EP2379671A2 - Elektronische vorrichtungen mit hoher lebensdauer - Google Patents

Elektronische vorrichtungen mit hoher lebensdauer

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Publication number
EP2379671A2
EP2379671A2 EP09835779A EP09835779A EP2379671A2 EP 2379671 A2 EP2379671 A2 EP 2379671A2 EP 09835779 A EP09835779 A EP 09835779A EP 09835779 A EP09835779 A EP 09835779A EP 2379671 A2 EP2379671 A2 EP 2379671A2
Authority
EP
European Patent Office
Prior art keywords
deuterated
layer
group
compound
organic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09835779A
Other languages
English (en)
French (fr)
Other versions
EP2379671A4 (de
Inventor
Vsevolod Rostovtsev
Weiying Gao
Gary A. Johansson
Yulong Shen
Adam Fennimore
Kalindi Dogra
Hong Meng
Weishi Wu
Michael Henry Howard Jr
Ralph Birchard Lloyd
Nora Sabina Radu
Norman Herron
Daniel David Lecloux
Eric Maurice Smith
Che-Hsiung Hsu
Kyung-Ho Park
Jeffrey A. Merlo
Christina M. Older
Jerald Feldman
Ying Wang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority claimed from PCT/US2009/069255 external-priority patent/WO2010075421A2/en
Publication of EP2379671A2 publication Critical patent/EP2379671A2/de
Publication of EP2379671A4 publication Critical patent/EP2379671A4/de
Withdrawn legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers

Definitions

  • This invention relates to electronic devices having at least one layer with a deuterated compound and having long active lifetimes.
  • Organic electronic devices that emit light such as light-emitting diodes that make up displays, are present in many different kinds of electronic equipment.
  • an organic active layer is sandwiched between two electrical contact layers. At least one of the electrical contact layers is light-transmitting so that light can pass through the electrical contact layer.
  • the organic active layer emits light through the light-transmitting electrical contact layer upon application of electricity across the electrical contact layers. It is well known to use organic electroluminescent compounds as the active component in light-emitting diodes.
  • Simple organic molecules such as anthracene, thiadiazole derivatives, and coumarin derivatives are known to show electroluminescence.
  • Semiconductive conjugated polymers have also been used as electroluminescent components, as has been disclosed in, for example, U.S. Patent 5,247,190, U.S. Patent 5,408,109, and Published European Patent Application 443 861.
  • the electroluminescent compound is present as a dopant in a host material.
  • organic charge-injection layers and/or charge-transport layers are present between the light-emitting layer and the anode and/or the cathode.
  • an organic light-emitting diode comprising an anode, a cathode, and an organic active layer therebetween, wherein the organic active layer comprises a deuterated compound and the device has a calculated half-life at I OOOnits of at least 5000 hours.
  • the organic active layer comprises deuterated conductive polymer and a fluohnated acid polymer.
  • the organic active layer comprises a deuterated hole transport compound having at least two diarylamino moieties.
  • the organic active layer comprises an electroluminescent compound selected from the group consisting of deuterated aminoanthracenes, deuterated aminochrysenes, deuterated metal quinolate complexes, and deuterated iridium complexes.
  • the organic active layer comprises (a) a host material selected from the group consisting of deuterated arylanthracenes, deuterated arylpyrenes, deuterated arylchrysenes, deuterated phenanthrolines, deuterated indolocarbazoles, and combinations thereof and (b) an electroactive dopant capable of electroluminescence having an emission maximum between 380 and 750 nm.
  • the organic active layer comprises an electron transport material selected from the group consisting of deuterated phenanthrolines, deuterated indolocarbazoles, and deuterated metal quinolates.
  • FIG. 1 includes an illustration of one example of an organic electronic device.
  • FIG. 2 includes another illustration of an organic electronic device.
  • Skilled artisans appreciate that objects in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the objects in the figures may be exaggerated relative to other objects to help to improve understanding of embodiments. DETAILED DESCRIPTION
  • aliphatic ring is intended to mean a cyclic group that does not have delocalized pi electrons. In some embodiments, the aliphatic ring has no unsaturation. In some embodiments, the ring has one double or triple bond.
  • alkoxy refers to the group RO-, where R is an alkyl.
  • alkyl is intended to mean a group derived from an aliphatic hydrocarbon having one point of attachment, and includes a linear, a branched, or a cyclic group. The term is intended to include heteroalkyls.
  • hydrocarbon alkyl refers to an alkyl group having no heteroatoms.
  • deuterated alkyl is a hydrocarbon alkyl having at least one available H replaced by D. In some embodiments, an alkyl group has from 1 -20 carbon atoms.
  • branched alkyl refers to an alkyl group having at least one secondary or tertiary carbon.
  • secondary alkyl refers to a branched alkyl group having a secondary carbon atom.
  • tertiary alkyl refers to a branched alkyl group having a tertiary carbon atom. In some embodiments, the branched alkyl group is attached via a secondary or tertiary carbon.
  • aryl is intended to mean a group derived from an aromatic hydrocarbon having one point of attachment.
  • aromatic compound is intended to mean an organic compound comprising at least one unsaturated cyclic group having delocalized pi electrons. The term is intended include heteroaryls.
  • hydrocarbon aryl is intended to mean aromatic compounds having no heteroatoms in the ring.
  • aryl includes groups which have a single ring and those which have multiple rings which can be joined by a single bond or fused together.
  • deuterated aryl refers to an aryl group having at least one available H bonded directly to the aryl replaced by D.
  • arylene is intended to mean a group derived from an aromatic hydrocarbon having two points of attachment. In some embodiments, an aryl group has from 3-60 carbon atoms.
  • aryloxy refers to the group RO-, where R is an aryl.
  • compound is intended to mean an electrically uncharged substance made up of molecules that further consist of atoms, wherein the atoms cannot be separated by physical means.
  • adjacent to when used to refer to layers in a device, does not necessarily mean that one layer is immediately next to another layer.
  • adjacent R groups is used to refer to R groups that are next to each other in a chemical formula (i.e., R groups that are on atoms joined by a bond).
  • conductive or “electrically conductive” as it refers to a material, is intended to mean a material which is inherently or intrinsically capable of electrical conductivity without the addition of carbon black or conductive metal particles.
  • deuterated is intended to mean that at least one H has been replaced by D.
  • the deuterium is present in at least 100 times the natural abundance level.
  • a “deuterated derivative” of compound X has the same structure as compound X, but with at least one D replacing an H.
  • dopant is intended to mean a material, within a layer including a host material, that changes the electronic characteristic(s) or the targeted wavelength(s) of radiation emission, reception, or filtering of the layer compared to the electronic characteristic(s) or the wavelength(s) of radiation emission, reception, or filtering of the layer in the absence of such material.
  • fluoro and the term “fluorinated” refer to a material in which at least one available H has been replaced by F.
  • electroactive when referring to a layer or material, is intended to mean a layer or material that exhibits electronic or electro- radiative properties.
  • an electroactive material electronically facilitates the operation of the device.
  • electroactive materials include, but are not limited to, materials which conduct, inject, transport, or block a charge, where the charge can be either an electron or a hole, and materials which emit radiation or exhibit a change in concentration of electron-hole pairs when receiving radiation.
  • inactive materials include, but are not limited to, planahzation materials, insulating materials, and environmental barrier materials.
  • An organic electroactive layer comprises an organic compound as the electroactive material.
  • organic includes organometallic materials.
  • half-life is intended to mean the time required for the device luminance to reach half the initial value.
  • the "observed half-life” is the half-life of the device measured at a constant current of 7 mA.
  • the “calculated half-life” is the half-life derived from the observed half-life and calculated for 1000 nits initial luminance. The half-life is measured in hours.
  • the prefix "hetero” indicates that one or more carbon atoms have been replaced with a different atom. In some embodiments, the different atom is N, O, or S.
  • host material is intended to mean a material to which a dopant is added.
  • the host material may or may not have electronic characteristics) or the ability to emit, receive, or filter radiation. In some embodiments, the host material is present in higher concentration.
  • layer is used interchangeably with the term “film” and refers to a coating covering a desired area.
  • the term is not limited by size.
  • the area can be as large as an entire device or as small as a specific functional area such as the actual visual display, or as small as a single sub-pixel.
  • Layers and films can be formed by any conventional deposition technique, including vapor deposition, liquid deposition (continuous and discontinuous techniques), and thermal transfer.
  • Continuous deposition techniques include but are not limited to, spin coating, gravure coating, curtain coating, dip coating, slot-die coating, spray coating, and continuous nozzle coating.
  • Discontinuous deposition techniques include, but are not limited to, ink jet printing, gravure printing, and screen printing.
  • organic electronic device or sometimes just “electronic device” is intended to mean a device including one or more organic semiconductor layers or materials.
  • substituents can be substituted or unsubstituted unless otherwise indicated.
  • the substituents are selected from the group consisting of D, halide, alkyl, alkoxy, aryl, aryloxy, cyano, and NR 2 , where R is alkyl or aryl.
  • the IUPAC numbering system is used throughout, where the groups from the Periodic Table are numbered from left to right as 1 -18 (CRC Handbook of Chemistry and Physics, 81 st Edition, 2000).
  • the device 100 has a first electrical contact layer, an anode layer 110 and a second electrical contact layer, a cathode layer 160, and an electroluminescent layer 140 between them.
  • Adjacent to the anode may be a hole injection layer 120, comprising hole injection material.
  • Adjacent to the hole injection layer may be a hole transport layer 130, comprising hole transport material.
  • Adjacent to the cathode may be an electron transport layer 150, comprising an electron transport material.
  • Devices may use one or more additional hole injection or hole transport layers (not shown) next to the anode 110 and/or one or more additional electron injection or electron transport layers (not shown) next to the cathode 160.
  • the light- emitting layer is pixellated, with subpixel units for each of the different colors.
  • An illustration of a pixellated device is shown in Figure 2.
  • the device 200 has anode 210, hole injection layer 220, hole transport layer 230, electroluminescent layer 240, electron transport layer 250, and cathode 260.
  • the electroluminescent layer is divided into subpixels 241 , 242, 243, which are repeated across the layer.
  • the subpixels represent red, blue and green color emission.
  • three different subpixel units are depicted in Figure 2, two or more than three subpixel units may be used.
  • Layers 120 through 150 are individually and collectively referred to as the electroactive layers. At least one of the electroactive layers is an organic electroactive layer comprising a deuterated material.
  • the deuterated materials may be used alone or in combination with other deuterated materials or non-deuterated materials.
  • the deuterated material is at least 10% deuterated. By this is meant that at least 10% of the H are replaced by D.
  • the deuterated material is at least 20% deuterated; in some embodiments, at least 30% deuterated; in some embodiments, at least 40% deuterated; in some embodiments, at least 50% deuterated; in some embodiments, at least 60% deuterated; in some embodiments, at least 70% deuterated; in some embodiments, at least 80% deuterated; in some embodiments, at least 90% deuterated.
  • the deuterated material is 100% deuterated.
  • the deuterated material is a hole injection material in layer 120.
  • at least one additional layer includes a deuterated material.
  • the additional layer is the hole transport layer 130.
  • the additional layer is the electroactive layer 140.
  • the additional layer is the electron transport layer 150.
  • the deuterated material is a hole transport material in layer 130.
  • at least one additional layer includes a deuterated material.
  • the additional layer is the hole injection layer 120.
  • the additional layer is the electroactive layer 140.
  • the additional layer is the electron transport layer 150.
  • the deuterated deuterated material is a host material for a dopant materials in electroactive layer 140. In some embodiments, the dopant material is also deuterated. In some embodiments, at least one additional layer includes a deuterated material.
  • the additional layer is the hole injection layer 120.
  • the additional layer is the hole transport layer 130. In some embodiments, the additional layer is the electron transport layer
  • the deuterated material is an electron transport material in layer 150.
  • at least one additional layer includes a deuterated material.
  • the additional layer is the hole injection layer 120.
  • the additional layer is the hole transport layer 130.
  • the additional layer is the electroactive layer 140.
  • an electronic device has deuterated materials in any combination of layers selected from the group consisting of the hole injection layer, the hole transport layer, the electroactive layer, and the electron transport layer. In some embodiments, all the organic active layers of the device include deuterated materials.
  • the devices have additional layers to aid in processing or to improve functionality. Any or all of these layers can include deuterated materials.
  • all the organic device layers comprise deuterated materials.
  • all the organic device layers consist essentially of deuterated materials.
  • the organic light-emitting diode comprises an anode, a cathode and has organic layers therebetween, wherein the organic layers are a hole injection layer, a hole transport layer, an electroluminescent layer, an electron transport layer, and a cathode, and wherein at least two of the organic layers consist essentially of deuterated material. In some embodiments, all of the organic layers consist essentially of deuterated material.
  • the different layers have the following range of thicknesses: anode 110, 500-5000 A, in one embodiment 1000-2000 A; hole injection layer 120, 50-2000 A, in one embodiment 200-1000 A; hole transport layer 130, 50-2000 A, in one embodiment 200-1000 A; electroactive layer 140, 10-2000 A, in one embodiment 100-1000 A; layer 150, 50-2000 A, in one embodiment 100-1000 A; cathode 160, 200-10000 A, in one embodiment 300-5000 A.
