Host Material for Electroluminescent Device

Abstract

To provide novel organic materials that have performance advantages over conventional organic materials when used in organic optoelectronic devices, particularly, organic light emitting devices (OLEDs).SOLUTION: The invention provides carbazole derivatives represented by the compounds A and B in the figure.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims priority to U.S. Provisional Patent Application No. 62 / 772,403, filed on November 28, 2018, the entire disclosure of which is incorporated herein by reference.

[0002] The present invention relates to compounds for use as hosts and devices such as organic light - emitting diodes containing the same.

Background Art

[0003] Optoelectronic devices using organic materials are becoming increasingly desirable for several reasons. Many of the materials used to fabricate such devices are relatively inexpensive, so organic optoelectronic devices have the potential for cost - advantages over inorganic devices. In addition, due to the inherent properties of organic materials such as flexibility, the materials can be well - suited for specific applications such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light - emitting diodes / devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials can have performance advantages over conventional materials. For example, the wavelength at which the organic light - emitting layer emits light can generally be easily adjusted with appropriate dopants.

[0004] OLEDs utilize thin organic films that emit light when a voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat - panel displays, lighting, and backlighting. Several OLED materials and configurations are described in Patent Document 1, Patent Document 2, and Patent Document 3, the entire disclosures of which are incorporated herein by reference.

[0005] One use of the phosphorescent light-emitting molecules is a full-color display. The industry standard for such displays requires pixels adapted to emit specific colors referred to as "saturated" colors. In particular, these standards require saturated red, green, and blue pixels. Alternatively, the OLED can be designed to emit white light. Conventional liquid crystal display emission from a white backlight is filtered using absorption filters to produce red, green, and blue emissions. A similar technique can also be used with OLEDs. The white OLED can be either a single EML device or a stacked structure. Colors can be measured using CIE coordinates well-known in the art.

[0006] An example of a green light-emitting molecule has the following structure:

Chemical formula

[0007] In this drawing and the subsequent drawings in this specification, the inventors depict the coordination bond from nitrogen to metal (here Ir) as a straight line.

[0008] As used herein, the term "organic" includes polymeric materials and small molecule organic materials that can be used to fabricate organic optoelectronic devices. "Small molecule" refers to any organic material that is not a polymer, and a "small molecule" can actually be quite large. A small molecule may include repeating units in some situations. For example, the use of a long-chain alkyl group as a substituent does not exclude a molecule from the "small molecule" class. A small molecule may be incorporated into a polymer, for example, as a pendant group on a polymer backbone or as part of the backbone. A small molecule can also serve as the core portion of a dendrimer consisting of a series of chemical shells built on the core portion. The core portion of the 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.

[0009] As used herein, "top" means the furthest from the substrate, while "bottom" means the closest to the substrate. When a first layer is described as being "disposed on" a second layer, the first layer is disposed further from the substrate. There may be other layers between the first layer and the second layer unless it is specified that the first layer is "in contact with" the second layer. For example, the cathode can be described as being "disposed on" the anode even if there are various organic layers in between.

[0010] As used herein, "solution processable" means capable of being dissolved, dispersed or transported in a liquid medium in either solution or suspension form and / or capable of being deposited from the medium.

[0011] A ligand may be referred to as "photoactive" if the ligand is considered to directly contribute to the photoactive properties of the luminescent material. A ligand may be referred to as "auxiliary" if the ligand is not considered to contribute to the photoactive properties of the luminescent material, but an auxiliary ligand can modify the properties of the photoactive ligand.

[0012] As used herein, and as generally understood by one of ordinary skill in the art, the first "highest occupied molecular orbital" (HOMO) or "lowest unoccupied molecular orbital" (LUMO) energy level is "greater than" or "higher than" the second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since the ionization potential (IP) is measured as a negative energy relative to the vacuum level, a higher HOMO energy level corresponds to an IP with a smaller absolute value (less negative IP). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) with a smaller absolute value (less negative EA). In 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 to be closer to the top of such a diagram than a "lower" HOMO or LUMO energy level.

[0013] As used herein, and as generally understood by one of ordinary skill in the art, if the first work function has a higher absolute value, the first work function is "greater than" or "higher than" the second work function. Since the work function is generally measured as a negative number relative to the vacuum level, this means that a "higher" work function is more negative. In a conventional energy level diagram with the vacuum level at the top, a "higher" work function is illustrated as being further away in the downward direction from the vacuum level. Thus, the definitions of the HOMO and LUMO energy levels follow a different convention than the work function.

[0014] Further details regarding OLEDs and the definitions described above can be found in Patent Document 4, which is hereby incorporated by reference in its entirety.

SUMMARY OF THE INVENTION

[0015] A compound of Formula I below.

CHEMICAL

[0016] Also disclosed is an OLED containing a compound of the present disclosure in an organic layer.

[0017] Consumer products containing the OLED are also disclosed.

Brief Description of the Drawings

[0018]

Figure 1

[0019]

Figure 2

Embodiments for Carrying Out the Invention

[0020] Generally, an OLED includes 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 move to the oppositely charged electrodes, respectively. When an electron and a hole are localized on the same molecule, an "exciton", which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted via a photoelectron emission mechanism when the exciton relaxes. In some cases, the exciton can be localized on an excimer or an exciplex. Non-radiative mechanisms such as thermal relaxation may occur, but are generally considered undesirable.

[0021] Initial OLEDs used luminescent molecules ("fluorescence") that emit light from their singlet state, as disclosed, for example, in U.S. Patent No. 4,769,292, which is incorporated herein by reference in its entirety. Fluorescent emission generally occurs within a time frame of less than 10 nanoseconds.

[0022] More recently, OLEDs having a luminescent material that emits light from a triplet state ("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"), which are incorporated herein by reference in their entirety. Phosphorescence is described in more detail in columns 5-6 of U.S. Patent No. 7,279,704, which is incorporated herein by reference.

