Nanopatch antenna outcoupling structures for use in OLEDs

Abstract

To provide a device that may include a light emissive layer, a first electrode layer, a plurality of nanoparticles and a material disposed between the first electrode layer and the plurality of nanoparticles.SOLUTION: The device may include a second electrode layer and a substrate, where the second electrode layer is disposed on the substrate, and the light emissive layer is disposed on the second electrode layer. The second electrode layer may be disposed on the substrate, the light emissive layer may be disposed on the second electrode layer, the first electrode layer may be disposed on the light emissive layer, a first dielectric layer of the material may be disposed on the first electrode layer, the plurality of nanoparticles may be disposed on the first dielectric layer, and a second dielectric layer may be disposed on the plurality of nanoparticles and the first dielectric layer.SELECTED DRAWING: Figure 3b

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Patent Application No. 62 / 817,284, filed March 12, 2019, U.S. Patent Application No. 62 / 870,272, filed July 3, 2019, U.S. Patent Application No. 62 / 817,368, filed March 12, 2019, and U.S. Patent Application No. 62 / 817,424, filed March 12, 2019, the disclosures of each of which are incorporated by reference in their entirety.

[0002] The present invention relates to outcoupling with nanopatch antennas that convert surface plasmon energy in the electrode layer of an OLED into visible light. [Background technology]

[0003] Optoelectronic devices that utilize 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 optoelectronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as flexibility, may make them well suited for certain applications, such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light-emitting diodes / devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials may have performance advantages over traditional materials. For example, the wavelength at which an organic light-emitting layer emits light can generally be easily tuned with appropriate dopants.

[0004] OLEDs utilize thin organic films that emit light when a voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, lighting and backlighting. Several OLED materials and configurations are described in U.S. Patent Nos. 5,393, 6,433, 6,511, 6,671, 6,781, and 7,933, 7,825, which are incorporated herein by reference in their entireties.

[0005] One application of phosphorescent emissive molecules is full color displays. Industry standards for such displays require pixels adapted to emit specific colors, referred to as "saturated" colors. In particular, these standards require saturated red, green, and blue pixels. Alternatively, OLEDs can be designed to emit white light. Conventional liquid crystal display emission from a white backlight is filtered with absorbing filters to produce red, green, and blue emission. Similar techniques can be used with OLEDs. White OLEDs can be either single EML devices or stacked structures. Color can be measured using CIE coordinates, which are well known in the art.

[0006] As used herein, the term "organic" includes polymeric and small molecule organic materials that can be used to fabricate organic optoelectronic devices. "Small molecule" refers to any organic material that is not a polymer, and "small molecules" can actually be quite large. Small molecules can include repeat units in some circumstances. For example, the use of long chain alkyl groups as a substituent does not remove a molecule from the "small molecule" class. Small molecules can be incorporated into polymers, for example, as pendant groups on a polymer backbone or as part of the backbone. Small molecules can 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 the dendrimer can be a fluorescent or phosphorescent small molecule emitter. Dendrimers can be "small molecules," and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.

[0007] As used herein, "top" means furthest from the substrate, while "bottom" means closest to the substrate. When a first layer is described as "disposed over" a second layer, the first layer is disposed further from the substrate. There may be other layers between the first and second layers, 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 may be various organic layers in between.

[0008] As used herein, "solution processable" means capable of being dissolved, dispersed or transported in and / or deposited from a liquid medium, either in the form of a solution or suspension.

[0009] A ligand may be referred to as "photoactive" if it is believed that the ligand directly contributes to the photoactive properties of the emissive material. A ligand may be referred to as "ancillary" if it is believed that the ligand does not contribute to the photoactive properties of the emissive material, although the ancillary ligand may modify the properties of the photoactive ligand.

[0010] As used herein, and as generally understood by those 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 (IPs) are measured as negative energies relative to the vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (a less negative IP). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (a less negative EA). In a conventional energy level diagram with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A "higher" HOMO or LUMO energy level appears closer to the top of such a diagram than a "lower" HOMO or LUMO energy level.

[0011] As used herein, as generally understood by those 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. Since work functions are generally measured as negative numbers relative to the vacuum level, this means that a "higher" work function is more negative. In a conventional energy level diagram with the vacuum level at the top, a "higher" work function is illustrated as being further away from the vacuum level in a downward direction. Thus, the definition of the HOMO and LUMO energy levels follows a different convention than work functions.

[0012] Further details regarding OLEDs and the above definitions can be found in US Pat. No. 6,399,633, which is incorporated herein by reference in its entirety. Summary of the Invention

[0013] According to one embodiment, an organic light emitting diode / device (OLED) is also provided. The OLED can include an anode, a cathode, and an organic layer disposed between the anode and the cathode. According to one embodiment, the organic light emitting device is incorporated into one or more devices selected from a consumer product, an electronic component module, and / or a lighting panel.

[0014] According to an embodiment, a device can include a light emitting layer, a first electrode layer, a plurality of nanoparticles, and a material disposed between the first electrode layer and the plurality of nanoparticles.

[0015] The device may include a second electrode layer and a substrate, the second electrode layer may be disposed on the substrate, and the light emitting layer may be disposed on the second electrode layer. At least one of the first electrode layer and the second electrode layer may be a metal, a semiconductor, and / or a transparent conductive oxide. The first electrode layer may be spaced from the light emitting layer by a predetermined threshold distance, the distance at which the total non-radiative (radiative) decay rate constant is equal to the total radiative decay rate constant. The material of the device may include at least one of an organic material, an oxide, and / or a dielectric material. The material may have a refractive index between 1 and 5. The light emitting layer of the device may include a transport layer. The light emitting layer may be an organic layer having emitter molecules.

[0016] The light-emitting layer of the device can include at least one of a fluorescent material, a phosphorescent material, a thermally activated delayed fluorescence (TADF) material, a quantum dot material, a metal-organic framework, a covalent-organic framework, and / or a perovskite nanocrystal.

[0017] The first electrode layer of the device may have a thickness between 5 nm and 300 nm. The device may include a nanopatch antenna, and the resonance of the nanopatch antenna may be tuned by at least one of changing the size of the nanoparticles, changing the ratio of the sizes of the nanoparticles, changing the shape of the nanoparticles, changing the material of the nanoparticles, adjusting the thickness of the material, changing the refractive index of the material, changing the refractive index of an additional layer disposed on the nanoparticles, changing the thickness of the first electrode layer, and / or changing the material of the first electrode layer. The nanoparticles may be formed from at least one of Ag particles, Al particles, Au particles, dielectric materials, semiconductor materials, alloys of metals, mixtures of dielectric materials, stacks of one or more materials, and / or a core of one material coated with a shell of a different material. At least one of the nanoparticles of the device may include an additional layer to provide lateral conduction between the nanoparticles. The nanoparticles may be coated with an oxide layer, and the thickness of the oxide layer may be selected to tune the plasmon resonance wavelength of the nanoparticles or the nanopatch antenna. The shape of the nanoparticles may be at least one of a cube, a sphere, an ellipsoid, a cylindrical three-dimensional object, a parallelepiped three-dimensional object, a rod-shaped three-dimensional object, a star-shaped three-dimensional object, a pyramidal three-dimensional object, and / or a multi-faceted three-dimensional object. At least one of the nanoparticles may have a size of 5 nm to 1000 nm.

[0018] The device can include a corrugated layer disposed on the substrate, wherein the second electrode layer, the light emitting layer, the first electrode layer, and / or the material are correspondingly corrugated.

[0019] The material of the device can include a dielectric layer disposed on the first electrode layer and an electrical contact layer disposed on the dielectric layer. The material can include a voltage tunable refractive index material between the electrical contact layer and the first electrode layer. The voltage tunable refractive index material can be zinc oxide doped with aluminum. The material can include an insulating layer. The first electrode layer of the device can be spaced from the light emitting layer by a predetermined threshold distance.

[0020] The predetermined threshold distance can be the distance at which the total non-radiative decay rate constant equals the total radiative decay rate constant. The device can include an additional layer disposed on the plurality of nanoparticles. The additional layer can include one or more emitter molecules. The additional layer can match the refractive index below the first electrode layer. The additional layer can have a thickness of 1000 nm or less.

[0021] The material of the device can include the light emitting layer. The plurality of nanoparticles and the first electrode layer can provide an electrical injection path for the device.

[0022] The device can include a substrate and a second electrode layer, the first electrode layer can be non-planar, the second electrode layer can be disposed on the substrate, the plurality of nanoparticles can be disposed on the second electrode layer, the light emitting layer can be non-planar and can be comprised in a material and can be disposed and conformed over the plurality of nanoparticles and the second electrode layer, and the first electrode layer can be disposed and conformed over the non-planar light emitting layer. At least one of the first electrode layer and the second electrode layer can be a metal, a semiconductor, and / or a transparent conductive oxide.

[0023] The device can include a substrate and a second electrode layer, the second electrode layer can be disposed on the substrate, the nanoparticles can be disposed in the second electrode layer, the light emitting layer can be included in the material and can be disposed on the second electrode layer including the plurality of nanoparticles, and the first electrode layer can be disposed on the light emitting layer. At least one of the first electrode layer and the second electrode layer can be a metal, a semiconductor, and / or a transparent conductive oxide.

[0024] The device can include a substrate and a second electrode layer, the material can be a first dielectric layer, the device can include a second dielectric layer, the second electrode layer can be disposed on the substrate, the light emitting layer can be disposed on the second electrode layer, the first electrode layer can be disposed on the light emitting layer, the first dielectric layer can be disposed on the first electrode layer, the plurality of nanoparticles can be disposed on the first dielectric layer, and the second dielectric layer can be disposed on the plurality of nanoparticles and the first dielectric layer. At least one of the first electrode layer and the second electrode layer can be a metal, a semiconductor, and / or a transparent conductive oxide. The first electrode layer can be spaced from the light emitting layer by a predetermined threshold distance, which is a distance at which a total non-radiative decay rate constant is equal to a total radiative decay rate constant. The first electrode layer may include at least one of Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, and / or Ca. The material may include at least one of an organic material, an oxide, and / or a dielectric material. The material may have a refractive index between 1 and 5. The light-emitting layer may include a transport layer. The light-emitting layer may be an organic layer having emitter molecules. The light-emitting layer may include at least one of a fluorescent material, a phosphorescent material, a thermally activated delayed fluorescence (TADF) material, a quantum dot material, a metal-organic framework, a covalent-organic framework, and / or a perovskite nanocrystal. The first electrode layer may have a thickness between 5 nm and 100 nm. The device can include a nanopatch antenna, and the resonance of the nanopatch antenna can be tuned by at least one of changing a size of the nanoparticles, changing a size ratio of the nanoparticles, changing a shape of the nanoparticles, changing a material of the nanoparticles, adjusting a thickness of the material, changing a refractive index of the material, changing a refractive index of an additional layer disposed on the nanoparticles, changing a thickness of the first electrode layer, and / or changing a material of the first electrode layer.The nanoparticles may be formed from at least one selected from the group consisting of Ag particles, Al particles, Au particles, dielectric materials, semiconductor materials, alloys of metals, mixtures of dielectric materials, stacks of one or more materials, and / or a core of one material coated with a shell of a different material. At least one of the nanoparticles of the device may include an additional layer to provide lateral conduction between the nanoparticles. The nanoparticles may be coated with an oxide layer, the thickness of the oxide layer being selected to tune the plasmon resonance wavelength of the nanoparticles or nanopatch antenna. The shape of the nanoparticles may be at least one of a cube, a sphere, an ellipsoid, a cylindrical three-dimensional object, a parallelepiped three-dimensional object, a rod-shaped three-dimensional object, a star-shaped three-dimensional object, a pyramidal three-dimensional object, and / or a multi-faceted three-dimensional object. The size of at least one of the nanoparticles may be between 5 nm and 1000 nm.

