Plasmonic oleds and vertical dipole emitters

Abstract

This application relates to plasmonic OLEDs and vertical dipole emitters. Compounds, formulations including compounds, and devices utilizing compounds are provided, where the device includes a substrate, a first electrode, an organic emissive layer including an organic emissive material disposed over the first electrode. The device includes an enhancement layer including a plasmonic material exhibiting surface plasmon resonance, the plasmonic material non-radiatively coupled to the organic emissive material and transferring excitation state energy from the organic emissive material to a non-radiative mode of surface plasmon polaritons. The enhancement layer is disposed at a distance from the organic emissive layer that is no more than a threshold distance, where, due to the presence of the enhancement layer, the organic emissive material has a total non-radiative decay rate constant and a total radiative decay rate constant. At least one of the organic emissive material and the organic emissive layer has a vertical dipole ratio (VDR) value equal to or greater than 0.33.

Description

[0001] Cross-reference of related applications

[0002] This application claims priority to U.S. Patent Application No. 63 / 050,562, filed July 10, 2020; U.S. Patent Application No. 63 / 058,410, filed July 29, 2020; U.S. Patent Application No. 63 / 072,550, filed August 31, 2020; and U.S. Patent Application No. 63 / 078,084, filed September 14, 2020, and to U.S. Patent Application No. 16 / 814, filed March 10, 2020. Part of the continuation application No. 858, which claims priority to U.S. Patent Application No. 62 / 817,368, filed March 12, 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, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure generally relates to compounds and arrangements for increasing the vertical dipole fraction in organic light-emitting diodes (OLEDs) and devices containing them to enhance the coupling of excited energy states to surface plasmon modes. Background Technology

[0004] For various reasons, optoelectronic devices utilizing organic materials are becoming increasingly popular. Many of the materials used to manufacture these devices are relatively inexpensive, thus organic optoelectronic devices have the potential to offer a cost advantage over inorganic devices. Furthermore, the inherent properties of organic materials, such as their flexibility, make them more suitable for specific 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 offer performance advantages over conventional materials.

[0005] OLEDs utilize organic thin films that emit light when a voltage is applied to the device. OLEDs are becoming an increasingly popular technology for applications such as flat panel displays, lighting, and backlighting.

[0006] One application of phosphorescent emitting molecules is in full-color displays. Industry standards for such displays require pixels suited to emitting specific colors (called "saturated" colors). Specifically, these standards require pixels saturated with red, green, and blue light. Alternatively, OLEDs can be designed to emit white light. In conventional liquid crystal displays, absorption filters are used to filter the emission from a white backlight to produce red, green, and blue emission. The same technology can be used for OLEDs. White OLEDs can be single-emitting-layer (EML) devices or stacked structures. Color can be measured using the CIE coordinate system, well-known in the field. Summary of the Invention

[0007] According to one embodiment, an apparatus is provided that may include a substrate, a first electrode, and an organic emission layer comprising an organic emission material disposed above the first electrode. The apparatus may include a reinforcement layer having a plasmonic material exhibiting surface plasmon resonance, the plasmonic material being nonradiatively coupled to the organic emission material and transferring excited-state energy from the organic emission material to the nonradiative mode of the surface plasmon polariton, the reinforcement layer being disposed on the organic emission layer. The reinforcement layer is configured such that its distance from the organic emission layer does not exceed a threshold distance. Due to the presence of the reinforcement layer, the organic emission material may have a total nonradiative decay rate constant and a total radiative decay rate constant, and the threshold distance may be a position where the total nonradiative decay rate constant is equal to the total radiative decay rate constant. At least one of the organic emission material and the organic emission layer may have a vertical dipole ratio (VDR) value equal to or greater than 0.33.

[0008] The organic emission layer of the device may have a VDR value equal to or greater than 0.33. The organic emission material of the device may have a VDR value equal to or greater than 0.33.

[0009] The organic emitting layer of the device may include a first layer having an organic emitting material and a second layer disposed adjacent to the first layer and containing a second material. The first and second layers may satisfy the condition 0 ≤ Ex - ΔE, where Ex is the lowest emission state energy level of the first or second layer, and ΔE is the difference between the highest highest occupied molecular orbital (HOMO) energy level and the lowest lowest unoccupied molecular orbital (LUMO) energy level within the organic emitting layer. Ex may be the lowest triplet (T1) energy level of the first layer, and the first layer is phosphorescent. In some embodiments, Ex may be the lowest singlet (S1) energy level of the first layer, and the first layer is fluorescent.

[0010] The organic emitting material of the device can be a phosphorescent material. The phosphorescent material can be a metal coordination complex having metal-carbon bonds and / or metal-nitrogen bonds and / or metal-oxygen bonds. The metal can be Ir, Rh, Re, Ru, Os, Pt, Au, and / or Cu. The phosphorescent material has the formula M(L 1 ) x(L 2 ) y (L 3 ) z L 1 L 2 and L 3 They can be the same or different, where x is 1, 2 or 3, where y is 0, 1 or 2, where z is 0, 1 or 2, where x+y+z can be the oxidation state of metal M, and where L 1 The following groups can be freely selected:

[0011]

[0012]

[0013] Where L 2 and L 3 Choose independently from the following groups: Where Y 1 To Y 13 Each can be independently selected from carbon and / or nitrogen, wherein Y' is selected from the group consisting of: BR e NR e PR e ,O,S,Se,C=O,S=O,SO2,CR e R f SiR e R f and GeR e R f , where R e and R f They can be fused or joined to form a ring, wherein R a R b R c and R d Each can independently represent monosubstituted to the maximum possible number of substitutions or no substitutions, where R a R b R c R d R e and R f Each can independently be hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, oxoboryl, and combinations thereof, wherein R a R b R cand R d Any two adjacent substituents may fused or joined to form a ring or a polydentate ligand.

[0014] Phosphorescent materials can have the following formula selected from the group consisting of: Ir(L A 3. Ir(L) A (L) B )2、Ir(L A )2(L B ), Ir(L A )2(L C ), Ir(L A (L) B (L) C ) and Pt(L A (L) B ), of which L in the Ir compound A L B and L C They are different from each other, among which L in Pt compounds A and L B They can be the same or different, and the L in the Pt compound is... A and L B They can be linked to form tetradentate ligands.

[0015] The organic emitting material of the device may be a fluorescent material. The fluorescent material may contain at least one organic group selected from the group consisting of:

[0016] And its aza analogues, wherein A is selected from the group consisting of: O, S, Se, NR' and CR'R", wherein each R' may be the same or different, and each R' is independently selected from the group consisting of: alkyl, cycloalkyl, aryl, heteroaryl and combinations thereof.

[0017] The fluorescent material of the device can be selected from the group consisting of:

[0018]

[0019] Where R 1 To R 5 Each independently represents a single substitution up to the maximum possible number of substitutions or no substitutions, where R 1 To R 5Each of the following substituents is independently hydrogen or selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphin, oxoboryl, and combinations thereof.

[0020] The organic emitting material of the device may be a thermally activated delayed fluorescence (TADF) material. The TADF material may contain at least one donor group and at least one acceptor group. In some embodiments, the TADF material may be a metal complex. The TADF material may be a non-metal complex. In some embodiments, the TADF material may be a Cu, Ag, or Au complex. The TADF material may contain at least one chemical moiety selected from the group consisting of:

[0021]

[0022] X is selected from the group consisting of O, S, Se and NR, wherein each R may be the same or different and each R is independently an acceptor group, an organic linker group bonded to the acceptor group or a terminal group selected from the group consisting of alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, aryl, heteroaryl and combinations thereof, and wherein each R' may be the same or different and each R' is independently selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl and combinations thereof.

[0023] The TADF material of the device may include at least one chemical moiety selected from the group consisting of: nitriles, isonitriles, boranes, fluorides, pyridines, pyrimidines, pyrazines, triazines, aza-carbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-triphenylene, imidazoles, pyrazoles, oxazoles, thiazoles, isoxazoles, isothiazoles, triazoles, thiadiazoles, and oxadiazoles.

[0024] The emission of the device may originate from a combination of materials within an organic emission layer. The combination of materials in the organic emission layer may include a first material and a second material, wherein an excited-state complex is formed within the organic emission layer. The excited-state complex is an emission state formed between the two materials. The energy of the excited-state complex can be determined by the energy difference between the lowest least unoccupied molecular orbital (LUMO) and the highest most occupied molecular orbital (HOMO) from all materials in the organic emission layer. The first and second materials may satisfy the condition 0 ≤ Ex - ΔE, where Ex is the lowest emission state energy level of either the first or second material, and ΔE is the difference between the highest HOMO energy level and the lowest LUMO energy level within the organic emission layer.

[0025] The organic emission layer may further comprise a host. The host may include at least one chemical group selected from the group consisting of: triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenene, azitrin, azicarbazole, azi-dibenzothiophene, azi-dibenzofuran, and azi-dibenzoselenene.

[0026] In some embodiments, the subject may be selected from the following group:

[0027]

[0028] And its combination.

[0029] The reinforcement layer of the device may include a second electrode layer.

[0030] In some embodiments, the device may include a template layer selected and arranged to orient the molecules of the organic emission layer. The template layer may align the dipoles of the organic emission material and increase the perpendicularity of the dipoles. The template layer may be within a threshold distance of the reinforcement layer.

[0031] The organic emission layer may include multiple sublayers. In some embodiments, the organic emission material emits from a dual state.

[0032] The device may include an outcoupling structure. The outcoupling structure may have multiple nanoparticles, and the device may have a material disposed between the reinforcing layer and the multiple nanoparticles. The multiple nanoparticles are formed from at least one of the following: Ag particles, Al particles, Ag-Al alloys, Au particles, Au-Ag alloys, dielectric materials, semiconductor materials, metal alloys, mixtures of dielectric materials, stacks of one or more materials, and / or a core of one type of material coated with a shell of a different type of material. At least one of the multiple nanoparticles may include an additional layer to provide lateral conduction between the multiple nanoparticles. The multiple nanoparticles may be coated. In some embodiments, the multiple nanoparticles may be metallic and coated with a non-metallic coating. The multiple nanoparticles may include at least one of a metal, a dielectric material, and / or a hybrid of a metal and a dielectric material.

[0033] The device may have multiple nanoparticles coated with an oxide layer. The thickness of the oxide layer can be selected to tune the plasmon resonance wavelength of the multiple nanoparticles or nanopatch antenna. The multiple nanoparticles may be colloidal synthetic nanoparticles formed from a solution. The multiple nanoparticles may be arranged in a periodic array, the periodic array having a predetermined array spacing. In some embodiments, the multiple nanoparticles may be arranged in a non-periodic array. The shape of the multiple nanoparticles may be at least one of the following: cube, sphere, globular, cylinder, parallelepiped, rod-shaped, star-shaped, pyramidal, and / or multifaceted three-dimensional objects. The size of at least one of the multiple nanoparticles may be from 5 nm to 1000 nm.

[0034] The device may include a dielectric layer disposed on a reinforcing layer and an electrical contact layer disposed on the dielectric layer. The material may be a voltage-adjustable refractive index material between the electrical contact layer and the first electrode. The voltage-adjustable refractive index material may be aluminum-doped zinc oxide. The material may include an insulating layer.

[0035] The first electrode of the device may include at least one of the following: metal, semiconductor, and / or transparent conductive oxide. The electrode layer of the device may include at least one of the following: Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, and / or Ca.

[0036] According to one embodiment, a consumer product may include a device having a substrate, a first electrode, and an organic emission layer comprising an organic emission material disposed above the first electrode. The device of the consumer product may include a reinforcement layer having a plasmonic material exhibiting surface plasmon resonance, the plasmonic material being nonradiatively coupled to the organic emission material and transferring excited-state energy from the organic emission material to the nonradiative mode of the surface plasmon polariton, the reinforcement layer being disposed on the organic emission layer. The reinforcement layer may be configured such that its distance from the organic emission layer does not exceed a threshold distance. Due to the presence of the reinforcement layer, the organic emission material has a total nonradiative decay rate constant and a total radiative decay rate constant, and the threshold distance is the position where the total nonradiative decay rate constant is equal to the total radiative decay rate constant. At least one of the organic emission material and the organic emission layer has a vertical dipole ratio (VDR) value equal to or greater than 0.33.

[0037] Consumer products can be at least one of the following: displays, lighting devices such as discrete light source devices or lighting panels, flat panel displays, curved displays, computer monitors, medical monitors, televisions, signs, lights for internal or external lighting and / or signaling, head-up displays, fully transparent or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, cellular phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptops, digital cameras, camcorders, viewfinders, microdisplays with a diagonal of less than 2 inches, 3D displays, vehicles, aviation displays, large-area walls, video walls containing multiple displays tiled together, theater or stadium screens, phototherapy devices, signs, augmented reality (AR) displays or virtual reality (VR) displays, display or visual elements in glasses or contact lenses, light-emitting diode (LED) wallpaper, LED ornaments, and clothing. Attached Figure Description

[0038] Figure 1 An organic light-emitting device is shown.

[0039] Figure 2 An inverted organic light-emitting device without an independent electron transport layer is demonstrated.

[0040] Figure 3a shows a conventional nanopatch antenna, which includes a material layer in which emitter molecules are embedded between nanoparticles and a metal layer.

[0041] Figure 3b illustrates a nanopatch antenna according to an embodiment of the disclosed subject matter, which includes emitter molecules disposed beneath a metal layer (i.e., an electrode layer) in the emitter layer.

[0042] Figure 3c A nanopatch antenna according to an embodiment of the disclosed subject matter is shown, which includes a cover layer disposed on nanoparticles, the nanoparticles including additional emitter molecules.

[0043] Figure 4a illustrates a dielectric material comprising multiple layers according to an embodiment of the disclosed subject matter.

[0044] Figure 4b illustrates two stacked dielectric materials comprising a thick dielectric layer and a thin nanoparticle adhesion layer according to an embodiment of the disclosed subject matter.

[0045] Figure 5a The illustration shows emitter molecules in an emitter layer placed beneath a metal layer (i.e., an electrode layer) in combination with an OLED stack according to an embodiment of the disclosed subject matter, wherein the emitter layer is within a threshold distance to the metal electrode, and a nanopatch antenna on top of the electrode radiates outward from the side having nanoparticles.

[0046] Figure 5b Examples of embodiments based on the disclosed subject matter are shown. Figure 5a A variant of the embodiment, wherein the stack can be corrugated for additional outcoupling of surface plasmon energy (SPR) modes.

[0047] Figure 6 The embodiments shown, based on the disclosed subject matter, demonstrate that the energy of excited emitter molecules can be quenched into the SPR mode in the cathode, generating an electric field that can be coupled to the gap mode of the nanopatch antenna, and radiating the energy outward in the form of light.

[0048] Figure 7 The presents computer simulations of electric field intensities Ex and Ey in the x and y directions, respectively, in a material layer of a nanopatch antenna utilizing nanocubes as nanoparticles, according to an embodiment of the disclosed subject matter, wherein the light outcoupled to the far field originates from the edge of the nanoparticles.

[0049] Figure 8 The embodiments shown depict a metal thin film (i.e., an electrode layer) that has been partially etched through the film thickness to create a corrugated top surface while maintaining a planar bottom surface, according to the disclosed subject matter.

[0050] Figure 9 The embodiments shown, based on the disclosed subject matter, demonstrate that the nanoparticle coating can provide an appropriate gap thickness between the nanoparticles and the metal film.

[0051] Figure 10 The embodiments shown are based on the disclosed subject matter, including an OLED that utilizes one or more materials having voltage-adjustable refractive indices for selecting the wavelength of emitted light in combination with a nanopatch antenna.

[0052] Figure 11 The illustration shows an embodiment of the disclosed subject matter, an OLED stack deposited in a dielectric region, and uses nanoparticles and a metal layer as electrodes to inject charge.

[0053] Figure 12a illustrates an embodiment of the disclosed subject matter, having metal nanoparticles deposited on top of electrodes and a substrate, thereby allowing charge injection from both indium tin oxide (ITO) and the metal nanoparticles into an OLED device.

[0054] Figure 12b shows an alternative planar OLED device to the planar OLED device shown in Figure 12a according to an embodiment of the disclosed subject matter.

[0055] Figure 13 This invention demonstrates a method for forming the bottom electrode of a planar electrically driven OLED as shown in FIG12b, based on an embodiment of the disclosed subject matter.

[0056] Figures 14a-14f illustrate examples of OLED devices with or without dielectric capping layers, based on embodiments of the disclosed subject matter, and of various nanostructures.

[0057] Figure 15 The embodiments of the disclosed subject matter demonstrate how the material composition of the nanostructure can be metal, dielectric, or some combination of both (i.e., hybrid).

[0058] Figure 16 The embodiments shown demonstrate that, based on the disclosed subject matter, particle shape can affect the frequency of resonant plasmon modes.

[0059] Figure 17 An example inorganic LED, illustrating an embodiment of the disclosed subject matter, may include a reinforcement layer (e.g., an electrode layer) and an outcoupling layer. Because the top P-type contactor is incorporated into the reinforcement layer in this embodiment, the bottom embodiment is able to achieve a larger light-emitting area.

[0060] Figure 18 An example structure of a reinforcement layer (e.g., an electrode layer) having a unit cell and sub-components is shown according to an embodiment of the disclosed subject matter.

[0061] Figure 19 An example device architecture is shown based on an embodiment of the disclosed subject matter, wherein the emission layer is placed within a threshold distance of the enhancement layer.

[0062] Figure 20 The presents a simulated mode analysis of the power fraction in plasmonic modes varying with electron transport layer (ETL) thickness for horizontal, vertical, or isotropic dipoles, based on embodiments of the disclosed subject matter.

[0063] Figure 21 The simulated fraction of power in plasmonic modes varying with ETL thickness is shown in an embodiment of the disclosed subject matter.

[0064] Figure 22 The diagram illustrates the p-polarized emission intensity as a function of angle for various subject-emitter combinations, based on embodiments of the disclosed subject matter.

[0065] Figure 23 A device stack is shown for comparing the effects of dipole orientation on top and bottom emission characteristics. According to an embodiment of the disclosed subject, the device incorporates a nanoparticle-based decoupling scheme to convert plasmonic energy into top-emitted photons.

[0066] According to the embodiments of the disclosed subject matter, Figures 24a-24d The exhibition is for those with Figure 23The diagram shows the external quantum efficiency (EQE) of the top emission (TE) or bottom emission (BE) device as a function of the distance between the emitter layer and the cathode. For these same devices, Figures 24b-24d show the ratios of TE / BE, TE+BE, and EL transient as a function of the distance between the emitter layer and the cathode, respectively.

[0067] Figure 25 Example compounds are shown based on embodiments of the disclosed subject matter.

[0068] Figure 26a A graph showing the quantum yield as a function of the distance between the luminescent material and the reinforcing film is presented, in which two threshold distances are determined.

[0069] Figure 26b A schematic plot showing how the temperature of an OLED changes with the distance between the light emitter and the enhancement film when there is no decoupling layer in a non-radiative OLED is displayed, where a threshold distance of 2 is determined on the graph. Detailed Implementation

[0070] A. Terminology

[0071] Unless otherwise specified, the following terms as used herein are defined as follows:

[0072] As used herein, the term "organic" includes both polymeric materials and small-molecule organic materials that can be used to manufacture organic optoelectronic devices. "Small molecule" refers to any organic material that is not a polymer, and "small molecule" can actually be quite large. In some cases, small molecules can include repeating units. For example, using long-chain alkyl groups as substituents does not remove a molecule from the "small molecule" category. Small molecules can also be incorporated into polymers, for example, as side groups on the polymer backbone or as part of the backbone. Small molecules can also act as the core portion of dendritic polymers, which consist of a series of chemical shells built on the core portion. The core portion of a dendritic polymer can be a fluorescent or phosphorescent small-molecule emitter. Dendritic polymers can be "small molecules," and all dendritic polymers currently used in the OLED field are considered small molecules.

