Patent Grant
9673401
The present disclosure generally relates to novel compounds containing carbazole and triazine with different number of phenyl units attached to their core. In particular, the disclosure relates to compositions and/or devices comprising these compounds as hosts for PHOLEDs.
The claimed invention was made by, on behalf of, and/or in connection with one or more of the following parties to a joint university corporation research agreement: Regents of the University of Michigan, Princeton University, University of Southern California, and the Universal Display Corporation. The agreement was in effect on and before the date the claimed invention was made, and the claimed invention was made as a result of activities undertaken within the scope of the agreement.
Opto-electronic devices that make use of organic materials are becoming increasingly desirable 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 for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials. For example, the wavelength at which an organic emissive layer emits light may generally be readily tuned with appropriate dopants.
OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting. Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.
One application for phosphorescent emissive molecules is a full color display. Industry standards for such a display call for pixels adapted to emit particular colors, referred to as “saturated” colors. In particular, these standards call for saturated red, green, and blue pixels. Color may be measured using CIE coordinates, which are well known to the art.
One example of a green emissive molecule is tris(2-phenylpyridine) iridium, denoted Ir(ppy)3, which has the following structure:
In this, and later figures herein, we depict the dative bond from nitrogen to metal (here, Ir) as a straight line.
As used herein, the term “organic” includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic devices. “Small molecule” refers to any organic material that is not a polymer, and “small molecules” may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the “small molecule” class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. The core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a “small molecule,” and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.
As used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. Where a first layer is described as “disposed over” a second layer, the first layer is disposed further away from substrate. There may be other layers between the first and second layer, unless it is specified that the first layer is “in contact with” the second layer. For example, a cathode may be described as “disposed over” an anode, even though there are various organic layers in between.
As used herein, “solution processible” means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.
A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.
As used herein, and as would be generally understood by one skilled in the art, a first “Highest Occupied Molecular Orbital” (HOMO) or “Lowest Unoccupied Molecular Orbital” (LUMO) energy level is “greater than” or “higher than” a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IP) are measured as a negative energy relative to a vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (an EA that is less negative). On a conventional energy level diagram, with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A “higher” HOMO or LUMO energy level appears closer to the top of such a diagram than a “lower” HOMO or LUMO energy level.
As used herein, and as would be generally understood by one skilled in the art, a first work function is “greater than” or “higher than” a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a “higher” work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a “higher” work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.
More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.
According to an aspect of the present disclosure, a compound having a structure according to Formula I:
wherein R1, R4 and R5 are independently selected from group consisting of non-fused aryl, non-fused heteroaryl, and combinations thereof; wherein L is selected from the group consisting of a bond, non-fused aryl, non-fused heteroaryl, and combinations thereof; wherein X1, X2, X3, X4, X5, X6, X7, Y1, Y2, and Y3 are each independently selected from the group consisting of CR and N; wherein at least two of Y1, Y2, and Y3 are N; and wherein each R can be same or different, and is independently selected from the group consisting of hydrogen, deuterium, non-fused aryl, non-fused heteroaryl and combinations thereof, is provided.
In one embodiment, R1 is selected from the group consisting of phenyl, biphenyl, terphenyl, tetraphenyl, pentaphenyl, pyridine, phenyl pyridine and pyridyl phenyl. In one embodiment, the compound of the claim 1, wherein L is selected from the group consisting of phenyl, pyridyl, biphenyl, terphenyl and a bond. In one embodiment, R4 is selected from the group consisting of phenyl, pyridyl, biphenyl, and terphenyl. In one embodiment, R5 is selected from the group consisting of phenyl, pyridyl, biphenyl, and terphenyl.
In one aspect, the compound consists of a compound having a structure according to Formula II:
wherein R2 and R3 can be same or different, and independently selected from the group consisting of hydrogen, deuterium, non-fused aryl, non-fused heteroaryl and combinations thereof.