[0025] The device can include a substrate and a second electrode layer, the material can be a first dielectric layer, the second electrode layer can be disposed on the substrate, the light emitting layer can be disposed on the second electrode layer, the first electrode layer can be disposed on the light emitting layer, the first dielectric layer can be disposed on the first electrode layer, and the plurality of nanoparticles can be disposed on the first dielectric layer. At least one of the first electrode layer and the second electrode layer can be a metal, a semiconductor, and / or a transparent conductive oxide.

[0026] The device can include a substrate and a second electrode layer, the material is a first dielectric layer and a second dielectric layer, the nanoparticles can be disposed in the second dielectric layer, the second dielectric layer and the nanoparticles can be disposed on the substrate, the first dielectric layer can be disposed on the second dielectric layer and the nanoparticles, the first electrode layer can be disposed on the first dielectric layer, the light emitting layer can be disposed on the first electrode, and the second electrode can be disposed on the light emitting layer. At least one of the first electrode layer and the second electrode layer can be a metal, a semiconductor, and / or a transparent conductive oxide.

[0027] The device can include a substrate and a second electrode layer, the material can be a first dielectric layer, the device can include a second dielectric layer, the first electrode layer can be disposed on the substrate, the first dielectric layer can be disposed on the first electrode layer, the plurality of nanoparticles can be disposed on the first dielectric layer, the second dielectric layer can be disposed on the plurality of nanoparticles and the first dielectric layer, the light emitting layer can be disposed on the second dielectric layer, and the second electrode layer can be disposed on the light emitting layer. At least one of the first electrode layer and the second electrode layer can be a metal, a semiconductor, and / or a transparent conductive oxide.

[0028] The device can include a substrate and a second electrode layer, the material is a first dielectric layer, the device can include a second dielectric layer, the second electrode layer can be disposed on the substrate, the light emitting layer can be disposed on the second electrode layer, the plurality of nanoparticles can be disposed on the light emitting layer, the second dielectric layer can be disposed on the plurality of nanoparticles and the light emitting layer, the first dielectric layer can be disposed on the second dielectric layer, and the first electrode layer can be disposed on the first dielectric layer. At least one of the first electrode layer and the second electrode layer can be a metal, a semiconductor, and / or a transparent conductive oxide.

[0029] The material of the device may include at least one of an organic material, an oxide, and / or a dielectric material. The material may include a first layer and a second layer, the first layer being thicker than the second layer. The first layer may be a dielectric material and the second layer may be a nanoparticle adhesion layer. The thickness of the first layer may be between 1 nm and 100 nm, and the thickness of the second layer may be less than 5 nm. The material may have a thickness of 1000 nm or less. The material of the device may have a refractive index between 1 and 5. The material may include at least a portion of a coating disposed on the plurality of nanoparticles. The coating disposed on the plurality of nanoparticles may be a dielectric coating.

[0030] The device may include a second electrode layer, and the light-emitting layer may be included in an organic light-emitting diode (OLED), the OLED being disposed between the first electrode layer and the second electrode layer. At least one of the first electrode layer and the second electrode layer may be a metal, a semiconductor, and / or a transparent conductive oxide. The light-emitting layer may include a transport layer. The light-emitting layer may be an organic layer having emitter molecules. The light-emitting layer may include at least one of a fluorescent material, a phosphorescent material, a thermally activated delayed fluorescence (TADF) material, a quantum dot material, a metal-organic framework, a covalent-organic framework, and / or a perovskite nanocrystal.

[0031] The first electrode layer of the device may be spaced from the light emitting layer by a predetermined threshold distance, the threshold distance being the distance at which the total non-radiative decay rate constant is equal to the total radiative decay rate constant. The first electrode layer may comprise at least one of Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, and / or Ca. The first electrode layer may be patterned with additional materials. The additional materials may comprise fluorescent emitters, phosphorescent emitters, quantum dots, metal-organic frameworks, covalent-organic frameworks, and / or perovskite nanocrystal light emitting elements. The first electrode layer may have a thickness of 5 nm to 300 nm. The first electrode layer of the device may have at least one non-planar surface.

[0032] The device can include a nanopatch antenna, and the resonance of the nanopatch antenna can be tuned by at least one of changing a size of the nanoparticles, changing a size ratio of the nanoparticles, changing a shape of the nanoparticles, changing a material of the nanoparticles, adjusting a thickness of the material, changing a refractive index of the material, changing a refractive index of an additional layer disposed on the nanoparticles, changing a thickness of the first electrode layer, and / or changing a material of the first electrode layer.

[0033] The nanoparticles of the device may be formed from at least one of Ag particles, Al particles, Au particles, dielectric materials, semiconductor materials, alloys of metals, mixtures of dielectric materials, stacks of one or more materials, and / or a core of one type of material coated with a shell of a different type of material.

[0034] At least one of the nanoparticles of the device may include an additional layer to provide lateral conduction between the nanoparticles. The nanoparticles may be coated with an oxide layer, the thickness of the oxide layer being selected to tune the plasmon resonance wavelength of the nanoparticles or nanopatch antenna. The nanoparticles may be colloidally synthesized nanoparticles formed from a solution. The shape of the nanoparticles may be at least one of a cube, a sphere, an ellipsoid, a cylindrical three-dimensional object, a parallelepiped three-dimensional object, a rod-shaped three-dimensional object, a star-shaped three-dimensional object, a pyramidal three-dimensional object, and / or a multi-faceted three-dimensional object. A size of at least one of the nanoparticles may be between 5 nm and 1000 nm. A size of at least one of the nanoparticles may be between 5 nm and 200 nm. A size of at least one of the nanoparticles may be between 5 nm and 100 nm.

[0035] According to an embodiment, a method can be provided that includes disposing a first electrode layer on a substrate, disposing a photoresist on the first electrode layer, etching the photoresist and at least a portion of the first electrode layer, depositing a metal in the remaining portions of the photoresist to match a depth of the etched portions of the first electrode layer, removing the metal and the photoresist to form nanoparticles from the deposited metal that are flush with a surface of the first electrode layer, disposing an emissive layer on the first electrode layer and the nanoparticles, and disposing a second electrode layer on the emissive layer. [Brief description of the drawings]

[0036] [Figure 1] FIG. 1 shows an organic light emitting device.

[0037] [Diagram 2] FIG. 2 shows an inverted organic light emitting device that does not have a separate electron transport layer.

[0038] [Figure 3a] FIG. 3a shows a conventional nanopatch antenna that includes a layer of material between the nanoparticles and the metal layer that has emitter molecules embedded therein.

[0039] [Figure 3b] FIG. 3b shows a nanopatch antenna comprising emitter molecules in a light-emitting layer disposed beneath a metal layer (ie, an electrode layer) according to an embodiment of the disclosed subject matter.

[0040] [Figure 3c] FIG. 3c illustrates a nanopatch antenna including a capping layer disposed on a nanoparticle that may include additional emitter molecules, according to an embodiment of the disclosed subject matter.

[0041] [Figure 4a] FIG. 4a illustrates a dielectric gap material comprising multiple layers, according to an embodiment of the disclosed subject matter.

[0042] [Figure 4b] FIG. 4b shows a two-layer gap including a thick dielectric layer and a thin nanoparticle adhesion layer according to an embodiment of the disclosed subject matter.

[0043] [Figure 5a] FIG. 5a shows emitter molecules in an emissive layer disposed under a metal layer (i.e., an electrode layer) in combination with an OLED stack according to an embodiment of the disclosed subject matter, where the emissive layer is within a threshold distance to the metal electrode and the nanopatch antenna above the electrode radiates from the side having the nanoparticles.

[0044] [Figure 5b] FIG. 5b shows a variation of the embodiment of FIG. 5a, in accordance with an embodiment of the disclosed subject matter, where the stack can be corrugated for additional outcoupling of SPR (surface plasmon energy) modes.

[0045] [Figure 6] FIG. 6 shows that, according to an embodiment of the disclosed subject matter, the energy of excited emitter molecules can be quenched into SPR modes at the cathode and coupled into nanopatch antenna gap modes, resulting in an electric field that can radiate the energy as light.

[0046] [Figure 7] FIG. 7 shows a computer simulation of the Ex and Ey electric field intensities in the x and y directions, respectively, in a material layer of a nanopatch antenna using nanocubes as nanoparticles according to an embodiment of the disclosed subject matter, showing that light outcoupled into the far field originates from the edge of the nanoparticle.

[0047] [Figure 8] FIG. 8 shows a thin metal film (ie, electrode layer) that has been etched partially through the film thickness to produce a corrugated top surface while maintaining a planar bottom surface, according to an embodiment of the disclosed subject matter.

[0048] [Figure 9] FIG. 9 illustrates that the nanoparticle coating, according to an embodiment of the disclosed subject matter, can provide an appropriate gap thickness between the nanoparticles and the metal film.

[0049] [Figure 10] FIG. 10 shows an OLED combined with a nanopatch antenna that utilizes a gap material with a voltage tunable refractive index to select the wavelength of emitted light, according to an embodiment of the disclosed subject matter.

[0050] [Figure 11] FIG. 11 shows an OLED stack deposited in the gap region using a metal layer as an electrode and nanoparticles to inject charges according to an embodiment of the disclosed subject matter.

[0051] [Figure 12a] FIG. 12a shows a nanopatch antenna OLED device having metal nanoparticles deposited on top of the electrodes and substrate, thereby enabling charge injection from ITO (indium tin oxide) and the metal nanoparticles, according to an embodiment of the disclosed subject matter.

[0052] [Figure 12b] FIG. 12b shows an alternative planar OLED device to that shown in FIG. 12a, according to an embodiment of the disclosed subject matter.

[0053] [Figure 13] FIG. 13 illustrates a method of forming the planar electrically-driven nanopatch antenna OLED shown in FIG. 12b according to an embodiment of the disclosed subject matter.

[0054] [Figure 14a] FIG. 14a shows an example of an OLED device having various nanostructures with a dielectric capping layer according to an embodiment of the disclosed subject matter. [Figure 14b] FIG. 14b shows an example of an OLED device having various nanostructures without a dielectric capping layer according to an embodiment of the disclosed subject matter. [Figure 14c] FIG. 14c shows an example of an OLED device having various nanostructures with a dielectric capping layer according to an embodiment of the disclosed subject matter. [Figure 14d] FIG. 14d shows an example of an OLED device having various nanostructures without a dielectric capping layer according to an embodiment of the disclosed subject matter. [Figure 14e]FIG. 14e shows an example of an OLED device having various nanostructures with a dielectric capping layer according to an embodiment of the disclosed subject matter. [Figure 14f] FIG. 14f shows an example of an OLED device having various nanostructures without a dielectric capping layer according to an embodiment of the disclosed subject matter.

[0055] [Figure 15] FIG. 15 illustrates how the material composition of the nanostructures can be metallic, dielectric, or a combination of the two (ie, a hybrid), according to embodiments of the disclosed subject matter.

[0056] [Figure 16] FIG. 16 illustrates that particle shape can affect resonant plasmon mode frequencies, according to embodiments of the disclosed subject matter. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0057] In general, 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 migrate to the oppositely charged electrode, respectively. When an electron and hole localize on the same molecule, an "exciton" is formed, which is a localized electron-hole pair having an excited energy state. Light is emitted via a photoemissive mechanism when the exciton relaxes. In some cases, the exciton may be localized on an excimer or exciplex. Non-radiative mechanisms such as thermal relaxation may also occur, but are generally considered undesirable.