  • the location of the electron-hole recombination zone in the device, and thus the emission spectrum of the device can be affected by the relative thickness of each layer.
  • the desired ratio of layer thicknesses will depend on the exact nature of the materials used.
  • the observed half-life of the device described herein is at least 200 hours. In some embodiments, the observed half-life is at least 400 hours; in some embodiments, at least 1000 hours.
  • the calculated half-life of the device described herein is at least 5000 hours.
  • the method for calculating the half-life at a given initial luminance is well known. The method has been described in, for example, Chu et. al., Appl. Phys. Lett. 89, 053503 (2006) and Wellmann et. al., SID Int. Symp. Digest Tech. Papers 2005,393.
  • the calculated half-life is at least 10,000 hours; in some embodiments, at least 20,000 hours; in some embodiments, at least 50,000 hours.
  • the hole injection layer 120 comprises hole injection material and may have one or more functions in an organic electronic device, including but not limited to, planarization of the underlying layer, charge transport and/or charge injection properties, scavenging of impurities such as oxygen or metal ions, and other aspects to facilitate or to improve the performance of the organic electronic device.
  • Hole injection materials may be polymers, oligomers, or small molecules. They may be vapor deposited or deposited from liquids which may be in the form of solutions, dispersions, suspensions, emulsions, colloidal mixtures, or other compositions.
  • the hole injection layer comprises deuterated material.
  • the deuterated material comprises a deuterated electrically conductive polymer.
  • deuterated electrically conductive polymer it is meant that the electrically conductive polymer itself, not including the associated polymeric acid, is deuterated.
  • the deuterated material comprises an electrically conductive polymer doped with a deuterated polymeric acid.
  • the deuterated material comprises a deuterated electrically conductive polymer doped with a deuterated polymeric acid.
  • the deuterated electrically conductive polymer is selected from the group consisting of deuterated polythiophenes, deuterated poly(selenophenes), deuterated poly(tellurophenes), deuterated polypyrroles, deuterated polyanilines, deuterated poly(4-amino-indoles), deuterated poly(7-amino-indoles), and deuterated polycyclic aromatic polymers, respectively.
  • polycyclic aromatic refers to compounds having more than one aromatic ring. The rings may be joined by one or more bonds, or they may be fused together.
  • aromatic ring is intended to include heteroaromatic rings.
  • a "polycyclic heteroaromatic" compound has at least one heteroaromatic ring.
  • the deuterated polycyclic aromatic polymers are deuterated poly(thienothiophenes).
  • the deuterated electrically conductive polymer is selected from the group consisting of deuterated poly(3,4- ethylenedioxythiophene), deuterated polyaniline, deuterated polypyrrole, deuterated poly(4-aminoindole), deuterated poly(7-aminoindole), deuterated poly(thieno(2,3-b)thiophene), deuterated poly(thieno(3,2-b)thiophene), and deuterated poly(thieno(3,4-b)thiophene).
  • the deuterated conductive polymer is at least 10% deuterated; in some embodiments, at least 20% deuterated; in some embodiments, at least 30% deuterated; in some embodiments, at least 40% deuterated; in some embodiments, at least 50% deuterated; in some embodiments, at least 60% deuterated; in some embodiments, at least 70% deuterated; in some embodiments, at least 80% deuterated; in some embodiments, at least 90% deuterated; in some embodiments, 100% deuterated.
  • the electrically conductive polymer is selected from the group consisting of poly(D 6 -3,4-ethylenedioxythiophene), poly(D 5 -pyrrole), poly(D 7 -aniline), poly(perdeutero-4-aminoindole), poly(perdeutero-7-aminoindole), poly(perdeutero-thieno(2,3-b)thiophene), poly(perdeutero-thieno(3,2-b)thiophene), and poly(perdeutero- thieno(3,4-b)thiophene).
  • the deuterated conductive polymer is doped with a non-fluorinated polymeric acid.
  • Any polymer having acidic groups with ionizable protons or deuterons can be used.
  • acidic groups include, but are not limited to, carboxylic acid groups, sulfonic acid groups, sulfonimide groups, phosphoric acid groups, phosphonic acid groups, and combinations thereof.
  • the acidic groups can all be the same, or the polymer may have more than one type of acidic group.
  • the acidic groups are selected from the group consisting of sulfonic acid groups, sulfonimide groups, and combinations thereof.
  • a sulfonimide group has the formula: -SO 2 -NH-SO 2 -R where R is an alkyl group.
  • suitable acids include, but are not limited to, poly(styrenesulfonic acid) ("PSSA”), poly(perdeutero- styrenesulfonic acid) (“D 8 -PSSA”), poly(2-acrylamido-2-methyl-1 - propanesulfonic acid) (“PAAMPSA”), poly(perdeutero-2-acrylamido-2- methyl-1 -propanesulfonic acid) (“Di 3 -PAAMPSA”), and mixtures thereof.
  • the deuterated conductive polymer doped with a non-fluorinated polymeric acid is further combined with a highly- fluohnated acid polymer ("HFAP").
  • the fluohnated acid polymer is a highly fluohnated acid polymer ("HFAP"), where at least 80% of the available hydrogens bonded to carbon have been replaced by fluorine.
  • the highly- fluohnated acid polymer (“HFAP”) can be any polymer which is highly- fluohnated and has acidic groups.
  • the acidic groups supply an ionizable proton, H + , or deuteron, D + .
  • the acidic group has a pKa of less than 3.
  • the acidic group has a pKa of less than 0.
  • the acidic group has a pKa of less than -5.
  • the acidic group can be attached directly to the polymer backbone, or it can be attached to side chains on the polymer backbone.
  • acidic groups include, but are not limited to, carboxylic acid groups, sulfonic acid groups, sulfonimide groups, phosphoric acid groups, phosphonic acid groups, and combinations thereof.
  • the acidic groups can all be the same, or the polymer may have more than one type of acidic group.
  • the acidic groups are selected from the group consisting of sulfonic acid groups, sulfonimide groups, and combinations thereof.
  • the HFAP is a deutero-acid with an acidic deuteron.
  • the HFAP is at least 90% fluorinated; in some embodiments, at least 95% fluorinated; in some embodiments, fully- fluorinated. In some embodiments where the HFAP is not fully-fluorinated, the HFAP is also deuterated.
  • the acidic groups are selected from the group consisting of sulfonic acid groups, sulfonimide groups, and combinations thereof. In some embodiments, the acidic groups are on a fluorinated side chain. In some embodiments, the fluorinated side chains are selected from alkyl groups, alkoxy groups, amido groups, ether groups, and combinations thereof, all of which are fully fluorinated.
  • the HFAP has a highly-fluorinated olefin backbone, with pendant highly-fluorinated alkyl sulfonate, highly- fluorinated ether sulfonate, highly-fluorinated ester sulfonate, or highly- fluorinated ether sulfonimide groups.
  • the HFAP is a perfluoroolefin having perfluoro-ether-sulfonic acid side chains.
  • the polymer is a copolymer of tetrafluoroethylene and perfluoro-3,6-dioxa-4-methyl-7-ortenesulfonic acid ("poly(TFE-PSEPVE)").
  • the deutero-acid analog is abbreviated as D-poly(TFE-PSEPVE).
  • the polymer is a copolymer of 1 ,1 -difluoroethylene and 2-(1 ,1 -difluoro-2-(thfluoromethyl)allyloxy)-1 ,1 ,2,2- tetrafluoroethanesulfonic acid.
  • the polymer is a copolymer of ethylene and 2-(2-(1 ,2,2-trifluorovinyloxy)-1 ,1 ,2,3,3,3- hexafluoropropoxy)-1 ,1 ,2,2-tetrafluoroethanesulfonic acid. These copolymers can be made as the corresponding sulfonyl fluoride polymer and then can be converted to the sulfonic acid form.
  • the deuterated conductive polymer is doped with a HFAP.
  • a HFAP a HFAP
  • the hole injection layer comprises a deuterated poly(3,4-ethylenedioxythiophene) ("d-PEDOT") doped with polystyrenesulfonic acid (“PSSA”). In some embodiments, the hole injection layer comprises poly(3,4-ethylenedioxythiophene) (“PEDOT”) doped with a deuterated polystyrenesulfonic acid (“d-PSSA”). In some embodiments, the hole injection layer comprises deuterated poly(3,4- ethylenedioxythiophene) doped with deuterated polystyrenesulfonic acid.
  • the d-PEDOT/d-PSSA is at least 50% deuterated; in some embodiments, at least 60% deuterated; in some embodiments, at least 70% deuterated; in some embodiments, at least 80% deuterated; in some embodiments, at least 90% deuterated; in some embodiments, 100% deuterated.
  • the hole injection layer consists essentially of a material selected from the group consisting of d-PEDOT/PSSA, PEDOT/d-PSSA, and d-PEDOT/d-PSSA. In some embodiments, the hole injection layer consists essentially of poly(D 6 -3,4- ethylenedioxythiophene) doped with D 8 -PSSA.
  • the hole injection layer comprises a deuterated polyaniline (“d-PANI”) doped with poly(2-acrylamido-2-methyl- 1 -propanesulfonic acid) (“PAAMPSA”). In some embodiments, the hole injection layer comprises polyaniline (“PANI”) doped with deuterated poly(2-acrylamido-2-methyl-1 -propanesulfonic acid) (“d-PAAMPSA”). In some embodiments, the hole injection layer comprises deuterated polyanilijne doped with deuterated poly(2-acrylamido-2-methyl-1 - propanesulfonic acid).
  • the d-PANI/d-PAAMPSA is at least 50% deuterated; in some embodiments, at least 60% deuterated; in some embodiments, at least 70% deuterated; in some embodiments, at least 80% deuterated; in some embodiments, at least 90% deuterated; in some embodiments, 100% deuterated.
  • the hole injection layer consists essentially of a material selected from the group consisting of d-PANI/PAAMPSA, PANI/d-PAAMPSA, and d-PANI/d- PAAMPSA. In some embodiments, the hole injection layer consists essentially of poly(D 7 -aniline) doped with Di 3 -PAAMPSA.
  • the hole injection layer comprises a deuterated polypyrrole ("d-PPy”) doped with polystyrenesulfonic acid (“PSSA”). In some embodiments, the hole injection layer comprises polypyrrole (“PPy”) doped with a deuterated polystyrenesulfonic acid (“d- PSSA”). In some embodiments, the hole injection layer comprises deuterated polypyrrole doped with deuterated polystyrenesulfonic acid.
  • PSSA polystyrenesulfonic acid
  • d- PSSA deuterated polystyrenesulfonic acid
  • the d-PPy/d-PSSA is at least 50% deuterated; in some embodiments, at least 60% deuterated; in some embodiments, at least 70% deuterated; in some embodiments, at least 80% deuterated; in some embodiments, at least 90% deuterated; in some embodiments, 100% deuterated.
  • the hole injection layer consists essentially of a material selected from the group consisting of d-PPy/PSSA, PPy/d-PSSA, and d-PPy/d-PSSA. In some embodiments, the hole injection layer consists essentially of poly(D 5 -pyrrole) doped with D 8 -PSSA.
  • the hole injection layer comprises a deuterated conductive polymer and a HFAP. In some embodiments, the hole injection layer comprises a deuterated conductive polymer doped with HFAP. In some embodiments, the hole injection layer consists essentially of a deuterated conductive polymer doped with HFAP. In some embodiments, the hole injection layer consists essentially of a deuterated conductive polymer doped with a perfluohnated sulfonic acid polymer.
  • the hole injection layer consists essentially of a deuterated conductive polymer doped with D-poly(TFE-PSEPVE), where the conductive polymer is selected from the group consisting of poly(D 6 - 3,4-ethylenedioxythiophene), poly(D 7 -aniline) and poly(D 5 -pyrrole).
  • the hole injection layer comprises charge transfer compounds, and the like, such as copper phthalocyanine, the tetrathiafulvalene-tetracyanoquinodimethane system (TTF-TCNQ) and deuterated analogs thereof.
  • charge transfer compounds such as copper phthalocyanine, the tetrathiafulvalene-tetracyanoquinodimethane system (TTF-TCNQ) and deuterated analogs thereof.
  • the hole transport layer 130 comprises hole transport material.
  • hole transport when referring to a layer, material, member, or structure, is intended to mean that such layer, material, member, or structure facilitates migration of positive charges through the thickness of such layer, material, member, or structure with relative efficiency and small loss of charge.
  • light-emitting materials may also have some hole transport properties, the terms "hole transport layer, material, member, or structure” are not intended to include a layer, material, member, or structure whose primary function is light emission.
  • Hole transport materials may be polymers, oligomers, or small molecules. They may be vapor deposited or deposited from liquids, which may be in the form of solutions, dispersions, suspensions, emulsions, colloidal mixtures, or other compositions. In some embodiments, the hole transport layer comprises deuterated material.
