Organic electroluminescent materials and devices

Abstract

The invention relates to organic electroluminescent materials and devices. Disclosed is an organic compound that can improve the performance of a phosphorescent organic light-emitting device containing indolocarbazole as an electron donor linked to an electron acceptor such as aza-triphenylene or dibenzoquinoxaline.

Description

[0001] This application is a divisional application of the application patent application with the application date of May 24, 2017, the application number of "201710374147.0", and the invention name of "Organic Electroluminescent Materials and Devices". TECHNICAL FIELD

[0002] The present invention relates to organic materials suitable for use in phosphorescent organic light emitting diode (PHOLED) devices, which contain indolocarbazole as electron donor connected to electron acceptors such as aza-triphenylene and dipyridoquinoxaline. BACKGROUND

[0003] Opto-electronic devices that make use of organic materials are becoming increasingly important for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential to be lower cost than alternative devices that use inorganic materials. In addition, the inherent properties of organic materials, such as their flexibility, can make them well suited for particular applications such as fabrication on flexible substrates. Examples of organic opto-electronic devices include organic light emitting diodes / devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic light detectors. For OLEDs, the active layer can be formed of organic small molecules, or oligomers, or polymers. Organic light emitting diodes (OLEDs) are used in the display and lighting fields. OLEDs have advantages of high luminance, wide viewing angle, and fast response time. OLEDs can be made in a full color display by using different colors of OLEDs. OLEDs can be made in a white light emitting device by using a white light emitting OLED or a combination of red, green, and blue light emitting OLEDs.

[0004] OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in the display and lighting fields, due to their low production cost, their sharpness, their efficiency, and their high information content. OLEDs can be made very thin and are lightweight so that the possibility of their use in flexible displays exists.

[0005] One application for phosphorescent emission is white light illumination. Industry standards exist for solid state lighting that require a white light illumination source. To make white light using phosphorescent emission, a combination of red, green, and blue light is needed. The combination of red, green, and blue light can be achieved by using three separate LEDs, each emitting a different color. Alternatively, a single LED can be used that emits white light. The white light emitting LED can be a single EML device or a stacked structure. The color of the light emitted by the white light emitting LED can be measured using CIE coordinates.

[0006] One example of a green emissive molecule is tris(2-phenylpyridine) iridium, denoted as Ir(ppy)3, which has the following structure:

[0007]

[0008] In this figure and in the figures later in this article, the valence bond from nitrogen to the metal (here, Ir) is depicted as a straight line.

[0009] As used herein, the term "organic" includes polymeric materials as well as small-molecule organic materials that can be used to manufacture organic optoelectronic devices. "Small molecule" refers to any organic material that is not a polymer, and "small molecule" can actually be quite large. In some cases, small molecules can include repeating units. For example, using long-chain alkyl groups as substituents does not remove the molecule from the "small molecule" category. Small molecules can also be incorporated into polymers, for example, as side groups on the polymer backbone or as part of the backbone. Small molecules can also act as the core portion of dendritic polymers, which consist of a series of chemical shells built upon the core portion. The core portion of a dendritic polymer can be a fluorescent or phosphorescent small-molecule emitter. Dendritic polymers can be "small molecules," and it is believed that all dendritic polymers currently used in the OLED field are small molecules.

[0010] As used herein, "top" means furthest from the substrate, and "bottom" means closest to the substrate. When the first layer is described as being "placed on" or "deposited on" the second layer, the first layer is positioned further from the substrate. Unless specified that the first layer is "in contact" with the second layer, other layers may exist between the first and second layers. For example, even if various organic layers exist between the cathode and anode, the cathode may still be described as being "placed on" or "deposited on" the anode.

[0011] As used herein, “solution-handleable” means capable of being dissolved, dispersed or transported in and / or deposited from a liquid medium in the form of a solution or suspension.

[0012] When a ligand is believed to directly contribute to the photosensitivity of the emitting material, the ligand can be called "photosensitive." When a ligand is believed not to contribute to the photosensitivity of the emitting material, the ligand can be called "auxiliary," but auxiliary ligands can alter the properties of photosensitivity ligands.

[0013] As used herein, and as will be understood by those skilled in the art, if a first energy level is closer to the vacuum level, then the first “highest occupied molecular orbital” (HOMO) or “lowest unoccupied molecular orbital” (LUMO) level is “greater” or “higher” than the second HOMO or LUMO level. Since the ionization potential (IP) is measured as a negative energy relative to the vacuum level, a higher HOMO level corresponds to a smaller absolute value of IP (less negative IP). Similarly, a higher LUMO level corresponds to a smaller absolute value of electron affinity (EA) (less negative EA). On a conventional energy level diagram, the vacuum level is at the top, and the LUMO levels of a material are higher than the HOMO levels of the same material. A “higher” HOMO or LUMO level appears to be closer to the top of this diagram than a “lower” HOMO or LUMO level.

[0014] As used herein, and as will be understood by those skilled in the art, if the first work function has a higher absolute value, then the first work function is “greater” or “higher” than the second work function. This is because work functions are typically measured as negative numbers relative to the vacuum level, thus implying that the “higher” work function is more negative. On a conventional energy level diagram, the vacuum level is at the top, and a “higher” work function is described as being farther from the vacuum level in the downward direction. Therefore, the definitions of HOMO and LUMO levels follow a different convention than those for work functions.

[0015] Further details regarding OLEDs and the definitions described above can be found in U.S. Patent No. 7,279,704, which is incorporated herein by reference in its entirety. Summary of the Invention

[0016] Organic materials containing indolocarbazole as an electron donor linked to electron acceptors such as azirmonene and dibenzoquinoxaline have been disclosed. These materials can be used in PHOLED devices. They can enhance device performance in terms of device lifetime, external quantum efficiency (EQE), and operating voltage.

[0017] According to one aspect of the present invention, a compound is disclosed having the following formula:

[0018] In equation I, R 1 and R 2 Each can independently represent a monosubstituted, disubstituted, trisubstituted, tetrasubstituted, or unsubstituted group; R 3 Indicates monosubstituted, disubstituted, or unsubstituted; R 5 Indicates monosubstituted, disubstituted, trisubstituted, tetrasubstituted, pentasubstituted, or unsubstituted; X 1 To X 4 Two of them are carbon, and the other two are nitrogen; L is a direct bond or an organic linking group; each R1 R 2 R 3 R 4 and R 5 Independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof; and any adjacent substituents optionally conjugate or fused to form a ring.

