Organic electroluminescent materials and devices

Abstract

The present invention relates to an organometallic complex for use as an emitter, wherein the molecules of the compound have an orientation factor greater than 0.67, and to a device such as an organic light-emitting diode comprising the same.

Description

Technology Field

[0001] Cross-reference of related applications

[0002] The present application claims priority to U.S. provisional application No. 62 / 330,412 filed May 2, 2016, U.S. provisional application No. 62 / 332,510 filed April 14, 2016, U.S. provisional application No. 62 / 291,960 filed February 5, 2016, U.S. provisional application No. 62 / 232,194 filed September 24, 2015, and U.S. provisional application No. 62 / 213,757 filed September 3, 2015, the contents of which are incorporated herein by reference in their entirety.

[0003] Parties to the Joint Research Agreement

[0004] The invention was completed by one or more of The Regents of the University of Michigan, Princeton University, University of Southern California, and The Universal Display Corporation, on their behalf and / or in connection therewith, pursuant to the Industry-Academic Joint Research Agreement. This Agreement entered into force on and prior to the date the invention was completed, and the invention was completed as a result of activities performed within the scope of the Agreement.

[0005] Field of the present invention

[0006] The present invention relates to a compound for use as an emitter and a device such as an organic light-emitting diode containing the same. Background Technology

[0007] Optoelectronic devices using organic materials are becoming increasingly important for various reasons. Since many of the materials used to manufacture such devices are relatively inexpensive, organic optoelectronic devices have potential in terms of economic advantages over inorganic devices. Furthermore, the inherent properties of organic materials, such as their flexibility, can make them highly suitable for specific applications, such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light-emitting diodes (OLEDs), organic phototransistors, organic photovoltaics, and organic photodetectors. In the case of 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 controlled with a suitable dopant.

[0008] OLEDs utilize organic thin films that emit light when voltage is applied to the device. OLEDs are an increasingly important technology for use in applications such as flat panel displays, lighting, and backlighting. Various OLED materials and structures are described in U.S. Patents No. 5,844,363, 6,303,238, and 5,707,745, the full text of which is incorporated herein by reference.

[0009] One application of phosphorescent emitting molecules is a full-color display. Industrial standards for such displays require pixels tuned to emit specific colors referred to as "saturated" colors. Specifically, these standards require saturated red, green, and blue pixels. Alternatively, OLEDs can be designed to emit white light. In conventional liquid crystal displays, light from a white backlight is filtered using absorption filters to produce red, green, and blue light. The same technique can be applied to OLEDs. A white OLED can be a single EML device or a stacked structure. Color can be measured using CIE coordinates known in the art.

[0010] An example of a green luminescent molecule is tris(2-phenylpyridine) iridium, represented as Ir(ppy)3 having the following chemical formula:

[0011]

[0012] In the chemical formulas herein and below, the applicant illustrates the coordination bond from nitrogen to a metal (hereafter Ir) as a straight line.

[0013] In this document, the term "organic" includes not only polymeric materials that can be used to manufacture organic optoelectronic devices, but also small molecule organic materials. "Small molecule" refers to any organic material that is not a polymer, and "small molecules" may actually be quite large. Small molecules may contain repeating units in some situations. 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 the polymer, for example, as side chains on the polymer main chain or as part of the main chain. Small molecules may also serve as the core portion of a dendrimer, which consists of a series of chemical shells formed 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 has been found that all dendrimers commonly used in the OLED field are small molecules.

[0014] As used herein, "top" means furthest from the substrate, and "bottom" means closest to the substrate. If the first layer is described as being "placed on top of" the second layer, the first layer is placed far from the substrate. If the first layer is not specified as being "in contact" with the second layer, other layers may exist between the first layer and the second layer. For example, even though various organic layers may exist between the cathode and the anode, the cathode may be described as being "placed on top of" the anode.

[0015] As used herein, "solution processability" means that it can be dissolved, dispersed, or transported in a liquid medium in the form of a solution or suspension, and / or deposited from a liquid medium.

[0016] If a ligand is found to directly contribute to the photoactive properties of a luminescent material, the ligand may be referred to as "photoactive." Even if an auxiliary ligand can alter the properties of the photoactive ligand, if the ligand is found not to contribute to the photoactive properties of the luminescent material, the ligand may be referred to as "auxiliary."

[0017] As used herein and as generally understood by those skilled in the art, when the first "highest occupied molecular orbital (HOMO)" or "lowest unoccupied molecular orbital (LUMO)" energy level approaches the vacuum energy level, the first energy level is "greater" or "higher" than the second HOMO or LUMO. Since the ionization potential (IP) is measured as negative energy with respect to the vacuum level, a higher HOMO energy level corresponds to an IP with a smaller absolute value (the negative value of IP is smaller). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) with a smaller absolute value (the negative value of EA is smaller). In a typical 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. This indicates that "higher" HOMO or LUMO energy levels are closer to the upper part of the diagram than "lower" HOMO or LUMO energy levels.

[0018] As used herein and as generally understood by those skilled in the art, if the absolute value of the first work function is greater, the first work function is "greater" or "higher" than the second work function. Since work functions are generally measured as negative numbers with respect to vacuum levels, this implies that the negative value of the "higher" work function is greater. In a typical energy level diagram with vacuum levels at the top, the "higher" work function is depicted as being further down from the vacuum level. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than those of work functions.

[0019] Details regarding OLEDs and the foregoing definitions can be found in U.S. Patent No. 7,279,704, the full text of which is incorporated herein by reference.

[0020] According to one embodiment, a compound having the following chemical formula is provided, wherein the molecule has an orientation factor value greater than 0.67:

[0021] M(L A ) h (L B ) y (L C ) z

[0022] In the above chemical formula,

[0023] Ligand L A , L B , and L C is selected from a group consisting of each independently doing:

[0024]

[0025]

[0026] ;

[0027] Each X 1 To X 13 is independently selected from the group consisting of carbon and nitrogen;

[0028] X is selected from the group consisting of BR', NR', PR', O, S, Se, C=O, S=O, SO2, CR'R", SiR'R", and GeR'R";

[0029] R' and R" are arbitrarily fused or combined to form a ring;

[0030] Each R a , R b , R c , and R d can represent a uniform substitution or the maximum possible number of substitutions or non-substitutions;

[0031] R', R", R a , R b , R c , and R d Each is 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;

[0032] R a , R b , R c , and R d Any two adjacent substituents among them may fuse or combine to form a ring or a multidentate ligand;

[0033] M is a metal having an atomic mass greater than 40;

[0034] h is 1 or 2 and;

[0035] y is 0, 1, or 2;

[0036] z is 0, 1, or 2, and;

[0037] h+y+z is the oxidation state of metal M.

[0038] According to another embodiment, a chemical formula (L) having a structure selected from the group consisting of the following A ) m Ir(L B ) 3-m A compound having is disclosed:

[0039]

[0040] In the above chemical formulas,

[0041] m is 1 or 2 and;

[0042] R 1 , R 2 , R 4 , and R 5 Each independently represents a uniform, bisubstitution, trisubstitution, quadruple substitution, or nonsubstitution;

[0043] R 3 represents unsubstitution, unsubstitution, trisubstitution, or nonsubstitution;

[0044] R 6 represents identical or non-identified substitution;

[0045] R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Each is independently selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, a portion thereof, or a fully deuteriumated or fluorinated variant.

[0046] According to another embodiment, an organic light-emitting diode / device (OLED) is also disclosed. The OLED may comprise an anode, a cathode, and an organic layer disposed between the anode and the cathode. The organic layer may comprise a compound having a chemical formula selected from the group consisting of the following chemical formulas:

[0047] M(L A ) h (L B ) y (L C ) z ,

[0048]

[0049] In the above chemical formula,

[0050] m is 1 or 2 and;

[0051] Ligand L A , L B , and L C is selected from a group consisting of each independently doing:

[0052]

[0053]

[0054] ;

[0055] Each X 1 To X 13 is independently selected from the group consisting of carbon and nitrogen;

[0056] X is selected from the group consisting of BR', NR', PR', O, S, Se, C=O, S=O, SO2, CR'R", SiR'R", and GeR'R";

[0057] R' and R" are arbitrarily fused or combined to form a ring;

[0058] Each R a , R b , R c , and R d can represent a uniform substitution or the maximum possible number of substitutions or non-substitutions;

[0059] R', R", R a , R b , R c , and R dEach is 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;

[0060] R a , R b , R c , and R d Any two adjacent substituents among them may fuse or combine to form a ring or a polydentate ligand;

[0061] M is a metal having an atomic mass greater than 40;

[0062] h is 1 or 2 and;

[0063] y is 0, 1, or 2;

[0064] z is 0, 1, or 2, and;

[0065] x+y+z is the oxidation state of metal M;

[0066] The molecule of the above compound has an orientation factor value exceeding 0.67;

[0067] R 1 , R 2 , R 4 , and R 5 Each independently represents a uniform, bisubstitution, trisubstitution, quadruple substitution, or nonsubstitution;

[0068] R 3 represents unsubstitution, unsubstitution, trisubstitution, or nonsubstitution;

[0069] R 6 represents identical or non-identified substitution;

[0070] R 1 , R 2 , R 3 , R 4 , R 5 and R6 Each is independently selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, partial or fully deuteriumated or fluorinated variants thereof, and combinations thereof.

