KR20220007542A - Nanopatch antenna outcoupling structure for use in oleds - Google Patents

Abstract

Embodiments of a disclosed subject matter provide an emissive layer, a first electrode layer, a plurality of nanoparticles and a material disposed between the first electrode layer and the plurality of nanoparticles. In some embodiments, a device can include a second electrode layer and a substrate, wherein the second electrode layer is disposed on the substrate, and the emissive layer is disposed on the second electrode layer. In some embodiments, a second electrode layer can be disposed on the substrate, the emissive layer can be disposed on the second electrode layer, the first electrode layer can be disposed on the emissive layer, a first dielectric layer of the material can be disposed on the first electrode layer, the plurality of nanoparticles can be disposed on the first dielectric layer, and a second dielectric layer can be disposed on the plurality of nanoparticles and the first dielectric layer. According to the present invention, stability of the device can be increased.

Description

NANOPATCH ANTENNA OUTCOUPLING STRUCTURE FOR USE IN OLEDS

CROSS REFERENCE TO RELATED APPLICATIONS

This application is based on U.S. Patent Application Serial No. 63/050,562, filed July 10, 2020, U.S. Patent Application Serial No. 63/058,410, filed July 29, 2020, U.S. Patent Application filed August 31, 2020 Application Serial No. 63/072,550 and U.S. Patent Application No. 63/078,084, filed on September 14, 2020, claiming priority, and U.S. Patent Application No. 62/817,368, filed March 12, 2019, 2019 U.S. Patent Application No. 62/817,284, filed March 12, 2019 U.S. Patent Application No. 62/870,272, filed July 3, 2019, and U.S. Patent Application No. 62/817,424, filed March 12, 2019 It is a continuation-in-part of U.S. Patent Application Serial No. 16/814,858, filed March 10, 2020, to which priority is claimed, the entire disclosures of each of which are incorporated herein by reference.

Field

The present invention relates to an outcoupling with a nanopatch antenna for converting surface plasmon energy of an electrode layer of a light emitting device into visible light.

Optoelectronic devices using organic materials are becoming increasingly important for several reasons. Because many of the materials used to make such devices are relatively inexpensive, organic optoelectronic devices have the potential for cost advantages over inorganic devices. In addition, the intrinsic properties of organic materials, such as their flexibility, make them highly suitable 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 can have performance advantages over conventional materials. For example, the wavelength at which the organic light emitting layer emits light can generally be easily adjusted with a suitable dopant.

OLEDs use thin organic films that emit light when a voltage is applied across the device. OLEDs are an increasingly important technology for use in applications such as flat panel displays, lighting and backlighting. Various OLED materials and configurations are described in US Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.

One application for phosphorescent emitting molecules is full color displays. The industry standard for such displays requires pixels tuned to emit a specific color, referred to as a “saturated” color. In particular, this criterion requires saturated red, green and blue pixels. Alternatively, the OLED may be designed to emit white light. In a typical liquid crystal display, emission from a white backlight is filtered using an absorption filter to produce red, green and blue emission. The same technique can also be used for OLEDs. The white OLED can be a single EML device or a stack structure. Color can be measured using CIE coordinates well known in the art.

As used herein, the term “organic” includes polymeric materials that can be used to fabricate organic optoelectronic devices, as well as small molecule organic materials. "Small molecule" refers to any organic material that is not a polymer, and a "small molecule" may actually be quite large. Small molecules may, in some circumstances, contain repeating units. For example, the use of a long chain alkyl group as a substituent does not exclude the molecule from the "small molecule" class. Small molecules may also be incorporated into polymers, for example, as pendant groups on the polymer backbone or as part of the backbone. Small molecules can also act as the core moiety of a dendrimer consisting of a series of chemical shells created on the core moiety. The core moiety of the dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a "small molecule", and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.

As used herein, "top" means furthest away from the substrate, and "bottom" means closest to the substrate. When a first layer is described as being “disposed over” a second layer, the first layer is disposed remote from the substrate. Other layers may exist between the first layer and the second layer unless the first layer is specified as being "in contact with" the second layer. For example, the cathode may be described as being “disposed over” the anode, although there are various organic layers between the cathode and the anode.

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

A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of the luminescent material. Although ancillary ligands may alter the properties of the photoactive ligand, a ligand may be referred to as “auxiliary” if the ligand is not believed to contribute to the photoactive properties of the luminescent material.

As used herein, and as generally understood by one of ordinary skill in the art, a first “highest occupied molecular orbital” (HOMO) or “least unoccupied molecular orbital” (HOMO) when the first energy level is closer to the vacuum energy level. The (LUMO) energy level is “greater than” or “higher” than the second HOMO or LUMO energy level. Since the ionization potential (IP) is measured as negative energy relative to the vacuum level, a higher HOMO energy level corresponds to an IP with a smaller absolute value (a less negative IP). Likewise, a higher LUMO energy level corresponds to an electron affinity (EA) with a smaller absolute value (less negative EA). In a conventional energy level diagram with a 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 the diagram than a “lower” HOMO or LUMO energy level.

As used herein, and as will generally be understood by one of ordinary skill in the art, the first workfunction is “greater than” or “higher” than the second workfunction if the absolute value of the first workfunction is greater. The work function is usually measured as a negative number with respect to the vacuum level, meaning that a “higher” work function is more negative. In a conventional energy level diagram with a vacuum level at the top, a “higher” workfunction is illustrated as further down from the vacuum level. Thus, the definition of HOMO and LUMO energy levels follows a different convention than work functions.

Further details and the foregoing definitions of OLEDs can be found in US Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.

outline

According to one embodiment, an organic light emitting diode/device (OLED) is also provided. An OLED may 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 integrated into one or more devices selected from consumer products, electronic component modules and/or lighting panels.

According to embodiments, a device may 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 may include a second electrode layer and a substrate, wherein the second electrode layer may be disposed over the substrate and the light emitting layer may be disposed over 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, wherein the total nonradiative decay rate constant is equal to the total radioactive 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 of 1-5. The light emitting layer of the device may include a transport layer. The light emitting layer may be an organic layer having emitter molecules.

The light emitting layer of the device may include 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 perov It may include at least one of skyte nanocrystals.

The first electrode layer of the device may be between 5 nm and 300 nm thick. The device may include a nanopatch antenna, wherein the resonance of the nanopatch antenna changes the size of the plurality of nanoparticles, changes the ratio of sizes of the plurality of nanoparticles, changes the shape of the plurality of nanoparticles, the plurality of nanoparticles change in the material of the particles, adjust the thickness of the material, change the refractive index of the material, change the refractive index of an additional layer disposed over the plurality of nanoparticles, change the thickness of the first electrode layer and/or change the material of the first electrode layer may be adjustable by at least one of The plurality of nanoparticles may be formed from at least one of Ag particles, Al particles, Au particles, dielectric material, semiconductor material, alloy of metal, mixture of dielectric material, stack of one or more materials, and/or core of one material. It may be coated with a shell of a different type of material. At least one of the plurality of nanoparticles of the device may include an additional layer to provide lateral conduction between the plurality of nanoparticles. The plurality of nanoparticles may be coated with an oxide layer, wherein the thickness of the oxide layer may be selected to tune the plasmon resonance wavelength of the plurality of nanoparticles or nanopatch antennas. The shape of the plurality of nanoparticles may be at least one of a cube, a sphere, a spheroid, a cylinder, a parallelepiped, a rod shape, a star shape, a pyramid, and/or a polyhedron. The size of at least one of the plurality of nanoparticles may be 5 nm to 1000 nm.

The device may include a corrugated layer disposed over a substrate, wherein the second electrode layer, the light emitting layer, the first electrode layer and/or the material is correspondingly corrugated.

The material of the device may include a dielectric layer disposed over the first electrode layer, and an electrical contact layer disposed over the dielectric layer. The material may include a voltage tunable refractive index material between the electrical contact layer and the first electrode layer. The voltage tunable refractive index material may be aluminum doped zinc oxide. The material may include an insulating layer. The first electrode layer of the device may be spaced apart from the light emitting layer by a predetermined threshold distance.

The predetermined threshold distance may be a distance where the total non-radioactive decay rate constant is equal to the total radioactive decay rate constant. The device may include an additional layer disposed over the plurality of nanoparticles. Additional layers may include one or more emitter molecules. The additional layer may match the refractive index under the first electrode layer. The further layer has a thickness of 1000 nm or less.

The material of the device may include a light emitting layer. The plurality of nanoparticles and the first electrode layer may provide an electrical injection path to the device.

The device can include a substrate and a second electrode layer, wherein the first electrode layer can be non-planar, wherein the second electrode layer can be disposed over the substrate, and the plurality of nanoparticles can be disposed over the second electrode layer, wherein the emissive layer may be non-planar and may be incorporated into a material, and may be disposed over and conform to the plurality of nanoparticles and the second electrode layer, wherein the first electrode layer may be disposed over and conform to the non-planar emissive 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 device can include a substrate and a second electrode layer, wherein the second electrode layer can be disposed over the substrate, and the nanoparticles can be disposed on the second electrode layer, wherein the light emitting layer can be included in a material, wherein the plurality of nanoparticles It may be disposed on a second electrode layer comprising a, wherein the first electrode layer is disposed on the light emitting 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 device may include a substrate and a second electrode layer, the material may be a first dielectric layer, and the device may include a second dielectric layer, wherein the second electrode layer may be disposed over the substrate, and the light emitting layer may be a second may be disposed over the electrode layer, a first electrode layer may be disposed over the light emitting layer, a first dielectric layer may be disposed over the first electrode layer, the plurality of nanoparticles may be disposed over the first dielectric layer, and a plurality of second dielectric layers of the nanoparticles and the first dielectric 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, wherein the total nonradiative decay rate constant is equal to the total radioactive decay rate constant. The first electrode layer includes 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 can do. 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 of 1-5. The light emitting layer may include a transport layer. The light emitting layer may be an organic layer having emitter molecules. The emission 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 covalently bonded organic framework, and/or a perovskite nanocrystal. The first electrode layer may have a thickness of 5 nm to 100 nm. The device may include a nanopatch antenna, wherein the resonance of the nanopatch antenna changes the size of the plurality of nanoparticles, changes the ratio of sizes of the plurality of nanoparticles, changes the shape of the plurality of nanoparticles, the plurality of nanoparticles change in the material of the particles, adjust the thickness of the material, change the refractive index of the material, change the refractive index of an additional layer disposed over the plurality of nanoparticles, change the thickness of the first electrode layer and/or change the material of the first electrode layer may be adjustable by at least one of The plurality of nanoparticles is 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 cores of one material It may be formed from at least one and coated with a shell of a different type of material. At least one of the plurality of nanoparticles of the device may include an additional layer to provide lateral conduction between the plurality of nanoparticles. The plurality of nanoparticles may be coated with an oxide layer, wherein the thickness of the oxide layer is selected to tune the plasmon resonance wavelength of the plurality of nanoparticles or nanopatch antennas. The shape of the plurality of nanoparticles may be at least one of a cube, a sphere, a spheroid, a cylinder, a parallelepiped, a rod shape, a star shape, a pyramid, and/or a polyhedron. The size of at least one of the plurality of nanoparticles may be 5 nm to 1000 nm.

The device may include a substrate and a second electrode layer, wherein the material may be a first dielectric layer, wherein the second electrode layer may be disposed over the substrate, the light emitting layer may be disposed over the second electrode layer, and the first electrode layer The silver may be disposed over the light emitting layer, the first dielectric layer may be disposed over the first electrode layer, and the plurality of nanoparticles may be disposed over the first dielectric 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 device may include a substrate and a second electrode layer, wherein the material is a first dielectric layer and a second dielectric layer, wherein the plurality of nanoparticles may be disposed in the second dielectric layer, wherein the second dielectric layer and the plurality of nanoparticles include The first dielectric layer can be disposed over the substrate, the first dielectric layer can be disposed over the second dielectric layer and the plurality of nanoparticles, the first electrode layer can be disposed over the first dielectric layer, the light emitting layer can be disposed over the first electrode, The second electrode may be disposed on the light emitting 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 device may include a substrate and a second electrode layer, the material may be a first dielectric layer, the device may include a second dielectric layer, the first electrode layer may be disposed over the substrate, and the first dielectric layer may be a first dielectric layer. can be disposed over the first electrode layer, the plurality of nanoparticles can be disposed over the first dielectric layer, the second dielectric layer can be disposed over the plurality of nanoparticles and the first dielectric layer, the light emitting layer can be disposed over the second dielectric layer, and , the second electrode layer may be disposed on the light emitting 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 device may include a substrate and a second electrode layer, the material may be a first dielectric layer, and the device may include a second dielectric layer, wherein the second electrode layer may be disposed over the substrate, and wherein the light emitting layer is over the second electrode layer. wherein the plurality of nanoparticles can be disposed over the light emitting layer, a second dielectric layer can be disposed over the plurality of nanoparticles and the light emitting layer, the first dielectric layer can be disposed over the second dielectric layer, the first electrode layer comprising: disposed over the first dielectric 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 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, wherein the first layer is thicker than the second layer. The first layer may be a dielectric material and the second layer may be a nanoparticle adhesive layer. The thickness of the first layer may be between 1 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 of 1-5. The material may include at least a portion of a coating disposed over the plurality of nanoparticles. The coating disposed over the plurality of nanoparticles may be a dielectric coating.

The device may include a second electrode layer, wherein the light emitting layer is comprised in an organic light emitting diode (OLED), wherein the OLED is 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 emission 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 covalently bonded organic framework, and/or a perovskite nanocrystal.

The first electrode layer of the device may be spaced apart from the light emitting layer by a predetermined threshold distance, wherein the threshold distance is a distance at which the total non-radiative decay rate constant is equal to the total radioactive decay rate constant. The first electrode layer includes 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 can do. The first electrode layer may be patterned with additional materials. Additional materials may include luminescent elements of fluorescent emitters, phosphorescent emitters, quantum dots, metal organic frameworks, covalently bonded organic frameworks and/or perovskite nanocrystals. 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.

The device may include a nanopatch antenna, wherein the resonance of the nanopatch antenna changes the size of the plurality of nanoparticles, changes the ratio of sizes of the plurality of nanoparticles, changes the shape of the plurality of nanoparticles, the plurality of nanoparticles change in the material of the particles, adjust the thickness of the material, change the refractive index of the material, change the refractive index of an additional layer disposed over the plurality of nanoparticles, change the thickness of the first electrode layer and/or change the material of the first electrode layer may be adjustable by at least one of

The plurality of nanoparticles of the device may be formed from at least one of Ag particles, Al particles, Au particles, dielectric material, semiconductor material, alloy of metal, mixture of dielectric material, stack of one or more materials, and/or core of one material. It can be formed and coated with a shell of a different type of material.

At least one of the plurality of nanoparticles of the device may include an additional layer to provide lateral conduction between the plurality of nanoparticles. The plurality of nanoparticles may be coated with an oxide layer, wherein the thickness of the oxide layer is selected to tune the plasmon resonance wavelength of the plurality of nanoparticles or nanopatch antennas. The plurality of nanoparticles may be colloidal synthetic nanoparticles formed from solution. The shape of the plurality of nanoparticles may be at least one of a cube, a sphere, a spheroid, a cylinder, a parallelepiped, a rod shape, a star shape, a pyramid, and/or a polyhedron. The size of at least one of the plurality of nanoparticles may be 5 nm to 1000 nm. The size of at least one of the plurality of nanoparticles may be 5 nm to 200 nm. The size of at least one of the plurality of nanoparticles may be 5 nm to 100 nm.

According to an embodiment, disposing a first electrode layer over a substrate, disposing a photoresist over the first electrode layer, etching at least a portion of the photoresist and the first electrode layer, over a portion of the remaining photoresist and the first electrode layer depositing metal to match the depth of the etched portion of A method may be provided that includes disposing a light emitting layer, and disposing a second electrode layer over the light emitting layer.

According to an embodiment, a device may include an inorganic light emitting layer, a first electrode layer, and an outcoupling structure. The first electrode layer may be spaced apart from the inorganic light emitting layer by a predetermined threshold distance, wherein the total non-radiative decay rate constant is equal to the total radioactive decay rate constant.

The first electrode layer of the device may be at least one of a metal, a stack of metal films and dielectric layers, a plasmonic, hyperbolic metamaterial, and/or an optically active metamaterial. The inorganic light emitting layer of the device is GaAs, AlGaAs, GaAsP, AlGaInP, GaP, GaAsP, GaN, InGaN, ZnSe, SiC, Si ₃ N ₄ , Si, Ge, Sapphire, BN, ZnO, AlGaN, perovskite and/or quantum It may be at least one of the constraint systems. The first electrode layer may be at least one of 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 nanoscale holes.

The outcoupling structure of the device may include Ag particles, Al particles, Ag-Al alloys, Au particles, Au-Ag alloys, dielectric materials, semiconductor materials, alloys of metals, mixtures of dielectric materials, stacks of one or more materials, and/or and may comprise a plurality of nanoparticles formed from at least one of the cores of one material and coated with a shell of a different type of material. The outcoupling structure may include a plurality of nanoparticles that are colloidal synthetic nanoparticles formed from solution. The outcoupling structure may include a plurality of nanoparticles arranged in a periodic array. The periodic array may have a predetermined array pitch. The outcoupling structure may include a plurality of nanoparticles arranged in an aperiodic array. In some embodiments, the outcoupling structure may comprise a plurality of nanoparticles, wherein the shape of the plurality of nanoparticles is a cube, a sphere, a spheroid, a cylinder, a parallelepiped, a rod shape, a star shape, a pyramid, and a polyhedron. It may be at least one of the objects.

