ORGANIC ELECTROLUMINESCENT DEVICES
20230413590 ยท 2023-12-21
Inventors
- Haridas MUNDOOR (Ewing, NJ, US)
- Nicholas J. THOMPSON (New Hope, PA, US)
- Vinod M. Menon (New York, NY, US)
Cpc classification
H10K50/852
ELECTRICITY
H10K59/876
ELECTRICITY
International classification
H10K50/115
ELECTRICITY
Abstract
Embodiments of the disclosed subject matter provide a device that may include an organic light emitting device (OLED) having a substrate, a first electrode disposed over the substrate, a second electrode disposed over the first electrode, and an organic emissive layer having a first surface positioned over a second surface is disposed between the first electrode and the second electrode. A nanoparticle layer may be disposed over the organic emissive layer and has a first surface that is positioned over a second surface. The nanoparticle layer may include a first plurality of nanoparticles comprising a dielectric material, and a surrounding medium. A distance from the second surface of the nanoparticle layer to the first surface of the organic emissive layer may be not more than 50 nm, and there may be a difference of at least 1.0 between a refractive index of the dielectric material and the surrounding medium.
Claims
1-76. (canceled)
77. A device comprising: an organic light emitting device (OLED) comprising: a substrate; a first electrode disposed over the substrate; a second electrode disposed over the first electrode; and an organic emissive layer disposed between the first electrode and the second electrode, the organic emissive layer having a first surface positioned over a second surface; and a nanoparticle layer disposed over the organic emissive layer, the nanoparticle layer having a first surface that is positioned over a second surface, the nanoparticle layer comprising: a first plurality of nanoparticles comprising a dielectric material; and a surrounding medium; wherein a distance from the bottom of the nanoparticle layer to the top of the organic emissive layer is not more than 50 nm, and wherein there is a difference of at least 1.0 between a refractive index of the dielectric material and the surrounding medium.
78. The device of claim 77, wherein the plurality of nanoparticles is disposed in an outcoupling layer disposed over the second electrode.
79. The device of claim 77, wherein at least some of the plurality of nanoparticles are integrated with the second electrode.
80. The device of claim 77, wherein the first plurality of nanoparticles includes at least one nanoparticle having a Mie scattering efficiency of 2-8 based on at least one selected from the group consisting of: a size of the nanoparticles, a shape of the nanoparticles, and a material refractive index of the nanoparticles.
81. The device of claim 77, wherein a refractive index of the plurality of nanoparticles is at least one selected from the group consisting of: at least 1.9, at least 2.1, at least 2.5, and less than 3.5.
82. The device of claim 77, wherein the plurality of nanoparticles is configured as at least one selected from the group consisting of: dimers, trimers, and a plurality of levels of units to be configured to output a non-Lambertian emission.
83. The device of claim 82, wherein the device is configured to emit at least one selected from the group consisting of: at least 60%, at least 70%, and at least 80% of the light through one side of the device side where the plurality nanoparticles are disposed.
84. The device of claim 77, wherein the first plurality of nanoparticles comprises two or more materials, each of the two or more materials having a different refractive index, homogeneously or inhomogeneously distributed within the outcoupling layer, wherein at least one of the two or more materials creates the difference of at least 1.0 between the refractive index of the at least one of the two or more materials and the surrounding medium.
85. The device of claim 77, further comprising: a transparent dielectric layer having a thickness at least 2 nm but not more than 50 nm minus a thickness of the electrode, wherein the transparent dielectric layer is disposed between the second electrode and the nanoparticle layer.
86. The device of claim 85, wherein a refractive index of the dielectric material is at least one selected from the group consisting of: less than 1.2, less than 1.5, less than 2, and less than 2.5.
87. The device of claim 77, wherein the device has a first side and a second side, wherein the first electrode comprises a reflective metal layer to reflect light to the first side of the device, wherein the second electrode is a transparent layer, and wherein the nanoparticle layer is disposed over the transparent layer, and wherein the organic emissive layer is disposed at least 75 nm from the reflective metal layer.
88. The device of claim 77, wherein the device has a first side and a second side, and light is emitted from both the first side and the second side.
89. The device of claim 77, wherein the device has a first side and a second side, and the device further comprises: a reflective layer disposed on the second side to direct emission of light to the first side of the device.
90. The device of claim 77, wherein the device has a first side and a second side, and the device further comprises: a distributed Bragg reflector (DBR) stack disposed to reflect light from a second side of the device.
91. The device of claim 77, wherein at least one selected from the group consisting of the first electrode and the second electrode is a transparent electrode.
92. The device of claim 91, wherein the second electrode is the transparent electrode, and the transparent electrode is disposed on the organic emissive layer.