[0023] FIG. 1 shows an organic light emitting device 100. The figure is not necessarily to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, a light emitting layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. Cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 may be fabricated by sequentially depositing the described layers. The properties and functions of these various layers, as well as examples of materials, are described in more detail in columns 6-10 of US7,279,704, which is incorporated herein by reference.

[0024] For each of these layers, further examples are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated herein by reference in its entirety. An example of a p-doped hole transport layer is as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety, of m-MTDATA with F at a molar ratio of 50:1 4-It is doped with TCNQ. Examples of luminescent materials and host materials are disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated herein by reference in its entirety. An example of an n-doped electron transport layer is Li-doped BPhen in a 1:1 molar ratio as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety. U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated herein by reference in their entireties, disclose examples of cathodes including a composite cathode having a thin layer of a metal such as Mg:Ag with a transparent, conductive, sputter-deposited ITO layer on top. The theory and use of blocking layers are described in more detail in U.S. Patent No. 6,097,147 and U.S. Patent Application Publication No. 2003 / 0230980, which are incorporated herein by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated herein by reference in its entirety. A description of the protective layer can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated herein by reference in its entirety.

[0025] Figure 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, a light-emitting layer 220, a hole transport layer 225, and an anode 230. The device 200 can be fabricated by sequentially depositing the described layers. The most common OLED configuration has a cathode disposed on top of the anode, and since the device 200 has a cathode 215 disposed under the anode 230, the device 200 can be referred to as an "inverted" OLED. Materials similar to those described for device 100 may be used in the corresponding layers of device 200. Figure 2 provides an example of how some layers can be omitted from the structure of device 100.

[0026] The simple layer structures illustrated in FIGS. 1 and 2 are provided as non-limiting examples, and it is understood that embodiments of the present invention may be used in connection with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be realized by combining the various layers described in various ways, or the layers may be omitted entirely based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Many of the examples provided herein describe the various layers as including a single material, but it is understood that combinations of materials such as mixtures of hosts and dopants, or more generally mixtures, may be used. Also, the layers may have various sub-layers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into light emitting layer 220 and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an "organic layer" disposed between a cathode and an anode. The organic layer may include a single layer or may further include multiple layers of different organic materials as described, for example, with respect to FIGS. 1 and 2.

[0027] Structures and materials not specifically described may be used, such as OLEDs (PLEDs) composed of a polymer material such as that disclosed in U.S. Patent No. 5,247,190 to Friend, which is incorporated herein by reference in its entirety. As a further example, an OLED having a single organic layer may be used. The OLEDs may be stacked, for example, as described in U.S. Patent No. 5,707,745 to Forrest, which is incorporated herein by reference in its entirety. The OLED structure may deviate from the simple layer structure illustrated in FIGS. 1 and 2. For example, the substrate may include an angled reflective surface for improving out-coupling, such as a mesa structure described in U.S. Patent No. 6,091,195 to Forrest, which is incorporated herein by reference in its entirety, and / or a dimpled structure described in U.S. Patent No. 5,834,893 to Bulovic, which is incorporated herein by reference in its entirety.

[0028] Unless otherwise specified, any of the layers of the various embodiments can be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation such as those described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated herein by reference in their entirety, inkjet, organic vapor deposition (OVPD) such as those described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated herein by reference in its entirety, and deposition by organic vapor jet printing (OVJP) such as those described in U.S. Pat. No. 7,431,968, which is incorporated herein by reference in its entirety. Other suitable deposition methods include spin coating and other solution-based processes. Solution-based processes are preferably performed in a nitrogen or inert atmosphere. For other layers, preferred methods include thermal evaporation. Preferred patterning methods include masks such as those described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated herein by reference in their entirety, deposition via cold welding, and patterning associated with some of the deposition methods such as inkjet and organic vapor jet printing (OVJP). Other methods may be used. The materials to be deposited can be modified to be compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups that are branched or unbranched and preferably contain at least 3 carbons can be used in small molecules to enhance the ability to undergo solution processing. Substituents having 20 or more carbons may be used, and a range of 3 to 20 carbons is preferred. Materials having an asymmetric structure may have better solution processability than those having a symmetric structure, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents can be used to enhance the ability of small molecules to undergo solution processing.

[0029] Devices fabricated in accordance with embodiments of the present invention may further include a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in an environment containing moisture, vapor, and / or gas, etc. The barrier layer can be deposited on the substrate, above, below, or adjacent to the electrodes, or on any other part of the device including the edges. The barrier layer may include a single layer or multiple layers. The barrier layer can be formed by various known chemical vapor deposition techniques and can include compositions having a single phase and compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate inorganic or organic compounds or both. Preferred barrier layers include mixtures of polymeric and non-polymeric materials as described in U.S. Patent No. 7,968,146, PCT Patent Application Nos. PCT / US2007 / 023098 and PCT / US2009 / 042829, which are hereby incorporated by reference in their entirety. For the materials to be considered a "mixture", the polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and / or simultaneously. The weight ratio of the polymeric material to the non-polymeric material can range from 95:5 to 5:95. The polymeric and non-polymeric materials can be made from the same precursor material. In one example, the mixture of polymeric and non-polymeric materials consists essentially of polymeric silicon and inorganic silicon.

[0030] Devices fabricated in accordance with embodiments of the present invention can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into various electrical products or intermediate components. Such electrical products or intermediate components include display screens, lighting devices (such as discrete light source devices or lighting panels, etc.) that can be utilized by end-user product manufacturers. Such electronic component modules can optionally include drive electronics and / or power supplies. Devices fabricated in accordance with embodiments of the present invention can be incorporated into a wide variety of consumer products having one or more incorporated electronic component modules (or units). Consumer products are disclosed that include OLEDs containing the compounds of the present disclosure in the organic layers of the OLEDs. Such consumer products include any type of product that includes one or more light sources and / or one or more certain types of display devices. Some examples of such consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, indoor or outdoor lighting and / or lights for signaling, head-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, microdisplays (displays less than 2 inches diagonal), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls including multiple displays arranged side by side, theater or stadium screens, phototherapy devices, and billboards. Various control mechanisms, including passive matrix and active matrix, can be used to control devices fabricated in accordance with the present invention. Many of the devices are intended for use within a temperature range comfortable for humans, such as from 18 degrees Celsius to 30 degrees Celsius, more preferably room temperature (20 - 25 degrees Celsius), but can also be used outside of this temperature range, for example, from -40 degrees Celsius to +80 degrees Celsius.