[0058] Early OLEDs used emissive molecules that emitted light from their singlet state ("fluorescence"), as disclosed, for example, in U.S. Patent No. 4,769,292, which is incorporated by reference in its entirety. Fluorescence emission typically occurs on a time frame of less than 10 nanoseconds.

[0059] More recently, OLEDs have been demonstrated that have emissive materials that emit light from triplet states ("phosphorescence"). Baldo et al., "Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices," Nature, Vol. 395, No. 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 further detail in U.S. Pat. No. 7,279,704, columns 5-6, which are incorporated by reference.

[0060] FIG. 1 shows an organic light-emitting device 100. The figures are not necessarily drawn to scale. The device 100 may include a substrate 110, an anode 115, a hole-injection layer 120, a hole-transport layer 125, an electron-blocking layer 130, an emissive 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 compound cathode having a first conductive layer 162 and a second conductive layer 164. The device 100 may be fabricated by depositing the layers described, in order. The properties and functions of these various layers, as well as example materials, are described in more detail in US Pat. No. 7,279,704, columns 6-10, which are incorporated by reference.

[0061] Further examples are available for each of these layers. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent 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 in 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. Patent 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 in 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. Patent Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, disclose examples of cathodes including composite cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, conductive, sputter-deposited ITO layer. The theory and use of blocking layers are described in more detail in U.S. Patent No. 6,097,147 and U.S. Patent Application Publication No. 2003 / 0230980, which are incorporated by reference in their entirety. 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 can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated by reference in its entirety.

[0062] FIG. 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 can be fabricated by depositing the layers described, in order. Because the most common OLED configuration has the cathode disposed above the anode, and device 200 has cathode 215 disposed below anode 230, device 200 can be referred to as an "inverted" OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. FIG. 2 provides an example of how some layers may be omitted from the structure of device 100.

[0063] The simple layer structures illustrated in Figures 1 and 2 are provided as non-limiting examples, and it is understood that embodiments of the present invention may be used in conjunction with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. A functional OLED may be achieved by combining the various layers described in various ways, or layers may be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. While many of the examples provided herein describe the various layers as including a single material, it is understood that combinations of materials, such as mixtures of hosts and dopants, or more generally mixtures, may be used. Layers may also 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 emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an "organic layer" disposed between a cathode and an anode. The organic layer may include a single layer, or may further include multiple layers of different organic materials, such as those described with respect to Figures 1 and 2.

[0064] Structures and materials not specifically described may be used, such as OLEDs (PLEDs) composed of polymeric materials such as those disclosed in U.S. Patent No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. As a further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example, as described in U.S. Patent No. 5,707,745 to Forrest et al., which is incorporated by reference in its entirety. OLED structures may deviate from the simple layered structures illustrated in Figures 1 and 2. For example, the substrate may include angled reflective surfaces to improve outcoupling, such as the mesa structures described in U.S. Patent No. 6,091,195 to Forrest et al. and / or the recessed structures described in U.S. Patent No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entirety.

[0065] In some embodiments disclosed herein, light-emitting layers or materials, such as light-emitting layer 135 and light-emitting layer 220 shown in FIG. 1 and FIG. 2, respectively, can include quantum dots. Unless otherwise indicated explicitly or by context as understood by one of ordinary skill in the art, a "light-emitting layer" or "light-emitting material" disclosed herein can include organic light-emitting and / or light-emitting materials that include quantum dots or equivalent structures. Such light-emitting layers can include only quantum dot materials that convert light emitted by another light-emitting material or other light emitters, or can also include said other light-emitting materials or other light emitters, or can emit light itself directly from the application of electric current. Similarly, color conversion layers, color filters, up-conversion layers or structures, or down-conversion layers or structures can include materials that include quantum dots, but such layers may not be considered "light-emitting layers" as disclosed herein. In general, an "emissive layer" or material is one that emits initial light that does not emit the initial light within the device, but can be converted by other layers, such as color filters or other color conversion layers, that can re-emit modified light of different spectral content based on the initial light emitted by the emissive layer.

[0066] Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For organic layers, preferred methods include deposition by thermal evaporation, such as those described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entirety, inkjet, organic vapor phase deposition (OVPD), such as those described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and organic vapor jet printing (OVJP), such as those 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 a nitrogen or inert atmosphere. For other layers, preferred methods include thermal evaporation. Preferred patterning methods include patterning associated with some of the deposition methods such as deposition through a mask, cold welding, such as those described in U.S. Patent Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entirety, and inkjet and OVJD. Other methods may be used. The material to be deposited may be modified to be compatible with the 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 with 20 or more carbons may be used, with 3-20 carbons being a preferred range. Materials with asymmetric structures may have better solution processability than those with symmetric structures, as asymmetric materials may be less prone to recrystallization. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.

[0067] Devices fabricated according to embodiments of the invention may further include a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment, including moisture, vapors and / or gases, etc. The barrier layer may be deposited on, under or next to the substrate, the electrodes, or on any other portion of the device, including the edges. The barrier layer may include 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 and compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate inorganic or organic compounds or both. Preferred barrier layers include mixtures of polymeric and non-polymeric materials, as described in U.S. Pat. No. 7,968,146, PCT Patent Application Nos. PCT / US2007 / 023098 and PCT / US2009 / 042829, which are incorporated herein by reference in their entireties. To be considered a "mixture", the polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and / or simultaneously. The weight ratio of polymeric to non-polymeric materials can be in the range of 95:5 to 5:95. The polymeric and non-polymeric materials can be made from the same precursor materials. In one example, the mixture of polymeric and non-polymeric materials consists essentially of polymeric silicon and inorganic silicon.

[0068] Devices made according to embodiments of the present invention can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into various electrical products or intermediate components. Such electrical products or intermediate components include display screens, lighting devices (such as discrete light source devices or lighting panels) that can be utilized by end-user product manufacturers. Such electronic component modules can optionally include driving electronics and / or power sources. Devices made 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. Disclosed are consumer products that include OLEDs that include compounds of the present disclosure in the organic layer of the OLED. Such consumer products include any type of product that includes one or more light sources and / or one or more display devices of some kind. Some examples of such consumer products include flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for indoor or outdoor illumination and / or signaling, heads-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, mobile phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, microdisplays (displays less than 2 inches diagonal), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls including multiple displays aligned together, theater or stadium screens, and signage. A variety of control mechanisms, including passive matrix and active matrix, can be used to control devices made according to the present invention. Many of the devices are intended for use within a temperature range that is comfortable for humans, such as 18 degrees Celsius to 30 degrees Celsius, and more preferably room temperature (20-25 degrees Celsius), but may also be used outside this temperature range, for example, between -40 degrees Celsius and +80 degrees Celsius.

[0069] The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may use the materials and structures. More generally, organic devices such as organic transistors may use the materials and structures.

[0070] In some embodiments, the OLED has one or more properties selected from the group consisting of flexible, rollable, foldable, stretchable, and bendable. In some embodiments, the OLED is transparent or semi-transparent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes.

[0071] In some embodiments, the OLED further comprises a layer comprising a delayed fluorescent emitter. In some embodiments, the OLED comprises an RGB pixel array or a white and color filter pixel array. In some embodiments, the OLED is a mobile device, a handheld device, or a wearable device. In some embodiments, the OLED is a display panel having a diagonal of less than 10 inches or an area of ​​less than 50 square inches. In some embodiments, the OLED is a display panel having a diagonal of at least 10 inches or an area of ​​at least 50 square inches. In some embodiments, the OLED is a lighting panel.

[0072] In some embodiments of the luminescent region, the luminescent region further comprises a host.

[0073] In some embodiments, the compound can be an emissive dopant. In some embodiments, the compound can generate luminescence via phosphorescence, fluorescence, thermally activated delayed fluorescence, or TADF (also known as E-type delayed fluorescence), triplet-triplet annihilation, or a combination of these processes.

[0074] The OLEDs disclosed herein can be incorporated into one or more of a consumer product, an electronic component module, and a lighting panel. The organic layer can be an emissive layer, and in some embodiments, the compound can be an emissive dopant, and in other embodiments, the compound can be a non-emissive dopant.

[0075] The organic layer may also include a host. In some embodiments, two or more hosts are preferred. In some embodiments, the host used may be a) a bipolar material, b) an electron transport material, c) a hole transport material, or d) a wide band gap material with little charge transport role. In some embodiments, the host may include a metal complex. The host may be an inorganic compound. Combination with other materials

[0076] The materials described herein as useful for a particular layer in an organic light-emitting device can be used in combination with a wide variety of other materials present in the device.For example, the emissive dopants disclosed herein can be used in 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 referenced below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and those skilled in the art can easily consult the literature to identify other materials that may be useful in combination.

[0077] A variety of materials may be used for the various emissive and non-emissive layers and arrangements disclosed herein. Examples of suitable materials are disclosed in U.S. Patent Application Publication No. 2017 / 0229663, which is incorporated by reference in its entirety. Conductive dopants:

[0078] The charge transport layer is doped with a conductive dopant to significantly change the density of charge carriers and therefore its conductivity. The conductivity can be increased by creating charge carriers in the matrix material or, depending on the type of dopant, a change in the Fermi level of the semiconductor can also be achieved. The hole transport layer can be doped with a p-type conductive dopant and an n-type conductive dopant is used in the electron transport layer. HIL / HTL:

[0079] The hole injection / transport material used in the present invention is not particularly limited, and any compound that is usually used as a hole injection / transport material may be used. EBL:

[0080] Electron blocking layers (EBLs) can be used to reduce the number of electrons and / or excitons that leave the emissive layer. The presence of such a blocking layer in a device can result in significantly higher efficiency and / or longer lifetime compared to a similar device lacking a blocking layer. Blocking layers can also be used to confine emission to desired regions of an OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or a higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or a higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in the EBL contains the same molecule or the same functional group as one of the hosts described below. host:

[0081] The light-emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as a light-emitting material, and may contain a host material using the metal complex as a dopant material. The host material is not particularly limited, and any metal complex or organic compound may be used as long as the triplet energy of the host is greater than that of the dopant. Any host material may be used with any dopant as long as the triplet criteria are met. HBL:

[0082] A hole blocking layer (HBL) can 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 can result in significantly higher efficiency and / or longer lifetime compared to a similar device lacking a blocking layer. A blocking layer can also be used to confine emission to a desired region of an OLED. In some embodiments, the HBL material has a lower HOMO (further away from the vacuum level) and / or a higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further away from the vacuum level) and / or a higher triplet energy than one or more of the hosts closest to the HBL interface. ETL:

[0083] The electron transport layer (ETL) may include a material capable of transporting electrons. The electron transport layer may be intrinsic (undoped) or doped. Doping may be used to enhance conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound may be used as long as it is typically used to transport electrons. Charge Generation Layer (CGL)

[0084] In tandem or stacked OLEDs, the CGL plays an important role in performance and consists of n-doped and p-doped layers for the injection of electrons and holes, respectively. The electrons and holes are supplied from the CGL and electrodes. The consumed electrons and holes in the CGL are replenished by electrons and holes injected from the cathode and anode, respectively, after which the bipolar current gradually reaches a steady state. Typical CGL materials contain n-type and p-type conductive dopants used in the transport layers.

[0085] When the light-emitting layer is within a threshold distance of a plasmon-active material such as a metal cathode and / or anode (e.g., an electrode layer), outcoupling energy in the form of light from SPR (surface plasmon energy) modes can be used to provide an OLED that lasts longer at display luminance. The threshold distance can be the distance at which the total non-radiative decay rate constant is equal to the total radiative decay rate constant, as disclosed in U.S. Pat. No. 9,960,386, which is incorporated by reference in its entirety.

[0086] Embodiments of the disclosed subject matter can convert the energy stored in the SPR mode of a plasmonically active material into visible light via a nanopatch antenna.

