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  • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
  • C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
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  • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
  • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
• • H—ELECTRICITY
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  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B33/00—Electroluminescent light sources
  • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
  • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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  • H05B33/00—Electroluminescent light sources
  • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
  • H05B33/20—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the material in which the electroluminescent material is embedded
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  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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  • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
  • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2603/00—Systems containing at least three condensed rings
  • C07C2603/02—Ortho- or ortho- and peri-condensed systems
  • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
  • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
  • C07C2603/24—Anthracenes; Hydrogenated anthracenes
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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2603/00—Systems containing at least three condensed rings
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  • C07C2603/40—Ortho- or ortho- and peri-condensed systems containing four condensed rings
  • C07C2603/42—Ortho- or ortho- and peri-condensed systems containing four condensed rings containing only six-membered rings
  • C07C2603/48—Chrysenes; Hydrogenated chrysenes
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  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1003—Carbocyclic compounds
  • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
• • 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
  • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene

Definitions

• This invention relates to electroactive compounds which are at least partially deuterated. It also relates to electronic devices in which at least one active layer includes such a compound. Description of the Related Art
• 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.
• organic electroluminescent compounds As the active component in light-emitting diodes. Simple organic molecules such as anthracene, thiadiazole derivatives, and coumahn 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. However, there is a continuing need for electroluminescent compounds. SUMMARY
• an electronic device comprising an active layer comprising the above compound.
• R 1 is the same or different at each occurrence and is selected from the group consisting of D, alkyl, alkoxy and aryl, where adjacent
• R 1 groups may be joined together to form a 5- or 6-membered aliphatic ring
• Ar 1 through Ar 4 are the same or different and are selected from the group consisting of aryl groups; a is the same or different at each occurrence and is an integer from
• an electronic device comprising an active layer comprising a compound of Formula I or Formula II.
• FIG. 1 includes an illustration of one example of an organic electronic device.
• 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 and deuterated alkyls. The term is intended to include substituted and unsubstituted groups.
• 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.
• 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 to include heteroaryls and deuterated aryls.
• 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 of the available H atoms which is 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. Any suitable ring position of the aryl moiety may be covalently linked to the defined chemical structure.
• a hydrocarbon aryl group has from 3-60 carbon atoms; in some embodiments, 6 to 30 carbon atoms.
• Heteroaryl groups may have from 3- 50 carbon atoms; in some embodiments, 3-30 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.
• charge transport when referring to a layer, material, member, or structure is intended to mean such layer, material, member, or structure facilitates migration of such charge through the thickness of such layer, material, member, or structure with relative efficiency and small loss of charge.
• Hole transport materials facilitate positive charge; electron transport material facilitate negative charge.
• light-emitting materials may also have some charge transport properties, the terms "charge, hole, or electron transport layer, material, member, or structure” are not intended to include a layer, material, member, or structure whose primary function is light emission.
• the term "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.
• the phrase "adjacent to,” when used to refer to layers in a device, does not necessarily mean that one layer is immediately next to another layer.
• the phrase “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).
• deuterated is intended to mean that at least one available H has been replaced by D.
• a compound or group that is X% deuterated has X% of the available H replaced by D.
• a compound or group which is deuterated is one in which deuterium is present in at least 100 times the natural abundance level.
• active refers to a layer or a material
• active 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, or 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, planarization materials, insulating materials, and environmental barrier materials.
• hetero indicates that one or more carbon atoms have been replaced with a different atom.
• the different atom is N, O, or S.
• 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.
• oxyalkyl is intended to mean a heteroalkyl group having one or more carbons replaced with oxygens. The term includes groups which are linked via an oxygen.
• silyl refers to the group R 3 Si-, where R is H, D , C1 -20 alkyl, fluoroalkyl, or aryl. In some embodiments, one or more carbons in an R alkyl group are replaced with Si. In some embodiments, the silyl groups are ⁇ eXyI) 2 Si(Me)CH 2 CH 2 Si(Me) 2 - and [CF 3 (CF 2 ) 6 CH 2 CH 2 ] 2 SiMe- .
• siloxane refers to the group (RO) 3 Si-, where R is H, D , C1-20 alkyl, or fluoroalkyl.
• substituents can be substituted or unsubstituted unless otherwise indicated.
• the substituents are selected from the group consisting of D, halide, alkyl, alkoxy, aryl, and cyano.