[0073] As used herein, "top" means furthest from the substrate, and "bottom" means closest to the substrate. When the first layer is described as being "placed" "above" the second layer, the first layer is placed further away from the substrate. Unless specified that the first layer "contacts" the second layer, other layers may exist between the first and second layers. For example, even if various organic layers exist between the cathode and anode, the cathode may still be described as being "placed" "above" the anode.

[0074] As used herein, “solution-handleable” means capable of dissolving, dispersing or transporting in and / or depositing from a liquid medium in the form of a solution or suspension.

[0075] When a ligand is considered to directly contribute to the photosensitivity of the emissive material, the ligand may be referred to as "photosensitive." When a ligand is considered not to contribute to the photosensitivity of the emissive material, the ligand may be referred to as "auxiliary," but auxiliary ligands can alter the properties of photosensitizing ligands.

[0076] As used herein, and as will generally be understood by those skilled in the art, if the first energy level is closer to the vacuum level, then the first "Highest Occupied Molecular Orbital" (HOMO) or "Lowest Unoccupied Molecular Orbital" (LUMO) level is "greater than" or "higher than" the second HOMO or LUMO level. Since the ionization potential (IP) is measured as a negative energy relative to the vacuum level, a higher HOMO level corresponds to an IP with a smaller absolute value (less negative IP). Similarly, a higher LUMO level corresponds to an electron affinity (EA) with a smaller absolute value (less negative EA). On a conventional energy level diagram with the vacuum level at the top, the LUMO levels of a material are higher than the HOMO levels of the same material. "Higher" HOMO or LUMO levels appear to be closer to the top of this diagram than "lower" HOMO or LUMO levels.

[0077] As used herein, and as will generally be understood by those skilled in the art, if the first work function has a higher absolute value, then the first work function is “greater” or “higher” than the second work function. This is because the work function is typically measured as a negative number relative to the vacuum level, meaning that the “higher” work function is more negative. On a conventional energy level diagram with the vacuum level at the top, the “higher” work function is illustrated as being farther from the vacuum level in the downward direction. Therefore, the definitions of HOMO and LUMO levels follow different rules than those for the work function.

[0078] The terms “halogen,” “halogen,” and “halogen group” are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

[0079] The term "acyl" refers to the substituted carbonyl group (C(O)-R). s ).

[0080] The term "ester" refers to the substituted oxycarbonyl group (-OC(O)-R). s or -C(O)-OR s ) group.

[0081] The term "ether" refers to -OR s Group.

[0082] The terms "thio-" or "thioether" are used interchangeably and refer to -SR s Group.

[0083] The term "sulfinyl" refers to -S(O)-R s Group.

[0084] The term "sulfonyl" refers to -SO2-R s Group.

[0085] The term "phosphin" refers to -P(R) s )3 groups, wherein each R s They can be the same or different.

[0086] The term "silyl" refers to -Si(R) s )3 groups, wherein each R s They can be the same or different.

[0087] The term "oxoboroyl" refers to -B(R) s )2 group or its Lewis adduct -B(R s )3 groups, of which R s They can be the same or different.

[0088] In each of the above, R s It can be hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. Preferred R s Choose from the following groups: alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0089] The term "alkyl" refers to and includes both straight-chain and branched alkyl groups. Preferred alkyl groups are those containing one to fifteen carbon atoms, and include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, etc. Additionally, the alkyl group may optionally be substituted.

[0090] The term "cycloalkyl" refers to and includes monocyclic, polycyclic, and spiroalkyl groups. Preferred cycloalkyl groups are those containing 3 to 12 cyclic 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 may optionally be substituted.

[0091] The terms "heteroalkyl" or "heterocyclic alkyl" refer to alkyl or cycloalkyl groups having at least one carbon atom substituted with a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Additionally, the heteroalkyl or heterocyclic alkyl group may optionally be substituted.

[0092] The term "alkenyl" refers to and includes both straight-chain and branched alkenyl groups. An alkenyl group is essentially an alkyl group comprising at least one carbon-carbon double bond in an alkyl chain. A cycloalkenyl group is essentially a cycloalkyl group comprising at least one carbon-carbon double bond in a cycloalkyl ring. The term "heteroalkenyl" as used herein refers to an alkenyl group in which at least one carbon atom is replaced by a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Preferred alkenyl, cycloalkenyl, or heteroalkenyl groups are those containing two to fifteen carbon atoms. Additionally, alkenyl, cycloalkenyl, or heteroalkenyl groups may optionally be substituted.

[0093] The term "alkynyl" refers to and includes both straight-chain and branched alkynyl groups. An alkynyl group is essentially an alkyl group comprising at least one carbon-carbon triple bond in an alkyl chain. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may optionally be substituted.

[0094] The terms "aralkyl" or "arylalkyl" are used interchangeably and refer to an alkyl group that has been substituted with an aryl group. Additionally, aralkyl groups may optionally be substituted.

[0095] The term "heterocyclic group" refers to and includes aromatic and non-aromatic cyclic groups containing at least one heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Aromatic heterocyclic groups are used interchangeably with heteroaryl groups. Preferred non-aromatic heterocyclic groups are heterocyclic groups containing 3 to 7 ring atoms, including at least one heteroatom, and include cyclic amines such as morpholino, piperidinyl, pyrrolyl, etc., and cyclic ethers / thioethers such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, etc. Additionally, the heterocyclic group may be optionally substituted.

[0096] The term "aryl" refers to and includes monocyclic aromatic hydrocarbon groups and polycyclic aromatic ring systems. A polycyclic system may have two or more rings in which two carbons are shared by two adjacent rings (the rings are "fused"), wherein at least one of the rings is an aromatic hydrocarbon group; for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Particularly preferred are aryl groups having six, ten, or twelve carbon atoms. Suitable aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, etc. Perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene, and naphthalene. Additionally, the aryl group may optionally be substituted.

[0097] The term "heteroaryl" refers to and includes monocyclic aromatic groups and polycyclic aromatic ring systems comprising at least one heteroatom. Heteroatoms include, but are not limited to, O, S, N, P, B, Si, and Se. In many cases, O, S, or N are preferred heteroatoms. Monocyclic heteroaromatic systems are preferably monocyclic rings having 5 or 6 ring atoms, and the rings may have one to six heteroatoms. Heteropolycyclic systems may have two or more rings in which two atoms are shared by two adjacent rings (the rings are "fused"), wherein at least one of the rings is a heteroaryl group, and other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Heteropolycyclic aromatic ring systems may have one to six heteroatoms on each ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indole-carbazole, pyridylindole, pyrrolo-dipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazol, pyridine, pyrazine, pyrimidine, pyrazine, triazine, oxazine, oxthiazine, oxadiazine, indole, benzimidazole, indazole, inoxazine, benzoxazole, benziisoxazole, benzothiazole, quinoline, isoquinoline, zoline, quinazole Phosphorus, quinoxaline, naphthidine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothiophenopyridine, thiophenodipyridine, benzoselenophenopyridine, and selelenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborane, 1,3-azaborane, 1,4-azaborane, borazynylene, and their aza analogs. Additionally, the heteroaryl group may optionally be substituted.

[0098] Among the aryl and heteroaryl groups listed above, triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, and benzimidazole, as well as their respective aza analogs, are of particular interest.

[0099] As used herein, the terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, ynyl, aralkyl, heterocycloyl, aryl, and heteroaryl are either unsubstituted or substituted independently by one or more general substituents.

[0100] In many cases, the substituents are generally selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, oxoboryl, and combinations thereof.

[0101] In some cases, preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, oxoboryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, oxoboryl, and combinations thereof.

[0102] In some cases, more preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, aryl, heteroaryl, thio, and combinations thereof.

[0103] In other cases, the most preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0104] The terms "substituted" and "substituted" refer to substituents other than H being bonded to the relevant position, such as carbon or nitrogen. For example, when R... 1 When representing a single substitution, then an R 1 It must not be H (i.e., substitution). Similarly, when R 1 When representing disubstituted substitution, then the two Rs 1 It must not be H. Similarly, when R... 1 When R represents zero or no substitution, 1 For example, it could be hydrogen with available valences in the ring atom, such as the carbon atom in benzene and the nitrogen atom in pyrrole, or simply none for ring atoms with fully saturated valences, such as the nitrogen atom in pyridine. The maximum possible number of substitutions in a ring structure will depend on the total number of available valences in the ring atoms.

[0105] As used herein, “combination thereof” means that one or more members of the applicable list are combined to form a known or chemically stable arrangement that can be conceived by one of ordinary skill in the art from the applicable list. For example, alkyl and deuterium can be combined to form partially or fully deuterated alkyl groups; halogen and alkyl groups can be combined to form haloalkyl substituents; and halogen, alkyl, and aryl groups can be combined to form haloaralkyl groups. In one instance, the term substitution includes a combination of two to four listed groups. In another instance, the term substitution includes a combination of two to three groups. In yet another instance, the term substitution includes a combination of two groups. Preferred combinations of substituents are combinations containing up to fifty atoms that are not hydrogen or deuterium, or combinations containing up to forty atoms that are not hydrogen or deuterium, or combinations containing up to thirty atoms that are not hydrogen or deuterium. In many cases, preferred combinations of substituents will include up to twenty atoms that are not hydrogen or deuterium.

[0106] The term "aza" in the phrases used herein, namely aza-dibenzofuran, aza-dibenzothiophene, etc., refers to the substitution of one or more CH groups in the corresponding aromatic ring by a nitrogen atom. For example, and without limitation, azatriphenylene covers dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. Other nitrogen analogs of the aza-derived compounds described above will be readily contemplated by those skilled in the art, and all such analogs are intended to be covered by the terminology set forth herein.

[0107] 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 (which are incorporated herein by reference in their entirety) describe the preparation of deuterium-substituted organometallic complexes. Further references to Ming Yan et al., Tetrahedron 2015, 71, 1425-30, and Atzrodt et al., Angewandte Chemie International Edition (Review) 2007, 46, 7744-65 (which are incorporated herein by reference in their entirety) describe efficient methods for the deuteration of methylene hydrogen in benzylamine and the replacement of aromatic cyclic hydrogens with deuterium, respectively.

[0108] It should be understood that when a molecular fragment is described as a substituent or additionally linked to another part, its name can be written as if it were a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or as if it were a whole molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of naming substituents or linked fragments are considered equivalent.

[0109] In some cases, a pair of adjacent substituents may optionally join or fuse into a ring. Preferred rings are five-, six-, or seven-membered carbon rings or heterocycles, including both cases where a portion of the ring formed by the pair of substituents is saturated and a portion of the ring formed by the pair of substituents is unsaturated. As used herein, “adjacent” means that the two substituents involved may be adjacent to each other on the same ring, or on two neighboring rings having two closest available substituted positions (such as the 2, 2' positions in biphenyl or the 1, 8 positions in naphthalene), provided that a stable fused ring system can be formed.

[0110] B. OLEDs, compounds, and devices disclosed herein

[0111] Outcoupling energy in the form of light from surface plasmon energy (SPR) modes can be used to provide OLEDs with longer lifetimes at display brightness when the emitting layer is within a threshold distance of the plasmon-active materials (such as metal cathodes and / or anodes, e.g., electrode layers). The threshold distance can be the distance where the total nonradiative decay rate constant is equal to the total radiative decay rate constant, as disclosed in U.S. Patent No. 9,960,386, which is incorporated herein by reference in its entirety. Figure 26a The quantum yield (QY) is plotted as a function of the distance of the emitting material from the electrode layer (e.g., a metal anode and / or cathode). QY begins to decrease after the non-radiative decay rate constant approaches the radiative decay rate, producing a QY peak at a specific distance. Figure 26b This schematically illustrates how the steady-state temperature of an OLED varies with the distance between the emitter and the electrode layer for a fixed operating current density. For larger distances between the emitter and the electrode layer, there is no increase in the radiative or non-radiative attenuation constant. The OLED temperature depends only on the total operating current density and the efficiency of the emitter. As the emitter is brought closer to the electrode layer, the radiative attenuation constant increases and the photon yield increases, reducing the heat generated in the OLED and lowering its steady-state temperature. For distances shorter than the threshold distance of 2, excitons on the light emitter are quenched with increasing heat and a rise in the OLED's normalized temperature. This depiction of the OLED temperature is accurate when the enhancement layer does not decouple a predetermined significant fraction of the energy in the form of light under surface plasmon resonance modes. If decoupling is incorporated into the enhancement layer or if a decoupling layer is used in the device, then this measurement of the threshold distance would be equivalent to removing the layer.

[0112] The embodiments of the disclosed subject matter can convert the energy stored in the SPR mode of the plasmonic active material into visible light via a nanopatch antenna.

[0113] Nanopatch antennas may include a planar metal film (e.g., an electrode layer), a spacer material (e.g., a dielectric material, etc.) disposed on the planar metal, and nanoparticles disposed on the spacer material, as shown in Figures 3a-3c. Figure 3a illustrates a conventional nanopatch antenna, which includes a spacer layer in which emitter molecules are embedded between nanoparticles and a metal layer. Figure 3b illustrates a nanopatch antenna according to an embodiment of the disclosed subject matter, wherein the emitter molecules in the emitter layer are placed below the metal layer (i.e., not in the spacer layer). Figure 3c Another embodiment of the disclosed subject matter is shown, which includes a capping layer disposed on top of the nanoparticles. In some embodiments, the capping layer may include additional emitter molecules.

[0114] The interstitial material can be organic (e.g., small molecule and / or polymeric materials) and can include oxides and / or other dielectric materials, including stacks, alloys, and / or mixtures of materials as shown, for example, in Figure 4a. That is, Figure 4a illustrates a dielectric material with multiple layers. Due to the higher electric field strength generated in the interstitial medium, this configuration can provide resonant plasmonic modes within the interstitial space. This large electric field can be used to enhance the emission rate of an emitter placed in the interstitial space, a phenomenon known as the Purcell effect. The nanopatch antenna can radiate energy from this plasmonic active mode outward with up to 50% efficiency.

[0115] In embodiments of the disclosed subject matter, the two stacked dielectric materials may include a thicker layer, which may be a primary dielectric gap material; and a thin layer, which may act as a nanoparticle adhesion layer to increase nanoparticle density and / or reduce nanoparticle aggregation or agglomeration, as shown in Figure 4b. For example, a polyelectrolyte layer (such as poly(styrene sulfonate) or poly(allylamine) hydrochloride) may carry electrostatic charges that may interact with electrostatic charges on a nanoparticle coating (e.g., poly(vinylpyrrolidone), which may be used to coat silver nanoparticles, carrying a negative electrostatic charge). While the sum of the thicknesses of these layers determines the total gap thickness, the adhesion layer thickness may be less than 5 nm, and the gap layer thickness may be between 1 and 100 nm, and more preferably between 1 and 50 nm.

[0116] While a Purcell factor of approximately 1000 can be achieved by placing the emitter within the nanopatch antenna gap, a Purcell factor of approximately 10 may be sufficient for enhancing the stability of phosphorescent OLED emitters. It may be difficult to fabricate an entire OLED stack that maintains high internal quantum efficiency within a typical nanopatch antenna gap thickness (typically 2-15 nm), let alone utilize nanoparticles as one of the OLED electrodes. Embodiments of the disclosed subject matter may provide an arrangement in which the emitter is placed beneath a planar metal, rather than within the antenna gap, as shown in Figure 3b. Variations in this arrangement may include additional capping layers disposed on nanoparticles that may include other emitter molecules, such as… Figure 3c As shown in the diagram, the refractive index of the hood layer can be matched to the other side of the metal layer, thereby improving the cross-coupling of the SPR mode through the metal layer and into the gap of the nanopatch antenna.

[0117] As shown in the arrangements of Figures 3b-3c, the emitter can be positioned such that it is within a threshold distance of a planar metal, which in turn acts as one of the OLED contacts (i.e., the cathode or anode). In one instance, emission may occur on the same device side as the nanoparticles, making this arrangement compatible with both top- and bottom-emission geometries.

[0118] In this arrangement, the Purcell enhancement that stabilizes the emitter may originate from its proximity to the planar metal contacts (e.g., electrode layers). Figure 5a The embodiments shown are based on the disclosed subject matter, wherein emitter molecules in an emitter layer placed below the metal layer (i.e., not in the interstitial layer) can be stacked with conventional OLEDs, wherein the emitter layer is within a threshold distance to the metal cathode, and a subsequent nanopatch antenna geometry on top of the cathode radiates outward from the side with nanoparticles.

[0119] In variations of this arrangement, the metal contacts or the entire device stack can be corrugated to enhance the decoupling of the SPR mode, such as... Figure 5b As shown in the diagram. This arrangement can reduce the maximum achievable Purcell enhancement to below that achieved by placing the emitter within the gap, but still achieves a Purcell factor ≥10. By placing the emitter within a threshold distance of the metal (e.g., an electrode layer), the emitter energy can be coupled into an SPR mode induced along the metal surface. For non-opaque metal films (e.g., Ag < 200 nm thick, Al and Au < 100 nm thick), this plasmonic mode can be coupled to the opposite side of the metal, where it can transfer its energy to the gap plasmonic mode and be converted into light via a nanopatch antenna, such as... Figure 6 As shown in the image.

[0120] In other words, Figure 6The energy is concentrated and radiated as light through the SPR mode. The excited emitter molecules quench their energy into the SPR mode in the cathode, generating an electric field that can then couple to the gap mode of the nanopatch antenna and radiate energy outward as light.

[0121] When nanocubes are used as nanoparticles in nanopatch antennas, the electric field strength may be highest at the inflection points of the nanocubes, such as... Figure 7 As shown in the simulation. That is to say, Figure 7 Simulations of the electric field intensities Ex and Ey in the x and y directions, respectively, are shown in the gap layer of a nanopatch antenna using nanocubes as nanoparticles. Figure 7 This demonstrates that the light coupled to the far field originates from the edge of the nanoparticle.

[0122] Tuning the resonance of a nanopatch antenna to align with the emission spectrum of a phosphor can be used to efficiently convert plasmonic energy into light. This tuning can be achieved by any number of methods, including but not limited to: changing the size of the nanoparticles, changing the shape of the nanoparticles (typically cubes, spheres, rods, disks, plates, stars, and variations of these shapes with other faces), changing the nanoparticle material (metal or dielectric), adjusting the thickness of the gap, changing the refractive index of the gap or the surrounding environment (e.g., by depositing an additional capping layer on top of the nanoparticles), and changing the thickness or type of the planar metal (e.g., said metal could be Ag, Al, and / or Au, with a thickness ranging from 5 nm to 100 nm). Ordered arrays of nanoparticles can be used to enhance decoupling efficiency and / or tune the resonant wavelength.

[0123] The planar metal film (e.g., electrode layer) and / or metal nanoparticles can be pure or alloyed, preferably Ag, Al, Ag-Al alloys, or Au. Other materials include, but are not limited to, Ir, Pt, Ni, Cu, W, Ta, Fe, and Cr. Additionally, the nanoparticles can be composed entirely of dielectric materials, which can be alloys of metals and dielectric materials, or can have a core of one type of material coated with a shell of different types of materials.

