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Definitions

• This disclosure relates in general to electroactive compositions that are useful in organic electronic devices.
• organic electroactive electronic devices such as organic light emitting diodes (“OLED”), that make up OLED displays
• OLED organic light emitting diodes
• the organic active layer is sandwiched between two electrical contact layers in an OLED display.
• the organic electroactive layer emits light through the light-transmitting electrical contact layer upon application of a voltage across the electrical contact layers.
• organic electroluminescent compounds As the active component in light-emitting diodes. Simple organic molecules, conjugated polymers, and organometallic complexes have been used.
• Devices that use electroactive materials frequently include one or more charge transport layers, which are positioned between an
• a device can contain two or more contact layers.
• a hole transport layer can be positioned between the electroactive layer and the hole-injecting contact layer.
• the hole-injecting contact layer may also be called the anode.
• An electron transport layer can be positioned between the electroactive layer and the electron-injecting contact layer.
• the electron-injecting contact layer may also be called the cathode.
• Charge transport materials can also be used as hosts in combination with the electroactive materials.
• an electroactive composition comprising a deuterated first host material and an electroluminescent dopant material, wherein the deuterated first host material is a compound having Formula I:
• Ar 1 to Ar 4 are the same or different and are aryl;
• Q is selected from the group consisting of multivalent aryl groups
• T is selected from the group consisting of (CR') a , S1R2, S, SO2, PR,
• R is the same or different at each occurrence and is selected from the group consisting of alkyl, and aryl;
• R' is the same or different at each occurrence and is selected from the group consisting of H, D, and alkyl;
• a is an integer from 1 -6;
• n is an integer from 0-6;
• electroactive composition which further comprises a second host material.
• organic electronic device comprising two electrical contact layers with an organic electroactive layer therebetween, wherein the electroactive layer comprises the electroactive composition described above.
• FIG. 1 includes an illustration of an exemplary organic device.
• FIG. 2 includes an illustration of an exemplary organic device.
• alkyl is intended to mean a group derived from an aliphatic hydrocarbon. In some embodiments, the alkyl group has from 1 - 20 carbon atoms.
• aryl is intended to mean a group derived from an aromatic hydrocarbon.
• 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 encompass both aromatic compounds having only carbon and hydrogen atoms, and heteroaromatic compounds wherein one or more of the carbon atoms within the cyclic group has been replaced by another atom, such as nitrogen, oxygen, sulfur, or the like. In some embodiments, the aryl group has from 4-30 carbon atoms.
• 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 term "charge transport layer, material, member, or structure” is not intended to include a layer, material, member, or structure whose primary function is light emission.
• deuterated is intended to mean that at least one H has been replaced by D.
• deuterated analog refers to a structural analog of a compound or group in which one or more available hydrogens have been replaced with deuterium. In a deuterated compound or deuterated analog, the deuterium is present in at least 100 times the natural abundance level.
• diopant 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 as it refers to a layer or a material, is intended to indicate a layer or material which electronically facilitates the operation of the device. Examples of 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, or materials which emit radiation or exhibit a change in concentration of electron-hole pairs when receiving radiation. Examples of inactive materials include, but are not limited to, planarization materials, insulating materials, and environmental barrier materials.
• electrosenescence refers to the emission of light from a material in response to an electric current passed through it.
• Electrode refers to a material that is capable of
• emission maximum is intended to mean the highest intensity of radiation emitted.
• the emission maximum has a
• fused aryl refers to an aryl group having two or more fused aromatic rings.
• HOMO refers to the highest occupied molecular orbital.
• the HOMO energy level is measured relative to vacuum level, as illustrated in FIG. 1A.
• the HOMO is given as a negative value, i.e. the vacuum level is set as zero and the bound electron energy levels are deeper than this.
• shallower it is meant that the level is closer to the vacuum level. This is illustrated in FIG. 1 B, where HOMO B is shallower than HOMO A.
• host material is intended to mean a material, usually in the form of a layer, to which a dopant may or may not be added.
• the host material may or may not have electronic characteristic(s) or the ability to emit, receive, or filter radiation.
• 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.
• the term "LUMO” refers to the lowest unoccupied molecular orbital.
• the LUMO energy level is measured relative to vacuum level in eV, as illustrated in FIG. 1A.
• the LUMO is a negative value, i.e. the vacuum level is set as zero and the bound electron energy levels are deeper than this.
• a "deeper” level is farther removed from vacuum level. This is illustrated in FIG. 1 B, where LUMO B is deeper than LUMO A.
• organic electronic device or sometimes just “electronic device,” is intended to mean a device including one or more organic semiconductor layers or materials.