The outcoupling structure may include a plurality of nanoparticles, and the device may include an adhesive layer disposed between the material and the plurality of nanoparticles. At least one property of the nanoparticles may be selected to alter the spectrum of light emitted by the emissive layer, or to alter the angular dependence of the light emitted by the emissive layer. The at least one selected characteristic may be the size of the nanoparticles, the composition of the nanoparticles and/or the distribution of the nanoparticles. The device may include at least one additional layer disposed over the plurality of nanoparticles. The device may include a material disposed between the first electrode and the plurality of nanoparticles. The device may include an organic transport material.

The device may include at least one of at least one color filter and at least one down-conversion layer disposed over the inorganic light emitting layer.

The inorganic light emitting layer of the device may be electroluminescent and may comprise a quantum confined material comprising a mixture of inorganic quantum confinement material that is at least one of CdS quantum dots, an organic transport layer and/or an inorganic transport layer.

The device may include an inorganic transport material. The device may include an inorganic transport material and an organic transport material.

The first electrode layer of the device may be between 5 nm and 1000 nm thick. The first electrode layer may be patterned with additional materials. The material may be layered or layered.

The outcoupling structure may comprise a plurality of nanoparticles, wherein at least one of the plurality of nanoparticles comprises an additional material to provide lateral conduction between the plurality of nanoparticles. The outcoupling structure may include a plurality of nanoparticles to be coated. The outcoupling structure may include a plurality of nanoparticles that are metallic and coated with a non-metallic coating.

In some embodiments, at least one additional layer of the device may match the refractive index under the first electrode layer. The thickness of the at least one further layer may be between 3000 nm and 1000 nm and/or between 1000 nm and 10 nm. The at least one additional layer may be transparent.

The outcoupling structure may include a plurality of nanoparticles comprising at least one of a metal, a dielectric material, and/or a hybrid of a metal and a dielectric material.

The outcoupling structure may include a plurality of nanoparticles, wherein the plurality of nanoparticles are coated with an oxide layer, wherein the thickness of the oxide layer is selected to tune the plasmon resonance wavelength of the plurality of nanoparticles or nanopatch antennas. do.

The outcoupling structure may include a plurality of nanoparticles, wherein at least one of the plurality of nanoparticles has a size between 5 nm and 1000 nm.

The device can include a material disposed over the first electrode, the material can be a dielectric layer disposed over the first electrode layer, and the electrical contact layer can be disposed over the dielectric layer. The material may include a voltage tunable refractive index material between the electrical contact layer and the first electrode layer. The voltage tunable refractive index material may be aluminum doped zinc oxide. The material may include an insulating layer.

The device may include nanoscale holes, wherein the arrangement of the pattern of nanoscale holes may be an array of nanoscale holes, a random arrangement of nanoscale holes, and/or a pseudo-random arrangement of holes.

The first electrode layer may include nano-sized features. The nanoscale features may be etched at least partially through the depth of the first electrode layer. The nanoscale features may include a bullseye pattern disposed over the first electrode layer or disposed over a gap material disposed over the first electrode layer. Nanoscale features may be disposed on at least one side of the first electrode layer. The size of the nanoscale features in the minimum direction may be at least 10 nm, at least 20 nm and/or between 50 nm and 750 nm.

The first electrode layer of the device may have a plurality of layers. Each layer of the plurality of layers may include a unit cell having a plurality of unit cell subcomponent layers. Each unit cell has a first unit cell subcomponent and a second unit cell subcomponent.

The inorganic light emitting layer may include at least one of GaAs and/or AlGaAs, wherein the outcoupling structure includes a plurality of nanoparticles, which may be at least one of Ag, Au, ITO, Si and/or Ge. The size of the nanoparticles may be 100-250 nm, and the wavelength of light emitted by the device may be 760 nm to 2000 nm.

The inorganic light emitting layer may comprise at least one of AlGaAs, GaAsP, AlGaInP and/or GaP, wherein the outcoupling structure comprises a plurality of nanoparticles, wherein the nanoparticles are Ag, Au, SiO ₂ , Si and/or at least one of Ge. The size of the nanoparticles may be 75-200 nm, and the wavelength of light emitted by the device may be greater than 610-760 nm.

The inorganic light emitting layer may comprise at least one of GaAsP, AlGaInP and/or GaP, wherein the outcoupling structure comprises a plurality of nanoparticles, wherein the nanoparticles are selected from among Ag, Au, SiO ₂ , Si and/or Ge. There may be at least one. The size of the nanoparticles may be 60-150 nm, and the wavelength of light emitted by the device may be 590-610 nm.

The inorganic light emitting layer may comprise at least one of GaAsP, AlGaInP and/or GaP, wherein the outcoupling structure comprises a plurality of nanoparticles, wherein the nanoparticles comprise _{at least one of Au, SiO 2} , Si and/or Ge. may include, the size of the nanoparticles may be 50-100 nm, and the wavelength of light emitted by the device may be 570-590 nm.

The inorganic light emitting layer may include at least one of GaAsP, AlGaInP, GaP, and/or InGaN/GaN. The outcoupling structure may comprise a plurality of nanoparticles, wherein the nanoparticles may comprise at least one _{of Ag, Al, Rh, Pt, SiO 2} , Si, Ge, and/or TiO _{2 , wherein the nanoparticles} The size of may be 40-125 nm and/or the wavelength of light emitted by the device may be 500-570 nm.

The inorganic light emitting layer may comprise at least one of ZnSe, InGaN, SiC and/or Si, wherein the outcoupling structure may comprise a plurality of nanoparticles, wherein the nanoparticles are Ag, Al, Rh, Pt and/or or TiO ₂ , wherein the size of the nanoparticles may be 40-125 nm and/or the wavelength of light emitted by the device may be 450-500 nm.

The inorganic light emitting layer may include InGaAs, wherein the outcoupling structure may include a plurality of nanoparticles, wherein the nanoparticles may include at least one _{of Al, Rh, Pt and/or TiO 2 , wherein} The size of the nanoparticles may be 50-100 nm, wherein the wavelength of light emitted by the device may be 400-450 nm.

The inorganic light emitting layer may comprise at least one of diamond, BN, AlN AlGaN and/or AlGaInN, wherein the outcoupling structure may comprise a plurality of nanoparticles, wherein the nanoparticles are Al, Rh, Pt and/or TiO ₂ , wherein the size of the nanoparticles may be 30-75 nm, wherein the wavelength of light emitted by the device may be 200 nm to 400 nm.

The inorganic light emitting layer may comprise a blue light emitting diode having a yellow phosphor, wherein the outcoupling structure may comprise a plurality of nanoparticles, wherein the nanoparticles are comprised of Ag, Al, Rh, Pt and/or TiO ₂ . It may include at least one selected from the group, wherein the size of the nanoparticles may be 40-125 nm, wherein white light may be emitted by the device.

The inorganic light emitting layer may include at least one of GaAs and/or AlGaAs, wherein the outcoupling structure may include a plurality of nanoparticles, wherein the nanoparticles are Ag, Au, ITO, Si, Ge, SiO ₂ , It may comprise at least one of Al, Rh and/or Pt, wherein the size of the nanoparticles may be 5-250 nm, wherein the wavelength of light emitted by the device may be 760 nm to 2000 nm.

The inorganic light emitting layer may include at least one of AlGaAs, GaAsP, AlGaInP and/or GaP, wherein the outcoupling structure may include a plurality of nanoparticles, wherein the nanoparticles are Ag, Au, SiO ₂ , Al, at least one of Rh, Pt, Si and/or Ge, wherein the size of the nanoparticles may be 5-200 nm, and the wavelength of light emitted by the device may be 610-760 nm.

The inorganic light emitting layer may include at least one of AlGaAs, GaAsP, AlGaInP and/or GaP, wherein the outcoupling structure may include a plurality of nanoparticles, wherein the nanoparticles are Ag, Au, SiO ₂ , Al, It may comprise at least one of Rh, Pt, Si and/or Ge, wherein the size of the nanoparticles may be 5-150 nm, and wherein the wavelength of light emitted by the device may be 590-610 nm.

The inorganic light emitting layer may include at least one selected from the group consisting of GaAsP, AlGaInP and/or GaP, wherein the outcoupling structure may include a plurality of nanoparticles, wherein the nanoparticles are Ag, Au, SiO ₂ , Al, Rh, Pt, Si and/or Ge, wherein the size of the nanoparticles can be 5-100 nm, and wherein the wavelength of light emitted by the device is 570-590 nm. can

The inorganic light emitting layer may include at least one of GaAsP, AlGaInP, GaP and/or InGaN/GaN, wherein the outcoupling structure may include a plurality of nanoparticles, wherein the nanoparticles are Ag, Al, Rh, Pt , SiO ₂ , TiO ₂ , Si and/or Ge, wherein the size of the nanoparticles may be 5-125 nm and/or wherein the wavelength of light emitted by the device is 500-570 may be nm.

The inorganic light emitting layer may comprise at least one of Se, InGaN, SiC and/or Si, wherein the outcoupling structure may comprise a plurality of nanoparticles, wherein the nanoparticles are Ag, Al, Rh, Pt and/or or TiO ₂ , wherein the size of the nanoparticles may be 5-125 nm, and wherein the wavelength of light emitted by the device may be 450-500 nm.

The inorganic light emitting layer may include InGaAs, wherein the outcoupling structure may include a plurality of nanoparticles, wherein the nanoparticles may include at least one selected from the group consisting _{of Al, Rh, Pt and/or TiO 2 .} Here, the size of the nanoparticles may be 5-100 nm, and the wavelength of light emitted by the device may be 400-450 nm.

The inorganic light emitting layer may include at least one of diamond (235 nm), BN, AlN, AlGaN and/or AlGaInN, wherein the outcoupling structure may include a plurality of nanoparticles, wherein the nanoparticles are Al, Rh , Pt and/or TiO ₂ , wherein the size of the nanoparticles may be 5-75 nm, and wherein the wavelength of light emitted by the device may be 200 nm to 400 nm.

The inorganic light emitting layer may comprise a blue light emitting diode having a yellow phosphor, wherein the outcoupling structure may comprise a plurality of nanoparticles, wherein the nanoparticles comprise at least one _{of Al, Rh, Pt and/or TiO 2 .} wherein the size of the nanoparticles may be 5-125 nm, wherein the light emitted by the device may be white light.

According to embodiments, a consumer product may include an inorganic light emitting layer, a first electrode layer, and an outcoupling structure. The first electrode layer may be spaced apart from the inorganic emissive layer by a predetermined threshold distance, wherein the total nonradiative decay rate constant is equal to the total radioactive decay rate constant. Consumer products include display screens, lighting devices such as discrete light source devices or lighting panels, flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, indoor or outdoor lighting and/or signaling lights, heads-up displays, full or Partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, phones, cell phones, tablets, phablets, personal digital assistants (PDAs), wearable devices , laptop computers, digital cameras, camcorders, viewfinders, micro displays less than 2 inches diagonal, 3D displays, vehicles, aerial displays, large-area walls, video walls with multiple displays tiled together, theater or stadium screens, phototherapy It may be at least one of a device, a signage, an augmented reality (AR) or virtual reality (VR) display, a display or visual element in glasses or contact lenses, light emitting diode (LED) wallpaper, LED jewelry and/or apparel.

According to embodiments, a device may include an inorganic light emitting layer, a first electrode layer, an outcoupling structure, and a material disposed between the first electrode and the outcoupling structure. The first electrode layer may be spaced apart from the inorganic emissive layer by a predetermined threshold distance, wherein the total nonradiative decay rate constant is equal to the total radioactive decay rate constant.

The first electrode layer may be at least one of a metal, a stack of metal films and dielectric layers, a plasmonic, hyperbolic metamaterial, and/or an optically active metamaterial. The first electrode layer includes 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 can do.

The inorganic light emitting layer is GaAs, AlGaAs, GaAsP, AlGaInP, GaP, GaAsP, GaN, InGaN, ZnSe, SiC, Si ₃ N ₄ , Si, Ge, sapphire, BN, ZnO, AlGaN, perovskite and/or quantum confinement system. may include at least one of A quantum confinement system may include particles having the size of an exciton's Bohr radius. The quantum confinement system may comprise at least one of an organic-inorganic perovskite mixture, CsPbBr ₃ , InP/ZnS, CuInS/ZnS, Si, Ge, C and/or peptide.

The outcoupling structure may include Ag particles, Al particles, Ag-Al alloys, Au particles, Au-Ag alloys, dielectric materials, semiconductor materials, alloys of metals, mixtures of dielectric materials, stacks of one or more materials, and/or one may comprise a plurality of nanoparticles formed from at least one of the cores of the material and coated with a shell of a different type of material. The outcoupling structure may include a plurality of nanoparticles that are colloidal synthetic nanoparticles formed from solution. The outcoupling structure may include a plurality of nanoparticles arranged in a periodic array. The periodic array may have a predetermined array pitch. The outcoupling structure may include a plurality of nanoparticles arranged in an aperiodic array. The outcoupling structure may comprise a plurality of nanoparticles, wherein the shape of the plurality of nanoparticles is at least one of a cube, a sphere, a spheroid, a cylinder, a parallelepiped, a rod, a star, a pyramid, and/or a polyhedron. one The outcoupling structure may include a plurality of nanoparticles, and the device may include an adhesive layer disposed between the material and the plurality of nanoparticles. The outcoupling structure may include a plurality of nanoparticles, and at least one of the plurality of nanoparticles may include an additional material to provide lateral conduction between the plurality of nanoparticles.

The first electrode layer of the device may be patterned with nanoscale holes.

The device may include an organic transport material.

The outcoupling structure of the device may include a plurality of nanoparticles, and the device may include at least one additional layer disposed over the plurality of nanoparticles. At least one additional layer may encapsulate the device. The at least one additional layer may include one or more emitter molecules. The at least one additional layer may have an index of refraction between 1.01 and 5. The at least one additional layer may change the color or efficiency of the light emission of the device.

1 shows an organic light emitting device.
2 shows an inverted organic light emitting device without a separate electron transport layer.
3A shows a conventional nanopatch antenna comprising a layer of material with emitter molecules embedded between nanoparticles and a metal layer.
3B depicts a nanopatch antenna comprising emitter molecules in a light emitting layer disposed below a metal layer (ie, an electrode layer) according to an embodiment of the disclosed subject matter.
3C depicts a nanopatch antenna comprising a capping layer disposed over nanoparticles that may include additional emitter molecules in accordance with embodiments of the disclosed subject matter.
4A illustrates a dielectric material comprising a plurality of layers in accordance with an embodiment of the disclosed subject matter.
4B depicts two stacked dielectric materials comprising a thick dielectric layer and a thin nanoparticle adhesive layer in accordance with an embodiment of the disclosed subject matter.
5A depicts emitter molecules in a light emitting layer disposed below a metal layer (ie, electrode layer) in combination with an OLED stack in accordance with an embodiment of the disclosed subject matter, wherein the light emitting layer is within a critical distance to the metal electrode and the nanopatch over the electrode; The antenna radiates to the side with the nanoparticles.
5B depicts a variation of the embodiment of FIG. 5A in which the stack may be corrugated for further outcoupling of surface plasmon energy (SPR) modes in accordance with embodiments of the disclosed subject matter.
6 shows that the energy of an excited emitter molecule can couple into a nanopatch antenna gap mode and quench it into an SPR mode at the cathode generating an electric field that can radiate the energy as light in accordance with an embodiment of the disclosed subject matter; show that there is
7 is an illustration of a material layer of a nanopatch antenna using a nanocube as a nanoparticle, in the x- and y-directions, respectively, in which the far outcoupled light originates from the edge of the nanoparticle in accordance with an embodiment of the disclosed subject matter; Computer simulations of electric field strength, Ex and Ey are shown.
8 depicts a thin metal film (ie, electrode layer) partially etched through the film thickness to produce a corrugated top surface while maintaining a planar bottom surface in accordance with an embodiment of the disclosed subject matter.
9 shows that nanoparticle coatings can provide an appropriate gap thickness between the nanoparticles and the metal film in accordance with embodiments of the disclosed subject matter.
10 depicts an OLED combined with a nanopatch antenna using material(s) having a voltage-tunable refractive index for selecting the wavelength of emitted light in accordance with an embodiment of the disclosed subject matter.
11 depicts an OLED stack using nanoparticles and metal layers as electrodes and deposited within a dielectric region to inject charge in accordance with an embodiment of the disclosed subject matter.
12A shows a nanopatch antenna OLED device having metal nanoparticles deposited over electrodes and substrates to allow charge injection from both ITO (indium tin oxide) and metal nanoparticles in accordance with an embodiment of the disclosed subject matter.
12B illustrates an alternative planar OLED device to that shown in FIG. 12A in accordance with an embodiment of the disclosed subject matter.
13 illustrates a method of forming a bottom electrode for a planar electrically driven OLED as shown in FIG. 12B in accordance with an embodiment of the disclosed subject matter.
14A-14F show examples of OLED devices having various nanostructures with or without dielectric capping layers in accordance with embodiments of the disclosed subject matter.
15 illustrates how the material composition of a nanostructure may be a metal, a dielectric, or some combination of the two (ie, a hybrid) according to an embodiment of the disclosed subject matter.
16 shows that particle shape can affect resonant plasmon mode frequency in accordance with embodiments of the disclosed subject matter.
17 depicts an example of an inorganic LED that may include an enhancement layer (eg, an electrode layer) and an outcoupling layer in accordance with embodiments of the disclosed subject matter. The bottom embodiment allows a larger area of light emission since in this embodiment the top contact p-type is incorporated into the enhancement layer.
18 shows a structural example of an enhancement layer (eg, electrode layer) having unit cells and sub-components according to an embodiment of the disclosed subject matter.
19A shows a plot of quantum yield as a function of distance of a luminescent material from an enhancement film with two critical distances identified.
19B shows a schematic diagram of the temperature of the OLED as a function of the distance of the light emitter from the enhancement film in the absence of an outcoupling layer for a non-emissive OLED with a critical distance 2 identified in the plot.