In one embodiment, the compound having a structure according to Formula II is selected from the group consisting of Compound 1 through Compound 602 listed in the table below, wherein Y1, R1, R2, R3, R4, R5 and L are as defined and wherein C is Carbon, N is nitrogen, H is hydrogen, A1 is
In one embodiment, the compound consists of a compound having the formula:
wherein the compound is selected from the group consisting of Compound 603 through Compound 686 listed in the table below, wherein R1, R2, R3, R4, and R5 are as defined and wherein H is hydrogen, A1 is
In one embodiment, the compound consists of a compound having the formula:
wherein the compound is selected from the group consisting of Compound 687 through Compound 770 listed in the table below, wherein R1, R2, R3, R4, and R5 are as defined and wherein H is hydrogen, A1 is
In one embodiment, the compound consists of a compound having the formula:
wherein the compound is selected from the group consisting of Compound 771 through Compound 854 listed in the table below, wherein R1, R2, R3, R4, and R5 are as defined and wherein H is hydrogen, A1 is
In one embodiment, the compound consists of a compound having the formula:
wherein the compound is selected from the group consisting of Compound 855 through Compound 938 listed in the table below, wherein R1, R2, R3, R4, and R5 are as defined and wherein H is hydrogen, A1 is
In one embodiment, the compound is selected from the group consisting of:
In one aspect, a formulation comprising a compound of Formula I is provided.
In one aspect, a first device comprising a first organic light emitting device, the first organic light emitting device comprising: an anode; a cathode; an organic layer, disposed between the anode and the cathode, wherein the organic layer further comprising a compound having a structure according to Formula I
wherein R1, R4 and R5 are independently selected from group consisting of non-fused aryl, non-fused heteroaryl, and combinations thereof; wherein L is selected from the group consisting of a bond, non-fused aryl, non-fused heteroaryl, and combinations thereof; wherein X1, X2, X3, X4, X5, X6, X7, Y1, Y2, and Y3 are each independently selected from the group consisting of CR and N; wherein at least two of Y1, Y2, and Y3 are N; and wherein each R can be same or different, and is independently selected from the group consisting of hydrogen, deuterium, non-fused aryl, non-fused heteroaryl and combinations thereof, is provided.
In one embodiment, R1 is selected from the group consisting of phenyl, biphenyl, terphenyl, tetraphenyl, pentaphenyl, pyridine, phenyl pyridine and pyridyl phenyl. In one embodiment, L is selected from the group consisting of phenyl, pyridyl, biphenyl, terphenyl and a bond. In one embodiment, R4 is selected from the group consisting of phenyl, pyridyl, biphenyl, and terphenyl. In one embodiment, R5 is selected from the group consisting of phenyl, pyridyl, biphenyl, and terphenyl. In one embodiment, the compound consists of a compound having a structure according to Formula II:
wherein R2 and R3 can be same or different, and independently selected from the group consisting of hydrogen, deuterium, non-fused aryl, non-fused heteroaryl and combinations thereof.
In one embodiment, the first device is an organic light-emitting device. In one embodiment, the first device comprises a lighting panel. In one embodiment, the compound is selected from the group consisting of:
In one embodiment, the compound is selected from Compounds 1 through 602. In one embodiment, the compound is selected from Compounds 603 to 686. In one embodiment, the compound is selected from Compounds 687 to 770. In one embodiment, the compound is selected from Compounds 771 to 854. In one embodiment, the compound is selected from Compounds 855 to 938.
In one embodiment, the first device is a consumer product. In one embodiment, the organic layer is an emissive layer and the compound of Formula I is a host. In one embodiment, the organic layer is a blocking layer and the compound having Formula I is a blocking material in the organic layer. In one embodiment, the organic layer is an electron transporting layer and the compound having Formula I is an electron transporting material in the organic layer. In a further embodiment, the compound comprising a first dopant material that is an emissive dopant comprising a transition metal complex having at least one ligand or part of the ligand if the ligand is more than bidentate selected from the group consisting of:
wherein Ra, Rb, and Rc may represent mono, di, tri or tetra substitutions; Ra, Rb, and Rc are 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 acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and two adjacent substituents of Ra, Rb, and Rc are optionally joined to form a fused ring or form a multidentate ligand.
Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an “exciton”, which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.
The initial OLEDs used emissive molecules that emitted light from their singlet states (“fluorescence”) as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.
More recently, OLEDs having emissive materials that emit light from triplet states (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, vol. 395, 151-154, 1998; (“Baldo-I”) and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), which are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference.
More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.
The simple layered structure illustrated in
Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in
Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP), such as described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink jet and OVJD. Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons is a preferred range. Materials with asymmetric structures may have better solution processibility than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.
Devices fabricated in accordance with embodiments of the present invention may further optionally comprise a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. The barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. The barrier layer may comprise a single layer, or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate an inorganic or an organic compound or both. The preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material as described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporated by reference in their entireties. To be considered a “mixture”, the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be created from the same precursor material. In one example, the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon.
Devices fabricated in accordance with embodiments of the invention may be incorporated into a wide variety of consumer products, including flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads up displays, fully transparent displays, flexible displays, laser printers, telephones, cell phones, personal digital assistants (PDAs), laptop computers, digital cameras, camcorders, viewfinders, micro-displays, vehicles, a large area wall, theater or stadium screen, or a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25 degrees C.).
The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.
The terms halo, halogen, alkyl, cycloalkyl, alkenyl, alkynyl, arylkyl, heterocyclic group, aryl, aromatic group, and heteroaryl are known to the art, and are defined in U.S. Pat. No. 7,279,704 at cols. 31-32, which are incorporated herein by reference.
According to an aspect of the present disclosure, a compound having a structure according to Formula I:
wherein R1, R4 and R5 are independently selected from group consisting of non-fused aryl, non-fused heteroaryl, and combinations thereof; wherein L is selected from the group consisting of a bond, non-fused aryl, non-fused heteroaryl, and combinations thereof; wherein X1, X2, X3, X4, X5, X6, X7, Y1, Y2, and Y3 are each independently selected from the group consisting of CR and N; wherein at least two of Y1, Y2, and Y3 are N; and wherein each R can be same or different, and is independently selected from the group consisting of hydrogen, deuterium, non-fused aryl, non-fused heteroaryl and combinations thereof, is provided.
In one embodiment, R1 is selected from the group consisting of phenyl, biphenyl, terphenyl, tetraphenyl, pentaphenyl, pyridine, phenyl pyridine and pyridyl phenyl. In one embodiment, the compound of the claim 1, wherein L is selected from the group consisting of phenyl, pyridyl, biphenyl, terphenyl and a bond. In one embodiment, R4 is selected from the group consisting of phenyl, pyridyl, biphenyl, and terphenyl. In one embodiment, R5 is selected from the group consisting of phenyl, pyridyl, biphenyl, and terphenyl.
In one aspect, the compound consists of a compound having a structure according to Formula II:
wherein R2 and R3 can be same or different, and independently selected from the group consisting of hydrogen, deuterium, non-fused aryl, non-fused heteroaryl and combinations thereof.