• sil refers to the group -SiR 3 , where R is the same or different at each occurrence and is selected from the group consisting of alkyl groups, and aryl groups.
• Tg refers to the glass transition temperature of a material.
• triplet energy refers to the lowest excited triplet state of a material, in eV. Triplet energies are reported as positive numbers and represent the energy of the triplet state above the ground state, usually a singlet state.
• substituents are selected from the group consisting of alkyl, alkoxy, aryl, and silyl.
• the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
• 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.
• “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
• Electroactive Composition The electroactive compositions described herein comprise: a deuterated first host material and an electroluminescent dopant material, wherein the deuterated first host material is a compound having Formula I:
• Ar 1 to Ar 4 are the same or different and are aryl;
• Q is selected from the group consisting of multivalent aryl groups
• T is selected from the group consisting of (CR') a , S1R2, S, SO2, PR,
• R is the same or different at each occurrence and is selected from the group consisting of alkyl, and aryl;
• R' is the same or different at each occurrence and is selected from the group consisting of H, D, and alkyl;
• a is an integer from 1 -6;
• n is an integer from 0-6;
• the deuterated host material has a solubility in toluene of at least 0.6 wt%. In some embodiments, the solubility in toluene is at least 1 wt%. In some embodiments, the deuterated first host material has a Tg greater than 95°.
• the electroactive composition further comprises a second host material.
• one of the host materials is a hole transport material and the other host material is an electron transport material.
• the first deuterated host is a hole transport material.
• the first deuterated host is an electron transport material.
• the second host material is deuterated.
• one of the host materials has a HOMO energy level shallower than or equal to -5.6 eV and the other host material has a LUMO deeper than -2.0 eV.
• the first deuterated host material has a HOMO energy level shallower than or equal to -5.6 eV.
• the first deuterated host material has a LUMO deeper than -2.0 eV.
• Methods for determining the HOMO energy level are well known and understood.
• the level is determined by ultraviolet photoelectron spectroscopy ("UPS").
• the HOMO is between -5.0 and -5.6 eV.
• the LUMO can be determined using inverse photoelectron spectroscopy ("I PES").
• the weight ratio of first host material to second host material is in the range of 99:1 to 1 :99. In some
• the ratio is in the range of 99:1 to 1 .5:1 ; in some
• the first host material is different from the second host material.
• the first and second host materials each have a solubility in toluene of at least 0.6 wt%. In some embodiments, the solubility is at least 1 wt%.
• the weight ratio of total host material (first host + second host, when present) to the dopant is in the range of 5:1 to 25:1 ; in some embodiments, from 10:1 to 20:1 .
• the electroactive composition comprises two or more electroluminescent dopant materials. In some embodiments, the composition comprises three dopants. In some embodiments, the electroactive composition consists essentially of the first host material and one or more dopant materials. In some embodiments, the electroactive composition consists essentially of the first host material, the second host material, and one or more electroluminescent dopant materials, as defined and in the ratios described above.
• compositions are useful as solution processible electroactive compositions for OLED devices.
• the resulting devices have high efficiency and long lifetimes.
• the materials are useful in any printed electronics application including photovoltaics and TFTs.
• the first host material has Formula I and is a deuterated material.
• the first host is at least 10% deuterated. By this is meant that at least 10% of the H are replaced by D.
• the first host is at least 20% deuterated; in some embodiments, the first host is at least 20% deuterated; in some
• the host is 100% deuterated.
• the deuteration can be present on the core Q moiety, on the aryl groups Ar 1 through Ar 4 , on substituent groups on the aryl groups, or any combination thereof.
• At least one D is on a substituent group on an aryl ring.
• the substituent group is selected from alkyl and aryl.
• At least one of Ar 1 through Ar 4 is a deuterated aryl.
• Ar 1 through Ar 4 are at least 10% deuterated.
• % deuterated or “% deuteration” is meant the ratio of deuterons to the total of hydrogens plus deuterons, expressed as a percentage.
• the deuteriums may be on the same or different Ar groups.
• 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; in some embodiments, 100% deuterated.
• adjacent Ar groups are joined together to form rings such as carbazole.
• adjacent means that the Ar groups are bonded to the same N.
• Ar 1 to Ar 4 are independently selected from the group consisting of phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthryl, naphthylphenyl, phenanthrylphenyl, and deuterated analogs thereof. Analogs higher than quaterphenyl can also be used, having 5-10 phenyl or deuterated phenyl rings.
• At least one of Ar 1 through Ar 4 has at least one substituent other than D.
• Substituent groups can be present in order to alter the physical or electronic properties of the host material.
