WO2015089028A1 - Compositions photoactives pour applications électroniques - Google Patents

Compositions photoactives pour applications électroniques Download PDF

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WO2015089028A1
WO2015089028A1 PCT/US2014/069276 US2014069276W WO2015089028A1 WO 2015089028 A1 WO2015089028 A1 WO 2015089028A1 US 2014069276 W US2014069276 W US 2014069276W WO 2015089028 A1 WO2015089028 A1 WO 2015089028A1
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group
formula
deuterated
aryl
composition
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PCT/US2014/069276
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Samuel R. DIAMOND
Weiying Gao
Weishi Wu
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E. I. Du Pont De Nemours And Company
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • 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
    • H05B33/20—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
    • 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
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • 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
    • 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

Definitions

  • This invention relates to photoactive compositions including binaphthyl derivative compounds which are useful in electronic devices. It also relates to electronic devices which include the photoactive
  • 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 eiectroactive 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 eiectroactive layer emits light through the light-transmitting electrical contact layer upon application of electricity across the electrical contact layers.
  • organic electroluminescent compounds As the eiectroactive component in light-emitting diodes. Simple organic molecules such as anthracene, thiadiazoie 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 443 881 in many cases the electroluminescent compound is present as a dopant in a host material.
  • composition comprising:
  • R 1 through R 4 are the same or different at each occurrence and are selected from the group consisting of D, alkyl, electron- withdrawing group, carbocyciic ary!, N ; 0,S ⁇ heteroaryi, and deuterated analogs of alkyl, electron-withdrawing group, carbocyciic aryi, and N.O,S-heteroaryI; with the proviso that at least one of R 1 and R 4 is not D;
  • a and d are independently an integer from 1 -5;
  • b and c are independently an integer from 0-6;
  • n is an integer from 1 -3;
  • an electronic device comprising a
  • photoactive layer comprising the above composition.
  • FIG. 1 includes a schematic diagram of another example of an organic electronic device.
  • FIG. 2 includes a schematic diagram of another example of an organic electronic device.
  • the phrase "adjacent to,” when used to refer to layers in a device, does not necessarily mean that one layer is
  • 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).
  • aliphatic ring is intended to mean a cyclic group that does not have deiocaiized 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 alkyi.
  • 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 heteroalkyis.
  • hydrocarbon alkyl refers to an alkyl group having no heteroatoms.
  • deuterated alkyl is a hydrocarbon alkyi having at least one available H replaced by D. In some embodiments, an alkyi group has from 1 -20 carbon atoms.
  • aryl is intended to mean a group derived from an aromatic compound 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. In some embodiments, a heteroaryl has 3-80 ring carbons.
  • 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.
  • hydrocarbon aryl is intended to mean a group derived from aromatic compounds having no heteroatoms in the ring. In some embodiments, a hydrocarbon aryl has 8-80 ring carbons.
  • 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 3-80 ring 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.
  • deuterated is intended to mean that at least one hydrogen has been replaced by deuterium, abbreviated herein as "D".
  • the deuterium is present in at least 100 times the natural abundance level.
  • a "deuterated analog" 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.
  • 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, planarization materials, insulating materials, and environmental barrier materials.
  • electron-withdrawing as it refers to a substituent group is intended to mean a group which decreases the electron density of an aromatic ring.
  • group derived from refers to a compound is intended to mean the radical formed from the compound by the removal of a hydrogen.
  • a phenyl group is a group derived from benzene.
  • hetero indicates that one or more carbon atoms have been replaced with a different atom.
  • the different atom is IM, 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 characteristic(s) 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.
  • luminescence refers to light emission that cannot be attributed merely to the temperature of the emitting body, but results from such causes as chemical reactions, electron bombardment,
  • the term “luminescent” refers to a material capable of luminescence.
  • the term “N-heterocycle” or “N-heferoaryi” refers to a material capable of luminescence.
  • heteroaromatic compound or group having at least one nitrogen in an aromatic ring is a heteroaromatic compound or group having at least one nitrogen in an aromatic ring.
  • N,0,S-heterocycle or “N,0,S-neteroaryi” refers to a heteroaromatic compound or group having at least one heteroatom in an aromatic ring, where the heteroatom is N, O, or S,
  • the N,0,S- heterocycle may have more than one type of heteroatom.
  • O-heterocycie or "O-heteroaryl” refers to a
  • heteroaromatic compound or group having at least one oxygen in an aromatic ring is a heteroaromatic compound or group having at least one oxygen in an aromatic ring.
  • organic electronic device or sometimes just “electronic device” is intended to mean a device including one or more organic semiconductor layers or materials.
  • organometailic refers to a material in which there is a carbon-meta! bond.
  • photoactive refers to a material that emits light when activated by an applied voltage (such as in a light emitting diode or chemical ceil) or responds to radiant energy and generates a signal with or without an applied bias voltage (such as in a photodetector or a
  • S-heterocycie or "S-heteroaryl” refers to a
  • heteroaromatic compound or group having at least one sulfur in an aromatic ring is a heteroaromatic compound or group having at least one sulfur in an aromatic ring.
  • siioxane refers to the group (RO)3Sh where R is H, D , C1 -20 alkyl, or f!uoroalky!.
  • sil refers to the group RaSi-, where R is H, D, C1 -20 alkyl, fluoroalkyl, or ary!. In some embodiments, one or more carbons in an R alkyl group are replaced with Si.
  • Ail groups can be substituted or unsubstituted unless otherwise indicated.
  • the substituents are selected from the group consisting of D, halide, aiky!, aikoxy, aryl, aryloxy, cyano, siiy!, siioxane, and NR 2 , where R is alkyl or aryl.
  • the lUPAC 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 s * Edition, 2000).
  • the photoactive composition comprises:
  • R 1 through R 4 are the same or different at each occurrence and are selected from the group consisting of D, alkyl, electron- withdrawing group, carbocyciic ary!, N ; 0,S ⁇ heteroaryl, and deuterated analogs of alkyl, electron-withdrawing group, carbocyciic aryi, and N,0,S-heteroaryI; with the proviso that at least one of R 1 and R 4 is not D;
  • a and d are independently an integer from 1 -5;
  • b and c are independently an integer from 0-6;
  • n is an integer from 1 -3;
  • the photoactive composition consists essentially of (a) a dopant capable of electroluminescence having an emission maximum less than 500 nm, (b) a first host compound having Formula I, and (c) a second host compound,
  • the amount of dopant present in the photoactive 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 having Formula I to second host is generally in the range of 1 :20 to 20:1 ; in some embodiments, 5:15 to 15:5.