[0087] As shown in Figures 3a-c, the nanopatch antenna can include a planar metal film (e.g., an electrode layer), a gap material (e.g., a dielectric material, etc.) disposed on the planar metal, and nanoparticles disposed on the gap material. Figure 3a illustrates a conventional nanopatch antenna that includes a gap layer between the nanoparticles and the metal layer with emitter molecules embedded therein. Figure 3b illustrates a nanopatch antenna according to an embodiment of the disclosed subject matter, where the emitter molecules in the emitter layer are disposed below the metal layer (i.e., not in the gap layer). Figure 3c illustrates another embodiment of the disclosed subject matter that includes a capping layer disposed over the nanoparticles. In some embodiments, the capping layer can include additional emitter molecules.

[0088] For example, as shown in FIG. 4a, the gap material can be organic (e.g., small molecule and / or polymeric materials), oxides, and / or other dielectric materials, including stacks, alloys, and / or mixtures of materials. That is, FIG. 4a shows a dielectric gap material with multiple layers. This configuration can provide a resonant plasmonic mode in the gap due to the high electric field strength generated in the gap medium. This large electric field can be used to increase the emissivity of a light emitter placed in the gap, known as the Purcell effect. The nanopatch antenna can radiate energy from this plasmonically active mode with up to 50% efficiency.

[0089] In an embodiment of the disclosed subject matter, as shown in FIG. 4b, the laminated gap layer includes two layers, including one thick layer that can be the main dielectric gap material and one thin layer that can act as a nanoparticle adhesion layer to increase nanoparticle density and / or reduce nanoparticle aggregation or clumping. For example, the polyelectrolyte layer (such as poly(styrenesulfonate) or poly(allylamine) hydrochloride) can carry electrostatic charges that can interact with the electrostatic charges on the nanoparticle coating (e.g., poly(vinylpyrrolidinone) used to coat silver nanoparticles and carrying negative electrostatic charges). While the sum of the thicknesses of these layers can determine the overall gap thickness, the thickness of the adhesion layer can be less than 5 nm and the thickness of the gap layer can be between 1 nm and 100 nm, more preferably between 1 nm and 50 nm.

[0090] Purcell factors on the order of 1000 can be achieved by disposing emitters in the nanopatch antenna gap, but Purcell factors on the order of 10 can be sufficient to enhance the stability of phosphorescent OLED emitters. It can be difficult to fabricate an entire OLED stack that maintains high internal quantum efficiency within a typical nanopatch antenna gap thickness, typically 2 nm to 15 nm, much less without using nanoparticles as one of the OLED electrodes. An embodiment of the disclosed subject matter can provide an arrangement in which the emitter is disposed under the planar metal rather than in the antenna gap, as shown in FIG. 3b. A variation of this arrangement can include an additional capping layer disposed on the nanoparticles that can contain additional emitter molecules, as shown in FIG. 3c. The capping layer can match the refractive index to the opposite side of the metal layer, thereby improving cross-coupling of SPR modes across the metal layer and into the nanopatch antenna gap.

[0091] As shown in the arrangement of Figures 3b-c, the light emitter can be arranged such that it is within a threshold distance of the planar metal, which then serves as one of the OLED contacts (i.e., either the cathode or anode). In one example, light emission can occur from the same side of the device as the nanoparticles, allowing this arrangement to accommodate both top and bottom emission geometries.

[0092] In this configuration, Purcell enhancement that stabilizes the emitter may result from proximity to a planar metal contact (e.g., an electrode layer). Figure 5a shows an embodiment of the disclosed subject matter in which emitter molecules in an emitter layer disposed below a metal layer (i.e., not in a gap layer) can be combined with a conventional OLED stack in which the emitter layer is within threshold to a metal cathode, with a subsequent nanopatch antenna geometry above the cathode emitting from the side with the nanoparticles.

[0093] In a variation of this configuration, the metal contacts or the entire device stack can be corrugated to enhance outcoupling of the SPR mode, as shown in FIG. 5b. This configuration reduces the maximum achievable Purcell enhancement below that achieved by placing the emitter in the gap, but a Purcell factor of ≧10 can be achieved. By placing the emitter within a threshold distance of the metal (e.g., electrode layer), the emitter energy can be coupled to the SPR mode guided along the surface of the metal. As shown in FIG. 6, in non-opaque metal films (e.g., Ag<200 nm thick, Al and Au<100 nm thick), this plasmon mode can couple to the other side of the metal and transfer the energy to the gap plasmon mode, which can be converted to light via the nanopatch antenna.

[0094] That is, Figure 6 shows that energy is funneled through the SPR mode and radiated as light. The energy of the excited emitter molecules is quenched in the cathode into the SPR mode, which then couples to the nanopatch antenna gap mode, resulting in an electric field that can radiate the energy as light.

[0095] When nanocubes are used as the nanoparticles in a nanopatch antenna, the electric field strength can be highest at the corners of the nanocubes, as shown in the simulation of Figure 7. That is, Figure 7 shows the simulation of the electric field strengths Ex and Ey in the x and y directions, respectively, in the gap layer of a nanopatch antenna utilizing nanocubes as nanoparticles. Figure 7 shows that light outcoupled into the far field occurs from the edges of the nanoparticles.

[0096] Tuning the resonance of the nanopatch antenna to match the emission spectrum of the phosphor allows for efficient conversion of plasmonic energy to light. Such tuning can be achieved by any of a number of methods, including, but not limited to, changing the size of the nanoparticles, changing the shape of the nanoparticles (typical shapes are cubes, spheres, rods, disks, plates, stars, and modifications of these shapes with additional faces), changing the material of the nanoparticles (metal or dielectric), tuning the gap thickness, changing the refractive index of the gap or the surrounding environment (e.g., by depositing an additional capping layer on the nanoparticles), and changing the planar metal thickness or metal type (e.g., the metal can be Ag, Al, and / or Au in the thickness range of 5 nm to 100 nm). Regular arrays of nanoparticles can be used to improve outcoupling efficiency and / or tune the resonant wavelength.

[0097] The planar metal film (e.g., electrode layer) and / or metal nanoparticles can be pure or alloyed, preferably Ag, Al, Ag-Al alloy, or Au. Some other materials include, but are not limited to, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr. Furthermore, the nanoparticles can be entirely composed of dielectric material, can be alloys of metals and dielectric materials, or can have a core of one type of material coated with a shell of a different type of material.

[0098] The gap thickness (e.g., material thickness) is 0 nm to 150 nm, more preferably 0 nm to 50 nm. When the gap is 0 nm (i.e., there is no gap), the nanoparticles can be disposed on a planar metal (e.g., electrode layer) and can have a corrugated morphology for outcoupling the SPR energy. The size of the nanoparticles for scattering light in the visible part of the spectral range (e.g., 400 nm to 700 nm wavelength) can be 5 nm to 1000 nm, depending on the material and shape of the nanoparticles. The gap can be a dielectric material such as an organic or metal oxide with a refractive index of 1 to 5.

[0099] A 0 nm gap can be achieved without the use of nanoparticles. In an exemplary device, as shown in FIG. 8, a planar metal film can be etched partially through the film thickness to form a corrugated top surface, while the bottom surface of the film can be planar. This can be accomplished, for example, by using focused ion beam milling. The corrugation can be done on the metal attached to the completed OLED device, or on a separate substrate on which the corrugated metal can be peeled off and attached to the OLED, or on a separate substrate on which the OLED can be grown.

[0100] In other embodiments of the disclosed subject matter, as shown in FIG. 9, the nanoparticles can be individually coated (e.g., by material) with a dielectric material that acts as part or all of the gap spacing. For example, the particles can be coated across the desired gap thickness, thereby reducing the gap layer to zero. In another example, a combination of the gap layer thickness and the nanoparticle coating can achieve the desired total spacer thickness. The nanoparticle coating can act as an adhesion layer to improve adhesion or increase the density of the nanoparticles to the layer on which they are deposited.

[0101] As shown in FIG. 10, the refractive index of the gap layer can affect the resonance of the nanopatch antenna, so the use of a gap material with a voltage-tunable refractive index can provide a way to tune the emission spectrum with a voltage applied between the metal cathode and the electrical contact layer underlying the nanoparticles. That is, FIG. 10 shows a schematic of an OLED combined with a nanopatch antenna utilizing a gap material with a voltage-tunable refractive index to select the wavelength of light emitted. In one example, zinc oxide doped with aluminum can be used as a voltage-tunable refractive index material, since the dielectric constant changes as the applied voltage changes the carrier concentration. In this case, a second insulating layer can be used in the gap to form the charge. In some embodiments, depending on the material properties of the voltage-tunable refractive index layer, the secondary insulating layer can be removed. This is useful when the OLED stack includes a white OLED, i.e., red, green, and blue emission, since the voltage-tunable nanopatch resonance acts as a color filter, selectively passing the desired colors. This effectively transforms the OLED into a three-terminal device by applying a voltage between the anode and cathode to operate the OLED, and a voltage applied between the cathode and an electrical contact layer underneath the nanoparticles to tune the nanopatch resonance and select the emission color.

[0102] That is, according to at least the embodiments shown in Figures 3a-10, a device can include a light emitting layer, a first electrode layer, a plurality of nanoparticles, and a material disposed between the first electrode layer and the plurality of nanoparticles. The first electrode layer of the device can have a thickness of 5 nm to 300 nm.

[0103] The device may include a second electrode layer and a substrate, the second electrode layer may be disposed on the substrate, and the light emitting layer may be disposed on the second electrode layer. At least one of the first electrode layer and the second electrode layer may be a metal, a semiconductor, and / or a transparent conductive oxide. The first electrode layer may be spaced from the light emitting layer by a predetermined threshold distance, the distance at which the total non-radiative decay rate constant is equal to the total radiative decay rate constant. The material of the device may include at least one of an organic material, an oxide, and / or a dielectric material. The material may have a refractive index between 1 and 5. The light emitting layer of the device may include a transport layer. The light emitting layer may be an organic layer having emitter molecules.

[0104] The light-emitting layer of the device can include at least one of a fluorescent material, a phosphorescent material, a thermally activated delayed fluorescence (TADF) material, a quantum dot material, a metal-organic framework, a covalent-organic framework, and / or a perovskite nanocrystal.

[0105] The device may include a nanopatch antenna, the resonance of which may be tuned by at least one of changing the size of the nanoparticles, changing the ratio of the sizes of the nanoparticles, changing the shape of the nanoparticles, changing the material of the nanoparticles, adjusting the thickness of the material, changing the refractive index of the material, changing the refractive index of an additional layer disposed on the nanoparticles, changing the thickness of the first electrode layer, and / or changing the material of the first electrode layer. The nanoparticles may be formed from at least one of Ag particles, Al particles, Au particles, a dielectric material, a semiconductor material, an alloy of metals, a mixture of dielectric materials, a stack of one or more materials, and a core of one material coated with a shell of a different material. At least one of the nanoparticles of the device may include an additional layer to provide lateral conduction between the nanoparticles. The nanoparticles may be coated with an oxide layer, the thickness of the oxide layer being selected to tune the plasmon resonance wavelength of the nanoparticles or the nanopatch antenna. The shape of the nanoparticles may be at least one of a cube, a sphere, an ellipsoid, a cylindrical three-dimensional object, a parallelepiped three-dimensional object, a rod-shaped three-dimensional object, a star-shaped three-dimensional object, a pyramidal three-dimensional object, and / or a multi-faceted three-dimensional object. At least one of the nanoparticles may have a size of 5 nm to 1000 nm.

[0106] As shown in FIG. 5b, the device can include a corrugated layer disposed on the substrate, where the second electrode layer, the light-emitting layer, the first electrode layer, and the material are correspondingly corrugated.

