Patent Application
20240122058
The present disclosure generally relates to deuterated organometallic compounds and formulations and their various uses including as emitters in devices such as organic light emitting diodes and related electronic devices.
Opto-electronic devices that make use of organic materials are becoming increasingly desirable for various reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting diodes/devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials.
OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting.
One application for phosphorescent emissive molecules is a full color display. Industry standards for such a display call for pixels adapted to emit particular colors, referred to as “saturated” colors. In particular, these standards call for saturated red, green, and blue pixels. Alternatively, the OLED can be designed to emit white light. In conventional liquid crystal displays emission from a white backlight is filtered using absorption filters to produce red, green and blue emission. The same technique can also be used with OLEDs. The white OLED can be either a single emissive layer (EML) device or a stack structure. Color may be measured using CIE coordinates, which are well known to the art.
In one aspect, the present disclosure provides a deuterated compound produced by a method comprising; heating a first compound in a solvent containing a deuterated material to an elevated temperature to generate the deuterated compound; and isolating the deuterated compound; wherein the first compound has at least 0.01 mg/mL solubility in the deuterated material at 25° C.; and wherein the elevated temperature is at least 50° C. and up to TD with TD being the boiling point of the solvent.
In another aspect, the present disclosure provides a deuterated compound comprising an aromatic ring coordinating to a metal through a direct bond or a one atom linker; wherein the aromatic ring is substituted by at least one D (deuterium) and at least one substituent selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof; and wherein the at least one substituent may be joined or fused with another substituent in the compound to form a ring.
In yet another aspect, the present disclosure provides a formulation comprising a deuterated compound as described herein.
In yet another aspect, the present disclosure provides an OLED having an organic layer comprising a deuterated compound as described herein.
In yet another aspect, the present disclosure provides a consumer product comprising an OLED with an organic layer comprising a deuterated compound as described herein.
Unless otherwise specified, the below terms used herein are defined as follows:
As used herein, the term “organic” includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic devices. “Small molecule” refers to any organic material that is not a polymer, and “small molecules” may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the “small molecule” class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. The core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a “small molecule,” and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.
As used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. Where a first layer is described as “disposed over” a second layer, the first layer is disposed further away from substrate. There may be other layers between the first and second layer, unless it is specified that the first layer is “in contact with” the second layer. For example, a cathode may be described as “disposed over” an anode, even though there are various organic layers in between.
As used herein, “solution processable” means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.
A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.
As used herein, and as would be generally understood by one skilled in the art, a first “Highest Occupied Molecular Orbital” (HOMO) or “Lowest Unoccupied Molecular Orbital” (LUMO) energy level is “greater than” or “higher than” a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IP) are measured as a negative energy relative to a vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (an EA that is less negative). On a conventional energy level diagram, with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A “higher” HOMO or LUMO energy level appears closer to the top of such a diagram than a “lower” HOMO or LUMO energy level.
As used herein, and as would be generally understood by one skilled in the art, a first work function is “greater than” or “higher than” a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a “higher” work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a “higher” work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.
The terms “halo,” “halogen,” and “halide” are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.
The term “acyl” refers to a substituted carbonyl radical (C(O)—Rs).
The term “ester” refers to a substituted oxycarbonyl (—O—C(O)—Rs or —C(O)—O—Rs) radical.
The term “ether” refers to an —ORs radical.
The terms “sulfanyl” or “thio-ether” are used interchangeably and refer to a —SRs radical.
The term “selenyl” refers to a —SeRs radical.
The term “sulfinyl” refers to a —S(O)—Rs radical.
The term “sulfonyl” refers to a —SO2—Rs radical.
The term “phosphino” refers to a —P(Rs)2 radical, wherein each Rs can be same or different.
The term “silyl” refers to a —Si(Rs)3 radical, wherein each Rs can be same or different.
The term “germyl” refers to a —Ge(Rs)3 radical, wherein each Rs can be same or different.
The term “boryl” refers to a —B(Rs)2 radical or its Lewis adduct —B(Rs)3 radical, wherein Rs can be same or different.
In each of the above, Rs can be hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combination thereof. Preferred Rs is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combination thereof.
The term “alkyl” refers to and includes both straight and branched chain alkyl radicals. Preferred alkyl groups are those containing from one to fifteen carbon atoms and includes methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and the like. Additionally, the alkyl group may be optionally substituted.
The term “cycloalkyl” refers to and includes monocyclic, polycyclic, and spiro alkyl radicals. Preferred cycloalkyl groups are those containing 3 to 12 ring carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, and the like. Additionally, the cycloalkyl group may be optionally substituted.
The terms “heteroalkyl” or “heterocycloalkyl” refer to an alkyl or a cycloalkyl radical, respectively, having at least one carbon atom replaced by a heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si and Se, preferably, O, S or N. Additionally, the heteroalkyl or heterocycloalkyl group may be optionally substituted.
The term “alkenyl” refers to and includes both straight and branched chain alkene radicals. Alkenyl groups are essentially alkyl groups that include at least one carbon-carbon double bond in the alkyl chain. Cycloalkenyl groups are essentially cycloalkyl groups that include at least one carbon-carbon double bond in the cycloalkyl ring. The term “heteroalkenyl” as used herein refers to an alkenyl radical having at least one carbon atom replaced by a heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably, O, S, or N. Preferred alkenyl, cycloalkenyl, or heteroalkenyl groups are those containing two to fifteen carbon atoms. Additionally, the alkenyl, cycloalkenyl, or heteroalkenyl group may be optionally substituted.
The term “alkynyl” refers to and includes both straight and branched chain alkyne radicals. Alkynyl groups are essentially alkyl groups that include at least one carbon-carbon triple bond in the alkyl chain. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may be optionally substituted.
The terms “aralkyl” or “arylalkyl” are used interchangeably and refer to an alkyl group that is substituted with an aryl group. Additionally, the aralkyl group may be optionally substituted.
The term “heterocyclic group” refers to and includes aromatic and non-aromatic cyclic radicals containing at least one heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably, O, S, or N. Hetero-aromatic cyclic radicals may be used interchangeably with heteroaryl. Preferred hetero-non-aromatic cyclic groups are those containing 3 to 7 ring atoms which includes at least one hetero atom, and includes cyclic amines such as morpholino, piperidino, pyrrolidino, and the like, and cyclic ethers/thio-ethers, such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and the like. Additionally, the heterocyclic group may be optionally substituted.
The term “aryl” refers to and includes both single-ring aromatic hydrocarbyl groups and polycyclic aromatic ring systems. The polycyclic rings may have two or more rings in which two carbons are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is an aromatic hydrocarbyl group, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Especially preferred is an aryl group having six carbons, ten carbons or twelve carbons. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, preferably phenyl, biphenyl, triphenyl, triphenylene, fluorene, and naphthalene. Additionally, the aryl group may be optionally substituted.
The term “heteroaryl” refers to and includes both single-ring aromatic groups and polycyclic aromatic ring systems that include at least one heteroatom. The heteroatoms include, but are not limited to O, S, N, P, B, Si, and Se. In many instances, O, S, or N are the preferred heteroatoms. Hetero-single ring aromatic systems are preferably single rings with 5 or 6 ring atoms, and the ring can have from one to six heteroatoms. The hetero-polycyclic ring systems can have two or more rings in which two atoms are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is a heteroaryl, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. The hetero-polycyclic aromatic ring systems can have from one to six heteroatoms per ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and aza-analogs thereof. Additionally, the heteroaryl group may be optionally substituted.
Of the aryl and heteroaryl groups listed above, the groups of triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, and benzimidazole, and the respective aza-analogs of each thereof are of particular interest.
The terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclic group, aryl, and heteroaryl, as used herein, are independently unsubstituted, or independently substituted, with one or more general substituents.
In many instances, the general substituents are selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, selenyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In some instances, the preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.