[0071] According to another embodiment, a formulation containing a compound having a chemical formula selected from the group consisting of the following chemical formulas is disclosed:

[0072] M(L A ) h (L B ) y (L C ) z ,

[0073]

[0074] In the above chemical formula,

[0075] m is 1 or 2 and;

[0076] Ligand L A , L B , and L C is selected from a group consisting of each independently doing:

[0077]

[0078]

[0079] ;

[0080] Each X 1 To X 13 is independently selected from the group consisting of carbon and nitrogen;

[0081] X is selected from the group consisting of BR', NR', PR', O, S, Se, C=O, S=O, SO2, CR'R", SiR'R", and GeR'R";

[0082] R' and R" are arbitrarily fused or combined to form a ring;

[0083] Each R a , R b , Rc , and R d can represent a uniform substitution or the maximum possible number of substitutions or non-substitutions;

[0084] R', R", R a , R b , R c , and R d Each is 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;

[0085] R a , R b , R c , and R d Any two adjacent substituents among them may fuse or combine to form a ring or a polydentate ligand;

[0086] M is a metal having an atomic mass greater than 40;

[0087] h is 1 or 2 and;

[0088] y is 0, 1, or 2;

[0089] z is 0, 1, or 2, and;

[0090] x+y+z is the oxidation state of metal M;

[0091] M(L A ) h (L B ) y (L C ) z The molecule has an orientation factor value exceeding 0.67;

[0092] R 1 , R 2 , R 4 , and R 5Each independently represents a uniform, bisubstitution, trisubstitution, quadruple substitution, or nonsubstitution;

[0093] R 3 represents unsubstitution, unsubstitution, trisubstitution, or nonsubstitution;

[0094] R 6 represents identical or non-identified substitution;

[0095] R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Each is independently selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, partial or fully deuteriumated or fluorinated variants thereof, and combinations thereof. Brief explanation of the drawing

[0096] Figure 1 illustrates an organic light-emitting diode. Figure 2 illustrates an inverted organic light-emitting diode that does not have a separate electron transport layer. Figure 3 shows the spectrum measured through a polarizer at an angle of 0 to 60° for the emitter of device Example 2 having the device structure defined in Table 1. Figure 4 shows the corresponding spectrum generated by SETFOS-4.1. Figure 5 shows the experimental angle dependence of integrated radiance normalized to a value of 0°. The ratio of integrated p / s radiance at an angle of 40° is 1.67. Figure 6 shows the p / s emission ratio simulated by the SETFOS-4.1 program versus the dipole orientation calibration. For this particular embodiment, the integrated p / s radiance ratio at an angle of 40° is 1.67, corresponding to a dipole orientation (DO) of 0.15. Figure 7 shows the observation angle for the radiance-p profile for different DOs. Figure 8 shows the observation angle when the radiance-s profile is different for DO. Figure 9 shows the correlation between the emitter orientation factor and the maximum estimated EQE in the device. Figure 10 shows the correlation between PLQY and emitter concentration for some emitters. The steric bulk of the emitter prevents self-quenching at high doping percentages. Specific details for implementing the invention

[0097] Generally, an OLED comprises one or more organic layers disposed between an anode and a cathode and electrically connected to them. When current is applied, the anode injects holes into the organic layer(s), and the cathode injects electrons. The injected holes and electrons move toward oppositely charged electrodes, respectively. When electrons and holes are localized on the same molecule, "excitons" are formed, which are localized electron-hole pairs having an excited energy state. Light is emitted when excitons relax via a photoluminescence mechanism. In some cases, excitons may be localized on excimers or exciplexes. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.

[0098] Early OLEDs used light-emitting molecules that emit light ("fluorescence") from a single-claim state, such as disclosed in, for example, U.S. Patent No. 4,769,292, the full text of which is incorporated herein by reference. Fluorescence emission generally occurs over a time period of less than 10 nanoseconds.

[0099] More recently, OLEDs having a light-emitting material that emits light ("phosphorescence") from a triplet state have been exemplified. Reference [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. See , vol. 75, No. 3, 4-6 (1999) ("Baldo-II"), the full text of which is incorporated herein by reference. Phosphorescence is described in more detail in columns 5-6 of U.S. Patent No. 7,279,704, incorporated by reference.

[0100] FIG. 1 illustrates an organic light-emitting device (100). The drawing is not necessarily drawn to scale. The 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 blocking layer (170). The cathode (160) is a compound cathode having a first conductive layer (162) and a second conductive layer (164). The device (100) may be manufactured by depositing layers in the order described. The properties and functions of the exemplary materials, as well as these various layers, are described more specifically in columns 6-10 of U.S. Patent No. 7,279,704, which are incorporated by reference.

[0101] Further examples for each of these layers are also available. For example, flexible and transparent substrate-anode combinations are disclosed in U.S. Patent No. 5,844,363, the full text of which is incorporated herein by reference. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ in a 50:1 molar ratio, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, the full text of which is incorporated herein by reference. Examples of luminescent and host materials are disclosed in U.S. Patent No. 6,303,238 (Thompson et al.), the full text of which is incorporated herein by reference. An example of an n-doped electron transport layer is BPhen doped with Li in a 1:1 molar ratio, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, the full text of which is incorporated herein by reference. Examples of cathodes are disclosed in U.S. Patents No. 5,703,436 and No. 5,707,745, the full text of which is incorporated herein by reference, including compound cathodes having thin layers of metals such as Mg:Ag with stacked transparent, electrically conductive sputter-deposited ITO layers. The theory and applications of blocking layers are described more specifically in U.S. Patent No. 6,097,147 and U.S. Patent Application Publication No. 2003 / 0230980, the full text of which is incorporated herein by reference. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, the full text of which is incorporated herein by reference. Descriptions of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174116, the full text of which is incorporated herein by reference.

[0102] FIG. 2 illustrates an inverted OLED (200). The device comprises 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 manufactured by stacking layers in the order described. Since the most common OLED structure has the cathode positioned above the anode and the device (200) has the cathode (215) positioned below the anode (230), the device (200) may be referred to as an "inverted" OLED. A material similar to that described for the device (100) may be used for the corresponding layer of the device (200). FIG. 2 provides an example of how some layers may be omitted from the structure of the device (100).

[0103] The simple stacked structure illustrated in FIGS. 1 and 2 is provided as a non-limiting example, and it should be understood that embodiments of the invention may be used in connection with various other structures. The specific materials and structures described are for illustrative purposes only, and other materials and structures may also be used. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be entirely omitted based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than these specifically described layers may be used. Although many examples provided herein describe various layers as comprising a single material, materials, such as a mixture of a host and a dopant, or more generally a mixture, may be used. Additionally, a layer may have a number of underlying layers. The names given herein for the various layers are not intended to be strictly limited. For example, in the device (200), the hole transport layer (225) transports holes and injects holes into the light-emitting layer (220), and may be described as a hole transport layer or a hole injection layer. In one embodiment, the OLED may be described as having an "organic layer" disposed between the cathode and the anode. This organic layer may comprise a single layer or may further comprise a plurality of layers of different organic materials, for example, as described in relation to FIGS. 1 and FIGS. 2.

[0104] OLEDs comprising structures and materials not specifically described, such as polymer materials (PLEDs) as described in U.S. Patent No. 5,247,190 (Friend et al.), may be used, the full text of which is incorporated herein by reference. As an additional example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example, as described in U.S. Patent No. 5,707,745 (Forrest et al.), the full text of which is incorporated herein by reference. OLED structures may deviate from the simple stacked structures shown in FIGS. 1 and 2. For example, the substrate may include an angled reflective surface to improve out-coupling, such as a mesa structure as described in U.S. Patent No. 6,091,195 (Forrest et al.) and / or a pit structure as described in U.S. Patent No. 5,834,893 (Bulovic et al.), the full text of which is incorporated herein by reference.

[0105] Unless otherwise specified, any layer of various embodiments may be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation as described in U.S. Patents No. 6,013,982 and 6,087,196 (the full text of which is incorporated herein by reference), ink-jet, organic vapor phase deposition (OVPD) as described in U.S. Patent No. 6,337,102 (Forrest et al.) (the full text of which is incorporated herein by reference), and organic vapor jet printing (OVJP) as described in U.S. Patent Application No. 7,431,968 (the full text of which is incorporated herein by reference). 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 other layers, preferred methods include thermal evaporation. Preferred pattern-forming methods include deposition through a mask, cold welding as described in U.S. Patents No. 6,294,398 and 6,468,819 (the full text of which is incorporated herein by reference), and pattern-forming associated with some deposition methods such as ink-jet and OVJD. The material to be deposited may be modified to be compatible with a specific deposition method. For example, substituents such as branched or unbranched alkyl and aryl groups, preferably containing three or more carbons, may be used on the small molecule to improve its solution processing capability. Substituents having 20 or more carbons may be used, with 3 to 20 carbons being a preferred range. Materials having an asymmetric structure may have better solution processing capabilities than those having a symmetric structure, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to improve the solution processing capability of the small molecule.

[0106] A device manufactured according to an embodiment of the present invention may additionally optionally include a blocking layer. One purpose of the blocking layer is to prevent the electrode and organic layer from being damaged by exposure to harmful species in an environment containing moisture, vapor and / or gas. The blocking layer may be deposited on the substrate, under the substrate, or on the side of the substrate, or on any other part of the device including the electrode or edge. The blocking layer may comprise a single layer or multiple layers. The blocking layer may be formed by various known chemical vapor deposition techniques and may comprise a composition having multiple phases as well as a composition having a single phase. Any suitable material or combination of materials may be used in the blocking layer. The blocking layer may incorporate inorganic or organic compounds, or both. A preferred blocking layer comprises a mixture 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, the full text of which is incorporated herein by reference. Considering the "mixture," the aforementioned polymer and non-polymer materials, including the blocking layer, must be deposited under the same reaction conditions and / or at the same time. The weight ratio of the polymer to the non-polymer material may be in the range of 95:5 to 5:95. The polymer and non-polymer materials may be produced from the same precursor material. In one example, the mixture of the polymer and non-polymer materials essentially consists of polymeric silicon and inorganic silicon.