• An optionally substituted group such as, but not limited to, alkyl or aryl, may be substituted with one or more substituents which may be the same or different.
• Each R' and R" is independently an optionally substituted alkyl, cycloalkyl, or aryl group.
• R' and R together with the nitrogen atom to which they are bound, can form a ring system in certain embodiments.
• Substituents may also be crosslinking groups.
• the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
• the compound described herein is a bis(diarylamino)anthracene or a bis(diarylamino)chrysene having at least one D.
• 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.
• the electroactive compound has Formula I or Formula II:
• R 1 is the same or different at each occurrence and is selected from the group consisting of D, alkyl, alkoxy and aryl, where adjacent
• R 1 groups may be joined together to form a 5- or 6-membered aliphatic ring;
• Ar 1 through Ar 4 are the same or different and are selected from the group consisting of aryl groups;
• a is the same or different at each occurrence and is an integer from
• the compounds are capable of red, green or blue emission.
• the deuteration is on a substituent group on an aryl ring.
• the aryl group having a deuterated substituent group can be can be the core anthracene group of Formula I or the core chrysene group of Formula II; 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 1 through Ar 4 .
• at least one of Ar 1 through Ar 4 is a deuterated aryl group.
• Ar 1 through Ar 4 are at least 10% deuterated. By this it is meant that at least 10% of all the available H bonded to aryl C in Ar 1 through Ar 4 are replaced with D.
• each aryl ring will have some D. In some embodiments, some, and not all of the aryl rings have D.
• Ar 1 through Ar 4 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 and the aryl groups.
• the compound of Formulae I and Il 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.
• both a 0. In some embodiments of Formula I, at least one a is greater than 0. In some embodiments, at least one R 1 is a hydrocarbon alkyl. In some embodiments, R 1 is a deuterated alkyl. In some embodiments, R 1 is selected from a branched hydrocarbon alkyl and a cyclic hydrocarbon alkyl.
• the bond to (R 1 ) a is intended to indicate that the R 1 group can be at any site on the two fused rings.
• both b 0.
• At least one b is greater than 0.
• at least one R 1 is a hydrocarbon alkyl.
• R 1 is selected from a branched hydrocarbon alkyl and a cyclic hydrocarbon alkyl.
• At least one of Ar 1 through Ar 4 has Formula
• R is the same or different at each occurrence and is selected from the group consisting of D, alkyl, alkoxy, aryl, silyl, and siloxane, or adjacent R 2 groups can be joined to form an aromatic ring; c is the same or different at each occurrence and is an integer from 0-4; d is the same or different at each occurrence and is an integer from 0-5; and m is the same or different at each occurrence and is an integer from O to 6.
• At least one of Ar 1 through Ar 4 has Formula
• R 2 is the same or different at each occurrence and is selected from the group consisting of D, alkyl, alkoxy, and aryl, or adjacent R 2 groups can be joined to form an aromatic ring; c is the same or different at each occurrence and is an integer from
• Ar 1 through Ar 4 is selected from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, phenylnapthyl, naphthylphenyl, and binaphthyl.
• Ar 1 through Ar 4 are perdeuterated. In some embodiments, Ar 1 through Ar 4 are perdeuterated, except for one alkyl group on a terminal aryl.
• the compounds are symmetrical with respect to the diarylamino groups.
• Ar 1 Ar 3
• Ar 2 Ar 4 .
• the compounds are non-symmetrical with respect to the diarylamino groups.
• Ar 1 is different from both Ar 3 and Ar 4 .
• Ar 2 is also different from both Ar 3 and Ar 4 .
• Some non-limiting examples of compounds having Formula I include Compounds E1 and E2 below:
• the non-deuterated analog compounds can be made using any technique that will yield a C-C or C-N bond.
• a variety of such techniques are known, such as Suzuki, Yamamoto, Stille, and Pd- or Ni-catalyzed C-N couplings.
• the new deuterated compound 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. Exemplary preparations are given in the Examples.
• the level of deuteration can be determined by NMR analysis and by mass spectrometry, such as Atmospheric Solids Analysis Probe Mass Spectrometry (ASAP-MS).