In some instances, the more preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, aryl, heteroaryl, sulfanyl, and combinations thereof.
In yet other instances, the most preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
The terms “substituted” and “substitution” refer to a substituent other than H that is bonded to the relevant position, e.g., a carbon or nitrogen. For example, when R1 represents mono-substitution, then one R1 must be other than H (i.e., a substitution). Similarly, when R1 represents di-substitution, then two of R1 must be other than H. Similarly, when R1 represents zero or no substitution, R1, for example, can be a hydrogen for available valencies of ring atoms, as in carbon atoms for benzene and the nitrogen atom in pyrrole, or simply represents nothing for ring atoms with fully filled valencies, e.g., the nitrogen atom in pyridine. The maximum number of substitutions possible in a ring structure will depend on the total number of available valencies in the ring atoms.
As used herein, “combinations thereof” indicates that one or more members of the applicable list are combined to form a known or chemically stable arrangement that one of ordinary skill in the art can envision from the applicable list. For example, an alkyl and deuterium can be combined to form a partial or fully deuterated alkyl group; a halogen and alkyl can be combined to form a halogenated alkyl substituent; and a halogen, alkyl, and aryl can be combined to form a halogenated arylalkyl. In one instance, the term substitution includes a combination of two to four of the listed groups. In another instance, the term substitution includes a combination of two to three groups. In yet another instance, the term substitution includes a combination of two groups. Preferred combinations of substituent groups are those that contain up to fifty atoms that are not hydrogen or deuterium, or those which include up to forty atoms that are not hydrogen or deuterium, or those that include up to thirty atoms that are not hydrogen or deuterium. In many instances, a preferred combination of substituent groups will include up to twenty atoms that are not hydrogen or deuterium.
The “aza” designation in the fragments described herein, i.e. aza-dibenzofuran, aza-dibenzothiophene, etc. means that one or more of the C—H groups in the respective aromatic ring can be replaced by a nitrogen atom, for example, and without any limitation, azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. One of ordinary skill in the art can readily envision other nitrogen analogs of the aza-derivatives described above, and all such analogs are intended to be encompassed by the terms as set forth herein.
As used herein, “deuterium” refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. Pat. No. 8,557,400, Patent Pub. No. WO 2006/095951, and U.S. Pat. Application Pub. No. US 2011/0037057, which are hereby incorporated by reference in their entireties, describe the making of deuterium-substituted organometallic complexes. Further reference is made to Ming Yan, et al., Tetrahedron 2015, 71, 1425-30 and Atzrodt et al., Angew. Chem. Int. Ed. (Reviews) 2007, 46, 7744-65, which are incorporated by reference in their entireties, describe the deuteration of the methylene hydrogens in benzyl amines and efficient pathways to replace aromatic ring hydrogens with deuterium, respectively.
It is to be understood that when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g. phenyl, phenylene, naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g. benzene, naphthalene, dibenzofuran). As used herein, these different ways of designating a substituent or attached fragment are considered to be equivalent.
In some instance, a pair of adjacent substituents can be optionally joined or fused into a ring. The preferred ring is a five, six, or seven-membered carbocyclic or heterocyclic ring, includes both instances where the portion of the ring formed by the pair of substituents is saturated and where the portion of the ring formed by the pair of substituents is unsaturated. As used herein, “adjacent” means that the two substituents involved can be on the same ring next to each other, or on two neighboring rings having the two closest available substitutable positions, such as 2, 2′ positions in a biphenyl, or 1, 8 position in a naphthalene, as long as they can form a stable fused ring system.
The present disclosure provides deuterated cyclometalated complex compounds derived from a process used to make such complex compounds. The proton-deuterium exchange occurs on the metal complex as opposed to on the ligand used to form the metal complex. Deuteration using this process yields exchange in positions that normally will not exchange on the neat ligand. This process therefore results in a product specific to the process and cannot easily be made via deuteration exchange of the corresponding ligand, and deuteration of the metal complex in specific positions can lead to an increase in lifetime of OLED devices made with such metal complexes. Deuterated emitter molecules have been considered to increase device lifetime performance. However, not every position of the hydrogen being deuterated can give the same advantage for the lifetime performance. During the device degradation process, only those most active hydrogen atoms give the major effect to the performance. For example, in a phosphorescent emitter, due to the center metal environment change, the positions of most active hydrogen atoms in the metal complex can be different from those in the ligand, and sometimes it is hard to predict which one. The progress described herein provides a great advantage for obtaining a final emitter complex having the most active hydrogen atoms being deuterated without searching for which one needs to be deuterated, because the disclosed deuteration process will happen at the most chemically active hydrogen positions first. Therefore, this process is very different from conventional pre-designed deuteration process, which normally deuterate the whole aromatic ring, or a very specific alkyl group. The conventional process is normally carried out by the feasibility of the synthetic route to obtain that particular deuterated group, and not based on the hydrogen activity of the final emitter complex. It unexpectedly turns out that the most active hydrogen positions in the emitter complex, for example the metal complex of the phosphorescent emitter, is quite different from what people have thought before.
In one aspect, the present disclosure provides a deuterated compound produced by a method that comprises: heating a first compound in a solvent containing a deuterated material to an elevated temperature to generate the deuterated compound; and isolating the deuterated compound; wherein the first compound has at least 0.01 mg/mL solubility in the deuterated material at 25° C.; and wherein the elevated temperature is at least 50° C. and up to TD with TD being the boiling point of the solvent.
In some embodiments, the first compound is a metal coordination compound. In some embodiments, the first compound is capable of functioning as an emitter, host, blocking layer material, transporting layer material, or injecting layer material in an organic light emitting device at room temperature. In some embodiments, the first compound may be a partially deuterated compound.
In some embodiments, the deuterated material is fully deuterated. In some embodiments, the deuterated material is partially deuterated. It should be understood that a solvent containing a deuterated material of the present disclosure may refer to a deuterated solvent, and it may refer to a partially deuterated solvent if it contains non-deuterated material. When it only contains a deuterated material, the solvent can also refer to be a partially deuterated solvent if the deuterated material is partially deuterated or a fully deuterated solvent if the deuterated material is fully deuterated.
In some embodiments, the deuterated material is selected from the group consisting of: d6-dimethylsulfoxide, CD3OD (d4-methanol), CD3CD2OD (d6-ethanol), C6D6(d6-benzene), C7D8(d8-toluene), d4-acetic acid, d6-acetone, d3-acetonitrile, d12-cyclohexane, D2O, d7-N,N-dimethylformamide, d8-1,4-dioxane, d2-methylene chloride, d5-pyridine, d8-tetrahydrofuran, d-trifluoroacetic acid, d3-trifluoroethanol, and combinations thereof. In some embodiments, the solvent only contains a deuterated material. In some of these embodiments, the deuterated material may be one or their combinations described above. In some embodiments, the solvent also includes a non-deuterated material. The non-deuterated material can be any of the organic solvent used in the common reaction. The non-deuterated material can be, for example, but not limited to, any of the non-deuterated version of the above deuterated material.