In one embodiment, the compound having a structure according to Formula II is selected from the group consisting of Compound 1 through Compound 602 listed in the table below (Table 1), wherein Y1, R1, R2, R3, R4, R5 and L are as defined and wherein C is Carbon, N is nitrogen, H is hydrogen, A1 is
In one embodiment, the compound consists of a compound having the formula:
wherein the compound is selected from the group consisting of Compound 603 through Compound 686 listed in the table below (Table 2), wherein R1, R2, R3, R4, and R5 are as defined and wherein H is hydrogen,
In one embodiment, the compound consists of a compound having the formula:
wherein the compound is selected from the group consisting of Compound 687 through Compound 770 listed in the table below (Table 3), wherein R1, R2, R3, R4, and R5 are as defined and wherein H is hydrogen, A1 is
In one embodiment, the compound consists of a compound having the formula:
wherein the compound is selected from the group consisting of Compound 771 through Compound 854 listed in the table below (Table 4), wherein R1, R2, R3, R4, and R5 are as defined and wherein H is hydrogen, A1 is
In one embodiment, the compound consists of a compound having the formula:
wherein the compound is selected from the group consisting of Compound 855 through Compound 938 listed in the table below (Table 5), wherein R1, R2, R3, R4, and R5 are as defined and wherein H is hydrogen, A1 is
In one embodiment, the compound is selected from the group consisting of:
In one aspect, a formulation comprising a compound of formula I is provided.
In one aspect, a first device comprising a first organic light emitting device, further comprising: an anode; a cathode; an organic layer, disposed between the anode and the cathode, wherein the organic layer further comprising a compound having a structure according to Formula I
wherein R1, R4 and R5 are independently selected from group consisting of non-fused aryl, non-fused heteroaryl, and combinations thereof; wherein L is selected from the group consisting of a bond, non-fused aryl, non-fused heteroaryl, and combinations thereof; wherein X1, X2, X3, X4, X5, X6, X7, Y1, Y2, and Y3 are each independently selected from the group consisting of CR and N; wherein at least two of Y1, Y2, and Y3 are N; and wherein each R can be same or different, and is independently selected from the group consisting of hydrogen, deuterium, non-fused aryl, non-fused heteroaryl and combinations thereof, is provided.
In one embodiment, R1 is selected from the group consisting of phenyl, biphenyl, terphenyl, tetraphenyl, pentaphenyl, pyridine, phenyl pyridine and pyridyl phenyl. In one embodiment, L is selected from the group consisting of phenyl, pyridyl, biphenyl, terphenyl and a bond. In one embodiment, R4 is selected from the group consisting of phenyl, pyridyl, biphenyl, and terphenyl. In one embodiment, R5 is selected from the group consisting of phenyl, pyridyl, biphenyl, and terphenyl. In one embodiment, the compound consists of a compound having a structure according to Formula II:
wherein R2 and R3 can be same or different, and independently selected from the group consisting of hydrogen, deuterium, non-fused aryl, non-fused heteroaryl and combinations thereof.
In one embodiment, the first device is an organic light-emitting device. In one embodiment, the first device comprises a lighting panel. In one embodiment, the compound is selected from the group consisting of:
In one embodiment, the compound is selected from the compounds 1 through 602. In one embodiment, the compound is selected from the compounds 603 to 686. In one embodiment, the compound is selected from the compounds 687 to 770. In one embodiment, the compound is selected from the compounds 771 to 854. In one embodiment, the compound is selected from the compounds 855 to 938.
In one embodiment, the first device is a consumer product. In one embodiment, the organic layer is an emissive layer and the compound of Formula I is a host. In one embodiment, the organic layer is a blocking layer and the compound having the formula I is a blocking material in the organic layer. In one embodiment, the organic layer is an electron transporting layer and the compound having the formula I is an electron transporting material in the organic layer. In a further embodiment, the compound comprising a first dopant material that is an emissive dopant comprising a transition metal complex having at least one ligand or part of the ligand if the ligand is more than bidentate selected from the group consisting of:
wherein Ra, Rb, and Rc may represent mono, di, tri or tetra substitutions; Ra, Rb, and Rc are 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 acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and two adjacent substituents of Ra, Rb, and Rc, are optionally joined to form a fused ring or form a multidentate ligand.
The exemplary compounds described herein comprise either carbazole or azacarbazole central unit. The compounds can be substituted directly at the 9-position with a triazine or a pyrimidine unit and with an aromatic unfused ring at the 1-position. The triazine linked to the 9-position of the carbazole can be further substituted by two similar aromatic rings or by two different substituents.