[0124] The gap thickness (e.g., material thickness) can be 0-150 nm, and more preferably 0-50 nm. When the gap is 0 nm (i.e., no gap), the nanoparticles can be disposed on a planar metal (e.g., an electrode layer) and can have a corrugated form to decouple SPR energy. Depending on the nanoparticle material and shape, the size of the nanoparticles used to scatter light in the visible portion of the spectral range (e.g., 400-700 nm wavelength) can be from 5 nm to 1000 nm. The gap can be a dielectric material with a refractive index of 1-5, such as an organic or metal oxide.

[0125] A gap of 0 nm can be achieved without using nanoparticles. Figure 8 In the example device shown, a planar metal film can be partially etched through its thickness to form a corrugated top surface, while the bottom surface of the film can be planar. This can be achieved, for example, by using focused ion beam milling. The corrugation can be performed on the metal attached to the completed OLED device, or on a separate substrate on which the corrugated metal can be peeled off and attached to the OLED, or on which the OLED can be grown.

[0126] In another embodiment of the disclosed subject matter, the nanoparticles may be individually coated with a dielectric material to serve as part or all of the gap spacing (e.g., through the material), such as Figure 9 As shown in the diagram. For example, particles can be coated with the desired entire gap thickness, thereby reducing the gap layer to zero. In another example, the combination of the gap layer thickness and the nanoparticle coating can achieve the desired total spacer thickness. The nanoparticle coating can act as an adhesion layer to improve the adhesion of nanoparticles to the layer on which they will be deposited or to increase the nanoparticle density on the layer.

[0127] Since the refractive index of the gap layer can affect the resonance of the nanopatch antenna, using a material with a voltage-tunable refractive index can provide a method for voltage-tuned emission spectra applied between the metal cathode and the electrical contact layer beneath the nanoparticles, such as... Figure 10 As shown in the image. That is to say, Figure 10 An OLED combined with a nanopatch antenna is schematically shown, utilizing a material 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 the voltage-tunable refractive index material because its dielectric constant changes as the applied voltage alters the carrier concentration. In this case, a second insulating layer can be used in the gaps to build up the charge. In some embodiments, depending on the material properties of the voltage-tunable refractive index layer, the secondary insulating layer can be removed. This can be useful when the OLED is stacked as a white OLED (i.e., containing red, green, and blue emission), as the voltage-tunable nanopatch resonance can act as a color filter to selectively pass through the desired color. This effectively transforms the OLED into a three-terminal device, where a voltage is applied between the anode and cathode operating the OLED, and a voltage is applied between the cathode and the electrical contact layer beneath the nanoparticles to tune the nanopatch resonance to select the emitted color.

[0128] That is, according to at least the embodiments shown in Figures 3a-10, the device may include an emitter layer, a first electrode layer, a plurality of nanoparticles, and a material disposed between the first electrode layer and the plurality of nanoparticles. The thickness of the first electrode layer of the device may be from 5 nm to 300 nm.

[0129] The device may include a second electrode layer and a substrate, wherein the second electrode layer may be disposed on the substrate, and an emission layer may be disposed on the second electrode layer. At least one of the first electrode layer and the second electrode layer may be a metal, a semiconductor, and / or a transparent conductive oxide. The first electrode layer may be spaced from the emission layer by a predetermined threshold distance, said predetermined threshold distance being the distance at which the total non-radiative attenuation rate constant is equal to the total radiative attenuation rate constant. The material of the device may include at least one of an organic material, an oxide, and / or a dielectric material. The refractive index of the material may be 1-5. The emission layer of the device may include a transport layer. The emission layer may be an organic layer having emitter molecules.

[0130] The emitting layer of the device may include at least one of the following: fluorescent material, phosphorescent material, thermally activated delayed fluorescence (TADF) material, quantum dot material, metal-organic framework, covalent organic framework and / or perovskite nanocrystals.

[0131] The device may include a nanopatch antenna, wherein the resonance of the nanopatch antenna can be tuned by at least one of the following: changing the size of a plurality of nanoparticles, changing the ratio of the sizes of the plurality of nanoparticles, changing the shape of the plurality of nanoparticles, changing the material of the plurality of nanoparticles, adjusting the thickness of the material, changing the refractive index of the material, changing the refractive index of an additional layer disposed on the plurality of nanoparticles, changing the thickness of a first electrode layer, and / or changing the material of the first electrode layer. The plurality of nanoparticles may be formed from at least one of the following: Ag particles, Al particles, Au particles, dielectric materials, semiconductor materials, metal alloys, mixtures of dielectric materials, a stack of one or more materials, and a core of one type of material coated with a shell of a different type of material. At least one of the plurality of nanoparticles in 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 the nanopatch antenna. The shape of the plurality of nanoparticles may be at least one of the following: cube, sphere, globular, cylinder, parallelepiped, rod-shaped, star-shaped, pyramidal, and / or multifaceted three-dimensional object. At least one of the multiple nanoparticles can be between 5 nm and 1000 nm in size.

[0132] The device may include a corrugated layer disposed on a substrate, wherein the second electrode layer, the emitter layer, the first electrode layer, and the material are correspondingly corrugated, such as... Figure 5b As shown in the image.

[0133] The device may be made of a dielectric layer disposed on a first electrode layer and an electrical contact layer disposed on the dielectric layer. The material may include a voltage-adjustable refractive index material between the electrical contact layer and the first electrode layer. The voltage-adjustable 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 from the emitting layer by a predetermined threshold distance. As discussed above, the predetermined threshold distance may be a distance where the total non-radiative attenuation constant is equal to the total radiative attenuation constant.

[0134] In some embodiments, the device may include an additional layer disposed on a plurality of nanoparticles. The additional layer may include one or more emitter molecules. The additional layer may match the refractive index beneath the first electrode layer. The thickness of the additional layer may be 1000 nm or less.

[0135] A nanopatch antenna (NPA) may include a planar metal film (e.g., an electrode layer), a gap material (e.g., a dielectric material, etc.) disposed on top of the planar metal, and nanoparticles (e.g., as shown in Figure 3a) disposed on top of the gap material. This configuration generates resonant plasmon modes due to the high electric field strength generated in the gap medium. This large electric field can be used to enhance the emission rate of an emitter placed in the gap, known as the Purcell effect, which in turn stabilizes the emitter to a detrimental process dependent on the emitter in the excited state. The nanopatch antenna can radiate energy from this plasmon-active mode outward with up to 50% efficiency. Previous NPA designs have typically been optically pumped (e.g., by laser).

[0136] In embodiments of the disclosed subject matter, the OLED stack can be disposed within the dielectric region or NPA gap, and the nanoparticles and planar metal can provide an electrical injection path to the device, such as Figure 11 As shown in the diagram. Traditionally, OLEDs 5 to 20 nm thick are not expected to function due to quenching to non-radiative modes. However, larger Purcell enhancements can allow phosphors to couple rapidly to radiative modes, overcoming the loss processes typically present in OLEDs 5 to 20 nm thick.

[0137] Since typical NPA gap thickness is approximately 2-15 nm, it appears impossible to fabricate an entire OLED stack that maintains high internal quantum efficiency within the nanopatch antenna gap. The large electric field present in the NPA gap at this thickness could potentially enhance the emission rate of the emitter placed within the gap by 1000 times. As discussed above, a Purcell factor of approximately 10 might be sufficient to enhance OLED emitter stability (e.g., phosphorescent OLED stability). In embodiments of the disclosed subject matter, some Purcell enhancement might be traded for a thicker NPA gap, which is more suitable for OLED stacking at a thickness of approximately 5-100 nm.

[0138] It appears impossible to inject charge using metal nanoparticles typically ranging in size from about 5 nm to 1000 nm. Embodiments of the disclosed subject matter provide devices to address this problem. Figure 12a illustrates a glass substrate coated with indium tin oxide (ITO) on which metal nanoparticles (typically Ag, Al, or Au) are dispersed. In one example device, these nanoparticles may have been prepared by solution casting or spin casting. In another instance, the nanoparticles can be processed directly onto the substrate via photolithography and subsequent metal lift-off. An OLED stack can be deposited on top of the metal nanoparticles and capped with metal electrodes (typically Ag, Al, or Au). This can form a corrugated device structure, as shown in Figure 12a.

[0139] For applications where ripples are undesirable, the apparatus shown in Figure 12b can be used. To form this apparatus, the nanoparticle component is etched into the ITO, but not completely through the ITO layer. In one example, due to the directional nature of the etching process, the etching can be performed using a reactive ion etching machine.

[0140] like Figure 13 As shown, the thickness of the deposited metal can be matched to the depth of the ITO etching, and the metal (Ag) on ​​the photoresist (PR) can be stripped. This can produce metal nanoparticles (NPs) flush with the top surface of the ITO. OLED stacks can then be grown on this planar substrate, with the planar metal deposited as top contacts to form an NPA OLED structure. Charge injection into the OLED can be performed by the nanoparticles or ITO.

[0141] exist Figures 12a-12b In the diagram, two individual NPAs are highlighted within the dashed box. Each NPA operates independently when the nanoparticles are spaced far enough apart that there is no coupling between them. In this case, the electric field (and therefore, Purcell enhancement) can be higher for emitter molecules located within an individual NPA than for emitter molecules outside it. This may cause some spatial variation in the emitter rate throughout the OLED emitter layer, but because the metal contacts are extremely close to all emitter molecules in the stack, all emitter molecules will sense an increase in photon state density and thus experience Purcell enhancement. When nanoparticles are arranged in an array such that coupling may occur between them, it can produce hybrid, spatially delocalized modes that can reduce variations in Purcell enhancement. In some embodiments, the nanoparticles may be close enough for them to form hybrid modes. In another embodiment, the nanoparticles may not be hybridized.

[0142] In some embodiments, the nanoparticles may be cubic, spherical, globular, cylindrical, parallelepiped, and / or rod-shaped. The size of the nanoparticles may vary from 5 nm to 1000 nm, and more preferably from 5 nm to 200 nm. The nanoparticles may be dielectric, semiconductor, or metallic.

[0143] The gap material can be a dielectric or a semiconductor, and has a refractive index of 1 to 15. The gap material can include at least one luminescent material, which can be a fluorescent material, a phosphorescent material, a thermally activated delayed fluorescence (TADF) material, or a quantum dot material. In some embodiments, one or more types of luminescent materials may be present. The gap can include a host material. The gap can include multiple material layers or may be only one layer. In some embodiments, the gap material can include a mixture of materials. The gap can have a thickness ranging from 0.1 nm to 100 nm.

[0144] The planar metal film can be pure or an alloy, preferably Ag, Al, Ag-Al alloy, or Au. Other materials include, but are not limited to, Ir, Pt, Ni, Cu, W, Ta, Fe, and Cr. The top side of the planar film can be patterned with additional material. Additional material can be present on the top of the metal film; this material can include light-emitting elements, including quantum dots.

[0145] In other words, Figure 11-1 In the embodiment shown in 2b, the device may include an emitter 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 the emitter 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 on the substrate, and the plurality of nanoparticles may be disposed on the second electrode layer, wherein the emitter layer may be non-planar and may be included in the material, and may be disposed on and adapted to the plurality of nanoparticles and the second electrode layer, and wherein the first electrode layer may be disposed on and adapted to the non-planar emitter 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.

[0146] like Figure 13 As shown, the method includes: placing a first electrode layer on a substrate, placing a photoresist on the first electrode layer, etching at least a portion of the photoresist and the first electrode layer, depositing metal on the remaining photoresist portion to match the depth of the etched portion of the first electrode layer, removing the metal and the photoresist to form nanoparticles from the deposited metal flush with the surface of the first electrode layer, placing an emission layer on the first electrode layer and the nanoparticles, and placing a second electrode layer on the emission layer.

[0147] Embodiments of the disclosed subject matter provide improved organic light-emitting diode (OLED) performance by using nanostructures having one or more different geometries, shapes, materials, and / or lattice symmetries. The nanostructures can enhance emissivity, increase surface plasmon polariton (SPP) mode decoupling, improve device stability, and / or provide far-field radiation patterns.

[0148] To effectively couple excited-state energies to plasmonic modes, the emitter or emitter layer can be placed within a threshold distance of the structure and / or layer that increases the photon density of states (as shown in Figures 14a-14f), subsequently producing enhanced emissivity, known as the Purcell effect described above. As discussed above, the threshold distance can be the distance at which the total nonradiative attenuation constant is equal to the total radiative attenuation constant.

[0149] The example apparatuses in Figures 14a-14f illustrate variations of nanostructured cathodes (cross-sectional views) according to embodiments of the disclosed subject matter. These include nanopores (which may also be referred to as nanostructures) that can be etched as follows: completely through the metal film (shown in Figures 14a, 14b), partially through the metal film (shown in Figures 14c, 14d), or some of which can be etched completely through the metal film while others are only partially etched (shown in Figures 14e, 14f). Figures 14a-14f illustrate variations in the end-capping of the nanostructured cathode with a dielectric layer (shown in Figures 14a, 14c, 14e) or without a dielectric layer (shown in Figures 14b, 14d, 14f) for the purpose of matching the refractive index with the refractive index below the cathode, in order to improve the cross-coupling of surface plasmon modes between metal film thicknesses. The profile of the pores (nanostructures) (i.e., whether the pore edges and / or sidewalls are likely to be perpendicular to the surface of the film or whether the pore sidewalls have a radius of curvature) can be used to tune the properties of the nanostructure array.

[0150] Nanostructures can be made of metals, dielectrics, or some combination thereof. Figure 15 Examples of different possible combinations of embodiments of the disclosed subject matter are shown. The use of composites (e.g., metals and dielectrics) provides flexibility in device design because the resonant frequencies of local modes can be tuned and / or selected by the composites used. For each of these materials, a tunable local electromagnetic mode is possible. Typical metals used include (but are not limited to) Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, and / or Ca, and may include stacks and / or alloys of these materials. Dielectrics used may include, but are not limited to: organic materials, titanium dioxide, silicon dioxide, silicon nitride, aluminum oxide, zinc oxide, nickel oxide, germanium oxide, lithium fluoride, magnesium fluoride, and / or molybdenum oxide.

[0151] Local electromagnetic resonances of a nanostructure or a portion thereof can be tuned by the shape of the nanostructure. The shape can include any cylindrical, spherical, and / or cubic shape, or any shape with single or multiple local resonances, such as... Figure 16 As shown in the diagram, the radii of curvature of the edges and / or corners in a faceted nanostructure can be used to tune the resonant frequencies of the nanostructure. Examples of multiple local resonance shapes can include ellipses and rectangles, which support multiple modes with different frequencies induced by the asymmetry of the nanostructure. For example, Figure 16 This demonstrates how different lengths and / or widths of rectangular nanostructures can generate two distinct resonant frequencies. These multi-frequency nanostructures can provide enhanced outcoupling for multi-wavelength or white-emitting OLEDs.

[0152] That is, in the embodiments shown in Figures 14a-16, the device may include an 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 on the substrate, the emitting layer is disposed on the second electrode layer, the first electrode layer is disposed on the emitting layer, the first dielectric layer is disposed on the first electrode layer, the plurality of nanoparticles are disposed on the first dielectric layer, and the second dielectric layer is disposed on 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 from the emitting layer by a predetermined threshold distance, said predetermined threshold distance being the distance at which the total nonradiative attenuation rate constant is equal to the total radiative attenuation rate constant. The material may include at least one selected from the group consisting of: organic materials, oxides, and dielectric materials. The refractive index of the material may be 1-5. The emitting layer may include a transport layer. The emitting layer may be an organic layer having emitter molecules. The emitting layer may include at least one of the following: fluorescent materials, phosphorescent materials, thermally activated delayed fluorescence (TADF) materials, quantum dot materials, metal-organic frameworks, covalent organic frameworks, and perovskite nanocrystals. The thickness of the first electrode layer may be from 5 nm to 300 nm.

[0153] The device may include a nanopatch antenna, wherein the resonance of the nanopatch antenna can be tuned by at least one of the following: changing the size of a plurality of nanoparticles, changing the ratio of the sizes of the plurality of nanoparticles, changing the shape of the plurality of nanoparticles, changing the material of the plurality of nanoparticles, adjusting the thickness of the material, changing the refractive index of the material, changing the refractive index of an additional layer disposed on the plurality of nanoparticles, changing the thickness of a first electrode layer, and / or changing the material of the first electrode layer. The plurality of nanoparticles may be formed from at least one of the following: Ag particles, Al particles, Au particles, dielectric materials, semiconductor materials, metal alloys, mixtures of dielectric materials, a stack of one or more materials, and a core of one type of material coated with a shell of a different type of material. At least one of the plurality of nanoparticles in 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 the nanopatch antenna. The shape of the plurality of nanoparticles may be at least one of the following: cube, sphere, globular, cylinder, parallelepiped, rod-shaped, star-shaped, pyramidal, and / or multifaceted three-dimensional object. At least one of the multiple nanoparticles can be between 5 nm and 1000 nm in size.

[0154] 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 on the substrate, an emitter layer may be disposed on the second electrode layer, a first electrode layer may be disposed on the emitter layer, a first dielectric layer may be disposed on the first electrode layer, and a plurality of nanoparticles may be disposed on 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.

[0155] The device may include a substrate and a second electrode layer, wherein the materials are a first dielectric layer and a second dielectric layer, wherein a plurality of nanoparticles may be disposed in the second dielectric layer, and wherein the second dielectric layer and the plurality of nanoparticles may be disposed on the substrate, the first dielectric layer may be disposed on the second dielectric layer and the plurality of nanoparticles, a first electrode layer may be disposed on the first dielectric layer, an emitter layer may be disposed on the first electrode, and a second electrode may be disposed on the emitter 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.

[0156] The device may include a substrate and a second electrode layer. The materials may be a first dielectric layer and a second dielectric layer. The first electrode layer may be disposed on the substrate, the first dielectric layer may be disposed on the first electrode layer, multiple nanoparticles may be disposed on the first dielectric layer, the second dielectric layer may be disposed on the multiple nanoparticles and the first dielectric layer, the emitter layer may be disposed on the second dielectric layer, and the second electrode layer may be disposed on the emitter layer.

[0157] The device may include a substrate and a second electrode layer, the materials of which are a first dielectric layer and a second dielectric layer. The second electrode layer may be disposed on the substrate, an emitter layer may be disposed on the second electrode layer, multiple nanoparticles may be disposed on the emitter layer, the second dielectric layer may be disposed on the multiple nanoparticles and the emitter layer, the first dielectric layer may be disposed on the second dielectric layer, and the first electrode layer may be disposed on 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.

[0158] The material of the device may include at least one of organic materials, oxides, and / or dielectric materials. 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 adhesion 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 thickness of the material may be 1000 nm or less. The refractive index of the material of the device may be 1-5. The material may include at least a portion of a coating disposed on a plurality of nanoparticles. The coating disposed on the plurality of nanoparticles may be a dielectric coating.

[0159] The device may include a second electrode layer, wherein the emission layer is included in an organic light-emitting diode (OLED), and wherein the OLED is disposed between the first electrode layer and the second electrode layer. At least one of the first and second electrode layers may be a metal, a semiconductor, and / or a transparent conductive oxide. The emission layer may include a transport layer. The emission layer may be an organic layer having emitter molecules. The emission layer may include at least one of the following: 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 perovskite nanocrystals.