  • the first host material having Formula I is present in an amount of 10-40% by weight, based on the total weight of the composition; in some
  • embodiments 15-30 by weight.
  • the photoactive compositions described herein can be formed into films using liquid deposition techniques.
  • the dopant is a material which is capable of electroluminescence having an emission maximum less than 500 nm.
  • the blue emission has color coordinates of 0.1 ⁇ x ⁇ 0.25 and y ⁇ 0.22, according to the CLE. chromaticity scale (Commission Internationale de L'Eciairage, 1931 ).
  • the dopant is deuterated. In some embodiments, the dopant is at least 10% deuterated. By this it is meant that at least 10% of the H are replaced by D. In some embodiments, the dopant 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 80% 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.
  • Electroluminescent (“EL”) materials which can be used as a dopant in the photoactive layer, include, but are not limited to, small molecule organic luminescent compounds, luminescent metal complexes, conjugated polymers, deuterated analogs thereof, and mixtures thereof.
  • blue light-emitting materials include, but are not limited to, complexes of Ir having phenylpyridine, pheny!imidazo!e, phenyltriazo!e, pyrazolo-pyridine, or pyrazoio-phenanthridine iigands; diarylanthracenes; diaminoanthracenes; diaminochrysenes; diaminopyrenes;
  • the dopant is a small molecule organic luminescent compound. In some embodiments, the dopant is selected from the group consisting of a non-polymeric spirobifluorene compound, a fluoranthene compound, and deuterated analogs thereof.
  • the dopant is a compound having aryl amine groups.
  • the photoactive dopant is selected from the formulae below:
  • A is the same or different at each occurrence and is an aromatic group having from 3-80 carbon atoms;
  • Q' is a single bond or an aromatic group having from 3-60 carbon atoms
  • p and q are independently an integer from 1 -8.
  • At least one of A and Q ! in each formula has at least three condensed rings.
  • p and q are equal to 1 .
  • deuteration is present.
  • Q' is a styryl or styrylphenyi group, or a deuterated analog thereof.
  • Q' is an aromatic group or deuterated aromatic group having at least two condensed rings.
  • Q' is selected from the group consisting of naphthalene, anthracene, chrysene, pyrene, tetracene, xanthene, perylene, coumarin, rhodamine, quinacridone, rubrene, benzofiuorene, and deuterated analogs thereof.
  • A is selected from the group consisting of phenyl, biphenyl, toiyl, naphthyi, naphthyipheriyi, anthracenyl, and deuterated analogs thereof.
  • the dopant has the formula below:
  • Y is the same or different at each occurrence and is an aromatic group having 3-60 carbon atoms
  • Q" is an aromatic group, a divalent triphenylamine residue group, or a single bond.
  • the dopant is an aryl acene. In some embodiments, the dopant is a non-symmetrical aryl acene.
  • the dopant is selected from the group consisting of amino-substituted chrysenes, amino-substituted
  • the dopant has Formula II
  • R 5 is the same or different at each occurrence and is selected from the group consisting of D, alkyl, alkoxy, aryl, silyi, siloxy, and deuterated analogs of alkyl, alkoxy, silyi, siloxy, and aryl, where adjacent R 5 groups may be joined together to form a 5- or 6- membered aliphatic ring or deuterated aliphatic ring;
  • Ar 1 through Ar 4 are the same or different and are selected from the group consisting of aryl groups and deuterated aryl groups; and e is the same or different at each occurrence and is an integer from 0 to 4.
  • Ar through Ar 4 are selected from the group consisting of phenyl, naphthyl, styryi, carbazolyl, an N,0,S- heterocycle, substituted derivatives thereof, deuterated analogs thereof, and a group of Formula a Formula a
  • R' and R" are the same or different at each occurrence and are selected from the group consisting of D, alkyl, aryl, silyl, aikoxy, aryioxy, cyano, vinyl, aliyi, and a deuterated analog of alkyl, aryl, silyl, aikoxy, aryloxy, vinyl, and ally!, or adjacent R groups can be joined together to form a 6-membered aromatic or deuterated aromatic ring;
  • p is an integer from 0-5;
  • q is 0 or 1 .
  • the dopant has Formula HI
  • Ar 1 through Ar 4 are the same or different and are selected from the group consisting of aryl groups and deuterated aryl groups; and f is the same or different at each occurrence and is an integer from
  • Ar 1 through Ar 4 are selected from the group consisting of phenyl, naph hyi, styryl, carbazolyl, an N,0,S- heterocycle, substituted derivatives thereof, deuterated analogs thereof, and a group of Formula a
  • R ! and R" are the same or different at each occurrence and are selected from the group consisting of D, alkyl, aryl, silyl, aikoxy, aryioxy, cyano, vinyl, ally!, and a deuterated analog of alkyl, aryl, silyl, aikoxy, aryioxy, vinyl, and allyl, or adjacent R groups can be joined together to form a 6-membered aromatic or deuterated aromatic ring;
  • p is an integer from 0-5;
  • q is 0 or 1 .
  • the dopant has Formula VI Formula VI
  • R & and R 9 are the same or different at each occurrence and are selected from the group consisting of D, alkyl, alkoxy, aryi, heteroaryl, silyi, siloxy, and deuterated alkyl, deuterated alkoxy, deuterated aryi, deuterated heteroaryl, deuterated silyl, and deuterated siloxy, where adjacent R 8 groups can be joined together to form a fused aromatic ring;
  • R 10 is the same or different at each occurrence and is selected from the group consisting of alkyl, aryi, and deuterated analogs thereof, where two alkyl R 10 groups can be joined together to make a cycloalkyl spiro ring, and where two R 10 phenyl groups can be joined to form a spiro fluorene group;
  • s is the same or different at each occurrence and is an integer from
  • t is an integer from 0 to 3.
  • R 8 there is at least one R 8 present which is an aryi, heteroaryl, or deuterated analog thereof.