[0031] The materials and structures described in this specification may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may use the materials and structures. More generally, organic devices such as organic transistors may use the materials and structures.

[0032] The terms "halo," "halogen," or "halide" are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

[0033] The term "acyl" refers to a substituted carbonyl group (C(O)-R s ).

[0034] The term "ester" refers to a substituted oxycarbonyl (-O-C(O)-R s or -C(O)-O-R s ) group.

[0035] The term "ether" refers to an -OR s group.

[0036] The terms "sulfanyl" or "thioether" are used interchangeably and refer to an -SR s group.

[0037] The term "sulfinyl" refers to an -S(O)-R s group.

[0038] The term "sulfonyl" refers to an -SO 2 -R s group.

[0039] The term "phosphino" refers to a -P(R s ) 3 group, and each R s may be the same or different.

[0040] The term "silyl" refers to an -Si(R s )3 refers to the base, and each R s may be the same or different.

[0041] In each of the above, R s is 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 combinations thereof. Preferred R s is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0042] The term "alkyl" refers to and includes both straight-chain and branched-chain alkyl groups. Preferred alkyl groups include those containing from 1 to 15 carbon atoms, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, and 2,2-dimethylpropyl. Further, the alkyl group can be optionally substituted.

[0043] The term "cycloalkyl" refers to and includes monocyclic, polycyclic, and spiroalkyl groups. Preferred cycloalkyl groups include those containing 3 to 12 ring carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, etc. Further, the cycloalkyl group can be optionally substituted.

[0044] The term "heteroalkyl" or "heterocycloalkyl" refers to an alkyl group or a cycloalkyl group having at least one carbon atom substituted by a heteroatom, respectively. Optionally, at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Further, the heteroalkyl group or the heterocycloalkyl group is optionally substituted.

[0045] The term "alkenyl" refers to and includes both straight-chain and branched-chain alkene groups. An alkenyl group is essentially an alkyl group containing at least one carbon-carbon double bond in the alkyl chain. A cycloalkenyl group is essentially a cycloalkyl group containing at least one carbon-carbon double bond in the cycloalkyl ring. As used herein, the term "heteroalkenyl" refers to an alkenyl group having at least one carbon atom substituted by a heteroatom. Optionally, 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 contain 2 to 15 carbon atoms. Further, the alkenyl, cycloalkenyl, or heteroalkenyl group is optionally substituted.

[0046] The term "alkynyl" refers to and includes both straight-chain and branched-chain alkyne groups. Preferred alkynyl groups contain 2 to 15 carbon atoms. Further, the alkynyl group is optionally substituted.

[0047] The terms "aralkyl" or "arylalkyl" are used interchangeably and refer to an alkyl group substituted by an aryl group. Further, the aralkyl group is optionally substituted.

[0048] The term "heterocyclic group" refers to and includes aromatic and non-aromatic cyclic groups 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. Heteroaromatic cyclic groups can be used interchangeably with heteroaryl. Preferred hetero non-aromatic cyclic groups contain 3 to 7 ring atoms, contain at least one heteroatom, and include cyclic amines such as morpholino, piperidino, pyrrolidino, and cyclic ethers / thioethers such as tetrahydrofuran, tetrahydropyran, and tetrahydrothiophene. Further, the heterocyclic group can be optionally substituted.

[0049] The term "aryl" refers to and includes both monocyclic aromatic hydrocarbyl groups and polycyclic aromatic ring systems. Polycyclic means having two or more rings where two adjacent rings (the rings are "fused") share two carbons, and at least one of the rings is an aromatic hydrocarbyl group. For example, the other rings can be cycloalkyl, cycloalkenyl, aryl, heterocycle, and / or heteroaryl. Preferred aryl groups contain 6 to 30 carbon atoms, preferably those containing 6 to 20 carbon atoms, and more preferably those containing 6 to 12 carbon atoms. Aryl groups having 6 carbons, 10 carbons, or 12 carbons are particularly preferred. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, etc., and phenyl, biphenyl, triphenyl, triphenylene, fluorene, and naphthalene are preferred. Further, the aryl group can be optionally substituted.

[0050] The term "heteroaryl" refers to and includes both monocyclic heteroaromatic groups and polycyclic aromatic ring systems containing at least one heteroatom. Examples of heteroatoms include, but are not limited to, O, S, N, P, B, Si, and Se. In many instances, O, S, or N are preferred heteroatoms. The hetero monocyclic aromatic system is preferably a monocyclic ring having 5 or 6 ring atoms, and the ring can have from 1 to 6 heteroatoms. The hetero polycyclic ring system can have two or more rings where two atoms are common to two adjacent rings (the rings are "fused"), and at least one of the rings is heteroaryl, for example, the other rings can be cycloalkyl, cycloalkenyl, aryl, heterocycle, and / or heteroaryl. The hetero polycyclic aromatic ring system can have from 1 to 6 heteroatoms per ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing from 3 to 30 carbon atoms, more preferably those containing from 3 to 20 carbon atoms, and even more preferably those containing from 3 to 12 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. Among them, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and their aza analogs are preferred. Further, the heteroaryl group can be optionally substituted.

[0051] Among 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 their respective aza analogs are of particular interest.

[0052] As used herein, the terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclic group, aryl, and heteroaryl are independently unsubstituted or substituted with one or more common substituents.

[0053] In many instances, said general substituents are selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, cyclic amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0054] In some instances, preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.