[0107] The material of the device can include a dielectric layer disposed on the first electrode layer and an electrical contact layer disposed on the dielectric layer. The material can include a voltage tunable refractive index material between the electrical contact layer and the first electrode layer. The voltage tunable refractive index material can be zinc oxide doped with aluminum. The material can include an insulating layer. The first electrode layer of the device can be spaced from the light emitting layer by a predetermined threshold distance. As noted above, the predetermined threshold distance can be the distance at which the total non-radiative decay rate constant is equal to the total radiative decay rate constant.

[0108] In some embodiments, the device can include an additional layer disposed on the plurality of nanoparticles. The additional layer can include one or more emitter molecules. The additional layer can match the refractive index below the first electrode layer. The additional layer can have a thickness of 1000 nm or less.

[0109] A nanopatch antenna (NPA) can include a planar metal film (e.g., an electrode layer), a gap material (e.g., a dielectric material, etc.) disposed on top of the metal planar film, and nanoparticles (e.g., as shown in FIG. 3a) disposed on top of the gap material. This configuration results in a resonant plasmonic mode due to the high electric field strength generated in the gap medium. This large electric field can be used to increase the emissivity of a light emitter disposed in the gap, known as the Purcell effect, which in turn stabilizes the emitter in a detrimental process that depends on the emitter being in an excited state. A nanopatch antenna can radiate energy from this plasmonically active mode with up to 50% efficiency. Previous NPA designs were typically optically pumped (e.g., by a laser).

[0110] In an embodiment of the disclosed subject matter, as shown in Figure 11, an OLED stack can be placed in the NPA gap and nanoparticles and planar metal can serve as electrical injection pathways into the device. Traditionally, OLEDs that are 5-20 nm thick were not expected to work due to extinction into non-radiative modes. However, the significant Purcell enhancement allows fast coupling of phosphorescence into radiative modes, out-competing the lossy processes normally present in 5-20 nm thick OLEDs.

[0111] Since typical NPA gap thicknesses are about 2 nm to about 15 nm, it may seem impossible to fabricate an entire OLED stack that maintains high internal quantum efficiency within the nanopatch antenna gap. The large electric field present in an NPA gap of this thickness may be able to increase the emissivity of an emitter placed in the gap by a factor of 1000. As noted above, a Purcell factor of about 10 may be sufficient to increase the stability of OLED emitters (e.g., the stability of phosphorescent OLEDs). In embodiments of the disclosed subject matter, some of the Purcell enhancement may be exchanged for a thicker NPA gap that is more suitable in OLED stacks with thicknesses of about 5 nm to about 100 nm.

[0112] Injecting charge through metal nanoparticles, typically about 5 nm to about 1000 nm in size, may seem infeasible. An embodiment of the disclosed subject matter provides a device to address this. FIG. 12a shows an indium tin oxide (ITO) coated glass substrate on which metal nanoparticles, typically Ag, Al, or Au, are dispersed. In one example device, these nanoparticles can be drop cast or spin cast from solution. In another example, the nanoparticles can be processed directly on the substrate via photolithography followed by metal liftoff. An OLED stack is deposited on top of the metal nanoparticles and covered with a metal electrode, typically Ag, Al, or Au. This can form a corrugated device structure, as shown in FIG. 12a.

[0113] In applications where corrugations are undesirable, the device shown in Figure 12b can be used. To form this device, nanoparticle features are etched into the ITO, but not completely through the ITO layer. In one example, the etching can be performed by a reactive ion etcher, based on the directional nature of the etching process.

[0114] As shown in Figure 13, a thickness of metal commensurate with the depth of the ITO etch can be deposited and a lift-off of the metal (Ag) on ​​the photoresist (PR) can be performed. This can result in metal nanoparticles (NP) that are flush with the top surface of the ITO. An OLED stack can then be grown on this planar substrate and with the planar metal deposited as the top contact to form the NPA OLED structure. Charge injection into the OLED can occur from either the nanoparticles or the ITO.

[0115] In Figures 12a-b, two individual NPAs are highlighted with dashed boxes. If the nanoparticles are far enough apart that there is no coupling between them, each NPA operates independently. In this case, the electric field (and therefore the Purcell enhancement) can be higher for emitter molecules located within an individual NPA than outside. This can result in some variation in the emitter rate spatially through the OLED's emissive layer, but because the metal contacts are in close proximity to all emitter molecules in the stack, all emitter molecules will sense an increased density of photon states and therefore experience Purcell enhancement. If the nanoparticles are formed in an array and coupling between the nanoparticles occurs, this can result in a hybrid, spatially delocalized mode that can reduce the variation in the Purcell enhancement. In some embodiments, the nanoparticles can be close enough that they form a hybrid mode. In other embodiments, the nanoparticles can not hybridize.

[0116] In some embodiments, the nanoparticles can be cubic, spherical, ellipsoidal, cylindrical, parallelepipedal, and / or rod-shaped. The nanoparticles can vary in size from 5 nm to 1000 nm, more preferably from 5 nm to 200 nm. The nanoparticles can be dielectric, semiconductor, or metallic.

[0117] The gap material can be a dielectric or a semiconductor and can have a refractive index between 1 and 15. The gap material can include at least one emissive material, which can be fluorescent, phosphorescent, thermally activated delayed fluorescence (TADF), or quantum dot. In some embodiments, there can be many emissive materials of one or more types. The gap can include a host material. The gap can include multiple layers of material or can be only one layer. In some embodiments, the gap material can include a mixture of materials. The gap can range in thickness from 0.1 nm to 100 nm.

[0118] The planar metal film can be pure or alloyed, preferably Ag, Al, Ag-Al alloy, or Au alloy. Some other materials include, but are not limited to, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr. The top surface of the planar film can be patterned with additional material. The top of the metal film can have additional material thereon, which can include light emitting elements including quantum dots.

[0119] That is, in the embodiment shown in Figures 11-12b, the device can include a light emitting layer, a first electrode layer, a plurality of nanoparticles, and a material disposed between the first electrode layer and the plurality of nanoparticles. The material of the device can include the light emitting layer. The plurality of nanoparticles and the first electrode layer can provide an electrical injection path to the device. The device can include a substrate and a second electrode layer, the first electrode layer can be non-planar, the second electrode layer can be disposed on the substrate, the plurality of nanoparticles can be disposed on the second electrode layer, the light emitting layer can be non-planar, can be included in the material, and can be disposed and conformed on the plurality of nanoparticles and the second electrode layer, and the first electrode layer can be disposed and conformed on the non-planar light emitting layer. At least one of the first electrode layer and the second electrode layer can be a metal, a semiconductor, and / or a transparent conductive oxide.

[0120] As shown in FIG. 13, the method includes disposing a first electrode layer on a substrate, disposing photoresist on the first electrode layer, etching the photoresist and at least a portion of the first electrode layer, depositing metal in the remaining portions of the photoresist to match a depth of the etched portions of the first electrode layer, removing the metal and the photoresist to form nanoparticles from the deposited metal that are flush with a surface of the first electrode layer, disposing an emissive layer on the first electrode layer and the nanoparticles, and disposing a second electrode layer on the emissive layer.

[0121] Embodiments of the disclosed subject matter provide improved organic light emitting diode (OLED) performance by using nanostructures having one or more of various geometries, shapes, materials, and / or lattice symmetries that can enhance the emission efficiency, increase surface plasmon polariton (SPP) mode outcoupling, improve device stability, and / or provide far-field radiation patterns.

[0122] To efficiently couple excited state energy to the plasmon mode, the emitter or layer can be placed within a threshold distance of structures and / or layers that increase the photon density state (as shown in Figures 14a-14f), which can then result in an enhancement of the emission rate, known as the Purcell effect, as described above. As described above, the threshold distance can be the distance at which the total non-radiative decay rate constant equals the total radiative decay rate constant.

[0123] The exemplary devices of Figures 14a-14f show variations of nanostructured cathodes (cross-sections) according to embodiments of the disclosed subject matter. These include nanoholes (which may also be referred to as nanostructures) that can be etched completely through the metal film (shown in Figures 14a and 14b), nanoholes that can be partially etched through the metal film (shown in Figures 14c and 14d), and nanoholes where some holes are etched completely through the metal film and others are partially etched (Figures 14e and 14f). Figures 14a-14f show variations where the nanostructured cathode is covered with a dielectric layer (shown in Figures 14a, 14c, and 14e) or where the nanostructured cathode does not have a dielectric layer (shown in Figures 14b, 14d, and 14f) in order to match the refractive index with that underneath the cathode in order to improve cross-coupling of surface plasmon modes across the thickness of the metal film. The profile of the holes (nanostructures), i.e., whether the edges and / or sidewalls of the holes can be perpendicular to the surface of the film or whether the sidewalls of the holes have a radius of curvature, can be used to tailor the properties of the nanostructure array.

[0124] The nanostructures can be made of metals, dielectrics, or some combination thereof. FIG. 15 shows some examples of various possible combinations according to embodiments of the disclosed subject matter. The use of composites (e.g., metals and dielectrics) can provide flexibility in the design of the device since the resonant frequencies of the localized modes can be tuned and / or selected depending on the composite used. For each of these materials, the localized electromagnetic modes can be tuned. Exemplary metals used include, but are not limited to, Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, and / or Ca, and can include stacks and / or alloys of these materials. Dielectrics used can include, but are not limited to, organic materials, titania, silicon dioxide, silicon nitride, aluminum oxide, zinc oxide, nickel oxide, germanium oxide, lithium fluoride, magnesium fluoride, and / or molybdenum oxide.

[0125] The localized electromagnetic resonance of a nanostructure or a portion of a nanostructure can be tuned by the shape of the nanostructure. The shape can include any cylindrical, spherical, and / or cubic shape, or any shape with single or multiple localized resonances, as shown in FIG. 16. The radius of curvature of the edges and / or corners in faceted nanostructures can be used to tune the resonant frequency of the nanostructure. Some examples of multiple localized resonance shapes can include ellipses and rectangles that support multiple modes at different frequencies caused by asymmetries in the nanostructure. For example, FIG. 16 shows how different lengths and / or widths of a rectangular nanostructure can result in two separate resonant frequencies. These multiple frequency nanostructures can provide enhanced outcoupling for multi-wavelength or white light emitting OLEDs.

[0126] That is, in the embodiment shown in Figures 14a-16, the device can include a light emitting layer, a first electrode layer, a plurality of nanoparticles, and a material disposed between the first electrode layer and the plurality of nanoparticles. The device can include a substrate and a second electrode layer, the material being a first dielectric layer and a second dielectric layer, the second electrode layer being disposed on the substrate, the light emitting layer being disposed on the second electrode layer, the first electrode layer being disposed on the light emitting layer, the first dielectric layer being disposed on the first electrode layer, the plurality of nanoparticles being disposed on the first dielectric layer, and the second dielectric layer being disposed on the plurality of nanoparticles and the first dielectric layer. At least one of the first electrode layer and the second electrode layer can be a metal, a semiconductor, and / or a transparent conductive oxide. The second electrode layer can be spaced from the light emitting layer by a predetermined threshold distance, the distance at which a total non-radiative decay rate constant is equal to a total radiative decay rate constant. The material may include at least one selected from the group consisting of an organic material, an oxide, and a dielectric material. The material may have a refractive index of 1 to 5. The light-emitting layer may include a transport layer. The light-emitting layer may be an organic layer having emitter molecules. The light-emitting layer may include at least one of a fluorescent material, a phosphorescent material, a thermally activated delayed fluorescence (TADF) material, a quantum dot material, a metal-organic framework, a covalent-organic framework, and a perovskite nanocrystal. The first electrode layer may have a thickness of 5 nm to 300 nm.