  • R & there is at least one R & present which is heteroaryl or deuterated heteroaryl.
  • the heteroaryl or deuterated heteroaryl group has at least one ring atom which is selected from the group consisting of N, O, and S.
  • R 8 there is at least one R 8 present which is selected from the group consisting of pyrrole, pyridine, carbazoie, imidazole, benzimidazoie, imidazoiobenzimidazole, triazoie, benzotriazoie, triazolopyridine, indolocarbazole, pbenanthroline, quinoline, isoquinoline, quinoxa!ine, furan, benzofuran, dibenzofuran, tbiophene, benzoihiophene, dibenzothiopbene, oxazoie, benzoxazo!e, thiazo!e, benzothiazole, substituted derivatives thereof, and deuterated analogs thereof.
  • R 8 is selected from the group consisting of phenyl, naphthyl, phenyl substituted with one or more aikyl groups, naphthyl substituted with one or more alky! groups, and deuterated analogs thereof.
  • any of the above embodiments of the dopant can be combined with one or more of the other embodiments of the dopant, so long as they are not mutually exclusive.
  • the skilled person would understand which embodiments were mutually exclusive and would thus readily be able to determine the combinations of embodiments that are contemplated by the present application.
  • small molecule organic blue dopants include, but are not limited to compounds D1 through D12 shown below.
  • the first host has Formula
  • R 1 through R 4 are the same or different at each occurrence and are selected from the group consisting of D, aikyl, electron- withdrawing group, carbocyciic ary!, N,0,S-heteroaryl, and deuterated analogs of aikyl, electron-withdrawing group, carbocyciic aryl, and N,0,S-heteroaryl; with the proviso that at least one of R 1 and R 4 is not D;
  • a and d are independently an integer from 1 -5;
  • b and c are independently an integer from 0-6;
  • n is an integer from 1 -3.
  • the compound is at least 10% deuterated. By this is meant that at least 10% of the H are replaced by D.
  • 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 compounds are 100% deuterated.
  • n .
  • n 2.
  • a 2.
  • b 1 .
  • b 2.
  • d 1 .
  • d 2.
  • d 3.
  • R 1 is deuterated.
  • At least one R 1 D.
  • At least one R 1 is an alkyi.
  • R 1 is an alkyi having 1 -12 carbons.
  • R 1 is an alkyi having 1 -8 carbons
  • At least one R 1 is an electron-withdrawing group (“EWG").
  • the EVVG is selected from the group consisting of fluoro, cyano, peril uoroaikyl, nitro,— S0 2 R, where R is aikyi or perfluoroaikyl, and combinations thereof.
  • at least one R 1 is selected from the group consisting of CN and perfluoroalkyl.
  • At least one R ! is a carbocyciic aryl.
  • At least one R 1 is selected from the group consisting of phenyl, biphenyi, terphenyi, naphthyl, phenanthryl, anthracenyi, phenylnaphthylene, naphthyiphenyiene, substituted derivatives thereof, and a group having Formula a, as defined above.
  • At least one R 1 is selected from the group consisting of phenyl, biphenyi, and naphthyl.
  • At least one R 1 has Formula a, as defined above.
  • At least one R ! is an alkyl-substituted carbocyciic aryL
  • At least one R 1 is an alkyl-substituted carbocyciic aryi having 8-24 ring carbons and 1 -12 aikyl carbons.
  • At least one R 1 is an alkyl-substituted carbocyciic aryi having 8-18 ring carbons and 1 -12 aikyl carbons.
  • At least one R 1 is an N-heteroaryl.
  • the N-heteraryl is derived from a compound selected from the group consisting of pyrrole, diazoies, benzodiazoies, pyridine, diazines, triazines, substituted derivatives thereof, and
  • R 1 is selected from the group consisting of a group derived from imidazole, benzimidazole, pyrazine, pyrimidine, pyridazine, and 1 ,3,5-triazine.
  • At least one R 1 is an O-heteroaryl.
  • the O-heteraryi is derived from a compound selected from the group consisting of benzopyran, dibenzopyran, benzofuran, dibenzofuran, substituted derivatives thereof, and deuterated analogs thereof.
  • At least one R 1 is selected from the group consisting of a group derived from dibenzopyran and a group derived from dibenzofuran.
  • At least one R 1 is an S-heteroaryl.
  • the S-heteroaryl is derived from a compound selected from the group consisting of benzothiophene, dibenzothiophene, substituted derivatives thereof, and deuterated analogs thereof.
  • At least one R 1 is an S-heteroaryl is derived from a dibenzothiophene.
  • R 2 is deuterated.
  • At least one R 2 D.
  • At least one R 2 is an alkyi.
  • R 2 is an alkyi having 1 -12 carbons.
  • R 2 is an alkyi having 1 -8 carbons.
  • At least one R 2 is selected from the group consisting of CN and perfluoroalkyl.
  • At least one R 2 is a carbocyciic aryt
  • At least one R 2 is selected from the group consisting of phenyl, biphenyl, terphenyi, naphthyl, phenanthryl, anthracenyl, phenyinaphthyiene, naphthylphenyiene, substituted derivatives thereof, and a group having Formula a, as defined above.
  • At least one R 2 is selected from the group consisting of phenyl, biphenyl, and naphthyl.
  • At least one R 2 has Formula a, as defined above.
  • At least one R 2 is an alkyi-substituted carbocyciic aryi.
  • At least one R 2 is an alkyi-substituted carbocyciic aryi having 8-24 ring carbons and 1 -12 aikyl carbons.
  • At least one R 2 is an alkyi-substituted carbocyciic aryi having 6-18 ring carbons and 1 -12 alkyi carbons.
  • R 2 is selected from the group consisting of a group derived from imidazole, benzimidazole, pyrazine, pyrimidine, pyridazine, and 1 ,3,5-triazine.
  • At least one R 2 is an O-heteroary!. In some embodiments, at least one R 2 is selected from the group consisting of a group derived from dibenzopyran and a group derived from dibenzofuran.
  • At least one R 2 is an S-heteroaryL
  • At least one R 2 is an S heteroaryl derived from dibenzothiophene.
  • R 3 is deuterated.
  • At least one R "5 D.