[0019] According to another aspect of the present invention, an OLED is disclosed, wherein the OLED comprises: an anode; a cathode; and an organic layer disposed between the anode and the cathode. The organic layer comprises a compound having the following formula:

[0020] In equation I, R 1 and R 2 Each can independently represent a monosubstituted, disubstituted, trisubstituted, tetrasubstituted, or unsubstituted group; R 3 Indicates monosubstituted, disubstituted, or unsubstituted; R 5 Indicates monosubstituted, disubstituted, trisubstituted, tetrasubstituted, pentasubstituted, or unsubstituted; X 1 To X 4 Two of them are carbon, and the other two are nitrogen; L is a direct bond or an organic linking group; each R 1 R 2 R 3 R 4 and R 5 Independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof; and any adjacent substituents optionally conjugate or fused to form a ring.

[0021] According to another aspect, a consumer product incorporating an OLED is disclosed, wherein the OLED comprises: an anode; a cathode; and an organic layer disposed between the anode and the cathode. The organic layer comprises a compound having a structure of Formula I.

[0022] According to another aspect, a formulation comprising a compound having the structure of Formula I is also disclosed. Attached Figure Description

[0023] Figure 1 An organic light-emitting device was displayed.

[0024] Figure 2 An inverted organic light-emitting device without a separate electron transport layer was demonstrated. Detailed Implementation

[0025] Generally, an OLED comprises at least one organic layer disposed between and electrically connected to the anode and cathode. When a current is applied, holes are injected into the anode and electrons into the organic layer at the cathode. The injected holes and electrons migrate toward the electrodes with opposite charges. When electrons and holes are confined to the same molecule, "excitons" are formed, which are localized electron-hole pairs with excited energy states. When excitons relax via photoemission mechanisms, light is emitted. In some cases, excitons may be confined to polarons or excited-state complexes. Non-radiative mechanisms (such as thermal relaxation) may also occur, but are generally considered undesirable.

[0026] Early OLEDs used emitting molecules that emitted light from a single state (“fluorescence”), as disclosed, for example, in U.S. Patent No. 4,769,292, which is incorporated herein by reference in its entirety. Fluorescence emission typically occurs in timeframes of less than 10 nanoseconds.

[0027] Recently, OLEDs with emitting materials that emit light from the triplet state (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, Vol. 395, pp. 151–154, 1998; (“Baldo-I”) and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., Vol. 75, No. 3, pp. 4–6 (1999) (“Baldo-II”), are incorporated herein by reference in their entirety. Phosphorescence is described in more detail in columns 5–6 of U.S. Patent No. 7,279,704, which is incorporated herein by reference.

[0028] Figure 1An organic light-emitting device 100 is shown. The figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emission layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. The cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 can be fabricated by sequentially depositing the described layers. The properties and functions of these various layers, as well as the example materials, are described in more detail in columns 6-10 of US 7,279,704, which is incorporated by reference.

[0029] There are numerous examples of each of these layers. For instance, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated herein by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety. Examples of emitter and host materials are disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated herein by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety. Examples of cathodes are disclosed in U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated herein by reference in their entirety. These cathodes comprise composite cathodes having a thin metal layer, such as Mg:Ag, overlaid with a transparent, conductive, sputter-deposited ITO layer. The principles and use of barrier layers are described in more detail in U.S. Patent No. 6,097,147 and U.S. Patent Application Publication No. 2003 / 0230980, which are also incorporated herein by reference in their entirety. Examples of implantation layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, which is also incorporated herein by reference in its entirety. A description of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is also incorporated herein by reference in its entirety.

[0030] Figure 2An inverted OLED 200 is shown. The device includes a substrate 210, a cathode 215, an emitter layer 220, a hole transport layer 225, and an anode 230. The device 200 can be fabricated by sequentially depositing the layers described herein. Because the most common OLED configuration has a cathode disposed on the anode, and the device 200 has a cathode 215 disposed beneath the anode 230, the device 200 can be referred to as an "inverted" OLED. Materials similar to those described with respect to device 100 can be used in the corresponding layers of the device 200. Figure 2 An example is provided of how some layers can be omitted from the structure of device 100.

[0031] Figure 1 and 2 The simple layered structures described herein are provided as non-limiting examples, and it should be understood that embodiments of the invention can be used in combination with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures can be used. A functional OLED can be realized by combining the described layers in different ways based on design, performance, and cost factors, or several layers can be omitted entirely. Other layers not specifically described may also be included. Materials different from those specifically described may be used. Although many examples provided herein describe various layers as comprising a single material, it should be understood that combinations of materials (e.g., mixtures of host and dopant) or more generally, mixtures may be used. Furthermore, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emitter layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise, for example, regarding Figure 1 and 2 Multiple layers of different organic materials are described.

[0032] Structures and materials not specifically described can also be used, such as OLEDs (PLEDs) containing polymeric materials, as disclosed in, for example, U.S. Patent No. 5,247,190 to Friend et al., which is incorporated herein by reference in its entirety. As another example, an OLED with a single organic layer can be used. OLEDs can be stacked, as described, for example, in No. 5,707,745 to Forrest et al., which is incorporated herein by reference in its entirety. The OLED structure can be detached... Figure 1 and 2The simple layered structure described herein. For example, the substrate may include angled reflective surfaces to improve out-coupling, such as the tabletop structure as described in U.S. Patent No. 6,091,195 to Forrest et al., and / or the recessed structure as described in U.S. Patent No. 5,834,893 to Bulovic et al., all of which are incorporated herein by reference in their entirety.

[0033] Unless otherwise specified, any of the layers in the various embodiments can be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation, inkjet printing (e.g., as described in U.S. Patent Nos. 6,013,982 and 6,087,196, which are incorporated herein by reference in their entirety), organic vapor deposition (OVPD) (e.g., as described in U.S. Patent No. 6,337,102 to Forrest et al., which are incorporated herein by reference in their entirety), and deposition by organic vapor jet printing (OVJP) (e.g., as described in U.S. Patent No. 7,431,968, which is incorporated herein by reference in its entirety). Other suitable deposition methods include spin coating and other solution-based processes. Solution-based processes are preferably performed in a nitrogen or inert atmosphere. For other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition via a mask, cold soldering (e.g., as described in U.S. Patents 6,294,398 and 6,468,819, which are incorporated herein by reference in their entirety), and patterning associated with some of the deposition methods such as inkjet printing and OVJP. Other methods may also be used. The material to be deposited can be modified to be compatible with a specific deposition method. For example, substituents such as alkyl and aryl groups, which are branched or unbranched and preferably contain at least three carbons, can be used in small molecules to enhance their solution handling ability. Substituents having 20 or more carbons can be used, with 3-20 carbons being a preferred range. Materials with asymmetric structures can have better solution handling ability than materials with symmetric structures because asymmetric materials can have a lower tendency to recrystallize. Dendritic polymer substituents can be used to enhance the solution handling ability of small molecules.