Generally, an OLED comprises one or more organic layers disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes into the organic layer(s) and the cathode injects electrons. The injected holes and electrons move toward the oppositely charged electrode, respectively. When electrons and holes are localized on the same molecule, an “exciton,” a localized electron-hole pair with an excited energy state, is created. Light is emitted when the exciton is relaxed via a light emission mechanism. In some cases, excitons may localize on excimers or exciplexes. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.

Early OLEDs used emissive molecules that emit light (“fluorescence”) from a singlet state, as disclosed, for example, in US Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescence emission generally occurs in a time frame of less than 10 nanoseconds.

More recently, OLEDs with emissive materials that emit light from the triplet state (“phosphorescence”) have been presented. See Baldo et al., "Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices," Nature, vol. 395, 151-154, 1998; ("Baldo-I") and Baldo et al., "Very high-efficiency green organic light-emitting devices based on electrophosphorescence," Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) ("Baldo-II")] is incorporated by reference in its entirety. Phosphorescence is described more specifically at columns 5-6 of US Pat. No. 7,279,704, which is incorporated by reference.

1 shows an organic light emitting device 100 . The drawings are not necessarily drawn to scale. The device 100 includes a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, a light emitting layer 135, a hole blocking layer 140, an electron transport layer ( 145 ), an electron injection layer 150 , a passivation 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 . Device 100 may be fabricated by depositing the layers in the order described. These various layers, as well as the properties and functions of exemplary materials, are described more specifically in US Pat. No. 7,279,704, columns 6-10, which is incorporated by reference.

More examples for each of these layers are also available. For example, a flexible and transparent substrate-anode combination is disclosed in US Pat. No. 5,844,363, which is incorporated by reference in its entirety. _{One example of a p-doped hole transport layer is m-MTDATA doped with F 4} -TCNQ in a molar ratio of 50:1, as disclosed in US Patent Application Publication No. 2003/0230980, which is incorporated herein by reference in its entirety. incorporated by reference. Examples of emitting and host materials are disclosed in US Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li in a molar ratio of 1:1, as disclosed in US Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, disclose examples of cathodes, including compound cathodes having thin layers of metals such as Mg:Ag with laminated transparent, electrically conductive sputter-deposited ITO layers. has been The theory and use of barrier layers are more specifically described in US Pat. No. 6,097,147 and US Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entirety. An example of an injection layer is provided in US Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of the protective layer can be found in US Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.

2 shows an inverted structure OLED 200 . The device includes a substrate 210 , a cathode 215 , a light emitting layer 220 , a hole transport layer 225 and an anode 230 . Device 200 may be fabricated by depositing the layers in the order described. Since the most common OLED configuration is one with the cathode disposed above the anode, and device 200 has the cathode 215 disposed below the anode 230, device 200 would be referred to as an “inverted” OLED. can Materials similar to those described with respect to device 100 may be used for that layer of device 200 . 2 provides an example of how some layers may be omitted from the structure of device 100 .

The simple stacked structures shown in Figures 1 and 2 are provided by way of non-limiting example, and it is understood that embodiments of the invention may be used in connection with a variety of other structures. The specific materials and structures described are illustrative in nature, and other materials and structures may be used. Functional OLEDs can be achieved by combining the various layers described in different ways, or layers can 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. Although many of the examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as mixtures of host and dopant, or more generally mixtures, may be used. In addition, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200 , hole transport layer 225 transports holes and injects holes into 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. This organic layer may comprise a single layer or may further comprise a plurality of layers of different organic materials, for example as described in connection with FIGS. 1 and 2 .

Structures and materials not specifically described may also be used, such as OLEDs (PLEDs) comprising polymeric materials as disclosed in US Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. As a further example, it is possible to use an OLED having a single organic layer. OLEDs may be stacked, for example, as described in US Pat. No. 5,707,745 (Forrest et al.), which is incorporated herein by reference in its entirety. The OLED structure may deviate from the simple stacked structure shown in FIGS. 1 and 2 . For example, the substrate may have a mesa structure as described in US Pat. No. 6,091,195 (Forrest et al.) and/or an out-coupled structure such as a pit structure described in US Pat. No. 5,834,893 (Bulovic et al.). It may include an angled reflective surface to improve out-coupling, these patents are incorporated herein by reference in their entirety.

In some embodiments disclosed herein, emissive layers or materials, such as emissive layer 135 and emissive layer 220 shown in FIGS. 1 and 2 , may each include quantum dots. A “light-emitting layer” or “light-emitting material” disclosed herein may include an organic light-emitting material and/or a light-emitting material comprising quantum dots or equivalent structures according to the understanding of one of ordinary skill in the art, unless expressly or otherwise indicated by context. have. Such a light emitting layer may comprise only a separate light emitting material or quantum dot material that converts light emitted by another emitter, or may also comprise a separate light emitting material or other emitter, or may comprise a separate light emitting material or other emitter, or directly from the application of an electric current. It can emit light by itself. Similarly, a color-altering layer, color filter, up-converting or down-converting layer or structure may include a material comprising quantum dots, but such a layer may not be considered a "light-emitting layer" as disclosed herein. In general, a “light-emitting layer” or material is one that emits initial light, which may be altered by other layers within the device, such as a color filter or other color-altering layer that does not itself emit the initial light in the light-emitting layer. may re-emit the altered light of different spectral content based on the initial light emitted by the

Unless otherwise specified, any layer of the various embodiments may be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation as described in U.S. Pat. Nos. 6,013,982 and 6,087,196 (which are incorporated by reference in their entirety), ink-jet, U.S. Pat. This patent document is incorporated by reference in its entirety) as described in organic vapor deposition (OVPD) and in US Pat. No. 7,431,968, which is incorporated by reference in its entirety, and organic vapor jet printing (OVJP) as described in its entirety. vapor deposition by Other suitable deposition methods include spin coating and other solution-based processes. The solution-based process is preferably carried out in nitrogen or in an inert atmosphere. For other layers, preferred methods include thermal evaporation. Preferred methods of pattern formation include deposition through a mask, cold welding as described in US Pat. pattern formation. Other methods may also be used. A material to be deposited may be modified to be compatible with a specific deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, preferably containing three or more carbons, can be used in small molecules to enhance their solution processing capability. Substituents having 20 or more carbons may be used, with 3 to 20 carbons being the preferred range. Because an asymmetric material may have a lower recrystallization tendency, a material having an asymmetric structure may have better solution processability than a material having a symmetric structure. Dendrimer substituents can be used to improve the solution processing capability of small molecules.

Devices fabricated in accordance with embodiments of the present invention may optionally further include a barrier layer. One purpose of barrier layers is to protect electrodes and organic layers from damage due to exposure to harmful species in environments containing moisture, vapors and/or gases, and the like. The barrier layer may be deposited over any other portion of the device, including the edge, over the electrode, or over the substrate, under the substrate, or next to the substrate. The barrier layer may include a single layer or multiple layers. The barrier layer may be formed by a variety of known chemical vapor deposition techniques and may include a composition having a single phase as well as a composition having a plurality of phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may include inorganic or organic compounds or both. Preferred barrier layers include mixtures of polymeric and non-polymeric materials as described in US Pat. No. 7,968,146, PCT Patent Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are incorporated herein by reference in their entirety. incorporated by reference. To be considered a "mixture", the aforementioned polymeric and non-polymeric materials comprising the barrier layer must be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymer to non-polymer material may be in the range of 95:5 to 5:95. Polymeric and non-polymeric materials can be produced from the same precursor material. In one example, the mixture of polymeric and non-polymeric materials consists essentially of polymeric silicon and inorganic silicon.

Devices fabricated in accordance with embodiments of the present invention may be incorporated within a wide variety of electronic component modules (or units) that may be incorporated within various electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, light emitting devices such as individual light source devices or lighting panels that can be used by end consumer product producers, and the like. Such electronic component modules may optionally include drive electronics and/or power source(s). Devices fabricated in accordance with embodiments of the present invention may be incorporated into a wide variety of consumer products that include one or more electronic component modules (or units) therein. A consumer product comprising an OLED comprising a compound of the present invention in an organic layer within the OLED is disclosed. Such consumer products would include any kind of product comprising one or more light source(s) and/or one or more visual displays of any kind. Some examples of such consumer products include flat panel displays, computer monitors, medical monitors, televisions, billboards, indoor or outdoor lighting and/or signaling lights, head-up displays, fully transparent or partially transparent displays, flexible displays, laser printers, telephones, Cell phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, micro displays (displays with a diagonal less than 2 inches), 3D displays, virtual or augmented reality displays, vehicles , video walls containing multiple displays tiled together, theater or stadium screens, and signage. A variety of control mechanisms, including passive matrix and active matrix, can be used to control devices fabricated in accordance with the present invention. Many devices are intended for use in a temperature range that is comfortable for humans, such as 18°C to 30°C, more preferably room temperature (20°C to 25°C), but may also be used at temperatures outside this temperature range, such as -40°C to 80°C. can be used

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 above materials and structures.

In some embodiments, the OLED has one or more properties selected from the group consisting of flexible, rollable, foldable, stretchable, and curved. In some embodiments, the OLED is transparent or translucent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes.

In some embodiments, the OLED further comprises a layer comprising a delayed fluorescent emitter. In some embodiments, the OLED comprises an arrangement of RGB pixels or an arrangement of white + color filter pixels. 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 an area of at least 10 inches diagonal or 50 square inches. In some embodiments, the OLED is a lighting panel.

In some embodiments of the light emitting region, the light emitting region further comprises a host.

In some embodiments, the compound may be a luminescent dopant. In some embodiments, the compound is capable of generating luminescence through phosphorescence, fluorescence, thermally activated delayed fluorescence, ie, TADF (also referred to as type E delayed fluorescence), triplet-triplet extinction, or a combination of these processes.

The OLEDs disclosed herein may be incorporated into one or more of consumer products, electronic component modules, and lighting panels. The organic layer can be an emissive layer, and the compound can be an emissive dopant in some embodiments, while the compound can be a non-emissive dopant in other embodiments.

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 broad bandgap material that plays little role in a) anode, b) electron transport, c) hole transport, or d) charge transport. In some embodiments, the host may comprise a metal complex. The host may be an inorganic compound.

Combination with other substances

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

A variety of materials may be used in the various emissive and non-emissive layers and arrangements disclosed herein. Examples of suitable materials are disclosed in US Patent Application Publication No. 2017/0229663, which is incorporated by reference in its entirety.

Conductive dopants:

The charge transport layer can be doped with a conductive dopant to substantially change its charge carrier density, which in turn will change its conductivity. Conductivity is increased by creating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor can also be achieved. The hole transport layer may be doped with a p-type conductive dopant and an n-type conductive dopant is used in the electron transport layer.

HIL/HTL:

The hole injection/transport material to be used in the present invention is not particularly limited, and any compound may be used as long as the compound is commonly used as a hole injection/transport material.

EBL:

An electron blocking layer (EBL) may be used to reduce the number of electrons and/or excitons leaving the emissive layer. The presence of such a blocking layer in the device can lead to significantly higher efficiencies and/or longer lifetimes when compared to similar devices without the blocking layer. A blocking layer can also be used to confine light emission to a desired area of the OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or more triplet energy than one or more of the hosts closest to the EBL interface. In one embodiment, the compound used in EBL contains the same molecule or functional group used as one of the hosts described below.

Host:

The light emitting layer of the organic EL device of the present invention preferably includes at least a metal complex as a light emitting material, and may include a host material using the metal complex as a dopant material. Examples of the host material are 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 the triplet energy of the dopant. Any host material may be used with any dopant as long as the triplet criterion is met.

HBL:

A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons leaving the emissive layer. The presence of such a blocking layer in the device can lead to significantly higher efficiencies and/or longer lifetimes when compared to similar devices without the blocking layer. A blocking layer can also be used to confine light emission to a desired area of the OLED. In some embodiments, the HBL material has a lower HOMO (far from the vacuum level) and/or higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the HBL interface.

ETL:

The electron transport layer (ETL) may include a material capable of transporting electrons. The electron transport layer may be native (undoped) or doped. Doping can be used to improve conductivity. Examples of the ETL material are not particularly limited, and any metal complex or organic compound may be used as long as they are conventionally used to transport electrons.

Charge Generation Layer (CGL):

In a tandem or stacked OLED, CGL plays an essential role in terms of performance, which consists of an n-doped layer and a p-doped layer for injecting electrons and holes, respectively. Electrons and holes are supplied from the CGL and the electrode. Electrons and holes consumed in the CGL are refilled by electrons and holes injected from the cathode and anode, respectively; After that, the bipolar current gradually reaches a steady state. Common CGL materials contain n and p conductive dopants used in the transport layer.

The outcoupling energy in the form of light from the surface plasmon energy (SPR) mode is an OLED having a longer lifetime in display luminance when the emissive layer is within a critical distance of a plasmonic active material, such as a metal cathode and/or anode (eg electrode layer). can be used to provide The critical distance may be the distance at which the total nonradiative decay rate constant is equal to the total radioactive decay rate constant as disclosed in US Pat. No. 9,960,386, incorporated herein by reference in its entirety. 19A shows a plot of the quantum yield (QY) as a function of the distance of the emissive layer from the electrode layer (eg, metal anode and/or cathode). When the non-radioactive decay rate constant approaches the value for the radioactive decay rate, QY begins to fall, producing a peak of QY at some specific distance. Figure 19b schematically shows the steady-state temperature of an OLED as the distance between the emissive layer and the electrode layer is varied for a fixed current density of operation. For larger distances of the luminescent material from the electrode layer, there is no improvement in the rate constant for radioactive or non-radiative decay. The temperature of an OLED depends only on the total current density of its operation and the efficiency of the luminescent material. As the luminescent material moves closer to the electrode layer, the radioactive decay rate constant increases, and the photon yield increases, reducing the heat generated at the OLED and the steady-state temperature of the OLED. For distances shorter than critical distance 2, the excitons on the light emitter are quenched as heat, and the normalized temperature of the OLED is increased. The above description of the OLED temperature applies when the enhancement layer does not outcouple a predetermined significant fraction of the energy as light in the surface plasmon mode. If there is outcoupling as part of the enhancement layer or if an outcoupling layer is used in the device, it must be removed in order to perform a critical distance measurement.

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

The nanopatch antenna may include a planar metal film (eg, an electrode layer), an interstitial material (eg, a dielectric material, etc.) disposed over the planar metal, and nanoparticles disposed over the interstitial material, as shown in FIGS. 3A-3C . 3A shows a conventional nanopatch antenna comprising an interstitial layer with emitter molecules embedded between nanoparticles and a metal layer. 3B shows a nanopatch antenna according to an embodiment of the disclosed subject matter, wherein the emitter molecules in the emissive layer are disposed below the metal layer (ie not in the interstitial layer). 3C depicts another embodiment of the disclosed subject matter comprising a capping layer disposed on top of nanoparticles. In some embodiments, the capping layer may include additional emitter molecules.

Interstitial materials may be organic (eg, small molecule and/or polymeric materials) and may include oxides and/or other dielectric materials including stacks, alloys and/or mixtures of materials, such as those shown in FIG. 4A . . That is, FIG. 4A shows a dielectric material having a plurality of layers. The structure can provide a resonant plasmon mode in the gap due to the high electric field strength generated in the gap medium. The large electric field can be used to enhance the emission rate of an emitter placed in a gap known as the Purcell effect. Nanopatch antennas can radiate energy from the plasmonic active mode with efficiencies of up to 50%.

In an embodiment of the disclosed subject matter, two stacked dielectric materials are one thicker layer, which may be the primary dielectric interstitial material, as shown in FIG. 4B , and increase nanoparticle density and/or prevent nanoparticle aggregation or agglomeration. Includes one thin layer that can act as a nanoparticle adhesion layer to reduce For example, a polyelectrolyte layer (such as poly(styrenesulfonate) or poly(allylamine) hydrochloride) can have an electrostatic charge that can interact with the electrostatic charge on the nanoparticle coating (such as can be used to coat silver nanoparticles). poly(vinylpyrrolidinone) has a negative electrostatic charge). The sum of the thicknesses of the above layers may determine the overall gap thickness, while the adhesive layer thickness may be less than 5 nm, and the gap layer thickness may be between 1 and 100 nm, more preferably between 1 and 50 nm.