  • At least one R 3 is an aikyL
  • R 3 is an alky! having 1 -12 carbons.
  • R J is an alkyi having 1 -8 carbons.
  • At least one R J is selected from the group consisting of CN and perfluoroalkyl.
  • At least one R 3 is a carbocyciic aryt
  • At least one R 3 is selected from the group consisting of phenyl, biphenyl, terphenyi, naphthyl, phenanthryl, anthracenyl, phenyinaphthyiene, naphthylphenyiene, substituted derivatives thereof, and a group having Formula a, as defined above.
  • At least one R 3 is selected from the group consisting of phenyl, biphenyl and naphthyl.
  • At least one R J has Formula a, as defined above.
  • At least one R 3 is an alkyi-substituted carbocyciic aryi.
  • At least one R 3 is an alkyi-substituted carbocyciic aryi having 8-24 ring carbons and 1 -12 aikyl carbons.
  • At least one R 3 is an alkyi-substituted carbocyciic aryi having 6-18 ring carbons and 1 -12 aikyl carbons.
  • R 3 is selected from the group consisting of a group derived from imidazole, benzimidazole, pyrazine, pyrimidine, pyridazine, and 1 ,3,5-triazine.
  • At least one R 3 is an O-heteroary!.
  • At least one R 3 is selected from the group consisting of a group derived from dibenzopyran and a group derived from dibenzofuran.
  • At least one R is an S-heteroaryi.
  • At least one R 3 is an S heteroaryl derived from dibenzothiophene.
  • R 4 is deuterated.
  • At least one R 4 D.
  • At least one R 4 is an alkyi
  • R 4 is an alkyi having 1 -12 carbons.
  • R 4 is an alkyi having 1 -8 carbons.
  • At least one R 4 is an electron-withdrawing group (“EWG").
  • At least one R 4 is selected from the group consisting of CN and perfluoroalkyl.
  • At least one R 4 is a carbocyciic ary! .
  • At least one R 4 is selected from the group consisting of phenyl, bipheny!, terphenyl, naphthyl, phenanthryl, anthracenyi, phenylnaphthyiene, naphthyiphenylene, substituted derivatives thereof, and a group having Formula a, as defined above.
  • At least one R 4 is selected from the group consisting of phenyl, biphenyl and naphthyl.
  • At least one R 4 has Formula a, as defined above.
  • At least one R 4 is an alky!-substituted carbocyciic aryL
  • At least one R 4 is an alkyl-substituted carbocyciic aryi having 6-24 ring carbons and 1 -12 alkyi carbons.
  • At least one R 4 is an alkyl-substituted carbocyciic aryi having 8-18 ring carbons and 1 -12 aikyl carbons.
  • At least one R 4 is an N-heteroaryl.
  • R 4 is selected from the group consisting of a group derived from imidazole, benzimidazole, pyrazine, pyrimidine, pyridazine, and 1 ,3,5-triazine. In some embodiments, at least one R 4 is an O-heteroary!.
  • At least one R 4 is selected from the group consisting of a group derived from dibenzopyran and a group derived from dibenzofuran.
  • At least one R 4 is an S-heteroaryi.
  • At least one R 4 is an S heteroary! derived from dibenzothiophene.
  • any of the above embodiments of Formula I can be combined with one or more of the other embodiments of Formula I, so long as they are not mutually exclusive.
  • the embodiment in which R 1 is deuterated can be combined with the embodiment in which R 1 is an alkyi having 1 -6 carbons, whereby R 1 is a deuterated alkyl having 1 -8 carbons.
  • the compounds having Formula I can be prepared by known coupling and substitution reactions. Such reactions are well-known and have been described extensively in the literature. Exemplary references include: Yamamoto, Progress in Polymer Science, Vol. 17, p 1 153 (1992);
  • the deuterated analog compounds can 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.
  • deuteration reactions have also been described in published PCT application WO 201 1/053334.
  • the second host is a compound that has a band gap of 3 eV or greater.
  • the second host is selected from the group consisting of indoiocarbazoies, chrysenes, phenanthrenes, triphenylenes, phenanthrolines, triazines, naphthalenes, anthracenes, tetraphenes, dibenzoanthracenes, pyrenes, quinolines, isoquinoiines, quinoxalines, pheny!pyridines, dibenzofurans, benzodifurans, metal quinolinate complexes, and deuterated analogs thereof.
  • the second host is selected from the group consisting of aryl-substituted anthracenes, ary!-substituted tetraphenes, aryl-substituted dibenzoanthracenes, aryl-substituted pyrenes, and deuterated analogs thereof.
  • the second host is deuterated. In some embodiments, the second host 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 second host is 100% deuterated. In some embodiments, the second host has Formula IV
  • R 6 is the same or different at each occurrence and is selected from the group consisting of D, alkyl, alkoxy, aryl, aryloxy, siloxane, sily!, and deuterated analogs of alkyl, alkoxy, aryl, aryloxy, siloxane and silyi, and where adjacent R° groups can be joined together to form a 8-membered fused aromatic or fused deuterated aromatic ring;
  • Ar° and Ar b are the same or different and are selected from the group consisting of aryl groups and deuterated aryl groups;
  • Ar'" and Ar 8 are the same or different and are selected from the group consisting of H, D, aryl groups, and deuterated aryl groups;
  • g is the same or different at each occurrence and is an integer from 0-4.
  • the compound is deuterated.
  • ail R 6 H or D.
  • ail R 6 D.
  • R 6 is a deuterated group. In some embodiments of Formula IV, at least one R 6 is alkyl having 1 -12 carbons.
  • At least one R b is silyi having 3-12 carbons.
  • Ar 5 is a deuterated group.
  • Ar 6 is a deuterated group.
  • Ar is a deuterated group.
  • Ar 8 is a deuterated group.
  • Ar 5 Ar 6 .
  • Ar 5 ⁇ Ar 8 In some embodiments of Formula IV, Ar 5 ⁇ Ar 8 .
  • Ar 7 Ar 2 .
  • Ar 7 ⁇ Ar 8 .
  • Ar 5 and Ar are selected from the group consisting of phenyl, naphthyl, phenanthryi, anthracenyl, and deuterated analogs thereof.