[0160] The first electrode layer of the device may be spaced from the emission layer by a predetermined threshold distance, wherein the threshold distance is the distance at which the total nonradiative attenuation constant is equal to the total radiative attenuation constant. The first electrode layer may include at least one of the following: Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, and / or Ca. The first electrode layer may be patterned with additional materials. Additional materials may include light-emitting elements such as fluorescent emitters, phosphorescent emitters, quantum dots, metal-organic frameworks, covalent organic frameworks, and / or perovskite nanocrystals. The thickness of the first electrode layer may be from 5 nm to 300 nm. The first electrode layer of the device may have at least one non-planar surface.

[0161] The device may include a nanopatch antenna, and the resonance of the nanopatch antenna may be tuned by at least one of the following: changing the size of a plurality of nanoparticles, changing the ratio of the sizes of a plurality of nanoparticles, changing the shape of a plurality of nanoparticles, changing the material of a plurality of nanoparticles, adjusting the thickness of the material, changing the refractive index of the material, changing the refractive index of an additional layer disposed on a plurality of nanoparticles, changing the thickness of a first electrode layer and / or changing the material of the first electrode layer.

[0162] The multiple nanoparticles of the device may be formed from at least one of the following: Ag particles, Al particles, Au particles, dielectric materials, semiconductor materials, metal alloys, mixtures of dielectric materials, stacks of one or more materials and / or a core of one type of material, and coated with a shell of different types of materials.

[0163] At least one of the plurality of nanoparticles in the device may include an additional layer to provide lateral conduction between the nanoparticles. The nanoparticles are coated with an oxide layer, wherein the thickness of the oxide layer is selected to tune the plasmon resonance wavelength of the nanoparticles or nanopatch antenna. The nanoparticles may be colloidal synthetic nanoparticles formed from a solution. The shape of the nanoparticles may be at least one of the following: cube, sphere, globular, cylinder, parallelepiped, rod-shaped, star-shaped, pyramidal, and multifaceted three-dimensional objects. The size of at least one of the nanoparticles may be from 5 nm to 1000 nm. The size of at least one of the nanoparticles may be from 5 nm to 200 nm. The size of at least one of the nanoparticles may be from 5 nm to 100 nm.

[0164] The device may include a substrate and a second electrode layer, wherein the second electrode layer may be disposed on the substrate and nanoparticles may be disposed in the second electrode layer, wherein an emission layer may be included in a material and disposed on the second electrode layer comprising a plurality of nanoparticles, and wherein a first electrode layer is disposed on the emission 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.

[0165] Inorganic light-emitting diodes (LEDs) are playing an increasingly prominent role in lighting and display applications. Some inorganic LEDs suffer from decoupling issues, including efficiency problems, angle dependence, and efficiency degradation at high brightness. While the physical sources of this "efficiency degradation" depend on the LED system (e.g., materials, device design, etc.), one explanation is that the degradation stems from luminescence quenching phenomena, such as Auger recombination, which reduce luminous efficiency through non-radiative processes. The likelihood of such luminescence quenching events increases with increasing local carrier density, as interactions may become more frequent.

[0166] The disclosed subject matter provides a device including a reinforcing layer. The reinforcing layer may be a plasmonic system, a hyperbolic metamaterial, and / or an optically active metamaterial, which is a material having both negative permittivity and negative permeability. Examples of the reinforcing layer may include stacks or uniformly spaced metal nanoparticles, metal cathode or anode thin films, metal films, and / or dielectric layers.

[0167] For example, Figure 5a The reinforcement layer is shown as a metal electrode. Variations in the reinforcement layer can be placed within a threshold distance of the recombination region, such as... Figure 5a As shown, to accelerate the emission rate, the excited-state energy is rapidly quenched to the surface plasmon modes of the enhancement layer due to the increased density of optical states. The threshold distance can be the distance where the total nonradiative attenuation constant is equal to the total radiative attenuation constant. This can reduce the efficiency degradation at higher current densities by reducing excited-state interactions.

[0168] In another instance, the enhancement layer can have multiple layers, such as Figure 17 As shown in the diagram. Each layer may include a unit cell having multiple unit cell sub-assembly layers. Each unit cell may have a first unit cell sub-assembly and a second unit cell sub-assembly.

[0169] Increased junction temperature in LEDs typically leads to reduced light output. This is especially true for yellow and / or red AlGaInP LEDs. Manufacturers often apply compensation circuitry to reduce this temperature-induced light loss, but this can result in a shorter LED lifetime. LED junction temperature can vary depending on ambient temperature, the current flowing through the LED, and / or the efficiency of surrounding materials, including any applied heatsinks. The enhancement layer of the disclosed object can reduce the excited-state lifetime of the LED and can reduce heating of the LED device, leading to increased stability of the LED device or any components in contact with it. By reducing the current flowing through the LED to produce a given light output, the resulting reduced junction temperature and / or thermal load on the device allows for a reduction in heatsinking and compensation circuitry. This can reduce manufacturing costs and / or complexity, and can reduce the size and / or form factor of the LED.

[0170] Although the efficiency degradation will decrease at higher current densities, the efficiency of embodiments of the disclosed subject matter may be lower than that without the reinforcement layer because many excited-state energies may be quenched into the nonradiative modes of the reinforcement layer. To restore device efficiency, some embodiments may include nanoscale, object-based decoupling structures. In some embodiments, the decoupling structure components may be included within the reinforcement layer.

[0171] In embodiments of the disclosed subject matter, the reinforcing layer and nanoscale decoupling structure comprise a planar metal, a dielectric gap material, and a nanoparticle layer. As used throughout, this can be a reinforcing layer with a nanopatch decoupling structure. This decoupling structure can convert plasmon energy back into photons and is not limited by the external quantum efficiency limit of the refractive index difference of a typical LED. That is, an LED with the reinforcing layer of the disclosed subject matter can match or exceed the efficiency of conventional devices without a reinforcing layer and decoupling structure. In some embodiments, the reinforcing layer may be a planar metal film and / or metal nanoparticles, and may be pure or an alloy, or a mixture thereof, preferably Ag, Al, Ag-Al alloys, or Au, as shown, for example, in Figures 14-14f. The reinforcing layer may be composed 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. The decoupling structure may include a thin film of metal cathode or anode, a stack of metal films, a dielectric layer and nanoparticles, a grating (e.g., a one-dimensional grating, a two-dimensional grating, a hexagonal grating, a target grating, etc.) and / or a distributed Bragg reflector. The grating may include a dielectric material, or a mixture of dielectric, semiconductor and metallic materials.

[0172] Nanoparticles can be composed entirely of dielectric materials. In some embodiments, nanoparticles may be metal alloys, dielectric materials, and / or may have a core of one type of material and a shell coated with a different type of material. Depending on the nanoparticle material and shape, typical nanoparticle sizes for scattering light in the visible portion of the spectrum can range from 5 nm to 1000 nm. If the LED is designed for emission in the near-infrared or infrared range, the particle size can range from 500 nm to 5000 nm. Table 1 below discloses example LED materials, reinforcement layers, and / or metal nanoparticle materials and / or particle size ranges. For visible emission, the gap thickness can range from 0 to 150 nm, more preferably from 0 to 50 nm (e.g., 400 to 700 nm), and for the infrared spectrum, the gap thickness can range from a larger gap (e.g., 700 nm to 1 mm). In cases where the gap may be 0 nm (i.e., no gap), nanoparticles can be placed directly on a planar metal top and can act as ripples to decouple surface plasmon energy. The gap can typically contain dielectric materials such as organic materials, metal oxides (crystalline or amorphous), and / or nitrides, with a refractive index of 1-5. Depending on the materials used, the refractive index of the gap can range from 1.01 to 5.

[0173] The nanopatch antenna resonance can be tuned by at least one of the following: changing the size of multiple nanoparticles, changing the shape of multiple nanoparticles, changing the material of multiple nanoparticles, adjusting the thickness of the material, changing the refractive index of the material layer, changing the refractive index of the material or an additional layer disposed on the multiple nanoparticles, changing the thickness of the electrode layer, and / or changing the material of the first electrode layer. The multiple nanoparticles can be formed from at least one of the following: Ag particles, Al particles, Au particles, dielectric materials, semiconductor materials, metal alloys, mixtures of dielectric materials, stacks of one or more materials, and / or a core of one type of material coated with a shell of a different type of material. At least one of the multiple nanoparticles in the device may include an additional layer to provide lateral conduction between the multiple nanoparticles. The multiple nanoparticles may be coated with an oxide layer, wherein the thickness of the oxide layer can be selected to tune the plasmon resonance wavelength of the multiple nanoparticles or the nanopatch antenna. The shape of the multiple nanoparticles can be at least one of the following: cube, sphere, globular, cylinder, parallelepiped, rod-shaped, star-shaped, pyramidal, and / or multifaceted three-dimensional objects. At least one of the multiple nanoparticles can be between 5 nm and 1000 nm in size.

[0174] In some embodiments, the device may include an additional layer disposed on a plurality of nanoparticles. The additional layer may include one or more emitter molecules or emitting materials, such as quantum dots, inorganic phosphors, etc. The additional layer may match the refractive index beneath the first electrode layer. The thickness of the additional layer is 1000 nm or less.

[0175] In some embodiments, multiple nanoparticles can be deposited via inkjet printing. In other embodiments, multiple nanoparticles can be deposited via a touch-based mechanism, such as brushing. In some embodiments, multiple nanoparticles can be deposited by jetting particles suspended in a solvent or aerosol. In other embodiments, multiple nanoparticles can be fabricated using a top-down approach, which may include a stripping process, a developing process, light-based lithography (such as photolithography or laser interference lithography) or area plate lithography, electron beam lithography, and / or focused ion milling. In some embodiments, multiple nanoparticles can be deposited via spin coating, blade scraping, slot-die coating, bar coating, and / or dip coating. Once deposited, the nanoparticles can be dried to remove any residual solvent, air, or moisture from the deposited surface. Such drying methods may include vacuum drying, nitrogen purging, high-efficiency particulate air (HEPA) filter drying, drying in a convection oven, surface tension gradient drying, IPA vapor vacuum drying, and / or centrifugal drying. In other embodiments, nanoparticles can be formed via self-assembly, including the assembly of the particles themselves or the self-assembly of another material, such as copolymers or polymers with nanoscale shapes. Multiple nanoparticles can be formed by depositing a second material onto the self-assembled material. After the formation of multiple nanoparticles, the self-assembled material may or may not be removed. In some embodiments, the LED, reinforcing layer, and / or nanoparticles can be encapsulated. Such encapsulation materials can include oxide coatings and epoxides, such as polyurethanes, silicones, etc.

[0176] In some embodiments, multiple nanoparticles can be formed in a variety of different sizes or shapes, rather than a single size or shape. This allows the resulting coupling layer or structure to effectively scatter light of multiple frequencies or colors under all identical layers.

[0177] In some embodiments, a white LED can be selectively decoupled from a specific wavelength range using a predetermined resonant nanoparticle decoupling structure. In this way, a white LED can be fabricated over a predetermined large area, and the resonance of the nanoparticle decoupling structure (via selected nanoparticle size, refractive index, etc.) can be used to generate sub-pixels of red, green, blue, and / or any other desired color.

[0178] Since the refractive index of the gap layer affects the resonance of the nanopatch antenna, incorporating a gap material with nonlinear optical properties and / or a voltage-tunable refractive index can tune the emission spectrum using a voltage applied between the metal cathode and the electrical contact layer beneath the nanoparticles. Figure 10As shown in the diagram. In one example, aluminum-doped zinc oxide can be used as a voltage-tunable refractive index material because its permittivity changes as the applied voltage alters the carrier concentration. In this case, a second insulating layer can be placed in the gap to build up the charge. Depending on the material properties of the voltage-tunable refractive index layer, this layer may not always be used. This is particularly useful when the LED is a white LED (i.e., an LED that emits red, green, and blue light), because the voltage-tunable nanopatch resonance can act as a color filter to selectively pass through the desired color. This can effectively convert the LED into a three-terminal device, where a voltage is applied between the anode and cathode operating the LED, and a voltage is applied between the cathode and the electrical contact layer beneath the nanoparticles, thereby tuning the nanopatch resonance to select the emitted color.

[0179] For individual LED subpixels, such as in a display, the resonance of the nanoparticle decoupling structure may be intentionally mismatched with the LED's native emission. In this way, the nanoparticle decoupling structure can act as a color filter to alter the peak wavelength. In another embodiment, a resonantally mismatched nanoparticle decoupling structure can be used to narrow the emission spectrum. For example, a green LED paired with a blue resonant decoupling structure can provide narrowing by reducing the LED's red light wavelength. Conversely, pairing a green LED with a red resonant decoupling structure can provide narrowing by reducing the LED's blue light wavelength.

[0180] In another embodiment, the device may include an emission coupling layer located at a predetermined position near the reinforcement layer, as shown in Figures 3a-3c. The emission coupling layer may include an emitting material that can be excited by energy from surface plasmon polaritons in the nearby reinforcement layer. The emitting material may be (but is not limited to) quantum dots, perovskite nanocrystals, metal-organic frameworks, covalent organic frameworks, thermally activated delayed fluorescence (TADF) emitters, fluorescent emitters, and / or phosphorescent organic emitters. In one example device, the emitting material may preferably have an absorption and emission spectrum exhibiting a small Stokes shift, such that a predetermined small redshift occurs between the excited state energy of the LED quenched in the reinforcement layer and the light emitted from the emission coupling layer. This can maintain the emission color of the device. In another example device, the emitting material can be selected to downconvert higher energy excitation (e.g., blue) to lower energy wavelengths (e.g., green or red). This allows a single LED structure to be used in each pixel of a display, where the color is selected by the emission coupling layer. For example, this can be achieved by depositing quantum dots of different sizes in the coupling layers of different pixels to tune the emission wavelength. The emission coupling layer may or may not be combined with a nanoparticle-based decoupling structure. In one embodiment, the emission coupling layer may be disposed between the reinforcing layer and the nanoparticles. In this case, the decoupling efficiency can be enhanced because the emissivity of the emitting material in the emission coupling layer may increase.

[0181] The arrangement of nanoparticles on the surface of the dielectric interlayer can be designed to suit the device application. In one embodiment, a random arrangement of nanoparticles can provide an approximate Lambertian emission profile, which may be preferred for lighting or display applications (e.g., where point source emission is not desirable). Inorganic LEDs tend to be affected by directional emission profiles, which may make random nanoparticle arrays particularly attractive for certain applications. In another embodiment, nanoparticles can be arranged in an array, thereby producing a dispersive emission profile that may be desired for some mobile applications or applications requiring maximum outcoupling of light regardless of angular dependence. Arrayed nanoparticles can achieve greater efficiency than randomly arranged nanoparticles, and selecting specific array spacing and duty cycles allows for tuning of array resonances, and thus enabling the achievement of outcoupling wavelengths that maximize array efficiency.

[0182] In other embodiments, the nanoparticles may be metallic and coated with a non-metallic coating. The nanoparticles may be placed directly on top of the reinforcing layer, such as... Figure 9As shown in the figure. In this embodiment, the refractive index of the coating can be between 1.01 and 5. The thickness of the coating can be from 3 nm to 1000 nm, more preferably from 3 nm to 100 nm. In one embodiment, the nanoparticle coating can serve as part or all of the gap spacing. This can be achieved by coating the particles with the desired total gap thickness, thereby reducing the capping layer to zero, or by combining the gap layer thickness with the nanoparticle coating to achieve the desired total spacer thickness. In addition, the nanoparticle coating can serve as an adhesion layer to improve the adhesion of the nanoparticles to the layers on which they can be deposited or to increase the nanoparticle density on the layers. The prepared nanoparticles are composed of Ag, Al, Ag-Al alloys, Au, Au-Ag alloys and / or Au-Al alloys. The reinforcing layer and / or nanoparticles can be composed of other materials including (but not limited to) Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ca, Ru, Pd, In and / or Bi. In embodiments, the metal core may include more than one material, such as Ag spheres coated with Rh and then coated with a dielectric material such as SiO2, etc. Figure 9 As shown in the image.

[0183] The reinforcing layer and / or nanoparticles may include planar metals, stacks of metal and dielectric layers, stacks of metal and semiconductor layers, and / or perforated metal layers, such as, for example Figure 15 and 18 As shown in the diagram. The dielectric material as part of the reinforcement layer may include, but is not limited to, oxides, fluorides, nitrides, and / or amorphous mixtures of materials. Other non-limiting examples of materials may include: combinations of materials listed as LED materials in Table 1 below, such as GeTe, InSb, InAs, Ge, GaSb, Si, GaAs, CdTe, AlSb, HgSe, AlAs, GaP, ScN, ZnTe, CdS, CuBr, CuI, AlP, SiC, CuCl, GaN, ZnS, BN, ZnO, GeO2, AlN, CsI, CsBr, NaBr, CsCl, KBr, KCl, and / or SiO2. The metal layer may include alloys and mixtures of metals, which 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. The reinforcement layer may be graphene, conductive oxide, and / or conductive nitride of an LED that is outside the visible range.

[0184] In some embodiments, the reinforcing layer can be patterned with nanoscale pores, as shown, for example, in Figures 14a-14f. These pores can be in an array, randomly arranged, or pseudo-randomly arranged. The size, shape, and / or orientation of the pores can set the frequency of light that can be decoupled from the reinforcing layer.

[0185] In some embodiments, the reinforcement layer may have a bullseye grating patterned on its top. In some embodiments, the reinforcement layer may have gaps and may have a bullseye grating patterned on top of the gap material. In some embodiments, the bullseye grating may be annular. In other embodiments, the bullseye grating may be elliptical.

[0186] In some embodiments, the reinforcing layer may be partially etched through to form a nanoscale outcoupling component on one side of the reinforcing layer, as shown, for example, in Figures 14a-14f. In some embodiments, nanoscale components may be present on both sides of the reinforcing layer. In some cases, when nanoscale components are present on both sides of the reinforcing layer, the minimum dimension of the component may exceed 10 nm; in other cases, the minimum dimension of the component may exceed 20 nm; and in still other cases, the minimum dimension of the component may exceed 50 nm.

[0187] For vertical LEDs, some embodiments can address the shielding problem from the top electrode because the excited state can be incoupling to the reinforcement layer over as many areas as possible, and the excited state can be decoupled from the nanoparticle-based outcoupling layer to the air. In some embodiments, the reinforcement layer can act as an electrical contact.

[0188] If the reinforcement layer acts as an electrical contact, then there is no longer any shielding of light emitted from the top. Surface plasmons can propagate in smooth silver at a distance of tens to hundreds of micrometers, meaning that excited states from the recombination region can couple to the reinforcement layer at one location on the device and to photons in free space at another location at a distance of tens to hundreds of micrometers. This can be achieved by carefully designing the lateral patterning of the coupling structure to eliminate shielding from the electrodes.

[0189] Using nanoscale decoupling structures can increase LED yield because the decoupling can have dispersion, which is designed to minimize dispersion due to the overall layer thickness of the wafer. Therefore, the final LED with the enhancement layer and decoupling can exhibit smaller variations across the entire wafer compared to a reference LED.

[0190] Devices manufactured according to embodiments of the present invention can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into various electronic products or intermediate components. Examples of such electronic products or intermediate components may include displays, lighting devices (such as discrete light source devices or lighting panels), etc., that can be utilized by end-user product manufacturers. Such electronic component modules may optionally include driving electronics and / or power supplies. Devices manufactured according to embodiments of the present invention can be incorporated into a wide variety of consumer products having one or more electronic component modules (or units) incorporated therein. Such consumer products may include any type of product that includes one or more light sources and / or one or more visual displays of a certain type. Examples of such consumer products may include flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for internal or external lighting and / or signaling, head-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, cellular phones, tablets, phablets, personal digital assistants (PDAs), laptops, digital cameras, camcorders, viewfinders, miniature displays, 3D displays, vehicles, aviation displays, large-area walls, theater or stadium screens or signs.