  • the hole transport material is at least 10% deuterated; in some embodiments, at least 20% deuterated; in some embodiments, at least 30% deuterated; in some embodiments, at least 40% deuterated; in some embodiments, at least 50% deuterated; in some embodiments, at least 60% deuterated; in some embodiments, at least 70% deuterated; in some embodiments, at least 80% deuterated; in some embodiments, at least 90% deuterated; in some embodiments, 100% deuterated.
  • the hole transport material is a deuterated compound having at least two diarylamino moieties per molecular formula unit.
  • the hole transport material is a deuterated triarylamine polymer.
  • Non-deuterated analogs of such materials have been described in, for example, published PCT application WO 2009/067419.
  • the hole transport material is a deuterated fluorene-tharylamine copolymer.
  • Non-deuterated analogs of such materials have been described in, for example, published U.S. patent applications US 2008/0071049 and US 2008/0097076.
  • Examples of non- deuterated analogs of crosslinkable hole transport polymers can be found in, for example, published US patent application 2005/0184287 and published PCT application WO 2005/052027.
  • the hole transport material is selected from the group consisting of deuterated triarylamine, deuterated carbazoles, deuterated fluorenes, polymers thereof, copolymers thereof, and combinations thereof.
  • the hole transport material is selected from the group consisting of deuterated polymeric triarylamines, deuterated polycarbazoles, deuterated polyfluorenes, deuterated polymeric triarylamines having conjugated moieties which are connected in a non-planar configuration, deuterated copolymers of fluorene and triarylamine, and combinations thereof.
  • the polymeric materials are crosslinkable.
  • the hole transport material has Formula I, Formula II, or Formula III: (Ar 2 ) 2 N— (Ar 1 )a— [T 1 -T 2 ] — (Ar 1 ) a — N(Ar 2 ) 2 (I)
  • Ar 1 is the same or different at each occurrence and is selected from the group consisting of phenylene, substituted phenylene, naphthylene, and substituted naphthylene;
  • Ar 2 is the same or different at each occurrence and is an aryl group
  • M is the same or different at each occurrence and is a conjugated moiety
  • T 1 and T 2 are independently the same or different at each occurrence and are conjugated moieties; a is the same or different at each occurrence and is an integer from
  • n is an integer greater than 1 ; wherein the compound is at least 10% deuterated.
  • the non-deuterated analogs of such materials have been described in published PCT application WO 2009/067419.
  • the deuteration is on a substituent group on an aryl ring.
  • the substituent group is selected from alkyl, aryl, alkoxy, and aryloxy.
  • the deuteration is on any one or more of the aryl groups Ar 1 and Ar 2 . In this case, at least one of Ar 1 and Ar 2 is a deuterated aryl group.
  • deuteration is present on the [T 1 - T 2 ] group. In some embodiments, both T 1 and T 2 are deuterated.
  • the deuteration is present on both the substituent groups and the Ar 1 and Ar 2 groups. In some embodiments of Formulae l-lll, the deuteration is present on both the [T 1 - T 2 ] group and the Ar 1 and Ar 2 groups. In some embodiments of Formulae l-lll, the deuteration is present on the substituent groups, the [T 1 - T 2 ] group, and the Ar 1 and Ar 2 groups.
  • At least one Ar 1 is a substituted phenyl with a substituent selected from the group consisting of alkyl, alkoxy, silyl, and a substituent with a crosslinking group.
  • a is 1 -3.
  • a is 1 -2.
  • a is 1.
  • e is 1 -4.
  • e is 1 -3.
  • e 1.
  • at least one Ar 1 has a substituent that has a crosslinking group.
  • At least one of Ar 2 has Formula a
  • R 1 is the same or different at each occurrence and is selected from the group consisting of D, alkyl, alkoxy, siloxane and, silyl; or adjacent R 1 groups may be joined to form an aromatic ring; f is the same or different at each occurrence and is an integer from
  • At least one of Ar 2 has Formula b:
  • R 1 is the same or different at each occurrence and is selected from the group consisting of D, alkyl, alkoxy, siloxane and, silyl; or adjacent R 1 groups may be joined to form an aromatic ring; f is the same or different at each occurrence and is an integer from
  • Ar 2 is selected from the group consisting of a group having Formula a, naphthyl, phenylnaphthyl, naphthylphenyl, and deuterated analogs thereof. In some embodiments, Ar 2 is selected from the group consisting phenyl, p-biphenyl, p-terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, and deuterated analogs thereof. In some embodiments, Ar 2 is selected from the group consisting of phenyl, biphenyl, terphenyl, and deuterated analogs thereof.
  • any of the aromatic rings in Formulae I - III may be substituted at any position.
  • the substituents may be present to improve one or more physical properties of the compound, such as solubility.
  • the substituents are selected from the group consisting of C-1-12 alkyl groups , C M2 alkoxy groups, silyl groups, and deuterated analogs thereof.
  • crosslinking substituents are present on at least one Ar 2 . In some embodiments, crosslinking substituents are present on at least one M moiety.
  • T 1 and T 2 are conjugated moieties.
  • T 1 and T 2 are aromatic moieties.
  • T 1 and T 2 are deuterated aromatic moieties.
  • T 1 and T 2 are selected from the group consisting of phenylene, napthylene, anthracenyl groups, and deuterated analogs thereof.
  • the T 1 - T 2 group introduces non-planarity into the backbone of the compound.
  • the moiety in T 1 that is directly linked to a moiety in T 2 is linked such that the T 1 moiety is oriented in a plane that is different from the moiety in T 2 to which it is linked.
  • other parts of the T 1 unit for example, substituents, may lie in one or more different planes, it is the plane of the linking moiety in T 1 and the linking moiety in T 2 in the compound backbone that provide the non-planarity.
  • the compounds are chiral. In general, they are formed as racemic mixtures. The compounds can also be in enantiomerically pure form.
  • the non-planarity can be viewed as the restriction to free rotation about the T 1 - T 2 bond. Rotation about that bond leads to racemization.
  • the half-life of racemization for T 1 - T 2 is greater than that for an unsubstituted biphenyl. In some embodiments, the half- life or racemization is 12 hours or greater at 2O 0 C.
  • [T 1 - T 2 ] is a substituted biphenylene group, , or deuterated analog thereof.
  • the term "biphenylene” is intended to mean a biphenyl group having two points of attachment to the compound backbone.
  • the term "biphenyl” is intended to mean a group having two phenyl units joined by a single bond.
  • the biphenylene group can be attached at one of the 2, 3-, 4-, or 5-positions and one of the 2', 3'-, 4'-, or 5'-positions.
  • the substituted biphenylene group has at least one substitutent in the 2-position.
  • the biphenylene group has substituents in at least the 2- and 2'-positions.
  • [T 1 - T 2 ] is a binaphthylene group, or deuterated analog thereof.
  • binaphthylene is intended to mean a binapthyl group having 2 points of attachment to the compound backbone.
  • binaphthyl is intended to mean a group having two naphthalene units joined by a single bond.
  • [T 1 - T 2 ] is a phenylene-naphthylene group, or deuterated analog thereof. In some embodiments, [T 1 - T 2 ] is a phenylene-1 -naphthylene group, which is attached to the compound backbone at one of the 3-, A-, or 5-positions in the phenylene and one of the 3-, A-, or 5-positions of the naphthylene.
  • [T 1 - T 2 ] is a phenylene-2-naphthylene group, which is attached to the compound backbone at one of the 3-, A-, or 5-positions in the phenylene and one of the A-, 5-, 6-, 7-, or 8-positions of the naphthylene.
  • the biphenylene, binaphthylene, and phenylene-naphthylene groups are substituted at one or more positions.
  • [T 1 - T 2 ] is a 1 ,1 -binaphthylene group, or deuterated analog thereof, which is attached to the compound backbone at the 4 and 4' positions, referred to as 4,4'-(1 ,1 -binaphthylene).
  • the 4,4'-(1 ,1 -binaphthylene) is the only isomer present. In some embodiments, two or more isomers are present. In some embodiments, the 4,4'-(1 ,1 -binaphthylene) is present with up to 50% by weight of a second isomer.
  • the second isomer is selected from the group consisting of 4,5'-(1 ,1 -binaphthylene), 4,6'-(1 ,1 - binaphthylene), and A, 7'-(1 ,1 -binaphthylene).
  • Formula III represents a copolymer in which there is at least one [T 1 - T 2 ] moiety and at least one other conjugated moiety, where the overall polymer is at least 10% deuterated.
  • the deuteration is in the first monomehc unit, with the subscript "b".
  • the deuteration is in the second monomeric unit, with the subscript "c”.
  • the deuteration is in the third monomeric unit, with the subscript "d”.
  • the deuteration is in two monomeric units. In some embodiments, one of the two monomeric units is the first monomeric unit. In some embodiments, the deuteration is in all three monomeric units.
  • deuterated hole transport compounds include Compounds HT1 through HT10 below.
  • Compound HT1 includes Compounds HT1 through HT10 below.
  • Ri Dy-propyl
  • Triarylamine polymer is Compound HT12.
  • hole transport materials include, but are not limited to: N,N'-diphenyl-N,N'-bis(3-methylphenyl)- [1 ,1'-biphenyl]-4,4'-diamine (TPD), 1 ,1 -bis[(di-4-tolylamino) phenyl]cyclohexane (TAPC), N,N'-bis(4-methylphenyl)-N,N'-bis(4- ethylphenyl)-[1 ,1 '-(3,3'-dimethyl)biphenyl]-4,4'-diamine (ETPD), tetrakis-(3- methylphenyl)-N,N,N',N'-2,5-phenylene
  • the hole transport layer is doped with a p- dopant, such as tetrafluorotetracyanoquinodimethane, perylene-3,4,9,10- tetracarboxylic-3,4,9,10-dianhydride, and deuterated analogs thereof.
  • a p- dopant such as tetrafluorotetracyanoquinodimethane, perylene-3,4,9,10- tetracarboxylic-3,4,9,10-dianhydride, and deuterated analogs thereof.
  • the electroluminescent layer 140 comprises electroluminescent material.
  • electroluminescent material refers to a material that emits light when activated by an applied voltage.
  • the electroluminescent layer 140 consists essentially of electroluminescent material.
  • the electroluminescent layer 140 comprises one or more dopants and one or more host compounds.
  • the electroluminescent layer 140 consists essentially of one or more dopants and one or more host compounds.
  • An electroluminescent dopant is a material which is capable of electroluminescence having an emission maximum between 380 and 750 nm. In some embodiments, the dopant emits red, green, or blue light.
  • the host compound is a compound, usually in the form of a layer, in which one or more dopants are dispersed and in which the one or more dopants are emissive.
  • the term "host material" refers to the total of all host compounds present. The host material may or may not have electronic characteristics) or the ability to emit, receive, or filter radiation.
  • the electroluminescent layer comprising at least one dopant and host material, the light emission is from the dopant. In some embodiments, the host material is present in larger concentration than the sum of all the dopants.
  • the electroluminescent layer 140 consists essentially of one or more dopants and one or more host compounds. In some embodiments, the electroluminescent layer 140 consists essentially of a dopant and a host compound. In some embodiments, the electroluminescent layer 140 consists essentially of a dopant and two host compounds.
  • the electroluminescent layer comprises deuterated material selected from the group consisting of deuterated electroluminescent material, deuterated host material, and combinations thereof.
  • Materials for the electroluminescent layer may be polymers, oligomers, small molecules, or combinations thereof. They may be vapor deposited or deposited from liquids, which may be in the form of solutions, dispersions, suspensions, emulsions, colloidal mixtures, or other compositions.
  • the amount of total dopant present in the electroluminescent composition is generally in the range of 3-20% by weight, based on the total weight of the composition; in some embodiments, 5-15% by weight.
  • the ratio of first host to second host is generally in the range of 1 :20 to 20:1 ; in some embodiments, 5:15 to 15:5.
  • the electroluminescent material can be selected from small molecule organic electroluminescent compounds, electroluminescent metal complexes, electroluminescent conjugated polymers, and mixtures thereof.
  • the electroluminescent material is deuterated. In some embodiments, the electroluminescent material is at least 10% deuterated; in some embodiments, at least 20% deuterated; in some embodiments, at least 30% deuterated; in some embodiments, at least 40% deuterated; in some embodiments, at least 50% deuterated; in some embodiments, at least 60% deuterated; in some embodiments, at least 70% deuterated; in some embodiments, at least 80% deuterated; in some embodiments, at least 90% deuterated; in some embodiments, 100% deuterated.
  • red light-emitting materials include, but are not limited to, cyclometalated complexes of Ir having phenylquinoline or phenylisoquinoline ligands, periflanthenes, fluoranthenes, perylenes, and deuterated analogs thereof.
  • Non-deuterated red light-emitting materials have been disclosed in, for example, US patent 6,875,524, and published US application 2005-0158577.
  • green light-emitting materials include, but are not limited to, cyclometalated complexes of Ir having phenylpyhdine ligands, diaminoanthracenes, polyphenylenevinylene polymers, and deuterated analogs thereof.
  • Non-deuterated green light-emitting materials have been disclosed in, for example, published PCT application WO 2007/021117.
  • blue light-emitting materials include, but are not limited to, diarylanthracenes, diaminochrysenes, diaminopyrenes, diaminostilbenes, cyclometalated complexes of Ir having phenylpyhdine ligands, polyfluorene polymers, and deuterated analogs thereof.