In some embodiments, the first compound has at least 0.025 mg/mL solubility in a deuterated solvent. In some embodiments, the first compound has at least 0.05 mg/mL solubility in a deuterated solvent. In some embodiments, the first compound has at least 0.075 mg/mL solubility in a deuterated solvent. In some embodiments, the first compound has at least 0.10 mg/mL solubility in a deuterated solvent. In some embodiments, the first compound has at least 0.25 mg/mL solubility in a deuterated solvent. In some embodiments, the first compound has at least 0.50 mg/mL solubility in a deuterated solvent. In some embodiments, the first compound has at least 0.75 mg/mL solubility in a deuterated solvent. In some embodiments, the first compound has at least 1.0 mg/mL solubility in a deuterated solvent. In some embodiments, the first compound has at least 2.0 mg/mL solubility in a deuterated solvent. In some embodiments, the first compound has at least 3.0 mg/mL solubility in a deuterated solvent. In some embodiments, the first compound has at least 4.0 mg/mL solubility in a deuterated solvent. In some embodiments, the first compound has at least 5.0 mg/mL solubility in a deuterated solvent. In some embodiments, the first compound has at least 0.025 mg/mL solubility in the solvent. In some embodiments, the first compound has at least 0.05 mg/mL solubility in the solvent. In some embodiments, the first compound has at least 0.075 mg/mL solubility in the solvent. In some embodiments, the first compound has at least 0.10 mg/mL solubility in the solvent. In some embodiments, the first compound has at least 0.25 mg/mL solubility in the solvent. In some embodiments, the first compound has at least 0.50 mg/mL solubility in the solvent. In some embodiments, the first compound has at least 0.75 mg/mL solubility in the solvent. In some embodiments, the first compound has at least 1.0 mg/mL solubility in the solvent. In some embodiments, the first compound has at least 2.0 mg/mL solubility in the solvent. In some embodiments, the first compound has at least 3.0 mg/mL solubility in the solvent. In some embodiments, the first compound has at least 4.0 mg/mL solubility in the solvent. In some embodiments, the first compound has at least 5.0 mg/mL solubility in the solvent.
In some embodiments, the elevated temperature is the boiling point of the deuterated solvent. In some embodiments, the elevated temperature is 5° C. higher than the boiling point of the deuterated solvent. In some embodiments, the elevated temperature is 10° C. higher than the boiling point of the deuterated solvent. In some embodiments, the elevated temperature is 15° C. higher than the boiling point of the deuterated solvent. In some embodiments, the elevated temperature is 20° C. higher than the boiling point of the deuterated solvent. In some embodiments, the elevated temperature is 25° C. higher than the boiling point of the deuterated solvent. In some embodiments, the elevated temperature is the temperature at at which the deuterated material boils.
In some embodiments, the elevated temperature is at least 75° C. and up to TD. In some embodiments, the elevated temperature is at least 100° C. and up to TD. In some embodiments, the elevated temperature is at least 125° C. and up to TD. In some embodiments, the elevated temperature is at least 150° C. and up to TD. In some embodiments, the elevated temperature is no lower than TD-80° C. In some embodiments, the elevated temperature is no lower than TD-70° C. In some embodiments, the elevated temperature is no lower than TD-60° C. In some embodiments, the elevated temperature is no lower than TD−50° C. In some embodiments, the elevated temperature is no lower than TD-40° C. In some embodiments, the elevated temperature is no lower than TD-30° C. In some embodiments, the elevated temperature is no lower than TD−20° C. In some embodiments, the elevated temperature is no lower than TD-10° C.
In some embodiments, the deuterated compound produced by the method described herein with at least 50% yield. In some embodiments, the deuterated compound produced by the method described herein with at least 60% yield. In some embodiments, the deuterated compound produced by the method described herein with at least 70% yield. In some embodiments, the deuterated compound produced by the method described herein with at least 80% yield. In some embodiments, the deuterated compound produced by the method described herein with at least 90% yield. In some embodiments, the deuterated compound produced by the method described herein with at least 95% yield. In some embodiments, the deuterated compound produced by the method described herein with at least 98% yield. In some embodiments, the deuterated compound produced by the method described herein with at least 99% yield.
In some embodiments, wherein the first compound has two or more H atoms. In some embodiments, the first compound has one or more non-aromatic H atoms and one or more aromatic rings with H atoms.
In some embodiments, the deuterated compound has at least two H atoms replaced with D when compared to the first compound.
In some embodiments, the deuterated compound has at least one aromatic H replaced with D when compared to the first compound. In some embodiments, the deuterated compound has at least two aromatic H replaced with D when compared to the first compound. In some embodiments, the deuterated compound has at least three aromatic H replaced with D when compared to the first compound. In some embodiments, the deuterated compound has at least four aromatic H replaced with D when compared to the first compound. In some embodiments, the deuterated compound has at least five aromatic H replaced with D when compared to the first compound. In some embodiments, the deuterated compound has the aromatic ring fully deuterated.
In some embodiments, the deuterated compound has at least one non-aromatic H replaced with D when compared to the first compound. In some embodiments, the deuterated compound has at least two non-aromatic H replaced with D when compared to the first compound. In some embodiments, the deuterated compound has at least three non-aromatic H replaced with D when compared to the first compound. In some embodiments, the deuterated compound has at least four non-aromatic H replaced with D when compared to the first compound. In some embodiments, the deuterated compound has at least five non-aromatic H replaced with D when compared to the first compound. In some embodiments, the deuterated compound has at least six non-aromatic H replaced with D when compared to the first compound. In some embodiments, the deuterated compound has at least seven non-aromatic H replaced with D when compared to the first compound. In some embodiments, the deuterated compound has at least eight non-aromatic H replaced with D when compared to the first compound. In some embodiments, the deuterated compound has at least nine non-aromatic H replaced with D when compared to the first compound. In some embodiments, the deuterated compound has at least ten non-aromatic H replaced with D when compared to the first compound. In some embodiments, the deuterated compound has at least eleven non-aromatic H replaced with D when compared to the first compound. In some embodiments, the deuterated compound has at least twelve non-aromatic H replaced with D when compared to the first compound. In some embodiments, the deuterated compound has all the non-aromatic H replaced with D.
In some embodiments, the deuterated compound has at least two H replaced with D at the same carbon atom when compared to the first compound.
In some embodiments, the deuterated compound has at least two H replaced with D at the two different carbon atoms when compared to the first compound.
In some embodiments, the deuterated compound has at least one H replaced with D on an aromatic ring when compared to the first compound; and wherein the aromatic ring is selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, and thiazole; and wherein the aromatic ring can be further fused or substituted.
In some embodiments, the deuterated compound is a single compound. In some embodiments, the deuterated compound is a mixture having different partially deuterated moieties. In some embodiments, the ratio of the mixture having different partially deuterated moieties may be controlled by the method, for example, by controlling the temperature.
In some embodiments, the elevated temperature is kept for at least 30 minutes. In some embodiments, the elevated temperature is kept for at least 1 hour. In some embodiments, the elevated temperature is kept for at least 5 hours. In some embodiments, the elevated temperature is kept for at least 10 hours. In some embodiments, the elevated temperature is kept for at least 15 hours. In some embodiments, the elevated temperature is kept for at least 20 hours. In some embodiments, the elevated temperature is kept for at least 24 hours. In some embodiments, the elevated temperature is kept for at least 36 hours. In some embodiments, the elevated temperature is kept for at least 48 hours.
In some embodiments, the method further comprises heating the first compound in a solvent containing a deuterated material with a base. In some of these embodiments, the base may be selected from the group consisting of sodium hydride, lithium diisopropylamide, sodium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide), potassium tert-butoxide, sodium tert-butoxide, potassium carbonate, sodium carbonate.
In some embodiments, the method further comprises heating the first compound in a solvent containing a deuterated material at atmosphere pressure. In some embodiments, the method further comprises heating the first compound in compound in a solvent containing a deuterated material under pressure at least 5 mm Hg higher than the atmosphere pressure. In some embodiments, the method further comprises heating the first compound compound in a solvent containing a deuterated material under pressure at least 10 mm Hg higher than the atmosphere pressure. In some embodiments, the method further comprises heating the first compound in a solvent containing a deuterated material under pressure at least 20 mm Hg higher than the atmosphere pressure. In some embodiments, the method further comprises heating the first compound compound in a solvent containing a deuterated material under pressure at least 30 mm Hg higher than the atmosphere pressure. In some embodiments, the method further comprises heating the first compound compound in a solvent containing a deuterated material under pressure at least 40 mm Hg higher than the atmosphere pressure. In some embodiments, the method further comprises heating the first compound in a solvent containing a deuterated material under pressure at least 50 mm Hg higher than the atmosphere pressure. In some embodiments, the method further compound in a solvent containing a deuterated material her comprises heating the first compound in compound in a solvent containing a deuterated material under pressure at least 60 mm Hg higher than the atmosphere pressure. In some embodiments, the method further comprises heating the first compound in a solvent containing a deuterated material under pressure at least 70 mm Hg higher than the atmosphere pressure. In some embodiments, the method further comprises heating the first compound compound in a solvent containing a deuterated material under pressure at least 76 mm Hg higher than the atmosphere pressure. In some of these embodiments, the solvent is partially deuterated. In some of these embodiments, the solvent is fully deuterated.