[0055] In some instances, preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, aryl, heteroaryl, sulfanyl, and combinations thereof.

[0056] In still other instances, more preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0057] The terms "substituted" and "substitution" refer to substituents other than H attached to the relevant position (e.g., carbon or nitrogen). For example, when R 1 represents monosubstitution, one R 1 must be other than H (i.e., substitution). Similarly, when R 1 represents disubstitution, two of R 1 must be other than H. Similarly, when R 1 represents unsubstitution, R 1It can be hydrogen at the available valence of the ring atom, such as in the case of carbon atoms in benzene and nitrogen atoms in pyrrole, or it represents nothing in the case of a ring atom having a completely filled valence (e.g., nitrogen in pyridine). The maximum number of possible substitutions in the ring structure depends on the total number of available valences at the ring atoms.

[0058] As used herein, "these combinations" indicates that one or more members of the applied list are combined to form a known or chemically stable arrangement that can be envisioned by one of ordinary skill in the art from the applied list. For example, alkyl and deuterium can be combined to form a partially or fully deuterated alkyl group; halogen and alkyl can be combined to form a halogenated alkyl substituent; halogen, alkyl, and aryl can be combined to form a halogenated arylalkyl. In one example, the term substitution includes combinations of 2 to 4 of the listed groups. In another example, the term substitution includes combinations of 2 to 3 groups. In yet another example, the term substitution includes combinations of 2 groups. Preferred combinations of substituents are those containing up to 50 atoms other than hydrogen or deuterium, or those containing up to 40 atoms other than hydrogen or deuterium, or those containing up to 30 atoms other than hydrogen or deuterium. In many examples, preferred combinations of substituents contain up to 20 atoms other than hydrogen or deuterium.

[0059] The term "aza" in the fragments described herein, such as in aza-dibenzofuran, aza-dibenzothiophene, etc., means that one or more of the C-H groups in each aromatic ring can be replaced by a nitrogen atom. For example, without limitation, aza-triphenylene 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 above-described aza derivatives, and it is intended that all such analogs are encompassed by the foregoing terms described herein.

[0060] 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. Patent No. 8,557,400, International Publication No. WO2006 / 095951, and U.S. Patent Application Publication No. 2011 / 0037057, which are incorporated herein by reference in their entireties, describe the preparation of organometallic complexes substituted with deuterium. Further references are made by Tetrahedron 2015, 71, 1425 - 30 (Ming Yan et al.) and Angew. Chem. Int. Ed. (Reviews) 2007, 46, 7744 - 65 (Atzrodt et al.), which are incorporated herein by reference in their entireties, and describe an efficient route for deuterating methylene hydrogens in benzylamine and substituting aromatic ring hydrogens with deuterium, respectively.

[0061] When a molecular fragment is described as being a substituent or as being attached to another moiety, it should be understood that its name may be described as a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuryl) or the entire molecule (e.g., benzene, naphthalene, dibenzofuran). It is understood that herein, these are considered equivalent even if the manner of display of the substituent or attached fragment is different.

[0062] In one example, a pair of adjacent substituents can optionally bond or condense to form a ring. Preferred rings are 5 - membered, 6 - membered, or 7 - membered carbocyclic or heterocyclic rings, including both examples where the ring portion formed by the pair of substituents is saturated and examples where the ring portion formed by the pair of substituents is unsaturated. As used herein, "adjacent" means that, as long as a stable fused - ring system can be formed, two relevant substituents can be adjacent to each other on the same ring or on two adjacent rings having the two closest available substitutable positions, such as the 2 - position and 2'-position in biphenyl and the 1 - position and 8 - position in naphthalene.

[0063] In one aspect, the present invention includes a compound of formula I below.

Chemical formula

[0064] In one embodiment, R, R’, R A , R B , and R C are each independently hydrogen, or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.)

[0065] In one embodiment, X 1 ~X 3 are each N. In one embodiment, X 1 is CR, and X 2 and X 3 are N. In one embodiment, X 2 is CR, and X 1 and X 3 are N. In one embodiment, X 1 is N, and X 2 and X 3 are CR.)

[0066] In one embodiment, each R is H.)

[0067] In one embodiment, each R A is H.)

[0068] In one embodiment, each R B is H.)

[0069] In one embodiment, each R C is H.)

[0070] In one embodiment, R 1 , R 2 , R 3 , and R 4is aryl or heteroaryl, respectively.

[0071] In one embodiment, R 1 and R 2 are joined to form a carbazole group.

[0072] In one embodiment, R 3 and R 4 are joined to form a carbazole group.

[0073] In one embodiment, R 1 and R 2 are joined to form a carbazole group, and R 3 and R 4 are joined to form a carbazole group.

[0074] In one embodiment, A 1 ~A 5 are each C. In one embodiment, A 5 is C and ring A is a 6-membered aromatic ring. In one embodiment, A 5 is N and ring A is a 5-membered aromatic ring.

[0075] In one embodiment, the compound is selected from the group consisting of the following.

Chemical formula

Chemical formula

[0076] In one embodiment, the compound is selected from the group consisting of compounds H1-B1-B1-B1 to H50-B60-B60-B60 based on the numbered formula Hn-Bi-Bj-Bk, where n is an integer from 1 to 50, and i, j, and k are independently integers from 1 to 60, and H1 to H50 have the following structures;

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0077] In one embodiment, the compound is selected from the group consisting of the following.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0078] In another aspect, the present invention includes an organic light-emitting device (OLED) including an anode, a cathode, and an organic layer disposed between the anode and the cathode and including a compound according to Formula I.

[0079] In one embodiment, the OLED further includes a sensitizer, and the organic layer includes an acceptor and a host; the acceptor is selected from the group consisting of a fluorescent emitter, a delayed fluorescent emitter, and combinations thereof; and the host is a compound of Formula I.

[0080] In some embodiments, the OLED has one or more properties selected from the group consisting of being flexible, rollable, foldable, stretchable, and bendable. In some embodiments, the OLED is transparent or translucent. In some embodiments, the OLED further includes a layer including carbon nanotubes.