  • Non- deuterated blue light-emitting materials have been disclosed in, for example, US patent 6,875,524, and published US applications 2007- 0292713 and 2007-0063638.
  • the dopant is an organometallic complex. In some embodiments, the dopant is a cyclometalated complex of iridium or platinum. Such materials when not deuterated have been disclosed in, for example, U.S. Patent 6,670,645 and Published PCT Applications WO 03/063555, WO 2004/016710, and WO 03/040257.
  • the dopant is a complex having the formula Ir(LI ) x (L2)y (L3) z ; where L1 is a monoanionic bidentate cyclometalating ligand coordinated through carbon and nitrogen;
  • L2 is a monoanionic bidentate ligand which is not coordinated through a carbon
  • L3 is a monodentate ligand
  • x is 1 -3
  • y and z are independently 0-2
  • x, y, and z are selected such that the iridium is hexacoordinate and the complex is electrically neutral.
  • L1 ligands include, but are not limited to phenylpyridines, phenylquinolines, phenylpyrimidines, phenylpyrazoles, thienylpyridines, thienylquinolines, thienylpyrimidines, and deuterated analogs thereof.
  • the term "quinolines" includes
  • the fluorinated derivatives can have one or more fluorine substituents. In some embodiments, there are 1 -3 fluorine substituents on the non-nitrogen ring of the ligand.
  • Monoanionic bidentate ligands L2 are well known in the art of metal coordination chemistry. In general these ligands have N, O, P, or S as coordinating atoms and form 5- or 6-membered rings when coordinated to the iridium.
  • Suitable coordinating groups include, but are not limited to, amino, imino, amido, alkoxide, carboxylate, phosphino, thiolate, and deuterated analogs thereof.
  • Suitable parent compounds for these ligands include ⁇ -dicarbonyls ( ⁇ -enolate ligands), and their N and S analogs; amino carboxylic acids (aminocarboxylate ligands); pyridine carboxylic acids (iminocarboxylate ligands); salicylic acid derivatives (salicylate ligands); hydroxyquinolines (hydroxyquinolinate ligands) and their S analogs; phosphinoalkanols (phosphinoalkoxide ligands); and deuterated analogs thereof.
  • Monodentate ligand L3 can be anionic or nonionic.
  • Anionic ligands include, but are not limited to, H " ("hydride") and ligands having C, O or S as coordinating atoms. Coordinating groups include, but are not limited to alkoxide, carboxylate, thiocarboxylate, dithiocarboxylate, sulfonate, thiolate, carbamate, dithiocarbamate, thiocarbazone anions, sulfonamide anions, and deuterated analogs thereof.
  • ligands listed above as L2 such as ⁇ -enolates and phosphinoakoxides, can act as monodentate ligands.
  • the monodentate ligand can also be a coordinating anion such as halide, cyanide, isocyanide, nitrate, sulfate, hexahaloantimonate, and the like. These ligands are generally available commercially.
  • the monodentate L3 ligand can also be a non-ionic ligand, such as CO, a monodentate phosphine ligand, or a deuterated monodentate phosphine ligand.
  • one or more of the ligands has at least one substituent selected from the group consisting of F and fluorinated alkyls.
  • iridium complex dopants can be made using standard synthetic techniques analogous to those described for non-deuterated analogs in, for example, US patent 6,670,645.
  • the electroluminescent material is a small organic compound.
  • small molecule luminescent compounds include, but are not limited to, chrysenes, pyrenes, perylenes, rubrenes, pehflanthenes, fluoranthenes, stilbenes, coumarins, anthracenes, thiadiazoles, derivatives thereof, deuterated analogs thereof, and mixtures thereof.
  • the electroluminescent material has one of the following structures:
  • the structure may be unsubstituted or further substituted with alkyl or aryl groups, and the compound is from 10% to 100% deuterated.
  • the dopant is selected from the group consisting of a non-polymeric spirobifluorene compound and a fluoranthene compound.
  • the electroluminescent material is a compound having aryl amine groups. In some embodiments, the electroluminescent material is selected from the formulae below:
  • A is the same or different at each occurrence and is an aromatic group having from 3-60 carbon atoms;
  • Q' is a single bond or an aromatic group having from 3-60 carbon atoms; p and q are the same or different and each is an integer from 1-6. In the above formulae the values of p and q may be limited by the available bonding sites on the core Q' group.
  • the compound is at least 10% deuterated; in some embodiments, at least 20% deuterated; in some embodiments, at least 30% deuterated; in some embodiments, at least 40% deuterated; in some embodiments, at least 50% deuterated; in some embodiments, at least 60% deuterated; in some embodiments, at least 70% deuterated; in some embodiments, at least 80% deuterated; in some embodiments, at least 90% deuterated; in some embodiments, 100% deuterated.
  • At least one of A and Q' in each formula has at least three condensed rings. In some embodiments, p and q are equal to 1.
  • Q' is a styryl or styrylphenyl group.
  • Q' is an aromatic group having at least two condensed rings.
  • Q' is selected from the group consisting of naphthalene, anthracene, benz[a]anthracene, dibenz[a,h]anthracene, fluoranthene, fluorene, spirofluorene, tetracene, chrysene, pyrene, tetracene, xanthene, perylene, coumarin, rhodamine, quinacridone, rubrene, substituted derivatives thereof, and deuterated analogs thereof.
  • A is selected from the group consisting of phenyl, biphenyl, tolyl, naphthyl, naphthylphenyl, anthracenyl, and deuterated analogs thereof.
  • the electroluminescent material has the structure
  • A is an aromatic group
  • p is 1 or 2
  • Q' is selected from the group consisting of:
  • R is the same or different at each occurrence and is selected from the group consisting of D, alkyl, alkoxy and aryl, where adjacent
  • R groups may be joined together to form a 5- or 6-membered aliphatic ring;
  • Ar is the same or different and is selected from the group consisting of aryl groups; wherein the compound has at least one D.
  • the dashed line in the formula is intended to indicate that the R group, when present, can be at any site on the core Q' group.
  • the electroluminescent material has the formula below:
  • Y is the same or different at each occurrence and is an aromatic group having 3-60 carbon atoms
  • the electroluminescent is an aryl acene or a deuterated analog thereof.
  • the electroluminescent material is a non-symmetrical aryl acene or a deuterated analog thereof.
  • the electroluminescent material is an anthracene derivative having Formula IV:
  • R 2 is the same or different at each occurrence and is selected from the group consisting of D, alkyl, alkoxy and aryl, where adjacent R 2 groups may be joined together to form a 5- or 6-membered aliphatic ring;
  • Ar 3 through Ar 6 are the same or different and are selected from the group consisting of aryl groups and deuterated aryl groups; h is the same or different at each occurrence and is an integer from
  • the electroluminescent material is a chrysene derivative having Formula V: Formula V
  • R 3 is the same or different at each occurrence and is selected from the group consisting of D, alkyl, alkoxy aryl, fluoro, cyano, nitro,
  • R 4 is alkyl or perfluoroalkyl, where adjacent R 3 groups may be joined together to form a 5- or 6-membered aliphatic ring;
  • Ar 3 through Ar 6 are the same or different and are selected from the group consisting of aryl groups; and i is the same or different at each occurrence and is an integer from
  • the deuteration is on a substituent group on an aryl ring.
  • the aryl group having a deuterated substituent group can be the core anthracene group of Formula IV or the core chrysene group of Formula V; or an aryl on the nitrogen; or a substituent aryl group.
  • the deuterated substituent group on an aryl ring is selected from alkyl, aryl, alkoxy, and aryloxy.
  • the substituent groups are at least 10% deuterated; in some embodiments, at least 20% deuterated; in some embodiments, at least 30% deuterated; in some embodiments, at least 40% deuterated; in some embodiments, at least 50% deuterated; in some embodiments, at least 60% deuterated; in some embodiments, at least 70% deuterated; in some embodiments, at least 80% deuterated; in some embodiments, at least 90% deuterated.
  • the deuteration is on any one or more of the aryl groups Ar 3 through Ar 6 . In this case, at least one of Ar 3 through Ar 6 is a deuterated aryl group. In some embodiments, Ar 3 through Ar 6 are at least 10% deuterated.
  • Ar 3 through Ar 6 are at least 20% deuterated; in some embodiments, at least 30% deuterated; in some embodiments, at least 40% deuterated; in some embodiments, at least 50% deuterated; in some embodiments, at least 60% deuterated; in some embodiments, at least 70% deuterated; in some embodiments, at least 80% deuterated; in some embodiments, at least 90% deuterated.
  • the deuteration is present on both the substituent groups (R 2 or R 3 ) and the aryl groups.
  • the compound of Formulae IV and V is at least 10% deuterated; in some embodiments, at least 20% deuterated; in some embodiments, at least 30% deuterated; in some embodiments, at least 40% deuterated; in some embodiments, at least 50% deuterated; in some embodiments, at least 60% deuterated; in some embodiments, at least 70% deuterated; in some embodiments, at least 80% deuterated; in some embodiments, at least 90% deuterated; in some embodiments, 100% deuterated.
  • the compound is symmetrical with respect to the amino groups.
  • Ar 3 Ar 5
  • Ar 4 Ar 6
  • Ar 3 may be the same as or different from Ar 4 .
  • the compound is not symmetrical with respect to the amino groups.
  • Ar 3 is different from both Ar 5 and Ar 6 .
  • Ar 3 may be the same as or different from Ar 4
  • Ar 4 may be the same as or different from each of Ar 5 and Ar 6 .
  • both h 0.
  • At least one h is greater than 0.
  • at least one R 2 is a hydrocarbon alkyl.
  • R 2 is a deuterated alkyl.
  • R 2 is selected from a branched hydrocarbon alkyl and a cyclic hydrocarbon alkyl.
  • the bond to (R 3 ) is intended to indicate that the R 3 group can be at any one or more sites on the two fused rings.
  • both i 0.
  • At least one i is greater than 0.
  • at least one R 3 is a hydrocarbon alkyl.
  • R 3 is selected from a branched hydrocarbon alkyl and a cyclic hydrocarbon alkyl.
  • Ar 3 through Ar 6 has Formula a or Formula b as shown above.
  • Ar 3 through Ar 6 is selected from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, phenylnapthyl, naphthylphenyl, and binaphthyl.
  • Ar 3 through Ar 6 are perdeuterated.
  • Ar 3 through Ar 6 are perdeuterated, except for one or more alkyl groups on a terminal aryl.
  • deuterated electroluminescent materials are shown as E1 through E13 below:
  • a single host compound or two or more host compounds may be present as the host material.
  • Non-deuterated examples of host compounds have been disclosed in, for example, US patent 7,362,796, and published US patent application 2006-0115676.
  • the host material is at least 10% deuterated; in some embodiments, at least 20% deuterated; in some embodiments, at least 30% deuterated; in some embodiments, at least 40% deuterated; in some embodiments, at least 50% deuterated; in some embodiments, at least 60% deuterated; in some embodiments, at least 70% deuterated; in some embodiments, at least 80% deuterated; in some embodiments, at least 90% deuterated.
  • the host material is 100% deuterated.
  • the host material is selected from the group consisting of anthracenes, chrysenes, pyrenes, phenanthrenes, triphenylenes, phenanthrolines, naphthalenes, anthracenes, quinolines, isoquinolines, quinoxalines, phenylpyridines, dibenzofurans, difuranobenzenes, metal quinolinate complexes, indolocarbazoles, benzimidazoles, triazolopyridines, diheteroarylphenyls, substituted derivatives thereof, deuterated analogs thereof, and combinations thereof.
  • the aforementioned host compounds have a substituent selected from the group consisting of aryl, alkyl, and deuterated analogs thereof.
  • the heteroaryl group is selected from the group consisting of pyridine, pyrazine, pyrimidine, pyridazine, triazines, tetrazines, quinazoline, quinoxaline, naphthylpyridines, heterobiaryl analogs thereof, heterotriaryl analogs thereof, and deuterated analogs thereof.
  • the host is selected from structures 1 -9, below, or a deuterated analog thereof.
  • R" H, D, CH 3 , CD 3 1,2-disubstituted shown
  • R is selected from aryl, heteroaryl, and alkyl.
  • the heteroaryl group is selected from structures 10-20 below, or a deuterated analog thereof.
  • the group is a heterobiaryl derivative or a heterotriaryl derivative.
  • the host material has one of the structures shown below
  • R is selected from aryl, heteroaryl, and alkyl and the compound may be deuterated.
  • the above structures are further substituted with aryl or heteroaryl groups.
  • the heteroaryl group is selected from structures 10-20 above, or a deuterated analog thereof.
  • the host material has Formula Vl:
  • Ar 7 is the same or different at each occurrence and is an aryl group;
  • Q is selected from the group consisting of multivalent aryl groups and
  • T is selected from the group consisting of (CR') a , SiR2, S, SO2, PR,
  • n is an integer from 0-6. While n can have a value from 0-6, it will be understood that for some Q groups the value of n is restricted by the chemistry of the group. In some embodiments, n is 0 or 1.