[0034] Devices manufactured according to embodiments of the present invention may optionally further include a barrier layer. One use of the barrier layer is to protect the electrodes and organic layers from damage caused by exposure to harmful substances in the environment, including moisture, vapors, and / or gases. The barrier layer may be deposited on, under, or adjacent to a substrate or electrode, or on any other part of the device, including edges. The barrier layer may comprise a single layer or multiple layers. The barrier layer can be formed using various known chemical vapor deposition techniques and may comprise compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate inorganic or organic compounds, or both. Preferred barrier layers comprise 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, which are incorporated herein by reference in their entirety. For the mixture to be considered a "mixture," the aforementioned polymeric and non-polymeric materials constituting the barrier layer should be deposited under the same reaction conditions and / or simultaneously. The weight ratio of polymeric material to non-polymeric material can range from 95:5 to 5:95. The polymeric and non-polymeric materials can be produced from the same precursor material. In one example, the mixture of polymeric and non-polymeric materials is essentially composed of polymeric silicon and inorganic silicon.

[0035] Devices manufactured according to embodiments of the present invention can be incorporated into a wide variety of electronic component modules (or units), which can be incorporated into various electronic products or intermediate components. Examples of such electronic products or intermediate components include displays, lighting devices (such as discrete light source devices or lighting panels), etc., which can be utilized by end-user product manufacturers. Such electronic component modules may optionally include driving electronics and / or power supplies. Devices manufactured according to embodiments of the present invention can be incorporated into a wide variety of consumer products having one or more electronic component modules (or units) incorporated therein. Such consumer products will include any kind of product containing one or more light sources and / or one or more of some type of visual display. Examples of such consumer products include flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for internal or external lighting and / or signaling, head-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, mobile phones, tablet computers, tablet phones, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, microdisplays (displays with a diagonal of less than 2 inches), 3D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple tiled displays, theater or stadium screens, and signage. Various control mechanisms, including passive and active matrices, can be used to control the devices manufactured according to the invention. Many of the devices are intended for use in temperature ranges comfortable for humans, such as 18 to 30 degrees Celsius, and more preferably at room temperature (20-25 degrees Celsius), but can be used outside this temperature range (e.g., -40 to +80 degrees Celsius).

[0036] The materials and structures described herein can be applied to devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors can use the materials and structures. More generally, organic devices such as organic transistors can use the materials and structures.

[0037] As used herein, the terms “halogen,” “halogen,” or “halogen” include fluorine, chlorine, bromine, and iodine.

[0038] As used herein, the term "alkyl" encompasses both straight-chain and branched alkyl groups. Preferred alkyl groups are those containing one to fifteen carbon atoms, and include 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 optionally be substituted.

[0039] As used herein, the term "cycloalkyl" encompasses cyclic alkyl groups. Preferred cycloalkyl groups are those containing 3 to 10 cyclic carbon atoms, and include cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, and the like. Additionally, the cycloalkyl group may optionally be substituted.

[0040] As used herein, the term "alkenyl" encompasses both straight-chain and branched alkenyl groups. Preferred alkenyl groups are those containing two to fifteen carbon atoms. Additionally, alkenyl groups may optionally be substituted.

[0041] As used herein, the term "alkynyl" encompasses both straight-chain and branched alkynyl groups. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may optionally be substituted.

[0042] As used herein, the terms “aralkyl” or “arylalkyl” are used interchangeably and cover alkyl groups having aromatic groups as substituents. Additionally, aralkyl groups may optionally be substituted.

[0043] As used herein, the term "heterocyclic group" encompasses both aromatic and non-aromatic cyclic radicals. Heteroaromatic cyclic radicals also refer to heteroaryl groups. Preferred heterocyclic non-aromatic cyclic groups are heterocyclic groups containing 3 to 7 ring atoms, including at least one heteroatom, and include cyclic amines such as morpholino, piperidinyl, pyrrolyl, etc., and cyclic ethers such as tetrahydrofuran, tetrahydropyran, etc. Furthermore, the heterocyclic group may optionally be substituted.

[0044] As used herein, the term "aryl" or "aromatic group" encompasses both monocyclic groups and polycyclic systems. A polycyclic system may have two or more rings in which two carbons are shared by two adjacent rings (the rings are "fused"), wherein at least one of the rings is aromatic; for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Particularly preferred are aryl groups having six, ten, or twelve carbon atoms. Suitable aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, leucine, perylene, and azulene, with phenyl, biphenyl, terphenyl, triphenylene, fluorene, and naphthalene being preferred. Additionally, the aryl group may optionally be substituted.

[0045] As used herein, the term "heteroaryl" encompasses a monocyclic heteroaryl aromatic group that may include one to five heteroatoms. The term "heteroaryl" also includes polycyclic heteroaryl aromatic systems having two or more rings shared by two adjacent rings (the rings being "fused"), wherein at least one of the rings is a heteroaryl, and other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Preferred heteroaryls are those containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenene, furan, thiophene, benzofuran, benzothiophene, benzoselenene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxthiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, and benzisoxazole. Benzothiazolium, quinoline, isoquinoline, cyclophosphine, quinazoline, quinoxaline, naphthidine, phthalazine, pteridine, dibenzopiperanium, acridine, phenazine, phenothiazine, phenoxazine, benzofuran-pyridine, furan-dipyridine, benzothieno-pyridine, thieno-dipyridine, benzoselen-phenieno-pyridine, and seleno-dipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborane, 1,3-azaborane, 1,4-azaborane, cycloborane, and their aza analogs. Additionally, the heteroaryl group may optionally be substituted.

[0046] Alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic, aryl, and heteroaryl groups may be unsubstituted or may be substituted by one or more substituents selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, cycloamino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphin, and combinations thereof.

[0047] As used in this article, "substituted" means that the substituent is not H bonded to the relevant position, such as carbon. Therefore, for example, in R... 1 When replaced by a single unit, then an R 1 It must not be H. Similarly, in R... 1 When replaced by two, then the two Rs 1 It must not be H. Similarly, in R... 1 When not replaced, R 1 It is hydrogen for all available locations.

[0048] The term "aza" in the fragments described herein (i.e., aza-dibenzofuran, aza-dibenzothiophene, etc.) indicates that one or more CH groups in the corresponding fragment can be substituted with nitrogen atoms. For example, and without limitation, azatriphenylene covers dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. Other nitrogen analogs of the aza-derived compounds described above will be readily contemplated by those skilled in the art, and all such analogs are intended to be covered by the terminology set forth herein.

[0049] It should be understood that when a molecular fragment is described as a substituent or additionally attached to another part, its name can be written as if it were a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or as if it were a whole molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of naming substituents or attached fragments are considered equivalent.

