/s, 2 A/s and 2 A/s respectively. The pressure in the vacuum chamber was l x lO^"7 Torr. The active area of the tested devices was about 0.1 cm . The devices were tested in a glove box under nitrogen.

The performance of the device is shown in Figure 11.

HTL Example 5 :

Indium tin oxide (ITO)-coated glass slides (Colorado Concept Coatings LLC) with a sheet resistivity of -15 Ω/sq were used as substrates for the OLEDs fabrication. The ITO substrates were masked with kapton tape and the exposed ITO was etched in acid vapor (1 :3 by volume, HN0₃: HC1) for 5 min at 60 °C. The substrates were cleaned in an ultrasonic bath in the following solutions: detergent water, distilled water, acetone, and isopropanol for 20 min in each step. At the end the substrates were blown dry with nitrogen. Subsequently, ITO substrates were 0₂ plasma treated for 2 min.

Emissive layer, consisting of a host - Compound D and an emitter - FIrpic (Lumtec) was deposited by co-evaporation of the two components at 0.88 A/s and 0.12 A/s respectively. The electron transport layer, BCP (Aldrich), the electron-injection layer, LiF (Aldrich), aluminum and silver were thermally evaporated at 1 A/s, 0.2 A/s, 2 A/s and 2 A/s respectively. The pressure in the vacuum chamber was l x lO^"7 Torr. The active area of the tested devices was about 0.1 cm . The devices were tested in a glove box under nitrogen.

The performance of the device is shown in Figure 12.

HTL Exam le 6:

Indium tin oxide (ITO)-coated glass slides (Colorado Concept Coatings LLC) with a sheet resistivity of -15 Ω/sq were used as substrates for the OLEDs fabrication. The ITO substrates were masked with kapton tape and the exposed ITO was etched in acid vapor (1 :3 by volume, FINO₃: HC1) for 5 min at 60 °C. The substrates were cleaned in an ultrasonic bath in the following solutions: detergent water, distilled water, acetone, and isopropanol for 20 min in each step. At the end the substrates were blown dry with nitrogen. Subsequently, ITO substrates were 0₂ plasma treated for 2 min.

Emissive layer, consisting of a host - Compound D and an emitter - FIrpic (Lumtec) was deposited by co-evaporation of the two components at 0.88 A/s and 0.12 A/s respectively. The electron transport layer, BCP (Aldrich), the electron-injection layer, LiF (Aldrich), aluminum and silver were thermally evaporated at 1 A/s, 0.2 A/, 2 A/s and 2 A/s respectively. The pressure in the vacuum chamber was l x lO^"7 Torr. The active area of the tested devices was about 0.1 cm . The devices were tested in a glove box under nitrogen.

The performance of the device is shown in Figure 13.

HTL Exam le 7:

Indium tin oxide (ITO)-coated glass slides (Colorado Concept Coatings LLC) with a sheet resistivity of -15 Ω/sq were used as substrates for the OLEDs fabrication. The ITO substrates were masked with kapton tape and the exposed ITO was etched in acid vapor (1 :3 by volume, FINOs: HC1) for 5 min at 60 °C. The substrates were cleaned in an ultrasonic bath in the following solutions: detergent water, distilled water, acetone, and isopropanol for 20 min in each step. At the end the substrates were blown dry with nitrogen. Subsequently, ITO substrates were 0₂ plasma treated for 2 min. Polymer A was processed in the glove box under nitrogen. 10 mg of Polymer A was dissolved in 1ml of anhydrous chlorobenzene (Aldrich). 35 nm thick films of the hole- transport material were spin-coated at 1500 rpm, acceleration 1,000 rpm/sec for 60 sec. The films r 20 minutes.

(Compound C)

Emissive layer, consisting of a host - Compound C and an emitter - FIrpic (Lumtec) was deposited by co-evaporation of the two components at 0.88 A/s and 0.12 A/s respectively. The electron transport layer, BCP (Aldrich), the electron-injection layer, LiF (Aldrich), aluminum and silver were thermally evaporated at 1 A/s, 0.2 A/s, 2 A/s and 2 A/s respectively. The pressure in the vacuum chamber was l x lO^"7 Torr. The active area of the tested devices was about 0.1 cm . The devices were tested in a glove box under nitrogen.

The performance of the device is shown in Figure 14.