[0191] 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 combined with sapphire chips), LED wallpaper, LED jewelry, and clothing.

[0192] Various control mechanisms can be used to control the devices manufactured according to the disclosed subject matter, including passive and active matrices. Most of the devices are intended for use within a temperature range that is comfortable for humans, such as 18°C ​​to 30°C, and more preferably at room temperature (20°C-25°C), but can be used outside this temperature range (e.g., -40°C to +80°C).

[0193] An apparatus manufactured according to the disclosed subject matter may include other components for controlling and manipulating light from the final product. These components include polarizers, color filters, and liquid crystals.

[0194] The inorganic LEDs of the disclosed subject matter can be manufactured from materials including (but not limited to): GaAs, AlGaAs, GaAsP, AlGaInP, GaP, GaAsP, GaN, InGaN, ZnSe, SiC, Si3N4, Si, Ge, sapphire, BN, ZnO, AlGaN, perovskite, and / or quantum confinement systems. Quantum confinement systems can include systems in which the size of the particles is approximately the exciton's Bohr radius, resulting in an increased band gap and emission states with energies higher than the bulk band gap. For example, CdS has a bulk band gap of approximately 2.42 eV (approximately 512 nm), while quantum dots (QDs) are made from CdS emitters of approximately 380 to 480 nm in size, at a size of 1-8 nm. The electroluminescent device can be constructed from a quantum confinement material, which may benefit from an enhancement layer for reducing excited-state transients. Electroluminescent devices based on quantum-confined materials have not yet been commercialized, indicating that stability improvements are possible in addition to efficiency gains for these systems. Some electroluminescent devices using quantum-confined materials can utilize mixtures of inorganic quantum-confined materials, such as CdS quantum dots, in the recombination region, along with organic or inorganic transport layers. For example, some EL quantum dot devices can use NPD as the hole transport layer and Alq3 as the electron transport layer, while others can use NPD as the hole transport layer and ZnO nanoparticles as the electron transport layer. Quantum-confined systems are not limited to inorganic semiconductors alone. For example, mixed organic-inorganic perovskite materials (such as CsPbBr3) can be formed to serve as emitter quantum dots as traps 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 from solution or suspension via spin coating or contact printing.

[0195] The orientation of the transition dipole can affect plasmon coupling efficiency and coupling distance, with coupling increasing as the dipole becomes more perpendicularly oriented. Therefore, perpendicularly oriented dipoles are preferred for planar or near-planar reinforcement layers. However, in practice, due to the surface roughness of the reinforcement layer, even perfectly horizontal dipoles may have some coupling efficiency for plasmon modes in planar and near-planar reinforcement layers.

[0196] The inorganic LEDs used in embodiments of the disclosed subject matter can be combined with one or more phosphorescent emitters to produce a wide range of colors from the LED (e.g., white). The phosphor can be placed: (a) in an epoxy resin used to encapsulate the LED, or (b) the phosphor can be placed away from the LED. The phosphor can act as a "downconversion" layer, designed to absorb photons from the LED and re-emit lower-energy photons. Other downconversion materials that can be used can be made of inorganic or organic phosphors, fluorescent materials, TADF, quantum dots, perovskite nanocrystals, metal-organic frameworks, or covalent-organic framework materials. Therefore, embodiments of the disclosed subject matter including a reinforcing layer and nanoscale decoupling can include metal and dielectric interstitial materials, and a nanoparticle layer can be placed between the inorganic LED and the phosphor or downconversion layer. The layers of the LED, metal, dielectric interstitial material, and / or nanoparticle device can be encapsulated with epoxy resin or a film including a downconversion medium. Downconversion materials can be placed outside of LEDs, metals, dielectric interstitial materials, and / or nanoparticle encapsulation layers.

[0197] Other options for generating white light may include: using a homoepitaxial ZnSe blue LED grown on a ZnSe substrate, which simultaneously generates blue light from the active region and emits yellow light from the substrate; and using GaN on a Si (or SiC or sapphire) substrate. One or more embodiments of the disclosed subject matter may be combined with these devices.

[0198] Devices manufactured according to embodiments of the disclosed subject matter can be combined with QNED (quantum dot nanounit) technology, wherein GaN-based blue light-emitting nanorod LEDs replace discrete inorganic LEDs as pixelated blue light sources in displays. The formation of GaN nanorods can be found in scientific and patent literature, such as in George et al., “Electrically Tunable Diffraction Efficiency from Gratings in Al-doped ZnO,” Applied Physics Letters 110, 071110 (2017), and in patent publication WO2020036278 entitled “Light Emitting Device, PIXEL STRUCTURE COMPRISING LIGHT EMITTING DEVICE, AND MANUFACTURING METHOD THEREFOR.” The disclosed embodiments can be combined with these devices.

[0199] Some embodiments may include a reinforcing layer and a nanoscale decoupling structure having a metal, dielectric interstitial material, and nanoparticle layers. This decoupling structure may be combined with a spacer (or surface plasmon amplification via radiation or stimulated emission of a plasmon laser) or a surface plasmon polariton (SPP) spacer or nanolaser, and convert plasmon energy back into photons.

[0200] LEDs formed using one or more embodiments of the disclosed subject matter can be fabricated directly on a wafer, and then removed and placed to create a larger electronic component module. Within said module, there may be additional LEDs that do not utilize the enhancement layer.

[0201] In some embodiments, LEDs formed with enhancement layers and decoupling structures can be directly patterned on a wafer or substrate, which is then incorporated into an electronic component module. In these cases, if it is desirable to eliminate the device (e.g., the desired peak wavelength), it can be eliminated by omitting the decoupling layer from the device, since omitting the enhancement layer would make the LED dimmer. In some embodiments where a full-color red, green, and blue (RGB) module is patterned on a single substrate, at least one color sub-pixel can have an enhancement layer and decoupling.

[0202] According to embodiments of the disclosed subject matter, a light-emitting diode and / or device (LED) can be provided. The LED may include a substrate, an anode (or P-type contactor), a cathode (n-type contactor), a recombination region disposed between the anode and cathode, and a reinforcement layer, such as, for example... Figure 17 As shown in the diagram. The recombination region may include an inorganic semiconductor 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.

[0203] Table 1 below shows non-limiting examples and particle size ranges of LED materials and potential reinforcing layer and / or metal nanoparticle materials, assuming that the dielectric layer between the reinforcing layer and the metal nanoparticle material has a refractive index of 1.5, and assuming that the nanoparticles are monodisperse monolayers. It can be assumed that the particle size is nanocube, and particles with variable length axes may have different ranges.

[0204]

[0205] Table 1

[0206] When nanoparticles aggregate, the resonant wavelength of the outcoupling can increase. For example, even large aggregates of UV-resonant particles can achieve IR NPA resonance. Therefore, considering agglomeration, some preferred embodiments and size distributions of LED semiconductor materials and nanoparticle outcoupling materials are provided. Table 2 below shows non-limiting examples and particle size ranges of LED materials and potential reinforcing layers and / or metal nanoparticle materials, assuming that the dielectric layer between the reinforcing layer and the metal nanoparticle-sized material has a refractive index of 1.5 and allows for nanoparticle aggregation.

[0207]

[0208] Table 2

[0209] As described above, embodiments of the disclosed subject matter may provide a device that may include an inorganic emitting layer, a first electrode layer (e.g., an enhancement layer), and an outcoupling structure. The first electrode layer may be spaced from the inorganic emitting layer at a predetermined threshold distance, said predetermined threshold distance being a distance where the total nonradiative attenuation constant is equal to the total radiative attenuation constant. The device may include at least one of at least one down-conversion layer and at least one color filter disposed on the inorganic emitting layer. The device may include an inorganic transport material. The device may include inorganic transport materials and / or organic transport materials.

[0210] The first electrode layer of the device can be at least one of the following: a metal, a stack of metal films and dielectric layers, a plasmonic system, a hyperbolic metamaterial, and / or an optically active metamaterial. The first electrode layer can be at least one of the following: Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, and / or Ca. The thickness of the first electrode layer can be from 5 nm to 1000 nm. The materials can be stacked or layered, and can have multiple layers. Each of the multiple layers can include a unit cell having multiple unit cell sub-assembly layers. Each unit cell can have a first unit cell sub-assembly and a second unit cell sub-assembly. In some embodiments, the first electrode layer can be patterned with additional material or can be patterned with nanoscale pores.

[0211] The device's decoupling structure may include multiple nanoparticles, which are formed from at least one of the following: Ag particles, Al particles, Ag-Al alloys, Au particles, Au-Ag alloys, dielectric materials, semiconductor materials, metal alloys, mixtures of dielectric materials, stacks of one or more materials, and / or a core of one type of material coated with a shell of different types of materials. The decoupling structure may include multiple nanoparticles that are colloidal nanoparticles synthesized from a solution. The decoupling structure may include multiple nanoparticles arranged in a periodic array, the periodic array having a predetermined array spacing. The decoupling structure may include multiple nanoparticles arranged in a non-periodic array. The shapes of the multiple nanoparticles may be at least one of the following: cubes, spheres, globular bodies, cylinders, parallelepipeds, rods, stars, pyramids, and multifaceted three-dimensional objects.

[0212] The decoupling structure may include multiple nanoparticles, and the device may include an adhesion layer disposed between the material and the multiple nanoparticles. At least one property of the nanoparticles may be selected to alter the spectrum of light emitted by the emitting layer, or to alter the angular dependence of the light emitted by the emitting layer. The selected property may be the size, composition, and / or distribution of the nanoparticles. The device may include at least one additional layer disposed on the multiple nanoparticles. The additional layer may match the refractive index beneath the first electrode layer. The thickness of the additional layer may be from 3000 nm to 1000 nm and / or from 1000 nm to 10 nm. The additional layer may be transparent. In some embodiments, the device may include a material disposed between the first electrode and the multiple nanoparticles. In some embodiments, the device may include an organic transport material.

[0213] The decoupling structure may include multiple nanoparticles, which include at least one of the following: metal, dielectric material, and / or a hybrid of metal and dielectric material. The multiple 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 multiple nanoparticles or nanopatch antenna. At least one of the multiple nanoparticles may have a size from 5 nm to 1000 nm. At least one of the multiple nanoparticles may include additional material to provide lateral conduction between the multiple nanoparticles. In some embodiments, the decoupling structure may include multiple coated nanoparticles. In some embodiments, the decoupling structure may have multiple nanoparticles that are metallic and coated with a non-metallic coating.

[0214] The inorganic emitter layer of the device may be at least one of the following: GaAs, AlGaAs, GaAsP, AlGaInP, GaP, GaAsP, GaN, InGaN, ZnSe, SiC, Si3N4, Si, Ge, sapphire, BN, ZnO, AlGaN, perovskite, and / or quantum confinement systems. The inorganic emitter layer may be electroluminescent and may include quantum confinement materials, such as CdS quantum dots, organic transport layers, and / or mixtures of inorganic quantum confinement materials for inorganic transport layers.

[0215] The inorganic emitting layer of the device may include at least one of GaAs and / or AlGaAs, wherein the outcoupling structure comprises multiple 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 the light emitted by the device may be from 760 nm to 2000 nm.

[0216] In some embodiments, the inorganic emitting layer of the device may include at least one of AlGaAs, GaAsP, AlGaInP, and / or GaP, wherein the outcoupling structure comprises a plurality of nanoparticles, and wherein the nanoparticles comprise at least one of Ag, Au, SiO2, Si, and / or Ge. The size of the nanoparticles may be 75-200 nm, and the wavelength of the light emitted by the device may be greater than 610-760 nm.

[0217] In some embodiments, the inorganic emitting layer of the device may include at least one of GaAsP, AlGaInP, and / or GaP, wherein the outcoupling structure comprises a plurality of nanoparticles, and wherein the nanoparticles may be at least one of Ag, Au, SiO2, Si, and / or Ge. The size of the nanoparticles may be 60-150 nm, and the wavelength of the light emitted by the device may be 590-610 nm.

[0218] In some embodiments, the inorganic emitting layer of the device may include at least one of GaAsP, AlGaInP, and / or GaP, wherein the outgoing structure comprises a plurality of nanoparticles, wherein the nanoparticles may include at least one of Au, SiO2, Si, and / or Ge, the size of the nanoparticles may be 50-100 nm, and the wavelength of the light emitted by the device may be 570-590 nm.

[0219] In some embodiments, the inorganic emitting layer of the device may include 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, SiO2, Si, Ge, and / or TiO2, wherein the size of the nanoparticles is 40-125 nm, and / or wherein the wavelength of the light emitted by the device may be 500-570 nm.

[0220] In some embodiments, the inorganic emitting layer of the device may include at least one of ZnSe, InGaN, SiC and / or Si, wherein the outcoupling structure may include a plurality of nanoparticles, wherein the nanoparticles include at least one of Ag, Al, Rh, Pt and / or TiO2, wherein the size of the nanoparticles may be 40-125 nm, and / or the wavelength of the light emitted by the device may be 450-500 nm.

[0221] In some embodiments, the inorganic emitting layer of the device 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 TiO2, wherein the size of the nanoparticles may be 50-100 nm, and wherein the wavelength of the light emitted by the device may be 400-450 nm.

[0222] In some embodiments, the inorganic emitting layer of the device may include at least one of diamond, BN, AlN, AlGaN, and / or AlGaInN, wherein the outcoupling structure may include a plurality of nanoparticles, wherein the nanoparticles may include at least one of Al, Rh, Pt, and / or TiO2, wherein the size of the nanoparticles may be 30-75 nm, and wherein the wavelength of the light emitted by the device may be 200 nm to 400 nm.

[0223] The inorganic emitting layer of the device may include a blue light-emitting diode with a yellow phosphor, wherein the outcoupling structure may include a plurality of nanoparticles, wherein the nanoparticles may include at least one selected from the group consisting of Ag, Al, Rh, Pt and / or TiO2, wherein the size of the nanoparticles may be 40-125 nm, and wherein the device may emit white light.

[0224] The inorganic emitting layer of the device may include at least one of gallium arsenide and / or AlGaAs, wherein the outgoing coupling structure may include a plurality of nanoparticles, wherein the nanoparticles may include at least one of Ag, Au, ITO, Si, Ge, SiO2, Al, Rh and / or Pt, wherein the size of the nanoparticles may be 5-250 nm, and wherein the wavelength of the light emitted by the device may be 760 nm to 2000 nm.

[0225] The inorganic emitting layer of the device may include at least one of AlGaAs, GaAsP, AlGaInP and / or GaP, wherein the outcoupling structure may include multiple nanoparticles, wherein the nanoparticles include at least one of Ag, Au, SiO2, Al, Rh, Pt, Si and / or Ge, wherein the size of the nanoparticles may be 5-200 nm, and the wavelength of the light emitted by the device may be 610-760 nm.

[0226] The inorganic emitting layer of the device may include at least one of AlGaAs, GaAsP, AlGaInP and / or GaP, wherein the outgoing coupling structure may include a plurality of nanoparticles, wherein the nanoparticles may include at least one of Ag, Au, SiO2, Al, Rh, Pt, Si and / or Ge, wherein the size of the nanoparticles may be 5-150 nm, and wherein the wavelength of the light emitted by the device may be 590-610 nm.

[0227] The inorganic 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 may include at least one of Ag, Au, SiO2, Al, Rh, Pt, Si and / or Ge, wherein the size of the nanoparticles may be 5-100 nm, and wherein the wavelength of the light emitted by the device may be 570-590 nm.

[0228] The inorganic emitting layer of the device 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 may include at least one of Ag, Al, Rh, Pt, SiO2, TiO2, Si and / or Ge, wherein the size of the nanoparticles may be 5-125 nm, and / or wherein the wavelength of the light emitted by the device may be 500-570 nm.

[0229] The inorganic 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 may include at least one of Ag, Al, Rh, Pt and / or TiO2, wherein the size of the nanoparticles may be 5-125 nm, and wherein the wavelength of the light emitted by the device may be 450-500 nm.

[0230] The inorganic emitting layer of the device includes InGaAs, wherein the outgoing coupling 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 TiO2, wherein the size of the nanoparticles may be 5-100 nm, and wherein the wavelength of the light emitted by the device may be 400-450 nm.

[0231] The inorganic emitting layer of the device 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 may include at least one of Al, Rh, Pt, and / or TiO2, wherein the size of the nanoparticles may be 5-75 nm, and wherein the wavelength of the light emitted by the device may be 200 nm to 400 nm.

[0232] The inorganic emitting layer of the device may include a blue light-emitting diode with a yellow phosphor, wherein the outcoupling structure may include a plurality of nanoparticles, wherein the nanoparticles may include at least one of Al, Rh, Pt and / or TiO2, wherein the size of the nanoparticles may be 5-125 nm, and wherein the light emitted by the device may be white light.

[0233] The device may include a material disposed above a first electrode, and the material may be a dielectric layer disposed on the first electrode layer, and an electrical contact layer may be disposed on the dielectric layer. The material may include a voltage-adjustable refractive index material between the electrical contact layer and the first electrode layer. The voltage-adjustable refractive index material may be aluminum-doped zinc oxide. The material may include an insulating layer.

[0234] The first electrode layer may include nanoscale components. The nanoscale components can be etched at least partially through the depth of the first electrode layer. The nanoscale components may include a target pattern disposed on the first electrode layer or on a spacer material disposed on the first electrode layer. The nanoscale components may be disposed on at least one side of the first electrode layer. The size of the nanoscale components in the minimum direction may be at least 10 nm, at least 20 nm, and / or from 50 nm to 750 nm. In some embodiments, the arrangement of the nanoscale hole pattern may be an array of nanoscale holes, a random arrangement of nanoscale holes, and / or a pseudo-random arrangement of holes.

[0235] In embodiments of the disclosed subject matter, the device may include an inorganic emitting layer, a first electrode layer, a decoupling structure, and a material disposed between the first electrode and the decoupling structure. The first electrode layer may be spaced from the inorganic emitting layer by a predetermined threshold distance, said predetermined threshold distance being the distance at which the total non-radiative attenuation rate constant is equal to the total radiative attenuation rate constant. The device may include an organic transport material.

[0236] The first electrode layer of the device may be at least one of the following: a metal, a stack of metal films and dielectric layers, a plasmonic system, a hyperbolic metamaterial, and / or an optically active metamaterial. The first electrode layer may include at least one of the following: Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, and / or Ca. The first electrode layer of the device may be patterned with nanoscale pores.

[0237] The inorganic emitter layer of the device may include at least one of the following: GaAs, AlGaAs, GaAsP, AlGaInP, GaP, GaAsP, GaN, InGaN, ZnSe, SiC, Si3N4, Si, Ge, sapphire, BN, ZnO, AlGaN, perovskite, and / or a quantum confinement system. The quantum confinement system may include particles having an exciton Bohr radius. The quantum confinement system may include at least one of the following: a hybrid organic-inorganic perovskite material, CsPbBr3, InP / ZnS, CuInS / ZnS, Si, Ge, C, and / or peptides.