[0050] According to one aspect of the present invention, a compound is disclosed having the following formula:

[0051] In equation I, R 1 and R 2 Each can independently represent a monosubstituted, disubstituted, trisubstituted, tetrasubstituted, or unsubstituted group; R 3 Indicates monosubstituted, disubstituted, or unsubstituted; R 5 Indicates monosubstituted, disubstituted, trisubstituted, tetrasubstituted, pentasubstituted, or unsubstituted; X 1 To X 4 Two of them are carbon, and the other two are nitrogen; L is a direct bond or an organic linking group; each R 1 R 2 R 3 R 4 and R 5 Independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof; and any adjacent substituents therein optionally conjoin or fuse to form a ring.

[0052] In some embodiments of the compounds of Formula I, the compounds are selected from the group consisting of:

[0053] Where R 6 and R 7 Each R independently represents a monosubstituted, disubstituted, trisubstituted, tetrasubstituted, or unsubstituted group; 6 and R7 Independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof; and R 6 and R 7 Any adjacent substituents may optionally join or fuse to form a ring.

[0054] In some embodiments of the compound of formula I, each R 1 R 2 R 3 R 4 and R 5 Independently selected from the group consisting of: aryl, substituted aryl, heteroaryl and substituted heteroaryl.

[0055] In some embodiments of compounds of formula I, L is a direct bond. In some embodiments, L is an organic linking group selected from the group consisting of aryl, substituted aryl, heteroaryl, substituted heteroaryl, amino, silyl, and combinations thereof.

[0056] In some embodiments of the compound of formula I, R 3 It is hydrogen. In some embodiments, R 1 and R 2 It is hydrogen.

[0057] In some embodiments of the compounds of Formula I, the compounds are selected from the group consisting of:

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087] According to one aspect of the present invention, an OLED is disclosed, comprising an anode; a cathode; and an organic layer disposed between the anode and the cathode. The organic layer comprises a compound having the following formula:

[0088] Where R 1 and R 2 Each can independently represent a monosubstituted, disubstituted, trisubstituted, tetrasubstituted, or unsubstituted group; where R 3 Indicates a monosubstituted, disubstituted, or unsubstituted group; where R 5 Indicates monosubstituted, disubstituted, trisubstituted, tetrasubstituted, pentasubstituted, or unsubstituted; where X 1To X 4 Two of them are carbon, and the other two are nitrogen; where L is a direct bond or an organic linking group; where each R 1 R 2 R 3 R 4 and R 5 Independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof; and any adjacent substituents therein optionally conjoin or fuse to form a ring.

[0089] In some embodiments of the OLED, the organic layer is an emitting layer, and the compound of formula I is the host. In some embodiments of the OLED, the organic layer further comprises a phosphorescent emitting dopant; wherein the emitting dopant is a transition metal complex having at least one ligand or a portion of the ligand when the ligand is more than bidentate, the ligand being selected from the group consisting of:

[0090]

[0091]

[0092] Each X 1 To X 13 Independently select groups composed of free carbon and nitrogen;

[0093] X is selected from the following groups: BR', NR', PR', O, S, Se, C=O, S=O, SO2, CR'R”, SiR'R”, and GeR'R”;

[0094] R' and R” are optionally fused or joined to form a ring;

[0095] Each R a R b R c and R d It can represent a single substituent to the maximum possible number of substituents or no substituents;

[0096] Among them, R', R”, R a R b R c and R dEach is independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof; and

[0097] Where R a R b R c and R d Any two adjacent substituents may optionally fuse or join to form a ring or a polydentate ligand.

[0098] In some embodiments of the OLED, the organic layer is a charge carrier blocking layer, and the compound of formula I is a charge carrier blocking material in the organic layer.

[0099] In some embodiments of the OLED, the organic layer is a charge carrier transport layer, and the compound of formula I is a charge carrier transport material in the organic layer.

[0100] In some embodiments of the OLED, the organic layer is an emitter layer, and the compound of formula I is an emitter.

[0101] In some embodiments of the OLED, the OLED emits light-emitting radiation at room temperature when a voltage is applied to the organic light-emitting device, and the light-emitting radiation includes a delayed fluorescence process.

[0102] In some embodiments of the OLED, the emitting layer further comprises a host material. In some embodiments, the emitting layer further comprises a first phosphorescent emitting material. In some embodiments, the emitting layer further comprises a second phosphorescent emitting material.

[0103] In some embodiments, the OLED emits white light at room temperature when a voltage is applied to the organic light-emitting device.

[0104] In some embodiments of the OLED, the compound comprising the structure according to Formula I emits blue light with a peak wavelength of about 400 nm to about 500 nm. In some embodiments, the compound comprising the structure according to Formula I emits yellow light with a peak wavelength of about 530 nm to about 580 nm.

[0105] According to another aspect, a consumer product incorporating an OLED is disclosed, wherein the OLED comprises: an anode; a cathode; and an organic layer disposed between the anode and the cathode, comprising a compound having the following formula:

[0106]

[0107] Where R 1 and R 2 Each can be independently represented as monosubstituted, disubstituted, trisubstituted, tetrasubstituted, or unsubstituted;

[0108] Where R 3 Indicates a single substituent, a disubstituent, or no substituent;

[0109] Where R 5 This indicates monosubstituted, disubstituted, trisubstituted, tetrasubstituted, pentasubstituted, or unsubstituted groups;

[0110] Where X 1 To X 4 Two of them are carbon, and the other two are nitrogen;

[0111] Where L is a direct bond or an organic linking group;

[0112] Each R 1 R 2 R 3 R 4 and R 5 Independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof; and

[0113] Any adjacent substituents may optionally join or fuse to form a ring.

[0114] In some embodiments, the consumer products are selected from the group consisting of: flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for internal or external lighting and / or signaling, head-up displays, fully transparent or partially transparent displays, flexible displays, laser printers, telephones, mobile phones, tablet computers, tablet phones, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, microdisplays, 3D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screens, and signs.

[0115] According to another aspect, a formulation comprising a compound having formula I is disclosed.

[0116] Synthesis Example

[0117] Synthetic compound Cmp D-2

[0118]

[0119] 5-Phenyl-5,8-dihydroindolo[2,3-c]carbazole (5 g, 15.04 mmol) was added to a three-necked round flask. Anhydrous DMF (100 mL) was added to the flask. Sodium hydride (1.203 g, 30.1 mmol) was added to the clear solution. The mixture was stirred for 1 hour. Then 4-([1,1'-biphenyl]-4-yl)-2-chloroquinazoline (5.72 g, 18.05 mmol) was added, and the mixture was stirred overnight at room temperature. The reaction mixture was quenched with ice / cold H2O (1.5 L). The mixture was stirred for 30 minutes. The yellow solid was filtered and washed with H2O (1 L). The solid was dried, suspended in toluene (500 mL), heated, and stirred for 30 minutes. The suspension was heated again and filtered. The solid was washed with toluene and passed through a silica stopper. The compound was suspended in DCM (100 mL) and acetone (250 mL). The suspension was heated and then stirred overnight at room temperature. It was filtered and washed with acetone (200 mL). The solid was dried under vacuum to give 5-(4-([1,1'-biphenyl]-4-yl)quinazolin-2-yl)-8-phenyl-5,8-dihydroindolo[2,3-c]carbazole (7.1 g, 77% yield, HPLC 99.99%). The structure was confirmed by NMR.