[0127] The device may include a nanopatch antenna, the resonance of which may be tuned by at least one of changing the size of the nanoparticles, changing the ratio of the sizes of the nanoparticles, changing the shape of the nanoparticles, changing the material of the nanoparticles, adjusting the thickness of the material, changing the refractive index of the material, changing the refractive index of an additional layer disposed on the nanoparticles, changing the thickness of the first electrode layer, and / or changing the material of the first electrode layer. The nanoparticles may be comprised of at least one of Ag particles, Al particles, Au particles, a dielectric material, a semiconductor material, an alloy of metals, a mixture of dielectric materials, a stack of one or more materials, and a core of one material coated with a shell of a different material. At least one of the nanoparticles of the device may include an additional layer to provide lateral conduction between the nanoparticles. The nanoparticles may be coated with an oxide layer, the thickness of the oxide layer being selected to tune the plasmon resonance wavelength of the nanoparticles or the nanopatch antenna. The shape of the nanoparticles may be at least one of a cube, a sphere, an ellipsoid, a cylindrical three-dimensional object, a parallelepiped three-dimensional object, a rod-shaped three-dimensional object, a star-shaped three-dimensional object, a pyramidal three-dimensional object, and / or a multi-faceted three-dimensional object. At least one of the nanoparticles may have a size of 5 nm to 1000 nm.

[0128] The device can include a substrate and a second electrode layer, the material can be a first dielectric layer, the second electrode layer can be disposed on the substrate, the light emitting layer can be disposed on the second electrode layer, the first electrode layer can be disposed on the light emitting layer, the first dielectric layer can be disposed on the first electrode layer, and the plurality of nanoparticles can be disposed on the first dielectric layer. At least one of the first electrode layer and the second electrode layer can be a metal, a semiconductor, and / or a transparent conductive oxide.

[0129] The device can include a substrate and a second electrode layer, the material is a first dielectric layer and a second dielectric layer, the nanoparticles can be disposed in the second dielectric layer, the second dielectric layer and the nanoparticles can be disposed on the substrate, the first dielectric layer can be disposed on the second dielectric layer and the nanoparticles, the first electrode layer can be disposed on the first dielectric layer, the light emitting layer can be disposed on the first electrode, and the second electrode can be disposed on the light emitting layer. At least one of the first electrode layer and the second electrode layer can be a metal, a semiconductor, and / or a transparent conductive oxide.

[0130] The device can include a substrate and a second electrode layer, the material can be a first dielectric layer and a second dielectric layer, the first electrode layer can be disposed on the substrate, the first dielectric layer can be disposed on the first electrode layer, the plurality of nanoparticles can be disposed on the first dielectric layer, the second dielectric layer can be disposed on the plurality of nanoparticles and the first dielectric layer, the light emitting layer can be disposed on the second dielectric layer, and the second electrode layer can be disposed on the light emitting layer.

[0131] The device can include a substrate and a second electrode layer, the material being a first dielectric layer and a second dielectric layer, the second electrode layer can be disposed on the substrate, the light emitting layer can be disposed on the second electrode layer, the plurality of nanoparticles can be disposed on the light emitting layer, the second dielectric layer can be disposed on the plurality of nanoparticles and the light emitting layer, the first dielectric layer can be disposed on the second dielectric layer, and the first electrode layer can be disposed on the first dielectric layer. At least one of the first electrode layer and the second electrode layer can be a metal, a semiconductor, and / or a transparent conductive oxide.

[0132] The material of the device may include at least one of an organic material, an oxide, and / or a dielectric material. The material may include a first layer and a second layer, the first layer being thicker than the second layer. The first layer may be a dielectric material and the second layer may be a nanoparticle adhesion layer. The thickness of the first layer may be between 1 nm and 100 nm, and the thickness of the second layer may be less than 5 nm. The material may have a thickness of 1000 nm or less. The material of the device may have a refractive index between 1 and 5. The material may include at least a portion of a coating disposed on the plurality of nanoparticles. The coating disposed on the plurality of nanoparticles may be a dielectric coating.

[0133] The device may include a second electrode layer, and the light-emitting layer may be included in an organic light-emitting diode (OLED), the OLED being disposed between the first electrode layer and the second electrode layer. At least one of the first electrode layer and the second electrode layer may be a metal, a semiconductor, and / or a transparent conductive oxide. The light-emitting layer may include a transport layer. The light-emitting layer may be an organic layer having emitter molecules. The light-emitting layer may include at least one of a fluorescent material, a phosphorescent material, a thermally activated delayed fluorescence (TADF) material, a quantum dot material, a metal-organic framework, a covalent-organic framework, and / or a perovskite nanocrystal.

[0134] The first electrode layer of the device may be spaced from the light emitting layer by a predetermined threshold distance, the threshold distance being the distance at which the total non-radiative decay rate constant is equal to the total radiative decay rate constant. The first electrode layer may comprise at least one of Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, and / or Ca. The first electrode layer may be patterned with additional materials. The additional materials may comprise fluorescent emitters, phosphorescent emitters, quantum dots, metal-organic frameworks, covalent-organic frameworks, and / or perovskite nanocrystal light emitting components. The first electrode layer may have a thickness of 5 nm to 300 nm. The first electrode layer of the device may have at least one non-planar surface.

[0135] The device can include a nanopatch antenna, and the resonance of the nanopatch antenna can be tuned by at least one of changing a size of the nanoparticles, changing a size ratio of the nanoparticles, changing a shape of the nanoparticles, changing a material of the nanoparticles, adjusting a thickness of the material, changing a refractive index of the material, changing a refractive index of an additional layer disposed on the nanoparticles, changing a thickness of the first electrode layer, and / or changing a material of the first electrode layer.

[0136] The nanoparticles of the device may be formed from at least one of Ag particles, Al particles, Au particles, dielectric materials, semiconductor materials, alloys of metals, mixtures of dielectric materials, stacks of one or more materials, and / or a core of one type of material coated with a shell of a different type of material.

[0137] At least one of the nanoparticles of the device may include an additional layer to provide lateral conduction between the nanoparticles. The nanoparticles may be coated with an oxide layer, the thickness of the oxide layer being selected to tune the plasmon resonance wavelength of the nanoparticles or nanopatch antenna. The nanoparticles may be colloidally synthesized nanoparticles formed from a solution. The shape of the nanoparticles may be at least one of a cube, a sphere, an ellipsoid, a cylindrical three-dimensional object, a parallelepiped three-dimensional object, a rod-shaped three-dimensional object, a star-shaped three-dimensional object, a pyramidal three-dimensional object, and a multi-faceted three-dimensional object. A size of at least one of the nanoparticles may be between 5 nm and 1000 nm. A size of at least one of the nanoparticles may be between 5 nm and 200 nm. A size of at least one of the nanoparticles may be between 5 nm and 100 nm.

[0138] The device can include a substrate and a second electrode layer, the second electrode layer can be disposed on the substrate, the nanoparticles can be disposed in the second electrode layer, the light emitting layer can be included in the material and can be disposed on the second electrode layer including the plurality of nanoparticles, and the first electrode layer can be disposed on the light emitting layer. At least one of the first electrode layer and the second electrode layer can be a metal, a semiconductor, and / or a transparent conductive oxide.

[0139] Devices made according to embodiments of the disclosed subject matter can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into various electrical products or intermediate components. Such electrical products or intermediate components include display screens, lighting devices (such as discrete light source devices or lighting panels) that can be utilized by end-user product manufacturers. Such electronic component modules can optionally include driving electronics and / or power sources. Devices made 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. Disclosed are consumer products that include OLEDs that include compounds of the present disclosure in the organic layer of the OLED. Such consumer products include any type of product that includes one or more light sources and / or one or more display devices of some kind. Some examples of such consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for indoor or outdoor illumination and / or signaling, heads-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, mobile phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, microdisplays (displays less than 2 inches diagonal), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls including multiple displays aligned together, theater or stadium screens, phototherapy devices, and signage. A variety of control mechanisms, including passive matrix and active matrix, can be used to control devices made according to the present invention. Many of the devices are intended for use within a temperature range that is comfortable for humans, such as 18 degrees Celsius to 30 degrees Celsius, and more preferably room temperature (20-25 degrees Celsius), but may also be used outside this temperature range, for example, from -40 degrees Celsius to +80 degrees Celsius.

[0140] The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may use the materials and structures. More generally, organic devices such as organic transistors may use the materials and structures.

[0141] The terms "halo," "halogen," or "halide" are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

[0142] The term "acyl" refers to a substituted carbonyl group (C(O)--Rs).

[0143] The term "ester" refers to a substituted oxycarbonyl (-OC(O)-Rs or -C(O)-O-Rs) group.

[0144] The term "ether" refers to the group --ORs.

[0145] The terms "sulfanyl" or "thioether" are used interchangeably and refer to the group --SR.sub.s.

[0146] The term "sulfinyl" refers to the group -S(O)-Rs.

[0147] The term "sulfonyl" refers to the group -SO2-Rs.

[0148] The term "phosphino" refers to the group -P(Rs)3, where each Rs can be the same or different.

[0149] The term "silyl" refers to the group -Si(Rs)3, where each Rs can be the same or different.

[0150] In each of the above, Rs can be hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. Preferred Rs are selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0151] The term "alkyl" refers to and includes both straight and branched chain alkyl groups. Preferred alkyl groups contain from 1 to 15 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, and 2,2-dimethylpropyl. Additionally, the alkyl groups are optionally substituted.

[0152] The term "cycloalkyl" refers to and includes monocyclic, polycyclic, and spiroalkyl groups. Preferred cycloalkyl groups are those containing from 3 to 12 ring carbon atoms and include cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, and the like. Additionally, the cycloalkyl groups are optionally substituted.

[0153] The term "heteroalkyl" or "heterocycloalkyl" refers to an alkyl or cycloalkyl group, respectively, having at least one carbon atom replaced by a heteroatom. Optionally, at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Furthermore, said heteroalkyl group or said heterocycloalkyl group is optionally substituted.

[0154] The term "alkenyl" refers to and includes both straight-chain and branched-chain alkene groups. An alkenyl group is essentially an alkyl group containing at least one carbon-carbon double bond in the alkyl chain. A cycloalkenyl group is essentially a cycloalkyl group containing at least one carbon-carbon double bond in the cycloalkyl ring. The term "heteroalkenyl" as used herein refers to an alkenyl group having at least one carbon atom replaced by a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Preferred alkenyl, cycloalkenyl, or heteroalkenyl groups are those containing 2 to 15 carbon atoms. Furthermore, the alkenyl, cycloalkenyl, or heteroalkenyl groups are optionally substituted.

[0155] The term "alkynyl" refers to and includes both straight and branched chain alkyne groups. Preferred alkynyl groups are those containing from 2 to 15 carbon atoms. Furthermore, said alkynyl groups are optionally substituted.

[0156] The terms "aralkyl" and "arylalkyl" are used interchangeably and refer to an alkyl group substituted with an aryl group, said aralkyl group being optionally substituted.

[0157] The term "heterocyclic group" refers to and includes aromatic and non-aromatic cyclic groups containing at least one heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Heteroaromatic cyclic groups may be used interchangeably with heteroaryl. Preferred hetero non-aromatic cyclic groups are those containing 3-7 ring atoms and contain at least one heteroatom, including cyclic amines such as morpholino, piperidino, pyrrolidino, and cyclic ethers / thioethers, such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and the like. Furthermore, the heterocyclic groups may be optionally substituted.