  • Ar 6 and Ar 6 are selected from the group consisting of phenyl, naphthyl, and deuterated analogs thereof.
  • Ar 5 and Ar 4 are selected from the group consisting of phenyl, naphthyl, phenanthryi, anthracenyl, phenyinaphthylene, naphthyiphenylene, deuterated derivatives thereof, and a group having Formula a, as described above.
  • Ar' and Ar 8 are selected from the group consisting of phenyl, biphenyl, terphenyl, naphthyl,
  • Ar 7 and Ar 8 have Formula a, as described above.
  • At least one of Ar through Ar 8 is a heteroaryi group.
  • the second host is a tetraphene having
  • R 7 is the same or different at each occurrence and is selected from the group consisting of D, alkyi, alkoxy, aryl, aryloxy, siloxane, silyl, and deuterated analogs of alkyi, aikoxy, aryl, aryloxy, siloxane and silyl,;
  • Ar 5 and Ar 6 are the same or different and are selected from the group consisting of aryi groups and deuterated aryl groups;
  • Ar' and Ar 8 are the same or different and are selected from the group consisting of H, D, aryl groups, and deuterated aryl groups;
  • g is an integer from 0-4;
  • h is the same or different at each occurrence and is an integer from
  • the compound is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
  • R 7 is a deuterated group.
  • At least one R 7 is aikyl having 1 -12 carbons.
  • At least one R 7 is silyl having 3-12 carbons.
  • Ar 5 is a deuterated group.
  • Ar b is a deuterated group. In some embodiments of Formula IV(a), Ar'' is a deuterated group.
  • Ar 8 is a deuterated group.
  • Ar 5 Ar 6 .
  • Ar' Ar 2 .
  • Ar 7 ⁇ Ar 8 .
  • Ar 5 and Ar 6 are selected from the group consisting of phenyl, naphthyl, phenanthryl, anthracenyl, and deuterated analogs thereof.
  • Ar 5 and Ar° are selected from the group consisting of phenyl, naphthyl, and deuterated analogs thereof.
  • Ar d and Ar 4 are selected from the group consisting of phenyl, naphthyl, phenanthryl, anthracenyl, phenyinaphthylene, naphthylphenylene, deuterated derivatives thereof, and a group having Formula a, as described above.
  • Ar 7 and Ar 8 are selected from the group consisting of phenyl, biphenyl, terphenyi, naphthyl, phenyinaphthylene, naphthylphenylene, and deuterated derivatives thereof.
  • Ar 7 and Ar 8 have Formula a, as described above.
  • At least one of Ar 5 through Ar 8 is a heteroaryl group.
  • the second host is a dibenzoanthracene having Formula IV(b) Formula IV(b)
  • R 7 is the same or different at each occurrence and is selected from the group consisting of D, alkyi, alkoxy, aryl, aryloxy, siloxane, silyl, and deuterated analogs of alkyi, aikoxy, aryl, aryloxy, siloxane and silyl,;
  • Ar" and Ar 6 are the same or different and are selected from the group consisting of aryi groups and deuterated aryl groups;
  • Ar' and Ar 8 are the same or different and are selected from the group consisting of H, D, aryl groups, and deuterated aryl groups;
  • h is the same or different at each occurrence and is an integer from 0-6.
  • R ' is a deuterated group.
  • At least one R 7 is alkyi having 1 -12 carbons.
  • At least one R 7 is siiyi having 3-12 carbons.
  • Ar 5 is a deuterated group.
  • Ar 6 is a deuterated group.
  • Ar 7 is a deuterated group.
  • Ar 8 is a deuterated group.
  • Ar 5 Ar 6 .
  • Ar 7 Ar 2 .
  • Ar' Ar 8 .
  • Ar 5 and Ar° are selected from the group consisting of phenyl, naphthyl, phenanthryl, anthracenyl, and deuterated analogs thereof.
  • Ar 5 and Ar 6 are selected from the group consisting of phenyl, naphthyl, and deuterated analogs thereof.
  • Ar 3 and Ar 4 are selected from the group consisting of phenyl, naphthyl, phenanthryl, anthracenyl, phenyinaphthylene, naphthylphenylene, deuterated derivatives thereof, and a group having Formula a, as described above.
  • Ar 7 and Ar & are selected from the group consisting of phenyl, biphenyl, terphenyi, naphthyl, phenyinaphthylene, naphthylphenylene, and deuterated derivatives thereof.
  • Ar 7 and Ar 8 have Formula a, as described above.
  • At least one of Ar 5 through Ar 8 is a heteroaryl group.
  • the second host is a pyrene compound.
  • the second host has Formula V Formula V wherein:
  • Ar 9 through Ar i 2 are the same or different at each occurrence and are selected from the group consisting of D, aryi, and deuterated aryl;
  • j is an integer from 1 -3;
  • k is an integer from 0-3;
  • n are the same or different and are integers from 0-2;
  • the compound is deuterated.
  • the compound is at least 50% deuterated.
  • Ar 9 is a deuterated group.
  • Ar 9 is an aryl having 6-30 ring carbons.
  • Ar 9 is selected from the group consisting of phenyl, biphenyl, terphenyi, quaterphenyi, naphthyi , binaphthyl, naphthylpheny!, and pheny!naphthyl.
  • Ar 10 is a deuterated group.
  • Ar 10 is an aryi having 6-30 ring carbons.
  • Ar 10 is selected from the group consisting of phenyl, biphenyl, terphenyi, quaterphenyi, naphthyi, binaphthyl, naphthy!phenyl, and phenylnaphthy!.
  • Ar 11 is D.
  • Ar 11 is phenyl
  • Ar 12 is D.
  • Ar 1 ⁇ is phenyl
  • second host compounds include, but are not limited to those shown below.
  • Organic electronic devices that may benefit from having one or more layers comprising the deuterated 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, light- emitting luminaire, or diode laser), (2) devices that detect signals through electronics processes (e.g., photodefectors, photoconducfive ceils, photoresistors, photoswiiches, phototransistors, phototubes, IR detectors), (3) devices that convert radiation into electrical energy, (e.g., a light-emitting diode, light-emitting diode display, light- emitting luminaire, or diode laser), (2) devices that detect signals through electronics processes (e.g., photodefectors, photoconducfive ceils, photoresistors, photoswiiches, 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 thin film transistor or diode).