[0107] The device manufactured according to an embodiment of the present invention may be incorporated into a wide variety of electronic component modules (or units) that can be introduced into various electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting elements such as individual light source elements or lighting panels, etc. that can be utilized by end-user product manufacturers. Such electronic component modules may, in some cases, include driving electronics and / or power(s). The device manufactured according to an embodiment of the present invention may be incorporated into a wide variety of consumer products in which one or more of the electronic component modules (or units) are introduced. Such consumer products include any type of product comprising one or more light source(s) and / or one or more of several types of image displays. Some examples of such consumer goods include flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for indoor or outdoor lighting and / or signaling, head-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, mobile phones, tablets, phablets, personal information terminals (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays, vehicles, large walls, theater or stadium screens, or signage. Various control mechanisms, including passive matrices and active matrices, can be used to control devices manufactured according to the present invention. Many devices are intended to be used in a temperature range that is comfortable for people, e.g., 18°C ​​to 30°C, more preferably at room temperature (20°C to 25°C), but may be used outside this temperature range, e.g., -40°C to +80°C.

[0108] 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 use these materials and structures. More generally, organic devices, such as organic transistors, may use these materials and structures.

[0109] The terms "halo" or "halogen" as used herein include fluorine, chlorine, bromine, and iodine.

[0110] As used herein, the term "alkyl" refers to both straight-chain and branched-chain alkyl radicals. A preferred alkyl group is one containing 1 to 15 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, etc. Additionally, the alkyl group may be optionally substituted.

[0111] The term "cycloalkyl" as used herein refers to a cyclic alkyl radical. A preferred cycloalkyl group contains 3 to 10 carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, etc. Additionally, the cycloalkyl group may be optionally substituted.

[0112] As used herein, the term "alkenyl" refers to both straight-chain and branched-chain alkene radicals. A preferred alkenyl group contains 2 to 15 carbon atoms. Additionally, the alkenyl group may be optionally substituted.

[0113] As used herein, the term "alkynyl" refers to both straight-chain and branched-chain alkyne radicals. A preferred alkynyl group contains 2 to 15 carbon atoms. Additionally, the alkynyl group may be optionally substituted.

[0114] As used herein, the terms "aryl-alkyl" or "aryl-alkyl" refer to alkyl groups having aromatic groups as substituents. Additionally, the aryl-alkyl group may be optionally substituted.

[0115] As used herein, the term "heterocyclic group" refers to aromatic and non-aromatic cyclic radicals. Hetero-aromatic cyclic radicals also refer to heteroaryls. A preferred hetero-non-aromatic cyclic group is a group containing 3 to 7 ring atoms containing one or more heteroatoms, and includes cyclic amines, e.g., morpholino, piperidino, pyrrolidino, etc., and cyclic ethers, e.g., tetrahydrofuran, tetrahydropyran, etc. Additionally, the heterocyclic group may be substituted as needed.

[0116] As used herein, "aryl" or "aromatic group" refers to monocyclic groups and polycyclic ring systems. Polycyclic rings may have two or more rings ("condensed" rings) in which two carbons are common to two adjacent rings, and one or more of the rings may be, for example, aromatic, while the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Preferred aryl groups are those containing 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Aryl groups having 6, 10, 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, preferably phenyl, biphenyl, triphenyl, triphenylene, fluorene, and naphthalene. Additionally, the aryl groups may be optionally substituted.

[0117] As used herein, the term "heteroaryl" comprises a single-ring hetero-aromatic group that may contain 1 to 5 heteroatoms. The term heteroaryl also comprises a polycyclic hetero-aromatic system having two or more rings, wherein two atoms are common to two adjacent rings (the rings are "fused") and one or more of the rings are heteroaryl, for example, the remaining rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Preferred heteroaryl groups are those containing 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. Suitable heteroaryl groups include dibenzothiophen, dibenzofuran, dibenzoselenopene, furan, thiophene, benzofuran, benzothiophene, benzoselenopene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazol, 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, sinoline, quinazolin, quinoxaline, naphthiridine, phthalazine, pteridine, xanthen, acridine, phenazine, Includes phenothiazine, phenoxazine, benzopuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenofenodipyridine, and selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenofen, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, and aza-analogs thereof. Additionally, the heteroaryl group may be substituted as needed.

[0118] Alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic, aryl, and heteroaryl groups may be optionally substituted with one or more substituents selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, 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.

[0119] As used herein, "substituted" indicates that a substituent other than H is bonded to a relevant position, e.g., a carbon. Thus, for example, R 1 In the case of this single substitution, one R 1 must be something other than H. Similarly, R 1 In this case of substitution, R 1 Two of them must be something other than H. Similarly, R 1 In this unsubstituted case, R 1 is hydrogen for all possible positions.

[0120] In the segments described herein, namely aza-dibenzofuran, aza-dibenzothiophene, etc., the designation "aza" implies that one or more of the CH groups in each segment may be substituted with nitrogen atoms; for example (but not limited thereto), azatriphenylene includes both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. Those skilled in the art may readily consider other nitrogen analogs of the aza derivatives described above, and all such analogs are deemed to encompass the terms described herein.

[0121] Those skilled in the art will understand that when a molecular segment is described as a substituent or, if not, is attached to another moiety, its name may be described as if it were a segment (e.g., phenyl, phenylene, naphthyl, dibenzofuryl) or as the whole molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, different notations of such substituents or attached segments are considered to be the same.

[0122] Iridium complexes having simple alkyl-substituted phenylpyridine ligands have been widely used as emitters in phosphorescent OLEDs. In some embodiments, the present disclosure discloses iridium complexes comprising substituted phenylpyridine ligands having specific substitution patterns or specific novel substitutions that form bulky groups on Ir complexes. Bulky groups on Pt complex ligands also exhibited higher EQE and less excimer formation. These substitutions unexpectedly improve device efficiency and lifetime. These substitutions also orient the metal complexes so that the transition dipole moments of the metal complexes are parallel to the OLED substrate, thereby increasing the external quantum efficiency of the emitter. Since light emission is perpendicular to the transition dipole of the emitter compound, the parallel orientation of the transition dipole moments of the emitter metal complexes increases the amount of light extracted from the OLED.

[0123] Measurement of emitter transition dipole moment orientation The orientation of the emitter transition dipole moment in OLEDs has received significant attention as one of the critical factors limiting external quantum efficiency. Recent literature has utilized and reported numerous different orientation measurement methods. Reported methods include angular photoluminescence profile measurements followed by optical simulations; integrating sphere EGE measurements of EL devices with or without out-coupled lenses using devices with a series of ETL thicknesses; and monochromatic electroluminescence far-field angle pattern measurements. All of these methods utilize commercially available optical simulation software for data calculation and interpretation.

[0124] The method disclosed below is designed to evaluate the orientation factor of multiple OLEDs used in devices having a standard set of materials. Typically, the materials are used in devices having structures optimized for maximum efficiency. The method requires a modified structure with varying layer thickness to increase the sensitivity of measured emission with respect to the emitter dipole orientation.

[0125] Selection of device structure A key factor in the study of dipole orientation in OLED emitters is aligning the structure of the sample device to enhance optical emission characteristics that are most sensitive to dipole orientation. In bottom-emission devices, when tuned to the maximum wavelength of the emission spectrum to generate a cavity effect, the distance from the reflective cathode to the emitter position becomes the dominant parameter. The cavity effect activated in this way can be best observed in angle measurements of polarized emission.

[0126] The above structure must provide a matrix that maintains the emitter at a well-defined position and path to activate the electroluminescence of the emitter. Although the above structure may constitute a composite optical system having multiple interfaces and include materials having different optical properties, it can be designed to create a distance between the reflective cathode and the emission site, which is a key factor defining the far-field pattern in air.

[0127]

[0128]

[0129] Carrier blocking layer for trapping emission sources in a thin EML.

[0130] ** Thick ETL resonating with yellow or green emission along with HBL and EML portions.

[0131] *** Thin 100 Å EML for confining the recombination zone (RZ) to a narrow region.

[0132] Table 1 shows examples of device structures that can be used to measure the orientation factor of yellow emitter compounds. The layer thicknesses provided in Table 1 are designed for measuring the yellow emitter orientation factor. Table 2 shows examples of device structures that can be used to measure the orientation factor of green emitter compounds. The layer thickness can be adjusted for red, green, or blue emitters depending on their emission wavelengths. A general rule is to maximize optical output through constructive interference between light reflected from the reflective electrode and light emitted from the RZ by adjusting the distance between the RZ, reflective electrode, and transparent electrode of the EML by controlling the thicknesses of the appropriate layers. The distance is adjusted by the device layer thickness and is proportional to the emission wavelength. Organic emitters are placed in a 100 Å-thick EML. The emission from organic emitters is usually not strictly monochromatic. Different parts of the spectrum interact differently with the light reflected by the cathode, thereby distorting the original spectrum. For this reason, the spectrum observed by far-field instruments may differ from the emitter's original PL spectrum.

[0133] Examples of materials for different components in the example device structure for measuring yellow and green emitter orientation factors are as follows:

[0134] ㆍ Anode: ITO;

[0135] ㆍ HIL: HATCN;

[0136] ㆍ HTL: , or ;

[0137] ㆍ EBL: ;

[0138] ㆍ EML consists of the following two hosts:

[0139] , and emitter;

[0140] ㆍ HBL: ;

[0141] ㆍ ETL: Liq and A mixed ETL consisting of;

[0142] ㆍ EIL: LiF or Liq; and

[0143] ㆍ Cathode: Al.

[0144] This material set must be adjusted according to the red, green, or blue emitter. Those skilled in the art will know how to adjust the material set for the red, green, or blue emitter. For the convenience of angular spectrum measurements, 5 mm 2 A relatively large pixel of was selected.

[0145] test : Emitter Example 2 of Table 3, Comp (L A147 )2Ir(L B184 The procedure for measuring the orientation factor for ) is now described. Spectral measurements of the device structure in Table 1 are performed using a calibrated spectrophotometer model PR740. Since the instrument utilizes a dot image projected onto a shutter with small perforations, a small parallax is expected when observing the object from a single angle. This needs to be corrected using simple geometry. At angles exceeding 50°, there is an additional effect of the instrument observing light reflection from the back glass cover of the device. For this reason, data taken at angles wider than 50° is used merely to indicate trends, and calculations are based only on data taken at angles between 30° and 50°. For most samples, the effect analyzed at 40° is strong enough to provide reliable data, so there is no need to quantify data obtained at wider angles.