• SEP-MS Atmospheric Solids Analysis Probe Mass Spectrometry
• the compounds described herein can be formed into films using liquid deposition techniques. Surprisingly and unexpectedly, these compounds have greatly improved properties when compared to analogous non-deuterated compounds. Electronic devices including an active layer with the compounds described herein, have greatly improved lifetimes. In addition, the lifetime increases are achieved in combination with high quantum efficiency and good color saturation. Furthermore, the deuterated compounds described herein have greater air tolerance than the non-deuterated analogs. This can result in greater processing tolerance both for the preparation and purification of the materials and in the formation of electronic devices using the materials.
• the new deuterated compounds described herein have utility as hole transport materials, as electroluminescent materials, and as hosts for elecgtroluminescent materials.
• Organic electronic devices that may benefit from having one or more layers comprising the electroluminescent materials described herein include, but are not limited to, (1 ) devices that convert electrical energy into radiation (e.g., a light-emitting diode, light emitting diode display, or diode laser), (2) devices that detect signals through electronics processes (e.g., photodetectors, photoconductive cells, photoresistors, photoswitches, phototransistors, phototubes, IR detectors), (3) devices that convert radiation into electrical energy, (e.g., a photovoltaic device or solar cell), and (4) devices that include one or more electronic components that include one or more organic semi-conductor layers (e.g., a transistor or diode).
• (1 ) devices that convert electrical energy into radiation e.g., a light-emitting diode, light emitting diode display, or diode laser
• devices that detect signals through electronics processes e.g., photodetectors, photoconductive cells, photoresistors,
• 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 electroactive layer 140 between them.
• Adjacent to the anode is a buffer layer 120.
• Adjacent to the buffer layer is 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.
• Layers 120 through 150 are individually and collectively referred to as the active layers.
• the different layers have the following range of thicknesses: anode 110, 500-5000 A, in one embodiment 1000-2000 A; buffer 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 electroactive layer 140 can be a light-emitting layer that is activated by an applied voltage (such as in a light-emitting diode or light-emitting electrochemical cell), or a layer of material that responds to radiant energy and generates a signal with or without an applied bias voltage (such as in a photodetector).
• photodetectors include photoconductive cells, photoresistors, photoswitches, phototransistors, and phototubes, and photovoltaic cells, as these terms are described in Markus, John, Electronics and Nucleonics Dictionary, 470 and 476 (McGraw-Hill, Inc. 1966).
• the new deuterated compounds are useful as hole transport materials in layer 130.
• at least one additional layer includes a deuterated material.
• the additional layer is the buffer layer 120.
• the additional layer is the electroactive layer 140.
• the additional layer is the electron transport layer 150.
• the new deuterated compounds are useful as host materials for electroactive materials in electroactive layer 140.
• the emissive material is also deuterated.
• at least one additional layer includes a deuterated material.
• the additional layer is the buffer layer 120.
• the additional layer is the hole transport layer 130.
• the additional layer is the electron transport layer 150.
• the new deuterated compounds are useful as electroactive materials in electroactive layer 140.
• a host is also present in the electroactive layer.
• the host material is also deuterated.
• at least one additional layer includes a deuterated material.
• the additional layer is the buffer layer 120.
• the additional layer is the hole transport layer 130.
• the additional layer is the electron transport layer 150
• the new deuterated compounds are useful as electron transport materials in layer 150.
• at least one additional layer includes a deuterated material.
• the additional layer is the buffer 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 buffer layer, the hole transport layer, the electroactive layer, and the electron transport layer.
• the devices have additional layers to aid in processing or to improve functionality. Any or all of these layers can include deuterated materials. In some embodiments, all the organic device layers comprise deuterated materials. In some embodiments, all the organic device layers consist essentially of deuterated materials. a. Electroactive layer The new deuterated compounds described herein are useful as electroactive materials in layer 140. The compounds can be used alone, or in combination with a host material.
• the electroactive layer consists essentially of a host material and the new deuterated compound decribed herein.
• the host is a bis-condensed cyclic aromatic compound.
• the host is an anthracene derivative compound.
• the compound has the formula: An - L- An where:
• An is an anthracene moiety; L is a divalent connecting group. In some embodiments of this formula, L is a single bond, -O-, -S-, - N(R)-, or an aromatic group. In some embodiments, An is a mono- or diphenylanthryl moiety.
• the host has the formula: A - An - A where:
• A is the same or different at each occurrence and is an aromatic group.