A Purcell factor of the order of 1,000 can be achieved by placing the emitter in the nanopatch antenna gap, while a Purcell factor of the order of 10 may be sufficient for improvement in phosphorescent OLED emitter stability. It can be difficult to fabricate an entire OLED stack that maintains high internal quantum efficiencies at typical nanopatch antenna gap thicknesses, typically 2-15 nm, and uses less nanoparticles as one of the OLED electrodes. Embodiments of the disclosed subject matter may provide an arrangement with the emitter placed under a planar metal instead of an antenna gap as shown in FIG. 3B . A variant of the arrangement may include an additional capping layer disposed over the nanoparticles, which may include additional emitter molecules, as shown in FIG. 3C . The capping layer can match the refractive index with the other side of the metal layer to improve cross-coupling of the SPR mode throughout the metal layer and to the nanopatch antenna gap.

As shown in the arrangement of Figures 3B-3C, the emitter may be positioned within a critical distance of the planar metal to again act as one of the OLED contacts (ie, the cathode or the anode). In one example, the emission may occur from the same side of the device as the nanoparticles, allowing the arrangement to conform to both top and bottom emission geometries.

In this configuration, the Purcell enhancement to stabilize the emitter may result from proximity to a planar metal contact (eg, electrode layer). FIG. 5a shows that emitter molecules in an emissive layer disposed below a metal layer (ie not in an interstitial layer) are typically such that the emissive layer is within a critical distance to the metal cathode and the subsequent nanopatch antenna geometry on the cathode is radiated from the side with the nanoparticles. shows an embodiment of the disclosed subject matter that can be combined with an OLED stack of

In a variant of the above configuration, the metal contacts or the entire device stack can be corrugated to enhance the outcoupling of the SPR mode, as shown in FIG. 5B . Although this configuration is lower than that achieved by placing the emitter within the gap, a Purcell factor of ≧10 may still reduce the maximum achievable Purcell enhancement that can be achieved. By placing the emitter within a critical distance of the metal (eg, the electrode layer), the emitter energy can be coupled to the SPR mode induced along the surface of the metal. For non-opaque metal films (eg Ag <200 nm thick, Al and Au <100 nm thick), the plasmonic mode transfers its energy to the interstitial plasmon mode as shown in FIG. 6 and via the nanopatch antenna It can be coupled to an opposing surface of a metal capable of diverting light.

That is, FIG. 6 shows that energy is concentrated through the SPR mode and emitted as light. The energy of the excited emitter molecule is quenched at the cathode in SPR mode, creating an electric field, which in turn can couple to the nanopatch antenna gap mode and radiate the energy as light.

When nanocubes are used as nanoparticles in nanopatch antennas, the strength of the electric field may be highest at the edges of the nanocubes, as shown by the simulation in FIG. 7 . That is, FIG. 7 shows simulations of electric field strengths in x- and y-directions, Ex and Ey, respectively, in the interstitial layer of a nanopatch antenna using nanocubes as nanoparticles. 7 shows that the far outcoupled light originates from the edge of the nanoparticles.

Converting the resonance of the nanopatch antenna to align with the emission spectrum of the phosphor can be an efficient conversion of plasmonic energy into light. Said transformation is a modification of nanoparticle size, modification of nanoparticle shape (typical shapes are cubes, spheres, rods, disks, plates, variations of said shape with features and additional faces), nanoparticulate materials (metals or dielectrics) ), control of interstitial thickness, altering the refractive index of the interstitial or surrounding environment (e.g., depositing an additional capping layer over the nanoparticles) and altering planar metal thickness or metal type (e.g., metals from 5 nm to may be Ag, Al, and/or Au with a thickness range of 100 nm); A ordered array of nanoparticles can be used to improve outcoupling efficiency and/or tune the resonance wavelength.

The planar metal film (eg electrode layer) and/or metal nanoparticles may be pure or alloy, 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. Nanoparticles may additionally consist entirely of dielectric material, may be alloys of metals and dielectric material, or may have a core of one material and may be coated with an outer shell of a different type of material.

The gap thickness (eg material thickness) may be 0-150 nm, more preferably 0-50 nm. When the gap is 0 nm (ie no gap), the nanoparticles can be disposed on a planar metal (eg, electrode layer) and have a wavy morphology that outcouples the SPR energy. The nanoparticle size for scattering light in the visible part of the spectral range (eg, 400-700 nm wavelength) can be from 5 nm to 1,000 nm depending on the nanoparticle material and shape. The gap may be a dielectric material having a refractive index of 1-5, such as an organic or metal oxide.

A gap of 0 nm can be achieved without the use of nanoparticles. In the device example shown in FIG. 8 , the planar metal film may be partially etched through the film thickness to form a corrugated top surface, and the bottom surface of the film may be planar. This can be achieved, for example, using focused ion beam milling. The corrugation processing can be performed on metal attached to the finished OLED device, or on a separate substrate on which the corrugated metal can be peeled off and attached to the OLED or on which the OLED can be grown.

In another embodiment of the disclosed subject matter, the nanoparticles may be individually coated with a dielectric material (eg, by a material) to act as part or all of the interstitial spacing as shown in FIG. 9 . For example, the particles can be coated to a desired overall interstitial thickness to reduce the interstitial layer to zero. In another example, the combination of interstitial layer thickness and nanoparticle coating can achieve a desired total spacer thickness. The nanoparticle coating can act as an adhesive layer to improve nanoparticle adhesion to the layer on which they are deposited or to increase the nanoparticle density thereon.

Since the refractive index of the interstitial layer(s) can affect the resonance of the nanopatch antenna, the use of a material with a voltage tunable refractive index is applied between the metallic cathode and the electrical contact layer underneath the nanoparticles as shown in FIG. 10 . It is possible to provide a way to tune the emission spectrum with an applied voltage. That is, FIG. 10 schematically shows an OLED combined with a nanopatch antenna that uses material(s) with a voltage-tunable refractive index to select the wavelength of the emitted light. In one example, aluminum doped zinc oxide can be used as a voltage tunable refractive index material because its permittivity changes when an applied voltage changes the carrier concentration. In this case, the second insulating layer may be used in the gap to accumulate electric charges. In some embodiments, the second insulating layer may be removed depending on the material properties of the voltage tunable refractive index layer. This can be useful when the OLED stack is a white OLED, i.e., contains red, green and blue emission, since the voltage tunable nanopatch resonance can act as a color filter to selectively pass the desired color. This effectively converts the OLED into a three-terminal device, the voltage applied between the anode and the cathode actuates the OLED, and the voltage applied between the cathode and the electrical contact layer below the nanoparticles is used to select the emitted color. Adjust the patch resonance.

That is, according to at least the embodiment illustrated in FIGS. 3A-10 , a device may 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 may have a thickness of 5 nm to 300 nm.

The device may include a second electrode layer and a substrate, wherein the second electrode layer may be disposed over the substrate and the light emitting layer may be disposed over 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 apart from the light emitting layer by a predetermined threshold distance, wherein the total non-radiative decay rate constant is equal to the total radioactive 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 of 1-5. The light emitting layer of the device may include a transport layer. The light emitting layer may be an organic layer having emitter molecules.

The light emitting layer of the device 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 covalently bonded organic framework, and/or a perovskite nanocrystal. .

The device may include a nanopatch antenna, wherein the resonance of the nanopatch antenna changes the size of the plurality of nanoparticles, changes the ratio of sizes of the plurality of nanoparticles, changes the shape of the plurality of nanoparticles, the plurality of nanoparticles at least one of altering the particle material, controlling the material thickness, changing the refractive index of the material, changing the refractive index of an additional layer disposed over the plurality of nanoparticles, changing the thickness of the first electrode layer and/or changing the first electrode layer material can be adjusted by The plurality of 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 a core of one material, , coated with a shell of a different type of material. At least one of the plurality of nanoparticles of the device may include an additional layer to provide lateral conduction between the plurality of nanoparticles. The plurality of nanoparticles may be coated with an oxide layer, wherein the thickness of the oxide layer is selected to tune the plasmon resonance wavelength of the plurality of nanoparticles or nanopatch antennas. The shape of the plurality of nanoparticles may be at least one of a cube, a sphere, a spheroid, a cylinder, a parallelepiped, a rod shape, a star shape, a pyramid, and/or a polyhedron. At least one size of the plurality of nanoparticles may be between 5 nm and 1,000 nm.

The device may include a second electrode layer, a light emitting layer, a first electrode layer and a corrugated layer disposed over a substrate to which a material is correspondingly corrugated as shown in FIG. 5B .

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

In some embodiments, the device may include an additional layer disposed over the plurality of nanoparticles. Additional layers may include one or more emitter molecules. The additional layer may match the refractive index under the first electrode layer. The additional layer may have a thickness of 1,000 nm or less.

A nanopatch antenna (NPA) may include a planar metal film (eg, an electrode layer), an interstitial material (eg, a dielectric material, etc.) disposed on top of the planar metal and nanoparticles disposed over the interstitial material (eg, FIG. 3A ). as shown in ). This configuration results in a resonant plasmon mode due to the high electric field strength generated in the interstitial medium. The large electric field can be used to enhance the emission rate of an interstitial emitter, known as the Purcell effect, which will stabilize the emitter to a detrimental process that relies on the emitter present in an excited state. Nanopatch antennas can radiate energy from this plasmonic active mode with efficiencies of up to 50%. Previous NPA designs are typically optically pumped (eg by a laser).

In an embodiment of the disclosed subject matter, an OLED stack may be disposed within a dielectric region or NPA gap as shown in FIG. 11 , and the nanoparticles and planar metal may provide an electrical injection path to the device. Typically, it is not expected that 5-20 nm thick OLEDs will operate due to quenching to a non-emissive mode. However, the large Purcell enhancement may allow for rapid coupling of the phosphor to the emissive mode, outperforming the lossy process typically present in OLEDs that are 5-20 nm thick.

Since typical NPA gap thicknesses are about 2-15 nm, it appears impractical to fabricate a full 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 can enhance the emission rate of an emitter disposed in the gap to about 1,000. As discussed above, a Purcell factor of the order of 10 may be sufficient for improvement in OLED emitter stability (eg phosphorescent OLED stability). In embodiments of the disclosed subject matter, some Purcell enhancements can be traded against thicker NPA gaps to better handle OLED stacks about 5-100 nm thick.

It appears impractical to inject charges through metal nanoparticles, typically on the order of 5 nm to 1,000 nm in size. Embodiments of the disclosed subject matter provide a device to address this. 12A shows an indium tin oxide (ITO) coated glass substrate in which metal nanoparticles, typically Ag, Al or Au are dispersed. In one device example, the nanoparticles can be drop cast or spin cast from solution. In another example, nanoparticles can be processed directly on a substrate by photolithography and subsequent metal liftoff. The OLED stack may be deposited over metal nanoparticles and capped with metal electrodes, typically Ag, Al or Au. This may form a corrugated device structure as shown in FIG. 12A .

For applications where a wavy treatment is not desirable, a device as shown in FIG. 12B may be used. To form the device, nanoparticle features are etched into the ITO, but not completely through the ITO layer. In one example, the etching may be performed with a reactive ion etchant due to the directional nature of the etching process.

As shown in FIG. 13 , the thickness of the metal may be deposited to match the depth of the ITO etching, and liftoff of the metal (Ag) on the photoresist (PR) may be performed. This can result in metal nanoparticles (NPs) flush with the top surface of the ITO. The OLED stack can then be grown on the planar substrate and the laminated planar metal as a top contact to form an NPA OLED structure. The injection of charge into the OLED can come from nanoparticles or ITO.

12A-12B, two individual NPAs are highlighted in dashed-line boxes. For nanoparticles that are sufficiently spaced apart from each other so that no coupling exists between the nanoparticles, each NPA operates independently. In this case, the electric field (and thus Purcell enhancement) may be higher for emitter molecules placed inside each NPA rather than outside. This could result in a slight change in emitter velocity spatially throughout the OLED emissive layer, but since the metal contact is closely present to every emitter molecule in the stack, every emitter molecule can sense the increased density of photon states and You will experience an improvement in Purcell. When nanoparticles are formed into an array such that coupling between nanoparticles can occur, this can result in hybrid spatially delocalized modes that can reduce alterations in Purcell enhancement. In some embodiments, nanoparticles may be sufficiently close to form hybridized modes. In another embodiment, the nanoparticles may not hybridize.

In some embodiments, the nanoparticles may be cubes, spheres, spheroids, cylinders, parallelepipeds, and/or rods. The nanoparticles can be varied in size from 5 nm to 1,000 nm, more preferably from 5 nm to 200 nm. Nanoparticles may be dielectrics, semiconductors, or metals.

The interstitial material may be a dielectric or semiconductor and has a refractive index of 1 to 15. The interstitial material may comprise at least one emissive material, which may be fluorescent, phosphorescent, thermally activated delayed fluorescence (TADF) or quantum dots. In some embodiments, there may be multiple light emitting materials of one or more types. The gap may include a host material. The interstices may comprise multiple layers of material or may comprise only one layer. In some embodiments, the interstitial material may comprise a mixture of materials. The gap may be in a thickness range of 0.1 nm to 100 nm.

The planar metal film may be pure or an alloy, 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. The top surface of the planar film may be patterned with additional materials. The top of the metal film may have additional material thereon; The material may include a light emitting member including quantum dots.

That is, in the embodiment shown in FIGS. 11-12B , the device may 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 may include a light emitting layer. The plurality of nanoparticles and the first electrode layer may provide an electrical injection path to the device. The device may include a substrate and a second electrode layer, wherein the first electrode layer may be non-planar, wherein the second electrode layer may be disposed over the substrate, and the plurality of nanoparticles may be disposed over the second electrode layer, Here, the light-emitting layer may be non-planar, may be included in a material, and may be disposed over and conform to the plurality of nanoparticles and the second electrode layer, wherein the first electrode layer may be disposed over and conform to the non-planar light-emitting 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.

As shown in FIG. 13 , the method comprises disposing a first electrode layer over a substrate, disposing a photoresist over the first electrode layer, etching the photoresist and at least a portion of the first electrode layer, and etching the remaining portion of the photoresist. depositing metal on the , removing the metal and photoresist to form nanoparticles from the deposited metal flush with the surface of the first electrode layer to match the depth of the etched portion of the first electrode layer, the first electrode layer and and disposing a light emitting layer on the nanoparticles, and disposing a second electrode layer over the light emitting layer.

Embodiments of the disclosed subject matter provide improved organic light emitting diode (OLED) performance using nanostructures having one or more different geometries, shapes, materials and/or lattice symmetries. Nanostructures can improve emissivity, increase surface plasmon polariton (SPP) mode outcoupling, improve device stability, and/or provide a far-field radiation pattern.

For efficient coupling of the excited state energy to the plasmonic mode, the emitter or emissive layer is placed within a critical distance of the structure and/or layer(s) that increase the photon density of the state (as shown in Figures 14a-14f). ), which can then lead to an enhanced release rate known as the Purcell effect described above. As discussed above, the critical distance may be a distance where the total non-radiative decay rate constant is equal to the total radioactive decay rate constant.

The device examples in FIGS. 14A-14F show variations (cross-sectional views) of cathodes with nanostructures in accordance with embodiments of the disclosed subject matter. It can be etched completely through the metal film (shown in FIGS. 14a, 14b), partially etched through the metal film (shown in FIGS. 14c, 14d), or some holes can be completely etched through the metal film The remaining holes are etched and contain nanoholes (which may also be referred to as nanostructures) that can only be partially etched (shown in FIGS. 14E-14F ). Figures 14a-14f show that a cathode with a nanostructure is capped with a dielectric layer to match the refractive index to that under the cathode to improve crosscoupling of surface plasmon modes throughout the thickness of the metal film (Figures 14a, 14c, 14e). variants (as shown in Figs. 14B, 14D and 14F) or without a dielectric layer (as shown in Figs. 14B, 14D and 14F). The profile of the holes (nanostructures), i.e. whether the hole edges and/or sidewalls are perpendicular to the surface of the film, or whether the sidewalls of the holes have a radius of curvature, can be used to tune the properties of an array with nanostructures. .

Nanostructures can be made of metals, dielectrics, or some combination thereof. 15 shows some examples of different possible combinations according to embodiments of the disclosed subject matter. The use of composites (eg, metals and dielectrics) provides flexibility in device design as the resonant frequency of the localized mode can be tuned and/or selected by the composite used. For each of these substances, the localized electromagnetic mode can be tuned. Common metals used include Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi and/or Ca. It may include, but is not limited to, stacks and/or alloys of the above materials. Dielectrics used may 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.

The localized electromagnetic resonance of a nanostructure or part of a nanostructure can be tuned by the shape of the nanostructure. The shape may include any cylindrical, spherical and/or cube-shaped or any shape with single or multiple localized resonances as shown in FIG. 16 . The radius of curvature for edges and/or corners in a multi-faceted nanostructure can be used to tune the resonant frequency of the nanostructure. Examples of some multiple localized resonant shapes may include ellipsoids and rectangles supporting multiple modes with different frequencies caused by the asymmetry of the nanostructure. For example, FIG. 16 shows how different lengths and/or widths of rectangular nanostructures can result in two distinct resonant frequencies. The plurality of frequency nanostructures can provide improved outcoupling in the case of multi-wavelength or white light-emitting OLEDs.