[0146] Comparing measured spectral data with simulated spectral data is the most sensitive measure of the matching quality between simulated data and actual emission. Since simulation software methods are based on the optical characteristics of the light source, the agreement between observed and simulated data confirms the validity of correcting the emitter's performance in the dipole orientation plane calculated using simulation. The ratio of measured p- to s-emission in the 30–50° range is strongly correlated with the orientation factor. Using the p- to s-radiance ratio eliminates potential problems caused by absolute correction of radiance measurements resulting from imperfections in the optical system.

[0147] spectrum Figure 3 shows the EL spectra of the device for Example 2 of the emitter structure shown in Table 1, taken at various angles from 0 to 60° through an s-polarizer. Table 4 shows the simulated angle-dependent s-EL spectra of the same device structure using the program SETFOS-4.1 by Fluxim.

[0148] Results and InterpretationThe details of the dependence of the estimated dipole orientation value on the angular data of the given spectrum and device structure are described below. The graph in Fig. 5 is based on data generated by simulation software for samples having the structure shown in Table 1 and the spectra matched as shown in Figs. 3 and 4. In this specific embodiment, the integrated p / s radiance ratio at an angle of 40° is 1.67, and the corresponding dipole orientation (DO) is 0.15 (Fig. 6). The DO values ​​generated by the simulation software represent the statistical distribution of vertical versus horizontal orientation. Vertical and horizontal orientations are relative to the substrate; vertical refers to a direction orthogonal to the substrate plane, and horizontal refers to a direction parallel to the substrate plane. In the case of one vertical direction and two horizontal directions, the DO value scale ranges from 0 (parallel or horizontal) to 0.33 (isotropic). The corresponding scales of 1 to 0.67 represent the percentage of the original EQE after loss due to dipole orientation. This value, defined as Θ=1-DO, is called the emitter orientation factor (Θ=1-0.15=0.85 in our example, or 85% of the maximum EQE) and is more widely used in experimental data. This represents the percentage of emitter dipoles aligned parallel to the substrate. The graphs in Figures 7 and 8 indicate that the angular response to dipole orientation at angles of 30–50° is stronger in p-emission than in s-emission. Furthermore, as the dipole orientation value increases, the p-radiance value rises, while the s-radiance decreases. The resulting p / s ratio, starting from an observation angle of 30°, exhibits very high sensitivity to dipole orientation. In the current measurements, an angle of 40° is selected because it represents the maximum difference between s-emission and p-emission and the highest sensitivity.

[0149] The fact that a material has a desirable orientation ('orientation factor') means that in a solid-state thin film, it has an anisotropic horizontal-to-vertical dipole ratio. That is, the horizontal-to-vertical dipole ratio exceeds 0.67:0.33 (for isotropic cases), e.g., 0.77:0.23. To put this differently, the orientation factor (Θ), the ratio of horizontal dipoles to total dipoles, exceeds 0.67.

[0150] Figure 9 shows the correlation obtained between the estimated maximum EQE and the orientation factor. A clear increase in EQE is observed as the orientation factor increases. As the orientation factor approaches 1, more emitter molecules are aligned parallel to the substrate, which is desirable for improving device efficiency.

[0151] The procedure for measuring emitter photoluminescence quantum yield (PLQY) in PMMA is disclosed here. General preparation and experiment for solid-state samples: PMMA and emitter (various wt%) were weighed and dissolved in toluene. The solution was filtered through a 2-micron filter and drop-casted onto a pre-cleaned quartz substrate. PL quantum efficiency measurements were performed on a Hamamatsu C9920 system equipped with a xenon lamp, an integrating sphere, and a Model C10027 photon multichannel analyzer.

[0152]

[0153] As indicated by the emitter orientation factor, the emitter orientation becomes more parallel as the bulkiness of the group on the 4-phenyl ring of the 2,4-diphenylpyridine ligand increases. The estimated EQE has been reported to have a direct correlation with the emitter orientation.

[0154]

[0155] Figure 10 shows the correlation of emitter PLQY in the thin film as a function of emitter concentration. Comp (L used in device CE2) A1 )2Ir(L B182For non-bulky emitters such as ), PLQY drops significantly with increasing emitter concentration exceeding 10%. However, for more bulky emitters (e.g., the emitters used in device Examples 2 and 9), PLQY does not decrease rapidly as emitter concentration increases. Thus, the steric volume of the emitter molecules prevents self-quenching at high emitter %.

[0156] From the above emitter orientation and PLQY measurements, it is concluded that emitters having a larger stereovolume in a specific direction on the molecule provide a more parallel orientation (with respect to the substrate of the OLED) and thus exhibit a higher EQE in the device. These emitter examples are illustrated below and listed in Tables 3 and 4.

[0157]

[0158] According to some embodiments of the present disclosure, a compound having the following chemical formula is disclosed:

[0159] M(L A ) h (L B ) y (L C ) z

[0160] In the above chemical formula, ligand L A , L B , and L C is selected from a group consisting of each independently doing:

[0161]

[0162]

[0163] ;

[0164] Each X 1 To X 13 is independently selected from the group consisting of carbon and nitrogen;

[0165] X is selected from the group consisting of BR', NR', PR', O, S, Se, C=O, S=O, SO2, CR'R", SiR'R", and GeR'R";

[0166] R' and R" are arbitrarily fused or combined to form a ring;

[0167] Each R a , R b , R c , and R d can represent a uniform substitution or the maximum possible number of substitutions or non-substitutions;

[0168] R', R", R a , R b , R c , and R d Each is 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;

[0169] R a , R b , R c , and R d Any two adjacent substituents among them may fuse or combine to form a ring or a polydentate ligand;

[0170] M is a metal having an atomic mass greater than 40;

[0171] h is 1 or 2 and;

[0172] y is 0, 1, or 2;

[0173] z is 0, 1, or 2, and;

[0174] x+y+z is the oxidation state of metal M;

[0175] M(L A ) h (L B) y (L C ) z The molecule has an orientation factor value greater than 0.67.

[0176] Chemical formula M(L A ) h (L B ) y (L C ) z In some embodiments of the compound having, M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Au, and Cu. In other embodiments, M is Ir or Pt.

[0177] In some embodiments, the molecule of the compound has an orientation factor value (Θ) of 0.75 or higher. In other embodiments, the molecule has an orientation factor value of 0.80 or higher. In other embodiments, the molecule has an orientation factor value of 0.85 or higher. In other embodiments, the molecule has an orientation factor value of 0.91 or higher. In other embodiments, the molecule has an orientation factor value of 0.92 or higher. In other embodiments, the molecule has an orientation factor value of 0.93 or higher. In some embodiments, the molecule has an orientation factor value of 0.94 or higher.

[0178] Chemical formula M(L A ) h (L B ) y (L C ) z In some embodiments of a compound having, R a , R b , R c , and R d One of them is a monosubstitution having 13 or more carbon atoms, and R a , R b , R c , and R d All of the rest have a maximum carbon number of 6.

[0179] Chemical formula M(L A ) h (LB ) y (L C ) z In some embodiments of a compound having, each X 1 To X 13 It is carbon.

[0180] Chemical formula M(L A ) h (L B ) y (L C ) z In some embodiments of a compound having the formula Ir(L A )2(L B has ).

[0181] Chemical formula Ir(L A )2(L B In an embodiment of a compound having ), L A has a chemical formula selected from the group consisting of:

[0182] ;

[0183] L B has the following chemical formula:

[0184] . In some other embodiments, L B is the chemical formula having; here, R e , R f , R h , and R i is independently selected from the group consisting of alkyl, cycloalkyl, aryl, and heteroaryl; R e , R f , R h , and R i At least one of them has two or more carbon atoms; R gIt is 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.

[0185] Chemical formula Ir(L A )2(L B In some embodiments of a compound having ), L A and L B is selected from a group consisting of different and each independently performing:

[0186]

[0187] .

[0188] Chemical formula Ir(L A )2(L B In some embodiments of a compound having ), L A and L B is selected from a group consisting of each independently doing:

[0189]

[0190] .

[0191] Chemical formula M(L A ) h (L B ) y (L C ) z In some embodiments of a compound having the formula Pt(L A )(L B Having ), and L in the above chemical formula A and L B is different. In some embodiments of the above compound, L A is L B It binds to form a tetralocerdate ligand.

[0192] Chemical formula M(L A ) h (LB ) y (L C ) z In some embodiments of a compound having, the compound has a chemical formula (L) having a structure selected from the group (Group 1) consisting of the following: A ) m Ir(L B ) 3-m has:

[0193]

[0194] In the above chemical formulas, m is 1 or 2; and R 1 , R 2 , R 4 , and R 5 Each independently represents a uniform, binary, tri-substitution, quadruple, or non-substitution; R 3 represents unsubstituted, unsubstituted, or trisubstituted, or nonsubstituted; R 1 , R 2 , R 3 , R 4 , and R 5 Each is independently selected from the group consisting of hydrogen, deuterium, C1 to C6 alkyl, C1 to C6 cycloalkyl, and partial or fully deuterided or fluorinated variants thereof; R 6 It is selected from the group consisting of alkyls having 7 or more carbon atoms, cycloalkyls having 7 or more carbon atoms, alkyl-cycloalkyls having 7 or more carbon atoms, and partial or fully deuteriumated or fluorinated variants thereof. In some embodiments of the compound, m is 2.

[0195] Chemical formula M(L A ) h (L B ) y (L C ) z In some embodiments of a compound having, the compound has a chemical formula (L) having a structure selected from the group consisting of: A ) m Ir(L B )3-m has:

[0196]

[0197] In the above chemical formulas, m is 1 or 2.