• the A groups are attached at the 9- and 10- positions of the anthracene moiety.
• A is selected from the group consisting naphthyl, naphthylphenylene, and naphthylnaphthylene.
• the compound is symmetrical and in some embodiments the compound is non-symmetrical.
• the host has the formula:
• At least one of A 1 and A 2 is a naphthyl group. In some embodiments, additional substituents are present.
• the host is selected from the group consisting of H1
• the electroactive layer consists essentially of the new deuterated material and one or more electroactive materials.
• 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.
• the buffer layer 120 comprises buffer 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.
• Buffer materials may be polymers, oligomers, or small molecules. They may be vapour deposited or deposited from liquids which may be in the form of solutions, dispersions, suspensions, emulsions, colloidal mixtures, or other compositions.
• the buffer layer can be formed with polymeric materials, such as polyaniline (PANI) or polyethylenedioxythiophene (PEDOT), which are often doped with protonic acids.
• the protonic acids can be, for example, poly(styrenesulfonic acid), poly(2-acrylamido-2-methyl-1 -propanesulfonic acid), and the like.
• the buffer layer can comprise charge transfer compounds, and the like, such as copper phthalocyanine and the tetrathiafulvalene- tetracyanoquinodimethane system (TTF-TCNQ).
• TTF-TCNQ tetrathiafulvalene- tetracyanoquinodimethane system
• the buffer layer comprises at least one electrically conductive polymer and at least one fluohnated acid polymer.
• Such materials have been described in, for example, published U.S. patent applications 2004-0102577, 2004-0127637, and 2005/205860
• the new deuterated compounds described herein have utility as hole transport materials.
• hole transporting molecules are: 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- phenyl
• hole transporting polymers are polyvinylcarbazole, (phenylmethyl)- polysilane, and polyaniline. It is also possible to obtain hole transporting polymers by doping hole transporting molecules such as those mentioned above into polymers such as polystyrene and polycarbonate. In some cases, triarylamine polymers are used, especially tharylamine-fluorene copolymers. In some cases, the polymers and copolymers are crosslinkable. Examples 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 layer is doped with a p-dopant, such as tetrafluorotetracyanoquinodimethane and perylene-3,4,9,10- tetracarboxylic-3,4,9,10-dianhydride.
• a p-dopant such as tetrafluorotetracyanoquinodimethane and perylene-3,4,9,10- tetracarboxylic-3,4,9,10-dianhydride.
• the new deuterated compounds described herein have utility as electron transport materials.
• electron transport materials which can be used in layer 150 include metal chelated oxinoid compounds, such as tris(8-hydroxyquinolato)aluminum (Alq3); bis(2-methyl-8-quinolinolato)(para-phenyl-phenolato)aluminum(lll)
• BAIQ 2-(4-biphenylyl)-5-(4-t-butylphenyl)- 1 ,3,4-oxadiazole (PBD) and 3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)- 1 ,2,4-triazole (TAZ), and 1 ,3,5-th(phenyl-2-benzimidazole)benzene (TPBI); quinoxaline derivatives such as 2,3-bis(4-fluorophenyl)quinoxaline; phenanthroline derivatives such as 9,10-diphenylphenanthroline (DPA) and 2,9-dimethyl-4,7-diphenyl-1 ,10-phenanthroline (DDPA); and mixtures thereof.
• DPA 9,10-diphenylphenanthroline
• DDPA 2,9-dimethyl-4,7-diphenyl-1 ,10-phenanthroline
• the electron-transport layer may also be doped with n-dopants, such as Cs or other alkali metals.
• Layer 150 can function both to facilitate electron transport, and also serve as a buffer layer or confinement layer to prevent quenching of the exciton at layer interfaces. Preferably, this layer promotes electron mobility and reduces exciton quenching.
• 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 buffer 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.
• 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 HOMO (highest occupied molecular orbital) of the hole transport material desirably aligns with the work function of the anode
• the LUMO (lowest un-occupied molecular orbital) of the electron transport material desirably aligns with the work function of the cathode.
• Chemical compatibility and sublimation temperature of the materials are also important considerations in selecting the electron and hole transport materials.
• the efficiency of devices made with the chrysene compounds described herein can be further improved by optimizing the other layers in the device.
• more efficient cathodes such as Ca, Ba or LiF can be used.