[0120] Synthetic compound Cmp D-17

[0121]

[0122] 5-Phenyl-5,8-dihydroindolo[2,3-c]carbazole (5 g, 15.04 mmol) was charged into a three-necked round flask. Anhydrous DMF (100 mL) was added to the flask. Sodium hydride (1.203 g, 30.1 mmol) was added to this clear solution. The reaction mixture became heterogeneous. It was stirred for 1 hour, and then 2-chloro-4-(naphth-2-yl)quinazoline (5.25 g, 18.05 mmol) was added to the reaction mixture. The reaction mixture turned brown. The mixture was stirred overnight at room temperature. The reaction mixture was quenched with ice-cold H2O (about 1 L). The mixture was stirred for 30 minutes. The yellow solid was filtered and washed with H2O. The solid was then wet-milled with hot toluene. The solid was then passed through a silica stopper and eluted with toluene. After drying, 5-(4-(naphthyl-2-yl)quinazolin-2-yl)-8-phenyl-5,8-dihydroindolo[2,3-c]carbazole (7 g, 11.93 mmol, 79% yield) was obtained as a yellow solid with 99.98% HPLC purity. The structure was confirmed by NMR.

[0123] Synthetic compound Cmp D-64

[0124]

[0125] 5-Phenylacetyl-5,8-dihydroindolo[2,3-c]carbazole (5.00 g, 15.04 mmol), 4-([1,1'-biphenyl]-4-yl)-2-(4-chlorophenyl)quinazoline (7.09 g, 18.05 mmol), sodium tert-butoxide (2.89 g, 30.1 mmol), and xylene (75 mL) were added under nitrogen atmosphere (bubbling under nitrogen for 20 min). Then, Pd2(dba)3 (0.826 g, 0.903 mmol) and dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphine (0.741 g, 1.805 mmol) were added. The reaction mixture was heated to reflux (129 °C) and maintained for 4 h. The reaction was considered complete by TLC analysis after 3 h. The dark brown reaction mixture was cooled to room temperature. The mixture was then filtered through a short diatomaceous earth pad and washed with CH2Cl2 (approximately 200 mL). After concentrating the filtrate, a crude product (approximately 20 g) in the form of a dark brown oil was obtained. The crude product was wet-milled with acetone (250 mL). A yellow-green solid was obtained, and it was wet-milled again with acetone to obtain a yellow-green solid. The sample was dissolved in hot toluene and filtered through a diatomaceous earth pad at room temperature. The diatomaceous earth was washed with toluene. The filtrate (10 g) was concentrated and subjected to silica gel (100 g) chromatography. The eluates collected with 30–50% DCM / heptane were combined and concentrated. The HPLC purity was 98.89%. The substance was dissolved in 300 mL of hot DCM. No solid formed after cooling to room temperature, so the product was precipitated with MeOH (220 mL). The resulting yellow solid was collected by filtration and analyzed by HPLC (99.90%). The product was dried under high vacuum for 5 hours. 1 The H NMR was consistent with the product, and 7.67 g (73.9% yield) was separated.

[0126] Synthetic compound Cmp D-70

[0127]

[0128] In a 250 mL flask, sodium hydride (0.800 g, 20.00 mmol) was slowly added to a solution of 5-(naphthyl-2-yl)-5,8-dihydroindolo[2,3-c]carbazole (3.82 g, 10.0 mmol) in anhydrous DMF (80 mL). The suspension was stirred at room temperature for 1 hour, and then 2-chloro-4-(naphthyl-2-yl)quinazoline (3.20 g, 11.00 mmol) was slowly added to the mixture. The mixture was stirred overnight at room temperature. The reaction was evaluated by TLC, which indicated approximately 20% unreacted starting material. Additional NaH (0.200 g, 5.0 mmol) was added to the reactants, and after stirring at room temperature for 1 hour, a quinazoline intermediate (0.800 g, 2.75 mmol) was added, and the mixture was stirred at room temperature for 6 hours. After the reaction was complete, the mixture was poured over ice water, and the resulting suspension was stirred at room temperature for 1 hour. The solid was then filtered, collected, and wet-milled with a mixture of MeOH-CH2Cl2-acetone to give 5-(naphthyl-2-yl)-8-(4-(naphthyl-2-yl)quinazolin-2-yl)-5,8-dihydroindolo[2,3-c]carbazole (5.85 g, 9.13 mmol, 91% yield) as a yellow solid with 99.34% HPLC purity. The structure was confirmed by NMR.

[0129] Synthetic compound Cmp D-82

[0130]

[0131] A 250 mL round flask equipped with a stir bar, an N2 inlet, and two septa was purged with nitrogen for 30 minutes. Then, 5-phenyl-5,8-dihydroindolo[2,3-c]carbazole (3.63 g, 10.92 mmol) was added, followed by anhydrous DMF (73 mL). Sodium hydride (0.874 g, 21.84 mmol) was added, and the reaction mixture was stirred for 1 hour. Subsequently, 4-([1,1'-biphenyl]-4-yl)-2-chloro-6-phenylquinazoline (5.15 g, 13.10 mmol) was added, and the mixture was washed with anhydrous DMF (10 mL) in two 5 mL aliquots. The reaction mixture was stirred overnight at room temperature. TLC (thin-layer chromatography) showed excellent conversion, and the reaction mixture was quenched by pouring it into ice / water (1 L) with stirring. The resulting suspension was filtered to give an orange solid. An orange solid (30 g) was dissolved in DCM and run through a silica stopper (150 g silica) using DCM as the eluent to yield 5-(4-([1,1'-biphenyl]-4-yl)-6-phenylquinazoline-2-yl)-8-phenyl-5,8-dihydroindolo[2,3-c]carbazole (7.1 g, 90% yield, HPLC 95%) with some overlap. The structure was confirmed by NMR.

[0132] Device Examples

[0133] All example devices were subjected to high vacuum (<10) -7 Manufactured by thermal evaporation. The anode electrode is... Indium tin oxide (ITO). The cathode is made of... Liq (lithium 8-hydroxyquinoline) then The device is composed of Al. Immediately after manufacturing, all devices are sealed in a nitrogen glove box (<1 ppm H₂O and O₂) with an epoxy-sealed glass lid, incorporating a desiccant into the packaging. The organic stack of the device examples consists of the following components sequentially from the ITO surface: HAT-CN is used as a hole injection layer (HIL); The HTM serves as a hole transport layer (HTL); thickness The emitter layer (EML) contains a main body of red emitter (RD) at 3% by weight. The Liq (lithium 8-hydroxyquinoline) doped with 40% ETM was used as the ETL. The host compounds Cmp D-17 and Cmp D-64 were used as Examples 1 and 2, and the C-host compound was used as Comparative Example CE1. The device structures are shown in Table 1 below.