• the substituents improve the processibility of the host material.
• the substituents increase the solubility and/or increase the Tg of the host material.
• the substituents are selected from the group consisting of alkyl groups, alkoxy groups, silyl groups, deuterated analogs thereof, and combinations thereof.
• Q is an aryl group having at least two fused rings. In some embodiments, Q has 3-5 fused aromatic rings. In some embodiments, Q is selected from the group consisting of anthracenes, chrysenes, pyrenes, phenanthrenes, triphenylenes, phenanthrolines, naphthalenes, anthracenes, quinolines, isoquinolines, quinoxalines, phenylpyridines, dibenzofurans, difuranobenzenes, indolocarbazoles, substituted derivatives thereof, and deuterated analogs thereof.
• m can have a value from 0-6, it will be understood that for some Q groups the value of m is restricted by the chemistry of the group. In some embodiments, m is 0 or 1 .
• R' is a fluorinated alkyl group. In some embodiments, R' is a perfluorinated alkyl group having 1 -5 carbons.
• the deuterated first host material has Formula II
• R 1 is the same or different at each occurrence and is selected from the group consisting of D, alkyl, alkoxy, silyl, and siloxane, or adjacent R 1 groups may be joined together to form a 5- or 6- membered aliphatic ring,
• Ar 1 and Ar 2 are the same or different and are aryl groups, a is an integer from 0 to 6;
• b is an integer from 0 to 2;
• c is an integer from 0 to 3.
• At least one R 1 is a branched alkyl group.
• the branched alkyl group is selected from the group consisting of a 2-propyl group, a t-butyl group, and deuterated analogs thereof.
• Ar 1 and Ar 2 are phenyl groups having one or more substituents selected from the group consisting of D, alkyl, silyl, phenyl, naphthyl, N-carbazolyl, fluorenyl, and deuterated analogs thereof.
• Ar 1 and Ar 2 are selected from the group consisting of phenyl, biphenyl, naphthyl, phenanthryl, anthracenyl, 4- naphthylphenyl, 4-phenanthrylphenyl, where any of the preceding groups may be further substituted with one or more substituents selected from the group consisting of D, alkyl groups, silyl groups, and phenyl, and a group having Formula III:
• R 2 is the same or different at each occurrence and is selected from the group consisting of H, D, alkyl, alkoxy, siloxane and silyl, or adjacent R 2 groups may be joined together to form an aromatic ring;
• n is the same or different at each occurrence and is an integer from 1 to 6.
• the deuterated first host material is a phenanthroline compound having Formula IV: Formula IV where:
• R 3 is the same or different and is selected from the group consisting of phenyl, naphthyl, naphthylphenyl, triphenylamino, carbazolylphenyl, and deuterated analogs thereof;
• R 4 and R 5 are the same or different and are selected from the group consisting of phenyl, biphenyl, naphthyl, naphthylphenyl,
• R 3 through R 5 are selected from the group consisting of phenyl, substituted phenyl, and deuterated analogs thereof.
• both R 3 are phenyl and R 4 and R 5 are selected from the group consisting of 2-naphthyl,
• R aryl, alkyl
• the R 3 groups are the same and are selected from the group consisting of phenyl, triphenylamino,
• the R 3 groups are selected from the group consisting of p-triphenylamino (where the point of attachment is para to the nitrogen), m-carbazolylphenyl (where the point of attachment is meta to the nitrogen), and deuterated analogs thereof.
• R 4 R 5 and is selected from the group consisting of triphenylamino, naphthylphenyl, triphenylamino, m- carbazolylphenyl, and deuterated analogs thereof.
• the first host material has a Tg greater than 95°C.
• the high Tg allows for the formation of smooth and robust films.
• DSC Differential Scanning Calorimetry
• TMA Thermo-Mechanical Analysis
• the Tg is measured by DSC.
• the Tg is between 100 and 150°C.
• the first host material has a triplet energy level greater than 2.0 eV. This is particularly useful when the dopant is an organometallic material in order to prevent quenching of the emission.
• the triplet energy can either be calculated a priori, or be measured using pulse radiolysis or low temperature luminescence spectroscopy.
• deuterated first host materials include, but are not limited to, compounds A1 to A19 below.
• the non-deuterated analogs of the first host compound can be prepared by known coupling and substitution reactions.
• the phenanthroline host compounds are made by Suzuki coupling of dichloro phenanthrolines with the boronic acid analog of the desired substituent.