In some embodiments, the deuterated compound is capable of emitting light from a triplet excited state to a ground singlet state in an OLED at room temperature.
In some embodiments, the deuterated compound is a metal coordination complex having a metal-carbon bond.
In some embodiments, the deuterated compound is a metal coordination complex having a metal-carbene bond.
In some embodiments, the deuterated compound is a metal coordination complex having a metal-nitrogen bond.
In some embodiments, the deuterated compound is a metal coordination complex having a metal-oxygen or metal-sulfur bond.
In some embodiments, the metal is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Au, Ag, and Cu. In some embodiments, the metal is Ir. In some embodiments, the metal is Pt.
In some embodiments, the deuterated compound has the formula of M(L1)x(L2)y(L3)z;
In some embodiments, L1 is selected from the group consisting of the following structures (LIST A2):
In some embodiments, the deuterated compound has a formula selected from the group consisting of Ir(LA)3, Ir(LA)(LB)2, Ir(LA)2(LB), Ir(LA)2(LC), Ir(LA)(LB)(LC), and Pt(LA)(LB);
It should be understood that LA can be L1, and LB and LC can be each independently L2 or L3 in the above embodiments and throughout the disclosure.
In some embodiments, the deuterated compound is a hexadentate Ir complex comprising three bidentate ligands with at least one bidentate ligand being substituted or unsubstituted phenylpyridine ligand, or substituted or unsubstituted acetylacetonate ligand.
In some embodiments, the deuterated compound is a tetradentate Pt complex comprising at least one Pt-carbene or Pt—O bond.
In some embodiments, the deuterated compound has a formula selected from the group consisting of the structures in the following LIST 1a:
In some embodiments, the deuterated compound has a formula selected from the group consisting of the structures in the following LIST 1b:
In some embodiments, the deuterated compound is a tetradentate Pt complex comprising a tetradentate ligand;
In some of the above embodiments, the at least one six-membered aryl or heteroaryl is selected from the group consisting of phenyl, pyridine, pyrimidine, pyrazine, pyridazine, and triazine. In some of the above embodiments, the at least one six-membered heteroaryl is pyridine.
In some of the above embodiments, the deuterated compound has a formula selected from the group consisting of the structures in the following LIST 1c:
In some of the above embodiments, the deuterated compound has a formula of
In some embodiments, the deuterated compound has a formula selected from the group consisting of the structures in the following LIST 1:
In some embodiments, the deuterated compound is selected from the group consisting of the structures in the following LIST 2:
In some embodiments, the deuterated compound is capable of functioning as a delayed fluorescent emitter in an OLED at room temperature.
In some embodiments, the deuterated compound is capable of functioning as a thermal activated delayed fluorescent emitter in an OLED at room temperature.
In some embodiments, the deuterated compound comprises at least one donor group and at least one acceptor group.
In some embodiments, the deuterated compound is a metal complex.
In some embodiments, the deuterated compound is a non-metal complex.
In some embodiments, the deuterated compound is a Cu, Ag, or Au complex.
In some embodiments, the deuterated compound comprises at least one of the chemical moieties selected from the group consisting of:
In some embodiments, the deuterated compound comprises at least one of the chemical moieties selected from the group consisting of nitrile, isonitrile, borane, fluoride, pyridine, pyrimidine, pyrazine, triazine, aza-carbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-triphenylene, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, thiadiazole, and oxadiazole.
In some embodiments, the deuterated compound is capable of functioning as a fluorescent emitter in an OLED at room temperature.
In some embodiments, the deuterated compound comprises at least one organic group selected from the group consisting of:
and aza analogues thereof;
In some embodiments, the deuterated compound is selected from the group consisting of:
In another aspect, the present disclosure also provides a compound being capable of functioning as an emitter in an organic light emitting device at room temperature; wherein the compound has at least one carbocyclic or heterocyclic ring bearing at least two substituents, one of the at least two substituents is deuterium, the remaining one of the at least two substituents is not hydrogen or deuterium. In some embodiments, the emitter is selected from the group consisting of a phosphorescent emitter, a delayed-fluorescent emitter, a fluorescent emitter. In some embodiments, the fluorescent emitter can be a singlet or doublet emitters. In some such embodiments, the singlet emitter can also include a TADF emitter. In some embodiments, the at least one carbocyclic or heterocyclic ring is an aryl or heteroaryl ring. In some embodiments, the remaining one of the at least two substituents is the general substituents as described herein except deuterium. In some embodiments, the remaining one of the at least two substituents is the preferred, more preferred, or most preferred substituents as described herein except deuterium. In some embodiments, the remaining one of the at least two substituents is a non-deuterated, partially or fully deuterated alkyl or cycloalkyl. In some embodiments, the remaining one of the at least two substituents is a non-deuterated, partially or fully deuterated phenyl. In some embodiments, the compound is a tetradentate Pt or Pd complex comprising a tetradentate ligand, or a hexadentate Jr complex comprising three bidentate ligands; wherein the tetradentate ligand and at least one of the bidentate ligand comprises at least one carbocyclic or heterocyclic ring bearing at least two substituents as described herein. In some embodiments, such carbocyclic or heterocyclic ring is a six-membered aryl or heteroaryl coordinating to the Pt, Pd, or Jr.
In some of the above embodiments, the six-membered aryl or heteroaryl is selected from the group consisting of phenyl, pyridine, pyrimidine, pyrazine, pyridazine, and triazine. In some of the above embodiments, six-membered aryl is phenyl, and the six-membered heteroaryl is pyridine.
In some of the above embodiments, the compound has a formula selected from the group consisting of:
In some of the above embodiments, the compound has a formula of
wherein one or more of the RB″ or RC″ is D. In some of the above embodiments, exactly one RB″ or RC″ is D. In some of the above embodiments, two RB″ or RC″ are D. In some of the above embodiments, D is meta to the N of pyridine. In some of the above embodiments, one RB″ is para to the N. In some of the above embodiments, one RB″ is selected from the group consisting of aryl, heteroaryl, alkyl, cycloalkyl, silyl, partially or fully deuterated variants thereof, partially or fully fluorinated variants thereof, and combinations thereof.
In another aspect, the present disclosure also provides a deuterated compound comprising an aromatic ring coordinating to a metal through a direct bond or a one atom linker;
It should be understood that the one atome linker is intended to mean the linking atom is one atom such as BR, BRR′, NR, PR, P(O)R, O, S, Se, C═O, C═S, C═Se, C═NR, C═CRR′, S═O, SO2, CR, CRR′, SiRR′, GeRR′ wherein R and R′ is each independently a hydrogen or a substituent selected from the group consisting of the general substituents as defined herein.
In some embodiments, the aromatic ring is a phenyl ring that directly coordinates to the metal. In some embodiments, the aromatic ring is a phenyl ring that coordinates to the metal through a O, or S linker. In some embodiments, the aromatic ring is a pyridine ring that directly coordinates to the metal.
In some embodiments, the metal is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Au, Ag, and Cu.
In some embodiments, the deuterated compound is capable of functioning as a phosphorescent emitter in an organic light emitting device at room temperature.