[0081] In some embodiments, the OLED further includes a layer including a delayed fluorescent emitter. In some embodiments, the OLED includes an RGB pixel array or a white and color filter pixel array. In some embodiments, the OLED is a mobile device, a handheld device, or a wearable device. In some embodiments, the OLED is a display panel having a diagonal less than 10 inches or an area less than 50 square inches. In some embodiments, the OLED is a display panel having a diagonal of at least 10 inches or an area of at least 50 square inches. In some embodiments, the OLED is a lighting panel.

[0082] The luminescent dopant can be a phosphorescent dopant and / or a fluorescent dopant. The organic layer can include a compound according to Formula I described herein and variants thereof as a host.

[0083] In one embodiment, the organic layer is a light-emitting layer, and the compound is a light-emitting dopant or a non-light-emitting dopant.

[0084] In one embodiment, the organic layer is a light-emitting layer, and the compound is a light-emitting dopant or a non-light-emitting dopant.

[0085] In one embodiment, the organic layer is a light-emitting layer including a luminescent substance and a host; the luminescent substance is selected from the group consisting of a phosphorescent luminescent substance, a fluorescent luminescent substance, a delayed fluorescent luminescent substance, and combinations thereof; the host is a compound of Formula I.

[0086] In one embodiment, the phosphorescent luminescent substance is a transition metal complex having at least one ligand selected from the group consisting of the following, or having a part of the ligand when the ligand is a bidentate or more: [Chemical formula] [Chemical formula] (In the formula, Y 1 ~Y 13 are each independently selected from the group consisting of carbon and nitrogen; Y' is BR e , NR e , PR e , O, S, Se, C=O, S=O, SO 2 , CR e R f , SiR e R f , and GeR e R f selected from the group consisting of; Re and R f may be condensed or joined to form a ring; R a 、R b 、R c 、and R d may each independently represent from mono-substitution to the maximum possible number of substitutions, or no substitution; R a 、R b 、R c 、R d 、R e 、and R f are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; R a 、R b 、R c 、and R d Any two adjacent substituents of may be condensed or joined to form a ring or form a multidentate ligand.)

[0087] In other aspects, the present invention includes consumer products including an organic light emitting device (OLED) including an anode, a cathode, and an organic layer disposed between the anode and the cathode and including a compound according to Formula I.

[0088] According to other aspects, formulations including the compounds described herein are also disclosed.

[0089] The OLEDs disclosed herein can be incorporated into one or more of consumer products, electronic component modules, and lighting panels.

[0090] In still other aspects of the present disclosure, formulations comprising the novel compounds disclosed herein are described. The formulation may also include one or more components selected from the group consisting of solvents, hosts, hole injection materials, hole transport materials, electron blocking materials, hole blocking materials, and electron transport layer materials disclosed herein.

[0091] The present disclosure encompasses any chemical structure comprising the novel compounds of the present disclosure, or monovalent or polyvalent variants thereof. In other words, the inventive compounds or monovalent or polyvalent variants thereof can be part of a larger chemical structure. Such chemical structures can be selected from the group consisting of monomers, polymers, macromolecules, and supramolecules (also known as supermolecules). 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 remainder 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 remainder of the chemical structure. In the case of a supramolecule, the inventive compound can also be incorporated into the supramolecular complex without covalent bonding. Combinations with other materials

[0092] The materials described herein as useful in particular layers in an organic light emitting device can be used in combination with a wide variety of other materials present in the device. For example, the emissive dopants disclosed herein can be used in combination with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes, and other layers that may be present. The materials described or referenced below are non-limiting examples of materials that can be useful in combination with the compounds disclosed herein, and one of ordinary skill in the art can readily review the literature to identify other materials that can be useful in combination. Conductive dopants:

[0093] The charge transport layer is doped with a conductive dopant, which greatly changes the density of charge carriers and thereby its conductivity. The conductivity can be increased by generating charge carriers in the matrix material or depending on the type of dopant, and a change in the Fermi level of the semiconductor can also be achieved. The hole transport layer can be doped with a p-type conductive dopant, and the n-type conductive dopant is used in the electron transport layer.

[0094] Non-limiting examples of conductive dopants that can be used in an OLED in combination with the materials disclosed herein are exemplified below along with the documents disclosing these materials. EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047, and US2012146012

Chemical formula

Chemical formula

[0095] The hole injection / transport materials used in the present invention are not particularly limited, and any compound may be used as long as the compound is typically used as a hole injection / transport material. Examples of materials include phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indolocarbazole derivatives; polymers containing fluorinated hydrocarbons; polymers having a conductive dopant; conductive polymers such as PEDOT / PSS; self-assembled monomers derived from compounds such as phosphonic acids and silane derivatives; MoO xMetal oxide derivatives such as; p-type semiconductor organic compounds such as 1,4,5,8,9,12-hexaazatriphenylene hexacarbonitrile; metal complexes, and crosslinkable compounds, but not limited thereto.

[0096] Examples of aromatic amine derivatives used in HIL or HTL include, but are not limited to, the following general structures.

Chemical formula

[0097] Ar 1 from Ar 9Each of them 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, azulene, etc.; 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, etc.; and the same or different types of groups selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups, and directly or through at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an aliphatic cyclic group, and are selected from the group consisting of 2 to 10 cyclic structural units bonded to each other. Each Ar can be unsubstituted or 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 acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino and combinations thereof.

[0098] In one embodiment, Ar 1 to Ar9 is selected independently from the group consisting of [Chem.] wherein k is an integer from 1 to 20; X to X 101 is C (including CH) or N; Z 108 is NAr 101 O, or S; Ar 1 has the same group as defined above. 1

[0099] Examples of metal complexes used in HIL or HTL include, but are not limited to, the following general formula. [Chem.] wherein Met is a metal that can have an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, and Y 101 and Y 102 are independently selected from C, N, O, P, and S; L 101 is a auxiliary ligand; k' is an integer value from 1 to the maximum number of ligands that can bind to the metal; and k'+k'' is the maximum number of ligands that can bind to the metal.