The compounds described in this disclosure were found to have surprising and unexpected properties when used as electron-transporting hosts in the emissive layer of an organic light-emitting device.
The present disclosure is based, at least in part, on the surprising and unexpected discovery that certain combinations of 1-arylated carbazole with either pyrimidine or triazine attached at the 9-position (nitrogen) of the carbazole contain two important parts, namely an electron rich part (carbazole) and an electron poor part (triazine). The substitution at the 1-position of the carbazole resulted in surprising and unexpected properties in order to provide steric hindrance which results twisting of the carbazole vs. triazine fragment. This substitution also enabled the compounds described herein to be completely amorphous and therefore they form higher quality films on the substrates.
As shown in the examples, non-exemplary compounds that do not have these characteristic substitution show worse performance characteristics and lifetimes compared to their 1-substituted counterpart as described in the present disclosure. The type of substituents on the carbazole and triazine are very important for the improved properties. It was found that small pendant groups were very efficient in providing good performance characteristics. The number of substituents were optimized and/or selected based on the glass transition temperature (TG) and deposition temperature (TD), which are very important factors in obtaining stable devices.
Generally, un-fused pendant groups that do not increase the rigidity of the material were used. For example, the carbazole, as well as the triazine groups, can be substituted with phenyl, biphenyl, terphenyl, and pyridine units. The known compounds that contain the triazine substituted carbazole usually contain other fused heterocycles like dibenzothiophene, dibenzofuran, or carbazole, which are unlike the compounds of the present disclosure comprising certain combinations of carbazole and triazine, both substituted with small and unfused pendant groups. Other dimer-like structures of such compounds are complicated to synthesize while not providing device improvement. The use of simple aryl units such as phenyl or pyridine makes the synthesis very straightforward and easy because of the availability of several commercial intermediates. Moreover, the TG and TD are much easier to adjust when using exemplary aryl units because their molecular weights are much smaller and increase these temperatures by a small amount compared to the bigger fused units.
In certain embodiments of the present disclosure, the three pendant groups on the triazine moiety can be different. The exemplary functionalization is having one larger group on one end of the triazine and two other small units which are usually the same (phenyl). As shown herein, exemplary compounds described herein can be very efficient materials (host and blocking layer OLEDs for green and red emissive layer) and can be obtained by having three different functional groups on the triazine. This allows more freedom in terms of chemistry and possibility for the synthesis of new materials. In certain aspects, the present disclosure is not limited to changing one third of the pendant groups on the triazine but all of them.
In general, the carbazole unit substituted with different triazine or pyrimidine units on the nitrogen combined with substitution with small pendant groups has great advantages as electron-transporting host. First of all, having a triazine unit on the carbazole moiety helps affording very good external quantum efficiency (EQE) and power efficacy (PE) in the devices. Furthermore, the addition of a pendant group at the 1-position on the carbazole lowers the driving voltage and also improves the lifetimes of the devices which are important problems to solve in the industry in order to have a viable host system and commercial development.
An organic light-emitting device is also provided. The device may include an anode, a cathode, and an organic emissive layer disposed between the anode and the cathode. The organic emissive layer may include a host and a phosphorescent dopant.
Combination with Other Materials
The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.
HIL/HTL:
A hole injecting/transporting material to be used in the present invention is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of the material include, but not limit to: a phthalocyanine or porphryin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and sliane derivatives; a metal oxide derivative, such as MoOx; a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.
Examples of aromatic amine derivatives used in HIL or HTL include, but not limit to the following general structures:
Each of Ar1 to Ar9 is selected from the group consisting aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; group consisting aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and group consisting 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Wherein each Ar is further substituted by a substituent 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 acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, Ar1 to Ar9 is independently selected from the group consisting of:
k is an integer from 1 to 20; X101 to X108 is C (including CH) or N; Z101 is NAr1, O, or S; Ar1 has the same group defined above.