In some embodiments, the aromatic ring is a 5-membered or 6-member aryl or heteroaryl ring.
In some embodiments, the aromatic ring is substituted by at least two D.
In some embodiments, the aromatic ring is substituted by at least three D.
In some embodiments, the aromatic ring is substituted by at least two substituents independently selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof.
In some embodiments, the at least one substituent is partially or fully deuterated, or partially or fully fluorinated.
In some embodiments, the at least one substituent is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, silyl, fluorine, and nitrile.
In some embodiments, the at least one substituent is joined or fused with another substituent in the compound to form a ring fused to the aromatic ring.
In some embodiments, the deuterated compound is capable of emitting light from a triplet excited state to a ground singlet state in an OLED at room temperature.
In some embodiments, the deuterated compound is a metal coordination complex having a metal-carbon bond.
In some embodiments, the deuterated compound is a metal coordination complex having a metal-carbene bond.
In some embodiments, the deuterated compound is a metal coordination complex having a metal-nitrogen bond.
In some embodiments, the deuterated compound is a metal coordination complex having a metal-oxygen or metal-sulfur bond.
In some embodiments, the metal is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Au, Ag, and Cu.
In some embodiments, the metal is Ir.
In some embodiments, the metal is Pt.
In some embodiments, the deuterated compound has the formula of M(L1)X(L2)y(L3)z;
In some embodiments, L1 is selected from the group consisting of LIST A2 as defined herein. wherein any two of Ra′, Rb′, Rc′, Rd′, and Re′ can be fused or joined to form a ring or form a multidentate ligand.
In some embodiments, the compound has a formula selected from the group consisting of Ir(LA)3, Ir(LA)(L)2, Ir(LA)2(LB), Ir(LA)2(LC), Ir(LA)(LB)(LC), and Pt(LA)(LB);
In some embodiments, the deuterated compound is a hexadentate Ir complex comprising three bidentate ligands with at least one bidentate ligand being substituted or unsubstituted phenylpyridine ligand, or substituted or unsubstituted acetylacetonate ligand.
In some embodiments, the deuterated compound is a tetradentate Pt complex comprising at least one Pt-carbene or Pt—O bond.
In some embodiments, the deuterated compound has a formula selected from the group consisting of the structures in the LIST 1a as defined herein.
In some embodiments, the deuterated compound has a formula selected from the group consisting of the structures in the LIST 1b as defined herein.
In some embodiments, the deuterated compound is a tetradentate Pt complex comprising a tetradentate ligand; wherein the tetradentate ligand comprises at least one six-membered aryl or heteroaryl coordinating to the Pt; wherein the at least one six-membered aryl or heteroaryl is partially or fully deuterated; and wherein the at least one six-membered aryl or heteroaryl can be further fused or substituted.
In some embodiments, the at least one six-membered aryl or heteroaryl is selected from the group consisting of phenyl, pyridine, pyrimidine, pyrazine, pyridazine, and triazine.
In some embodiments, the deuterated compound has a formula selected from the group consisting of the structures in the LIST 1c as defined herein.
In some embodiments, the deuterated compound has a formula of
In some embodiments, in the structures of LIST 1b or 1c, at least one RC″ is D, and at least one RC″ is not H or D. In some such embodiments, two RC″ are D, and the remaining two RC″ are not H or D. In some such embodiments, two RC″ of D are at the meta positions to the carbon atom substituted by the oxygen atom. In some such embodiments, two RC″ at the meta positions to the carbon atom bonding to the imidazole ring are alkyl groups having at least two, three, four, or five carbon atoms. In some embodiments, at least one RB″ is D, and at least one RB″ is not H or D. In some such embodiments, two RB″ are D, and one RB″ is not H or D. In some such embodiments, two RB″ of D are at the meta positions to the N atom of the pyridine. In some embodiments, the RB″ para to the N of pyridine is a substituted or unsubstituted phenyl. In some of such embodiments, the substituted phenyl can be partially or fully deuterated, or partially or fully fluorinated. In some of such embodiments, the substituted phenyl is substituted by at least one silyl or germyl group.
In some embodiments, RA1″ is selected from the group consisting of:
In some embodiments, the moiety G in the structure of
is selected from the group consisting of:
In some embodiments, the moiety H in the structure of
is selected from the group consisting of:
In some embodiments, the compound has the following formula:
wherein RA1″, moiety G, and moiety H are described above, RT is selected from the group consisting of:
and RY is selected from the group consisting of:
In some embodiments, the compound has the formula of Pt—(RAx)(RTy)(RYz)(Gp)(Hq) corresponding to the above structure; wherein x is an integer from 1 to 21, y is an integer from 1 to 4, z is an integer from 1 to 8, p is an integer from 1 to 12, and q is an integer from 1 to 43; and the compound is selected from the group consisting of Pt—(RA1)(RT1)(RY1)(G1)(H1) to Pt—(RA21)(RT4)(RY8)(G12)(H43).
In some embodiments, the deuterated compound is selected from the group consisting of LIST 1 as defined herein.
In some of the above embodiments, the deuterated compound is selected from the group consisting of LIST 2 as defined herein.
In yet another aspect, the present disclosure further provides a deuterated Pt or Pd compound. The deuterated compound comprises an aromatic ring coordinating to Pt or Pd through a direct bond or a one atom linker; wherein the aromatic ring is substituted by at least one D.
In some embodiments, the deuterated compound comprises a five-membered heteroaryl coordinating to the Pt or Pd. In some embodiments, the five-membered heteroaryl is imidazole, or imidazole derived carbene. In some embodiments, the aromatic ring is substituted by at least two D. In some embodiments, the aromatic ring is partially deuterated. In some embodiments, the aromatic ring is a phenyl ring that directly coordinates to the metal. In some embodiments, the aromatic ring is a phenyl ring that coordinates to the metal through a O, or S linker. In some embodiments, the aromatic ring is a pyridine ring that directly coordinates to the metal.
In some embodiments, the deuterated compound as described herein can be at least 30% deuterated, at least 40% deuterated, at least 50% deuterated, at least 60% deuterated, at least 70% deuterated, at least 80% deuterated, at least 90% deuterated, at least 95% deuterated, at least 99% deuterated, or 100% deuterated. As used herein, percent deuteration has its ordinary meaning and includes the percent of possible hydrogen atoms (e.g., positions that are hydrogen or deuterium) that are replaced by deuterium atoms.
In some embodiments of heteroleptic compound having the formula of M(L1)x(L2)y(L3)z as defined herein; wherein the ligand L1 has a first substituent R1, where the first substituent R1 has a first atom a-I that is the farthest away from the metal M among all atoms in the ligand L1. Additionally, the ligand L2, if present, has a second substituent RII, where the second substituent RII has a first atom a-II that is the farthest away from the metal M among all atoms in the ligand L2. Furthermore, the ligand L3, if present, has a third substituent RIII, where the third substituent RIII has a first atom a-III that is the farthest away from the metal M among all atoms in the ligand L3.
In such heteroleptic compounds, vectors VD1, VD2, and VD3 can be defined that are defined as follows. VD1 represents the direction from the metal M to the first atom a-I and the vector VD1 has a value D1 that represents the straightline distance between the metal M and the first atom a-I in the first substituent RI. VD represents the direction from the metal M to the first atom a-II and the vector VD has a value D2 that represents the straightline distance between the metal M and the first atom a-II in the second substituent RII. VD3 represents the direction from the metal M to the first atom a-III and the vector VD3 has a value D3 that represents the straightline distance between the metal M and the first atom a-III in the third substituent RIII.