[0238] The device's decoupling structure may include multiple nanoparticles, which are formed from at least one of the following: Ag particles, Al particles, Ag-Al alloys, Au particles, Au-Ag alloys, dielectric materials, semiconductor materials, metal alloys, mixtures of dielectric materials, stacks of one or more materials, and / or a core of one type of material coated with a shell of different types of materials. The decoupling structure may include multiple nanoparticles that are colloidal nanoparticles synthesized from a solution. The decoupling structure may include multiple nanoparticles arranged in a periodic array. The periodic array may have a predetermined array spacing. The decoupling structure may include multiple nanoparticles arranged in a non-periodic array. The decoupling structure may include multiple nanoparticles, wherein the shape of the multiple nanoparticles is selected from at least one of the following groups: cube, sphere, globular, cylinder, parallelepiped, rod-shaped, star-shaped, pyramidal, and / or multifaceted three-dimensional objects. The decoupling structure may include multiple nanoparticles, and the device may include an adhesion layer disposed between the material and the multiple nanoparticles. The out-coupling structure may include multiple nanoparticles, and at least one of the multiple nanoparticles may include additional material to provide lateral conduction between the multiple nanoparticles.

[0239] The device's outcoupling structure may include multiple nanoparticles, and the device may include at least one additional layer disposed on the multiple nanoparticles. The at least one additional layer may encapsulate the device. The at least one additional layer may include one or more emitter molecules. The refractive index of the at least one additional layer may be between 1.01 and 5. The at least one additional layer may alter the emission color or efficiency of the device.

[0240] Organic light-emitting devices (OLEDs) configured to couple most or all of the excited-state energy to surface plasmon modes can provide more stable devices. This is achieved by utilizing the fact that when the emitting layer is placed on... Figure 19 The increased density of optical states within the threshold distance of the enhancement layer shown increases the radiative and non-radiative rates of the emitter of the device, thereby reducing the steady-state exciton group density and decreasing destabilizing excited-state interactions. As used throughout, the threshold distance can be the distance where the total non-radiative attenuation rate constant is equal to the total radiative attenuation rate constant. Embodiments of the disclosed subject matter provide efficient coupling of excited-state energies to surface plasmon modes. Figures 19-20 As shown, and as used throughout, the vertical dipole can have a transition dipole moment perpendicular to the reinforcement layer. Compared to the horizontal dipole, the vertical dipole is most effectively coupled and has a greater distance from the reinforcement layer. And, as used throughout, the horizontal dipole can have a transition dipole moment parallel to the reinforcement layer. Figure 20 In this context, the electron transport layer (ETL) thickness can be a representative of the distance between the dipole and the enhancement layer. Embodiments of the disclosed subject matter can provide devices comprising materials and / or material layer designs with an increased vertical dipole fraction to enhance excited-state energy coupling to surface plasmon modes.

[0241] In other words, embodiments of the disclosed subject matter provide a combination of devices and materials that can increase the vertical dipole fraction. Emitter molecules in other devices typically use chemical substances to achieve the desired molecular orientation. Other device configurations are taught to be away from the vertical dipole because the dipole increases coupling with plasmonic modes, which are considered energy loss paths in conventional and / or commercial OLED designs.

[0242] In OLEDs, the excited-state complex or charge-transfer (CT) state can be formed if it is the lowest energy state in the device. The excited-state complex or CT state can be formed between the emitter and its host component or between adjacent molecules at the interface with the emissive layer (EML). In phosphorescent devices, if condition 0 is met... <E ET -ΔE, then excited-state complexes can form and contribute to the emission spectrum, where E ETIt can be the lowest triplet state (T1) energy of the phosphor, and the CT state energy (ΔE) can be the energy difference between the HOMO level of the material with the highest HOMO energy in the organic emission layer and the LUMO level of the material with the lowest LUMO energy in the organic emission layer. In a fluorescent device, if the condition 0 < E is satisfied... ES -ΔE, then excited-state complexes can form and contribute to the emission spectrum, where E ES It can be the lowest singlet state (S1) energy.

[0243] In one embodiment, a layer adjacent to the stacked EML (typically, but not limited to, a barrier or transport layer) can be selected such that its energy level satisfies the above conditions to form an excited-state complex across the layer interface, such as... Figure 21 As shown in the diagram, the excited-state complex dipole can be vertically oriented perpendicular to the reinforcement layer, thereby achieving strong coupling with plasmon modes. For where 0 ≤ E ET Under the condition of -ΔE, the formation of an excited-state complex with a vertical dipole can occur, resulting in the energy-efficient coupling of the excited-state complex into surface plasmon modes, which can provide a more stable device.

[0244] In another embodiment, the host may influence the orientation of the emitter molecules. Figure 22 The data show that although compound 13 did not exhibit angle-dependent differences when doped into either compound 8 or compound 15, when compound 14 was doped into compound 15, compound 14 showed a significant enhancement in wide-angle p-polarized emission intensity compared to compound 8. Given that compound 13 remained unchanged and exhibited isotropic emission in both hosts, the variation in emission of compound 14 between hosts can be attributed to the unexpectedly large increase in the vertical dipole ratio (VDR) of compound 14 in compound 15. VDR represents the fraction of vertically oriented transition dipoles in the EML and can be considered the overall average dipole orientation of all emitter molecules in the EML. Figure 22 The measured VDR values ​​for various main components and emitter combinations are shown in Table 3 below.

[0245] Main body: Launcher VDR Compound 15: Compound 14 (10%) 0.47±0.05 Compound 15: Compound 13 (10%) 0.32±0.05 Compound 8: Compound 14 (10%) 0.34±0.05 Compound 8: Compound 13 (10%) 0.29±0.05

[0246] Table 3

[0247] In another embodiment, the template layer can be used to orient the emitter molecules. Growing zinc phthalocyanine (ZnPc) on a thin template layer of copper iodide allows the ZnPc molecules to be placed more horizontally than without a template layer. A thin layer of the small organic molecule hexaazabenzanphenanthrene-hexacarboxynitrile (HAT-CN) can template the growth of copper phthalocyanine (CuPc) and can orient the molecules more horizontally. The template layer can be used to align the emission dipoles more vertically. Embodiments of the disclosed subject matter provide templated EML within the threshold distance of the enhancement layer.

[0248] The emission layer VDR can be measured on a film (with or without a template layer) that constitutes the emission layer in an OLED device. The emission material VDR can be measured in a film whose emission spectrum is attributed to the material, most preferably a film composed of the material and an inert component.

[0249] Figures 24a-24d This demonstrates the effect of varying the VDR on device performance for several different red emitters with similar emission peak wavelengths. For example... Figure 5a and Figure 23 The device shown can use a nanoparticle-based outcoupling scheme to extract energy from plasmonic modes and convert it into photons emitted from the top side of the device as top emission (TE) light. Bottom emission (BE) light can be controlled by directly generating photons without undergoing exciton recombination of plasmonic modes, which can be referred to as “residual emission”. In this example device structure, the reinforcement layer can be a metal cathode. In Figure 24a, the external quantum efficiency (EQE) of BE and TE is plotted as a function of the distance from the edge of the EML to the cathode. As the EML moves closer to the cathode, BE decreases as more excited-state energies are coupled to the surface plasmonic modes. For the same reason, when the distance between the EML and the cathode is reduced to approximately At that time, TE may increase. In comparison At shorter distances, excited-state energies can couple to lossy, high-k modes and / or form other substances in the metal, such as electron-hole pairs. Higher VDR emitters can couple energy to plasmonic modes more efficiently at greater distances from the metal cathode, resulting in a positive correlation between TE, EQE, and VDR, and a negative correlation between BE, EQE, and VDR. Because lossy mode coupling at close range between the EML and the metal cathode reduces both TE and BE equally, the TE / BE ratios of various VDR emitters can be compared. Higher VDR emitters can have higher TE / BE ratios. This ratio can continue to increase as the emitter is brought closer to the metal cathode. This ratio can account for any differences in inherent emitter efficiency. These trends can be expected based on the tendency of more vertically aligned transition dipole emitters to couple to plasmonic modes more efficiently. A normalized plot of the sum of TE, BE, and EQE can be drawn as a function of the distance of the EML from the cathode for various VDR emitters, as shown in Figure 24c. As VDR increases, the decrease in TE+BE EQE becomes slower. This indicates that the emitter layer within the OLED can be configured with a higher fraction of vertical emitters (higher VDR) to reduce loss mode coupling and increase the device's TE EQE and total EQE. This underscores the importance of high VDR emitter molecule and emitter layer design for plasmonic OLEDs. High VDR can enhance coupling with plasmonic modes while simultaneously reducing coupling with loss modes. As shown in Figure 24d, the relative increase in EL transients can be greater with increasing VDR. That is, at a given EML distance from the enhancement layer, high VDR can be used to achieve faster EL transients, thus enabling improved device stability, and / or higher VDR EMLs placed further from the enhancement layer can achieve the same or faster EL transients as lower VDR EMLs placed closer to the enhancement layer, thereby allowing greater OLED design flexibility.

[0250] The OLED is grown on a glass substrate pre-coated with an indium tin oxide (ITO) layer, exhibiting a sheet resistance of 15 Ω / sq. Prior to the deposition or coating of any organic layer, the substrate is degreased with a solvent and then treated with oxygen plasma at 50 W for 1.5 minutes at 100 mTorr and UV ozone for 5 minutes. The OLED is further grown by thermal evaporation under high vacuum (<10 Ω·cm). -6 Manufacturing in China Figure 23 and 24a-24d The device in question. The anode electrode is... Indium tin oxide (ITO). Figure 25 Example compounds are shown. The device example has an organic layer consisting of: sequentially extending from an ITO surface, ... Thick compound 1 (HIL) Compound 2 (HTL) layer, Compound 3 (EBL), Compound 4 (EML) is doped with 18% of compound 5 and 3% of compounds [9, 10, 11, 12]. Compound 4 (BL), Compound 7 (ETL) doped with 35% compound 6 Compound 7 (EIL), Ca, followed by Ag (cathode) Compound 2 (interstitial layer) and topped with a spin-cast 100nm Ag nanocube in a 7mg / ml solution. All devices were immediately sealed in a nitrogen glove box (<1ppm H2O and O2) with an epoxy-sealed glass lid after fabrication, incorporating a desiccant into the packaging. Doping percentage is by volume. Also performed by thermal evaporation in a high vacuum (<10... -6 Manufacturing in China Figure 22 The membrane in the film. The membrane has an organic layer consisting of, in sequence from the substrate, Compound 8, or compound 13 or 14, is doped with 10% of compound 13 or 14. Compound 15 is doped with 10% of compound 13 or 14. Figure 22 In this study, the p-polarized emission intensity as a function of angle was measured using a Fluxim Phelos instrument. A 405nm LED was used for photoexcitation. The sample consisted of a doped (emitting) layer encapsulated on a glass substrate attached to a hemispherical prism with a refractive index-matching liquid. For the same emitter layer film on a silicon wafer, optical constants were measured and fitted using a Woollam M2000 variable-angle ellipsometry. The VDR value was obtained by fitting P-polarized emission data using FluximSetfos software by using the measured optical constants and varying the emitter VDR, emission intensity, and exciton distribution.

[0251] In embodiments of the disclosed subject matter as described above, the device may include a substrate, a first electrode, and an organic emitting layer. The first electrode of the device may include at least one of the following: a metal, a semiconductor, and / or a transparent conductive oxide. The electrode layer of the device may include at least one of the following: Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, and / or Ca. The organic emitting layer may include an organic emitting material and may be disposed on the first electrode. The reinforcement layer of the device may include a plasmonic material exhibiting surface plasmon resonance, the plasmonic material being nonradiatively coupled to the organic emitting material and transferring excited-state energy from the organic emitting material to the nonradiative mode of surface plasmon polaritons, and the reinforcement layer may be disposed on the organic emitting layer. The reinforcement layer is configured such that the distance from the organic emitting layer does not exceed a threshold distance. The reinforcement layer of the device may include a second electrode layer. Due to the presence of the enhancement layer, the organic emitting material of the device can have a total nonradiative attenuation constant and a total radiative attenuation constant, and the threshold distance can be the position where the total nonradiative attenuation constant is equal to the total radiative attenuation constant. At least one of the organic emitting material and the organic emitting layer can have a vertical dipole ratio (VDR) value equal to or greater than 0.33.

[0252] In some embodiments, the organic emitting layer of the device may have a VDR value equal to or greater than 0.33. The organic emitting material of the device may have a VDR value equal to or greater than 0.33.

[0253] The organic emitting layer of the device may include a first layer having an organic emitting material and a second layer disposed adjacent to the first layer and containing a second material. The first and second layers may satisfy the condition 0 ≤ Ex - ΔE, where Ex is the lowest emission state energy level of the first or second layer, and ΔE is the difference between the highest highest occupied molecular orbital (HOMO) energy level and the lowest lowest unoccupied molecular orbital (LUMO) energy level within the organic emitting layer. Ex may be the lowest triplet (T1) energy level of the first layer, and the first layer is phosphorescent. In some embodiments, Ex may be the lowest singlet (S1) energy level of the first layer, and the first layer is fluorescent.

[0254] The organic emission layer of the device may further comprise a body. The body may include at least one chemical group selected from the group consisting of: triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenene, azirtriphenylene, azircarbazole, azir-dibenzothiophene, azir-dibenzofuran and / or azir-dibenzoselenene.

[0255] In some embodiments, the body in the organic emitter layer may be selected from the following group:

[0256]

[0257] and / or combinations thereof.

[0258] In some embodiments, the device may include a template layer selected and arranged to orient the molecules of the organic emission layer. The template layer may align the dipoles of the organic emission material and increase the perpendicularity of the dipoles. As used throughout, the perpendicular dipoles may be perpendicular to the substrate / electrode interface, and the increase in the perpendicularity of the dipoles may be such that the template layer makes the dipoles more perpendicular than they would be without the template layer. The template layer may be within a threshold distance of the reinforcement layer.

[0259] The organic emitting layer may include multiple sublayers. In some embodiments, the organic emitting material emits from a doublet state. The organic emitting material may include a fluorescent material with an S1 value (i.e., the lowest singlet state energy level) lower than a T1 value (i.e., the lowest triplet (T1) state energy level).

[0260] The emission of the device may originate from a combination of materials within the organic emission layer. The material combination of the organic emission layer may include a first material and a second material, wherein an excited-state complex is formed within the organic emission layer. The first and second materials may satisfy the condition 0 ≤ Ex - ΔE, where Ex is the lowest emission state energy level of the first or second material, and ΔE is the difference between the highest highest occupied molecular orbital (HOMO) energy level and the lowest lowest unoccupied molecular orbital (LUMO) energy level within the organic emission layer.

[0261] The organic emitting material of the device can be a phosphorescent material. The phosphorescent material can be a metal coordination complex having metal-carbon bonds and / or metal-nitrogen bonds and / or metal-oxygen bonds. The metal can be Ir, Rh, Re, Ru, Os, Pt, Au, and / or Cu.

[0262] In some embodiments, the phosphorescent material of the device may have the formula M(L) 1 ) x (L 2 ) y (L 3 ) z L 1 L 2 and L 3 They can be the same or different, where x is 1, 2 or 3, where y is 0, 1 or 2, where z is 0, 1 or 2, where x+y+z can be the oxidation state of metal M, and where L 1 The following groups can be freely selected:

[0263]

[0264]

[0265] Where L 2 and L 3 Choose independently from the following groups:

[0266] Where Y 1 To Y 13 Each can be independently selected from carbon and / or nitrogen, wherein Y' is selected from the group consisting of: BR e NR e PR e ,O,S,Se,C=O,S=O,SO2,CR e R f SiR e R f and GeR e R f , where R e and R f They can be fused or joined to form a ring, wherein R a R b R c and R d Each can independently represent monosubstituted to the maximum possible number of substitutions or no substitutions, where R a R b R c R d R e and R f Each can independently be hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, oxoboryl, and combinations thereof, wherein R a R b R c and R d Any two adjacent substituents may fused or joined to form a ring or a polydentate ligand.

[0267] In some embodiments, the phosphorescent material of the device may have a formula selected from the group consisting of: Ir(L A 3. Ir(L) A (L) B )2、Ir(L A )2(L B ), Ir(L A )2(L C ), Ir(L A (L)B (L) C ) and Pt(L A (L) B ), of which L in the Ir compound A L B and L C They are different from each other, among which L in Pt compounds A and L B They can be the same or different, and the L in the Pt compound is... A and L B They can be linked to form tetradentate ligands.

[0268] The organic emitting material of the device may be a fluorescent material. The fluorescent material may contain at least one organic group selected from the group consisting of:

[0269] And its aza analogues, wherein A is selected from the group consisting of: O, S, Se, NR' and CR'R", wherein each R' may be the same or different, and each R' is independently selected from the group consisting of: alkyl, cycloalkyl, aryl, heteroaryl and combinations thereof.

[0270] The fluorescent material of the device can be selected from the group consisting of:

[0271]

[0272] Where R 1 To R 5 Each independently represents a single substitution up to the maximum possible number of substitutions or no substitutions, where R 1 To R 5 Each of the following substituents is independently hydrogen or selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphin, oxoboryl, and combinations thereof.

[0273] In some embodiments, the organic emitting material of the device may be a thermally activated delayed fluorescence (TADF) material. The TADF material may have at least one donor group and at least one acceptor group. The TADF material may be a metal complex and / or a non-metal complex. In some embodiments, the TADF material may be a Cu, Ag, or Au complex.

[0274] The TADF material of the device may include at least one chemical component selected from the following group:

[0275]

[0276] Wherein X is selected from the group consisting of O, S, Se, and NR, wherein each R may be the same or different and each R is independently an acceptor group, an organic linker group bonded to the acceptor group, or an end group selected from the group consisting of alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, aryl, heteroaryl, and combinations thereof, and wherein each R' may be the same or different and each R' is independently selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and / or combinations thereof. In some embodiments, the TADF material of the device may include at least one chemical portion selected from the group consisting of nitriles, isonitriles, boranes, fluorides, pyridines, pyrimidines, pyrazines, triazines, aza-carbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-triphenylene, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, thiadiazole, and oxadiazole.

[0277] In some embodiments, the device may include an outcoupling structure. The outcoupling structure may have multiple nanoparticles, and the device may have a material disposed between a reinforcing layer and the multiple nanoparticles. The multiple nanoparticles are formed from at least one of the following: Ag particles, Al particles, Ag-Al alloys, Au particles, Au-Ag alloys, dielectric materials, semiconductor materials, metal alloys, mixtures of dielectric materials, stacks of one or more materials, and / or a core of one type of material coated with a shell of a different type of material. At least one of the multiple nanoparticles may include an additional layer to provide lateral conduction between the multiple nanoparticles. The multiple nanoparticles may be coated. In some embodiments, the multiple nanoparticles may be metallic and coated with a non-metallic coating. The multiple nanoparticles may include at least one of a metal, a dielectric material, and / or a hybrid of a metal and a dielectric material.

[0278] The device may have multiple nanoparticles coated with an oxide layer. The thickness of the oxide layer can be selected to tune the plasmon resonance wavelength of the multiple nanoparticles or nanopatch antenna. The multiple nanoparticles may be colloidal synthetic nanoparticles formed from a solution. The multiple nanoparticles may be arranged in a periodic array, the periodic array having a predetermined array spacing. In some embodiments, the multiple nanoparticles may be arranged in a non-periodic array. The shape of the multiple nanoparticles may be at least one of the following: cube, sphere, globular, cylinder, parallelepiped, rod-shaped, star-shaped, pyramidal, and / or multifaceted three-dimensional objects. The size of at least one of the multiple nanoparticles may be from 5 nm to 1000 nm.