  • adjacent Ar groups are joined together to form rings such as carbazole.
  • adjacent means that the Ar groups are bonded to the same N.
  • Ar 7 is independently selected from the group consisting of phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthryl, naphthylphenyl, phenanthrylphenyl, and deuterated analogs thereof. Analogs higher than quaterphenyl, having 5-10 phenyl rings, can also be used.
  • At least one of Ar 7 has at least one substituent.
  • Substituent groups can be present in order to alter the physical or electronic properties of the host material. In some embodiments, the substituents improve the processibility of the host material. In some embodiments, the substituents increase the solubility and/or increase the Tg of the host material. In some embodiments, the substituents are selected from the group consisting of D, alkyl groups, alkoxy groups, silyl groups, siloxane, and combinations thereof.
  • Q is an aryl group having at least two fused rings. In some embodiments, Q has 3-5 fused aromatic rings. In some embodiments, Q is selected from the group consisting of anthracenes, chrysenes, pyrenes, phenanthrenes, triphenylenes, phenanthrolines, naphthalenes, anthracenes, quinolines, isoquinolines, quinoxalines, phenylpyridines, dibenzofurans, difuranobenzenes, indolocarbazoles, substituted derivatives thereof, and deuterated analogs thereof.
  • the host compound has Formula VII: 1 Formula VII
  • R 4 through R 11 are the same or different at each occurrence and are selected from the group consisting of H, D, alkyl, alkoxy, aryl, aryloxy, siloxane, and silyl;
  • Ar 8 and Ar 9 are the same or different and are selected from the group consisting of aryl groups;
  • Ar 10 and Ar 11 are the same or different and are selected from the group consisting of H, D, and aryl groups, wherein there is at least one D.
  • the at least one D is on a substituent group on an aryl ring. In some embodiments, the substituent group is selected from alkyl and aryl. In some embodiments of Formula VII, at least one of R 4 through R 11 is D. In some embodiments, at least two of R 4 through R 11 are D. In some embodiments, at least three are D; in some embodiments, at least four are D; in some embodiments, at least five are D; in some embodiments, at least six are D; in some embodiments, at least seven are D. In some embodiments, all of R 4 through R 11 are D.
  • R 4 through R 11 are selected from H and D. In some embodiments, one of R 4 through R 11 are D and seven are H. In some embodiments, two of R 4 through R 11 are D and six are H. In some embodiments, three of R 4 through R 11 are D and five are H. In some embodiments, four of R 4 through R 11 are D, and four are H. In some embodiments, five of R 4 through R 11 are D and three are H. In some embodiments, six of R 4 through R 11 are D and two are H. In some embodiments, seven of R 4 through R 11 are D and one is H. In some embodiments, eight of R 4 through R 11 are D.
  • R 4 through R 11 is selected from alkyl, alkoxy, aryl, aryloxy, siloxane, and silyl, and the remainder of R 4 through R 11 are selected from H and D.
  • R 5 is selected from alkyl, alkoxy, aryl, aryloxy, siloxane, and silyl.
  • R 5 is selected from alkyl and aryl.
  • R 5 is selected from deuterated alkyl and deuterated aryl.
  • R 5 is selected from deuterated aryl having at least 10% deuteration.
  • R 5 is selected from deuterated aryl having at least 20% deuteration; in some embodiments, at least 30% deuteration; in some embodiments, at least 40% deuteration; in some embodiments, at least 50% deuteration; in some embodiments, at least 60% deuteration; in some embodiments, at least 70% deuteration; in some embodiments, at least 80% deuteration; in some embodiments, at least 90% deuteration .
  • R 2 is selected from deuterated aryl having 100% deuteration.
  • Ar 11 is a deuterated aryl. In some embodiments, Ar 10 and Ar 11 are selected from D and deuterated aryls.
  • Ar 8 through Ar 11 are at least 10% deuterated. In some embodiments of Formula VII, Ar 8 through Ar 11 are at least 20% deuterated; in some embodiments, at least 30% deuterated; in some embodiments, at least 40% deuterated; in some embodiments, at least 50% deuterated; in some embodiments, at least 60% deuterated; in some embodiments, at least 70% deuterated; in some embodiments, at least 80% deuterated; in some embodiments, at least 90% deuterated; in some embodiments, 100% deuterated.
  • the compound of Formula VII is at least 10% deuterated; in some embodiments, at least 20% deuterated; in some embodiments, at least 30% deuterated; in some embodiments, at least 40% deuterated; in some embodiments, at least 50% deuterated; in some embodiments, at least 60% deuterated; in some embodiments, at least 70% deuterated; in some embodiments, at least 80% deuterated; in some embodiments, at least 90% deuterated. In some embodiments, the compound is 100% deuterated.
  • Ar 8 and Ar 9 are selected from the group consisting of phenyl, naphthyl, phenanthryl, anthracenyl, and deuterated analogs thereof. In some embodiments, Ar 8 and Ar 9 are selected from the group consisting of phenyl, naphthyl, and deuterated analogs thereof. In some embodiments, Ar 10 and Ar 11 are selected from the group consisting of phenyl, naphthyl, phenanthryl, anthracenyl, phenylnaphthylene, naphthylphenylene, deuterated derivatives thereof, and a group having Formula a or Formula b, as shown above.
  • At least one of Ar 8 through Ar 11 is a heteroaryl group.
  • the heteroaryl group is deuterated.
  • the heteroaryl group is at least 10% deuterated; in some embodiments, at least 20% deuterated; in some embodiments, at least 30% deuterated; in some embodiments, at least 40% deuterated; in some embodiments, at least 50% deuterated; in some embodiments, at least 60% deuterated; in some embodiments, at least 70% deuterated; in some embodiments, at least 80% deuterated; in some embodiments, at least 90% deuterated.
  • the heteroaryl group is 100% deuterated.
  • the heteroaryl group is selected from carbazole, benzofuran, dibenzofuran, and deuterated derivatives thereof.
  • At least one of R 4 through R 11 is D and at least one of Ar 8 through Ar 11 is a deuterated aryl.
  • the compound is at least 10% deuterated.
  • the compound is at least 20% deuterated; in some embodiments, at least 30% deuterated; in some embodiments, at least 40% deuterated; in some embodiments, at least 50% deuterated; in some embodiments, at least 60% deuterated; in some embodiments, at least 70% deuterated; in some embodiments, at least 80% deuterated; in some embodiments, at least 90% deuterated.
  • the compound is 100% deuterated.
  • the host compound has Formula VIII
  • R 12 is the same or different at each occurrence and is selected from the group consisting of D, alkyl, alkoxy, silyl, and siloxane, or adjacent R 12 groups may be joined together to form a 5- or 6- membered aliphatic ring,
  • Ar 12 and Ar 13 are the same or different and are aryl groups, j is an integer from 0 to 6; k is an integer from 0 to 2; and I is an integer from 0 to 3; wherein there is at least one D.
  • the branched alkyl group is 2-propyl group, a t- butyl group, or a deuterated analog thereof.
  • Ar 12 and Ar 13 are phenyl groups having a substituent selected from the group consisting of D, alkyl, silyl, phenyl, naphthyl, N-carbazolyl, and fluorenyl.
  • Ar 12 and Ar 13 are selected from the group consisting of phenyl, biphenyl, naphthyl, phenanthryl, anthracenyl, 4- naphthylphenyl, 4-phenanthrylphenyl, deuterated analogs thereof, and a group having Formula a or Formula b, as shown above.
  • the host compound has Formula IX
  • R ,13 is the same or different and is selected from the group consisting of phenyl, biphenyl, naphthyl, naphthylphenyl, triphenylamino, carbazolylphenyl, and deuterated analogs thereof; and one of the following conditions is met:
  • R 14 R 15 and is selected from the group consisting of H, D, phenyl, biphenyl, naphthyl, naphthylphenyl, arylanthracenyl, phenanthryl, triphenylamino, carbazolylphenyl, and deuterated analogs thereof; or
  • R 14 is selected from the group consisting of H, D, phenyl, and deutero-phenyl;
  • R 15 is selected from the group consisting of phenyl, biphenyl, naphthyl, naphthylphenyl, arylanthracenyl, phenanthryl, triphenylamino, carbazolylphenyl, and deuterated analogs thereof; wherein there is at least one D.
  • the R 13 groups are selected from the group consisting of phenyl, triphenylamino, carbazolylphenyl, and deuterated analogs thereof. In some embodiments, the R 13 groups are selected from the group consisting of 4-triphenylamino, m-carbazolylphenyl, and deuterated analogs thereof.
  • R 13 R 14 and is selected from the group consisting of triphenylamino, naphthylphenyl, arylanthracenyl, m- carbazolylphenyl, and deuterated analogs thereof.
  • the host has Formula X or Formula Xl
  • R ,16 is the same or different at each occurrence and is selected from the group consisting of hydrogen, deuterium, phenyl, biphenyl, naphthyl, naphthylphenyl, phenanthryl, triphenylamino, carbazolyl, carbazolylphenyl, and deuterated derivatives thereof;
  • R 17 is H or D; and
  • Q'" is an aryl group; wherein there is at least one D.
  • Q'" is selected from the group consisting of phenylene, naphthylene, biphenylene, binaphthylene, and deuterated derivatives thereof. In some embodiments, Q'" is selected from the group consisting of 1 ,4-phenylene, 2,6-naphthylene, 4,4'-biphenylene, 4,4'-(1 ,V- binaphthylene), and deuterated derivatives thereof.
  • the host is a deuterated indolocarbazole having Formula XII or Formula XIII:
  • Ar 14 is an aromatic electron transporting group
  • Ar 15 is selected from the group consisting of aryl groups and aromatic electron transporting groups.
  • R 18 and R 19 are the same or different at each occurrence and are selected from the group consisting of H, D and aryl; wherein the compound has at least one D.
  • deuterium is present on a moiety selected from the group consisting of the indolocarbazole core, an aryl ring, a substituent group on an aryl ring, and combinations thereof.
  • Ar 14 is an aromatic electron transporting group.
  • the aromatic electron transporting group is a nitrogen- containing heteroaromatic group.
  • nitrogen-containing heteroaromatic groups which are electron transporting include, but are not limited to those shown below.
  • Ar 16 is an aryl group
  • R 20 is the same or different at each occurrence and is selected from the group consisting of D, alkyl, alkoxy, aryl, aryloxy, siloxane, and silyl; m is an integer from 0-4; n is an integer from 0-3; o is an integer from 0-2; p is an integer from 0-5; q is O or 1 ; and r is an integer from 0-6.
  • the group can be bonded to the nitrogen on the core at any of the positions indicated with the wavy line.
  • R 20 is selected from the group consisting of D and aryl. In some embodiments, R 20 is a nitrogen- containing heteroaromatic electron transporting group.
  • Ar 15 is an aromatic electron transporting group as discussed above. In some embodiments, Ar 15 is selected from the group consisting of phenyl, naphthyl, phenanthryl, anthracenyl, phenylnaphthylene, naphthylphenylene, deuterated derivatives thereof, and a group having Formula a or Formula b, as discussed above.
  • the host material is selected from the group consisting of deuterated diarylanthracenes, deuterated aminochrysenes, deuterated diarylchrysenes, deuterated diarylpyrenes, deuterated indolocarbazoles, deuterated phenanthrolines, and combinations thereof.
  • deuterated host compounds include
  • the electron transport layer 150 comprises electron transport material.
  • electron transport when referring to a layer, material, member, or structure, is intended to mean that such layer, material, member, or structure facilitates migration of negative charges through the thickness of such layer, material, member, or structure with relative efficiency and small loss of charge.
  • light-emitting materials may also have some electron transport properties, the terms "electron transport layer, material, member, or structure” are not intended to include a layer, material, member, or structure whose primary function is light emission.
  • Electron transport materials may be polymers, oligomers, or small molecules. They may be vapor deposited or deposited from liquids, which may be in the form of solutions, dispersions, suspensions, emulsions, colloidal mixtures, or other compositions.
  • the electron transport layer comprises deuterated material.
  • the electron transport material is at least 10% deuterated; in some embodiments, at least 20% deuterated; in some embodiments, at least 30% deuterated; in some embodiments, at least 40% deuterated; in some embodiments, at least 50% deuterated; in some embodiments, at least 60% deuterated; in some embodiments, at least 70% deuterated; in some embodiments, at least 80% deuterated; in some embodiments, at least 90% deuterated; in some embodiments, 100% deuterated.
  • the electron transport layer 150 comprises a deuterated phenanthroline derivative having Formula IX, Formula X, or Formula Xl, as discussed above. In some embodiments, the electron transport layer 150 consists essentially of a deuterated phenanthroline derivative having Formula IX, Formula X, or Formula Xl.
  • the electron transport layer 150 comprises a deuterated indolocarbazole derivative having Formula XII or Formula XIII, as discussed above. In some embodiments, the electron transport layer 150 consists essentially of a deuterated indolocarbazole derivative having Formula XII or Formula XIII.
  • the electron transport layer comprises a material selected from the group consisting of deuterated benzimidazoles, deuterated triazolopyridines and deuterated diheteroarylphenyls.
  • the electron transport layer 150 comprises a deuterated metal chelated oxinoid compound.