HTL Exam le 8:

Emissive layer, consisting of a host - Compound C and an emitter - Ir(ppy)₃ (Lumtec) was deposited by co-evaporation of the two components at 0.94 A/s and 0.06 A/s respectively. The electron transport layer, BCP (Aldrich), the electron-injection layer, LiF (Aldrich), aluminum and silver were thermally evaporated at 1 A/s, 0.2 A/s, 2 A/s and 2 A/s respectively. The pressure in the vacuum chamber was l x lO^"7 Torr. The active area of the tested devices was about 0.1 cm . The devices were tested in a glove box under nitrogen.

The performance of the device is shown in Figure 15.

HTL Exam le 9:

Emissive layer, consisting of a host - CBP (Lumtec) and an emitter - Ir(ppy)₃ (Lumtec) was deposited by co-evaporation of the two components at 0.94 A/s and 0.06 A/s respectively. The electron transport layer, BCP (Aldrich), the electron-injection layer, LiF (Aldrich), aluminum and silver were thermally evaporated at 1 A/s, 0.2 A/s, 2 A/s and 2 A/s respectively. The pressure in the vacuum chamber was l x lO^"7 Torr. The active area of the tested devices was about 0.1 cm . The devices were tested in a glove box under nitrogen.

The performance of the device is shown in Figure 16.

HTL Exam le 10:

Immediately after 0₂ plasma treatment of the ITO slides, PEDOT:PSS AI4083 (Clevios) was spin-coated at 5000 rpm, acceleration - 928 rpm/s for 60 sec. Subsequently, the films were heated on a hot plate at 140°C for 15 min. PEDOT:PSS was deposited in air. Polymer A was processed in the glove box under nitrogen. 10 mg of Polymer A was dissolved in 1ml of anhydrous chlorobenzene (Aldrich). 35 nm thick films of the hole- transport material were spin-coated at 1500 rpm, acceleration 1,000 rpm/sec for 60 sec. The films were then heated on a hot plate at 120 °C for 20 minutes.

The performance of the device is shown in Figure 17.

HTL Example 11

nm)

The hole-injection layer, M0O₃ (Aldrich) and gold were thermally evaporated at 0.2 A/s and 2 A/s respectively. The pressure in the vacuum chamber was 1 x 10^"7 Torr. The active area of the tested devices was about 0.01 cm . The devices were tested in a glove box under nitrogen.

As shown in Figure 18, current density for the hole only devices fabrication with the polymers having pendant triscarbazole groups have high charge density compared to hole only devices having polyvinylcarbazole (PVK), which suggests that the polymers having triscarbazole pendants groups have higher hole mobility. High hole mobility makes the polymers having triscarbazole pendants groups good materials for a variety of organic electronic devices. Additionally, M0O₃ may be a better hole injection layer for some polymers having triscarbazole pendants groups than PEDOT:PSS.

HTL Example 12:

Polymer A was processed in the glove box under nitrogen. 10 mg of Polymer A was dissolved in 1ml of anhydrous chlorobenzene (Aldrich). 35 nm thick films of the hole- transport material were spin-coated at 1500 rpm, acceleration 1,000 rpm/sec for 60 sec. The films 0 minutes.

(Compound G)

Emissive layer, consisting of a host - Compound G and an emitter - Ir(ppy)₃ (Lumtec) was deposited by co -evaporation of the two components at 0.94 A/s and 0.06 A/s respectively. The electron transport layer, BCP (Aldrich), the electron-injection layer, LiF (Aldrich), aluminum and silver were thermally evaporated at 1 A/s, 0.2 A/s, 2 A/s and 2 A/s respectively. The pressure in the vacuum chamber was 1 x 10^"7 Torr. The active area of the tested devices was about 0.1 cm . The devices were tested in a glove box under nitrogen.

The performance of the device is shown in Figure 19.

HTL Example 13:

οϋ . {IS n m )

no

Gtass

The hole injection layer, M0O₃ (Aldrich) was thermally evaporated at 0.2 A/s. The pressure in the vacuum chamber was 1 x 10^"7 Torr. Polymer A was processed in the glove box under nitrogen. 10 mg of Polymer A was dissolved in 1ml of anhydrous chlorobenzene (Aldrich). 35 nm thick films of the hole- transport material were spin-coated at 1500 rpm, acceleration 1,000 rpm/sec for 60 sec. The films were then heated on a hot plate at 120 °C for 20 minutes.

The performance of the device is shown in Figure 20.