• the new deuterated compounds can then be prepared in a similar manner using deuterated precursor materials or, more generally, by treating the non-deuterated compound with deuterated solvent, such as d6-benzene, in the presence of a Lewis acid H/D exchange catalyst, such as aluminum trichloride or ethyl aluminum chloride, or acids such as CF 3 COOD, DCI, etc. 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).
• the starting materials of the perdeuterated or partially deuterated aromatic compounds or alkyl compounds can be purchased from commercial sources or can be obtained using known methods. Some examples of such methods can be found in a) "Efficient H/D Exchange Reactions of Alkyl-Substituted Benzene Derivatives by Means of the Pd/C-H2-D2O System" Hiroyoshi Esaki, Fumiyo Aoki, Miho Umemura, Masatsugu Kato, Tomohiro Maegawa, Yasunari Monguchi, and Hironao Sajiki Chem. Eur. J. 2007, 13, 4052 - 4063.
• the compounds described herein can be formed into films using liquid deposition techniques. Surprisingly and unexpectedly, these compounds can 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 without any significant detrimental effect on other device properties. In some embodiments, lifetime is increased 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 dopant is an electroactive material which is capable of electroluminescence having an emission maximum between 380 and 750 nm. In some embodiments, the dopant emits red, green, or blue light. In some embodiments, the dopant is also deuterated.
• the dopant is at least 10% deuterated; in some embodiments, at least 20% deuterated; in some embodiments, at least 30% deuterated; in some embodiments, at least 40% deuterated; in some embodiments, at least 50% deuterated; in some embodiments, at least 60% deuterated; in some embodiments, at least 70% deuterated; in some embodiments, at least 80% deuterated; in some embodiments, at least 90% deuterated; in some embodiments, 100% deuterated.
• Electroluminescent dopant materials include small molecule organic luminescent compounds, luminescent metal complexes, and combinations thereof.
• small molecule luminescent compounds include, but are not limited to, pyrene, perylene, rubrene, coumarin, derivatives thereof, and mixtures thereof.
• metal complexes include, but are not limited to, metal chelated oxinoid compounds, such as tris(8- hydroxyquinolato)aluminum (AIQ); cyclometalated iridium and platinum electroluminescent compounds, such as complexes of iridium with phenylpyridine, phenylquinoline, phenylisoquinoline or phenylpyrimidine ligands.
• red light-emitting materials include, but are not limited to, cyclometalated complexes of Ir having phenylquinoline or
• Red light-emitting materials have been disclosed in, for example, US patent 6,875,524, and published US application 2005-0158577.
• green light-emitting materials include, but are not limited to, bis(diarylamino)anthracenes, and polyphenylenevinylene polymers. Green light-emitting materials have been disclosed in, for example, published PCT application WO 2007/021 1 17.
• blue light-emitting materials include, but are not limited to, diarylanthracenes, diaminochrysenes, diaminopyrenes, and
• the dopant is an organometallic complex. In some embodiments, the dopant is a cyclometalated complex of iridium or platinum. Such materials have been disclosed in, for example, U.S.
• the dopant is an organometallic complex having the formula lr(L1 ) a (L2) b (L3) c ;
• L1 is a monoanionic bidentate cyclometalating ligand coordinated through carbon and nitrogen;
• L2 is a monoanionic bidentate ligand which is not coordinated
• L3 is a monodentate ligand
• a 1 -3;
• b and c are independently 0-2;
• a, b, and c are selected such that the iridium is hexacoordinate and the complex is electrically neutral.
• formulae include, but are not limited to, lr(L1 )3;
• L1 ligands examples include, but are not limited to
• phenylpyridines phenylquinolines, phenylpyrimidines, phenylpyrazoles, thienylpyridines, thienylquinolines, thienylpyrimidines, and deuterated analogs thereof.
• quinolines includes “isoquinolines” unless otherwise specified.
• the fluorinated derivatives can have one or more fluorine substituents. In some embodiments, there are 1 -3 fluorine substituents on the non-nitrogen ring of the ligand.
• Monoanionic bidentate ligands L2 are well known in the art of metal coordination chemistry.
• these ligands have N, O, P, or S as coordinating atoms and form 5- or 6-membered rings when coordinated to the iridium.
• Suitable coordinating groups include amino, imino, amido, alkoxide, carboxylate, phosphino, thiolate, and the like.
• suitable parent compounds for these ligands include ⁇ -dicarbonyls
• amino carboxylic acids aminocarboxylate ligands
• pyridine carboxylic acids aminocarboxylate ligands
• salicylic acid derivatives salicylate ligands
• hydroxyquinolines hydroxyquinolinate ligands
• phosphinoalkanols phosphinoalkoxide ligands
• Monodentate ligand L3 can be anionic or nonionic.