• Shaped substrates and novel hole transport materials that result in a reduction in operating voltage or increase quantum efficiency are also applicable.
• Additional layers can also be added to tailor the energy levels of the various layers and facilitate electroluminescence.
• the compounds of the invention often are fluorescent and photoluminescent and can be useful in applications other than OLEDs, such as oxygen sensitive indicators and as fluorescent indicators in bioassays.
• This example illustrates the preparation of a non-deuterated electroluminescent material, Comparative Compound A.
• the aldehyde solution was added to the reaction mixture dropwise over 45 minutes. Reaction was left to stir at room temperature for 24 hours (orange color went away). Silica gel was added to the reaction mixture and volatiles were removed under reduced pressure. The crude product was purified by column chromatography on silica gel using 5-10 % dichloromethane in hexanes. The product was isolated as a mixture of cis- and trans-isomers (6.3 g, 89 %) and used without separation. The structure was confirmed by 1 H NMR.
• 1-(4-te/f-Butylstyryl)naphthalenes (4.0 g, 14.0 mmol) were dissolved in dry toluene (1 I) in a one-liter photochemical vessel, equipped with nitrogen inlet and a stirbar.
• a bottle of dry propylene oxide was cooled in ice-water before 100 ml of the epoxide was withdrawn with a syringe and added to the reaction mixture.
• Iodine (3.61 g, 14.2 mmol) was added last.
• Condenser was attached on top of the photochemical vessel and halogen lamp (Hanovia, 450W) was turned on.
• reaction mixture was added to the reaction mixture, stirred for 10 minutes and followed by sodium te/t-butoxide (0.35 g, 3.62 mmol) and 5 ml of dry toluene. After another 10 minutes, the reaction flask was brought out of the drybox, attached to a nitrogen line and stirred at 110 0 C overnight. Next day, reaction mixture was cooled to room temperature and filtered through a two-inch plug of silica gel and Celite, washing with 500 ml of dichloromethane. Removal of volatiles under reduced pressure gave a dark brown oil. The crude product was further purified by flash chromatography on silica gel using lsolera purification system from Biotage. The resulting solid was washed with methanol and then recrystallized from hot hexane to yield 0.26 g (25 %) of the product. The structure was confirmed by 1 H NMR.
• Comparative Example B This example illustrates the preparation of a non-deuterated electroluminescent material, Comparative Compound B
• This example illustrates the preparation of a compound having Formula I, Compound E1.
• This compound was prepared from 9,10-dibromo-2,6di-te/f- butylanthracene and di(perdeuterophenyl)amine using the procedure described above for Comparative Compound B. Yield 0.55 g.
• the structure of Compound E1 was confirmed by 1 H NMR.
• ITO Indium Tin Oxide
• buffer layer Buffer 1 (50 nm)
• hole transport layer polymer P1 (20 nm)
• electroactive layer 13:1 host H1 :dopant (40 nm)
• electron transport layer a metal quinolate derivative (10 nm)
• cathode CsF/AI (0.7/100 nm)
• 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. Immediately before device fabrication the cleaned, patterned ITO substrates were treated with UV ozone for 10 minutes.
• an aqueous dispersion of Buffer 1 was spin-coated over the ITO surface and heated to remove solvent.
• the substrates were then spin-coated with a solution of a hole transport material, and then heated to remove solvent.
• the substrates were spin-coated with the emissive 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. 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 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 density needed to run the device.
• the unit is a cd/A.
• the power efficiency is the current efficiency divided by the operating voltage.
• the unit is Im/W.
• Table 1 The current efficiency of the device at a certain voltage is determined by dividing the electroluminescence radiance of the LED by the current density needed to run the device.
• the unit is a cd/A.
• the power efficiency is the current efficiency divided by the operating voltage.
• the unit is Im/W.
• Table 1 The device data is given in Table 1.
• CE current efficiency
• CIEx and CIEy are the x and y color coordinates according to the C. I. E. chromaticity scale (Commission Internationale de L'Eclairage, 1931 ).
• Lum. ⁇ A Life is defined as the time in hours for a device to reach one- half the initial luminance.
• OLED devices were fabricated as described above for Example 3.
• the device data (average of three devices) is given in Table 2.
• the relative lifetime of devices made with the anthracene dopants having Formula I are significantly better than devices made with the anthracene dopant comparative Compound B.

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