HTL Exam le 14:

(20

The performance of the device is shown in Figure 21.

HTL Example 15 :

Polymer A was processed in the glove box under nitrogen. 10 mg of Polymer A was dissolved in 1ml of anhydrous chlorobenzene (Aldrich). 35 nm thick films of the hole- transport material were spin-coated at 1500 rpm, acceleration 1 ,000 rpm/sec for 60 sec. The films were then heated on a hot plate at 120 °C for 20 minutes. Emissive layer, consisting of a host - Compound G and an emitter - FIrpic (Lumtec) was deposited by co-evaporation of the two components at 0.88 A/s and 0.12 A/s

The performance of the device is shown in Figure 22.

HTL Example 16:

The hole injection layer, M0O₃ (Aldrich) was thermally evaporated at 0.2 A/s. The pressure in the vacuum chamber was 1 x 10^"7 Torr.

Polymer A was processed in the glove box under nitrogen. 10 mg of Polymer A was dissolved in 1ml of anhydrous chlorobenzene (Aldrich). 35 nm thick films of the hole- transport material were spin-coated at 1500 rpm, acceleration 1,000 rpm/sec for 60 sec. The films were then heated on a hot plate at 120 °C for 20 minutes. Emissive layer, consisting of a host - Compound G and an emitter - FIrpic (Lumtec) was deposited by co-evaporation of the two components at 0.88 A/s and 0.12 A/s

The performance of the device is shown in Figure 23.

HTL Exam le 17:

Immediately after 0₂ plasma treatment of the ITO slides, PEDOT:PSS AI4083 (Clevios) was spin-coated at 5000 rpm, acceleration - 928 rpm s for 60 sec. Subsequently, the films were heated on a hot plate at 140°C for 15 min. PEDOT:PSS was deposited in air.

The performance of the device is shown in Figure 24.

HTL Example 18:

(Compound E)

Emissive layer, consisting of the Compound E host and emitter was prepared in the following way in the glove box: 10 mg of Compound E was dissolved in 1 ml acetonitrile and 10 mg of FIrpic (Lumtec) in 1 ml of acetonitrile. 128 μΐ of FIrpic was added to 1 ml of the solution of Compound E. The solution was then spin-coated onto the HTL at 1000 rpm, 1000 rpm / sec, 60 sec. The films were dried at 75 °C for 10-15 min.

The electron transport layer, BCP (Aldrich), the electron-injection layer, LiF

(Aldrich), aluminum and silver were thermally evaporated at 1 A/s, 0.2 A/s, 2 A/s and 2 A/s respectively. The pressure in the vacuum chamber was 1 x 10^"7 Torr. The active area of the tested devices was about 0.1 cm . The devices were tested in a glove box under nitrogen.

The performance of the device is shown in Figure 25.

HTL Example 19: yE At Ag (2.5/60 rtm/lOU nm)

BCP (50 nm )

Compoun d E^ lr Sc 12 t. % (35

Polymer A {3-5 nm )

PEDOT:PSS (50 nm)

!TO

Glass

Indium tin oxide (ITO)-coated glass slides (Colorado Concept Coatings LLC) with a sheet resistivity of -15 Ω/sq were used as substrates for the OLEDs fabrication. The ITO substrates were masked with kapton tape and the exposed ITO was etched in acid vapor (1 :3 by volume, HNO3 : HC1) for 5 min at 60 °C. The substrates were cleaned in an ultrasonic bath in the following solutions: detergent water, distilled water, acetone, and isopropanol for 20 min in each step. At the end the substrates were blown dry with nitrogen. Subsequently, ITO substrates were 0₂ plasma treated for 2 min.

The electron transport layer, BCP (Aldrich), the electron-injection layer, LiF

The performance of the device is shown in Figure 26.

HTL Example 20:

UE/Af/Ag (2.5/60 rem/100 nm)

BCP (50 nm)

Compound F:Flrpic 12 wt. % (35 nm)

Polymer A (35 nm)

ITO

Glass

Indium tin oxide (ITO)-coated glass slides (Colorado Concept Coatings LLC) with a sheet resistivity of -15 Ω/sq were used as substrates for the OLEDs fabrication. The ITO substrates were masked with kapton tape and the exposed ITO was etched in acid vapor (1 :3 by volume, ΗΝ0₃: HC1) for 5 min at 60 °C. The substrates were cleaned in an ultrasonic bath in the following solutions: detergent water, distilled water, acetone, and isopropanol for 20 min in each step. At the end the substrates were blown dry with nitrogen. Subsequently, ITO substrates were 0₂ plasma treated for 2 min.