That is, in the embodiment illustrated in FIGS. 14A-16 , the device may 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 may include a substrate and a second electrode layer, the material being a first dielectric layer and a second dielectric layer, wherein the second electrode layer is disposed over the substrate, the light emitting layer is disposed over the second electrode layer, and the first electrode layer is over the light emitting layer. wherein the first dielectric layer is disposed over the first electrode layer, the plurality of nanoparticles is disposed over the first dielectric layer, and a second dielectric layer is disposed over the plurality of nanoparticles and the first dielectric 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 second electrode layer may be spaced apart from the light emitting layer by a predetermined threshold distance, wherein the total non-radiative decay rate constant is equal to the total radioactive 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 1-5. The light emitting layer may include a transport layer. The light emitting layer may be an organic layer having emitter molecules. The emission 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 covalently bonded organic framework, and a perovskite nanocrystal. The first electrode layer may have a thickness of 5 nm to 300 nm.

The device may include a nanopatch antenna, wherein the resonance of the nanopatch antenna changes the size of the plurality of nanoparticles, changes the ratio of sizes of the plurality of nanoparticles, changes the shape of the plurality of nanoparticles, the plurality of nanoparticles changing the material of the particles, controlling the thickness of the material, changing the refractive index of the material, changing the refractive index of an additional layer disposed over the plurality of nanoparticles, changing the thickness of the first electrode layer and/or changing the material of the first electrode layer It can be adjusted by at least one of. The plurality of 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 a core of one material, , coated with a shell of a different type of material. At least one of the plurality of nanoparticles of the device may include an additional layer to provide lateral conduction between the plurality of nanoparticles. The plurality of nanoparticles may be coated with an oxide layer, wherein the thickness of the oxide layer is selected to tune the plasmon resonance wavelength of the plurality of nanoparticles or nanopatch antennas. The shape of the plurality of nanoparticles may be at least one of a cube, a sphere, a spheroid, a cylinder, a parallelepiped, a rod shape, a star shape, a pyramid, and/or a polyhedron. The size of at least one of the plurality of nanoparticles may be 5 nm to 1,000 nm.

The device may include a substrate and a second electrode layer, wherein the material may be a first dielectric layer, wherein the second electrode layer may be disposed over the substrate, the light emitting layer may be disposed over the second electrode layer, and the first electrode layer The silver may be disposed over the light emitting layer, the first dielectric layer may be disposed over the first electrode layer, and the plurality of nanoparticles may be disposed over the first dielectric 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 device may include a substrate and a second electrode layer, wherein the material is a first dielectric layer and a second dielectric layer, wherein the plurality of nanoparticles may be disposed in the second dielectric layer, the second dielectric layer and the plurality of nanoparticles comprising: may be disposed over the substrate, the first dielectric layer may be disposed over the second dielectric layer and the plurality of nanoparticles, the first electrode layer may be disposed over the first dielectric layer, the light emitting layer may be disposed over the first electrode, The second electrode may be disposed on the light emitting 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 device may include a substrate and a second electrode layer, the material may be a first dielectric layer, a second dielectric layer, the first electrode layer may be disposed over the substrate, the first dielectric layer may be disposed over the first electrode layer, and , the plurality of nanoparticles may be disposed over the first dielectric layer, the second dielectric layer may be disposed over the plurality of nanoparticles and the first dielectric layer, the light emitting layer may be disposed over the second dielectric layer, and the second electrode layer may be disposed over the light emitting layer. can be placed.

The device may include a substrate and a second electrode layer, wherein the material is a first dielectric layer and a second dielectric layer, wherein the second electrode layer may be disposed over the substrate, and the light emitting layer may be disposed over the second electrode layer, the plurality of The nanoparticles may be disposed over the light-emitting layer, a second dielectric layer may be disposed over the plurality of nanoparticles and the light-emitting layer, the first dielectric layer may be disposed over the second dielectric layer, and the first electrode layer disposed over the first dielectric 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 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, wherein the first layer is thicker than the second layer. The first layer may be a dielectric material and the second layer may be a nanoparticle adhesive layer. The thickness of the first layer may be between 1 and 100 nm, and the thickness of the second layer may be less than 5 nm. The material may have a thickness of 1,000 nm or less. The material of the device may have a refractive index of 1-5. The material may include at least a portion of a coating disposed over the plurality of nanoparticles. The coating disposed over the plurality of nanoparticles may be a dielectric coating.

The device may include a second electrode layer, wherein the light emitting layer is contained within an organic light emitting diode (OLED), the OLED 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 emission 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 covalently bonded organic framework, and/or a perovskite nanocrystal.

The first electrode layer of the device may be spaced apart from the emissive layer by a predetermined threshold distance, wherein the critical distance is a distance at which the total non-radiative decay rate constant is equal to the total radioactive decay rate constant. The first electrode layer includes 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 can do. The first electrode layer may be patterned with additional materials. Additional materials may include fluorescent emitters, phosphorescent emitters, quantum dots, metal organic frameworks, covalently bonded organic frameworks and/or light emitting members of perovskite nanocrystals. 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.

The device may include a nanopatch antenna, wherein the resonance of the nanopatch antenna changes the size of the plurality of nanoparticles, changes the ratio of sizes of the plurality of nanoparticles, changes the shape of the plurality of nanoparticles, the plurality of nanoparticles of changing the material of, adjusting the thickness of the material, changing the refractive index of the material, changing the refractive index of an additional layer disposed over the plurality of nanoparticles, changing the thickness of the first electrode layer and/or changing the material of the first electrode layer It can be adjusted by at least one.

The plurality of nanoparticles of the device are 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 cores of one material. may be coated with a shell of a different type of material.

At least one of the plurality of nanoparticles of the device may include an additional layer to provide lateral conduction between the plurality of nanoparticles. The plurality of nanoparticles is coated with an oxide layer, wherein the thickness of the oxide layer is selected to tune the plasmon resonance wavelength of the plurality of nanoparticles or nanopatch antennas. The plurality of nanoparticles may be colloidal synthetic nanoparticles formed from solution. The shape of the plurality of nanoparticles may be at least one of a cube, a sphere, a spheroid, a cylinder, a parallelepiped, a rod shape, a star shape, a pyramid, and a polyhedral object. The size of at least one of the plurality of nanoparticles may be 5 nm to 1,000 nm. At least one of the plurality of nanoparticles may have a size of 5 nm to 200 nm. The size of at least one of the plurality of nanoparticles may be between 5 nm and 100 nm.

The device can include a substrate, a second electrode layer, wherein the second electrode layer can be disposed over the substrate, and the nanoparticles can be disposed on the second electrode layer, wherein the light emitting layer can be included in a material, the plurality of nanoparticles It may be disposed on the second electrode layer including, the first electrode layer is disposed on the light emitting 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.

Inorganic light emitting diodes (LEDs) are gaining a reputation for lighting and display applications. Some inorganic light emitting diodes suffer from outcoupling issues, including efficiency roll-off at high luminance, as well as efficiency issues and angle dependence. The physical origin of the “droop” depends on the LED system (eg, material, device design, etc.), but the droop comes from luminescence quenching phenomena, such as Auger recombination, that reduce luminous efficiency through non-radiative processes. It is explained as originating. As interactions may be more common, the likelihood of the luminescence quenching event increases with increasing local carrier density.

The disclosed subject matter provides a device comprising an enhancement layer. The enhancement layer may be a plasmonic, hyperbolic metamaterial and/or optically active metamaterial, which is a material having both a negative permittivity and a negative transmittance. Examples of enhancement layers may include metal cathode or anode thin films, stacks of metal films and/or dielectric layers, or uniformly spaced metal nanoparticles.

For example, FIG. 5A shows the enhancement layer as a metal electrode. Due to the increased density of optical states that rapidly quench the excited state energy into the surface plasmon mode of the enhancement layer, the strain in the enhancement layer can be placed within a critical distance of the recombination zone as shown in Figure 5a to accelerate the emission rate. . The critical distance may be a distance at which the total non-radioactive decay rate constant is equal to the total radioactive decay rate constant. This can reduce the excited state interactions and thus reduce the efficiency roll-off at high current densities. As used throughout this application, a critical distance may be a distance in which the total non-radioactive decay rate constant is equal to the total radioactive decay rate constant.

In another example, the enhancement layer may have a plurality of layers as shown in FIG. 17 . Each layer may include a unit cell having a plurality of unit cell subcomponent layers. Each unit cell may have a first unit cell subcomponent and a second unit cell subcomponent.

An increased junction temperature in an LED typically results in a decreased light output. This is especially true for yellow and/or red AlGaInP LEDs. Manufacturers sometimes apply compensation circuitry to mitigate the light loss with temperature, but this can lead to a reduction in the lifetime of the LED. The LED junction temperature may depend on the ambient temperature including any applied heat-sinking features, the current through the LED and/or the efficiency of the surrounding material. The enhancement layer of the disclosed subject matter can reduce the excited state lifetime of the LED, and can reduce heating of the LED device, thereby increasing the stability of the LED device or any component in contact with the LED device. By reducing the current through the LED to produce a given light output, the resulting reduced junction temperature and/or thermal load to the device may allow for reduced heat sink and compensation circuitry. This may reduce manufacturing cost and/or complexity, and may reduce the size and/or form factor of the LED.

Notwithstanding the reduced efficiency roll-off at high current densities, embodiments of the disclosed subject matter can be at lower efficiencies than in the absence of the enhancement layer, where much greater excited state energy can be quenched into the non-radiative mode of the enhancement layer. Because. To restore device efficiency, some embodiments may include outcoupling structures based on nanoscale objects. In some embodiments, outcoupling structure features may be included in the enhancement layer.

In an embodiment of the disclosed subject matter, a nanoscale outcoupling comprising an enhancement layer and a layer of planar metal, dielectric interstitial material, and nanoparticles. As used herein, it can be an enhancement layer with a nanopatch outcoupling structure. Such an outcoupling structure may convert plasmonic energy back to photons and may not be constrained by the index contrast external quantum efficiency limits of conventional LEDs. That is, an LED having an enhancement layer of the disclosed subject matter can meet or exceed typical device efficiencies without the enhancement layer and outcoupling structure. In some embodiments, for example, as shown in FIGS. 14A-14F , the enhancement layer may be a planar metal film and/or metal nanoparticles, may be pure or an alloy or mixture, preferably Ag, Al, Ag-Al It may be an alloy or Au. The enhancement layer may be formed of one or more other materials, such as Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ca, Ru, Pd, In and/or Bi. can be made with The outcoupling structure may be a metal cathode or anode thin film, a stack of metal films, a dielectric layer and nanoparticles, a grating (eg, one-dimensional grating, two-dimensional grating, hexagonal grating, bullseye grating, etc.) and/or dispersed Braggs. (Bragg) may contain a reflector. The grating may comprise a dielectric material or a mixture of dielectric, semiconducting and metallic materials.

Nanoparticles may consist entirely of dielectric material. In some embodiments, the nanoparticles may be an alloy of a metal, may be a dielectric material, and/or may have a core of one material, and may be coated with a shell of a different type of material. Typical nanoparticle sizes for scattering of light in the visible portion of the spectrum can range from 5 nm to 1,000 nm, depending on the nanoparticle material and shape. When the LED is designed for emission in the near infrared or infrared, the particle size can be in the range of 500 nm to 5,000 nm. Table 1 below discloses examples of LED materials, enhancement layers and/or metal nanoparticle materials and/or particle size ranges. The gap thickness is in the range of 0-150 nm, more preferably 0-50 nm for visible emission (eg 400-700 nm), and can be larger gaps for infrared spectrum (eg 700 nm-1 mm). have. If the gap can be 0 nm (ie no gap), the nanoparticles can be directly on top of the planar metal and act in a wavy shape to outcouple the surface plasmon energy. The gap may be made of a dielectric material, typically having an index of refraction of 1-5, such as an organic material, a metal oxide (crystalline or amorphous) and/or a nitride. The refractive index of the gap may range from 1.01 to 5 depending on the material used.

Nanopatch antenna resonance changes the size of the plurality of nanoparticles, changes the shape of the plurality of nanoparticles, changes the material of the plurality of nanoparticles, controls the thickness of the material, changes the refractive index of the material layer, on the plurality of nanoparticles It may be adjusted by at least one of a change in the refractive index of the disposed material or additional layer, a change in the electrode layer thickness and/or a change in the material of the first electrode layer. The plurality of 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 cores of one material. and are coated with a shell of a different type of material. At least one of the plurality of nanoparticles of the device may include an additional layer to provide lateral conduction between the plurality of nanoparticles. The plurality of nanoparticles may be coated with an oxide layer, wherein the thickness of the oxide layer may be selected to tune the plasmon resonance wavelength of the plurality of nanoparticles or nanopatch antennas. The shape of the plurality of nanoparticles may be at least one of a cube, a sphere, a spheroid, a cylinder, a parallelepiped, a rod shape, a star shape, a pyramid, and/or a polyhedron. The size of at least one of the plurality of nanoparticles may be 5 nm to 1,000 nm.

In some embodiments, the device may include an additional layer disposed over the plurality of nanoparticles. Additional layers may include one or more emitter molecules or emissive materials, such as quantum dots, inorganic phosphors, and the like. The additional layer may match the refractive index under the first electrode layer. The further layer has a thickness of 1,000 nm or less.

In some embodiments, the plurality of nanoparticles may be deposited by inkjet printing. In other embodiments, the plurality of nanoparticles may be deposited by a mechanism involving touch, such as brushing. In some embodiments, the plurality of nanoparticles may be deposited by spraying particles suspended in a solvent or aerosol. In other embodiments, the plurality of nanoparticles comprises a lift-off process, a developing process, a light-based lithography such as photolithography or laser interference lithography or zone plate lithography, an electron beam lithography process, and/or a focused ion milling process. It can be manufactured using a top-down approach. In some embodiments, the plurality of nanoparticles may be deposited by spin coating, a doctor blading process, slot-die coating, bar coating, and/or dip coating. When the nanoparticles are deposited, a drying process can be used to remove any residual solvent, air or moisture from the deposition surface. The drying method may include vacuum drying, nitrogen blow off, HEPA (High Efficiency Particulate Air) drying, drying in a convection oven, surface tension gradient drying, IPA vapor vacuum drying and/or spin drying. . In other embodiments, nanoparticles may be formed by self-assembly comprising the assembly of the particles themselves or by self-assembly of another material, such as a nano-scale shape of a copolymer or polymer. The plurality of nanoparticles may be formed by depositing a second material on the self-assembled material. The self-assembled material may or may not be removable after formation of the plurality of nanoparticles. In some embodiments, LEDs, enhancement layers and/or nanoparticles may be encapsulated. The encapsulating material may include oxide coatings and epoxies such as polyurethanes, silicones, and the like.

In some embodiments, the plurality of nanoparticles may be formed in a plurality of different sizes or shapes rather than a single size or shape. This may enable the outcoupling layer or structure to efficiently scatter light of all multiple frequencies or colors having the same layer.

In some embodiments, a white LED may use a nanoparticle outcoupling structure of a predetermined resonance to selectively outcouple a specific wavelength range. In that way, white LEDs can be fabricated over a large, predetermined area, and the resonance of the nanoparticle outcoupling structure (due to the nanoparticle size, refractive index, etc. selected) can be subordinated to red, green, blue and/or any other desired color. It can be used to create pixels.

Since the refractive index of the interstitial layer(s) affects the resonance of the nanopatch antenna, the incorporation of interstitial materials with nonlinear optical properties and/or voltage tunable refractive indices is associated with the metal cathode and metal cathode beneath the nanoparticles as shown in FIG. The emission spectrum can be tuned by the voltage applied between the electrical contact layers. In one example, aluminum doped zinc oxide can be used as a voltage tunable refractive index material because its permittivity changes when an applied voltage changes the carrier concentration. In this case, the second insulating layer may be disposed in the gap to accumulate electric charges. The second layer may not always be used depending on the material properties of the voltage tunable refractive index layer. This is particularly useful if the LED is a white LED (ie an LED with red, green and blue emission), since the voltage tunable nanopatch resonance can act as a color filter that selectively passes the desired color. This can effectively turn the LED into a three-terminal device, in which a voltage applied between the anode and cathode actuates the LED, and a voltage applied between the cathode and the electrical contact layer under the nanoparticles selects the emitted color. To tune the nanopatch resonance.

In the case of individual LED subpixels, such as in displays, the resonance of the nanoparticle outcoupling structure may be intentionally mismatched from the LED's spontaneous emission. In that way, the nanoparticle outcoupling structure can act as a color filter that shifts the peak wavelength. In another embodiment, a nanoparticle outcoupling structure that is not resonance-matched can be used to narrow the emission spectrum. For example, a green LED paired with a blue resonant outcoupling structure may reduce the red wavelength of the LED to provide narrowing. Conversely, pairing a green LED with a red resonant outcoupling structure can reduce the blue wavelength of the LED to provide narrowing.