• Anionic ligands include, but are not limited to, H " ("hydride") and ligands having C, O or S as coordinating atoms. Coordinating groups include, but are not limited to alkoxide, carboxylate, thiocarboxylate, dithiocarboxylate, sulfonate, thiolate, carbamate, dithiocarbamate, thiocarbazone anions, sulfonamide anions, deuterated analogs thereof, and the like.
• ligands listed above as L2 such as ⁇ -enolates and phosphinoakoxides, can act as monodentate ligands.
• the monodentate ligand can also be a coordinating anion such as halide, cyanide, isocyanide, nitrate, sulfate,
• hexahaloantimonate and the like. These ligands are generally available commercially.
• the monodentate L3 ligand can also be a non-ionic ligand, such as CO or a monodentate phosphine ligand.
• one or more of the ligands has at least one substituent selected from the group consisting of F and fluorinated alkyls.
• the iridium complex dopants can be made using standard synthetic techniques as described in, for example, US patent 6,670,645.
• the dopant is a red light-emitting organometallic compound.
• red dopants are compounds D1 through D7 below.
• the electroactive dopant is selected from the group consisting of a non-polymeric spirobifluorene compound, a fluoranthene compound, and deuterated analogs thereof.
• the electroactive dopant is a compound having aryl amine groups. In some embodiments, the electroactive dopant is selected from the formulae below:
• A is the same or different at each occurrence and is an aromatic group having from 3-60 carbon atoms;
• Q' is a single bond or an aromatic group having from 3-60 carbon atoms
• n and m are independently an integer from 1 -6.
• n and m may be limited by the number of available sites on the core Q' group.
• At least one of A and Q' in each formula has at least three condensed rings. In some embodiments, m and n are equal to 1 .
• Q' is a styryl or styrylphenyl group.
• Q' is an aromatic group having at least two condensed rings. In some embodiments, Q' is selected from the group consisting of naphthalene, anthracene, benz[a]anthracene,
• dibenz[a,h]anthracene fluoranthene, fluorene, spirofluorene, tetracene, chrysene, pyrene, tetracene, xanthene, perylene, coumarin, rhodamine, quinacridone, rubrene, substituted derivatives thereof, and deuterated analogs thereof.
• A is selected from the group consisting of phenyl, biphenyl, tolyl, naphthyl, naphthylphenyl, anthracenyl, and deuterated analogs thereof.
• the electroluminescent material has the structure
• R is the same or different at each occurrence and is selected from the group consisting of D, alkyl, alkoxy and aryl, where adjacent R groups may be joined together to form a 5- or 6-membered aliphatic ring;
• Ar is the same or different and is selected from the group consisting of aryl groups.
• the dashed line in the formula is intended to indicate that the R group, when present, can be at any site on the core Q' group.
• the electroactive dopant has the formula below: where:
• 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 electroactive dopant is an aryl acene. In some embodiments, the electroactive dopant is a non-symmetrical aryl acene.
• the electroactive dopant is a chrysene derivative.
• chrysene is intended to mean 1 ,2- benzophenanthrene.
• the electroactive dopant is a chrysene having aryl substituents. In some embodiments, the
• electroactive dopant is a chrysene having arylamino substituents. In some embodiments, the electroactive dopant is a chrysene having two different arylamino substituents. In some embodiments, the chrysene derivative has a deep blue emission.
• separate electroactive compositions with different dopants are used to provide different colors.
• the dopants are selected to have red, green, and blue emission.
• red refers to light having a wavelength maximum in the range of 600-700 nm
• green refers to light having a wavelength maximum in the range of 500-600 nm
• blue refers to light having a wavelength maximum in the range of 400-500 nm.
• small molecule organic dopant materials include, but are not limited to, compounds D8 to D13 below.
• a second host material is present in the electroactive composition.
• the second host material is an optional component.
• the second host is at least 10% deuterated. By this is meant that at least 10% of the H are replaced by D.
• the second host 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 second host is 100% deuterated.
• the second host can be any of the materials discussed above for the first host material.
• the second host material is selected from the group consisting of phenanthrolines, quinoxalines, phenylpyridines, benzodifurans, difuranobenzenes, indolocarbazoles, benzimidazoles, triazolopyridines, diheteroarylphenyls, metal quinolinate complexes, substituted derivatives thereof, deuterated analogs thereof, and combinations thereof.
• the aforementioned second host compounds have a substituent selected from the group consisting of aryl, alkyl, and deuterated analogs thereof.