Polymer A was processed in the glove box under nitrogen. 10 mg of Polymer A was dissolved in 1ml of anhydrous chlorobenzene (Aldrich). 35 nm thick films of the hole- transport material were spin-coated at 1500 rpm, acceleration 1,000 rpm/sec for 60 sec. The films w 20 minutes.

(Compound F)

Emissive layer, consisting of the Compound F host and emitter was prepared in the following way in the glove box: 10 mg of Compound F was dissolved in 1 ml acetonitrile and 10 mg of FIrpic (Lumtec) in 1 ml of acetonitrile. 128 μΐ of FIrpic was added to 1 ml of the solution of Compound F. The solution was then spin-coated onto the HTL at 1000 rpm, 1000 rpm / sec, 60 sec. The films were dried at 75 °C for 10-15 min.

The electron transport layer, BCP (Aldrich), the electron-injection layer, LiF

The performance of the device is shown in Figure 27.

HTL Examples 21-88:

Additional devices are fabricated similar to those described above. The devices of Examples 21-88 each comprises (i) a glass/ITO substrate, (ii) a hole injection layer selected from M0O₃ and PEDOT:PSS, (iii) a hole transport layer comprising Polymer A, (iv) an emissive layer comprising an ambipolar host selected from Compound HI to H14 and a guest emitter selected from Ir(ppy)₃ and FIrpic, (v) an electron transport layer selected from BCP, TAZ, TmPyPB, TpPyPB and TmPPPyTz, and (vi) a layer of Li/Al/Ag (2.5/60/100 nm) for Examples 21-81 and Li/Al/A g (2.5/50/100 nm) for Examples 82-88.

The device structures for Examp es 21-88 are described in the following Table.

TmPyPB TpPyPB

Claims

1. A solution-processable composition suitable for making electroluminescence devices, comprising at least one first polymer, said first polymer comprising at least one first polymer subunit represented by formula (I) or formula (II):

wherein Rl, R2, R3, R4, R5, R6, R7, R8, R9, RIO, Rl l, R12, R13, R14, R15, R16, R17 and R18 are each independently a hydrogen, a halogen, an optionally substituted alkyl, an optionally substituted aryl, an optionally substituted heteroalkyl, or an optionally substituted heteroaryl;

wherein L is a linker group that comprises at least one carbon atom but does not comprise any 2-phenyl-5-phenyl-l,3,4-oxadiazole group; and

wherein X, Y and Z are each independently H, alkyl, fluoroalkyl or fluoride.

2. The solution-processable composition of claim 1, wherein L is an optionally substituted alkylene, an optionally substituted arylene, an optionally substituted

heteroalkylene, or an optionally substituted hetero arylene.

3. The solution-processable composition of claim 1, wherein L is an alkylene, an oxyalkylene, an oxyarylene, or an ether.

4. The solution-processable composition of claim 1, wherein Rl, R2, R3, R4, R5, R6, R7, R8, R9, RIO, Rl l, R12, R13, R14, R15, R16, R17 and R18 are each a hydrogen.

5. The solution-processable composition of claim 1, wherein at least one of Rl, R2, R3, R4, R5, R6, R7, R8, R9, RIO, Rl l, R12, R13, R14, R15, R16, R17 and R18 is an optionally substituted carbazole group.

6. The solution-processable composition of claim 1, wherein at least four of Rl, R2, R3, R4, R5, R6, R7, R8, R9, RIO, Rl l, R12, R13, R14, R15, R16, R17 and R18 are optionally substituted carbazole groups.

7. The solution-processable composition of claim 1, wherein the first polymer subunit is represented by formula (III), formula (IV), or formula (V):

(V)

8. The solution-processable composition of claim 1, wherein the first polymer subunit is represented by formula (VI) or formula (VII):

(vii)

9. The solution-processable composition of claim 1, wherein the first polymer subunit is selected from the group consisting of:

wherein n = 0 - 12.

10. The solution-processable composition of claim 1, wherein the first polymer subunit comprises at least one of X, Y or Z which is F or f uoroalkyl.

11. The solution-processable composition of claim 1 , wherein the first polymer is a homopolymer.

12. The solution-processable composition of claim 1, wherein the first polymer is a copolymer comprising in the polymer backbone a second polymer subunit.