[0100] In one embodiment, (Y 101 -Y 102 ) is a 2-phenylpyridine derivative. In another embodiment, (Y 101 -Y 102 ) is a carbene ligand. In another embodiment, Met is selected from Ir, Pt, Os, and Zn. In a further embodiment, the metal complex has a minimum oxidation potential of less than about 0.6 V in solution with respect to the Fc + / Fc couple.

[0101] Non-limiting examples of HIL materials and HTL materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below along with the literature disclosing these 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, US06517957, 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, US5061569, US5639914, WO05075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO2013018530, WO2013039073, WO2013087142, WO2013118812, WO2013120577, WO2013157367, WO2013175747, WO2014002873, WO2014015935, WO2014015937, WO2014030872, WO2014030921, WO2014034791, WO2014104514, WO2014157018 [Chemistry] [Chemistry] [Chemistry] [Chemistry] [Chemistry] [Chemistry] [Chemistry] EBL:

[0102] The electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons exiting the light-emitting layer. The presence of such a blocking layer in the device can result in significantly higher efficiency and / or longer lifetime compared to a similar device lacking the blocking layer. Also, the blocking layer can be used to limit light emission to a desired region of the 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 the EBL contains the same molecule or the same functional group as that used as one of the hosts described below. Additional host:

[0103] The light-emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as a light-emitting dopant material, and may contain one or more additional host materials using the metal complex as a dopant material. The host material is not particularly limited, and any metal complex or organic compound can be used as long as the triplet energy of the host is greater than that of the dopant. Any host material can be used together with any dopant as long as the triplet criterion is satisfied.

[0104] Examples of metal complexes used as host materials preferably have the following general formula.

Chemical formula

[0105] In one aspect, the metal complex is the following complex.

Chemical formula

[0106] In another aspect, Met is selected from Ir and Pt. In a further aspect, (Y 103 -Y 104 ) is a carbene ligand.

[0107] In one aspect, the host compound comprises at least one selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; 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 at least one selected from the group consisting of 2 to 10 cyclic structural units which are the same or different groups selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups and are bonded to each other directly or via at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit, and an aliphatic cyclic group. Each group is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, 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, and combinations thereof.

[0108] In one aspect, the host compound contains at least one of the following groups in the molecule.

Chemical formula

[0109] Non-limiting examples of additional host materials that can be used in an OLED in combination with the host compounds disclosed herein are exemplified below together with the documents disclosing these 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, US7154114, 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, US9466803

Chem.

Chem.

Chem.

Chem.

Chem.

[0110] Examples of the phosphor are not particularly limited, and any compound can be used as long as the compound is typically used as a phosphor material. Suitable phosphor materials include those capable of generating light through phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence; see, for example, U.S. Patent Application Publication No. 15 / 700,352, which is incorporated herein by reference in its entirety), triplet-triplet annihilation, or a combination of these processes, but are not limited thereto. In some embodiments, the luminescent dopant can be a racemic mixture or can be enriched in one enantiomer.

[0111] Non-limiting examples of phosphor materials that can be used in an OLED in combination with the materials disclosed herein are illustrated below along with the documents that disclose these materials. CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP2013110263, JP4478555, KR1020090133652, KR20120032054, KR20130043460, TW201332980, US06699599, US06916554, 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, US6303238, US6413656, US6653654, US6670645, US6687266, US6835469, US6921915, US7279704, US7332232, US7378162, US7534505, US7675228, US7728137, US7740957, US7759489, US7951947, US8067099, US8592586, US8871361, 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, [Chemistry] [Chemistry] [Chemistry] [Chemistry] [Chemistry] [Chemistry] HBL:

[0112] Using a hole blocking layer (HBL), the number of holes and / or excitons emitted from the light emitting layer can be reduced. The presence of such a blocking layer in the device can result in significantly higher efficiency and / or longer lifetime compared to a similar device lacking the blocking layer. Also, a blocking layer can be used to limit light emission to a desired region of the OLED. In some embodiments, the HBL material has a lower HOMO (farther 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 (farther from the vacuum level) and / or higher triplet energy than one or more of the hosts closest to the HBL interface.

[0113] In one aspect, the compound used in the HBL contains the same molecule or the same functional group as when used in the host described above.

[0114] In another aspect, the compound used in the HBL contains at least one of the following groups in the molecule. [Chemistry] where k is an integer from 1 to 20; L 101 is another ligand, and k' is an integer from 1 to 3. ETL:

[0115] The electron transport layer (ETL) may include materials capable of transporting electrons. The electron transport layer may be intrinsic (undoped) or may be doped. Doping can be used to enhance conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound may be used as long as it is typically used for transporting electrons.

[0116] In one aspect, the compound used in the ETL contains at least one of the following groups in the molecule.

Chemical formula

Chemical formula

[0117] In another aspect, the metal complex used in the ETL contains, but is not limited to, the following general formula.

Chemical formula

[0118] Non-limiting examples of ETL materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below along with the documents disclosing these 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, US6656612, US8415031, WO2003060956, WO2007111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO2011105373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535

Chem.

Chem.

Chem.

Chem.

[0119] In tandem or stacked OLEDs, the CGL plays an important role in performance and consists of an n-doped layer and a p-doped layer for electron and hole injection, respectively. Electrons and holes are supplied from the CGL and the electrodes. The consumed electrons and holes in the CGL are replenished by the electrons and holes injected from the cathode and anode, respectively, and then the bipolar current gradually reaches a stable state. Typical CGL materials include n-type and p-type conductive dopants used in the transport layer.