[0198] Chemical formula M(L A ) h (L B ) y (L C ) z In some embodiments of a compound having, the compound has a chemical formula (L) having a structure selected from Group 1. A ) m Ir(L B ) 3-m having, wherein m is 1 or 2 in the above chemical formula; R 2 , R 3 , R 4 , and R 5 Each is independently selected from the group consisting of hydrogen, deuterium, methyl, ethyl, propyl, isopropyl, and combinations thereof.

[0199] Chemical formula M(L A ) h (L B ) y (L C ) z In some embodiments of a compound having, the compound has a chemical formula (L) having a structure selected from Group 1. A ) m Ir(L B ) 3-m having, wherein m is 1 or 2 in the above chemical formula; R 6 It is selected from the group consisting of alkyl having 8 or more carbon atoms, cycloalkyl having 8 or more carbon atoms, alkyl-cycloalkyl having 8 or more carbon atoms, and partial or fully deuteriumated or fluorinated variants thereof.

[0200] Chemical formula M(L A ) h (L B ) y (L C ) zIn some embodiments of a compound having, the compound has a chemical formula (L) having a structure selected from Group 1. A ) m Ir(L B ) 3-m having, wherein m is 1 or 2 in the above chemical formula; R 3 , R 4 , and R 5 Each is hydrogen.

[0201] Chemical formula M(L A ) h (L B ) y (L C ) z In some embodiments of a compound having the formula (L A ) m Ir(L B ) 3-m having, wherein m is 1 or 2 in the above chemical formula; L A is selected from the group consisting of:

[0202]

[0203]

[0204]

[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214] Chemical formula M(L A ) h(L B ) y (L C ) z In some embodiments of a compound having the formula (L A ) m Ir(L B ) 3-m having, wherein m is 1 or 2 in the above chemical formula; L B is L as described below B1 to L B227 Selected from a group consisting of:

[0215]

[0216]

[0217]

[0218]

[0219]

[0220]

[0221]

[0222]

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231] A chemical formula (L) having a structure selected from group 1 A ) m Ir(L B ) 3-m (Here, LA is L A1 to L A225 In some embodiments of a compound of (one of which is one of) said compound, said compound is of the formula Ir(L Aj )2(L Bk )(here, x = 227 j + k - It is 227, and, j is an integer from 1 to 225, and k (where is an integer from 1 to 227) a compound having x am.

[0232] A chemical formula (L) having a structure selected from group 1 A )Pt(L B )(here, L A is L A1 to L A225 In some embodiments of a compound of (one of which is) said compound, said compound is of the formula Pt(L A j )(L B k )(here, y = 227 j + k - It is 227, and, j is an integer from 1 to 225, and k (where is an integer from 1 to 227) a compound having y is. L B1 to L B227 It has a structure as defined above.

[0233] According to another aspect of the present disclosure, the formula (L A ) m Ir(L B ) 3-m A compound having is disclosed, said compound having a structure selected from the group consisting of (group 2):

[0234]

[0235] In the above chemical formulas,

[0236] m is 1 or 2 and;

[0237] R 1 , R2 , R 4 , and R 5 Each independently represents a uniform, bisubstitution, trisubstitution, quadruple substitution, or nonsubstitution;

[0238] R 3 represents unsubstitution, unsubstitution, trisubstitution, or nonsubstitution;

[0239] R 6 represents identical or non-identified substitution;

[0240] R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Each is independently selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, partial or fully deuteriumated or fluorinated variants thereof, and combinations thereof.

[0241] In some embodiments of a compound having a structure selected from Group 2, R 1 , R 2 , R 3 , R 4 , and R 5 Each is independently selected from the group consisting of hydrogen, deuterium, C1 to C6 alkyl, C1 to C6 cycloalkyl, and partial or fully deuterided or fluorinated variants thereof; R 6 It is selected from the group consisting of alkyl having 7 or more carbon atoms, cycloalkyl having 7 or more carbon atoms, alkyl-cycloalkyl having 7 or more carbon atoms, and partial or fully deuteriumated or fluorinated variants thereof.

[0242] In some embodiments of a compound having a structure selected from group 2, m is 2.

[0243] In some embodiments of a compound having a structure selected from Group 2, R 1 , R 2 , R 3 , R 4 , and R5 Each is independently selected from the group consisting of hydrogen, deuterium, methyl, ethyl, propyl, isopropyl, and combinations thereof.

[0244] In some embodiments of a compound having a structure selected from Group 2, R 6 It is selected from the group consisting of alkyl having 8 or more carbon atoms, cycloalkyl having 8 or more carbon atoms, alkyl-cycloalkyl having 8 or more carbon atoms, and partial or fully deuteriumated or fluorinated variants thereof.

[0245] In some embodiments of a compound having a structure selected from Group 2, R 3 , R 4 , and R 5 Each is hydrogen.

[0246] In some embodiments of a compound having a structure selected from Group 2, L A is the L listed above A1 to L A225 It is selected from a group consisting of.

[0247] In some embodiments of a compound having a structure selected from Group 2, L B is L B1 to L B227 It is selected from the group consisting of L B1 to L B227 The structure of is illustrated above.

[0248] According to another aspect of the present disclosure, an OLED is disclosed comprising an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound having a chemical formula selected from the group consisting of the following chemical formulas:

[0249] M(L A ) h (L B ) y (L C ) z ,

[0250]

[0251] In the above chemical formulas, m is 1 or 2;

[0252] Ligand L A , L B , and L C is selected from a group consisting of each independently doing:

[0253]

[0254]

[0255] ;

[0256] Each X 1 To X 13 is independently selected from the group consisting of carbon and nitrogen;

[0257] X is selected from the group consisting of BR', NR', PR', O, S, Se, C=O, S=O, SO2, CR'R", SiR'R", and GeR'R";

[0258] R' and R" are arbitrarily fused or combined to form a ring;

[0259] Each R a , R b , R c , and R d can represent a uniform substitution or the maximum possible number of substitutions or non-substitutions;

[0260] R', R", R a , R b , R c , and R d Each is 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;

[0261] R a , R b , R c , and R d Any two adjacent substituents among them may fuse or combine to form a ring or a polydentate ligand;

[0262] M is a metal having an atomic mass greater than 40;

[0263] h is 1 or 2 and;

[0264] y is 0, 1, or 2;

[0265] z is 0, 1, or 2, and;

[0266] x+y+z is the oxidation state of metal M;

[0267] M(L A ) h (L B ) y (L C ) z The molecule has an orientation factor value exceeding 0.67;

[0268] R 1 , R 2 , R 4 , and R 5 Each independently represents a uniform, bisubstitution, trisubstitution, quadruple substitution, or nonsubstitution;

[0269] R 3 represents unsubstitution, unsubstitution, trisubstitution, or nonsubstitution;

[0270] R 6 represents identical or non-identified substitution;

[0271] R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Each is independently selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, partial or fully deuteriumated or fluorinated variants thereof, and combinations thereof.

[0272] In some embodiments, the OLED is introduced within a device selected from the group consisting of consumer goods, electronic component modules, and lighting panels.

[0273] In some embodiments of the OLED, the organic layer is a light-emitting layer and the compound may be a light-emitting dopant or a non-light-emitting dopant.

[0274] When discussing the device structure illustrated in FIG. 1, other functional layers of the OLED may be provided between the organic layer and the anode and / or between the organic layer and the cathode. Accordingly, depending on a specific embodiment, the organic layer containing the novel compound of the present disclosure may be placed directly on an interlayer or on an electrode substrate.

[0275] In some embodiments of the OLED, the organic layer further comprises a host, said host comprises a benzofered thiophene or a benzofered furan containing triphenylene; any substituent in the host is independently C n H 2n+1 , OC n H 2n+1 , OAr1, N(C n H 2n+1 )2, N(Ar1)(Ar2), CH=CH-C n H 2n+1 , C≡CC n H 2n+1 , Ar1, Ar1-Ar2, C n H 2n - A non-fusion substituent selected from the group consisting of -Ar1 or a non-substituent; where n is 1 to 10; Ar1 ​​and Ar2 are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.

[0276] In some embodiments of the OLED, the organic layer further comprises a host, said host comprises one or more chemical groups selected from the group consisting of triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenopene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenopene.

[0277] In some embodiments of the OLED, the organic layer further comprises a host, said host is selected from the group consisting of:

[0278]

[0279] , and combinations thereof.

[0280] In some embodiments of the OLED, the organic layer further comprises a host, and the host comprises a metal complex.

[0281] In some embodiments, the compound may be a luminescent dopant. In some embodiments, the compound may produce luminescence through phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence), triplet-triplet quenching, or a combination of these processes.

[0282] According to another aspect, a formulation comprising a compound having a chemical formula selected from the group consisting of the following chemical formulas is disclosed:

[0283] M(L A ) h (L B ) y (L C ) z ,

[0284]

[0285] In the above chemical formula,

[0286] m is 1 or 2 and;

[0287] Ligand L A , L B , and LC is selected from a group consisting of each independently doing:

[0288]

[0289]

[0290] ;

[0291] Each X 1 To X 13 is independently selected from the group consisting of carbon and nitrogen;

[0292] X is selected from the group consisting of BR', NR', PR', O, S, Se, C=O, S=O, SO2, CR'R", SiR'R", and GeR'R";

[0293] R' and R" are arbitrarily fused or combined to form a ring;

[0294] Each R a , R b , R c , and R d can represent a uniform substitution or the maximum possible number of substitutions or non-substitutions;

[0295] R', R", R a , R b , R c , and R d Each is 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;

[0296] R a , R b , R c , and R d Any two adjacent substituents among them may fuse or combine to form a ring or a polydentate ligand;

[0297] M is a metal having an atomic mass greater than 40;

[0298] h is 1 or 2 and;

[0299] y is 0, 1, or 2;

[0300] z is 0, 1, or 2, and;

[0301] x+y+z is the oxidation state of metal M;

[0302] M(L A ) h (L B ) y (L C ) z The molecule has an orientation factor value exceeding 0.67;

[0303] R 1 , R 2 , R 4 , and R 5 Each independently represents a uniform, bisubstitution, trisubstitution, quadruple substitution, or nonsubstitution;

[0304] R 3 represents unsubstitution, unsubstitution, trisubstitution, or nonsubstitution;

[0305] R 6 represents identical or non-identified substitution;

[0306] R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Each is independently selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, partial or fully deuteriumated or fluorinated variants thereof, and combinations thereof.