[0279] The device may include a dielectric layer disposed on a reinforcing layer and an electrical contact layer disposed on the dielectric layer. The material may be a voltage-adjustable refractive index material between the electrical contact layer and the first electrode. The voltage-adjustable refractive index material may be aluminum-doped zinc oxide. The material may include an insulating layer.

[0280] According to one embodiment, a consumer product may include a device having a substrate, a first electrode, and an organic emission layer comprising an organic emission material disposed above the first electrode. The device of the consumer product may include a reinforcement layer having a plasmonic material exhibiting surface plasmon resonance, the plasmonic material being nonradiatively coupled to the organic emission material and transferring excited-state energy from the organic emission material to the nonradiative mode of the surface plasmon polariton, the reinforcement layer being disposed on the organic emission layer. The reinforcement layer may be configured such that its distance from the organic emission layer does not exceed a threshold distance. Due to the presence of the reinforcement layer, the organic emission material has a total nonradiative decay rate constant and a total radiative decay rate constant, and the threshold distance is the position where the total nonradiative decay rate constant is equal to the total radiative decay rate constant. At least one of the organic emission material and the organic emission layer has a vertical dipole ratio (VDR) value equal to or greater than 0.33.

[0281] Consumer products can be at least one of the following: displays, lighting devices such as discrete light source devices or lighting panels, flat panel displays, curved displays, computer monitors, medical monitors, televisions, signs, lights for internal or external lighting and / or signaling, head-up displays, fully transparent or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, cellular phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptops, digital cameras, camcorders, viewfinders, microdisplays with a diagonal of less than 2 inches, 3D displays, vehicles, aviation displays, large-area walls, video walls containing multiple displays tiled together, theater or stadium screens, phototherapy devices, signs, augmented reality (AR) displays or virtual reality (VR) displays, display or visual elements in glasses or contact lenses, light-emitting diode (LED) wallpaper, LED ornaments, and clothing.

[0282] In some embodiments, the organic layer may further comprise a body comprising a triphenylene containing benzofused thiophene or benzofused furan, wherein any substituent in the body is a non-fused substituent independently selected from the group consisting of: C n H 2n+1 OC n H 2n+1 ,OAr1,N(C n H 2n+12. N(Ar1)(Ar2), CH=CH-C n H 2n+1 C≡CC n H 2n+1 Ar1, Ar1-Ar2, C n H 2n -Ar1 or unsubstituted, wherein n is 1 to 10; and wherein Ar1 and Ar2 are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole and their heteroaromatic analogs.

[0283] In some embodiments, the organic layer may further comprise a body comprising at least one chemical group selected from the group consisting of: triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenene, azitrin, azicarbazole, azi-dibenzothiophene, azi-dibenzofuran, and azi-dibenzoselenene.

[0284] In some embodiments, the subject may be selected from the following group of subjects:

[0285]

[0286] And its combination.

[0287] In some embodiments, the organic layer may further comprise a body, wherein the body comprises a metal complex.

[0288] In some embodiments, the compound as described herein may be a sensitizer; wherein the device may further include a receptor; and wherein the receptor may be selected from the group consisting of fluorescent emitters, delayed fluorescent emitters, and combinations thereof.

[0289] In another aspect, the OLED of this disclosure may also include an emission region containing compounds as disclosed in the above compound portion of this disclosure.

[0290] In some embodiments, at least one of an anode, cathode, or new layer disposed above the organic emitting layer serves as a reinforcement layer. The reinforcement layer comprises a plasmonic material exhibiting surface plasmon resonance, which is nonradiatively coupled to the emitter material and transfers excited-state energy from the emitter material to the nonradiative mode of the surface plasmon polariton. The reinforcement layer is positioned at a distance from the organic emitting layer not exceeding a threshold distance, wherein, due to the presence of the reinforcement layer, the emitter material has a total nonradiative decay rate constant and a total radiative decay rate constant, and the threshold distance is the position where the total nonradiative decay rate constant equals the total radiative decay rate constant. In some embodiments, the OLED further comprises an external coupling layer. In some embodiments, the external coupling layer is disposed on the reinforcement layer on the opposite side of the organic emitting layer. In some embodiments, the external coupling layer is disposed on the emitting layer on the side opposite to the reinforcement layer, but still externally couples energy from the surface plasmon polariton modes of the reinforcement layer. The external coupling layer scatters energy from the surface plasmon polaritons. In some embodiments, this energy is scattered as photons into free space. In other embodiments, energy is scattered from the surface plasmon modes of the device into other modes, such as, but not limited to, organic waveguide modes, substrate modes, or another waveguide mode. If energy is scattered into the non-free-space modes of the OLED, other external coupling schemes can be combined to extract the energy into free space. In some embodiments, one or more intermediary layers may be disposed between the enhancement layer and the external coupling layer. Examples of intermediary layers may be dielectric materials, including organic, inorganic, perovskite, and oxide materials, and may comprise stacks and / or mixtures of these materials.

[0291] The enhancement layer alters the effective properties of the medium in which the emitter material resides, thereby causing any or all of the following: reduced emissivity, altered emission profile, emission intensity varying with angle, altered emitter material stability, altered OLED efficiency, and reduced roll-off efficiency of the OLED device. Placing the enhancement layer on the cathode side, anode side, or both sides produces an OLED device that utilizes any of the aforementioned effects. In addition to the specific functional layers mentioned herein and illustrated in the various OLED examples shown in the figures, the OLED according to this disclosure may also include any other functional layers commonly found in OLEDs.

[0292] The reinforcing layer may comprise a plasmonic material, an optically active metamaterial, or a hyperbolic metamaterial. As used herein, a plasmonic material is a material in which the real part of the dielectric constant crosses zero in the visible or ultraviolet region of the electromagnetic spectrum. In some embodiments, the plasmonic material comprises at least one metal. In such embodiments, the metal may include at least one of the following: Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca, alloys or mixtures of these materials, and stacks of these materials. Typically, metamaterials are media composed of different materials, wherein the overall effect of the medium differs from the sum of its material components. Specifically, we define an optically active metamaterial as a material that simultaneously possesses negative permittivity and negative permeability. On the other hand, a hyperbolic metamaterial is an anisotropic medium in which the permittivity or permeability has different signs for different spatial orientations. Optically active metamaterials and hyperbolic metamaterials differ significantly from many other photonic structures, such as distributed Bragg reflectors (DBRs), because the medium should exhibit uniformity along the propagation direction over the long scale of the light wavelength. Using terminology understandable to those skilled in the art, the dielectric constant of the metamaterial along the propagation direction can be described by an effective dielectric approximation. Plasmon materials and metamaterials offer methods for controlling light propagation, which can enhance OLED performance in a variety of ways.

[0293] In some embodiments, the enhancement layer is configured as a planar layer. In other embodiments, the enhancement layer has wavelength-sized features arranged periodically, quasi-periodicly, or randomly, or subwavelength-sized features arranged periodically, quasi-periodicly, or randomly. In some embodiments, the wavelength-sized features and subwavelength-sized features have sharp edges.

[0294] In some embodiments, the outer coupling layer is characterized by a wavelength size arranged periodically, quasi-periodicly, or randomly, or by a subwavelength size arranged periodically, quasi-periodicly, or randomly. In some embodiments, the outer coupling layer may be composed of a plurality of nanoparticles, and in other embodiments, the outer coupling layer is composed of a plurality of nanoparticles disposed on a material. In these embodiments, the outer coupling can be adjusted by at least one of the following: changing the size of the plurality of nanoparticles, changing the shape of the plurality of nanoparticles, changing the material of the plurality of nanoparticles, adjusting the thickness of the material, changing the refractive index of the material or an additional layer disposed on the plurality of nanoparticles, changing the thickness of the reinforcing layer, and / or changing the material of the reinforcing layer. The plurality of nanoparticles of the device may be formed from at least one of the following: metal, dielectric material, semiconductor material, metal alloy, mixture of dielectric materials, stack or layering of one or more materials, and / or a core of one type of material coated with a shell of another type of material. In some embodiments, the outer coupling layer is composed of at least metal nanoparticles, wherein the metal is selected from the group consisting of: Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca, alloys or mixtures of these materials, and stacks of these materials. Multiple nanoparticles may have additional layers disposed on them. In some embodiments, the outer coupling layer can be used to tune the polarization of the emission. Changing the size and periodicity of the outer coupling layer can select the polarization type preferentially coupled to air. In some embodiments, the outer coupling layer also functions as an electrode of the device.

[0295] In another aspect, this disclosure also provides a consumer product comprising an organic light-emitting device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise compounds as disclosed in the above compound section of this disclosure.

[0296] In some embodiments, a consumer product includes an organic light-emitting device (OLED) having an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer may include the technology described herein as 1.

[0297] In some embodiments, a consumer product may be one of the following: a flat panel display, a computer monitor, a medical monitor, a television set, a signboard, a light for internal or external lighting and / or signaling, a head-up display, a fully transparent or partially transparent display, a flexible display, a laser printer, a telephone, a cellular telephone, a tablet computer, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a microdisplay with a diagonal of less than 2 inches, a 3D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising multiple displays tiled together, a theater or stadium screen, a phototherapy device, and a sign.

[0298] Generally, an OLED comprises at least one organic layer disposed between and electrically connected to both the anode and cathode. When a current is applied, holes are injected into the anode and electrons into the organic layer from the cathode. The injected holes and electrons migrate toward their respective oppositely charged electrodes. When electrons and holes are localized on the same molecule, an "exciton" is formed, which is a localized electron-hole pair with an excited energy state. When the exciton relaxes through a photoemission mechanism, light is emitted. In some cases, excitons may be localized on excimers or excited-state complexes. Non-radiative mechanisms (such as thermal relaxation) may also occur, but are generally considered undesirable.

[0299] Certain OLED materials and configurations are described in U.S. Patents 5,844,363, 6,303,238 and 5,707,745, which are incorporated herein by reference in their entirety.

[0300] Early OLEDs used emitting molecules that emitted light from a single state (“fluorescence”), as disclosed, for example, in U.S. Patent No. 4,769,292, which is incorporated herein by reference in its entirety. Fluorescence emission typically occurs within timeframes of less than 10 nanoseconds.

[0301] Recently, OLEDs with emitting materials that emit light from the triplet state (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, Vol. 395, 151-154, 1998 (“Baldo-I”); and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Applied Physics Letters, Vol. 75, 3, 4-6 (1999) (“Baldo-II”), are incorporated herein by reference in their entirety. Phosphorescence is described in more detail in columns 5-6 of U.S. Patent No. 7,279,704, which is incorporated herein by reference.

[0302] Figure 1 An organic light-emitting device 100 is shown. The figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emission layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a blocking layer 170. The cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 can be fabricated by sequentially depositing the layers. The properties and functions of these various layers and example materials are described in more detail in columns 6-10 of US 7,279,704, which is incorporated herein by reference.

[0303] Further examples of each of these layers are available. For instance, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated herein by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ in a 50:1 molar ratio, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety. Examples of luminescent and host materials are disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated herein by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li in a 1:1 molar ratio, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety. Examples of cathodes, comprising composite cathodes having a thin layer of metal (e.g., Mg:Ag) having an overlying transparent, conductive, sputtered ITO layer, are disclosed in their entirety in U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated herein by reference in their entirety. Theories and uses of barrier layers are described in more detail in U.S. Patent No. 6,097,147 and U.S. Patent Application Publication No. 2003 / 0230980, which are incorporated herein by reference in their entirety. Examples of implantation layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated herein by reference in its entirety. Descriptions of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated herein by reference in its entirety.

[0304] Figure 2 An inverted OLED 200 is shown. The device includes a substrate 210, a cathode 215, an emitter layer 220, a hole transport layer 225, and an anode 230. The device 200 can be fabricated by sequentially depositing these layers. Because the most common OLED configuration has a cathode disposed above the anode, and the device 200 has a cathode 215 disposed below the anode 230, the device 200 can be referred to as an "inverted" OLED. Materials similar to those described with respect to device 100 can be used in the corresponding layers of the device 200. Figure 2 Provide an example of how some layers can be omitted from the structure of device 100.

[0305] Figure 1 and 2The simple layered structures described herein are provided by way of non-limiting examples, and it should be understood that embodiments of this disclosure can be used in conjunction with a variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures can be used. Functional OLEDs can be obtained by combining the various layers described in different ways, or the 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 examples provided herein describe various layers as comprising a single material, it should be understood that combinations of materials, such as mixtures of host and dopant, or more generally, mixtures, can be used. Furthermore, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emitter layer 220, and can be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise, for example, regarding Figure 1 and 2 Multiple layers of the different organic materials mentioned above.

[0306] Structures and materials not specifically described can also be used, such as OLEDs (PLEDs) containing polymeric materials, as disclosed in, for example, U.S. Patent No. 5,247,190 to Friend et al., which is incorporated herein by reference in its entirety. By another example, OLEDs with a single organic layer can be used. OLEDs can be stacked, for example, as described in, U.S. Patent No. 5,707,745 to Forrest et al., which is incorporated herein by reference in its entirety. OLED structures can be deviated from... Figure 1 and 2 The simple layered structure described herein. For example, the substrate may include angled reflective surfaces to improve out-coupling, such as the tabletop structure described in U.S. Patent No. 6,091,195 to Forrest et al., and / or the recessed structure described in U.S. Patent No. 5,834,893 to Bulovic et al., which are incorporated herein by reference in their entirety.

[0307] Unless otherwise specified, any of the layers in the various embodiments may be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation, inkjet printing (as described in U.S. Patent Nos. 6,013,982 and 6,087,196, which are incorporated herein by reference in their entirety), organic vapor deposition (OVPD) (as described in U.S. Patent No. 6,337,102 by Forrest et al., which are incorporated herein by reference in their entirety), and deposition by organic vapor jet printing (OVJP) (as described in U.S. Patent No. 7,431,968, which is incorporated herein by reference in its entirety). Other suitable deposition methods include spin coating and other solution-based processes. Solution-based processes are preferably performed in a nitrogen or inert atmosphere. For other layers, preferred methods include thermal evaporation. Preferred patterning methods include patterning via mask deposition, cold soldering (as described in U.S. Patents 6,294,398 and 6,468,819, which are incorporated herein by reference in their entirety), and some of the methods associated with deposition methods such as inkjet and organic vapor jet printing (OVJP). Other methods may also be used. The material to be deposited may be modified to suit a particular deposition method. For example, branched or unbranched substituents, preferably containing at least three carbons, such as alkyl and aryl groups, may be used in small molecules to enhance their solution handling ability. Substituents having 20 or more carbons may be used, with 3 to 20 carbons being a preferred range. Materials with asymmetric structures may have better solution handleability than materials with symmetric structures because asymmetric materials may have a lower tendency to recrystallize. Dendritic polymer substituents may be used to enhance the solution handling ability of small molecules.

[0308] The device manufactured according to embodiments of this disclosure may optionally further include a barrier layer. One use of the barrier layer is to protect the electrodes and organic layers from damage caused by exposure to harmful substances in an environment including moisture, vapor, and / or gases. The barrier layer may be deposited on, under, or adjacent to a substrate or electrode, or on any other part of the device, including edges. The barrier layer may comprise a single layer or multiple layers. The barrier layer can be formed using a variety of known chemical vapor deposition techniques and may comprise compositions having a single phase and compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may contain inorganic or organic compounds, or both. Preferred barrier layers comprise a mixture of polymeric and non-polymeric materials, as described in U.S. Patent No. 7,968,146, PCT Patent Application Nos. PCT / US2007 / 023098 and PCT / US2009 / 042829, which are incorporated herein by reference in their entirety. For the process to be considered a "mixture," the aforementioned polymeric and non-polymeric materials constituting the barrier layer should be deposited and / or deposited simultaneously under the same reaction conditions. The weight ratio of polymeric to non-polymeric materials can range from 95:5 to 5:95. The polymeric and non-polymeric materials can be produced from the same precursor material. In one example, the mixture of polymeric and non-polymeric materials is essentially composed of polymeric silicon and inorganic silicon.

[0309] The apparatus manufactured according to embodiments of this disclosure can be incorporated into a wide variety of electronic component modules (or units), which can be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include displays, lighting devices (such as discrete light source devices or lighting panels), etc., which can be utilized by end-user product manufacturers. The electronic component module may optionally include driving electronics and / or a power supply. The apparatus manufactured according to embodiments of this disclosure can be incorporated into a wide variety of consumer products having one or more electronic component modules (or units) incorporated therein. A consumer product incorporating an OLED is disclosed, wherein the OLED includes compounds of this disclosure in its organic layer. The consumer product should include any kind of product containing one or more light sources and / or one or more of some type of visual display. Examples of the consumer products described include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for internal or external lighting and / or signaling, head-up displays, fully transparent or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, cellular phones, tablet computers, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, microdisplays (displays with a diagonal of less than 2 inches), 3D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple tiled displays, theater or stadium screens, phototherapy devices, and signage. Various control mechanisms, including passive and active matrices, can be used to control the devices manufactured according to this disclosure. Many of the devices are intended for use in temperature ranges comfortable for humans, such as 18°C ​​to 30°C, and more preferably at room temperature (20-25°C), but can be used outside this temperature range (e.g., -40°C to +80°C).

[0310] Further details regarding OLEDs and the definitions described above can be found in U.S. Patent No. 7,279,704, which is incorporated herein by reference in its entirety.

[0311] The materials and structures described herein can be applied to devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors can utilize the materials and structures described herein. More generally, organic devices such as organic transistors can utilize the materials and structures described herein.

[0312] In some embodiments, the OLED has one or more features selected from the group consisting of: flexible, rollable, foldable, stretchable, and bendable. In some embodiments, the OLED is transparent or translucent. In some embodiments, the OLED further comprises a layer including carbon nanotubes.

[0313] In some embodiments, the OLED further comprises a layer including a delayed phosphor emitter. In some embodiments, the OLED comprises an RGB pixel arrangement or a white pixel arrangement with a color filter. 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 with 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 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.

[0314] In some embodiments, the compound may be an emission dopant. In some embodiments, the compound may generate emission via phosphorescence, fluorescence, thermally activated delayed fluorescence (TADF, also known as E-type delayed fluorescence, see, for example, U.S. Application No. 15 / 700,352, which is incorporated herein by reference in its entirety), triplet-triplet annihilation, or a combination of these processes. In some embodiments, the emission dopant may be a racemic mixture or may be enriched with one enantiomer. In some embodiments, the compound may be homogeneous (each ligand is identical). In some embodiments, the compound may be mixed (at least one ligand is different from the others). In some embodiments, when more than one ligand coordinated to a metal is present, the ligands may all be identical. In some other embodiments, at least one ligand is different from the others. In some embodiments, each ligand may be different from each other. This also applies in embodiments where a ligand coordinated to a metal may be linked to other ligands coordinated to the metal to form a tridentate, tetradentate, pentadentate, or hexadentate ligand. Therefore, in the case where the coordinating ligands are linked together, in some embodiments all the ligands may be the same, and in some other embodiments at least one of the linking ligands may be different from (multiple) other ligands.

[0315] In some embodiments, the compound can be used as a phosphorescent sensitizer in an OLED, wherein one or more layers in the OLED contain acceptors in the form of one or more fluorescent and / or delayed-motion fluorescent emitters. In some embodiments, the compound can be used as a component of an excited-state complex to be used as a sensitizer. As a phosphorescent sensitizer, the compound must be able to transfer energy to the acceptor and the acceptor to emit energy or further transfer energy to the final emitter. The acceptor concentration can range from 0.001% to 100%. The acceptor can 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 can be generated by any one or all of the sensitizer, the acceptor, and the final emitter.