  • organic semi-conductor layers e.g., a thin film transistor or diode.
  • the compounds of the invention often can be useful in applications such as oxygen sensitive indicators and as luminescent indicators in bioassays.
  • an organic electronic device comprises at least one layer comprising the photoactive composition as discussed above.
  • FIG. 1 An example of an organic electronic device structure is shown in FIG. 1 .
  • the device 100 has a first electrical contact layer, an anode layer 1 10 and a second electrical contact layer, a cathode layer 180, and a photoactive layer 140 between them.
  • Adjacent to the anode may be a hole injection layer 120.
  • 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 1 10 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 electroactive layers.
  • the photoactive layer 140 is pixeiiated, as shown in FIG. 2.
  • Layer 140 is divided into pixel or subpixel units 141 , 142, and 143 which are repeated over the layer.
  • Each of the pixel or subpixel units represents a different color.
  • the subpixel units are for red, green, and blue. Although three subpixel units are shown in the figure, two or more than three may be used.
  • the different layers have the following range of thicknesses: anode 1 10, 500-5000 A, in one embodiment 1000-2000 A; hole injection layer 120, 50-2600 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. In some embodiments, the devices have additional layers to aid in processing or to improve functionality.
  • the photoactive 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 examples include photoconductive cells, photoresistors, photoswitches, phototransistors, and phototubes, and photovoltaic ceils, as these terms are described in Markus, John, Electronics and Nucleonics Dictionary, 470 and 476 (McGraw-Hill, Inc. 1966).
  • Devices with light-emitting layers may be used to form displays or for lighting applications, such as white light luminaires,
  • an electronic device comprises at least one photoactive layer positioned between two electrical contact layers, wherein the photoactive layer comprises (a) a dopant capable of
  • an electronic device comprises at least one photoactive layer positioned between two electrical contact layers, wherein the photoactive layer consists essentially of (a) a dopant capable of electroluminescence having an emission maximum less than 500 nm, (b) a compound having Formula I, and (c) a second host comprising a diaylanthracene compound.
  • the other layers in the device can be made of any materials that are known to be useful in such layers.
  • the anode 1 10 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 1 1 metals, the metals in Groups 4-8, 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 1 10 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 (1 1 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 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 vapour 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 can be formed with polymeric materials, such as po!yaniline (PAN! or poiyethy!enedioxythiophene (PEDOT), which are often doped with protonic acids.
  • the protonic acids can be, for example, poly(styrenesu!fonic acid), poly(2-acrylamido-2-methyl-1 - propanesuifonic acid), and the like.
  • the hole injection layer can comprise charge transfer compounds, and the like, such as copper phthalocyanine and the tetrathiafulvalene- tetracyanoquinodimethane system (TTF-TCNG).
  • charge transfer compounds such as copper phthalocyanine and the tetrathiafulvalene- tetracyanoquinodimethane system (TTF-TCNG).
  • the hole injection layer comprises at least one electrically conductive polymer and at least one fluorinafed acid polymer.
  • electrically conductive polymer and at least one fluorinafed acid polymer.
  • hole transport materials for layer 130 have been summarized for example, in Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Vol. 18, p. 837-880, 1998, by Y. Wang. Both hole transporting molecules and polymers can be used. Commonly used hole transporting molecules are: N,N ! -diphenyl-N,N'-bis(3-mefhylphenyl)- [1 ,1 '-biphenyl]-4,4'-diamine (TPD), 1 ,1 -bis[(di-4-tolylamino)
  • TAPC phenyijcyclohexane
  • EPD phenyijcyclohexane
  • PDA phenyijcyclohexane
  • hole transporting polymers are po!yvinylcarbazole, (phenylmethyi)- polysilane, and poiyaniline. 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 triarylamine-fiuorene copolymers. In some cases, the polymers and copolymers are
  • the hole transport layer further comprises a p-dopant.
  • the hole transport layer is doped with a p-dopant.
  • p-dopants include, but are not limited to, tetrafluorotetracyanoquinodimethane (F4-TCNQ) and perylene- 3,4,9,10-tetracarboxylic-3,4,9,10-dianhydride (PTCDA).
  • the electron transport layer 150 comprises the compound having at least one unit of Formula i.
  • electron transport materials which can be used in layer 150 include, but are not limited to, metal chelated oxinoid compounds, including metal quinolate derivatives such as tris(8-hydroxyquino!ato)aluminum (A!Q), bis(2-methyi-8-quinolinoiato)(p-phenylphenolato) aluminum (BAiq), tetrakis-(8-hydroxyquinolato)hafnium (HfQ) and tetrakis ⁇ 8- hydroxyquino!ato)zirconium (ZrQ); and azoie compounds such as 2- (4- biphenyiyi )-5-(4-t-butylphenyi)-1 ,3,4-oxadiazole (PBD), 3-(4-biphenyiyl)-4- phenyl-5-(4-t-butylphenyl)-1 ,2,4-triazole (
  • the electron transport layer further comprises an n-dopant.
  • N-dopant materials are well known.
  • cobaitocene tefrathianaphthacene, bis(ethylenedithio)tetrathiafuivalene, heterocyclic radicals or diradicals, and the dimers, oligomers, polymers, dsspsro compounds and poiycycles of heterocyclic radical or diradicals.
  • 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 nonmefal 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.
  • LiF, CsF, and Li 2 0 can also be deposited between the organic layer and the cathode layer to lower the operating voltage.
  • anode 1 10 and hole injection layer 120 there can be a layer (not shown) between the anode 1 10 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, fiuorocarbons, silanes, or an ultra-thin layer of a metal, such as Pt.
  • some or all of anode layer 1 10, eiectroactive 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.
  • 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-roii 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.
  • temperature of the materials may also be considerations in selecting the electron and hole transport materials.
  • !t is understood that the efficiency of devices made with the triazine 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.
  • This example illustrates the preparation of Compound 1 , 4,4' ⁇ bis(3- (naphthaien-1 -yl)phenyl)-1 ,1 '-binaphtha!ene.
  • This example illustrates the preparation of Compound 2, 2,2'- Dimethyl-4,4'-di(4-naphthalen-1 -yl-phenyl)-binaphthalene.