• the heteroaryl group is selected from the group consisting of pyridine, pyrazine, pyrimidine, pyridazine, triazines, tetrazines, quinazoline, quinoxaline, naphthylpyridines, heterobiaryl analogs thereof, heterotriaryl analogs thereof, and deuterated analogs thereof.
• the second host is selected from structures 1 -9, below, or a deuterated analog thereof.
• R is selected from aryl, heteroaryl, and alkyl.
• the heteroaryl group is selected from structures 10-20 below, or a deuterated analog thereof.
• the group is a heterobiaryl derivative or a heterotriaryl derivative.
• the second host material has one of the structures shown below
• R is selected from aryl, heteroaryl, and alkyl.
• the above structures are further substituted with aryl or heteroaryl groups.
• the heteroaryl group is selected from structures 10-20 above, or a deuterated analog thereof.
• the second host material also has a triplet energy level greater than 2.0 eV. This is particularly useful when the dopant is an organometallic material in order to prevent quenching of the emission. In some embodiments, both the first host material and the second host material have a triplet energy level greater than 2.0 eV.
• the second host compounds can be made by known synthetic techniques.
• Organic electronic devices that may benefit from having the electroactive composition 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, biosensors), (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, photoswitches, phototrans
• an organic light-emitting device comprises: an anode
• electroactive layer comprises the composition described above.
• the device 100 has a first electrical contact layer, an anode layer 1 10 and a second electrical contact layer, a cathode layer 160, and an electroactive layer 140 between them.
• Adjacent to the anode is a hole injection layer 120.
• Adjacent to the hole injection 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 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 active layers.
• the electroactive layer 140 is pixellated, 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, 50-3000 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 examples 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 electroactive layer comprises the electroactive composition described above.
• the electroactive layer can be formed by liquid deposition from a liquid composition, as described below. In some embodiments, the electroactive layer is formed by vapor deposition.
• three different electroactive compositions are applied by liquid deposition to form red, green, and blue subpixels.
• each of the colored subpixels is formed using new electroactive compositions as described herein.
• the host materials are the same for all of the colors.
• different host materials are used for the different colors.
• Other Device Layers are used for the different colors.
• 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 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 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 (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 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 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 hole injection layer can comprise charge transfer compounds, and the like, such as copper phthalocyanine and the tetrathiafulvalene- tetracyanoquinodimethane system (TTF-TCNQ).
• charge transfer compounds such as copper phthalocyanine and the tetrathiafulvalene- tetracyanoquinodimethane system (TTF-TCNQ).
• the hole injection layer comprises at least one electrically conductive polymer and at least one fluorinated acid polymer.
• electrically conductive polymer and at least one fluorinated 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. 837-860, 1996, 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-methylphenyl)- [1 ,1'-biphenyl]-4,4'-diamine (TPD), 1 ,1 -bis[(di-4-tolylamino)
• TAPC phenyljcyclohexane
• EPD phenyljcyclohexane
• PDA tetrakis-(3- methylphenyl)-N,N,N',N'-2,5-phenylenediamine
• TPS p-(diethylamino)benzaldehyde
• DEH diphenylhydrazone
• TPA triphenylamine
• MPMP bis[4-(N,N- diethylamino)-2-methylphenyl](4-methylphenyl)methane
• 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 triarylamine-fluorene 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).
• electron transport materials which can be used for layer 150 include, but are not limited to, metal chelated oxinoid
• metal quinolate derivatives such as tris(8- hydroxyquinolato)aluminum (AIQ), bis(2-methyl-8-quinolinolato)(p- phenylphenolato) aluminum (BAIq), tetrakis-(8-hydroxyquinolato)hafnium (HfQ) and tetrakis-(8-hydroxyquinolato)zirconium (ZrQ); and azole compounds such as 2- (4-biphenylyl)-5-(4-t-butylphenyl)-1 ,3,4-oxadiazole (PBD), 3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1 ,2,4-triazole (TAZ), and 1 ,3,5-tri(phenyl-2-benzimidazole)benzene (TPBI); quinoxaline derivatives such as 2,3-bis(4-fluorophenyl)quinoxaline; phenan
• the electron transport layer further comprises an n-dopant.
• N-dopant materials are well known.
• 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-containing organometallic compounds, LiF, and Li 2 O 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, fluorocarbons, silanes, or an ultra-thin layer of a metal, such as Pt.
• some or all of anode layer 1 10, 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 layers can be formed by any deposition technique, or combinations of techniques, including vapor deposition, liquid deposition, and thermal transfer. 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-roll techniques, ink-jet printing, continuous nozzle printing, screen-printing, gravure printing and the like.