[0316] According to another aspect, a formulation comprising the compounds described herein is also disclosed.

[0317] The OLEDs disclosed herein can be incorporated into one or more consumer products, electronic component modules, and lighting panels. The organic layer can be an emission layer, and the compound can be an emission dopant in some embodiments, while in other embodiments it can be a non-emission dopant.

[0318] In another aspect of the invention, a formulation comprising the novel compounds disclosed herein is described. The formulation may include one or more components selected from the group consisting of: solvents, a host, hole injection materials, hole transport materials, electron blocking materials, hole blocking materials, and electron transport materials.

[0319] This disclosure covers any chemical structure comprising the novel compounds of this disclosure or their monovalent or multivalent variants. In other words, the compounds of the present invention or their monovalent or multivalent variants may be part of a larger chemical structure. Such chemical structures may be selected from the group consisting of monomers, polymers, macromolecules, and supramolecules (also referred to as supermolecules). As used herein, a "monovalent variant of a compound" refers to a portion that is identical to the compound but in which one hydrogen has been removed and replaced by a bond to the remainder of the chemical structure. As used herein, a "multivalent variant of a compound" refers to a portion that is identical to the compound but in which more than one hydrogen has been removed and replaced by one or more bonds to the remainder of the chemical structure. In the case of supramolecular compounds, the compounds of the present invention may also be incorporated into supramolecular complexes without covalent bonds.

[0320] C. Combinations of the compounds disclosed herein with other materials

[0321] The materials described herein for use in specific layers of organic light-emitting devices can be used in combination with a variety of other materials present in the device. For example, the emission dopants disclosed herein can be used in combination with a wide variety of host layers, transport layers, blocking layers, injection layers, electrodes, and other possible layers. The materials described or mentioned below are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and those skilled in the art can readily consult the literature to identify other materials that can be used in combination.

[0322] a) Conductive dopants:

[0323] Charge transport layers can be doped with conductive dopants to substantially alter their charge carrier density, which in turn changes their conductivity. Conductivity is increased by creating charge carriers in the matrix material and, depending on the type of dopant, can also achieve changes in the Fermi level of the semiconductor. Hole transport layers can be doped with p-type conductive dopants, while n-type conductive dopants are used in electron transport layers.

[0324] Non-limiting examples of conductive dopants that can be used in conjunction with the materials disclosed herein in OLEDs are illustrated in the following references: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047 and US2012146012.

[0325]

[0326] b) HIL / HTL:

[0327] The hole injection / transport materials used in this disclosure are not particularly limited, and any compound may be used, provided that the compound is commonly used as a hole injection / transport material. Examples of materials include (but are not limited to): phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indole-carbazole derivatives; polymers containing fluorinated hydrocarbons; polymers with conductive dopants; conductive polymers, such as PEDOT / PSS; self-assembled monomers derived from compounds such as phosphonic acids and silane derivatives; and metal oxide derivatives, such as MoO. xp-type semiconductive organic compounds, such as 1,4,5,8,9,12-hexaazatriphenylhexacarbonitrile; metal complexes; and crosslinkable compounds.

[0328] Examples of aromatic amine derivatives used for HIL or HTL include (but are not limited to) the following general structures:

[0329]

[0330] Ar 1 To Ar 9 Each of these is selected from the group consisting of, for example, aromatic hydrocarbon cyclic compounds such as: benzene, biphenyl, terphenyl, triphenylene, naphthalene, anthracene, fenene, fluorene, pyrene, Perylene and azurite; the group consisting of, for example, aromatic heterocyclic compounds such as: dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridinylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxthiazine, oxadiazine, indole, benzimidazole, indazole, inoxazine, benzoxazole, benziisoxazole, benzothiazole, quinoline, isoquinoline, zoline, quinazoline Quinoxaline, naphthidine, phthalazine, pteridine, oxanthracene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothiophenopyridine, thiophenodipyridine, benzoselenophenepyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units, said cyclic structural units being groups of the same or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups and bonded to each other directly or via at least one of oxygen, nitrogen, sulfur, silicon, phosphorus, boron, chain structural units, and aliphatic cyclic groups. Each Ar may be unsubstituted or may be substituted with a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl and combinations thereof.

[0331] In one aspect, Ar 1 To Ar 9 Choose independently from the following groups:

[0332]

[0333] Where k is an integer from 1 to 20; X 101 To X 108 It is C (including CH) or N; Z 101 It is NAr 1, O or S; Ar 1 It has the same functional groups as defined above.

[0334] Examples of metal complexes used in HIL or HTL include (but are not limited to) the following general formulas:

[0335]

[0336] Met is a metal with an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, Y 101 and Y 102 Independently selected from C, N, O, P, and S; L 101 It is an auxiliary ligand; k' is an integer value from 1 to the maximum number of ligands that can be bound to the metal; and k'+k" is the maximum number of ligands that can be bound to the metal.

[0337] In one aspect, (Y) 101 -Y 102 (Y) is a 2-phenylpyridine derivative. In another aspect, (Y) 101 -Y 102 Met is a carbapenem ligand. In another aspect, Met is selected from Ir, Pt, Os, and Zn. In yet another aspect, the metal complex possesses properties compared to Fc. + The minimum oxidation potential in solution with / Fc coupling is less than about 0.6V.

[0338] Non-limiting examples of HIL and HTL materials in OLEDs that can be used in combination with the materials disclosed herein are illustrated below, along with references to those materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, J P2007091719, JP2008021687, JP2014-009196, KR20110088898, KR2013007 7473, TW201139402, US06517957, US20020158242, US20030162053, US2005 0123751, US20060182993, US20060240279, US20070145888, US2007018187 4. US20070278938, US20080014464, US20080091025, US20080106190, US200 80124572, US20080145707, US20080220265, US20080233434, US20080303417, US2008107919, US20090115320, US20090167161, US2009066235, US201 1007385, US20110163302, US2011240968, US2011278551, US2012205642, US2013241401, US20140117329, US2014183517, US5061569, US5639914, WO0 5075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO2013018530, WO2013039073, WO201 3087142, WO2013118812, WO2013120577, WO2013157367, WO2013175747, WO 2014002873, WO2014015935, WO2014015937, WO2014030872, WO2014030921,WO2014034791, WO2014104514, WO2014157018. ,

[0339]

[0340]

[0341]

[0342]

[0343]

[0344]

[0345] c) EBL:

[0346] An electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons leaving the emitter layer. The presence of such a blocking layer in a device can result in generally higher efficiency and / or longer lifetime compared to similar devices lacking a blocking layer. Furthermore, the blocking layer can be used to confine emission to a desired area of ​​the OLED. In some embodiments, the EBL material has a higher LUMO (closer to vacuum level) and / or higher triplet energy compared to the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO and / or higher triplet energy compared to one or more of the bodies closest to the EBL interface. In one aspect, the compound used in the EBL contains the same molecules or the same functional groups as those used in one of the bodies described below.

[0347] d) Main body:

[0348] The light-emitting layer of the organic EL device disclosed herein preferably contains at least a metal complex as the light-emitting material, and may contain a host material using a 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 can be used with any dopant, as long as the triplet criterion is satisfied.

[0349] Examples of metal complexes used as the host preferably have the following general formula:

[0350]

[0351] Where Met is a metal; (Y) 103 -Y 104 ) is a bidentate ligand, Y 103 and Y 104Independently selected from C, N, O, P, and S; L 101 It is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be bound to the metal; and k'+k" is the maximum number of ligands that can be bound to the metal.

[0352] In one respect, metal complexes are:

[0353]

[0354] (ON) is a bidentate ligand of a metal that coordinates with O and N atoms.

[0355] In the other case, Met is selected from Ir and Pt. In the other case, (Y 103 -Y 104 ) is a carbaene ligand.

[0356] In one aspect, the host compound contains at least one selected from the group consisting of, for example, aromatic hydrocarbon cyclic compounds such as: benzene, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, fenene, fluorene, pyrene, etc. Perylene and azurite; the group consisting of, for example, aromatic heterocyclic compounds such as: dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridinylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxthiazine, oxadiazine, indole, benzimidazole, indazole, inoxazine, benzoxazole, benziisoxazole, benzothiazole, quinoline, isoquinoline, zoline, quinazoline Quinoxaline, naphthidine, phthalazine, pteridine, oxanthracene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothiophenopyridine, thiophenodipyridine, benzoselenophenepyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units, said cyclic structural units being groups of the same or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups and bonded to each other directly or via at least one of oxygen, nitrogen, sulfur, silicon, phosphorus, boron, chain structural units, and aliphatic cyclic groups. Each option in each group may be unsubstituted or may be substituted by substituents selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphin, and combinations thereof.

[0357] In one aspect, the host compound contains at least one of the following groups in its molecule:

[0358]

[0359] Where R 101 The group consisting of the following is selected: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof, and when it is aryl or heteroaryl, it has a definition similar to that of Ar mentioned above. k is an integer from 0 to 20 or from 1 to 20. X 101 To X 108 Independently selected from C (including CH) or N. Z 101 and Z 102 Independently selected from NR 101 、O or S.

[0360] Non-limiting examples of material combinations disclosed herein used as host materials in OLEDs are illustrated below, along with references to those materials: EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060280965, US2009 0017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, U S20140225088, US2014034914, US7154114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO200 6114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO2009066779, WO20090 86028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO2012128298, WO2012133644, WO2012133 649. WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472, US20170263869, US20160163995, US9466803,

[0361]

[0362]

[0363]

[0364]

[0365]

[0366]

[0367] e) Other emitters:

[0368] One or more other emitter dopants may be used in conjunction with the compounds of the present invention. Examples of other emitter dopants are not particularly limited, and any compound may be used, as long as the compound is commonly used as an emitter material. Examples of suitable emitter materials include (but are not limited to) compounds that can produce emission via phosphorescence, fluorescence, thermally activated delayed fluorescence (i.e., TADF, also known as E-type delayed fluorescence), triplet-triplet annihilation, or a combination of these processes.

[0369] Non-limiting examples of emitter materials in OLEDs that can be used in conjunction with the material combinations disclosed herein are illustrated below, along with references to those materials: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP2013110263, JP4478555, KR1020090133652, KR201200 32054, KR20130043460, TW201332980, US06699599, US06916554, US200100 19782, US20020034656, US20030068526, US20030072964, US20030138657, U U.S. 20060202194, US20060251923, US20070034863, US20070087321, US200701 03060, US20070111026, US20070190359, US20070231600, US2007034863, US 2007104979, US2007104980, US2007138437, US2007224450, US2007278936 , US20080020237, US20080233410, US20080261076, US20080297033, US2008 05851, US2008161567, US2008210930, US20090039776, US20090108737, US 20090115322, US20090179555, US2009085476, US2009104472, US201000905 91. US20100148663, US20100244004, US20100295032, US2010102716, US20 10105902, US2010244004, US2010270916, US20110057559, US20110108822,US20110204333、US2011215710、US2011227049、US2011285275、US2012292601、US20130146848、US2013033172、US2013165653、US2013181190、US2013334521、US20140246656、US2014103305、US6303238、US6413656、US6653654、US6670645、US6687266、US6835469、US6921915、US7279704、US7332232、US7378162、US7534505、US7675228、US7728137、US7740957、US7759489、US7951947、US8067099、US8592586、US8871361、WO06081973、WO06121811、WO07018067、WO07108362、WO07115970、WO07115981、WO08035571、WO2002015645、WO2003040257、WO2005019373、WO2006056418、WO2008054584、WO2008078800、WO2008096609、WO2008101842、WO2009000673、WO2009050281、WO2009100991、WO2010028151、WO2010054731、WO2010086089、WO2010118029、WO2011044988、WO2011051404、WO2011107491、WO2012020327、WO2012163471、WO2013094620、WO2013107487、WO2013174471、WO2014007565、WO2014008982、WO2014023377、WO2014024131、WO2014031977、WO2014038456、WO2014112450。、

[0370]

[0371]

[0372]

[0373]

[0374]

[0375]

[0376] f)HBL:

[0377] Hole blocking layers (HBLs) can be used to reduce the number of holes and / or excitons leaving the emitter layer. The presence of such blocking layers in a device can result in generally higher efficiency and / or longer lifetime compared to similar devices lacking a blocking layer. Furthermore, blocking layers can be used to confine emission to a desired area of ​​the OLED. In some embodiments, the HBL material has a lower HOMO (farthest from vacuum level) and / or higher triplet energy compared to the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO and / or higher triplet energy compared to one or more of the bodies closest to the HBL interface.

[0378] In one aspect, the compounds used in HBL contain the same molecules or the same functional groups as those used in the subject described above.

[0379] In another aspect, the compounds used in HBL contain at least one of the following groups in their molecules:

[0380] Where k is an integer from 1 to 20; L 101 It is another ligand, and k' is an integer from 1 to 3.

[0381] g)ETL:

[0382] An electron transport layer (ETL) may comprise a material capable of transporting electrons. The ETL may be intrinsic (undoped) or doped. Doping can be used to enhance conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound may be used, provided it is typically used for electron transport.

[0383] In one aspect, the compounds used in ETL contain at least one of the following groups in their molecules:

[0384]

[0385] Where R 101 The group consisting of the following is selected: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof, which, when aryl or heteroaryl, have a similar definition to Ar as described above. 1To Ar 3 It has a similar definition to Ar mentioned above. k is an integer from 1 to 20. X 101 To X 108 Selected from C (including CH) or N.

[0386] In another aspect, the metal complexes used in ETL contain (but are not limited to) the following general formula:

[0387]

[0388] Wherein (ON) or (NN) are bidentate ligands of metals that coordinate with atoms O, N or N, N; L 101 It is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be bonded to the metal.

[0389] Non-limiting examples of ETL materials that can be used in OLEDs with the material combinations disclosed herein are illustrated below, along with references to those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US20 10108990, US2011156017, US2011210320, US2012193612, US2012214993, US201401 4925, US2014014927, US20140284580, US6656612, US8415031, WO2003060956, WO20 07111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO201110 5373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535,

[0390]

[0391]

[0392]

[0393] h) Charge Generation Layer (CGL)

[0394] In tandem or stacked OLEDs, the conduction layer (CGL) plays a fundamental role in performance. It consists of an n-doped layer and a p-doped layer, respectively, for injecting electrons and holes. Electrons and holes are supplied by the CGL and the electrodes. Electrons and holes consumed in the CGL are refilled by electrons and holes injected from the cathode and anode, respectively; subsequently, the bipolar current gradually reaches a steady state. Typical CGL materials include n- and p-conductive dopants used in the transport layer.

[0395] In any of the compounds mentioned above used in each layer of an OLED device, hydrogen atoms can be partially or fully deuterated. Therefore, any specifically listed substituents, such as (but not limited to) methyl, phenyl, pyridyl, etc., can be in their undeuterated, partially deuterated, and fully deuterated forms. Similarly, substituent classes (e.g., (but not limited to) alkyl, aryl, cycloalkyl, heteroaryl, etc.) can also be in their undeuterated, partially deuterated, and fully deuterated forms.

[0396] It should be understood that the various embodiments described herein are merely examples and are not intended to limit the scope of the invention. For instance, many of the materials and structures described herein can be substituted with other materials and structures without departing from the spirit of the invention. The claimed invention may therefore include variations of the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It should be understood that various theories regarding why the invention works are not intended to be limiting.

Claims

1. An organic light-emitting diode device, comprising: Substrate; First electrode; An organic emission layer containing organic emission material is disposed above the first electrode; A reinforcement layer comprising a plasmonic material exhibiting surface plasmon resonance, the plasmonic material being nonradiatively coupled to the organic emitter material and transferring excited-state energy from the organic emitter material to the nonradiative mode of surface plasmon polaritons, the reinforcement layer being disposed on the organic emitter layer. The enhancement layer is configured such that its distance from the organic emitting layer does not exceed a threshold distance. in, Due to the presence of the enhancement layer, the organic emissive material has a total nonradiative attenuation constant and a total radiative attenuation constant, and the threshold distance is the position where the total nonradiative attenuation constant is equal to the total radiative attenuation constant; as well as The organic emission material and the organic emission layer have at least one of a vertical dipole ratio (VDR) of 0.33 or greater.

2. The apparatus of claim 1, wherein the organic emission layer has a VDR value equal to or greater than 0.

33.

3. The apparatus of claim 1, wherein the organic emissive material has a VDR value equal to or greater than 0.

33.

4. The apparatus of claim 1, wherein the organic emission layer comprises: The first layer contains the organic emissive material; and The second layer is disposed adjacent to the first layer and contains a second material.

5. The apparatus of claim 4, wherein the first layer and the second layer satisfy the condition 0 ≤ Ex - ΔE, where Ex is the lowest emission state energy level of the first layer or the second layer, and ΔE is the difference between the highest highest occupied molecular orbital (HOMO) energy level and the lowest lowest unoccupied molecular orbital (LUMO) energy level within the organic emission layer.

6. The apparatus of claim 5, wherein Ex is the lowest triplet (T1) energy level of the first layer, and the first layer is phosphorescent.

7. The apparatus of claim 5, wherein Ex is the lowest singlet state (S1) energy level of the first layer, and the first layer is fluorescent.

8. The apparatus according to claim 1, wherein the organic emitting material is a phosphorescent material.

9. The apparatus according to claim 1, wherein the organic emitting material is a fluorescent material.

10. The apparatus of claim 1, wherein the enhancement layer comprises a second electrode layer.

11. The apparatus of claim 1, further comprising a template layer selected and arranged to orient the molecules of the organic emission layer.

12. The apparatus of claim 11, wherein the template layer aligns the dipole of the organic emissive material and increases the perpendicularity of the dipole.

13. The apparatus of claim 11, wherein the template layer is within the threshold distance of the reinforcing layer.

14. A consumer product comprising: Organic light-emitting diode device, comprising: Substrate; First electrode; An organic emission layer containing organic emission material is disposed above the first electrode; A reinforcement layer comprising a plasmonic material exhibiting surface plasmon resonance, the plasmonic material being nonradiatively coupled to the organic emitter material and transferring excited-state energy from the organic emitter material to the nonradiative mode of surface plasmon polaritons, the reinforcement layer being disposed on the organic emitter layer. The enhancement layer is configured such that its distance from the organic emitting layer does not exceed a threshold distance. in, Due to the presence of the enhancement layer, the organic emissive material has a total nonradiative attenuation rate constant and a total radiative attenuation rate constant, and the threshold distance is the position where the total nonradiative attenuation rate constant is equal to the total radiative attenuation rate constant. The organic emission material and the organic emission layer have at least one of a vertical dipole ratio (VDR) of 0.33 or greater.

15. The consumer product of claim 14, wherein the consumer product is at least one type selected from the group consisting of: displays, lighting devices, computer monitors, medical monitors, televisions, billboards, laser printers, telephones, tablet computers, tablet phones, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, vehicles, large-area walls, theater or stadium screens, phototherapy devices, signs, displays or visual elements in eyeglasses, LED wallpaper, LED ornaments, and clothing.

16. The consumer product of claim 14, wherein the consumer product is at least one type selected from the group consisting of: flat panel displays, curved displays, head-up displays, fully transparent or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, microdisplays with a diagonal of less than 2 inches, 3D displays, aviation displays, video walls comprising multiple displays tiled together, augmented reality (AR) displays or virtual reality (VR) displays, lights for internal or external lighting and / or signaling, cellular phones, and display or visual elements in contact lenses.

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