[0134] The chemical structure of the materials used in the device is shown below:

[0135]

[0136] After manufacturing, at DC 80mA / cm 2 The EL, JVL, and lifetime of the measuring device are measured. An acceleration factor of 2 is assumed, starting from 80 mA / cm². 2 LT data is calculated at 1,000 nits for LT95. Device performance is shown in Table 2 below.

[0137] Table 1. Device Instance Layer Structure

[0138]

[0139]

[0140] Table 2. Device performance of Example 1 and CE1

[0141]

[0142] Device data show that the compounds Cmp D-17 and Cmp D-64 of this invention exhibit superior performance compared to the comparative C-body compound in terms of voltage, external quantum efficiency (EQE), luminous efficiency (LE), power efficiency (PE), and lifetime (LT95). Synthesis of the comparative example of the C2-body failed due to steric hindrance, indicating that the C2-body is highly unstable. These experimental results demonstrate that the red body containing 5,8-dihydroindolo[2,3-c]carbazole exhibits better device performance than the red body containing other indolocarbazoles (such as 11,12-dihydroindolo[2,3-a]carbazole).

[0143] Combination with other materials

[0144] The materials described herein for use in specific layers of organic light-emitting devices can be used in combination with a variety of other materials present in said devices. For example, the emission dopants disclosed herein can be used in combination with a variety of host layers, transport layers, barrier layers, injection layers, electrodes, and other possible layers. The materials described or mentioned below are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and those skilled in the art can readily consult the literature to identify other materials that can be used in combination.

[0145] Conductive dopants:

[0146] Charge transport layers can be doped with conductive dopants to substantially alter their charge carrier density, which in turn changes their conductivity. Conductivity is increased by generating charge carriers in the matrix material and, depending on the type of dopant, can also achieve changes in the Fermi level of the semiconductor. Hole transport layers can be doped with p-type conductive dopants, while n-type conductive dopants are used in electron transport layers.

[0147] Non-limiting examples of conductive dopants that can be used in conjunction with the materials disclosed herein for OLEDs are illustrated in the following references: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804 and US2012146012.

[0148]

[0149] HIL / HTL:

[0150] The hole injection / delivery materials used in this invention are not particularly limited, and any compound can be used, provided that the compound is typically used as a hole injection / delivery material. Examples of such materials include (but are not limited to): phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indole-carbazole derivatives; polymers containing fluorinated hydrocarbons; polymers with conductive dopants; conductive polymers, such as PEDOT / PSS; self-assembled monomers derived from compounds such as phosphonic acids and silane derivatives; and metal oxide derivatives, such as MoO. x p-type semiconductor organic compounds, such as 1,4,5,8,9,12-hexaazatriphenylhexacarbonitrile; metal complexes, and crosslinkable compounds.

[0151] Examples of aromatic amine derivatives used in HILs or HTLs include (but are not limited to) the following general formula structures:

[0152]

[0153] Ar 1 To Ar 9 Each of these is selected from the group consisting of aromatic cyclic hydrocarbons, such as benzene, biphenyl, biphenylene, triphenylene, naphthalene, anthracene, fennel, fluorene, pyrene, olean, perylene, and azulene; and from the group consisting of aromatic heterocyclic compounds, such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridinylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxthiazine, oxadiazine, indole, benzimidazole, indazole, indolodiazole Azides, benzoxazoles, benzoisoxazoles, benzothiazoles, quinoline, isoquinoline, cycloline, quinazoline, quinoxaline, naphthidine, phthalazine, pteridine, dibenzopiperan, acridine, phenazine, phenothiazine, phenoxazine, benzofuran-pyridine, furan-dipyridine, benzothiophene-pyridine, thiophene-dipyridine, benzoselene-pyridine, and selelene-dipyridine; and a group consisting of 2 to 10 cyclic structural units, said structural units being groups of the same or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups, and being bonded to each other directly or via at least one of oxygen, nitrogen, sulfur, silicon, phosphorus, boron, chain structural units, and aliphatic cyclic groups. Each Ar may be unsubstituted or may be substituted with a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphin, and combinations thereof.

[0154] In one respect, Ar 1 To Ar 9 Choose independently from the following groups:

[0155]

[0156] Where k is an integer from 1 to 20; X 101 To X 108 It is C (including CH) or N; Z 101 It is NAr 1 , O or S; Ar 1 Having the same functional groups as defined above.

[0157] Examples of metal complexes used in HIL or HTL include (but are not limited to) the following general formulas:

[0158]

[0159] Met is a metal that can have an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, Y 101 and Y 102 Independently selected from C, N, O, P, and S; L 101 It is an auxiliary ligand; k' is an integer value from 1 to the maximum number of ligands that can be connected to the metal; and k'+k" is the maximum number of ligands that can be connected to the metal.

[0160] In one respect, (Y) 101 -Y 102 (Y) is a 2-phenylpyridine derivative. On the other hand, (Y) 101 -Y 102 Met is a carbapenem ligand. On the other hand, Met is selected from Ir, Pt, Os, and Zn. On the other hand, the metal complex has a relative voltage of less than about 0.6 V with respect to Fc. + The minimum oxidation potential in solution for / Fc pairs.

[0161] Non-limiting examples of HIL and HTL materials for OLEDs that can be used in combination with the materials disclosed herein are illustrated below, along with references to those materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, JP 2007091719, JP2008021687, JP2014-009196, KR20110088898, KR20130077 473. TW201139402, US06517957, US20020158242, US20030162053, US20050 123751, US20060182993, US20060240279, US20070145888, US20070181874, US20070278938, US20080014464, US20080091025, US20080106190, US200 80124572, US20080145707, US20080220265, US20080233434, US20080303417, US2008107919, US20090115320, US20090167161, US2009066235, US201 1007385, US20110163302, US2011240968, US2011278551, US2012205642, US2013241401, US20140117329, US2014183517, US5061569, US5639914, WO0 5075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO2013018530, WO2013039073, WO201 3087142, WO2013118812, WO2013120577, WO2013157367, WO2013175747, WO 2014002873, WO2014015935, WO2014015937, WO2014030872, WO2014030921,WO2014034791, WO2014104514, WO2014157018,

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168]

[0169] EBL:

[0170] An electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons leaving the emitter layer. The presence of such a blocking layer in a device can result in substantially higher efficiency and / or longer lifetime compared to similar devices lacking a blocking layer. Furthermore, the blocking layer can be used to confine emission to a desired area of ​​the OLED. In some embodiments, the EBL material has a higher LUMO (closer to vacuum level) and / or higher triplet energy compared to the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO and / or higher triplet energy compared to one or more of the bodies closest to the EBL interface. In one aspect, the compound used in the EBL contains the same molecules or the same functional groups as those used in one of the bodies described below.