In such heteroleptic compounds, a sphere having a radius r is defined whose center is the metal M and the radius r is the smallest radius that will allow the sphere to enclose all atoms in the compound that are not part of the substituents RI, RII and RIII; and where at least one of D1, D2, and D3 is greater than the radius r by at least 1.5 Å. In some embodiments, at least one of D1, D2, and D3 is greater than the radius r by at least 2.9, 3.0, 4.3, 4.4, 5.2, 5.9, 7.3, 8.8, 10.3, 13.1, 17.6, or 19.1 Å.
In some embodiments of such heteroleptic compound, the compound has a transition dipole moment axis and angles are defined between the transition dipole moment axis and the vectors VD1, VD2, and VD3, where at least one of the angles between the transition dipole moment axis and the vectors VD1, VD2, and VD3 is less than 40°. In some embodiments, at least one of the angles between the transition dipole moment axis and the vectors VD1, VD2, and VD3 is less than 30°. In some embodiments, at least one of the angles between the transition dipole moment axis and the vectors VD1, VD2, and VD3 is less than 20°. In some embodiments, at least one of the angles between the transition dipole moment axis and the vectors VD1, VD2, and VD3 is less than 15°. In some embodiments, at least one of the angles between the transition dipole moment axis and the vectors VD1, VD2, and VD3 is less than 10°. In some embodiments, at least two of the angles between the transition dipole moment axis and the vectors VD1, VD2, and VD3 are less than 20°. In some embodiments, at least two of the angles between the transition dipole moment axis and the vectors VD1, VD2, and VD3 are less than 15°. In some embodiments, at least two of the angles between the transition dipole moment axis and the vectors VD1, VD2, and VD3 are less than 10°.
In some embodiments, all three angles between the transition dipole moment axis and the vectors VD1, VD2, and VD3 are less than 20°. In some embodiments, all three angles between the transition dipole moment axis and the vectors VD1, VD2, and VD3 are less than 15°. In some embodiments, all three angles between the transition dipole moment axis and the vectors VD1, VD2, and VD3 are less than 10°.
In some embodiments of such heteroleptic compounds, the compound has a vertical dipole ratio (VDR) of 0.33 or less. In some embodiments of such heteroleptic compounds, the compound has a VDR of 0.30 or less. In some embodiments of such heteroleptic compounds, the compound has a VDR of 0.25 or less. In some embodiments of such heteroleptic compounds, the compound has a VDR of 0.20 or less. In some embodiments of such heteroleptic compounds, the compound has a VDR of 0.15 or less.
One of ordinary skill in the art would readily understand the meaning of the terms transition dipole moment axis of a compound and vertical dipole ratio of a compound. Nevertheless, the meaning of these terms can be found in U.S. Pat. No. 10,672,997 whose disclosure is incorporated herein by reference in its entirety. In U.S. Pat. No. 10,672,997, horizontal dipole ratio (HDR) of a compound, rather than VDR, is discussed. However, one skilled in the art readily understands that VDR=1−HDR.
In another aspect, the present disclosure also provides an OLED device comprising a first organic layer that contains a deuterated compound as disclosed in the above compounds section of the present disclosure.
In some embodiments, the OLED comprises: an anode; a cathode; and an organic layer disposed between the anode and the cathode, where the organic layer comprises a compound as described herein.
In some embodiments, the organic layer may be an emissive layer and the deuterated compound as described herein may be an emissive dopant or a non-emissive dopant.
In some embodiments, the organic layer may further comprise a host, wherein the host comprises a triphenylene containing benzo-fused thiophene or benzo-fused furan, wherein any substituent in the host is an unfused substituent independently selected from the group consisting of CnH2n+1, OCnH2n+1, OAr1, N(CnH2n+1)2, N(Ar1)(Ar2), CH═CH—CnH2n+1, C≡CCnH2n+1, Ar1, Ar1-Ar2, CnH2n-Ar1, or no substitution, wherein n is an integer from 1 to 10; and wherein Ar1 and Ar2 are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.
In some embodiments, the organic layer may further comprise a host, wherein host comprises at least one chemical group selected from the group consisting of triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, triazine, boryl, silyl, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and aza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene).
In some embodiments, the host may be selected from the HOST Group 1 consisting of:
In some embodiments, the host may be selected from the HOST Group 2 consisting of:
and combinations thereof.
In some embodiments, the organic layer may further comprise a host, wherein the host comprises a metal complex.
In some embodiments, the emissive layer can comprise two hosts, a first host and a second host. In some embodiments, the first host is a hole transporting host, and the second host is an electron transporting host. In some embodiments, the first host and the second host can form an exciplex.
In some embodiments, the compound as described herein may be a sensitizer; wherein the device may further comprise an acceptor; and wherein the acceptor may be selected from the group consisting of fluorescent emitter, delayed fluorescence emitter, and combination thereof.
In yet another aspect, the OLED of the present disclosure may also comprise an emissive region containing a compound as disclosed in the above compounds section of the present disclosure.
In some embodiments, the emissive region can comprise a compound as described herein.
In some embodiments, at least one of the anode, the cathode, or a new layer disposed over the organic emissive layer functions as an enhancement layer. The enhancement layer comprises a plasmonic material exhibiting surface plasmon resonance that non-radiatively couples to the emitter material and transfers excited state energy from the emitter material to non-radiative mode of surface plasmon polariton. The enhancement layer is provided no more than a threshold distance away from the organic emissive layer, wherein the emitter material has a total non-radiative decay rate constant and a total radiative decay rate constant due to the presence of the enhancement layer and the threshold distance is where the total non-radiative decay rate constant is equal to the total radiative decay rate constant. In some embodiments, the OLED further comprises an outcoupling layer. In some embodiments, the outcoupling layer is disposed over the enhancement layer on the opposite side of the organic emissive layer. In some embodiments, the outcoupling layer is disposed on opposite side of the emissive layer from the enhancement layer but still outcouples energy from the surface plasmon mode of the enhancement layer. The outcoupling layer scatters the energy from the surface plasmon polaritons. In some embodiments this energy is scattered as photons to free space. In other embodiments, the energy is scattered from the surface plasmon mode into other modes of the device such as but not limited to the organic waveguide mode, the substrate mode, or another waveguiding mode. If energy is scattered to the non-free space mode of the OLED other outcoupling schemes could be incorporated to extract that energy to free space. In some embodiments, one or more intervening layer can be disposed between the enhancement layer and the outcoupling layer. The examples for interventing layer(s) can be dielectric materials, including organic, inorganic, perovskites, oxides, and may include stacks and/or mixtures of these materials.
The enhancement layer modifies the effective properties of the medium in which the emitter material resides resulting in any or all of the following: a decreased rate of emission, a modification of emission line-shape, a change in emission intensity with angle, a change in the stability of the emitter material, a change in the efficiency of the OLED, and reduced efficiency roll-off of the OLED device. Placement of the enhancement layer on the cathode side, anode side, or on both sides results in OLED devices which take advantage of any of the above-mentioned effects. In addition to the specific functional layers mentioned herein and illustrated in the various OLED examples shown in the figures, the OLEDs according to the present disclosure may include any of the other functional layers often found in OLEDs.
The enhancement layer can be comprised of plasmonic materials, optically active metamaterials, or hyperbolic metamaterials. As used herein, a plasmonic material is a material in which the real part of the dielectric constant crosses zero in the visible or ultraviolet region of the electromagnetic spectrum. In some embodiments, the plasmonic material includes at least one metal. In such embodiments the metal may include at least one of Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca alloys or mixtures of these materials, and stacks of these materials. In general, a metamaterial is a medium composed of different materials where the medium as a whole acts differently than the sum of its material parts. In particular, we define optically active metamaterials as materials which have both negative permittivity and negative permeability. Hyperbolic metamaterials, on the other hand, are anisotropic media in which the permittivity or permeability are of different sign for different spatial directions. Optically active metamaterials and hyperbolic metamaterials are strictly distinguished from many other photonic structures such as Distributed Bragg Reflectors (“DBRs”) in that the medium should appear uniform in the direction of propagation on the length scale of the wavelength of light. Using terminology that one skilled in the art can understand: the dielectric constant of the metamaterials in the direction of propagation can be described with the effective medium approximation. Plasmonic materials and metamaterials provide methods for controlling the propagation of light that can enhance OLED performance in a number of ways.