  • deuterated metal quinolate derivatives such as deuterated tris(8- hydroxyquinolato)aluminum (d-AIQ), deuterated bis(2-methyl-8- quinolinolato)(p-phenylphenolato) aluminum (d-BAIq), deuterated tetrakis- ( ⁇ -hydroxyquinolato)hafnium (d-HfQ) and deuterated tetrakis-(8- hydroxyquinolato)zirconium (d-ZrQ).
  • deuterated metal quinolate derivatives such as deuterated tris(8- hydroxyquinolato)aluminum (d-AIQ), deuterated bis(2-methyl-8- quinolinolato)(p-phenylphenolato) aluminum (d-BAIq), deuterated tetrakis- ( ⁇ -hydroxyquinolato)hafnium (d-HfQ) and de
  • the electron transport layer comprises an electron transport material selected from the group consisting of deuterated phenanthrolines, deuterated indolocarbazoles, deuterated benzimidazoles, deuterated triazolopyridines, deuterated diheteroarylphenyls, deuterated metal quinolates, and combinations thereof.
  • the electron transport layer consists essentially of an electron transport material selected from the group consisting of deuterated phenanthrolines, deuterated indolocarbazoles, deuterated benzimidazoles, deuterated triazolopyridines, deuterated diheteroarylphenyls, deuterated metal quinolates, and combinations thereof.
  • Examples of other electron transport materials which can be used in the electron transport layer 150 include azole compounds such as 2- (4-biphenylyl)-5-(4-t-butylphenyl)-1 ,3,4-oxadiazole (PBD), 3-(4-biphenylyl)- 4-phenyl-5-(4-t-butylphenyl)-1 ,2,4-triazole (TAZ), and 1 ,3,5-tri(phenyl-2- benzimidazole)benzene (TPBI); quinoxaline derivatives such as 2,3-bis(4- fluorophenyl)quinoxaline; triazines; fullerenes; deuterated analogs of any of the preceding material; and mixtures thereof.
  • azole compounds such as 2- (4-biphenylyl)-5-(4-t-butylphenyl)-1 ,3,4-oxadiazole (PBD), 3-(4-biphenylyl)- 4-phenyl-5-
  • the electron transport layer further comprises an n-dopant.
  • N-dopant materials are well known.
  • each display pixel is divided into three subpixels, each emitting one of the three primary display colors, red, green, and blue.
  • the different color are applied by a liquid deposition technique, there is a need to prevent the spreading of the liquid colored materials (i.e., inks) and color mixing, from one subpixel to the next.
  • chemical containment layer is intended to mean a patterned layer that contains or restrains the spread of a liquid material by surface energy effects rather than physical barrier structures.
  • the term "contained” when referring to a layer, is intended to mean that the layer does not spread significantly beyond the area where it is deposited.
  • surface energy is the energy required to create a unit area of a surface from a material. A characteristic of surface energy is that liquid materials with a given surface energy will not wet surfaces with a lower surface energy.
  • the chemical containment layer comprises deuterated material.
  • the chemical containment material is at least 10% deuterated; in some embodiments, at least 20% deuterated; in some embodiments, at least 30% deuterated; in some embodiments, at least 40% deuterated; in some embodiments, at least 50% deuterated; in some embodiments, at least 60% deuterated; in some embodiments, at least 70% deuterated; in some embodiments, at least 80% deuterated; in some embodiments, at least 90% deuterated; in some embodiments, 100% deuterated.
  • the chemical containment layer is applied over the hole injection layer and contains both the hole transport layer and the electroluminescent layer. In some embodiments, the chemical containment layer is applied over the hole transport layer and contains the electroluminescent layer. For devices made starting from the cathode side, the chemical containment layer can be applied over the electron injection layer or the electron transport layer. In some embodiments, the chemical containment layer is formed on a first layer using a priming layer, where the priming layer has a surface energy that is significantly different than the surface energy of the first layer. The priming layer is applied overall on the first layer. The priming layer is then exposed to radiation in a pattern to form exposed areas and unexposed areas.
  • the priming layer is then developed to effectively remove the priming layer from either the exposed areas or the unexposed areas.
  • the result is a patterned priming layer on the first layer.
  • the patterned priming layer is the chemical containment layer.
  • By the terms “effectively remove” and “effective removal” it is meant that the priming layer is essentially completely removed in either the exposed or unexposed areas.
  • the priming layer may also be partially removed in the other areas, so that the remaining pattern of priming layer may be thinner than the original priming layer.
  • the pattern of priming layer has a surface energy that is higher than the surface energy of the first layer.
  • a second layer is formed by liquid deposition over and on the pattern of priming layer on the first layer.
  • the pattern of priming layer has a surface energy that is lower than the surface energy of the first layer.
  • a second layer is formed by liquid deposition over and on the first layer in the areas where the priming layer has been removed. This process and non- deuterated materials have been described in published U.S. patent application US 2007/0205409.
  • One way to determine the relative surface energies is to compare the contact angle of a given liquid on the first organic layer to the contact angle of the same liquid on the priming layer after exposure and development (hereinafter referred to as the "developed priming layer"). The contact angle increases with decreasing surface energy.
  • a variety of manufacturers make equipment capable of measuring contact angles.
  • the surface energy of the first layer is layer than the surface energy of the priming layer.
  • the first layer has a contact angle with anisole of greater than 40 0 C; in some embodiments, greater than 50°; in some embodiments, greater than 60°; in some embodiments, greater than 70°.
  • the developed priming layer has a contact angle with anisole of less than 30°; in some embodiments, less than 20°; in some embodiments, less than 10°.
  • the contact angle with the developed priming layer is at least 20° lower than the contact angle with the first layer; In some embodiments, for a given solvent, the contact angle with the developed priming layer is at least 30° lower than the contact angle with the first layer; In some embodiments, for a given solvent, the contact angle with the developed priming layer is at least 40° lower than the contact angle with the first layer.
  • the priming layer comprises a composition which, when exposed to radiation reacts to form a material that is either more or less removable from the underlying first layer, relative to unexposed priming material. This change must be enough to allow physical differentiation of the exposed and non-exposed areas and development.
  • the priming layer comprises a radiation- hardenable composition.
  • the priming layer when exposed to radiation, can become less soluble or dispersable in a liquid medium, less tacky, less soft, less flowable, less liftable, or less absorbable. Other physical properties may also be affected.
  • the priming layer consists essentially of one or more radiation-sensitive materials. In one embodiment, the priming layer consists essentially of a material which, when exposed to radiation, hardens, or becomes less soluble, swellable, or dispersible in a liquid medium, or becomes less tacky or absorbable. In one embodiment, the priming layer consists essentially of a material having radiation polymerizable groups. Examples of such groups include, but are not limited to olefins, acrylates, methacrylates and vinyl ethers. In one embodiment, the priming material has two or more polymerizable groups which can result in crosslinking.
  • the priming layer consists essentially of at least one reactive material and at least one radiation-sensitive material.
  • the radiation-sensitive material when exposed to radiation, generates an active species that initiates the reaction of the reactive material.
  • radiation-sensitive materials include, but are not limited to, those that generate free radicals, acids, or combinations thereof.
  • the reactive material is polymerizable or crosslinkable. The material polymerization or crosslinking reaction is initiated or catalyzed by the active species.
  • the reactive material is an ethylenically unsaturated compound and the radiation-sensitive material generates free radicals. Ethylenically unsaturated compounds include, but are not limited to, acrylates, methacrylates, vinyl compounds, and combinations thereof.
  • radiation-sensitive materials that generate free radicals
  • radiation-sensitive materials which generate free radicals include, but are not limited to, quinones, benzophenones, benzoin ethers, aryl ketones, peroxides, biimidazoles, benzyl dimethyl ketal, hydroxyl alkyl phenyl acetophone, dialkoxy actophenone, trimethylbenzoyl phosphine oxide derivatives, aminoketones, benzoyl cyclohexanol, methyl thio phenyl morpholino ketones, morpholino phenyl amino ketones, alpha halogennoacetophenones, oxysulfonyl ketones, sulfonyl ketones, oxysulfonyl ketones, sulfonyl ketones, benzoyl oxime esters, thioxanthrones, camphorquinones, ketocoumarins, and Michler's
  • the radiation-sensitive material is generally present in amounts from 0.001 % to 10.0% based on the total weight of the priming layer.
  • the reactive material can undergo polymerization initiated by acid, and the radiation-sensitive material generates acid.
  • reactive materials include, but are not limited to, epoxies.
  • radiation-sensitive materials which generate acid include, but are not limited to, sulfonium and iodonium salts, such as diphenyliodonium hexafluorophosphate.
  • the priming layer comprises a radiation- softenable composition. In this case, when exposed to radiation, the priming layer can become more soluble or dispersable in a liquid medium, more tacky, more soft, more flowable, more liftable, or more absorbable. Other physical properties may also be affected.
  • the priming layer consists essentially of a material which, when exposed to radiation, softens, or becomes more soluble, swellable, or dispersible in a liquid medium, or becomes more tacky or absorbable.
  • the reactive material is a phenolic resin and the radiation-sensitive material is a diazonaphthoquinone.
  • the priming layer consists essentially of at least one polymer which undergoes backbone degradation when exposed to deep UV radiation, having a wavelength in the range of 200-300 nm.
  • polymers undergoing such degradation include, but are not limited to, polyacrylates, polymethacrylates, polyketones, polysulfones, copolymers thereof, and mixtures thereof.
  • Other radiation-sensitive systems that are known in the art can be used as well.
  • the priming layer reacts with the underlying area when exposed to radiation.
  • the exact mechanism of this reaction will depend on the materials used.
  • the priming layer is effectively removed in the unexposed areas by a suitable development treatment.
  • the priming layer is removed only in the unexposed areas.
  • the priming layer is partially removed in the exposed areas as well, leaving a thinner layer in those areas.
  • the priming layer that remains in the exposed areas is less than 5 ⁇ A in thickness.
  • the priming layer that remains in the exposed areas is essentially a monolayer in thickness.
  • the priming material is deuterated. The term "deuterated" is intended to mean that at least one H has been replaced by D.
  • deuterated analog refers to a structural analog of a compound or group in which one or more available hydrogens have been replaced with deuterium.
  • the deuterium is present in at least 100 times the natural abundance level.
  • the priming material is at least 10% deuterated. By this it is meant that at least 10% of the hydrogens have been replaced by deuterium.
  • the priming material is at least 20% deuterated; in some embodiments, at least 30% deuterated; in some embodiments, at least 40% deuterated; in some embodiments, at least 50% deuterated; in some embodiments, at least 60% deuterated; in some embodiments, at least 70% deuterated; in some embodiments, at least 80% deuterated; in some embodiments, at elast 90% deuterated; in some embodiments, 100% deuterated.
  • the priming layer can be applied by any known deposition process. In one embodiment, the priming layer is applied without adding it to a solvent. In one embodiment, the priming layer is applied by vapor deposition. In one embodiment, the priming layer is applied by a condensation process. If the priming layer is applied by condensation from the vapor phase, and the surface layer temperature is too high during vapor condensation, the priming layer can migrate into the pores or free volume of an organic substrate surface. In some embodiments, the organic substrate is maintained at a temperature below the glass transition temperature or the melting temperature of the substrate materials. The temperature can be maintained by any known techniques, such as placing the first layer on a surface which is cooled with flowing liquids or gases.
  • the priming layer is applied to a temporary support prior to the condensation step, to form a uniform coating of priming layer.
  • This can be accomplished by any deposition method, including liquid deposition, vapor deposition, and thermal transfer.
  • the priming layer is deposited on the temporary support by a continuous liquid deposition technique. The choice of liquid medium for depositing the priming layer will depend on the exact nature of the priming layer itself.
  • the material is deposited by spin coating. The coated temporary support is then used as the source for heating to form the vapor for the condensation step.
  • the priming layer can be accomplished utilizing either continuous or batch processes. For instance, in a batch process, one or more devices would be coated simultaneously with the priming layer and then exposed simultaneously to a source of radiation. In a continuous process, devices transported on a belt or other conveyer device would pass a station when they are sequentially coated with priming layer and then continue past a station where they are sequentially exposed to a source of radiation. Portions of the process may be continuous while other portions of the process may be batch.
  • the priming material is a liquid at room temperature and is applied by liquid deposition over the first layer. The liquid priming material may be film-forming or it may be absorbed or adsorbed onto the surface of the first layer.
  • the liquid priming material is cooled to a temperature below its melting point in order to form a second layer over the first layer.
  • the priming material is not a liquid at room temperature and is heated to a temperature above its melting point, deposited on the first layer, and cooled to room temperature to form a second layer over the first layer.
  • the priming layer is deposited from a second liquid composition.
  • the liquid deposition method can be continuous or discontinuous, as described above.
  • the priming liquid composition is deposited using a continuous liquid deposition method. The choice of liquid medium for depositing the priming layer will depend on the exact nature of the priming material itself.
  • the priming layer After the priming layer is formed, it is exposed to radiation.
  • the type of radiation used will depend upon the sensitivity of the priming layer as discussed above.