In another embodiment, the device may include an emissive outcoupling layer within a predetermined proximity to the enhancement layer as shown in FIGS. 3A-3C . The emission outcoupling layer(s) may include a light emitting material capable of being excited by the energy of a surface plasmon polariton in an adjacent enhancement layer. The luminescent material can be, but is not limited to, quantum dots, perovskite nanocrystals, metal organic frameworks, covalently bonded organic frameworks, thermally activated delayed fluorescence (TADF) emitters, fluorescent emitters, and/or phosphorescent organic emitters. . In the device example, the light emitting material has absorption and emission spectra demonstrating small Stokes shifts, such that a predetermined small difference between the LED excited state energy quenched by the enhancement layer and light emitted from the emission outcoupling layer(s) It may be beneficial for a red shift to occur. This may preserve the emission color of the device. In another example of the device, the luminescent material may be selected to down-convert higher energy excitation (eg, blue) to a lower energy wavelength (eg, green or red). This allows a single LED structure to be used per pixel of the display, and the color is selected by the emission outcoupling layer. For example, this can be achieved by depositing quantum dots of different sizes on the outcoupling layer(s) of different pixels to tune the emission wavelength. The emission outcoupling layer may or may not be combined with a nanoparticle based outcoupling structure. In one embodiment, an emission outcoupling layer may be disposed between the enhancement layer and the nanoparticles. In this case, the radiation speed of the light emitting material in the emission outcoupling layer can be accelerated, so that the outcoupling efficiency can be improved.

The array of nanoparticles on the surface of the dielectric interstices can be designed to fit the device application. In one embodiment, the random arrangement of nanoparticles yields a near Lambertian emission profile that may be desirable for use in lighting applications or display applications (eg, where point source emission is not desired). can provide Inorganic LEDs tend to undergo directed emission profiles, which can create random nanoparticle arrays of particular interest in certain applications. In another embodiment, the nanoparticles may be arranged in an array to result in a dispersed emission profile that may be desired for some mobile applications or in applications requiring maximum outcoupling of light, regardless of angular dependence. Nanoparticles arranged in an array can achieve greater efficiencies than randomly arranged nanoparticles, and the choice of a specific array pitch and duty cycle depends on the array resonance and thus the outcoupling wavelength at which the array has maximum efficiency. to be able to adjust

In other embodiments, the nanoparticles may be metallic and coated with a non-metallic coating. The nanoparticles can be placed directly on top of the enhancement layer as shown in FIG. 9 . In this embodiment, the refractive index of the coating may be from 1.01 to 5. The thickness of the coating may be between 3 nm and 1,000 nm, more preferably between 3 nm and 100 nm. In one embodiment, the nanoparticle coating may act as part or all of the interstitial spacing. This can be achieved by coating the particles with the desired overall interstitial thickness, reducing the cap layer to zero, or a combination of interstitial layer thickness and nanoparticle coating to achieve the desired total spacer thickness. Additionally, the nanoparticle coating can act as an adhesive layer to increase nanoparticle density or improve nanoparticle adhesion to a layer that can be deposited. The nanoparticles may be made of Ag, Al, Ag-Al alloy, Au, Au-Ag alloy and/or Au-Al alloy. Enhancement layer and/or nanoparticles include Ag, al Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ca, Ru, Pd, In and/or Bi However, it may be made of other materials, but not limited thereto. In an embodiment, the metallic core may comprise Ag spheres coated in more than one material, such as Rh, and then coated with a dielectric material, such as _{SiO 2 , as shown in FIG. 9 .}

Enhancement layers and/or nanoparticles may include planar metals, stacks of metal and dielectric layers, stacks of metal and semiconducting layers, and/or perforated metal layers, for example as shown in FIGS. 15 and 18 . Dielectric materials that are part of the enhancement layer include, but are not limited to, oxides, fluorides, nitrides, and/or amorphous mixtures of such materials. Other non-limiting materials include combinations of materials presented as LED materials in Table 1 shown below, GeTe, InSb, InAs, Ge, GaSb, Si, GaAs, CdTe, AlSb, HgSe, AlAs, GaP, ScN, ZnTe, CdS, CuBr , CuI, AlP, SiC, CuCl, GaN, ZnS, BN, ZnO, GeO ₂ , AlN, CsI, CsBr, NaBr, CsCl, KBr, KCl and/or SiO ₂ . The metal layer may include Ag, Au, Al, Zn, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ca, Ru, Pd, In and/or Bi. alloys and mixtures of metals. The enhancement layer may be graphene, conductive oxide and/or conductive nitride for LEDs outside the visible range.

In some embodiments, the enhancement layer may be patterned with nanoscale holes, such as shown in FIGS. 14A-14F . Such holes may be present in an array, may be randomly arranged, or may be pseudo-randomly arranged. The size, shape and/or orientation of the hole may set the frequency of light that may be outcoupled from the enhancement layer.

In some embodiments, the enhancement layer may have a patterned bullseye grating thereon. In some embodiments, the enhancement layer may have a gap and may have a patterned bullseye grating on top of the gap material. In some embodiments, the bullseye grating may be circular. In other embodiments, the bullseye grating may be oval.

In some embodiments, the enhancement layer may be partially etched on one side of the enhancement layer to form nanoscale outcoupling features, such as as shown in FIGS. 14A-14F . In some embodiments, nano-sized features may be present on both sides of the enhancement layer. In some cases where there are nano-sized features on both sides of the enhancement layer, the minimum dimension of the feature may exceed 10 nm, in other cases the minimum dimension of the feature may exceed 20 nm, and in other cases the feature The minimum dimension of may exceed 50 nm.

For vertical LEDs, some embodiments allow incoupling of the excited states of the enhancement layer over as many areas as possible, where the excited states can be outcoupled from the nanoparticle-based outcoupling layer to air. Therefore, it is possible to solve the problem of shading from the upper electrode. In some embodiments, the enhancement layer may act as an electrical contact.

When the enhancement layer acts as an electrical contact, there is no longer any shade of light emitted from the top. Surface plasmons can propagate up to 10 to hundreds of micrometers in smooth silver, where excited states from the recombination zone can couple to the enhancement layer at one location in the device, and at another location up to 10 to hundreds of micrometers in the device. means that it can be outcoupled to photons in glass space. This can exclude shading from the electrode by careful design of the side patterning of the outcoupling structure.

The use of nano-sized outcoupling structures can increase LED yield, since the outcoupling can have dispersion designed to minimize dispersion due to layer thickness across the wafer. Thus, the final LED with the enhancement layer and outcoupling may exhibit less strain across the wafer compared to the reference LED.

Devices manufactured according to embodiments of the present invention may be incorporated into a wide variety of electronic component modules (or units) that may be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components may include display screens, lighting devices, such as discrete light source devices or lighting panels, etc. that may be used by an end user product manufacturer. The electronic component module may optionally include driving electronic components and/or power source(s). Devices manufactured in accordance with the present invention may be incorporated into a wide variety of consumer products having one or more of the electronic component modules (or units) incorporated therein. The consumer product may comprise any type of product comprising one or more of one or more light source(s) and/or some type of visual display. Some examples of such consumer products include flat panel displays, computer monitors, medical monitors, televisions, billboards, indoor or outdoor lighting and/or signaling lights, heads-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, cell phones. , tablet, phablet, personal digital assistant (PDA), laptop computer, digital camera, camcorder, viewfinder, micro display, 3D display, vehicle, aerial display, large-area wall, theater or stadium screen or signage .

Other examples of such consumer products include augmented reality/virtual reality (AR/VR) displays, displays or visual elements in glasses or contact lenses (e.g. micro LEDs in combination with sapphire chips), LED wallpaper, LED jewelry and apparel. .

A variety of control mechanisms may be used to control devices fabricated according to the disclosed subject matter, including passive and active matrices. Many devices are intended for use in a temperature range comfortable for humans, such as 18°C to 30°C, more preferably room temperature (20-25°C), but may be used at temperatures outside this temperature range, such as -40°C to +80°C. can

Devices made according to the disclosed subject matter may include other components for controlling and manipulating light from the final product. The components include polarizers, color filters and liquid crystals.

Inorganic LEDs of the disclosed subject matter are GaAs, AlGaAs, GaAsP, AlGaInP, GaP, GaAsP, GaN, InGaN, ZnSe, SiC, Si ₃ N ₄ , Si, Ge, sapphire, BN, ZnO, AlGaN, perovskite and/or It may be made from materials which may include, but are not limited to, quantum confinement systems. Quantum confinement systems can include systems in which the size of the particle is near the size of the Bohr radius of the exciton, resulting in an increase in the bandgap of the material and a higher luminescent state than the bulk bandgap energy. For example, the bulk bandgap of CdS is about 2.42 eV (~ 512 nm), and when the quantum dots (QDs) have a size of 1-8 nm, they are generated from a CdS emitter of about 380 to 480 nm. Electroluminescent devices can be made of quantum confinement materials that can benefit from enhancement layers to reduce excited state transients. Electroluminescent devices based on quantum confinement materials have not yet been commercialized, indicating that there may be stability improvements in addition to the improvements in efficiency achieved for these systems. Some electroluminescent devices using quantum confinement materials may use a mixture of inorganic quantum confinement materials within the recombination zone, such as CdS quantum dots, with an organic or inorganic transport layer. For example, some EL quantum dot devices may _{use NPD as the hole transport layer and Alq 3} as the electron transport layer, while others may use NPD as the hole transport layer and ZnO nanoparticles as the electron transport layer. Quantum confinement systems are not limited to inorganic semiconductors. The same is true of mixed organic-inorganic perovskite materials such as _{CsPbBr 3} from emitting quantum dots, which can be used for example in EL devices. Other heavy metal-free quantum dot materials include InP/ZnS, CuInS/ZnS, Si, Ge and C or peptides. Typically, QD materials can be deposited by spin coating or contact printing from solution or suspension.

Transition dipole orientation can affect plasmonic coupling efficiency and coupling distance, with more vertically oriented dipoles increasing coupling. Therefore, vertically oriented dipoles are most desirable for enhancement layers that are planar or nearly planar. In practice, however, due to the surface roughness of the enhancement layer, a perfectly horizontal dipole may have some coupling efficiency to the plasmonic mode of the planar and nearly planar enhancement layer.

Inorganic LEDs used in embodiments of the disclosed subject matter may be combined with one or more phosphorescent emitters to produce a wide range of colors (eg, white) from the LEDs. The phosphor(s) may (a) be disposed in the epoxy used to encapsulate the LED or (b) the phosphor may be disposed remotely from the LED. The phosphor absorbs photons from the LED and can act as a 'down-converting' layer designed to re-emit lower energy photons. Other downconversion materials available may be made of inorganic or organic phosphor, fluorescent, TADF, quantum dots, perovskite nanocrystals, metal organic frameworks or covalently bonded organic framework materials. Thus, embodiments of the disclosed subject matter comprising enhancement layers and nano-sized outcouplings may include metal and dielectric interstitial materials, wherein a layer of nanoparticles may be disposed between an inorganic LED and a phosphor or down-converting layer. have. Layers of LEDs, metals, dielectric interstitial materials and/or nanoparticle devices may be encapsulated with an epoxy or film comprising a down conversion medium. The down conversion material may be disposed outside the layers of the LED, metal, dielectric interstitial material and/or nanoparticle encapsulation.

Other options for generating white light include the use of homoepitaxial ZnSe blue LEDs grown on ZnSe substrates, which simultaneously produce blue light from the active region and yellow emission from the substrate; and GaN on a Si (or SiC or sapphire) substrate. One or more embodiments of the disclosed subject matter may be combined with such devices.

Devices fabricated according to embodiments of the disclosed subject matter can be combined with QNED technology (quantum dot nanocells) where GaN-based blue emitting nanorod LEDs replace discrete inorganic LEDs as pixelated blue light sources in displays. Formation of GaN nanorods is described in scientific and patent literature, such as Electrically Tunable Diffraction Efficiency from Gratings in Al-doped ZnO" by George et al., Applied Physics Letters 110, 071110 (2017) and "Light-emitting devices, light-emitting devices. A pixel structure comprising the same and a method for manufacturing the same” can be found in patent publication WO2020036278. The disclosed embodiments can be combined with the above device.

Some embodiments may include an enhancement layer and a nano-sized outcoupling structure having a layer of metal, dielectric interstitial material, and nanoparticles. The outcoupling structure may be combined with a spacer (or surface plasmon amplification by radiation or stimulated emission of a plasmonic laser) or a surface plasmon polariton (SPP) spacer or nanolaser, which will convert the plasmonic energy back to photons .

LEDs formed using one or more embodiments of the disclosed subject matter can be fabricated directly on a wafer, then selected and placed to create larger electronic component modules. Within the module there may be additional LEDs that do not use enhancement layers.

In some embodiments, LEDs formed with the enhancement layer and the outcoupling structure can be patterned directly on a wafer or substrate and then incorporated into an electronic component module. In such a case, if it is desired to exclude a device (eg, an ideal peak wavelength), it can be excluded by not including an outcoupling layer on the device, since not including an enhancement layer makes the LED darker. In some embodiments of patterning red, green, blue (RGB) full color modules on a single substrate, at least one color subpixel may have an enhancement layer and outcoupling.

According to embodiments of the disclosed subject matter, a light emitting diode and/or device (LED) may be provided. For example, as shown in FIG. 17 , an LED may include a substrate, an anode (or p-type contact), a cathode (n-type contact), and an enhancement layer and a recombination zone disposed between the anode and cathode. The recombination zone may include an inorganic semiconducting quantum well. According to embodiments, the light emitting device may be incorporated into one or more devices, such as consumer products, electronic component modules, lighting panels and/or signs or displays.

Table 1 below provides non-limiting examples of LED materials and potential enhancement layer and/or metal nanoparticle materials and particle size ranges, and estimates a dielectric layer between the enhancement layer and the metal nano-sized material having a refractive index of 1.5 and nano Assume a monodisperse monolayer of particles. The particle size can be estimated as nanocubes, and particles with variable length axes can have different ranges.

When the nanoparticles aggregate together, the resonance wavelength of the outcoupling can be increased. For example, large agglomeration of uniform UV resonant particles can achieve IR NPA resonance. So, given agglomeration, some preferred embodiments of LED semiconductor materials and nanoparticle outcoupling materials and size distributions are provided. Table 2 below estimates the dielectric layer between the metal nano-sized material and the enhancement layer having a refractive index of 1.5, and allows for nanoparticle agglomeration, without limitation of LED materials and potential enhancement layers and/or metal nanoparticle materials and particle size ranges. give a typical example.

As described above, embodiments of the disclosed subject matter may provide devices that may include an inorganic light emitting layer, a first electrode layer (eg, enhancement layer), and an outcoupling structure. The first electrode layer may be spaced apart from the inorganic light emitting layer by a predetermined threshold distance, wherein the total nonradiative decay rate constant is equal to the total radioactive decay rate constant. The device may include at least one of at least one color filter and at least one down conversion layer disposed over the inorganic light emitting layer. The device may include an inorganic transport material. The device may include an inorganic transport material and/or an organic transport material.

The first electrode layer of the device may be at least one of a metal, a stack of metal films and dielectric layers, a plasmonic, hyperbolic metamaterial and/or optionally an active metamaterial. The first electrode layer may be at least one of 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 have a thickness of 5 nm to 1,000 nm. The material may be layered or layered and may have multiple layers. Each layer of the plurality of layers may include a unit cell having a plurality of unit cell subcomponent layers. Each unit cell may have a first unit cell subcomponent and a second unit cell subcomponent. In some embodiments, the first electrode layer can be patterned with additional materials or can be patterned with nano-sized holes.

The outcoupling structure of the device comprises at least one Ag particle, an Al particle, an Ag-Al alloy, an Au particle, an Au-Ag alloy, a dielectric material, a semiconductor material, an alloy of a metal, a mixture of dielectric materials, a stack of one or more materials, and or a plurality of nanoparticles formed from a core of one material and coated with a shell of a different type of material. The outcoupling structure may include a plurality of nanoparticles that are colloidal synthetic nanoparticles formed from solution. The outcoupling structure may include a plurality of nanoparticles arranged in a periodic array having a predetermined array pitch. The outcoupling structure may include a plurality of nanoparticles arranged in an aperiodic array. The shape of the plurality of nanoparticles may be at least one of a cube, a sphere, a spheroid, a cylinder, a parallelepiped, a rod shape, a star shape, a pyramid, and a polyhedral object.

The outcoupling structure may include a plurality of nanoparticles, and the device may include an adhesive layer disposed between the material and the plurality of nanoparticles. At least one property of the nanoparticles may be selected to alter the spectrum of light emitted by the emissive layer or to alter the angular dependence of the light emitted by the emissive layer. The properties selected may be the size of the nanoparticles, the composition of the nanoparticles and/or the distribution of the nanoparticles. The device may include at least one additional layer disposed over the plurality of nanoparticles. The additional layer may match the refractive index under the first electrode layer. The thickness of the additional layer may be between 3,000 nm and 1,000 nm and/or between 1,000 nm and 10 nm. Additional layers may be transparent. In some embodiments, a device may include a material disposed between the first electrode and the plurality of nanoparticles. In some embodiments, the device may include an organic transport material.