Examples of metal complexes used in HIL or HTL include, but not limit to the following general formula:
wherein Met is a metal; (Y101—Y102) is a bidentate ligand, Y101 and Y102 are independently selected from C, N, O, P, and S; L101 is an another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.
In one aspect, (Y101—Y102) is a 2-phenylpyridine derivative. In another aspect, (Y101—Y102) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os, and Zn. In a further aspect, the metal complex has a smallest oxidation potential in solution vs. Fc+/Fc couple less than about 0.6 V.
Host:
The light emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as light emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. While the Table below categorizes host materials as preferred for devices that emit various colors, any host material may be used with any dopant so long as the triplet criterion is satisfied.
Examples of metal complexes used as host are preferred to have the following general formula:
wherein Met is a metal; (Y103—Y104) is a bidentate ligand, Y103 and Y104 are independently selected from C, N, O, P, and S; L101 is an another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.
In one aspect, the metal complexes are:
wherein (O—N) is a bidentate ligand, having metal coordinated to atoms O and N.
In another aspect, Met is selected from Ir and Pt. In a further aspect, (Y103—Y104) is a carbene ligand.
Examples of organic compounds used as host are selected from the group consisting aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; group consisting aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and group consisting 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atome, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Wherein each group is further substituted by a substituent 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 acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, host compound contains at least one of the following groups in the molecule:
wherein R101 to R107 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 acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. k is an integer from 1 to 20; k″′ is an integer from 0 to 20. X101 to X108 is selected from C (including CH) or N. Z101 and Z102 is selected from NR101, O, or S.
HBL:
A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED.
In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above.
In another aspect, compound used in HBL contains at least one of the following groups in the molecule:
k is an integer from 1 to 20; L101 is an another ligand, k′ is an integer from 1 to 3.
ETL:
Electron transport layer (ETL) may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.
In one aspect, compound used in ETL contains at least one of the following groups in the molecule:
wherein R101 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 acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. Ar1 to Ar3 has the similar definition as Ar's mentioned above. k is an integer from 1 to 20. X101 to X108 is selected from C (including CH) or N.
In another aspect, the metal complexes used in ETL contains, but not limit to the following general formula:
(O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L101 is another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal.
In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. Thus, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. encompasses undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also encompass undeuterated, partially deuterated, and fully deuterated versions thereof.
In addition to and/or in combination with the materials disclosed herein, many hole injection materials, hole transporting materials, host materials, dopant materials, exiton/hole blocking layer materials, electron transporting and electron injecting materials may be used in an OLED. Non-limiting examples of the materials that may be used in an OLED in combination with materials disclosed herein are listed in Table XXX below. Table XXX lists non-limiting classes of materials, non-limiting examples of compounds for each class, and references that disclose the materials.
All reactions were carried out under nitrogen atmosphere unless specified otherwise. All solvents for reactions are anhydrous and used as received from commercial sources.
1-Bromo-9H-carbazole (1.0 g, 4.06 mmol) was dissolved in DMF (20 ml). Sodium hydride (0.146 g, 6.10 mmol, 60% dispersion in mineral oil) was then added to the solution and it immediately turned yellow with some bubbling. After 1 h of stirring at room temperature, 2-chloro-4,6-diphenyl-1,3,5-triazine (1.63 g, 6.10 mmol) was added in one portion. The reaction was allowed to stir at room temperature for 2 days before adding 100 mL of water to quench the reaction. The precipitate was collected by filtration, solubilized in DCM and coated on Celite to purify by column chromatography on silica gel eluted with 25% of dichloromethane (DCM) in heptanes. Because of some solubility issues, the separation was not efficient. After evaporating of the solvent, the solid was triturated in EtOH 2 times to afford 1-bromo-9-(4,6-diphenyl-1,3,5-triazin-2-yl)-9H-carbazole (1.5 g, 77% yield) as a white powder.