[0158] The term "aryl" refers to and includes both monocyclic aromatic hydrocarbyl groups and polycyclic aromatic ring systems. A polycyclic ring can have two or more rings with two carbons shared between two adjacent rings (the rings being "fused"), at least one of the rings being an aromatic hydrocarbyl group, for example, the other rings can be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Preferred aryl groups are those containing 6 to 30 carbon atoms, preferably those containing 6 to 20 carbon atoms, and more preferably those containing 6 to 12 carbon atoms. Aryl groups having 6 carbons, 10 carbons, or 12 carbons are particularly preferred. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, with phenyl, biphenyl, triphenyl, triphenylene, fluorene, and naphthalene being preferred. Furthermore, the aryl groups are optionally substituted.

[0159] The term "heteroaryl" refers to and includes both monocyclic aromatic groups and polycyclic aromatic ring systems containing at least one heteroatom. Heteroatoms include, but are not limited to, O, S, N, P, B, Si, and Se. In many instances, O, S, or N are the preferred heteroatoms. Heteromonocyclic aromatic systems are preferably monocyclic rings having 5 or 6 ring atoms, and the rings can have 1 to 6 heteroatoms. Heteropolycyclic ring systems can have two or more rings in which two atoms are common to two adjacent rings (the rings are "fused"), and at least one of the rings is heteroaryl, e.g., the other rings can be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Heteropolycyclic aromatic ring systems can have 1 to 6 heteroatoms per ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing 3 to 30 carbon atoms, preferably those containing 3 to 20 carbon atoms, and more preferably those containing 3 to 12 carbon atoms.Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benziso ... Examples of heteroaryl groups include benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, with dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and aza analogs thereof being preferred. Additionally, the heteroaryl groups are optionally substituted.

[0160] Of the aryl and heteroaryl groups listed above, the triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, and benzimidazole groups, and their respective aza analogues, are of particular interest.

[0161] As used herein, the terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclic, aryl, and heteroaryl are independently unsubstituted or independently substituted with one or more common substituents.

[0162] In many instances, the typical substituents are selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0163] In some instances, preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.

[0164] In some instances, preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, aryl, heteroaryl, sulfanyl, and combinations thereof.

[0165] In yet other instances, more preferred common substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0166] The terms "substituted" and "substitution" refer to a substituent other than H attached to the relevant position (e.g., carbon or nitrogen). For example, if R1 represents monosubstitution, then one R1 must be other than H (i.e., substituted). Similarly, if R1 represents disubstitution, then two of R1 must be other than H. Similarly, if R1 represents no substitution, then R1 can be hydrogen at the available valence of a ring atom, as in the case of carbon atoms in benzene and nitrogen atoms in pyrrole, or simply nothing in the case of ring atoms with fully filled valences (e.g., nitrogen in pyridine). The maximum number of substitutions possible in a ring structure depends on the total number of available valences at the ring atoms.

[0167] As used herein, "combinations thereof" refers to one or more members of the applicable list being combined to form a known or chemically stable configuration that one of skill in the art can conceive from the applicable list. For example, alkyl and deuterium can be combined to form a partially or fully deuterated alkyl group; halogen and alkyl can be combined to form a halogenated alkyl substituent; halogen, alkyl, and aryl can be combined to form a halogenated aryl alkyl. In one example, the term substituted includes combinations of 2-4 of the listed groups. In another example, the term substituted includes combinations of 2-3 groups. In yet another example, the term substituted includes combinations of 2 groups. Preferred combinations of substituents include those that contain up to 50 atoms that are not hydrogen or deuterium, or those that contain up to 40 atoms that are not hydrogen or deuterium, or those that contain up to 30 atoms that are not hydrogen or deuterium. In many examples, preferred combinations of substituents include up to 20 atoms that are not hydrogen or deuterium.

[0168] The designation "aza" in the fragments described herein, such as aza-dibenzofuran, aza-dibenzothiophene, etc., means that one or more of the CH groups in each fragment can be replaced by a nitrogen atom, for example, but not by way of limitation, azatriphenylene includes both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. One of skill in the art can easily imagine other nitrogen analogs of the above-mentioned aza derivatives, and all such analogs are intended to be encompassed by the terms described herein.

[0169] As used herein, "deuterium" refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. Pat. No. 8,557,400, International Publication No. WO 2006 / 095951, and U.S. Patent Application Publication No. 2011 / 0037057, the contents of which are incorporated by reference in their entirety, describe the preparation of deuterium-substituted organometallic complexes. Further reference is made to Tetrahedron 2015, 71, 1425-30 (Ming Yan et al.) and Angew. Chem. Int. Ed. (Reviews) 2007, 46, 7744-65 (Atzrodt et al.), the contents of which are incorporated by reference in their entirety, which describe efficient routes for the deuteration of methylene hydrogens in benzylamines and the replacement of aromatic ring hydrogens with deuterium, respectively.

[0170] It is understood that when a molecular fragment is described as being a substituent or attached to another moiety, the name may be described as being the fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuryl) or the entire molecule (e.g., benzene, naphthalene, dibenzofuran). Different designations of the substituents or attached fragments are considered equivalent herein.

[0171] In some cases, the adjacent substituents of a pair can be optionally bonded or fused to form a ring. Preferred rings are 5-, 6-, or 7-membered carbocyclic or heterocyclic rings, including both cases where the portion of the ring formed by the pair of substituents is saturated and cases where the portion of the ring formed by the pair of substituents is unsaturated. As used herein, "adjacent" means that the two related substituents can be on the same ring adjacent to each other, or on the two adjacent rings with the two nearest available substitutable positions, such as 2- and 2'-positions in biphenyl and 1- and 8-positions in naphthalene, as long as a stable fused ring system can be formed.

[0172] In some embodiments, the OLED has one or more properties selected from the group consisting of flexible, rollable, foldable, stretchable, and bendable. In some embodiments, the OLED is transparent or semi-transparent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes.

[0173] In some embodiments, the OLED further comprises a layer comprising a delayed fluorescent emitter. In some embodiments, the OLED comprises an RGB pixel array or a white and color filter pixel array. In some embodiments, the OLED is a mobile device, a handheld device, or a wearable device. In some embodiments, the OLED is a display panel having a diagonal of less than 10 inches or an area of ​​less than 50 square inches. In some embodiments, the OLED is a display panel having a diagonal of at least 10 inches or an area of ​​at least 50 square inches. In some embodiments, the OLED is a lighting panel.

[0174] In some embodiments, the emissive dopant can generate emission via phosphorescence, fluorescence, thermally activated delayed fluorescence, or TADF (also called E-type delayed fluorescence; see, e.g., U.S. Patent Application Publication No. 15 / 700,352, which is incorporated by reference in its entirety), triplet-triplet annihilation, or a combination of these processes. In some embodiments, the emissive dopant can be a racemic mixture or can be enriched in one enantiomer.

[0175] In some embodiments, the organic layer may include a phosphorescent sensitizer in an OLED, and one or more layers in the OLED may include an acceptor in the form of one or more fluorescent and / or delayed fluorescent emitters. In some embodiments, the sensitizer may be one component of an exciplex. As a phosphorescent sensitizer, the compound must be capable of energy transfer to the acceptor, which releases energy or further transfers energy to the final emitter. The acceptor concentration may range from 0.001% to 100%. The acceptor may be in the same layer as the phosphorescent sensitizer, or in one or more different layers. In some embodiments, the acceptor is a TADF emitter. In some embodiments, the acceptor is a fluorescent emitter. In some embodiments, the emission may come from any or all of the sensitizer, the acceptor, and the final emitter.

[0176] The OLEDs disclosed herein can be incorporated into one or more of a consumer product, an electronic component module, and a lighting panel. The organic layer can be an emissive layer, and in some embodiments, the compound can be an emissive dopant, and in other embodiments, the compound can be a non-emissive dopant.

[0177] The organic layer may also include a host. In some embodiments, two or more hosts are preferred. In some embodiments, the host used may be a) a bipolar material, b) an electron transport material, c) a hole transport material, or d) a wide band gap material with little charge transport role. In some embodiments, the host may include a metal complex. The host may be a triphenylene containing benzo-fused thiophene or benzo-fused furan. Any substituents in the host may be independently selected from the group consisting of CnH2n+1, OCnH2n+1, OAr1, N(CnH2n+1)2, N(Ar1)(Ar2), CH=CH-CnH2n+1, C≡C-CnH2n+1, Ar1, Ar1-Ar2, and CnH2n-Ar1, or the host is unsubstituted. In the above substituents, n can range from 1 to 10, and Ar1 and Ar2 can be independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof. The host can be an inorganic compound, such as Zn-containing inorganic materials, such as ZnS.

[0178] The host may be a compound containing at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene. The host may include a metal complex. The host may be a specific compound selected from the group consisting of, but is not limited to, the following: [ka] [ka]

[0179] More information on possible hosts is provided below. Combination with other materials

[0180] The OLEDs disclosed herein can be incorporated. The materials described herein as useful for a particular layer in an organic light-emitting device can be used in combination with a wide variety of other materials present in the device. For example, the emissive dopants disclosed herein can be used in 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 referenced below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and those skilled in the art can easily consult the literature to identify other materials that may be useful in combination. Conductive dopants:

[0181] The charge transport layer is doped with a conductive dopant to significantly change the density of charge carriers and therefore its conductivity. The conductivity can be increased by creating charge carriers in the matrix material or, depending on the type of dopant, a change in the Fermi level of the semiconductor can also be achieved. The hole transport layer can be doped with a p-type conductive dopant and an n-type conductive dopant is used in the electron transport layer. HIL / HTL:

[0182] The hole injection / transport material 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 injection / transport material.Examples of materials include, but are not limited to, phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indolocarbazole derivatives; polymers containing fluorocarbons; polymers with conductive dopants; conductive polymers such as PEDOT / PSS; self-assembly monomers derived from compounds such as phosphonic acid and silane derivatives; metal oxide derivatives such as MoOx; p-type semiconductor organic compounds such as 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile; metal complexes, and crosslinkable compounds.

[0183] Examples of aromatic amine derivatives used in the HIL or HTL include, but are not limited to, the following general structure: [ka] Each of Ar1 to Ar9 is a group consisting of aromatic hydrocarbon ring compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridyl indole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, and aromatic heterocyclic compounds such as 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 aromatic hydrocarbon ring groups and aromatic heterocyclic groups, which may be of the same or different types and have 2 to 10 cyclic structural units bonded to each other directly or via at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an aliphatic cyclic group. Each Ar can be unsubstituted or substituted with substituents selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0184] In one embodiment, Ar1 to Ar9 are [ka] are independently selected from the group consisting of: In the formula, k is an integer from 1 to 20; X101 to X108 are C (including CH) or N; Z101 is NAr1, O, or S; and Ar1 has the same groups as defined above.

[0185] Examples of metal complexes used in the HIL or HTL include, but are not limited to, those of the general formula: [ka] wherein Met is a metal that may have an atomic weight greater than 40; (Y101-Y102) is a bidentate ligand, where Y101 and Y102 are independently selected from C, N, O, P, and S; L101 is an ancillary ligand; k' is an integer value from 1 to the maximum number of ligands that may be bound to the metal; and k'+k'' is the maximum number of ligands that may be bound to the metal.

[0186] In one embodiment, (Y101-Y102) is a 2-phenylpyridine derivative. In another embodiment, (Y101-Y102) is a carbene ligand. In another embodiment, Met is selected from Ir, Pt, Os, and Zn. In a further embodiment, the metal complex has a minimum oxidation potential in solution of less than about 0.6 V relative to the Fc+ / Fc couple. EBL:

[0187] Electron blocking layers (EBLs) can be used to reduce the number of electrons and / or excitons that leave the emissive layer. The presence of such a blocking layer in a device can result in significantly higher efficiency and / or longer lifetime compared to a similar device lacking a blocking layer. Blocking layers can also be used to confine emission to desired regions of an OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or a higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or a higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in the EBL contains the same molecule or the same functional group used as one of the hosts described below. host:

[0188] The light-emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as a light-emitting material, and may contain a host material using the metal complex as a dopant material. The host material is not particularly limited, and any metal complex or organic compound may be used as long as the triplet energy of the host is greater than that of the dopant. Any host material may be used with any dopant as long as the triplet criteria are met.