• the process for making an organic light- emitting device comprises: providing a substrate having a patterned anode thereon;
• composition comprising (a) a deuterated first host material, (b) an electroluminescent dopant material, and (c) a liquid medium;
• liquid composition is intended to include a liquid medium in which one or more materials are dissolved to form a solution, a liquid medium in which one or more materials are dispersed to form a
• dispersion or a liquid medium in which one or more materials are suspended to form a suspension or an emulsion.
• the process further comprises:
• the hole transport layer is formed by depositing a second liquid composition comprising a hole transport material in a second liquid medium.
• the process further comprises:
• the electron transport layer is formed by depositing a third liquid composition comprising an electron transport material in a third liquid medium.
• Any known liquid deposition technique or combination of techniques can be used, including continuous and discontinuous techniques.
• Examples of continuous liquid deposition techniques include, but are not limited to spin coating, gravure coating, curtain coating, dip coating, slot- die coating, spray coating, and continuous nozzle printing.
• Examples of discontinuous deposition techniques include, but are not limited to, ink jet printing, gravure printing, and screen printing.
• the electroactive layer is formed in a pattern by a method selected from continuous nozzle coating and ink jet printing.
• the nozzle printing can be considered a continuous technique, a pattern can be formed by placing the nozzle over only the desired areas for layer formation. For example, patterns of continuous rows can be formed.
• a suitable liquid medium for a particular composition to be deposited can be readily determined by one skilled in the art. For some applications, it is desirable that the compounds be dissolved in nonaqueous solvents.
• non-aqueous solvents can be relatively polar, such as Ci to C20 alcohols, ethers, and acid esters, or can be relatively non-polar such as Ci to C12 alkanes or aromatics such as toluene, xylenes, trifluorotoluene and the like.
• Another suitable liquid for use in making the liquid composition, either as a solution or dispersion as described herein, comprising the new compound includes, but not limited to, a chlorinated hydrocarbon (such as methylene chloride, chloroform, chlorobenzene), an aromatic hydrocarbon (such as a substituted or non- substituted toluene or xylenes, including trifluorotoluene), a polar solvent (such as tetrahydrofuran (THF), N-methyl pyrrolidone (NMP)), an ester (such as ethylacetate), an alcohol (such as isopropanol), a ketone (such as cyclopentatone), or any mixture thereof.
• a chlorinated hydrocarbon such as methylene chloride, chloroform, chlorobenzene
• aromatic hydrocarbon such as a substituted or non- substituted toluene or xylenes, including trifluorotoluene
• a polar solvent such as
• the weight ratio of total host material (first host together with second host, when present) to the dopant is in the range of 5:1 to 25:1 .
• the material is dried to form a layer. Any conventional drying technique can be used, including heating, vacuum, and combinations thereof.
• the device is fabricated by liquid deposition of the hole injection layer, the hole transport layer, and the electroactive layer, and by vapor deposition of the anode, the electron transport layer, an electron injection layer and the cathode.
• Example 1 This example illustrates the preparation of deuterated host compound A1 .
• Reaction mixture was then cooled to -75 °C and 4- bromobenzaldehyde (21.0 g, 1 13.6 mmol) dissolved in dry THF (ca. 75 ml) was added dropwise over 30 min, keeping the temp at -75°C. Residual aldehyde was washed out of the addition funnel with 20 mL of THF.
• reaction mixture was left in the cold bath to gradually warm up to rt while stirring overnight. Next day, reaction was quenched with water (30 ml) and volatiles were removed on the rotavap. Residue was stirred in 500 ml of hexane and then filtered. Solids were washed with hexane. Filtrate was concentrated to give crude product which was purified by column chromatography (0-100% CH 2 CI 2 in hexanes). Yield 17.7g (50%).
• 3-bromochrysene (2 g, 6.5 mmol) was placed into a flask and dissolved in 100 ml of dry C-6D 6 .
• Aluminum trichloride (0.26 g, 1 .95 mmol) was added next, followed by 20 ml of additional C 6 D 6 .
• perdeutero-4-aminobiphenyl 0.542 g, 3.04 mmol
• perdeutero-4-bromo-1 ,1 ':3',1 "-terphenyl 0.89 g, 2.76 mmol
• Tris(tert-butyl)phosphine 0.022 g, 0.11 mmol
• perdeutero-N-([1 ,1 '-biphenyl]-4-yl)-[1 ,1':3',1 "-terphenyl]-4- amine 0.49 g, 2.02 mmol
• perdeutero-3-bromochrysene 0.59 g, 1 .85 mmol
• Tris(tert-butyl)phosphine (7.5 mg, 0.037 mmol) and tris(dibenzylideneacetone) dipalladium(O) (17 mg, 0.019 mmol) were dissolved in 10 ml of dry toluene and stirred for 10 minutes.