The outcoupling structure may include a plurality of nanoparticles comprising at least one of a metal, a dielectric material, and/or a hybrid of a metal and a dielectric material. The plurality of nanoparticles may be coated with an oxide layer, the thickness of which is selected to tune the plasmon resonance wavelength of the plurality of nanoparticles or nanopatch antennas. The size of at least one of the plurality of nanoparticles may be 5 nm to 1,000 nm. At least one of the plurality of nanoparticles may include an additional material that provides lateral conduction between the plurality of nanoparticles. In some embodiments, the outcoupling structure may comprise a plurality of nanoparticles that are coated. In some embodiments, the outcoupling structure may have a plurality of nanoparticles coated with a metallic, non-metallic coating.

The inorganic light emitting layer of the device is GaAs, AlGaAs, GaAsP, AlGaInP, GaP, GaAsP, GaN, InGaN, ZnSe, SiC, Si ₃ N ₄ , Si, Ge, Sapphire, BN, ZnO, AlGaN, perovskite and/or quantum It may be at least one of the constraint systems. The inorganic emissive layer may be electroluminescent and may comprise a quantum confinement material comprising a mixture of inorganic quantum confinement materials such as CdS quantum dots, an organic transport layer and/or an inorganic transport layer.

The inorganic light emitting layer of the device may comprise at least one of GaAs and/or AlGaAs, wherein the outcoupling structure comprises a plurality of nanoparticles, which may be at least one of Ag, Au, ITO, Si and/or Ge. The size of the nanoparticles may be 100-250 nm, and the wavelength of light emitted by the device may be 760 nm to 2,000 nm.

In some embodiments, the inorganic light emitting layer of the device may comprise at least one of AlGaAs, GaAsP, AlGaInP and/or GaP, wherein the outcoupling structure comprises a plurality of nanoparticles, wherein the nanoparticles are Ag, Au, SiO ₂ , at least one of Si and/or Ge. The size of the nanoparticles may be 75-200 nm, and the wavelength of light emitted by the device may be greater than 610-760 nm.

In some embodiments, the inorganic light emitting layer of the device may comprise at least one of GaAsP, AlGaInP and/or GaP, wherein the outcoupling structure comprises a plurality of nanoparticles, wherein the nanoparticles are Ag, Au, SiO ₂ , It may be at least one of Si and/or Ge. The size of the nanoparticles may be 60-150 nm, and the wavelength of light emitted by the device may be 590-610 nm.

In some embodiments, the inorganic light emitting layer of the device may comprise at least one of GaAsP, AlGaInP and/or GaP, wherein the outcoupling structure comprises a plurality of nanoparticles, wherein the nanoparticles comprise Au, SiO ₂ , Si and / or at least one of Ge, the size of the nanoparticles may be 50-100 nm, and the wavelength of light emitted by the device may be 570-590 nm.

In some embodiments, the inorganic light emitting layer of the device may comprise at least one of GaAsP, AlGaInP, GaP, and/or InGaN/GaN. The outcoupling structure may include a plurality of nanoparticles, wherein the nanoparticles may include at least one _{of Ag, Al, Rh, Pt, SiO 2} , Si, Ge, and/or TiO _{2 , wherein the nanoparticles} The size may be 40-125 nm and/or the wavelength of light emitted by the device may be 500-570 nm.

In some embodiments, the inorganic light emitting layer of the device can comprise at least one of ZnSe, InGaN, SiC and/or Si, wherein the outcoupling structure can comprise a plurality of nanoparticles, wherein the nanoparticles are Ag; at least one of Al, Rh, Pt and/or TiO ₂ , wherein the size of the nanoparticles may be 40-125 nm and/or the wavelength of light emitted by the device may be 450-500 nm.

In some embodiments, the inorganic light emitting layer of the device can comprise InGaAs, wherein the outcoupling structure can comprise a plurality of nanoparticles, wherein the nanoparticles are at least one _{of Al, Rh, Pt and/or TiO 2} may include, and the size of the nanoparticles may be 50-100 nm, and the wavelength of light emitted by the device may be 400-450 nm.

In some embodiments, the inorganic light emitting layer of the device can comprise at least one of diamond, BN, AlN AlGaN and/or AlGaInN, wherein the outcoupling structure can comprise a plurality of nanoparticles, wherein the nanoparticles are Al; It may include at least one of Rh, Pt and/or TiO ₂ , the size of the nanoparticles may be 30-75 nm, and the wavelength of light emitted by the device may be 200 nm to 400 nm.

The inorganic light emitting layer of the device may comprise a blue light emitting diode having a yellow phosphor, wherein the outcoupling structure may comprise a plurality of nanoparticles, wherein the nanoparticles are composed of Ag, Al, Rh, Pt and/or TiO ₂ . and at least one selected from the group consisting of, wherein the size of the nanoparticles may be 40-125 nm, and white light may be emitted by the device.

The inorganic light emitting layer of the device may include at least one of GaAs and/or AlGaAs, wherein the outcoupling structure may include a plurality of nanoparticles, wherein the nanoparticles are Ag, Au, ITO, Si, Ge, SiO ₂ , Al, Rh and/or Pt, the size of the nanoparticles may be 5-250 nm, and the wavelength of light emitted by the device may be 760 nm to 2,000 nm.

The inorganic light emitting layer of the device may include at least one of AlGaAs, GaAsP, AlGaInP and/or GaP, wherein the outcoupling structure may include a plurality of nanoparticles, wherein the nanoparticles are Ag, Au, SiO ₂ , Al , Rh, Pt, Si and/or Ge, wherein the size of the nanoparticles may be 5-200 nm, and the wavelength of light emitted by the device may be 610-760 nm.

The inorganic light emitting layer of the device may comprise at least one of AlGaAs, GaAsP, AlGaInP and/or GaP, wherein the outcoupling structure may comprise a plurality of nanoparticles, wherein the nanoparticles Ag, Au, SiO ₂ , Al , Rh, Pt, Si and/or Ge, the size of the nanoparticles may be 5-150 nm, and the wavelength of light emitted by the device may be 590-610 nm.

The inorganic light emitting layer of the device may include at least one selected from the group consisting of GaAsP, AlGaInP and/or GaP, wherein the outcoupling structure may include a plurality of nanoparticles, wherein the nanoparticles are Ag, Au, SiO ₂ , Al, Rh, Pt, Si and/or Ge, the size of the nanoparticles may be 5-100 nm, and the wavelength of light emitted by the device may be 570-590 nm.

The inorganic light emitting layer of the device may comprise at least one of GaAsP, AlGaInP, GaP and/or InGaN/GaN, wherein the outcoupling structure may comprise a plurality of nanoparticles, wherein the nanoparticles are Ag, Al, Rh, may comprise at least one of Pt, SiO ₂ , TiO ₂ , Si and/or Ge, the size of the nanoparticles may be 5-125 nm and/or the wavelength of light emitted by the device may be 500-570 nm can

The inorganic light emitting layer of the device may include at least one of Se, InGaN, SiC and/or Si, wherein the outcoupling structure may include a plurality of nanoparticles, wherein the nanoparticles include Ag, Al, Rh, Pt and / or _{at least one of TiO 2} , the size of the nanoparticles may be 5-125 nm, and the wavelength of light emitted by the device may be 450-500 nm.

The inorganic light emitting layer of the device comprises InGaAs, wherein the outcoupling structure can comprise a plurality of nanoparticles, wherein the nanoparticles can comprise at least one selected from the group consisting _{of Al, Rh, Pt and/or TiO 2} And, the size of the nanoparticles may be 5-100 nm, and the wavelength of light emitted by the device may be 400-450 nm.

The inorganic light emitting layer of the device may comprise at least one of diamond (235 nm), BN, AlN, AlGaN and/or AlGaInN, wherein the outcoupling structure may comprise a plurality of nanoparticles, wherein the nanoparticles are Al; It may include at least one of Rh, Pt and/or TiO ₂ , the size of the nanoparticles may be 5-75 nm, and the wavelength of light emitted by the device may be 200 nm to 400 nm.

The inorganic light emitting layer of the device may comprise a blue light emitting diode having a yellow phosphor, wherein the outcoupling structure may comprise a plurality of nanoparticles, wherein the nanoparticles are at least one _{of Al, Rh, Pt and/or TiO 2 .} may include, the size of the nanoparticles may be 5-125 nm, and the light emitted by the device may be white light.

The device may include a material disposed over the first electrode, the material may be a dielectric layer disposed over the first electrode layer, and the electrical contact layer may be disposed over the dielectric layer. The material may include a voltage tunable refractive index material between the electrical contact layer and the first electrode layer. The voltage tunable refractive index material may be aluminum doped zinc oxide. The material may include an insulating layer.

The first electrode layer may include nano-sized features. The nano-sized features may be etched at least partially through the depth of the first electrode layer. The nano-sized features may include a bullseye pattern disposed over the first electrode layer or disposed over an interstitial material disposed over the first electrode layer. The nano-sized features may be disposed on at least one side of the first electrode layer. The size of the nanoscale features in the minimum direction may be at least 10 nm, at least 20 nm, and/or between 50 nm and 750 nm. In some embodiments, the arrangement of the pattern of nano-sized holes may be an array of nano-sized holes, a random arrangement of nano-sized holes, and/or a pseudo-random arrangement of holes.

In embodiments of the disclosed subject matter, a device may include an inorganic light emitting layer, a first electrode layer, an outcoupling structure, and a material disposed between the first electrode and the outcoupling structure. The first electrode layer may be spaced apart from the inorganic light emitting layer by a predetermined threshold distance, wherein the total nonradiative decay rate constant is equal to the total radioactive decay rate constant. The device may include an organic transport material.

The first electrode layer of the device may be at least one of a metal, a stack of metal films and dielectric layers, a plasmonic, hyperbolic metamaterial, and/or an optically active metamaterial. The first electrode layer includes 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 can do. The first electrode layer of the device may be patterned with nano-scale holes.

The inorganic light emitting layer of the device is GaAs, AlGaAs, GaAsP, AlGaInP, GaP, GaAsP, GaN, InGaN, ZnSe, SiC, Si ₃ N ₄ , Si, Ge, Sapphire, BN, ZnO, AlGaN, perovskite and/or quantum It may include at least one of the constraint systems. A quantum confinement system may include particles having the size of an exciton's Bohr radius. The quantum confinement system may comprise at least one of a mixed organic-inorganic perovskite material, CsPbBr ₃ , InP/ZnS, CuInS/ZnS, Si, Ge, C and/or peptide.

The outcoupling structure of the device may include Ag particles, Al particles, Ag-Al alloys, Au particles, Au-Ag alloys, dielectric materials, semiconductor materials, alloys of metals, mixtures of dielectric materials, stacks of one or more materials, and/or one and may comprise a plurality of nanoparticles formed from at least one of the cores of a species of material and coated with a shell of a different type of material. The outcoupling structure may include a plurality of nanoparticles that are colloidal synthetic nanoparticles formed from solution. The outcoupling structure may include a plurality of nanoparticles arranged in a periodic array. The periodic array may have a predetermined array pitch. The outcoupling structure may include a plurality of nanoparticles arranged in an aperiodic array. The outcoupling structure may comprise a plurality of nanoparticles, wherein the shape of the plurality of nanoparticles is comprised of a cube, a sphere, a spheroid, a cylinder, a parallelepiped, a rod-shaped, a star-shaped, a pyramid, and/or a polyhedral object. at least one selected from the group. The outcoupling structure may include a plurality of nanoparticles, and the device may include a material and an adhesive layer disposed between the plurality of nanoparticles. The outcoupling structure may include a plurality of nanoparticles, and at least one of the plurality of nanoparticles may include an additional material that provides lateral conduction between the plurality of nanoparticles.

The outcoupling structure of the device may include a plurality of nanoparticles, and the device may include at least one additional layer disposed over the plurality of nanoparticles. At least one additional layer may encapsulate the device. The at least one additional layer may include one or more emitter molecules. The at least one additional layer may have an index of refraction between 1.01 and 5. The at least one additional layer may change the color or efficiency of the emission of the device.

Devices fabricated in accordance with embodiments of the disclosed subject matter may be incorporated within a wide variety of electronic component modules (or units) that may be incorporated within various electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, light emitting devices such as individual light source devices or lighting panels that can be used by end consumer product producers, and the like. Such electronic component modules may optionally include drive electronics and/or power source(s). Devices fabricated in accordance with embodiments of the present invention may be incorporated into a wide variety of consumer products that include one or more electronic component modules (or units) therein. A consumer product comprising an OLED comprising a compound of the present invention in an organic layer within the OLED is disclosed. Such consumer products would include any kind of product comprising one or more light source(s) and/or one or more visual displays of any kind. Some examples of such consumer products are flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, indoor or outdoor lighting and/or signaling lights, head-up displays, fully or partially transparent displays, flexible displays, rollable displays. , foldable displays, stretchable displays, laser printers, telephones, cell phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, micro displays (2 inches diagonally) displays), 3D displays, virtual or augmented reality displays, vehicles, video walls including multiple displays tiled 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 fabricated in accordance with the present invention. Many devices are intended for use in a temperature range conducive to human comfort, such as 18°C to 30°C, more preferably room temperature (20°C to 25°C), but outside this temperature range, such as -40°C to +80°C. can also be used in

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 above materials and structures.

The terms “halo”, “halogen” or “halide” are used interchangeably and refer to fluorine, chlorine, bromine and iodine.

The term “acyl” refers to a substituted carbonyl radical (C(O)—R _s ).

The term “ester” refers to a substituted oxycarbonyl (—OC(O)—R _s or —C(O)—OR _s ) radical.

The term “ether” refers to the _{—OR s radical.}

The terms "sulfanyl" or "thio-ether" are used interchangeably and refer to the _{-SR s radical.}

The term “sulfinyl” refers to the —S(O)—R _s radical.

The term “sulfonyl” refers to the _{—SO 2} —R _{s radical.}

The term “phosphino” refers to the —P(R _s ) ₃ radical, wherein each R _s may be the same or different.

The term “silyl” refers to the —Si(R _s ) ₃ radical, wherein each R _s may be the same or different.

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

The term “alkyl” refers to and includes both straight-chain or branched-chain alkyl radicals. Preferred alkyl groups containing 1 to 15 carbon atoms are methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3 -methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl and the like. Additionally, the alkyl group is optionally substituted.

The term “cycloalkyl” refers to and includes monocyclic, polycyclic, and spiro alkyl radicals. Preferred cycloalkyl groups are those containing 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. etc. Additionally, the cycloalkyl group is optionally substituted.

The terms “heteroalkyl” or “heterocycloalkyl” refer to an alkyl or cycloalkyl radical having one or more carbon atoms each substituted by a heteroatom. Optionally, one or more heteroatoms are selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Additionally, a heteroalkyl or heterocycloalkyl group is optionally substituted.

The term “alkenyl” refers to and includes both straight and branched chain alkene radicals. An alkenyl group is essentially an alkyl group containing one or more carbon-carbon double bonds in the alkyl chain. A cycloalkenyl group is essentially a cycloalkyl group comprising one or more carbon-carbon double bonds within the cycloalkyl ring. As used herein, the term “heteroalkenyl” refers to an alkenyl radical having one or more carbon atoms substituted by a heteroatom. Optionally, one or more heteroatoms are selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Preferred alkenyl, cycloalkenyl, or heteroalkenyl groups are those containing from 2 to 15 carbon atoms. Additionally, an alkenyl, cycloalkenyl, or heteroalkenyl group is optionally substituted.

The term “alkynyl” refers to and includes both straight and branched chain alkyne radicals. Preferred alkynyl groups are those containing from 2 to 15 carbon atoms. Additionally, an alkynyl group is optionally substituted.

The terms “aralkyl” or “arylalkyl” are used interchangeably and refer to an alkyl group substituted with an aryl group. Additionally, an aralkyl group is optionally substituted.

The term “heterocyclic group” refers to and includes aromatic and non-aromatic cyclic radicals containing one or more heteroatoms. Optionally, one or more heteroatoms are selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Heteraromatic cyclic radicals may also be used interchangeably with heteroaryl. Preferred heterononaromatic cyclic groups contain one or more heteroatoms and include cyclic amines such as morpholino, piperidino, pyrrolidino and the like, and cyclic ethers such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene and the like. / those containing 3 to 7 ring atoms, including thio-ethers. Additionally, heterocyclic groups may be optionally substituted.

The term “aryl” refers to and includes both single ring aromatic hydrocarbyl groups and polycyclic aromatic ring systems. A polycyclic ring may have two or more rings in which two carbons are common to two adjacent rings (these rings being "fused"), wherein at least one of the rings is an aromatic hydrocarbyl group, for example, Other rings may be cycloalkyl, cycloalkenyl, aryl, heterocycle and/or heteroaryl. Preferred aryl groups are those containing from 6 to 30 carbon atoms, preferably from 6 to 20 carbon atoms, more preferably from 6 to 12 carbon atoms. Particular preference is given to aryl groups having 6, 10 or 12 carbons. Suitable aryl groups are phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene and azulene, preferably phenyl, biphenyl , triphenyl, triphenylene, fluorene and naphthalene. Additionally, the aryl group is optionally substituted.