  • Tetrakis(triphenylphospine) palladium (59mg, 0.051 mmol) was added to the reaction, the vial capped, and the mixture heated at 80 C overnight in the hood. UPLC sample at 2 hours and overnight shows no more starting material, therefore the reaction was cooled and worked up. The two layers were separated and the toluene layer concentrated to give the crude material as a gooey brown solid which was further purified by column chromatography on silica gel (with 0.5 inch Florisil® top layer) using 10% DCM in hexane as eluent, yielding 1 g (85%) of a white foamy solid (UPLC purity 98.89% with maybe the presence of the 4,5'- stereoisomer). (NMR# 759999) (D100195-096)
  • This example illustrates the preparation of Compound 4, 4-bromo- '-(4-(naphthalen-1 -yl)phenyl)-1 ,1 '-binaphthyl.
  • Tetrakis(triphenylphospine) palladiunn (520 mg, 0.45 mmol) was added and the system was purged for another 15 min. The reaction was stirred and refluxed in an oil bath at 95 °C under nitrogen for 18 hours. UPLC analysis indicated that the product formed as a major component (-63%) together with about 17% of starting dibromide and 17% of disubstituted by-product. After cooling, the mixture was filtered through a Celite® pad to remove the insoluble materials. The solution was washed with diluted HCI (10%), water and saturated brine. The solvent was removed by rotary evaporation.
  • This example illustrates the preparation of Compound 7, 4-(3- (naphthalen-1 -yl)phenyl)-4'-(4-(3-(naphthalen-1 -yl)phenyl)naphthalen-1 - -1 ,1 '-binaphthyl.
  • ,4-Dibromonaphthalene (5.72 g, 20 mmoi), propane ⁇ 1 ,3-diamine (0.30 g , 4.00 mmoi), Cul (0.17 g 2 mmoi), sodium iodide (12.00 g, 80 mmoi) and 1 -pentanoi (150 mL) were charged to a 500m L round bottom flask equipped with stir bar, heating bath, and reflux condenser. The reaction was stirred and refiuxed in an oil bath at 130 °C under nitrogen for 18 hours. UPLC analysis indicated that only about 50% of bromide had been converted to iodide.
  • the reaction was stirred and refluxed in an oil bath at 95 °C under nitrogen for 18 hours. After cooling, the organic phase was separated, washed with water, diluted HCI (10%), and saturated brine and then dried with MgS0 4 . The solution was filtered through a silica gel plug and the solvent was removed by removed by rotary evaporation. The material was re-dissolved in DC (20 mL) and the solution was added dropwise to methanol (300 mL) with stirring. After settling under ambient condition for 2 hours, the precipitate was collected by filtration. The crude product was dried in a vacuum oven overnight to give 2.4 g of off white material in 87% purity based on UPLC analysis. The material was subjected to further separation by automated
  • Compound 9 was prepared by dissolving Compound 1 , from Synthesis Example 1 , in d6-benzene and slow!y adding d-trifiic acid. The solution was stirred overnight in a drybox. The solution was then quenched with 10st% sodium carbonate in D20. The organic layer was separated, dried with magnesium sulfate, and purified by column chromatography, followed by precipitation.
  • Tetrakis(triphenylphospine)palladium (0) (235 mg, 0.2 mmol) was added and the system was purged for another 15 min. The reaction was stirred and refluxed in an oil bath at 95 °C under nitrogen for 18 hour. During the time the reaction solution turned to light brown color. After cooling, the organic phase was separated, washed with water (60 mL), diluted HCI (10%, 60 mL) and saturated brine (60 mL), and dried with MgS0 4 . The solution was filtered through a Silica gel plug and the solvent was removed by rotary evaporation. The material was re-dissolved in DCM (20 mL) and the solution was added dropwise to methanol (300 mL) with stirring.
  • anthracen-9-yl trifluoromethanesulfonate 8,0 g, 18.40 mmoi
  • Napthalen-2-yl-boronic acid 3.78 g 22.1 mmol
  • potassium phosphate tribasic 17.50g, 82.0 mmoi
  • palladium(Ii) acetate (0.41 g, 1 .8 mmoi)
  • tricyciohexylphosphine 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.
  • naphthalen-1 -yi-1 -boronic (14.2g, 82.8mmoi)
  • acid 1 -bromo-2-iodobenzene (25.8g, 91 .2 mmoi)
  • the product was further purified as described in published U.S. patent application 2008-0138855, to achieve an HPLC purity of at least 99.9% and an impurity absorbance no greater than 0.01 .
  • This example illustrates the preparation of a host compound H1 1 .
  • the non-deuterated analog is prepared first. Take 0.39g of the dibromochrysene (1 mM) in glove box and add 0.75g (2.1 mM) sec amine and 0.22g t-BuONa (2.2mM) with 1 GmL toluene. Add 0.15g Pd2DBA3 (0.15mM), 0.06g P(t-Bu)3 (Q.30mM) dissolved in toluene. Mix and heat in giove box in mantle at 1 10C under nitrogen for 1 hr. Solution immediately is dark purple but on reaching -80C it is dark yellow brown with noticeable blue luminescence. Warm at ⁇ 8QC overnight. Cool and work up by removing from glove box and filter through a b-alumina/fiorisil plug eiuting with toluene. Product is pale yellow and quite soluble. The blue
  • luminescent material elutes from the column as a pale yellowgreen solution. Evaporate to low volume and add methanol to ppt yellow solid with blue PL in ⁇ 0.5g yield. TLC shows single blue spot running at the solvent front in toluene. Material is very soluble in toluene
  • Deuteration to form dopant D9 can be carried out in a manner analogous to that for host H1 1 , described above.
  • This example illustrates how dopant D10 could be made.
  • the compound could be made using a procedure analogous to Synthesis Example 10, Step 1 , using 6,12-dibromochrysene and the perdeutero analog of the amine compound.
  • HIJ-1 an electrically conductive polymer doped with 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.
  • 70a HT-1 a triaryiamine-containing copolymer.
  • Such materials have been described in, for example, published PCT application WO 2009/067419.
  • ET-1 a metal quinoiate complex
  • 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, !nc 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 isopropanoi, and dried in a stream of nitrogen.