13. The solution-processable composition of claim 1, wherein the first polymer is a copolymer comprising in the polymer backbone a second polymer subunit, said second polymer subunit comprises one or more moieties selected from the group consisting of electron transporters, solubilizing groups, compatibilizing groups, and crosslinking groups.

14. The solution-processable composition of claim 1, wherein the first polymer subunit further comprises one or more moieties selected from the group consisting of electron transporters, solubilizing groups, and compatibilizing groups.

15. The solution-processable composition of claim 1, wherein the first polymer has a weight average molecular weight (Mw) of at least 10,000Da.

16. The solution-processable composition of claim 1, wherein the first polymer has a weight average molecular weight (Mw) of at least 100,000Da.

17. The solution-processable composition of claim 1, wherein the first polymer has a glass temperature (Tg) of at least 200°C.

18. The solution-processable composition of claim 1, wherein the first polymer has a glass temperature (Tg) of at least 250°C.

19. The solution-processable composition of claim 1, wherein the first polymer does not comprises any oxadiazole group.

20. The solution-processable composition of claim 1, wherein the first polymer is suitable for transporting holes.

21. The solution-processable composition of claim 1, wherein the first polymer has higher hole mobility than PVK.

22. The solution-processable composition of claim 1, wherein the first polymer has a reversible first oxidation step.

23. The solution-processable composition of claim 1 that comprises a blend of a first fluorinated polymer according to claim 10 and a second non-fluorinated polymer.

24. The solution-processable composition of claim 1 further comprises a second polymer suitable for transporting electrons.

25. The solution-processable composition of claim 1 further comprises a second polymer suitable for transporting electrons, wherein said second polymer comprises at least one oxadiazole, triazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine or tetrazine group.

26. The solution-processable composition of claim 1 further comprises an organometallic emitter.

27. The solution-processable composition of claim 1 further comprises one or more organometallic emitters selected from orange, green and blue phosphorescent emitters.

28. An emissive layer comprising the solution-processed composition of claim 1.

29. A hole transport layer comprising the solution-processed composition of claim

1.

30. A hole injection layer comprising the solution-processed composition of claim 1 and a p-dopant.

31. The hole injection layer of claim 30, wherein the dopant is a soluble complex of Mo(VI) or Cr(VI).

32. An electroluminescence device comprising the emissive layer of claim 28.

33. An electroluminescence device comprising the hole transport layer of claim

29.

34. An electroluminescence device comprising the hole injection layer of claim

30.

35. The electroluminescence device of claim 32, wherein the electroluminescence device comprises a hole transport layer fabricated also by solution deposition.

36. The electroluminescence device of claim 33, wherein the emissive layer comprises a bis(organo-sulfonyl)-biaryl host fabricated also by solution deposition.

37. The electroluminescence device of claim 32, wherein the emissive layer comprises a phosphorescent green emitter, and wherein the external quantum efficiency of the electroluminescence device at 1,000 cd/m is at least 5%, at least 10%, or at least 15%.

38. The electroluminescence device of claim 33, wherein the electroluminescence device comprises an emissive layer comprising a phosphorescent green emitter, and wherein the external quantum efficiency of the electroluminescence device at 1,000 cd/m is at least 5%, at least 10%, or at least 15%.

39. The electroluminescence device of claim 33, wherein the electroluminescence device comprises an emissive layer comprising a phosphorescent blue emitter, and wherein the external quantum efficiency of the electroluminescence device at 1,000 cd/m is at least 5%, at least 10%, or at least 15%.

40. A method comprising:

providing a substrate comprising an anode layer and optionally comprising a hole injection layer;

depositing a hole transport layer from a first solution onto the substrate; and wherein the first solution comprises the solution-processable composition of claim 1 ;

depositing an emissive layer from a second solution onto the hole transport layer; and

wherein the second solution comprises a bis(organo-sulfonyl)-biaryl host.

41. A method comprising :

depositing a hole transport layer from a first solution onto the substrate; depositing an emissive layer from a second solution onto the hole transport layer; and

wherein the second solution comprises the solution-processable composition of claim 1.

42. The method of claim 41, wherein the first solution comprises a crosslinking material that is crosslinked thermally or photochemically before the deposition of the emissive layer.

43. The composition of solution-processable composition of claim 1, wherein the first polymer does not comprise a crosslinking group.