The term “heteroaryl” refers to and includes both single ring aromatic groups and polycyclic aromatic ring systems containing one or more heteroatoms. Heteroatoms include, but are not limited to, O, S, N, P, B, Si, and Se. In many instances, O, S, or N is a preferred heteroatom. The heteroaromatic single ring system is preferably a single ring having 5 or 6 ring atoms, and the ring may have 1 to 6 heteroatoms. Heteropolycyclic ring systems may have two or more rings in which two carbons are common to two adjacent rings (these rings being "fused"), wherein at least one of the rings is heteroaryl, for example, Other rings may be cycloalkyl, cycloalkenyl, aryl, heterocycle and/or heteroaryl. The hetero polycyclic aromatic ring system may have 1 to 6 heteroatoms per ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing from 3 to 30 carbon atoms, preferably from 3 to 20 carbon atoms, more preferably from 3 to 12 carbon atoms. Suitable heteroaryl groups are 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, oxathia Gin, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine , pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine, Preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine , 1,4-azaborine, borazine and aza-analogs thereof. Additionally, the heteroaryl group is optionally substituted.

Of the aryl and heteroaryl groups listed above, triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine Of particular interest are the groups of , triazines, and benzimidazoles, and their respective respective aza-analogs.

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

In many cases, common substituents are 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.

In some cases, preferred general substituents are deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.

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

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

The terms “substituted” and “substituted” refer to a substituent other than H that is bonded to the position concerned, such as carbon or nitrogen. For example, when R ¹ represents mono-substitution, one R ¹ must be other than H (ie, substitution). Similarly, when R ¹ represents disubstitution, ^{two of R 1} must be other than H. Similarly, when R ¹ represents unsubstitution, R ¹ may be hydrogen with respect to the available valencies of the ring atoms, such as, for example, the carbon atom of benzene and the nitrogen atom of pyrrole, or simply a ring atom having a fully charged valence. , eg, for the nitrogen atom of pyridine. The maximum number of substitutions possible in a ring structure depends on the total number of valences available at the ring atoms.

As used herein, "combination thereof" indicates that one or more elements of the applicable list are combined to form a known or chemically stable arrangement that one of ordinary skill in the art would envision from that list. For example, alkyl and deuterium may be combined to form a partially or fully deuterated alkyl group; Halogen and alkyl may be combined to form a halogenated alkyl substituent; Halogen, alkyl, and aryl may be combined to form a halogenated arylalkyl. In one instance, the term substitution includes combinations of 2 to 4 of the listed groups. In other instances, the term substitution includes combinations of two to three groups. In still other instances, the term substitution includes a combination of two groups. Preferred combinations of substituents are those containing up to 50 atoms that are not hydrogen or deuterium, or those containing up to 40 atoms that are not hydrogen or deuterium, or those containing up to 30 atoms that are not hydrogen or deuterium. will include In many cases, a preferred combination of substituents will include up to 20 atoms that are not hydrogen, or deuterium.

The designation "aza" in the fragments described herein, i.e., azadibenzofuran, azadibenzothiophene, etc., means that one or more of the CH groups in each segment may be replaced with a nitrogen atom, e.g., aza Triphenylene includes, but is not limited to, both dibenzo[ f,h ]quinoxaline and dibenzo[ f,h]quinoline. One of ordinary skill in the art can readily contemplate other nitrogen analogs of the aza-derivatives described above, all of which are intended to encompass the terms described herein.

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

When a molecular segment is described as being a substituent or otherwise described as being bound to another moiety, its designation is as if it were the segment (eg phenyl, phenylene, naphthyl, dibenzofuryl) or the entire molecule (eg benzene). , naphthalene, dibenzofuran). As used herein, different designations of such substituents or bound segments are considered equivalent.

In some cases, pairs of adjacent substituents may be optionally linked or fused to form a ring. Preferred rings are 5-, 6- or 7-membered carbocyclic or heterocyclic rings, both when part of the ring formed by a pair of substituents is saturated and when part of the ring formed by a pair of substituents is unsaturated. do. As used herein, "adjacent" means having the two closest substitutable positions, such as the 2, 2' positions of biphenyl, or the 1, 8 positions of naphthalene, so long as they are capable of forming a stable fused ring system. This means that two related substituents may be present on two neighboring rings, or on the same ring next to each other.

In some embodiments, the OLED has one or more properties selected from the group consisting of flexible, rollable, foldable, stretchable, and curved properties. In some embodiments, the OLED is transparent or translucent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes.

In some embodiments, the OLED further comprises a layer comprising a delayed fluorescent emitter. In some embodiments, the OLED comprises an arrangement of RGB pixels, or an arrangement of white plus color filter pixels. In some embodiments, the OLED is a mobile device, a hand held device, or a wearable device. In some embodiments, the OLED is a display panel that is less than 10 inches diagonal or less than 50 square inches in area. In some embodiments, the OLED is a display panel with 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.

In some embodiments, the luminescent dopant is phosphorescent, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as type E delayed fluorescence; see, e.g., U.S. Patent Application Serial No. 15/700,352, which is incorporated herein by reference in its entirety). included), triplet-triplet annihilation, or a combination of these processes can produce luminescence. In some embodiments, the luminescent dopant may be a racemic mixture, or may be enriched in one enantiomer.

In some embodiments, the organic layer may contain a phosphorescent sensitizer in the OLED, wherein one or a plurality of layers in the OLED contain one or more acceptors in the form of fluorescent and/or delayed fluorescent emitters. In some embodiments, the sensitizer may be one component of Exciplex. As a phosphorescent sensitizer, the compound must be able to transfer energy to an acceptor, which either releases energy or further transfers energy to a 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, emission may occur from some or all of the sensitizer, acceptor, and final emitter.

The OLEDs disclosed herein may be incorporated into one or more of consumer products, electronic component modules, and lighting panels. The organic layer may be an emissive layer, and the compound may be an emissive dopant in some embodiments, while the compound may be a non-emissive dopant in other embodiments.

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 wide band gap material with little role in a) bipolar, b) electron transport, c) hole transport, or d) charge transport. In some embodiments, the host may comprise a metal complex. The host may be a benzo fused thiophene containing triphenylene or a benzo fused furan. Any substituent in the host is independently C _n H _2n+1 , OC _n H _2n+1 , OAr ₁ , N(C _n H _2n+1 ) ₂ , N(Ar ₁ )(Ar ₂ ), CH=CH— can be a non-fused substituent selected from the group consisting of C _n H _{2n+1 , C≡CC n} H _2n+1 , Ar ₁ , Ar ₁ -Ar ₂ , and C _n H _2n -Ar _{1 , or the host is a substituent} do not have In the above substituents, n may range from 1 to 10; Ar ₁ and Ar ₂ may be independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof. The host may be an inorganic compound. For example, it may be a Zn-containing inorganic material, such as ZnS.

Host is triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran and aza-dibenzocelene It may be a compound comprising at least one chemical group selected from the group consisting of nophene. The host may include a metal complex. The host may be a specific compound selected from the group consisting of the following formula and combinations thereof, but is not limited thereto:

Additional information on possible hosts is provided below.

Combination with other substances

The OLEDs disclosed herein may be incorporated. The materials described herein as useful for certain layers in organic light emitting devices can be used in combination with a wide variety of other materials present in the device. For example, the emissive dopants disclosed herein can be used in combination with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes, and other layers that may be present. The materials described or referenced below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of ordinary skill in the art can readily refer to the literature to identify other materials that may be useful in combination. have.

Conductive dopants:

The charge transport layer can be doped with a conductive dopant to substantially change its charge carrier density, which in turn will change its conductivity. Conductivity is increased by creating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor can also be achieved. The hole transport layer may be doped with a p-type conductive dopant and an n-type conductive dopant is used in the electron transport layer.

HIL/HTL:

The hole injection/transport material to be used in the present invention is not particularly limited, and any compound may be used as long as the compound is commonly used as a hole injection/transport material. Non-limiting examples of substances include phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indolocarbazole derivatives; polymers comprising fluorohydrocarbons; polymers with conductive dopants; conductive polymers such as PEDOT/PSS; self-assembling monomers derived from compounds such as phosphonic acids and silane derivatives; metal oxide derivatives such as MoO _x ; p-type semiconductor organic compounds such as 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile; metal complexes and crosslinkable compounds.

Non-limiting examples of aromatic amine derivatives used in HIL or HTL include the structural formula:

each Ar ¹ to Ar ⁹ is an aromatic hydrocarbon cyclic compound such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene and azulene the group consisting of; 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, oxadia gin, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, Aromatic heterocyclics such as xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine the group consisting of compounds; and 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, which is the same type or a different type group selected from an aromatic hydrocarbon cyclic group and an aromatic heterocyclic group. It is selected from the group consisting of 2 to 10 cyclic structural units bonded through the above or directly bonded to each other. Each Ar can be unsubstituted or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, may be substituted with a substituent selected from the group consisting of alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one embodiment, Ar ¹ to Ar ⁹ are independently selected from the group consisting of:

where k is an integer from 1 to 20; X ¹⁰¹ to X ¹⁰⁸ are C (including CH) or N; Z ¹⁰¹ is NAr ¹ , O or S; Ar ¹ has the same group as defined above.

Non-limiting examples of metal complexes used in HIL or HTL include the formula:

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

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

EBL:

An electron blocking layer (EBL) may be used to reduce the number of electrons and/or excitons leaving the emissive layer. The presence of such a blocking layer in the device can lead to significantly higher efficiencies and/or longer lifetimes when compared to similar devices without the blocking layer. A blocking layer can also be used to confine light emission to a desired area of the OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the EBL interface. In one embodiment, the compound used in EBL contains the same molecule or functional group as used as one of the hosts described below.

Host:

The light emitting layer of the organic EL device of the present invention preferably includes at least a metal complex as a light emitting material, and may include a host material using the metal complex as a dopant material. Examples of the host material are 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 the triplet energy of the dopant. Any host material may be used with any dopant as long as the triplet criterion is met.

Examples of metal complexes used as hosts preferably have the following formula:

where Met is a metal; (Y ¹⁰³ -Y ¹⁰⁴ ) is a bidentate ligand, and Y ¹⁰³ and Y ¹⁰⁴ are independently selected from C, N, O, P and S; L ¹⁰¹ is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be bound to the metal; k'+k" is the maximum number of ligands that can be bound to a metal.

In one aspect, the metal complex comprises:

이며, 여기서 (O-N)은 원자 O 및 N에 배위 결합된 금속을 갖는 2좌 리간드이다.

where (ON) is a bidentate ligand having a metal coordinated to the atoms O and N.

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

Examples of other organic compounds used as hosts include aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene , the group consisting of perylene and azulene; Aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, p Rolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine , oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, Phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenofe the group consisting of nodipyridine; and a group of the same type or a different type selected from an aromatic hydrocarbon cyclic group and an aromatic heterocyclic group and is 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. It is selected from the group consisting of 2 to 10 cyclic structural units bonded through the above or directly bonded to each other. Each option within each group may be unsubstituted or 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.

In one embodiment, the host compound contains one or more of the following groups in the molecule:

wherein R ¹⁰¹ is 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; It has a similar definition to Ar. k is an integer from 0 to 20 or 1 to 20; X ¹⁰¹ to X ¹⁰⁸ are independently selected from C (including CH) or N. Z ¹⁰¹ and Z ¹⁰² are independently ^{selected from NR 101} , O or S.

Emitter:

One or more emitter dopants may be used in combination with the compounds of the present invention. Examples of the emitter dopant are not particularly limited, and any compound may be used as long as it is typically used as an emitter material. Examples of suitable emitter materials are phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as type E delayed fluorescence), triplet-triplet extinction, or a combination of these processes that can produce luminescence. compounds with, but are not limited to.

HBL:

A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons leaving the emissive layer. The presence of such a blocking layer in the device can lead to significantly higher efficiencies and/or longer lifetimes when compared to similar devices without the blocking layer. A blocking layer can also be used to confine light emission to a desired area of the OLED. In some embodiments, the HBL material has a lower HOMO (far from the vacuum level) and/or higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the HBL interface.

In one embodiment, the compounds used in HBL contain the same molecules of use or the same functional groups as the hosts described above.

In another embodiment, the compound used in HBL contains one or more of the following groups in the molecule:

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

ETL:

The electron transport layer (ETL) may include a material capable of transporting electrons. The electron transport layer may be native (undoped) or doped. Doping can be used to improve conductivity. Examples of the ETL material are not particularly limited, and any metal complex or organic compound may be used as long as they are conventionally used to transport electrons.

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

wherein R ¹⁰¹ is 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; It has a definition similar to Ar. Ar ¹ to Ar ³ have similar definitions to Ar described above. k is an integer from 1 to 20; X ¹⁰¹ to X ¹⁰⁸ are selected from C (including CH) or N.

In another embodiment, metal complexes used in ETL include, but are not limited to:

wherein (ON) or (NN) is a bidentate ligand having a metal coordinated to the atoms O, N or N, N; L ¹⁰¹ is another ligand; k' is an integer value from 1 to the maximum number of ligands to which a metal can be bound.

Charge Generation Layer (CGL)

In a tandem or stacked OLED, CGL plays an essential role in terms of performance, which consists of an n-doped layer and a p-doped layer for injecting electrons and holes, respectively. Electrons and holes are supplied from the CGL and electrodes. Electrons and holes consumed in the CGL are refilled by electrons and holes injected from the cathode and anode, respectively; After that, the bipolar current gradually reaches a steady state. Common CGL materials contain n and p conductive dopants used in the transport layer.

In any of the aforementioned compounds used in each layer of the OLED device, the hydrogen atoms may be partially or completely deuterated. Accordingly, any of the specifically enumerated substituents, such as, but not limited to, methyl, phenyl, pyridyl, and the like, may be in their undeuterated, partially deuterated and fully deuterated forms. Likewise, substituent types such as, but not limited to, alkyl, aryl, cycloalkyl, heteroaryl, and the like can also be deuterated, partially deuterated, and fully deuterated forms thereof.

It is to be understood that the various embodiments described herein are illustrative only and are not intended to limit the scope of the present invention. For example, many of the materials and structures described herein may be substituted for other materials and structures without departing from the spirit of the invention. Accordingly, the invention as claimed may include modifications deriving from the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It should be understood that there is no intention to limit the various theories as to why the present invention works.

Claims (15)

inorganic light emitting layer;
a first electrode layer; and
outcoupling structure
A device comprising:
The first electrode layer is spaced apart from the inorganic light emitting layer by a predetermined threshold distance, wherein a total non-radiative decay rate constant is a distance equal to a total radiative decay rate constant. . The device of claim 1 , wherein the first electrode layer is at least one selected from the group consisting of a metal, a stack of a metal film and a dielectric layer, a plasmonic system, a hyperbolic metamaterial, and an optically active metamaterial. According to claim 1, wherein the inorganic light emitting layer is GaAs, AlGaAs, GaAsP, AlGaInP, GaP, GaAsP, GaN, InGaN, ZnSe, SiC, Si ₃ N ₄ ,Si, Ge, sapphire, BN, ZnO, AlGaN, perovskite And a device comprising at least one selected from the group consisting of a quantum confined system. According to claim 1, wherein the first electrode layer is Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi and Ca A device consisting of at least one selected from the group consisting of. The method of claim 1, wherein the outcoupling structure comprises Ag particles, Al particles, Ag-Al alloys, Au particles, Au-Ag alloys, dielectric materials, semiconductor materials, alloys of metals, mixtures of dielectric materials, 1 A device comprising a plurality of nanoparticles formed of at least one selected from the group consisting of a stack of one or more species of material and a core of one material and coated with a shell of a different type of material. The device of claim 1 , wherein the outcoupling structure comprises a plurality of nanoparticles that are colloidal synthetic nanoparticles formed from solution. The device of claim 1 , wherein the outcoupling structure comprises a plurality of nanoparticles arranged in a periodic array. 8. The device of claim 7, wherein the periodic array has a predetermined array pitch. The device of claim 1 , wherein the outcoupling structure comprises a plurality of nanoparticles arranged in an aperiodic array. The device of claim 1 , wherein the first electrode layer is patterned with nanoscale holes. The method of claim 1 , wherein the outcoupling structure comprises a plurality of nanoparticles,
A device wherein at least one property of the nanoparticles is selected to modify the spectrum of light emitted by the light emitting layer, or to change the angular dependence of the light emitted by the light emitting layer. The device of claim 11 , 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. The device of claim 1 , wherein the outcoupling structure comprises a plurality of nanoparticles, and wherein the device further comprises at least one additional layer disposed over the plurality of nanoparticles. The method of claim 1 , wherein the outcoupling structure comprises a plurality of nanoparticles,
wherein the device further comprises a material disposed between the first electrode and the plurality of nanoparticles. inorganic light emitting layer;
a first electrode layer; and
outcoupling structure
As a consumer product comprising:
the first electrode layer is spaced apart from the inorganic light emitting layer by a predetermined threshold distance, wherein the total non-radiative decay rate constant is a distance equal to the total radioactive decay rate constant;
Consumer products include display screens, lighting devices such as discrete light source devices or lighting panels, flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, indoor or outdoor lighting and/or signaling lights, head-up displays. , fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, cell phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras , camcorders, viewfinders, micro displays less than 2 inches diagonal, 3D displays, vehicles, aerial displays, large-area walls, video walls with multiple displays tiled together, theater or stadium screens, phototherapy devices, signage, augmented reality A device which is at least one selected from the group consisting of (AR) or virtual reality (VR) displays, displays or visual elements in glasses or contact lenses, light emitting diode (LED) wallpaper, LED jewelry and clothing.

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