  • the exposure is patternwise. As used herein, the term "patternwise" indicates that only selected portions of a material or layer are exposed. Patternwise exposure can be achieved using any known imaging technique. In one embodiment, the pattern is achieved by exposing through a mask. In one embodiment, the pattern is achieved by exposing only select portions with a rastered laser. The time of exposure can range from seconds to minutes, depending upon the specific chemistry of the priming layer used. When lasers are used, much shorter exposure times are used for each individual area, depending upon the power of the laser.
  • the exposure step can be carried out in air or in an inert atmosphere, depending upon the sensitivity of the materials.
  • the radiation is selected from the group consisting of ultra-violet radiation (10-390 nm), visible radiation (390-770 nm), infrared radiation (770-10 6 nm), and combinations thereof, including simultaneous and serial treatments.
  • the radiation is selected from visible radiation and ultraviolet radiation.
  • the radiation has a wavelength in the range of 300 to 450 nm.
  • the radiation is deep UV (200-300 nm).
  • the ultraviolet radiation has a wavelength between 300 and 400 nm.
  • the radiation has a wavelength in the range of 400 to 450 nm.
  • the radiation is thermal radiation.
  • the exposure to radiation is carried out by heating.
  • the temperature and duration for the heating step is such that at least one physical property of the priming layer is changed, without damaging any underlying layers of the light-emitting areas.
  • the heating temperature is less than 250 0 C. In one embodiment, the heating temperature is less than 150 0 C.
  • the priming layer is developed. Development can be accomplished by any known technique. Such techniques have been used extensively in the photoresist and printing art. Examples of development techniques include, but are not limited to, application of heat (evaporation), treatment with a liquid medium (washing), treatment with an absorbant material (blotting), treatment with a tacky material, and the like.
  • the development step results in effective removal of the priming layer in either the exposed or unexposed areas.
  • the priming layer then remains in either the unexposed or exposed areas, respectively.
  • the priming layer may also be partially removed in the unexposed or exposed areas, but enough must remain in order for there to be a wettability difference between the exposed and unexposed areas.
  • the priming layer may be effectively removed in the unexposed areas and a part of the thickness removed in the exposed areas.
  • the development step results in effective removal of the priming layer in the unexposed areas.
  • the exposure of the priming layer to radiation results in a change in the solubility or dispersibility of the priming layer in solvents.
  • development can be accomplished by a wet development treatment. The treatment usually involves washing with a solvent which dissolves, disperses or lifts off one type of area.
  • the patternwise exposure to radiation results in
  • the exposure of the priming layer to radiation results in a reaction which changes the volatility of the priming layer in exposed areas.
  • development can be accomplished by a thermal development treatment.
  • the treatment involves heating to a temperature above the volatilization or sublimation temperature of the more volatile material and below the temperature at which the material is thermally reactive.
  • the material would be heated at a temperature above the sublimation temperature and below the thermal polymerization temperature.
  • priming materials which have a temperature of thermal reactivity that is close to or below the volatilization temperature, may not be able to be developed in this manner.
  • the exposure of the priming layer to radiation results in a change in the temperature at which the material melts, softens or flows.
  • development can be accomplished by a dry development treatment.
  • a dry development treatment can include contacting an outermost surface of the element with an absorbent surface to absorb or wick away the softer portions. This dry development can be carried out at an elevated temperature, so long as it does not further affect the properties of the remaining areas.
  • the development step results in areas of priming layer that remain and areas in which the underlying first layer is uncovered.
  • the priming layer comprises a hole transport material.
  • the priming layer comprises a material selected from the group consisting of triarylamines, carbazoles, fluorenes, polymers thereof, copolymers thereof, deuterated analogs thereof, and combinations thereof.
  • the priming layer comprises a material selected from the group consisting of polymeric triarylamines, polycarbazoles, polyfluorenes, polymeric triarylamines having conjugated moieties which are connected in a non-planar configuration, copolymers of fluorene and triarylamine, deuterated analogs thereof, and combinations thereof.
  • the polymeric materials are crosslinkable.
  • the priming layer comprises an electron transport material. In some embodiments, the priming layer comprises a metal chelated oxinoid compound. In some embodiments, the priming layer comprises a metal quinolate derivative. In some embodiments, the priming layer comprises a material selected from the group consisting of tris(8-hydroxyquinolato)aluminum, bis(2-methyl-8-quinolinolato)(p- phenylphenolato) aluminum, tetrakis-(8-hydroxyquinolato)hafnium, and tetrakis-(8-hydroxyquinolato)zirconium. In some embodiments, the priming layer consists essentially of a material selected from the group consisting of polymeric triarylamines, polycarbazoles, polyfluorenes, copolymers thereof, and metal quinolates.
  • the hole injection layer comprises a conductive polymer doped with a fluorinated acid polymer and the priming layer consists essentially of a hole transport material.
  • the hole transport material is a triarylamine polymer.
  • the priming material is selected from the group consisting of polymeric triarylamines having conjugated moieties which are connected in a non-planar configuration, compounds having at least one fluorene moiety and at least two triarylamine moieties, and deuterated analogs thereof.
  • the polymeric triarylamines have Formula I, Formula II, or Formula III, as described above.
  • Some exemplary compounds which can be used as a priming layer include deuterated fluorene, deuterated polyfluorene, deuterated polyvinylcarbazole, Compounds HT1 through HT12, ET3 and ET4.
  • the other layers in the device can be made of any materials that are known to be useful in such layers.
  • the anode 110 is an electrode that is particularly efficient for injecting positive charge carriers. It can be made of, for example, materials containing a metal, mixed metal, alloy, metal oxide or mixed- metal oxide, or it can be a conducting polymer, or mixtures thereof. Suitable metals include the Group 11 metals, the metals in Groups 4-6, and the Group 8-10 transition metals. If the anode is to be light- transmitting, mixed-metal oxides of Groups 12, 13 and 14 metals, such as indium-tin-oxide, are generally used.
  • the anode 110 can also comprise an organic material such as polyaniline as described in “Flexible light- emitting diodes made from soluble conducting polymer,” Nature vol. 357, pp 477-479 (11 June 1992). At least one of the anode and cathode is desirably at least partially transparent to allow the generated light to be observed.
  • organic material such as polyaniline as described in “Flexible light- emitting diodes made from soluble conducting polymer,” Nature vol. 357, pp 477-479 (11 June 1992).
  • At least one of the anode and cathode is desirably at least partially transparent to allow the generated light to be observed.
  • the cathode 160 is an electrode that is particularly efficient for injecting electrons or negative charge carriers.
  • the cathode can be any metal or nonmetal having a lower work function than the anode.
  • Materials for the cathode can be selected from alkali metals of Group 1 (e.g., Li, Cs), the Group 2 (alkaline earth) metals, the Group 12 metals, including the rare earth elements and lanthanides, and the actinides. Materials such as aluminum, indium, calcium, barium, samarium and magnesium, as well as combinations, can be used.
  • Li- or Cs-containing organometallic compounds, LiF, CsF, and Li 2 O can also be deposited between the organic layer and the cathode layer to lower the operating voltage.
  • anode 110 there can be a layer (not shown) between the anode 110 and hole injection layer 120 to control the amount of positive charge injected and/or to provide band-gap matching of the layers, or to function as a protective layer.
  • Layers that are known in the art can be used, such as copper phthalocyanine, silicon oxy-nitride, fluorocarbons, silanes, or an ultra-thin layer of a metal, such as Pt.
  • some or all of anode layer 110, active layers 120, 130, 140, and 150, or cathode layer 160 can be surface-treated to increase charge carrier transport efficiency.
  • the choice of materials for each of the component layers is preferably determined by balancing the positive and negative charges in the emitter layer to provide a device with high electroluminescence efficiency. Any or all of these layer can contain deuterated materials.
  • each functional layer can be made up of more than one layer.
  • the device can be prepared by a variety of techniques, including sequential vapor deposition of the individual layers on a suitable substrate. Substrates such as glass, plastics, and metals can be used. Conventional vapor deposition techniques can be used, such as thermal evaporation, chemical vapor deposition, and the like. Alternatively, the organic layers can be applied from solutions or dispersions in suitable solvents, using conventional coating or printing techniques, including but not limited to spin-coating, dip-coating, roll-to-roll techniques, ink-jet printing, screen- printing, gravure printing and the like.
  • the process for making an organic light- emitting device comprises: providing a substrate having a patterned anode thereon; forming an electroactive layer by depositing a first liquid composition comprising (a) a deuterated a deuterated electroactive material and (b) a liquid medium; and forming a cathode overall.
  • liquid composition is intended to include a liquid medium in which one or more materials are dissolved to form a solution, a liquid medium in which one or more materials are dispersed to form a dispersion, or a liquid medium in which one or more materials are suspended to form a suspension or an emulsion.
  • the deuterated electroactive material is a deuterated hole injection material.
  • the deuterated electroactive material is a deuterated hole transport material. In some embodiments of the above process, the deuterated electroactive material is a deuterated electroluminescent material. In some embodiments of the above process, the deuterated electroactive material is a deuterated host material. In some embodiments of the above process, the deuterated electroactive material is a deuterated electron transport material. In some embodiments of the above process, the deuterated electroactive material is a deuterated chemical containment material.
  • the process further comprises: forming a second electroactive layer by depositing a second liquid composition comprising a second deuterated electroactive material in a second liquid medium.
  • the second deuterated electroactive material is selected from the group consisting of deuterated hole injection material, deuterated hole transport material, deuterated electroluminescent material, deuterated host material, deuterated electron transport material, and deuterated chemical containment material. Any known liquid deposition technique or combination of techniques can be used, including continuous and discontinuous techniques. Examples of continuous liquid deposition techniques include, but are not limited to spin coating, gravure coating, curtain coating, dip coating, slot- die coating, spray coating, and continuous nozzle printing.
  • discontinuous deposition techniques include, but are not limited to, ink jet printing, gravure printing, and screen printing.
  • the electroactive layer is formed in a pattern by a method selected from continuous nozzle coating and ink jet printing.
  • the nozzle printing can be considered a continuous technique, a pattern can be formed by placing the nozzle over only the desired areas for layer formation. For example, patterns of continuous rows can be formed.
  • a suitable liquid medium for a particular composition to be deposited can be readily determined by one skilled in the art.
  • the compounds be dissolved in nonaqueous solvents.
  • non-aqueous solvents can be relatively polar, such as Ci to C20 alcohols, ethers, and acid esters, or can be relatively non-polar such as Ci to Ci 2 alkanes or aromatics such as toluene, xylenes, trifluorotoluene and the like.
  • Another suitable liquid for use in making the liquid composition, either as a solution or dispersion as described herein, comprising the new compound includes, but not limited to, a chlorinated hydrocarbon (such as methylene chloride, chloroform, chlorobenzene), an aromatic hydrocarbon (such as a substituted or non- substituted toluene or xylenes, including trifluorotoluene), a polar solvent (such as tetrahydrofuran (THF), N-methyl pyrrolidone (NMP)), an ester (such as ethylacetate), an alcohol (such as isopropanol), a ketone (such as cyclopentatone), or any mixture thereof.
  • a chlorinated hydrocarbon such as methylene chloride, chloroform, chlorobenzene
  • aromatic hydrocarbon such as a substituted or non- substituted toluene or xylenes, including trifluorotoluene
  • a polar solvent such as
  • the material is dried to form a layer. Any conventional drying technique can be used, including heating, vacuum, and combinations thereof.
  • the device is fabricated by liquid deposition of the hole injection layer, the hole transport layer, and the electroactive layer, and by vapor deposition of the anode, the electron transport layer, an electron injection layer and the cathode.
  • the non-deuterated analogs of the compounds described herein can be prepared by known coupling and substitution reactions.
  • the new deuterated compounds can then be prepared in a similar manner using deuterated precursor materials or, more generally, by treating the non- deuterated compound with deuterated solvent, such as d6-benzene, in the presence of a Lewis acid H/D exchange catalyst, such as aluminum trichloride or ethyl aluminum chloride, or acids such as CF 3 COOD, DCI, etc.
  • a Lewis acid H/D exchange catalyst such as aluminum trichloride or ethyl aluminum chloride, or acids such as CF 3 COOD, DCI, etc.
  • a Lewis acid H/D exchange catalyst such as aluminum trichloride or ethyl aluminum chloride
  • acids such as CF 3 COOD, DCI, etc.
  • the starting materials of the perdeuterated or partially deuterated aromatic compounds or alkyl compounds can be purchased from commercial sources or can be obtained using known methods. Some examples of such methods can be found in a) "Efficient H/D Exchange Reactions of Alkyl-Substituted Benzene Derivatives by Means of the Pd/C-H2-D2O System" Hiroyoshi Esaki, Fumiyo Aoki, Miho Umemura, Masatsugu Kato, Tomohiro Maegawa, Yasunari Monguchi, and Hironao Sajiki Chem. Eur. J. 2007, 13, 4052 - 4063.
  • This example illustrates the preparation of a deuterated hole injection material, D-HIJ-1.