[0189] Examples of metal complexes used as host materials preferably have the general formula: [ka] 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 another ligand; k' is an integer value from 1 to the maximum number of ligands that may be bound to the metal; and k'+k'' is the maximum number of ligands that may be bound to the metal.

[0190] In one embodiment, the metal complex is a complex: [ka] where (ON) is a bidentate ligand with the metal coordinated to atoms O and N.

[0191] In another embodiment, Met is selected from Ir and Pt. In a further embodiment, (Y103-Y104) is a carbene ligand.

[0192] Other organic compounds include the group consisting of aromatic hydrocarbon ring compounds such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridyl indole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoline, and aromatic heterocyclic compounds such as xazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine; and aromatic hydrocarbon ring groups and aromatic heterocyclic groups, which may be of the same or different types and have 2 to 10 cyclic structural units bonded to each other directly or via at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an aliphatic cyclic group. Each option within each group can be unsubstituted or substituted with a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0193] In one embodiment, the host compound contains at least one of the following groups in the molecule: [ka] [ka] In the formula, R101 is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when it is aryl or heteroaryl, it has the same definition as that of Ar mentioned above. k is an integer from 0 to 20 or 1 to 20. X101 to X108 are independently selected from C (including CH) or N. Z101 and Z102 are independently selected from NR101, O, or S. Illuminant:

[0194] One or more emitter dopants can be used with the compounds of the present disclosure. Examples of the emitter dopants are not particularly limited, and any compound can be used as long as the compound is typically used as an emitter material. Examples of suitable emitter materials include, but are not limited to, compounds that can generate luminescence 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. HBL:

[0195] A hole blocking layer (HBL) can 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 can result in significantly higher efficiency and / or longer lifetime compared to a similar device lacking a blocking layer. A blocking layer can also be used to confine emission to a desired region of an OLED. In some embodiments, the HBL material has a lower HOMO (further away from the vacuum level) and / or a higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further away from the vacuum level) and / or a higher triplet energy than one or more of the hosts closest to the HBL interface.

[0196] In one embodiment, the compounds used in the HBL contain the same molecules or the same functional groups as those used in the hosts described above.

[0197] In another embodiment, the compound used in the HBL comprises at least one of the following groups in the molecule: [ka] where k is an integer from 1 to 20; L101 is another ligand, and k' is an integer from 1 to 3. ETL:

[0198] The electron transport layer (ETL) may include a material capable of transporting electrons. The electron transport layer may be intrinsic (undoped) or doped. Doping may be used to enhance conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound may be used as long as it is typically used to transport electrons.

[0199] In one embodiment, the compound used in the ETL contains at least one of the following groups in the molecule: [ka] [ka] In the formula, R101 is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when it is aryl or heteroaryl, it has the same definition as that of Ar mentioned above. Ar1 to Ar3 have the same definition as that of Ar mentioned above. k is an integer from 1 to 20. X101 to X108 are selected from C (including CH) or N.

[0200] In another embodiment, the metal complex used in the ETL comprises, but is not limited to, the following general formula: [ka] where (ON) or (NN) is a bidentate ligand with the metal coordinated to atoms O, N or N,N; L101 is another ligand; and k' is an integer value from 1 to the maximum number of ligands that may be bound to the metal. Charge Generation Layer (CGL)

[0201] In tandem or stacked OLEDs, the CGL plays an important role in performance and consists of n-doped and p-doped layers for the injection of electrons and holes, respectively. The electrons and holes are supplied from the CGL and electrodes. The consumed electrons and holes in the CGL are replenished by electrons and holes injected from the cathode and anode, respectively, after which the bipolar current gradually reaches a steady state. Typical CGL materials contain n-type and p-type conductive dopants used in the transport layers.

[0202] In any of the above-mentioned compounds used in each layer of an OLED device, the hydrogen atoms may be partially or fully deuterated. Thus, any of the specifically mentioned substituents, such as but not limited to methyl, phenyl, pyridyl, etc., can be their non-deuterated, partially deuterated, and fully deuterated versions. Similarly, the classes of substituents, such as but not limited to alkyl, aryl, cycloalkyl, heteroaryl, etc., can be their non-deuterated, partially deuterated, and fully deuterated versions.

[0203] It is understood that the various embodiments described herein are merely exemplary and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein can be substituted with other materials and structures without departing from the spirit of the invention. Thus, the invention as claimed may include variations from the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It is understood that the various theories of why the invention works are not intended to be limiting. [Prior art documents] [Patent documents]

[0204] [Patent Document 1] U.S. Pat. No. 5,844,363 [Patent Document 2] U.S. Patent No. 6,303,238 [Patent Document 3] U.S. Patent No. 5,707,745 [Patent Document 4] U.S. Patent No. 7,279,704 [Explanation of symbols]

[0205] 100 Organic Light Emitting Device 110 Substrate 115 Anode 120 Hole injection layer 125 Hole transport layer 130 Electron Blocking Layer 135 Light-emitting layer 140 Hole Blocking Layer 145 Electron transport layer 150 Electron injection layer 155 Protective layer 160 Cathode 162 First conductive layer 164 Second conductive layer 170 Barrier Layer 200 Inverted OLED, device 210 Substrate 215 Cathode 220 Light-emitting layer 225 Hole transport layer 230 Anode

Claims

1. A substrate; a first electrode layer disposed above the substrate; a light emitting layer above the first electrode layer; a second electrode layer above the light emitting layer; a plurality of nanoparticles above the second electrode layer, the plurality of nanoparticles being formed from at least one selected from the group consisting of Ag particles, Al particles, Au particles, a dielectric material, a semiconductor material, an alloy of metals, a mixture of dielectric materials, a stack of one or more materials, and a core of one type of material coated with a shell of a different type of material; further comprising a dielectric layer disposed above the second electrode layer and below the plurality of nanoparticles; However, the device does not include those in which the dielectric layer is less than 50 nm thick.

2. 10. The device of claim 1, wherein the second electrode layer is spaced from the light emitting layer by a predetermined threshold distance, the distance at which a total non-radiative decay rate constant equals a total radiative decay rate constant.

3. 10. The device of claim 1, wherein the light-emitting layer comprises at least one selected from the group consisting of a fluorescent material, a phosphorescent material, a thermally activated delayed fluorescent (TADF) material, a quantum dot material, a metal-organic framework, a covalent organic framework, and a perovskite nanocrystal.

4. The device of claim 1 , wherein the first electrode layer comprises at least one selected from the group consisting of a metal, a semiconductor, or a transparent conductive oxide.

5. The device of claim 1 , wherein the second electrode layer comprises at least one selected from the group consisting of a metal, a semiconductor, or a transparent conductive oxide.

6. 6. The device of claim 5, wherein the second electrode layer comprises at least one selected from the group consisting of Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, and Ca.

7. the second electrode layer, the dielectric layer, and the plurality of nanoparticles comprise a nanopatch antenna; 2. The device of claim 1, wherein the resonance of the nanopatch antenna is tunable by at least one selected from the group consisting of changing the size of the nanoparticles, changing the size ratio of the nanoparticles, changing the shape of the nanoparticles, changing the material of the nanoparticles, adjusting the thickness of the material, changing the refractive index of the dielectric layer, changing the refractive index of an additional layer disposed on the nanoparticles, changing the thickness of the second electrode layer, and changing the material of the second electrode layer.

8. 10. The device of claim 1, further comprising a material layer disposed beneath the plurality of nanoparticles, the material layer comprising at least one selected from the group consisting of an organic material and one or more oxide materials.

9. The device of claim 1 , wherein the light-emitting layer is an organic layer made of emitter molecules.

10. 10. The device of claim 1, wherein the shape of the nanoparticles is selected from the group consisting of cubes, spheres, spheroids, cylinders, parallelepipeds, rods, stars, pyramidal shapes, and multi-sided three-dimensional objects.

11. The device of claim 1 , wherein the dielectric layer has a refractive index of 1-5.

12. The device of claim 1 , wherein at least one of the nanoparticles has a size between 5 nm and 1000 nm.

13. The device of claim 1 , wherein at least one of the nanoparticles has a size between 5 nm and 200 nm.

14. The device of claim 1 , wherein at least one of the nanoparticles has a size between 5 nm and 100 nm.

15. 8. The device of claim 7, wherein the plurality of nanoparticles are coated with a dielectric capping layer, the thickness of the dielectric capping layer being selected to tune the plasmon resonance wavelength of the plurality of nanoparticles or the nanopatch antenna.

16. The device of claim 1, wherein the second electrode layer comprises at least one selected from the group consisting of metals, stacks of metal films and dielectric layers, plasmonic systems, bipolar metamaterials, and optically active metamaterials.

17. The device of claim 1 , wherein the plurality of nanoparticles are colloidally synthesized from a solution.

18. The device of claim 1 , wherein the plurality of nanoparticles are arranged in an array.

19. The device of claim 18 , wherein the array is an ordered array.

20. 2. The device of claim 1, wherein the plurality of nanoparticles disposed above the second electrode layer are formed from at least one selected from the group consisting of Ag particles, Al particles, Au particles, a dielectric material, a semiconductor material, an alloy of metals, a mixture of dielectric materials, a stack of one or more materials, and a core of one type of material coated with a shell of a different type of material, and include nano-sized holes within the second electrode layer.

21. 10. The device of claim 1, further comprising at least one of at least one downconverter and at least one color filter disposed above the light-emitting layer.

22. The device of claim 1, further comprising a nanoparticle adhesion layer positioned between the second electrode layer and the plurality of nanoparticles and in contact with the nanoparticles, the nanoparticle adhesion layer being a layer less than 5 nm thick having the function of increasing the density of the nanoparticles and / or reducing agglomeration or clumping of the nanoparticles.

23. 10. The device of claim 1, wherein at least one property of the plurality of nanoparticles is selected to change the spectrum of light emitted by the light emitting layer, change the angular dependence of light emitted by the light emitting layer, or the like.

24. 24. The device of claim 23, wherein the at least one property is selected from the group consisting of a size of the nanoparticles, a composition of the nanoparticles, and a distribution of the nanoparticles.

25. The device of claim 1 further comprising an organic transport layer.

26. The device of claim 1 , wherein the light-emitting layer comprises an organic light-emitting layer comprising an organic light-emitting material.

27. The organic light-emitting layer is a first layer including the organic light-emitting material; a second layer immediately adjacent to the first layer, the second layer comprising a second material.

28. 27. The device of claim 26, wherein the organic light-emitting material is a phosphorescent material.

29. 27. The device of claim 26, wherein the organic light-emitting material is a fluorescent material.

30. 27. The device of claim 26, wherein the organic light-emitting material is a thermally activated delayed fluorescent (TADF) material.

31. 27. The device of claim 26, wherein light emission results from combinations of materials within the organic light emitting material.

32. 32. The device of claim 31, wherein the combination of materials of the organic light-emitting layer comprises a first material and a second material, and an exciplex is formed in the organic light-emitting layer.

33. 27. The device of claim 26, wherein the organic light emitting material emits from a doublet state.

34. The device of claim 1 , further comprising a capping layer over the plurality of nanoparticles.

35. The device of claim 34 , wherein the capping layer comprises one or more emitter molecules.

36. 35. The device of claim 34, wherein the capping layer has a refractive index matching an opposite side of the second electrode layer.

37. The device of claim 1 , further comprising a barrier layer above the plurality of nanoparticles.

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