[0307] The OLED disclosed herein may be introduced into one or more of consumer goods, electronic component modules, and lighting panels. In some embodiments, the organic layer may be a light-emitting layer and the compound may be a light-emitting dopant, and in other embodiments, the compound may be a non-light-emitting dopant.

[0308] The organic layer may also include a host. In some embodiments, two or more hosts are preferred. In some embodiments, the host may be a) bipolar, b) electron transport, c) hole transport, or d) a wide band gap material with little role in charge transport. In some embodiments, the host may include a metal complex. The host may be a triphenylene-containing benzo-fused thiophene or a benzo-fused furan. Any substituent within the host is independently C n H 2n+1 , OC n H 2n+1 , OAr1, N(C n H 2n+1 )2, N(Ar1)(Ar2), CH=CH-C n H 2n+1 , C≡CC n H 2n+1 , Ar1, Ar1-Ar2 and C n H 2n It may be a non-fusion substituent selected from the group consisting of -Ar1, or it may be unsubstituted. In the said substituent, n may be in the range of 1 to 10; Ar1 ​​and Ar2 may independently be selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof. The host may be an inorganic compound. For example, it may be a Zn-containing inorganic material, such as ZnS.

[0309] The above host may be a compound comprising one or more chemical groups selected from the group consisting of triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenopene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenopene. The above host may include a metal complex. The above host may be a specific compound selected from the group consisting of the following, but is not limited thereto:

[0310]

[0311]

[0312] and combinations thereof.

[0313] Additional information regarding available hosts is provided below.

[0314] In another aspect of the present disclosure, a formulation comprising a compound according to Formula I is disclosed. The formulation may comprise one or more components selected from the group consisting of solvents, hosts, hole injection materials, hole transport materials, and electron transport layer materials disclosed herein.

[0315] Combination with other substances

[0316] The materials described herein as useful for a specific layer in an organic light-emitting device may be used in combination with various other materials present in the device. For example, the light-emitting dopant disclosed herein may be used in combination with a host, a transport layer, a blocking layer, an injection layer, an electrode, and other layers that may be present. The materials described or referred to below are non-limiting materials that may be useful in combination with the compounds disclosed herein, and those skilled in the art may readily refer to literature identifying other materials that may be useful in combination.

[0317] Conductivity dopant:

[0318] The charge transport layer can be doped with a conductive dopant to substantially alter the charge carrier density, which will change its conductivity. Conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, changes 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 an n-type conductive dopant is used in the electron transport layer.

[0319] Non-limiting examples of conductive dopants that can be used in OLEDs with the materials disclosed herein are exemplified below in conjunction with the references disclosing these materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804 and US2012146012.

[0320]

[0321]

[0322] HIL / HTL:

[0323] The hole injection / transport material intended for use in the present invention is not specifically limited, and any compound may be used as long as the compound is used as a hole injection / transport material. Non-limiting examples of materials include phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indolocarbazole derivatives; polymers comprising fluorohydrocarbons; polymers having conductive dopants; conductive polymers, e.g., PEDOT / PSS; self-assembling monomers derived from compounds such as phosphonic acids and silane derivatives; and metal oxide derivatives, e.g., MoO₂ x ; p-type semiconductor organic compounds, such as 1,4,5,8,9,12-hexaazatriphenylene hexacarbonitrile; metal complexes and crosslinkable compounds may be examples.

[0324] Non-limiting examples of aromatic amine derivatives used in HIL or HTL include the following chemical formulas:

[0325]

[0326] Each Ar 1 or Ar 9is a group composed of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; Dibenzothiophen, Dibenzofuran, Dibenzoselenopene, Furan, Thiophene, Benzofuran, Benzothiophene, Benzoselenopene, Carbazole, Indolocarbazole, Pyridylindole, Pyrrolodipyridine, Pyrazol, 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, Sinolin, Quinazolin, Quinoxaline, Naphthiridine, Phthalasine, Pteridine, Xanthen, Acridine, Phenazine, Phenothiazine, Phenoxazine, A group consisting of aromatic heterocyclic compounds such as benzopyridine, propipyridine, benzothiopyridine, thienodipyridine, benzoselenofenodipyridine, and selenofenofenodipyridine; and a group consisting of 2 to 10 cyclic structural units that are of the same or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups, and are bonded to each other directly or through one or more of the following: 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 Ar may be substituted or unsubstituted with a substituent selected from the group consisting of 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.

[0327] In one embodiment, Ar 1 or Ar 9 is selected from a group consisting of doing it independently:

[0328]

[0329] k is an integer from 1 to 20; X 101 To X 108 is C (including CH) or N; Z 101 eu NAr 1 , O or S and; Ar 1 It has the same structure as defined above.

[0330] Non-limiting examples of metal complexes used in HIL or HTL include the following:

[0331]

[0332] Met is a metal that can have an atomic weight greater than 40; (Y 101 -Y 102 ) is a 2-position ligand, and Y 101 and Y 102 is independently selected from C, N, O, P, and S; L 101 is an auxiliary ligand; k' is an integer value of the maximum number of ligands that can be bound to the metal, from 1 to; and k'+k" is the maximum number of ligands that can be bound to the metal.

[0333] In one mode, (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 in solution of less than about 0.6 V versus Fc + / Fc have a couple.

[0334] Non-limiting examples of HIL and HTL materials that can be used in OLEDs together with the materials disclosed herein are exemplified below together with the references 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,

[0335]

[0336]

[0337]

[0338]

[0339]

[0340]

[0341]

[0342] .

[0343] EBL:

[0344] An electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons leaving the emissive layer. The presence of such a blocking layer within the device can lead to substantially higher efficiency and / or a longer lifetime compared to a similar device without a blocking layer. Additionally, the blocking layer can be used to confine light emission to a desired area of ​​the OLED. In some embodiments, the EBL material has a higher LUMO (closer to vacuum level) and / or a higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to vacuum level) and / or a higher triplet energy than one or more of the hosts closest to the EBL interface. In one embodiment, the compound used for the EBL contains the same molecule or the same functional group used as one of the hosts described below.

[0345] Host:

[0346] The light-emitting layer of the organic EL device of the present invention preferably comprises at least a metal complex as a light-emitting material and may comprise a host material using a metal complex as a dopant material. Examples of host materials are not specifically limited, but any metal complex or organic compound may be used as long as the triplet energy of the host is greater than that of the dopant. Any host material may be used with any dopant as long as the triplet criterion is satisfied.

[0347] An example of a metal complex used as a host preferably has the following chemical formula:

[0348]

[0349] Met is a metal; (Y 103 -Y 104 ) is a 2-position ligand, and Y 103 and Y 104 is independently selected from C, N, O, P, and S; L 101 is another ligand; k' is an integer value of the maximum number of ligands to which the metal can be bound, ranging from 1 to the maximum number of ligands to which the metal can be bound; and k'+k" is the maximum number of ligands to which the metal can be bound.

[0350] In one embodiment, the metal complex am.

[0351] (ON) is a dubate ligand having a metal coordinately bonded to atoms O and N.

[0352] In another embodiment, Met is selected from Ir and Pt. In an additional embodiment, (Y 103 -Y 104 ) is a carbene ligand.

[0353] Examples of organic compounds used as hosts are the group consisting of aromatic hydrocarbon cyclic compounds, such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; Aromatic heterocyclic compounds, e.g., dibenzothiophene, dibenzofuran, dibenzoselenopene, furan, thiophene, benzofuran, benzothiophene, benzoselenopene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazol, 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, quinazolin, quinoxaline, naphthiridine, phthalazine, pteridine, xanthen, acridine, It is selected from the group consisting of phenazine, phenothiazine, phenoxazine, benzopuropyridine, purodipyridine, benzothienopyridine, thienodipyridine, benzoselenofenofyridine and selenophenodipyridine; and from the group consisting of 2 to 10 cyclic structural units that are of the same or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups and are directly bonded to each other or bonded by one or more of oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, boron atoms, chain structural units and aliphatic cyclic groups. Here, the option in each group may be substituted or unsubstituted with a substituent selected from the group consisting of 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.

[0354] In one embodiment, the host compound comprises one or more of the following groups in the molecule:

[0355]

[0356] R 101 to R 107 Each is independently selected from the group consisting of hydrogen, deuterium, halogen, 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, and if aryl or heteroaryl, has a definition similar to that of the aforementioned Ar. k is an integer from 0 to 20 or from 1 to 20; k"' is an integer from 0 to 20. X 101 To X 108 is selected from C (including CH) or N.

[0357] Z 101 and Z 102 is NR 101 , is selected from O or S.

[0358] Non-limiting examples of host materials that can be used in OLEDs with the materials disclosed herein are exemplified below together with the references 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,

[0359]

[0360]

[0361]

[0362]

[0363]

[0364] Additional emitter:

[0365] One or more additional emitter dopants may be used with the compounds of the present disclosure. Examples of additional emitter dopants are not particularly limited, and any compound that is typically used as an emitter material may be used. Examples of suitable emitter materials include, but are not limited to, compounds capable of producing luminescence by phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also called E-type delayed fluorescence), triplet-triplet quenching, or a combination of these processes.

[0366] Non-limiting examples of emitter materials that can be used in OLEDs with the materials disclosed herein are exemplified below together with the references disclosing 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.,

[0367]

[0368]

[0369]

[0370]

[0371]

[0372]

[0373] HBL:

[0374] A hole blocking layer (HBL) can be used to reduce the number of holes and / or excitons leaving the emissive layer. The presence of such a blocking layer within the device can exhibit substantially higher efficiency and / or longer lifetime compared to similar devices lacking a blocking layer. Additionally, the blocking layer can be used to localize emission to desired areas of the 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.