In some embodiments, the enhancement layer is provided as a planar layer. In other embodiments, the enhancement layer has wavelength-sized features that are arranged periodically, quasi-periodically, or randomly, or sub-wavelength-sized features that are arranged periodically, quasi-periodically, or randomly. In some embodiments, the wavelength-sized features and the sub-wavelength-sized features have sharp edges.
In some embodiments, the outcoupling layer has wavelength-sized features that are arranged periodically, quasi-periodically, or randomly, or sub-wavelength-sized features that are arranged periodically, quasi-periodically, or randomly. In some embodiments, the outcoupling layer may be composed of a plurality of nanoparticles and in other embodiments the outcoupling layer is composed of a pluraility of nanoparticles disposed over a material. In these embodiments the outcoupling may be tunable by at least one of varying a size of the plurality of nanoparticles, varying a shape of the plurality of nanoparticles, changing a material of the plurality of nanoparticles, adjusting a thickness of the material, changing the refractive index of the material or an additional layer disposed on the plurality of nanoparticles, varying a thickness of the enhancement layer, and/or varying the material of the enhancement layer. The plurality of nanoparticles of the device may be formed from at least one of metal, dielectric material, semiconductor materials, an alloy of metal, a mixture of dielectric materials, a stack or layering of one or more materials, and/or a core of one type of material and that is coated with a shell of a different type of material. In some embodiments, the outcoupling layer is composed of at least metal nanoparticles wherein the metal is selected from the group consisting of Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca, alloys or mixtures of these materials, and stacks of these materials. The plurality of nanoparticles may have additional layer disposed over them. In some embodiments, the polarization of the emission can be tuned using the outcoupling layer. Varying the dimensionality and periodicity of the outcoupling layer can select a type of polarization that is preferentially outcoupled to air. In some embodiments the outcoupling layer also acts as an electrode of the device.
In yet another aspect, the present disclosure also provides a consumer product comprising an organic light-emitting device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a compound as disclosed in the above compounds section of the present disclosure.
In some embodiments, the consumer product comprises an OLED having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise CLAIM 1 as described herein.
In some embodiments, the consumer product can be one of a flat panel display, a computer monitor, a medical monitor, a television, a billboard, a light for interior or exterior illumination and/or signaling, a heads-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a cell phone, tablet, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a micro-display that is less than 2 inches diagonal, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising multiple displays tiled together, a theater or stadium screen, a light therapy device, and a sign.
Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an “exciton,” which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.
Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.
The initial OLEDs used emissive molecules that emitted light from their singlet states (“fluorescence”) as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.
More recently, OLEDs having emissive materials that emit light from triplet states (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, vol. 395, 151-154, 1998; (“Baldo-I”) and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference.
More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.
The simple layered structure illustrated in
Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in
Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP, also referred to as organic vapor jet deposition (OVJD)), such as described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink-jet and organic vapor jet printing (OVJP). Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons are a preferred range. Materials with asymmetric structures may have better solution processability than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.
Devices fabricated in accordance with embodiments of the present disclosure may further optionally comprise a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. The barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. The barrier layer may comprise a single layer, or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate an inorganic or an organic compound or both. The preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material as described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporated by reference in their entireties. To be considered a “mixture”, the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be created from the same precursor material. In one example, the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon.
Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices such as discrete light source devices or lighting panels, etc. that can be utilized by the end-user product manufacturers. Such electronic component modules can optionally include the driving electronics and/or power source(s). Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of consumer products that have one or more of the electronic component modules (or units) incorporated therein. A consumer product comprising an OLED that includes the compound of the present disclosure in the organic layer in the OLED is disclosed. Such consumer products would include any kind of products that include one or more light source(s) and/or one or more of some type of visual displays. Some examples of such consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, mobile phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, micro-displays (displays that are less than 2 inches diagonal), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screen, a light therapy device, and a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present disclosure, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25° C.), but could be used outside this temperature range, for example, from −40 degree C. to +80° C.
More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.
The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.
In some embodiments, the OLED has one or more characteristics selected from the group consisting of being flexible, being rollable, being foldable, being stretchable, and being curved. In some embodiments, the OLED is transparent or semi-transparent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes.
In some embodiments, the OLED further comprises a layer comprising a delayed fluorescent emitter. In some embodiments, the OLED comprises a RGB pixel arrangement or white plus color filter pixel arrangement. In some embodiments, the OLED is a mobile device, a hand held device, or a wearable device. In some embodiments, the OLED is a display panel having less than 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a display panel having at least 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a lighting panel.
In some embodiments, the compound can be an emissive dopant. In some embodiments, the compound can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence; see, e.g., U.S. application Ser. No. 15/700,352, which is hereby incorporated by reference in its entirety), triplet-triplet annihilation, or combinations of these processes. In some embodiments, the emissive dopant can be a racemic mixture, or can be enriched in one enantiomer. In some embodiments, the compound can be homoleptic (each ligand is the same). In some embodiments, the compound can be heteroleptic (at least one ligand is different from others). When there are more than one ligand coordinated to a metal, the ligands can all be the same in some embodiments. In some other embodiments, at least one ligand is different from the other ligands. In some embodiments, every ligand can be different from each other. This is also true in embodiments where a ligand being coordinated to a metal can be linked with other ligands being coordinated to that metal to form a tridentate, tetradentate, pentadentate, or hexadentate ligands. Thus, where the coordinating ligands are being linked together, all of the ligands can be the same in some embodiments, and at least one of the ligands being linked can be different from the other ligand(s) in some other embodiments.
In some embodiments, the compound can be used as a phosphorescent sensitizer in an OLED where one or multiple layers in the OLED contains an acceptor in the form of one or more fluorescent and/or delayed fluorescence emitters. In some embodiments, the compound can be used as one component of an exciplex to be used as a sensitizer. As a phosphorescent sensitizer, the compound must be capable of energy transfer to the acceptor and the acceptor will emit the energy or further transfer energy to a final emitter. The acceptor concentrations can range from 0.001% to 100%. The acceptor could be in either the same layer as the phosphorescent sensitizer or in one or more different layers. In some embodiments, the acceptor is a TADF emitter. In some embodiments, the acceptor is a fluorescent emitter. In some embodiments, the emission can arise from any or all of the sensitizer, acceptor, and final emitter.
According to another aspect, a formulation comprising the compound described herein is also disclosed.
The OLED disclosed herein can be incorporated into one or more of a consumer product, an electronic component module, and a lighting panel. The organic layer can be an emissive layer and the compound can be an emissive dopant in some embodiments, while the compound can be a non-emissive dopant in other embodiments.
In yet another aspect of the present disclosure, a formulation that comprises the novel compound disclosed herein is described. The formulation can include one or more components selected from the group consisting of a solvent, a host, a hole injection material, hole transport material, electron blocking material, hole blocking material, and an electron transport material, disclosed herein.
The present disclosure encompasses any chemical structure comprising the novel compound of the present disclosure, or a monovalent or polyvalent variant thereof. In other words, the inventive compound, or a monovalent or polyvalent variant thereof, can be a part of a larger chemical structure. Such chemical structure can be selected from the group consisting of a monomer, a polymer, a macromolecule, and a supramolecule (also known as supermolecule). As used herein, a “monovalent variant of a compound” refers to a moiety that is identical to the compound except that one hydrogen has been removed and replaced with a bond to the rest of the chemical structure. As used herein, a “polyvalent variant of a compound” refers to a moiety that is identical to the compound except that more than one hydrogen has been removed and replaced with a bond or bonds to the rest of the chemical structure. In the instance of a supramolecule, the inventive compound can also be incorporated into the supramolecule complex without covalent bonds.