[0120] In any of the above-mentioned compounds used in each layer of the OLED device, a hydrogen atom may be partially or fully deuterated. Thus, any specifically mentioned substituents such as, but not limited to, methyl, phenyl, pyridyl, etc. include their non-deuterated, partially deuterated, and fully deuterated versions. Similarly, classes of substituents such as, but not limited to, alkyl, aryl, cycloalkyl, heteroaryl, etc. also include their non-deuterated, partially deuterated, and fully deuterated versions.

[0121] It is understood that the various embodiments described herein are merely by way of example and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein can be replaced with other materials and structures without departing from the spirit of the invention. Thus, the invention as claimed can include variations from the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It is understood that the various theories as to why the invention works are not intended to be limiting. Experimental section

Chemical formula

[0122] Into a 2 L flask dried by flame, 9H-carbazole (54.4 g, 325 mmol) and anhydrous THF (1 L) were charged under nitrogen. The resulting solution was cooled to -70 °C, and n-BuLi (130 mL, 325 mmol) was added dropwise. The resulting mixture was warmed to room temperature and then gradually transferred via cannula under nitrogen to a three-necked 3 L flask containing a solution of 2,4,6-trichloro-1,3,5-triazine (30 g, 163 mmol) in THF (200 mL). The resulting mixture was then heated at 60 °C overnight. The reaction mixture was cooled to room temperature and quenched with water. The resulting precipitate was filtered, washed with water and then warm EtOH (about 500 mL), and dried to give 9,9'-(6-chloro-1,3,5-triazine-2,4-diyl)bis(9H-carbazole) (53.8 g, 121 mmol, 74.2% yield) as a yellow solid. Synthesis of 9-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-9H-carbazole: [Chemical formula]

[0123] Into a flame-dried 1 L three-necked flask equipped with a stirrer bar and a thermowell, 9-(2-bromophenyl)-9H-carbazole (40 g, 124 mmol) and anhydrous THF (621 ml) were added under nitrogen. The resulting solution was cooled to -72 °C, and sec-butyllithium (155 ml, 217 mmol) was added dropwise over 40 minutes. The mixture was warmed to -40 °C over 90 minutes. After confirming complete consumption of 9-(2-bromophenyl)-9H-carbazole by TLC, the mixture was cooled to -78 °C, and 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (44.3 ml, 217 mmol) was added dropwise. The reaction mixture was gradually warmed to room temperature and stirred overnight. Thereafter, the reaction mixture was cooled in an ice bath and carefully quenched with saturated aqueous ammonium chloride solution (100 mL), followed by 100 mL of water. The organic phase was separated, and the aqueous phase was extracted with CH 2 Cl 2 . The combined organic phases were dried over Na 2 SO 4 , concentrated, dried, and 9-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-9H-carbazole (44.3 g, 120 mmol, 97% yield) was obtained as an off-white solid. Synthesis of 9,9’-(6-(2-(9H-carbazol-9-yl)phenyl)-1,3,5-triazine-2,4-diyl)bis(9H-carbazole) (Compound A): [Chemical formula]

[0124] Into a pressure vial, 9,9’-(6-chloro-1,3,5-triazine-2,4-diyl)bis(9H-carbazole) (18.11 g, 40.6 mmol), 9-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-9H-carbazole (15 g, 40.6 mmol), and K 2 CO 3(16.84 g, 122 mmol) was charged. THF (148 ml) and water (55.4 ml) were added, and the mixture was degassed with nitrogen for 10 minutes. Then, Pd(Ph 3 P) 4 (4.69 g, 4.06 mmol) was added, and the resulting mixture was further degassed with nitrogen. The reaction mixture was sealed and heated at 90 °C for 72 hours. The reaction was cooled to room temperature and then quenched with water (100 mL). The resulting gray precipitate was filtered and washed with MeOH. Then, the solid was dissolved in DCM (1 L), passed through a short silica plug, and reprecipitated with MeOH (1 L). It was triturated with acetone (750 mL), and the solid was filtered overnight to obtain 23.1 g (87% yield) of 9,9'-(6-(2-(9H-carbazol-9-yl)phenyl)-1,3,5-triazine-2,4-diyl)bis(9H-carbazole) (Compound A). Synthesis of Compound B Synthesis of 9,9'-(2-chloropyrimidine-4,6-diyl)bis(9H-carbazole): [Chemical formula]

[0125] Sodium hydride (60 wt%, 80 g, 2009 mmol) and THF (1605 ml) were charged into a 5 L flask dried by flame. The mixture was stirred under nitrogen and cooled to -5 °C. Then, 9H-carbazole (112 g, 670 mmol) was added little by little, and the resulting mixture was stirred for 15 minutes. A solution of 2,4,6-trichloropyrimidine (82 g, 447 mmol) in THF (1958 ml) was added dropwise at -5 °C and then warmed to room temperature. After stirring overnight at room temperature, the reaction mixture was cooled to 0 °C and quenched with water (250 mL). The resulting solid was filtered, triturated with heptane (1 L), then EtOAc (1 L), and further triturated with THF and EtOH to obtain 9,9'-(2-chloropyrimidine-4,6-diyl)bis(9H-carbazole) (57 g, 128 mmol, 38.3% yield) as a white solid. Synthesis of 9,9’-(6-(2-(9H-carbazol-9-yl)phenyl)-1,3,5-triazine-2,4-diyl)bis(9H-carbazole) (Compound B): [Chemical formula]

[0126] Into a pressure vial, 9,9’-(2-chloropyrimidine-4,6-diyl)bis(9H-carbazole) (21.57 g, 48.5 mmol), 9-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-9H-carbazole (20 g, 48.5 mmol), and K2CO3 (20.10 g, 145 mmol) were charged. THF (176 ml) and water (66 ml) were added, and the mixture was degassed with nitrogen for 10 minutes. Then, Pd(Ph3P)4 (5.6 g, 4.85 mmol) was added, and the resulting mixture was then degassed with nitrogen. The reaction mixture was sealed and heated at 90 °C for 72 hours. The reaction mixture was cooled to room temperature and then quenched with water (100 mL). The resulting gray precipitate was filtered, washed with water and MeOH, and 30 g (yield 95%) of 9,9’-(2-(2-(9H-carbazol-9-yl)phenyl)pyrimidine-4,6-diyl)bis(9H-carbazole) was obtained. Device compound: [Chemical formula]

[0127] Materials having this chemical formula were observed to provide significantly increased stability. In Table 1, the device characteristics of the electron-type host E-host-1 and Compound A are compared. It was found that Compound A is 16.7 times more stable than E-host-1. [Table 1]

[0128] Compound B was also found to have significantly increased stability compared to E-host-2 (see Table 2). Note that the energy levels of the E-hosts compared in each table are almost the same.