[0171] Other entities:

[0172] The light-emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as a light-emitting dopant material, and may contain one or more other host materials that use metal complexes as dopant materials. Examples of host materials are not particularly limited, and any metal complex or organic compound can be used, as long as the triplet energy of the host is greater than the triplet energy of the dopant. Any host material can be used with any dopant, as long as the triplet criterion is satisfied.

[0173] Examples of metal complexes used as the host preferably have the following general formula:

[0174]

[0175] Where Met is a metal; (Y) 103 -Y 104) is a bidentate ligand, Y 103 and Y 104 Independently selected from C, N, O, P, and S; L 101 It is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be connected to the metal; and k'+k" is the maximum number of ligands that can be connected to the metal.

[0176] In one respect, metal complexes are:

[0177]

[0178] (ON) is a bidentate ligand of a metal that coordinates with O and N atoms.

[0179] On the other hand, Met is selected from Ir and Pt. On the other hand, (Y 103 -Y 104 ) is a carbaene ligand.

[0180] Examples of other organic compounds used as other main components are selected from the group consisting of aromatic hydrocarbon ring compounds, such as benzene, biphenyl, biphenylene, triphenylene, naphthalene, anthracene, fennel, fluorene, pyrene, olean, perylene, and azulene; and from the group consisting of aromatic heterocyclic compounds, such as dibenzothiophene, dibenzofuran, dibenzoselenene, furan, thiophene, benzofuran, benzothiophene, benzoselenene, carbazole, indolocarbazole, pyridinylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxthiazine, oxadiazine, indole, benzimidazole, indole, and indole. The group consisting of azoles, indoxaazines, benzoxazoles, benzoisoxaazoles, benzothiazolium, quinoline, isoquinoline, cycloline, quinazoline, quinoxaline, naphthidine, phthalazine, pteridine, dibenzopiperan, acridine, phenazine, phenothiazine, phenoxazine, benzofuran-pyridine, furan-dipyridine, benzothiophene-pyridine, thiophene-dipyridine, benzoselene-pyridine, and selelene-dipyridine; and the group consisting of 2 to 10 cyclic structural units, said structural units being groups of the same or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups, and being bonded to each other directly or via at least one of oxygen, nitrogen, sulfur, silicon, phosphorus, boron, chain structural units, and aliphatic cyclic groups. Each of these groups is further substituted with substituents selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphin, and combinations thereof.

[0181] In one respect, the host compound contains at least one of the following groups in its molecule:

[0182]

[0183] Where R 101 To R 107 Independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof, when it is aryl or heteroaryl, it has a similar definition to Ar above. 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 Selected from C (including CH) or N.

[0184] Z 101 and Z 102 Selected from NR 101 、O or S.

[0185] Non-limiting examples of other host materials that can be used in combination with the host compounds disclosed herein for OLEDs are illustrated below, along with references to those materials: EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060 280965, US20090017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US201000849 66. US20100187984, US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, US20140 01446, US20140183503, US20140225088, US2014034914, US7154114, WO2001039234, WO2004093207, WO2005014551, WO2005 089025, WO2006072002, WO2006114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO20 09066778, WO2009066779, WO2009086028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO 2012128298, WO2012133644, WO2012133649, WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472,

[0186]

[0187]

[0188]

[0189]

[0190] Launcher:

[0191] The examples of emitters are not particularly limited, and any compound can be used, as long as it is typically used as an emitter material. Examples of suitable emitter materials include (but are not limited to) compounds that can produce emission via phosphorescence, fluorescence, thermally activated delayed fluorescence (i.e., TADF, also known as E-type delayed fluorescence), triplet-triplet annihilation, or a combination of these processes.

[0192] Non-limiting examples of emitter materials for OLEDs that can be used in conjunction with the material combinations disclosed herein are illustrated below, along with references to those materials: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP2013110263, JP4478555, KR1020090133652, KR2012003 2054, KR20130043460, TW201332980, US06699599, US06916554, US20010019782, US20020034656, US20030068526, US20030072964, US20030138657, US 20050123788, US20050244673, US2005123791, US2005260449, US20060008 670、US20060065890、US20060127696、US20060134459、US20060134462、US2 0060202194, US20060251923, US20070034863, US20070087321, US20070103060, US20070111026, US20070190359, US20070231600, US2007034863, US 2007104979, US2007104980, US2007138437, US2007224450, US2007278936 , US20080020237, US20080233410, US20080261076, US20080297033, US2008 05851, US2008161567, US2008210930, US20090039776, US20090108737, US 20090115322, US20090179555, US2009085476, US2009104472, US201000905 91. US20100148663, US20100244004, US20100295032, US2010102716, US20 10105902, 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、

[0193]

[0194]

[0195]

[0196]

[0197]

[0198] HBL:

[0199] A hole blocking layer (HBL) can be used to reduce the number of holes and / or excitons leaving the emitter layer. The presence of such a blocking layer in a device can result in substantially higher efficiency and / or longer lifetime compared to similar devices lacking a blocking layer. Furthermore, the blocking layer can be used to confine emission to a desired area of ​​the OLED. In some embodiments, the HBL material has a lower HOMO (farthest from vacuum level) and / or higher triplet energy compared to the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO and / or higher triplet energy compared to one or more of the bodies closest to the HBL interface.

[0200] In one respect, the compounds used in HBL contain the same molecules or the same functional groups used as the aforementioned main body.

[0201] On the other hand, the compounds used in HBL contain at least one of the following groups in their molecules:

[0202]

[0203] Where k is an integer from 1 to 20; L 101 It is another ligand, and k' is an integer from 1 to 3.

[0204] ETL:

[0205] An electron transport layer (ETL) can comprise a material capable of transporting electrons. The ETL can be intrinsic (undoped) or doped. Doping can be used to enhance conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound can be used, as long as it is typically used for electron transport.

[0206] In one respect, the compounds used in ETL contain at least one of the following groups in their molecules:

[0207]

[0208] Where R 101 The group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof, when it is aryl or heteroaryl, has a similar definition to Ar as described above. 1 To Ar 3It has a similar definition to Ar above. k is an integer from 1 to 20. X 101 To X 108 Selected from C (including CH) or N.

[0209] On the other hand, the metal complexes used in ETL include (but are not limited to) the following general formulas:

[0210]

[0211] Wherein (ON) or (NN) are bidentate ligands of a metal that coordinate with atoms O, N or N, N; L 101 It is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be bonded to a metal.