[0375] In one embodiment, the compound used in the HBL comprises the same functional group or the same molecule used as the aforementioned host.

[0376] In another embodiment, the compound used in the HBL comprises one or more of the following groups in the molecule:

[0377]

[0378] k is an integer from 1 to 20; L 101 is another ligand, and k' is an integer from 1 to 3.

[0379] ETL:

[0380] The electron transport layer (ETL) may comprise a material capable of transporting electrons. The electron transport layer may be native (undoped) or doped. Doping may be used to enhance conductivity. Examples of ETL materials are not specifically limited, and any metal complex or organic compound may be used as long as it is typically used to transport electrons.

[0381] In one embodiment, the compound used for ETL comprises one or more of the following groups in the molecule:

[0382]

[0383] R 101 It is 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, and if it is aryl or heteroaryl, it has a definition similar to that of the aforementioned Ar. 1 or Ar 3 has a definition similar to the aforementioned Ar. k is an integer from 1 to 20. X 101 To X 108 It is selected from C (including CH) or N.

[0384] In another embodiment, the metal complex used in the ETL includes, but is not limited to, the following chemical formulas:

[0385]

[0386] (ON) or (NN) is a dubate ligand having a metal coordinately bonded to atoms O, N or N,N; L 101 is another ligand; k' is an integer value of the maximum number of ligands that can be bound to the metal, ranging from 1 to 1.

[0387] Non-limiting examples of ETL materials that can be used in OLEDs with the materials disclosed herein are exemplified below together with the references 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,

[0388]

[0389]

[0390]

[0391] Charge generation layer (CGL)

[0392] In tandem or stacked OLEDs, the CGL plays an essential role in performance and consists of an n-doping layer and a p-doping layer for the injection of electrons and holes, respectively. Electrons and holes are supplied from the CGL and the electrodes. Electrons and holes consumed in the CGL are recharged by electrons and holes injected from the cathode and anode, respectively, and subsequently, the bipolar current gradually reaches a rectified state. Typical CGL materials include n and p conductive dopants used in the transport layers.

[0393] In any of the aforementioned compounds used in each layer of the OLED device, hydrogen atoms may be partially or completely deuterinated. Accordingly, any specifically listed substituents such as methyl, phenyl, pyridyl, etc. (not limited to) may be non-deuterinated, partially deuterinated, and completely deuterinated versions thereof. Likewise, substituents of classes such as alkyl, aryl, cycloalkyl, heteroaryl, etc. (not limited to) may also be non-deuterinated, partially deuterinated, and completely deuterinated versions thereof.

[0394] experiment

[0395] Synthesis Examples

[0396] 1. Comp (L A1 )2Ir(L B196 Synthesis of )

[0397]

[0398] In a 500 mL round-bottom flask, 1-bromo-4-chlorobenzene (9.60 g, 50.1 mmol), 2-phenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (11.75 g, 41.8 mmol), Pd(PPh3)4 (2.415 g, 2.090 mmol), sodium carbonate (13.29 g, 125 mmol), DME (200 mL), and water (100 mL) were added and refluxed overnight. The reaction mixture was worked up and purified to obtain 9.1 g of the desired product (yield 89%). The desired product was identified by GC and NMR.

[0399]

[0400] Neopentyboronic acid (5.0 g, 43.1 mmol), dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphane (SPhos) (1.112 g, 2.71 mmol), Pd2(dba)3 (0.620 g, 0.677 mmol), potassium phosphate (21.57 g, 102 mmol), water (25 ml), and toluene (250 ml) were added to a 500 mL round-bottom flask. The reaction mixture was degassed by bubbling in nitrogen for 15 minutes, then heated in an oil bath and refluxed for 24 hours. The reaction was cooled and purified by silica column chromatography to obtain 8.0 g of the desired product (78.3% yield).

[0401]

[0402] This deuteriumation reaction Tetrahedron It was performed based on the procedures in the literature disclosed in 71(2015)1425-1430.

[0403]

[0404] In a 100 mL round-bottom flask, iridium precursor (1.7 g, 2.38 mmol), 4-(4-(2,2-dimethylpropyl-11-d2)phenyl)pyridine (1.8 g, 5.93 mmol), ethanol (25 mL), and methanol (25 mL) were added, heated under nitrogen in an oil bath, and refluxed at 80°C for 2 days. The reaction mixture was purified by silica column chromatography to obtain 0.9 g (47% yield) of the desired product, which was confirmed by LC-MS and NMR.

[0405] 2. Comp (L A147 )2Ir(L B184 Synthesis of )

[0406]

[0407] In a 100 mL flask, iridium precursor (2.5 g, 3.20 mmol), 4-(4-(methyl-d3)phenyl)-2-phenylpyridine (2.382 g, 9.59 mmol), ethanol (25 mL), and methanol (25 mL) were added. The reaction mixture was heated under nitrogen in an oil bath and refluxed at 80°C for 15 hours. The reaction was allowed to cool to room temperature, and the solid was filtered, washed with methanol, and dried. The yellow solid was further purified by silica column chromatography to obtain 1.25 g of product (yield 48.9%), which was confirmed by LC-MS and NMR.

[0408] 3. Comp (L A147 )2Ir(L B86 Synthesis of )

[0409]

[0410] In a 500 mL round-bottom flask, iridium precursor (2 g, 2.56 mmol), 4-(4-((1S,2S,4R)-bicyclo[2.2.1]heptane-2-yl-2-d)phenyl)-2-phenylpyridine (2.104 g, 6.45 mmol), ethanol (40 mL), and methanol (40 mL) were added, and the mixture was refluxed at 80°C for 23 hours. The reaction mixture was cooled and filtered. The collected yellow solid was subjected to silica column chromatography to obtain the desired product (0.61 g, 26% yield).

[0411] 4. Comp (L A147 )2Ir(L B109 Synthesis of )

[0412]

[0413] 1-phenyladamantan (2 g, 9.42 mmol), CCl4 (40 mL), and dibromine (19.40 mL, 377 mmol) were placed in a 100 mL flask, stirred overnight, and protected from light. The reaction mixture was slowly poured into ice water and quenched with sodium thiosulfate. The reaction mixture was extracted with ethyl acetate. The organic portion was evaporated to obtain the desired product (2.74 g, 100%).

[0414]

[0415] In a 250 mL flask, 1-(4-bromophenyl)adamantan (2.76 g, 9.48 mmol), 2-phenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (4.00 g, 14.22 mmol), diacetoxypalladium (0.064 g, 0.284 mmol), dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphane (SPhos) (0.233 g, 0.569 mmol), K3PO4 (4.02 g, 18.95 mmol), toluene (30 mL), and water (3 mL) were added. The reaction mixture was heated at 100°C overnight and treated with an aqueous walk-up of EtOAc. The organic portion was combined and column chromatography was performed to obtain the desired product (2.46 g, 71%).

[0416]

[0417] Iridium precursor (2.0 g, 2.56 mmol), 4-(4-(adamantan-1-yl)phenyl)-2-phenylpyridine (2.10 g, 5.75 mmol), ethanol (25 mL), and methanol (25 mL) were placed in a 500 mL flask. The reaction mixture was heated at 80°C for 5 days. The reaction mixture was filtered, and the collected precipitate was subjected to column chromatography to obtain the desired product (0.74 g, 31%). The desired product was identified by NMR and LC-MS.

[0418] 5. Comp (L A147 )2Ir(L B88 Synthesis of )

[0419]

[0420] (Nitrooxy)silver (0.137 g, 0.805 mmol) was placed in a 100 mL flask, followed by the addition of 100 mL of anhydrous ether and (1R,2S,4S)-2-bromobicyclo[2.2.1]heptane (3.45 mL, 26.8 mmol). Subsequently, (4-chlorobenzyl)magnesium chloride (0.5 M solution in 2-MeTHF, 77 mL, 38.5 mmol) was added dropwise over 20 minutes using an addition funnel. The reaction mixture was stirred overnight at room temperature. The reaction mixture was diluted with water and extracted with ether. The organic fractions were combined and column chromatography was performed to obtain the desired product (2.48 g, 41%).

[0421]

[0422] (1R,2R,4S)-2-(4-chlorobenzyl)bicyclo[2.2.1]heptane (2.48 g, 11.23 mmol), 2-phenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (4.11 g, 14.61 mmol), diacetoxypalladium (0.076 g, 0.337 mmol), dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphane (SPhos) (0.277 g, 0.674 mmol), K3PO4 (4.77 g, 22.47 mmol), toluene (30 mL), and water (3.00 mL) were added to a 250 mL flask. The reaction mixture was heated overnight at 105°C. The reaction mixture was treated with an aqueous walk-up and extracted with ethyl acetate. The organic fractions were combined and subjected to silica column chromatography to obtain a pure product (3.69 g, 97%).

[0423]

[0424] Tetrahedron A deuteriumation reaction was performed based on the procedure in the literature disclosed in 71(2015)1425-1430.

[0425]

[0426] In a 500 mL round-bottom flask, iridium precursor (2.8 g, 3.58 mmol), 4-(4-(((1R,2S,4S)-bicyclo[2.2.1]heptane-2-yl)methyl-d2)phenyl)-2-phenylpyridine (2.446 g, 7.16 mmol), ethanol (25 mL), and MeOH (25 mL) were added. The reaction mixture was heated at 80°C for 4 days. The reaction mixture was filtered, the precipitate was collected, and purified by silica column chromatography to obtain the desired product (1 g, 30.7%).