  • TFE tetrafluoroethylene
  • PSEPVE 4-methyl-7-octenesulfonic acid
  • the tray was then cooled to below O 0 C to freeze the water dispersion first. Once freezed, it was subjected to a partial vacuum pressure no higher than 1 mm Hg until most of water was removed. The partially dried solids were then taken up to about 30 0 C under the vacuum pressure to completely remove the moisture without coalescing the polymer. 21 g of the solid flakes of non-deuterated poly(TFE-PSEPVE), pre- dried in a vacuum oven to remove water, were placed in a metal cylindrical tube pre-purged with nitrogen. 15Og D 2 O purchased from Cambridge Isotope Lab, Inc. was immediately added to the poly(TFE-PSEPVE) containing tube.
  • the tube was capped and heated to about 270 0 C in a pressure lab for a short period time before cooled down to RT. to ensure conversion of the solid flakes to poly(TFE-PSEPVE) colloidal dispersion in D 2 O. Moreover, the proton in poly(TFE-PSEPVE) in the overwhelming excess of deuterium has been exchanged with deuterium to complete deuteration of poly(TFE-PSEPVE).
  • the deuterated poly(TFE-PSEPVE) (“D-poly(TFE-PSEPVE)"
  • dispersion in D 2 O was further processed to remove larger particles.
  • the D-poly(TFE-PSEPVE) weight% in the D 2 O dispersion was determined to be 11.34 wt.%, based on the total weight of the dispersion, by a gravimetric method, b. Direct process to form a deutero-HFAP.and a dispersion of the deutero-HFAP in deuterium oxide (D 2 O).
  • a copolymer of tetrafluoroethylene (“TFE”) and perfluoro-3,6-dioxa- 4-methyl-7-octenesulfonic acid (“PSEPVE”) can be deuterated and made into a colloidal dispersion in D 2 O in the following manner.
  • PoIy(TFE- PSEPVE) resin having one proton in sulfonic acid for every 987 gram (weight of the copolymer per one acidic site) can be made into D2O dispersion using a procedure similar to the procedure in US Patent 6,150,426, Example 1 , Part 2, except that the temperature is approximately 270°C and D 2 O is used instead of water.
  • Preparation of a deuterated electrically conductive polymer doped with a deuterated HFAP Preparation of a deuterated electrically conductive polymer doped with a deuterated HFAP.
  • Deuterated pyrrole, (“D 5 -Py”) (Formula wt.: 72.12) was purchased from Aldrich Chemical Company (Milwaukee, Wl). This brown-colored liquid was fractionally distilled under reduced pressure prior to use. The colorless distillate was characterized by 13 C NMR spectroscopy to confirm the structure.
  • D-poly(TFE-PSEPVE)/D 2 O dispersion Polymerization of D 5 -Py in D-poly(TFE-PSEPVE)/D 2 O dispersion was carried out in the following manner. 70.2g of the D-poly(TFE- PSEPVE)/D 2 O prepared in Example 1 was weighed in to a 50OmL resin kettle first before added additional 14g D 2 O. The amount of D-poly(TFE- PSEPVE)/D 2 O represents 8.14mmol of acid. The kettle was capped with a glass lid having an overhead stirrer.
  • poly(D 5 -Py)/D- poly(TFE-PSEPVE) was treated with ion-exchanged resin again to further purify the dispersion in which it only contained 1.79ppm of sulfate, and 0.79ppm of chloride. Solid% of the dispersion was determined to be 4.3% and pH was determined to be 5.2. Electrical conductivity of cast film baked at 275 0 C in a dry box for 30 minutes was measured to be ⁇ 1x10 ⁇ 6 S/cm at room temperature.
  • the compound is made according to the scheme below.
  • Compound Y2 can be made from Compound Y1 using a procedure analogous to the preparation of intermediate Compound C1 above. Compound Y2 is purified using chromatography.
  • Step 1 Preparation of deuterated 4-bromobiphenyl.
  • a solution of 4-bromobiphenyl (4.66 g, 20.0 mmol) in C6D6 (20 ml_) was purged with nitrogen for 30 min.
  • a 1.0 M solution of ethyl aluminum dichloride solution in hexanes (4.0 ml_, 4.0 mmol) was added dropwise via syringe and the reaction mixture was heated at reflux for 50 min under nitrogen atmosphere.
  • deuterium oxide (20 ml_) is added, the mixture is shaken, and the layers are separated. The organic phase is dried over magnesium sulfate, filtered and concentrated by rotary evaporation.
  • a 3-neck round bottom flask equipped with a magnetic stirrer, thermometer and reflux condenser topped with a gas inlet adaptor in the closed position was charged with Y5 (986 mg, 0.92 mmol), Y6 (1.30 g, 3.55 mmol), tris(dibenzylideneacetone)dipalladium(0) (124 mg, 14.8 mol %), bis(diphenylphosphinoferrocene) (151 mg, 29.6 mol %) and toluene (20 ml_) through the open neck.
  • the mixture was diluted with 500 ml_ THF and filtered through a plug of silica and celite and the volatiles were removed from the filtrate under reduced pressure.
  • the yellow oil was purified by flash column chromatography on silica gel using hexanes as eluent.
  • the product was obtained as a white solid in 80.0 % (19.8 g). Analysis by NMR indicated the material to be compound 2 having structure given above.
  • 2,2'-Dipyridyl (0.195 g, 1.252 mmol) and 1 ,5-cyclooctadiene (0.135 g, 1.252 mmol) were weighed into a scintillation vial and dissolved in 3.79 g N 1 N'- dimethylformamide.
  • the solution was added to the Schlenk tube.
  • the Schlenk tube was inserted into an aluminum block and the block was heated and stirred on a hotplate/stirrer at a setpoint that resulted in an internal temperature of 60 0 C.
  • the catalyst system was held at 60 0 C for 45 minutes and then raised to 65 °C.
  • the monomer solution in toluene was added to the Schlenk tube and the tube was sealed.
  • Synthesis Example 4 This example illustrates the preparation of a deuterated electroluminescent material, E4 shown below.
  • This example illustrates the preparation of a deuterated host compound, H14.
  • This compound can be prepared according to the following scheme:
  • anthracen-9-yl trifluoromethanesulfonate (6.0 g, 18.40 mmol)
  • Napthalen-2-yl-boronic acid (3.78 g 22.1 mmol)
  • potassium phosphate tribasic (17.5Og, 82.0 mmol)
  • palladium(ll) acetate (0.41 g, 1.8 mmol)
  • tricyclohexylphosphine 0.52 g, 1.8 mmol
  • THF 100 ml_
  • reaction mixture was purged with nitrogen and degassed water (50 ml_) was added by syringe. A condenser was then added and the reaction was refluxed overnight. The reaction was monitored by TLC. Upon completion the reaction mixture was cooled to room temperature. The organic layer was separated and the aqueous layer was extracted with DCM. The organic fractions were combined, washed with brine and dried with magnesium sulfate. The solvent was removed under reduced pressure. The resulting solid was washed with acetone and hexane and filtered. Purification by column chromatography on silica gel afforded 4.03 g (72%) of product as pale yellow crystalline material. Synthesis of compound 4:
  • the product was further purified as described in published U.S. patent application 2008-0138655, to achieve an HPLC purity of at least 99.9% and an impurity absorbance no greater than 0.01.
  • the deuterated host compound H14 was made from comparative Compound A.
  • the product was further purified as described in published U.S. patent application 2008-0138655, to achieve an HPLC purity of at least 99.9% and an impurity absorbance no greater than 0.01.
  • the material was determined to have the same level of purity as comparative compound A, from above.
  • HIJ-A and HIJ-B are aqueous dispersions of an electrically conductive polymer and a polymeric fluorinated sulfonic acid. Such materials have been described in, for example, published U.S. patent applications US 2004/0102577, US 2004/0127637, US 2005/0205860, and published PCT application WO 2009/018009.
  • Polymer PoI-A is a non-crosslinked arylamine polymer (20 nm)
  • ELM-A and ELM-B are electroluminescent bis(diarylamino)chrysene compounds having blue emission
  • Host A is a diarylanthracene compound
  • ET-A is a metal quinolate derivative (10 nm)
  • the hole injection layer was D 5 -PPy/D- poly(TFE- PSEPVE) from Synthesis Example 1.
  • Device Example 2 deuterated material was present in the hole transport layer.
  • the hole transport layer was HT5 from Synthesis Example 2.
  • Device Example 3 deuterated material was present in the electroluminescent layer.
  • the electroluminescent material was E4 from Synthesis Example 4.
  • the anode was indium tin oxide (ITO), the electron injection layer was CsF, and the cathode was Al (100nm).
  • the anode had a thickness of 50nm; in Example 3, the anode thickness was 180nm.
  • the electron injection layer had a thickness of 1 nm; in Example 5 the electron injection thickness was 0.7nm.
  • Table 1 The materials and the thicknesses for the other layers are summarized in Table 1 below.
  • HIL hole injection layer
  • HTL hole transport layer
  • EML electroluminescent layer
  • ETL electron transport layer
  • Ratio hostdopant by weight
  • OLED devices were fabricated by a combination of solution processing and thermal evaporation techniques.
  • Patterned indium tin oxide (ITO) coated glass substrates from Thin Film Devices, lnc were used. These ITO substrates are based on Corning 1737 glass coated with ITO having a sheet resistance of 30 ohms/square and 80% light transmission.
  • the patterned ITO substrates were cleaned ultrasonically in aqueous detergent solution and rinsed with distilled water.
  • the patterned ITO was subsequently cleaned ultrasonically in acetone, rinsed with isopropanol, and dried in a stream of nitrogen.
  • the cleaned, patterned ITO substrates were treated with UV ozone for 10 minutes.
  • an aqueous dispersion of the hole injection material was spin- coated over the ITO surface and heated to remove solvent.
  • the substrates were then spin-coated with a solution of the hole transport material, and then heated to remove solvent.
  • the substrates were spin-coated with the electroluminescent layer solution, and heated to remove solvent.
  • the substrates were masked and placed in a vacuum chamber.
  • the electron transport layer was deposited by thermal evaporation, followed by a layer of CsF as the electron injection layer.
  • Masks were then changed in vacuo and a layer of Al was deposited by thermal evaporation to form the cathode.
  • the chamber was vented, and the devices were encapsulated using a glass lid, dessicant, and UV curable epoxy.
  • the OLED samples were characterized by measuring their (1 ) current-voltage (I-V) curves, (2) electroluminescence radiance versus voltage, and (3) electroluminescence spectra versus voltage. All three measurements were performed at the same time and controlled by a computer.
  • the current efficiency of the device at a certain voltage is determined by dividing the electroluminescence radiance of the LED by the current needed to run the device. The unit is a cd/A.
  • the power efficiency is the current efficiency multiplied by pi, divided by the operating voltage.
  • the unit is Im/W.
  • T70 is the time in hours for a device to reach 70% of the initial luminance at the lifetest luminance given. Calculated T70 is the projected time to reach 70% of the initial luminance at 1000 nits using an acceleration factor of 1.7.
  • the time to reach 70% luminance was determined, rather than the half-life.
  • the calculated half-life will be even greater than the calculated time to reach 70% luminance.
  • the half- life at 1000 nits is clearly greater than 10,000 hours
  • Example 7 This example illustrates an electronic device having a deuterated priming layer formed by liquid deposition, where the hole transport layer and electroluminescent layer are also formed by liquid deposition.
  • ELM-B (40 nm)
  • electron transport layer ET-A (10 nm)
  • cathode CsF/AI (1/100 nm)
  • OLED devices were fabricated by a combination of solution processing and thermal evaporation techniques.
  • the ITO substrate is based on Corning 1737 glass coated with ITO having a sheet resistance of 30 ohms/square and 80% light transmission.
  • the patterned ITO substrate was cleaned ultrasonically in aqueous detergent solution and rinsed with distilled water.
  • the patterned ITO was subsequently cleaned ultrasonically in acetone, rinsed with isopropanol, and dried in a stream of nitrogen.
  • patterned ITO substrate was treated with UV ozone for 10 minutes.
  • an aqueous dispersion of HIJ-B was spin-coated over the ITO surface and heated to remove solvent.
  • a priming layer was formed by spin coating a toluene solution of HT11 onto the hole injection layer.
  • the priming layer was imagewise exposed at 248 nm with a dosage of 100 mJ/cm 2 .
  • the priming layer was developed by spraying with anisole while spinning at 2000 rpm for 60s and then dried by spinning for 30s.
  • the substrates were then spin-coated with a solution of a hole transport material, and then heated to remove solvent.
  • the electroluminescent layer was deposited by spin coating from a methyl benzoate solution, and then heated to remove solvent. After cooling, the substrates were masked and placed in a vacuum chamber. The electron transport material was then deposited by thermal evaporation, followed by a layer of CsF. Masks were then changed in vacuo and a layer of Al was deposited by thermal evaporation. The chamber was vented, and the devices were encapsulated using a glass lid, dessicant, and UV curable epoxy.
  • the OLED sample was characterized as described above.
  • Example 8 This example illustrates an electronic device having an electroluminescent layer containing a deuterated host and a deuterated electroluminescent dopant.
  • the devices with at least one layer containing deuterated material had a calculated half-life of greater than 5000 hours.
  • the calculated half-life is greater than 50,000 hours.

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