  • the substrates were then spin-coated with a toluene solution of HT-1 , and then heated to remove solvent. After cooling the substrates were spin-coated with a methyl benzoate solution of the host(s) and dopant, and heated to remove solvent. The substrates were masked and placed in a vacuum chamber. A layer of ET-1 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 devices had the following structure on a glass substrate:
  • Anode ITO ("ITO"), 50 nm
  • Hole injection layer HIJ-1 , 50 nm
  • Hole transport layer HT-1 , 14 nm
  • Photoactive layer 40 nm, materials are given in Table 1 below
  • Electron transport layer ET-1 , 10 nm
  • Ratio weight ratio of dopant:first host:second host
  • the OLED samples were characterized by measuring their (1 ) current-voltage (!-V) curves, (2) electroluminescence radiance versus voltage . , and (3) electroiuminescence 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 Irn/W.
  • the color coordinates were determined using either a Minolta CS-100 meter or a Photoresearch PR-705 meter.
  • the photoactive layer had a chrysene dopant in a combination of two hosts: a first host having Formula I (Compound 9) and a second diarylanthracene host.
  • the photoactive layer had the chrysene dopant in a single host which was a diarylanthracene compound.
  • the photoactive layer had a chrysene dopant in a combination of two hosts: a first host having Formula I (Compound 9) and a second deuterated diarylanthracene host.
  • the photoactive layer had the chrysene dopant in a single host which was a deuterated diarylanthracene compound.
  • Ail data @ 1000 nits; C.E. current efficiency; E.Q.E is the external quantum efficiency; V is voltage, in insectss; CIEx and CIEy are the x and y color coordinates according to the CLE. chromaiicity scale (Commission Internationale de L'Eciairage, 1931 ); T80 is the time to reach 80% initial luminance at 12 mA/cm2 and 32' 3 C; T70 is the time to reach 70% initial luminance at 12 mA/cm2 and 32°C,
  • Ail data @ 1000 nits; C.E. current efficiency; E.Q.E is the external quantum efficiency; V is voltage, in volts; GIEx and CIEy are the x and y color coordinates according to the C LE. chromaiicity scale (Commission Internationale de L'Eciairage, 1931 ); T80 is the time to reach 80% initial luminance at 12 mA/cm2 and 32 '3 C; T70 is the time to reach 70% initial luminance at 12 mA cm2 and 32°C.
  • the photoactive layer had a chrysene dopant in a combination of two hosts: a first host having Formula ! (Compound 9) and a second deuterated diarylanthracene host, in different ratios.
  • the photoactive layer had the chrysene dopant in a single host which was a deuterated diarylanthracene
  • the photoactive layer had the chrysene dopant in a single host which was Compound 9.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Spectroscopy & Molecular Physics (AREA)
  • Organic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention concerne une composition comprenant (a) un dopant permettant une électroluminescence ayant un maximum d'émission inférieur à 500 nm ; (b) un premier composé hôte répondant à la formule I et (c) un second composé hôte qui consiste en un composé diarylanthracène. Dans la formule I : R1 à R4 sont identiques ou différents à chaque occurrence et représentent D, un alkyle, un groupe attracteur d'électrons, un aryle carbocyclique, N, O, un groupe S-hétéroaryle, ou des analogues deutérés d'un alkyle, d'un groupe attracteur d'électrons, d'un aryle carbocyclique, de N, d'O, d'un groupe S-hétéroaryle ; a et d représentent indépendamment un nombre entier situé dans la plage allant de 1 à 5 ; b et c représentent indépendamment un nombre entier situé dans la plage allant de 0 à 6; et n est un nombre entier situé dans la plage allant de 1 à 3. R1 et/ou R4 sont autres que D.
PCT/US2014/069276 2013-12-11 2014-12-09 Compositions photoactives pour applications électroniques WO2015089028A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018095384A1 (fr) * 2016-11-23 2018-05-31 广州华睿光电材料有限公司 Composé cyclique fusionné deutéré, polymère, mélange et composition, et dispositif électronique organique
WO2021145711A1 (fr) * 2020-01-16 2021-07-22 주식회사 엘지화학 Dispositif électroluminescent organique
US11795185B2 (en) 2017-12-13 2023-10-24 Lg Display Co., Ltd. Compound for electron-transport material and organic light emitting diode including the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6872475B2 (en) * 2002-12-03 2005-03-29 Canon Kabushiki Kaisha Binaphthalene derivatives for organic electro-luminescent devices
WO2008150822A2 (fr) * 2007-06-01 2008-12-11 E.I. Du Pont De Nemours And Company Matériaux de transport de charge pour des applications luminescentes
WO2012021315A2 (fr) * 2010-08-11 2012-02-16 E. I. Du Pont De Nemours And Company Composé électroactif et composition et dispositif électronique fabriqué avec la composition
WO2013106041A2 (fr) * 2011-04-08 2013-07-18 E. I. Du Pont De Nemours And Company Dispositif électronique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6872475B2 (en) * 2002-12-03 2005-03-29 Canon Kabushiki Kaisha Binaphthalene derivatives for organic electro-luminescent devices
WO2008150822A2 (fr) * 2007-06-01 2008-12-11 E.I. Du Pont De Nemours And Company Matériaux de transport de charge pour des applications luminescentes
WO2012021315A2 (fr) * 2010-08-11 2012-02-16 E. I. Du Pont De Nemours And Company Composé électroactif et composition et dispositif électronique fabriqué avec la composition
WO2013106041A2 (fr) * 2011-04-08 2013-07-18 E. I. Du Pont De Nemours And Company Dispositif électronique

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018095384A1 (fr) * 2016-11-23 2018-05-31 广州华睿光电材料有限公司 Composé cyclique fusionné deutéré, polymère, mélange et composition, et dispositif électronique organique
CN109790087A (zh) * 2016-11-23 2019-05-21 广州华睿光电材料有限公司 氘代稠环化合物、高聚物、混合物、组合物以及有机电子器件
US11795185B2 (en) 2017-12-13 2023-10-24 Lg Display Co., Ltd. Compound for electron-transport material and organic light emitting diode including the same
WO2021145711A1 (fr) * 2020-01-16 2021-07-22 주식회사 엘지화학 Dispositif électroluminescent organique

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