D. Combination of the Compounds of the Present Disclosure with Other Materials
The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.
A charge transport layer can be doped with conductivity dopants to substantially alter its density of charge carriers, which will in turn alter its conductivity. The conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor may also be achieved. Hole-transporting layer can be doped by p-type conductivity dopants and n-type conductivity dopants are used in the electron-transporting layer.
Non-limiting examples of the conductivity dopants that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047, and US2012146012.
A hole injecting/transporting material to be used in the present disclosure is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of the material include, but are not limited to: a phthalocyanine or porphyrin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and silane derivatives; a metal oxide derivative, such as MoOx; a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.
Examples of aromatic amine derivatives used in HIL or HTL include, but not limit to the following general structures:
Each of Ar1 to Ar9 is selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each Ar may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, Ar1 to Ar9 is independently selected from the group consisting of:
Examples of metal complexes used in HIL or HTL include, but are not limited to the following general formula:
In one aspect, (Y101-Y102) is a 2-phenylpyridine derivative. In another aspect, (Y101-Y102) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os, and Zn. In a further aspect, the metal complex has a smallest oxidation potential in solution vs. Fc*/Fc couple less than about 0.6 V.
Non-limiting examples of the HIL and HTL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, JP2007091719, JP2008021687, JP2014-009196, KR20110088898, KR20130077473, TW201139402, U.S. Ser. No. 06/517,957, US20020158242, US20030162053, US20050123751, US20060182993, US20060240279, US20070145888, US20070181874, US20070278938, US20080014464, US20080091025, US20080106190, US20080124572, US20080145707, US20080220265, US20080233434, US20080303417, US2008107919, US20090115320, US20090167161, US2009066235, US2011007385, US20110163302, US2011240968, US2011278551, US2012205642, US2013241401, US20140117329, US2014183517, U.S. Pat. Nos. 5,061,569, 5,639,914, WO05075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO2013018530, WO2013039073, WO2013087142, WO2013118812, WO2013120577, WO2013157367, WO2013175747, WO2014002873, WO2014015935, WO2014015937, WO2014030872, WO2014030921, WO2014034791, WO2014104514, WO2014157018.
An electron blocking layer (EBL) may be used to reduce the number of electrons and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies, and/or longer lifetime, as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in EBL contains the same molecule or the same functional groups used as one of the hosts described below.
The light emitting layer of the organic EL device of the present disclosure preferably contains at least a metal complex as light emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. Any host material may be used with any dopant so long as the triplet criteria is satisfied.
Examples of metal complexes used as host are preferred to have the following general formula:
In one aspect, the metal complexes are:
In another aspect, Met is selected from Ir and Pt. In a further aspect, (Y103-Y104) is a carbene ligand.
In one aspect, the host compound contains at least one of the following groups selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each option within each group may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, the host compound contains at least one of the following groups in the molecule:
Non-limiting examples of the host materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060280965, US20090017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, US20140225088, US2014034914, U.S. Pat. No. 7,154,114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO2006114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO2009066779, WO2009086028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO2012128298, WO2012133644, WO2012133649, WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472, US20170263869, US20160163995, U.S. Pat. No. 9,466,803,
One or more additional emitter dopants may be used in conjunction with the compound of the present disclosure. Examples of the additional emitter dopants are not particularly limited, and any compounds may be used as long as the compounds are typically used as emitter materials. Examples of suitable emitter materials include, but are not limited to, compounds which can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence), triplet-triplet annihilation, or combinations of these processes.
Non-limiting examples of the emitter materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP2013110263, JP4478555, KR1020090133652, KR20120032054, KR20130043460, TW201332980, U.S. Ser. No. 06/699,599, U.S. Ser. No. 06/916,554, US20010019782, US20020034656, US20030068526, US20030072964, US20030138657, US20050123788, US20050244673, US2005123791, US2005260449, US20060008670, US20060065890, US20060127696, US20060134459, US20060134462, US20060202194, US20060251923, US20070034863, US20070087321, US20070103060, US20070111026, US20070190359, US20070231600, US2007034863, US2007104979, US2007104980, US2007138437, US2007224450, US2007278936, US20080020237, US20080233410, US20080261076, US20080297033, US200805851, US2008161567, US2008210930, US20090039776, US20090108737, US20090115322, US20090179555, US2009085476, US2009104472, US20100090591, US20100148663, US20100244004, US20100295032, US2010102716, US2010105902, US2010244004, US2010270916, US20110057559, US20110108822, US20110204333, US2011215710, US2011227049, US2011285275, US2012292601, US20130146848, US2013033172, US2013165653, US2013181190, US2013334521, US20140246656, US2014103305, U.S. Pat. Nos. 6,303,238, 6,413,656, 6,653,654, 6,670,645, 6,687,266, 6,835,469, 6,921,915, 7,279,704, 7,332,232, 7,378,162, 7,534,505, 7,675,228, 7,728,137, 7,740,957, 7,759,489, 7,951,947, 8,067,099, 8,592,586, 8,871,361, WO06081973, WO06121811, WO07018067, WO07108362, WO07115970, WO07115981, WO08035571, WO2002015645, WO2003040257, WO2005019373, WO2006056418, WO2008054584, WO2008078800, WO2008096609, WO2008101842, WO2009000673, WO2009050281, WO2009100991, WO2010028151, WO2010054731, WO2010086089, WO2010118029, WO2011044988, WO2011051404, WO2011107491, WO2012020327, WO2012163471, WO2013094620, WO2013107487, WO2013174471, WO2014007565, WO2014008982, WO2014023377, WO2014024131, WO2014031977, WO2014038456, WO2014112450.
A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies and/or longer lifetime as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the HBL interface.
In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above.
In another aspect, compound used in HBL contains at least one of the following groups in the molecule:
Electron transport layer (ETL) may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.
In one aspect, compound used in ETL contains at least one of the following groups in the molecule:
In another aspect, the metal complexes used in ETL contains, but not limit to the following general formula:
Non-limiting examples of the ETL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US2010108990, US2011156017, US2011210320, US2012193612, US2012214993, US2014014925, US2014014927, US20140284580, U.S. Pat. Nos. 6,656,612, 8,415,031, WO2003060956, WO2007111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO2011105373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535
In tandem or stacked OLEDs, the CGL plays an essential role in the performance, which is composed of an n-doped layer and a p-doped layer for injection of electrons and holes, respectively. Electrons and holes are supplied from the CGL and electrodes. The consumed electrons and holes in the CGL are refilled by the electrons and holes injected from the cathode and anode, respectively; then, the bipolar currents reach a steady state gradually. Typical CGL materials include n and p conductivity dopants used in the transport layers.
In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. The minimum amount of hydrogen of the compound being deuterated is selected from the group consisting of 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, and 100%. Thus, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. may be undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also may be undeuterated, partially deuterated, and fully deuterated versions thereof.
It is understood that the various embodiments described herein are by way of example only and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. The present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting.
It should also be understood that different embodiments of all the compounds and devices described herein may be interchangeable if those embodiments are also applicable under other aspects of the entire disclosure.
Experimental Data
The following examples have been carried out by using the method described herein. The final products are confirmed by 1H NMR.
This application claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Applications No. 63/403,169, filed on Sep. 1, 2022, No. 63/426,729, filed on Nov. 19, 2022, No. 63/432,083, filed on Dec. 13, 2022, No. 63/442,524, filed on Feb. 1, 2023, and No. 63/503,984, filed on May 24, 2023, the entire contents of all the above referenced applications are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| 63403169 | Sep 2022 | US | |
| 63426729 | Nov 2022 | US | |
| 63432083 | Dec 2022 | US | |
| 63442524 | Feb 2023 | US | |
| 63503984 | May 2023 | US |