Table 2

[0129] OLED devices were grown on glass substrates pre-coated with an indium tin oxide (ITO) layer having a sheet resistance of 15 Ω / square. Before deposition or coating of the organic layer, the substrate was degreased with a solvent and then treated with oxygen plasma at 50 W for 1.5 minutes and with UV ozone for 5 minutes at 100 mTorr.

[0130] The devices in Tables 1 and 2 were fabricated by thermal evaporation under high vacuum (<10-6 Torr). The anode electrode was 750 Å of indium tin oxide (ITO). The device examples had an organic layer consisting of, in order from the ITO surface, a 100 Å thick Compound 1 (HIL), a 250 Å layer of Compound 2 (HTL), a 50 Å Compound 3 (EBL), a 300 Å Compound 3 (EML) doped with 60% E-type host and 12% of Compound 4, a 50 Å E-type host (BL), a 300 Å Compound 5 (ETL) doped with 35% of Compound 6, a 10 Å Compound 5 (EIL), and a 1,000 Å Al (cathode). All devices were encapsulated immediately after fabrication with a glass lid sealed with an epoxy resin in a nitrogen glove box (<1 ppm of H2O and O2), and a moisture getter was placed in the package. The doping rate is in volume percent. 10 mA / cm 2 and the device characteristics at 1000 nits were based on those of the comparative compounds E-host-1 and E-host-2.

Prior Art Documents

Patent Documents

[0131]

Patent Document 1

Patent Document 2

[0132] 100 Organic light-emitting device 110 Substrate 115 Anode 120 Hole injection layer 125 Hole transport layer 130 Electron blocking layer 135 Light-emitting layer 140 Hole blocking layer 145 Electron transport layer 150 Electron injection layer 155 Protection layer 160 Cathode 162 First conductive layer 164 Second conductive layer 170 Barrier layer 200 Inverted OLED, device 210 Substrate 215 Cathode 220 Light-emitting layer 225 Hole transport layer 230 Anode

Claims

1. A material for an organic light emitting device (OLED) of formula I: 【Chemistry 1】 (Wherein, ring A is a 6-membered aromatic ring; R Ａ , R Ｂ , and R Ｃ each independently represents the maximum allowable substitution from mono, or represents no substitution; Y １ is a direct bond; X １ ~X ３ are each N or CR; X １ ~X ３ at least two of are N; A １ ~A ５ are each independently C; The maximum number of N atoms that can be bonded together in each ring is 2; R 1 and R 2 are bonded to form an unsubstituted or substituted carbazole group, and R 3 and R 4 are bonded to form an unsubstituted or substituted carbazole group, where the substituted carbazole has the following structure: 【Chemistry 2】 Except that; R, R A, R Ｂ , and R Ｃ are each independently 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, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; Any two substituents may be bonded or fused together to form a ring. A material for an organic light emitting device (OLED), excluding a compound in which three R C are carbazole groups.

2. R, R A, R Ｂ , and R Ｃ 13. The material of claim 1, wherein each is independently hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.

3. X １ ~X ３ are each N; X １ is CR, and X ２ and X ３ is N; or X ２ is CR, and X １ and X ３ The material of claim 1 , wherein

4. The material is selected from the group consisting of compounds H1-B4-B4-B4 through compounds H50-B60-B60-B60 based on the numbered formula Hn-Bi-Bj-Bk, where n is an integer from 1 to 50, and i, j, and k are each independently integers from 4 to 60, where Bi and Bj are each independently B4, B6, B8, B9, B13, B14, B15, B18, B19-B28, B31, B34, B35, B 40-B43, B46, B47, B50, B51, B54, B55, B58-B60; Bk is limited to those selected from B4, B6, B7, B8, B9, B13, B14, B15, B16, B17, B18, B19-B28, B31, B34, B35, B40-B43, B46, B47, B50, B51, B54, B55, B58-B60; and H1-H50 have the following structure: 【Chemistry 3】 【Chemistry 4】 【Chemistry 5】 【Chemistry 6】 (Wherein, B4 to B60 have the following structure.) 【Chemistry 7】 【Chemistry 8】

5. The material described in claim 1, wherein the material is selected from the group consisting of the following: 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】 【Chemistry 16】 6. An organic layer comprising a compound represented by formula I. 【Chemistry 17】 (Wherein, ring A is a 6-membered aromatic ring; R A , R B , and R C each independently represent the maximum allowable substitution from mono or no substitution; Y 1 is a direct bond; X 1 to X 3 are each N or CR; At least two of X 1 to X 3 are N; A 1 to A 5 are each independently C; The maximum number of N atoms that can be bonded together in each ring is 2; R 1 and R 2 are joined to form an unsubstituted or substituted carbazole group, and R 3 and R 4 are joined to form an unsubstituted or substituted carbazole group, wherein the substituted carbazole has the following structure: 【Chemistry 18】 Except that; R, R A , R B , and R C are each independently 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, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; Any two substituents may be bonded or fused together to form a ring; However, this does not include a compound in which three R C s are carbazole groups.)

7. The organic layer of claim 6, wherein the organic layer is an emissive layer comprising an emitter and a host; the emitter is selected from the group consisting of phosphorescent emitters, fluorescent emitters, delayed fluorescent emitters, and combinations thereof; and the host is a compound of formula I.

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