[1,1′-Biphenyl]-4-ylboronic acid (3.11 g, 15.71 mmol), 1-bromo-9-(4,6-diphenyl-1,3,5-triazin-2-yl)-9H-carbazole (3.75 g, 7.86 mmol), and anhydrous potassium phosphate (4.17 g, 19.64 mmol) were mixed with 50 mL of toluene and 5 mL of water. The mixture was degassed by bubbling nitrogen for 30 minutes followed by the addition of Tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3) (0.719 g, 0.786 mmol) and dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphine (SPhOS) (1.290 g, 3.14 mmol). The reaction was heated to reflux for 24 h. Thin layer chromatography (TLC) indicated the reaction goes to completion. Ethyl acetate and water were added to the mixture and the organic and aqueous layers were decanted. The aqueous layer was washed two times with ethyl acetate. The combined organic layers were washed with brine and water and dried with sodium sulfate. The crude material was coated on celite and purified by column chromatography with 15-30% gradient mixture of DCM in heptanes. After evaporation of the solvent, the solid was triturated with EtOH and then the collected solid was recrystallized from heptanes and toluene. The target, Compound 2,1-([1,1′-biphenyl]-4-yl)-9-(4,6-diphenyl-1,3,5-triazin-2-yl)-9H-carbazole (2.7 g, 62% yield) was afforded as white crystals with a good purity (99.9%).
1-Bromo-9H-carbazole (2.9 g, 11.78 mmol) was dissolved in DMF (Volume: 58.9 ml) and sodium hydride (0.707 g, 17.68 mmol, 60% dispersion in mineral oil) was added to the solution, which quickly turned yellow. Once the bubbling from the reaction stopped (around 2 hours), 2-([1,1′-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine (5.06 g, 14.73 mmol) was added as one portion. The reaction was allowed at room temperature over two days. After completion, the mixture was poured into a mixture of 25% of methanol in water. The product was extracted with DCM and washed with brine and water. The white solid was triturated from methanol one time and one more time using heptanes. The material (5.79 g, 89% yield) was approximately 90% pure and was used in the next step without further purification.
[1,1′-Biphenyl]-4-ylboronic acid (2.86 g, 14.45 mmol), 9-(4-([1,1′-biphenyl]-4-yl)-6-phenyl-1,3,5-triazin-2-yl)-1-bromo-9H-carbazole (4.00 g, 7.23 mmol), and potassium phosphate (3.84 g, 18.07 mmol) were mixed in 50 mL of toluene and 5 mL of water. The mixture was degassed by bubbling nitrogen, followed by addition of Pd2(dba)3 (0.662 g, 0.723 mmol) and dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphine (SPhOS) (1.187 g, 2.89 mmol). The reaction was heated to reflux for 18 h. Upon cooling down to room temperature, the mixture was extracted using ethyl acetate. The combined organic fractions were washed with brine and water. The crude material was coated on Celite and purified by column chromatography eluted with 15%-30% gradient mixture of DCM in heptanes. The powder was solubilized in DCM and i-propanol was added. The DCM was slowly evaporated out of the mixture to obtain precipitation of the target with better purity (99.6%). Then, the target material, Compound 30, was purified using column chromatography (30% DCM in Heptanes) and 1.2 g (26% yield).
3,6-Dibromo-9H-carbazole (10.0 g, 30.8 mmol), phenylboronic acid (8.25 g, 67.7 mmol) Pd2(dba)3 (0.564 g, 0.615 mmol), dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphine (SPhOS) (1.011 g, 2.462 mmol), and potassium phosphate hydrate (28.3 g, 123 mmol) were dissolved in the mixture of toluene (350 mL) and water (40 mL) in a three-necked flask. The mixture was degassed by bubbling nitrogen, then it was heated to reflux overnight. After completion of the reaction, the mixture partitioned between ethyl acetate and water. The aqueous layer was washed 3 times with ethyl acetate and the combined organic layers were washed with brine and water. The crude compound was purified by column chromatography on silica gel, eluted with hexane/DCM 1/1 (v/v) mixture. The target compound was obtained as a white solid (7.4 g, 75% yield).