• the catalyst solution was added to the reaction mixture, stirred for 5 minutes and followed by sodium tert-butoxide (0.194 g, 2.02 mmol) and 20 ml of dry toluene. After another 10 minutes, the reaction flask was brought out of the drybox and placed into an 80 °C bath to stir overnight.
• reaction mixture was cooled to room temperature and filtered through a three-inch plug of silica gel and topped with half an inch of Celite, washing with 400 ml of chloroform. Removal of volatiles under reduced pressure gave a yellow solid. Crude product was purified by column
• Compound A1 had a Tg of about 110°C.
• the solubility in both toluene and anisole was greater than 20 mg/ml.
• This example illustrates the preparation of deuterated host compound A17.
• Compound B-1 had a Tg of about 220°C.
• the solubility in toluene was
• step (d) above (1.925 g) was dissolved in C 6 D 6 (200 mL) to which CF 3 OSO 2 D (13.2 mL) was added dropwise.
• the reaction mixture was allowed to stir at room temperate overnight and then it was quenched with saturated
• Compound A17 had a Tg of about 220°C.
• the solubility in toluene was 24.7 mg/ml.
• the solubility in anisole was 23.3 mg/ml.
• This example illustrates the preparation of a non-deuterated second host compound, Compound B-2.
• Reaction mixture was then cooled to -75 °C and 4- bromobenzaldehyde (21.0 g, 1 13.6 mmol) dissolved in dry THF (ca. 75 ml) was added dropwise over 30 min, keeping the temp at -75°C. Residual aldehyde was washed out of the addition funnel with 20 mL of THF.
• reaction mixture was left in the cold bath to gradually warm up to rt while stirring overnight. Next day, reaction was quenched with water (30 ml) and volatiles were removed on the rotavap. Residue was stirred in 500 ml of hexane and then filtered. Solids were washed with hexane. Filtrate was concentrated to give crude product which was purified by column chromatography (0-100% CH 2 CI 2 in hexanes). Yield 17.7g (50%).
• N-([1 ,1 '-biphenyl]-4-yl)-[1 ,1 ':3M "-terphenyl]-4-amine (2.02 mmol) and 3-bromochrysene (1 .85 mmol) were combined in a thick-walled glass tube and dissolved in 20 ml of dry toluene.
• Tris(tert-butyl)phosphine (7.5 mg, 0.037 mmol) and tris(dibenzylideneacetone) dipalladium(O) (17 mg, 0.019 mmol) were dissolved in 10 ml of dry toluene and stirred for 10 minutes.
• the catalyst solution was added to the reaction mixture, stirred for 5 minutes and followed by sodium tert-butoxide (0.194 g, 2.02 mmol) and 20 ml of dry toluene. After another 10 minutes, the reaction flask was brought out of the drybox and placed into an 80 °C bath to stir overnight. Next day, reaction mixture was cooled to room temperature and filtered through a three-inch plug of silica gel and topped with half an inch of Celite, washing with 400 ml of chloroform. Removal of volatiles under reduced pressure gave a yellow solid. Crude product was purified by column chromatography with chloroform in hexane. Yield 1 .05g (87.5%) of a white solid. Identity and purity of the product were established by 1 H NMR, mass spectrometry and liquid chromatography.
• Compound B-2 had a Tg of about 216°C.
• the solubility in toluene was 22.8 mg/ml.
• the solubility in anisole was 22.2 mg/ml.
• the devices had the following structure on a glass substrate:
• ITO Indium Tin Oxide
• hole injection layer HIJ-1 (50 nm), which is an aqueous dispersion of an electrically conductive polymer and a polymeric fluorinated sulfonic acid.
• HIJ-1 50 nm
• 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.
• hole transport layer HT-1 (20 nm), which is an triarylamine- containing copolymer. Such materials have been described in, for example, published PCT application WO 2009/067419. electroluminescent layer is shown in Table 1 . In all cases, the
• dopant was D7.
• 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, Inc 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.
• ITO substrates were treated with UV ozone for 10 minutes.
• an aqueous dispersion of HIJ-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 solution of the electroactive layer materials in toluene, 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 (l-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 results are given in Table 2.
• E.Q.E is the external quantum efficiency
• P.E. is the power efficiency
• RawT50 is the time in hours for a device to reach one-half the initial luminance at the lifetest luminance given.
• Projected T50 is the projected lifetime at 1000 nits using an acceleration factor of 1 .8.

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