[0212] Non-limiting examples of ETL materials for OLEDs that can be used in conjunction with the material combinations disclosed herein are illustrated below, along with references to those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US20 10108990, US2011156017, US2011210320, US2012193612, US2012214993, US201401 4925, US2014014927, US20140284580, US6656612, US8415031, WO2003060956, WO20 07111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO201110 5373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535,

[0213]

[0214]

[0215]

[0216] Charge generation layer (CGL)

[0217] In tandem or stacked OLEDs, the conduction layer (CGL) plays a fundamental role in performance. It consists of an n-doped layer and a p-doped layer, respectively, for injecting electrons and holes. Electrons and holes are supplied by the CGL and the electrodes. Electrons and holes consumed in the CGL are refilled by electrons and holes injected from the cathode and anode, respectively; subsequently, the bipolar current gradually reaches a steady state. Typical CGL materials include n- and p-conductive dopants used in the transport layer.

[0218] In any of the compounds described above used in each layer of an OLED device, hydrogen atoms may be partially or fully deuterated. Therefore, any specifically listed substituents (e.g., but not limited to, methyl, phenyl, pyridyl, etc.) encompass their undeuterated, partially deuterated, and fully deuterated forms. Similarly, substituent classes (e.g., but not limited to, alkyl, aryl, cycloalkyl, heteroaryl, etc.) also encompass their undeuterated, partially deuterated, and fully deuterated forms.

[0219] It should be understood that the various embodiments described herein are merely examples and are not intended to limit the scope of the invention. For instance, many of the materials and structures described herein can be replaced with other materials and structures without departing from the spirit of the invention. The invention as claimed may therefore include variations of the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It should be understood that various theories regarding why the invention works are not intended to be limiting.

Claims

1. A compound having the following formula: Where R 1 and R 2 Each can be independently represented as monosubstituted, disubstituted, trisubstituted, tetrasubstituted, or unsubstituted; Where R 3 Indicates a single substituent, a disubstituent, or no substituent; Where R 5 This indicates monosubstituted, disubstituted, trisubstituted, tetrasubstituted, pentasubstituted, or unsubstituted groups; Where X 1 To X 4 Two of them are carbon, and the other two are nitrogen; Where L is a direct bond or an organic linking group; Each R 1 R 2 R 3 R 4 and R 5 Independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof; and Any adjacent substituents may optionally join or fuse to form a ring.

2. The compound of claim 1, wherein the compound is selected from the group consisting of: Where R 6 and R 7 Each can be independently represented as monosubstituted, disubstituted, trisubstituted, tetrasubstituted, or unsubstituted; Each R 6 and R 7 Independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof; and Where R 6 and R 7 Any adjacent substituents may optionally join or fuse to form a ring.

3. The compound according to claim 1, wherein each R 1 R 2 R 3 R 4 and R 5 Independently selected from the group consisting of: aryl, substituted aryl, heteroaryl and substituted heteroaryl.

4. The compound according to claim 1, wherein L is a direct bond.

5. The compound according to claim 1, wherein L is an organic linking group selected from the group consisting of aryl, substituted aryl, heteroaryl, substituted heteroaryl, amino, silyl, and combinations thereof.

6. The compound according to claim 1, wherein R 3 It is hydrogen.

7. The compound according to claim 1, wherein R 1 and R 2 It is hydrogen.

8. The compound of claim 1, wherein the compound is selected from the group consisting of:

9. An organic light-emitting device (OLED) comprising: anode; cathode; and An organic layer disposed between the anode and the cathode comprises a compound having the following formula: Where R 1 and R 2 Each can be independently represented as monosubstituted, disubstituted, trisubstituted, tetrasubstituted, or unsubstituted; Where R 3 Indicates a single substituent, a disubstituent, or no substituent; Where R 5 This indicates monosubstituted, disubstituted, trisubstituted, tetrasubstituted, pentasubstituted, or unsubstituted groups; Where X 1 To X 4 Two of them are carbon, and the other two are nitrogen; Where L is a direct bond or an organic linking group; Each R 1 R 2 R 3 R 4 and R 5 Independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof; and Any adjacent substituents may optionally join or fuse to form a ring.

10. The OLED of claim 9, wherein the organic layer is an emitting layer and the compound of formula I is the host.

11. The OLED of claim 9, wherein the organic layer further comprises a phosphorescent dopant; wherein The emission dopant is a transition metal complex having at least one ligand or, when the ligand is more than bidentate, a portion of the ligand, wherein the ligand is selected from the group consisting of: Each X 1 To X 13 Independently select groups composed of free carbon and nitrogen; X is selected from the following groups: 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 joined to form a ring; Each R a R b R c and R d It can represent a single substituent to the maximum possible number of substituents or no substituents; Among them, R', R”, R a R b R c and R d Each is independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof; and Where R a R b R c and R d Any two adjacent substituents may optionally fuse or join to form a ring or a polydentate ligand.

12. The OLED of claim 9, wherein the organic layer is a charge carrier blocking layer, and the compound of formula I is a charge carrier blocking material in the organic layer.

13. The OLED of claim 9, wherein the organic layer is a charge carrier transport layer, and the compound of formula I is a charge carrier transport material in the organic layer.

14. The OLED of claim 9, wherein the organic layer is an emitter, and the compound of formula I is an emitter.

15. The OLED of claim 14, wherein the OLED emits luminescent radiation at room temperature when a voltage is applied to the organic light-emitting device, and wherein the luminescent radiation comprises a delayed fluorescence process.

16. The OLED of claim 14, wherein the emitting layer further comprises a host material or a first phosphorescent emitting material.

17. The OLED of claim 11, wherein the ligand is:

18. The OLED of claim 17, wherein the emission dopant is:

19. A consumer product comprising an organic light-emitting device, the organic light-emitting device comprising: anode; cathode; and An organic layer disposed between the anode and the cathode comprises a compound having the following formula: Where R 1 and R 2 Each can be independently represented as monosubstituted, disubstituted, trisubstituted, tetrasubstituted, or unsubstituted; Where R 3 Indicates a single substituent, a disubstituent, or no substituent; Where R 5 This indicates monosubstituted, disubstituted, trisubstituted, tetrasubstituted, pentasubstituted, or unsubstituted groups; Where X 1 To X 4 Two of them are carbon, and the other two are nitrogen; Where L is a direct bond or an organic linking group; Each R 1 R 2 R 3 R 4 and R 5 Independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof; and Any adjacent substituents may optionally join or fuse to form a ring.

20. The consumer product of claim 19, wherein the consumer product is selected from the group consisting of: flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for internal or external lighting and / or signaling, head-up displays, fully transparent or partially transparent displays, flexible displays, laser printers, telephones, mobile phones, tablet computers, tablet phones, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, microdisplays, 3D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screens, and signs.

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