[0427] 6. Comp (L A147 )2Ir(L B225 Synthesis of )

[0428]

[0429] 2-(4-bromophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (10.5 g, 37.1 mmol), dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphane (SPhos) (0.914 g, 2.226 mmol), and diacetoxypalladium (0.250 g, 1.113 mmol) were added to a 500 mL flask. A solution of (cyclopentylmethyl)zinc(II) chloride (20.48 g, 111 mmol) was transferred to the reaction flask via a cannula. The reaction mixture was stirred overnight at room temperature. The reaction mixture was diluted with a saturated ammonium chloride solution and extracted with ethyl acetate. The organic fractions were combined, and silica column chromatography was performed to obtain the desired product (7.10 g, 67%).

[0430]

[0431] 4-chloro-2-phenylpyridine (3.92 g, 20.67 mmol), 2-(4-(cyclopentylmethyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7.10 g, 24.80 mmol), Pd2(dba)3 (0.379 g, 0.413 mmol), dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphane (SPhos) (0.679 g, 1.654 mmol), K3PO4 (13.16 g, 62.0 mmol), toluene (70 mL), and water (7.0 mL) were added to a 250 mL flask. The reaction was heated overnight at 100°C. The reaction mixture was treated with an aqueous walk-up and extracted with EtOAc. The organic portion was combined and column chromatography was performed to obtain the product (5.71 g, 88%).

[0432]

[0433] Tetrahedron A deuteriumation reaction was performed based on the procedure in the literature disclosed in 71(2015)1425-1430.

[0434]

[0435] Iridium precursor (2.22 g, 2.84 mmol), 4-(4-(cyclopentylmethyl-d2)phenyl)-2-phenylpyridine (1.791 g, 5.68 mmol), ethanol (25 mL), and MeOH (25.00 mL) were placed in a 100 mL round-bottom flask. The reaction mixture was heated at 68 °C for 5 days. The reaction mixture was filtered, and the collected precipitate was subjected to column chromatography to obtain the desired product (0.9 g, 36%).

[0436] 7. Comp (L A153 )2Ir(L B86 Synthesis of )

[0437]

[0438] 2,4-dibromo-pyridine (9.45 g, 40.4 mmol), 4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane (11.37 g, 55.7 mmol), diacetoxypalladium (0.569 g, 2.53 mmol), triphenylphosphane (2.66 g, 10.13 mmol), potassium hydroxide (5.68 g, 101 mmol), and acetonitrile (600 mL) were added to a 1000 mL round-bottom flask. The reaction mixture was heated at 60°C for 50 hours. The reaction mixture was treated with an aqueous walk-up of EtOAc. The organic fractions were combined, and silica column chromatography was performed to obtain the desired product (9.45 g, 80%).

[0439]

[0440] 4-bromo-2-phenylpyridine (9.52 g, 35.8 mmol), (4-chlorophenyl)boronic acid (6.94 g, 44.4 mmol), diacetoxypalladium (0.453 g, 2.018 mmol), triphenylphosphane (1.059 g, 4.04 mmol), K2CO3 (11.16 g, 81 mmol), acetonitrile (200 mL), and MeOH (100 mL) were added to a 500 mL round-bottom flask. The reaction was heated at 40°C for 21 hours. The reaction mixture was diluted with water and extracted with ethyl acetate. The organic portion was evaporated. The residue was subjected to column chromatography to obtain the desired compound (9.52 g, 89%).

[0441]

[0442] 4-(4-chlorophenyl)-2-phenylpyridine (3 g, 11.29 mmol), lithium chloride (6.52 g, 154 mmol), PEPPSI-Ipr (0.460 g, 0.677 mmol), and ((1S,2R,4R)-bicyclo[2.2.1]heptane-2-yl)zinc(II) bromide in THF (79 ml, 39.5 mmol) were added to a 250 mL flask. The reaction mixture was stirred overnight at room temperature. The reaction mixture was diluted with water and extracted with ethyl acetate. The organic fractions were combined and column chromatography was performed to obtain (3.67 g, 100%).

[0443]

[0444] Tetrahedron A deuteriumation reaction was performed based on the procedure in the literature disclosed in 71(2015)1425-1430.

[0445]

[0446] Iridium precursor (4.28 g, 5.24 mmol), 4-(4-((1S,2S,4R)-bicyclo[2.2.1]heptane-2-yl-2-d)phenyl)-2-phenylpyridine (4.36 g, 13.36 mmol), ethanol (40 mL), and methanol (40 mL) were placed in a 500 mL flask and heated at 70°C for 50 hours. The reaction mixture was filtered, the yellow solid was collected, and column chromatography was performed to obtain the desired product (1.18 g).

[0447] Device Example

[0448] All embodiment elements are in a high vacuum (<10 -7It was fabricated by thermal evaporation (Torr). The anode electrode was 750 Å indium tin oxide (ITO). The cathode consisted of 10 Å Liq (8-hydroxyquinoline lithium) followed by 1,000 Å Al. Immediately after fabrication, the device was sealed in a nitrogen glove box (<1 ppm H2O and O2) with a glass lid sealed with epoxy resin, and a moisture getter was placed inside the package. The stack of the device example was sequentially, from the ITO surface, 100 Å HATCN as the hole injection layer (HIL); 450 Å HTM as the hole transport layer (HTL); It consists of a 50 Å EBM as an electron blocking layer, a 400 Å emissive layer (EML) comprising a two-component host (H1:H2 1:1 ratio) and 12% emitter (the present invention or comparative emitter example), and a 350 Å Liq (8-hydroxyquinoline lithium) doped with 40% ETM as an electron transport layer ETL. The chemical structure of the device material is shown below.

[0449]

[0450]

[0451] Table 5 shows the layer thickness and material of the device.

[0452]

[0453] The correlation between device EQE and emitter orientation factor was verified using emitter Examples 1, 2, 5, 7, 8, 9, 10 and CE2. The device EQE measured at 1,000 nit is shown in Table 6.

[0454]

[0455] The increase in device EQE observed as the emitter orientation factor increases demonstrates that EQE is directly correlated with emitter orientation.

[0456] It should be understood that the various embodiments described herein are merely illustrative and are not intended to limit the scope of the invention. For example, most of the materials and structures described herein may be replaced with other materials and structures without departing from the spirit of the invention. The claimed invention may include variations from the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art accordingly. It will be understood that various theories regarding why the invention is effective are not intended to be limiting.

Claims

Claim 1 As a material for use in OLEDs, the chemical formula Ir(L A )2(L B A material comprising a compound having ): in the above chemical formula, ligand L A Is Igo, ligand L B is selected from the group consisting of: Each X 1 To X 10 is carbon; X is selected from the group consisting of BR', NR', PR', O, S, Se, C=O, S=O, SO2, CR'R", SiR'R", and GeR'R"; R' and R" are optionally fused or bonded to form a ring; and each R a and R b can represent all substitutions or the maximum possible number of substitutions or non-substitutions, provided that ligand L A R of a and R b Each independently represents monosubstituted, bisubstituted, trisubstituted, or tetrasubstituted, having one or more non-hydrogen substituents; R', R", R a and R b Each is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, carboxylic acid, nitrile, isonitrile, sulfanyl, phosphino, and combinations thereof; R a and R b Any two adjacent substituents among them are arbitrarily fused or combined to form a ring; ligand L A R of a It does not fuse or combine to form a ring; ligand L A R of a and R b Each is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, silyl, alkenyl, aryl, heteroaryl, nitrile, and combinations thereof; ligand L B R of a or R b One or more of the substituents comprise one or more substituents, and one or more of the substituents comprise a phenyl group, wherein the phenyl group is substituted with one or more substituents having a total straight-chain or branched-chain alkyl carbon number of 5 or more, and one or more of the substituents are partially or fully deuterinized, provided that the ligand L B go When, ligand L A R of b is not a phenyl group. Claim 2 Delete Claim 3 In paragraph 1, ligand L B R of a or R b One of them is a monosubstituted material having 13 or more carbon atoms. Claim 4 delete Claim 5 delete Claim 6 delete Claim 7 In paragraph 1, ligand L B Is Ingredients. Claim 8 delete Claim 9 In claim 1, a material having a structure selected from the group consisting of the following: In the above chemical formulas, m is 2 and R 1 and R 2 Each independently represents monosubstituted, bisubstituted, trisubstituted, or tetrasubstituted, having one or more non-hydrogen substituents; R 4 and R 5 Each independently represents a uniform, binary, tri-substitution, quadruple, or non-substitution;R 3 represents unsubstituted, unsubstituted, trisubstituted, or nonsubstituted;R 1 and R 2 Each is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, silyl, alkenyl, aryl, heteroaryl, nitrile, and combinations thereof; R 3 , R 4 , R 5 and R 6 Each is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, carboxylic acid, nitrile, isonitrile, sulfanyl, phosphino, and combinations thereof; R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Any two adjacent substituents among them may fuse or combine to form a ring, provided that only two R 1 It does not fuse or combine to form a ring; R 6 ... comprises one or more substituents having a total straight-chain or branched-chain alkyl number of 5 or more, or R 3 , R 4 and R 5 One or more of them comprise a phenyl group substituted with one or more substituents having a total straight-chain or branched-chain alkyl carbon number of 5 or more, and R 3 , R 4 , R 5 and R 6 One or more of them are partially or completely deuterided; provided that R 2 is not a phenyl group. Claim 10 In Paragraph 9, R 6 A material selected from the group consisting of alkyl having five or more straight-chain or branched-chain alkyl carbon atoms, alkyl-cycloalkyl having five or more straight-chain or branched-chain alkyl carbon atoms, and partial or fully deuteriumated or fluorinated variants thereof. Claim 11 In paragraph 1, ligand L A is selected from a group consisting of each acting independently: ,ligand L A R of c is ligand L in paragraph 1 A R of a Selected from the defined group for; ligand L B A material selected from a group consisting of each independently: ,ligand L B R of c and R d Each independently ligand L in paragraph 1 B R of a and R b Selected from the group defined for; provided that ligand L B go When, ligand L A R of b is not a phenyl group. Claim 12 delete Claim 13 delete Claim 14 delete Claim 15 delete Claim 16 delete Claim 17 delete Claim 18 Delete Claim 19 delete Claim 20 delete

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