3,6-Diphenyl-9H-carbazole (4.00 g, 12.52 mmol) was dissolved in anhydrous DMF (170 mL) and treated with NaH (0.751 g, 18.79 mmol, 60% dispersion in mineral oil) while stirring vigorously at room temperature providing yellow solution. Once H2 evolution stopped, the solution was stirred for 1 hour, and then treated with 2-chloro-4,6-diphenyl-1,3,5-triazine (5.03 g, 18.79 mmol), and left stirred overnight at room temperature. After stirring for ˜30 minutes, reaction solution had significant white precipitate swirling around. The crude mixture was quenched with water and filtered. The white precipitate was washed with water, MeOH, and EtOH. The material was recrystallized from toluene (400 mL) to obtain the target, Comparative Compound 1 with 99.86% purity. One more recrystallization from toluene gave a purity of 100% to afford 6.0 g (87% yield).
Material used in the devices:
All example devices were fabricated by high vacuum (<10−7 Torr) thermal evaporation. The anode electrode is 1200 Å of indium tin oxide (ITO). The cathode consisted of 10 Å of LiF followed by 1,000 Å of Al. All devices are encapsulated with a glass lid sealed with an epoxy resin in a nitrogen glove box (<1 ppm of H2O and O2) immediately after fabrication, and a moisture getter was incorporated inside the package.
The organic stack of the OLED device consisted of sequentially from the ITO surface, 100 Å of HAT-CN as the hole injection layer (HIL), 400 Å of NPD as the hole transporting layer (HTL), 300 Å of the emissive layer (EML) which contains the compound of Formula 1, Compound SD, and Compound D, 550 Å of AlQ3 as the electron transporting layer (ETL) and 10 Å of LiF as the electron injection layer (EIL). The device structure is shown in
1All values in this table are relative numbers (arbitrary units—a.u.) except for the CIE coordinates.
2Calculated assuming accelerated factor: 2.0
Table 8 is a summary of the device data. The luminous efficiency (LE), external quantum efficiency (EQE) and power efficiency (PE) were measured at 1000 nits, while the lifetime (LT95%) was defined as the time required for the device to decay to 95% of its initial luminance under a constant current density of 40 mA/cm2. Compounds such as Comparative Compound 1, which does not contain any substitution at the 1-position of the carbazole does not perform as well as Compound 2 which combines the triazine substitution on the nitrogen of the carbazole and substitution at the 1-position of the carbazole. As shown in Table 2, when the device contains Compound 2 in the emissive layer, its driving voltage is lower. Moreover, the luminous efficacy (LE), external quantum efficiency (EQE), power efficacy (PE) and operational lifetime (LT95%) are all improved compared to the devices which contain Comparative Compound 1 as the host. The performances are also improved when the blocking layer (BL) is Compound 2 compared to BAlQ. The best device obtained with Compound 2 (in relative numbers—compared to Comparative Compound 1) in this study showed a x value from the CIE of 0.661, a driving voltage of 0.78, an LE of 1.2, an EQE of 1.2, a PE of 1.6, and finally an LT95% (measured at 1000 nits) of more than 4 times than the lifetime of the comparative example. However, performances obtained with Compound 30 are less impressive than what has been obtained with Compound 2 (Table 2). The best device obtained with Compound 30 in this study showed a x value from the CIE of 0.661, a driving voltage of 1.1, an LE of 1.1, an EQE of 1.1, a PE of 1.0, and finally an LT95% (measured at 1000 nits) of almost 3 times the lifetime of the comparative example.
It is understood that the various embodiments described herein are by way of example only, and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. The present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting.
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| Number | Date | Country | |
|---|---|---|---|
| 20150001471 A1 | Jan 2015 | US |