93. The device of claim 92, wherein an in-plane dimension of the nanoparticles is at least one selected from the group consisting of: 200-400 nm, 400-600 nm, and 600-800 nm, wherein the in-plane dimension is in a plane that is horizontal to the substrate, and wherein a distance in an out-of-plane dimension between the nanoparticles is at least one selected from the group consisting of: 25-75 nm, 75-200 nm, 200-400 nm, and 400-600 nm, wherein the out-of-plane dimension is in a plane perpendicular to the substrate.
94. The device of claim 77, wherein an in-plane dimension of the nanoparticles is at least one selected from the group consisting of: 200-400 nm, 400-600 nm, and 600-800 nm, wherein the in-plane dimension is in a plane that is horizontal to the substrate and wherein a distance in an out-of-plane dimension between the nanoparticles is at least one selected from the group consisting of: 25-75 nm, 75-200 nm, 200-400 nm, and 400-600 nm, wherein the out-of-plane dimension is in a plane perpendicular to the substrate.
95. The device of claim 77, wherein the device is at least one type selected from the group consisting of: a flat panel display, a curved display, a computer monitor, a medical monitor, a television, a billboard, a light for interior or exterior illumination and/or signaling, a heads-up display, a fully or partially transparent display, a flexible display, a rollable display, a foldable display, a stretchable display, a laser printer, a telephone, a cell phone, tablet, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a micro-display that is less than 2 inches diagonal, a 3-D display, a virtual reality or augmented reality display, a vehicle, an automotive display, video walls comprising multiple displays tiled together, a theater or stadium screen, and a sign.
96. A device comprising: an organic light emitting device (OLED) comprising: a substrate; a first electrode disposed over the substrate; a second electrode disposed over the first electrode; and an organic emissive layer disposed between the first electrode and the second electrode, the organic emissive layer having a first surface positioned over a second surface; and a nanoparticle layer disposed over the organic emissive layer, the nanoparticle layer having a first surface that is positioned over a second surface, the nanoparticle layer comprising: a plurality of nanoparticles comprising a dielectric material; and a surrounding medium; wherein the organic emissive layer directly couples to Mie scattering modes of the plurality of nanoparticles, and wherein a distance from the second surface of the nanoparticle layer to the first surface of the organic emissive layer is at least one selected from the group consisting of: not more than , not more than , and not more than 1/10 of a peak emission wavelength capable of being emitted by the organic emissive layer.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0056]
[0057]
[0058]
[0059]
[0060]
[0061]
[0062]
[0063]
[0064]
[0065]
DETAILED DESCRIPTION
[0066] Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an exciton, which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.
[0067] The initial OLEDs used emissive molecules that emitted light from their singlet states (fluorescence) as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.
[0068] More recently, OLEDs having emissive materials that emit light from triplet states (phosphorescence) have been demonstrated. Baldo et al., Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices, Nature, vol. 395, 151-154, 1998; (Baldo-I) and Baldo et al., Very high-efficiency green organic light-emitting devices based on electrophosphorescence, Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) (Baldo-II), are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference.
[0069]
[0070] More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F.sub.4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is Bphen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. Barrier layer 170 may be a single- or multi-layer barrier and may cover or surround the other layers of the device. The barrier layer 170 may also surround the substrate 110, and/or it may be arranged between the substrate and the other layers of the device. The barrier also may be referred to as an encapsulant, encapsulation layer, protective layer, or permeation barrier, and typically provides protection against permeation by moisture, ambient air, and other similar materials through to the other layers of the device. Examples of barrier layer materials and structures are provided in U.S. Pat. Nos. 6,537,688, 6,597,111, 6,664,137, 6,835,950, 6,888,305, 6,888,307, 6,897,474, 7,187,119, and 7,683,534, each of which is incorporated by reference in its entirety.
[0071]
[0072] The simple layered structure illustrated in
[0073] Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in
[0074] In some embodiments disclosed herein, emissive layers or materials, such as emissive layer 135 and emissive layer 220 shown in
[0075] Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP), such as described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink-jet and OVJD. Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons is a preferred range. Materials with asymmetric structures may have better solution processibility than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.
[0076] Devices fabricated in accordance with embodiments of the present invention may further optionally comprise a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. The barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. The barrier layer may comprise a single layer, or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate an inorganic or an organic compound or both. The preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material as described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporated by reference in their entireties. To be considered a mixture, the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be created from the same precursor material. In one example, the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon.
[0077] In some embodiments, at least one of the anode, the cathode, or a new layer disposed over the organic emissive layer functions as an enhancement layer. The enhancement layer comprises a plasmonic material exhibiting surface plasmon resonance that non-radiatively couples to the emitter material and transfers excited state energy from the emitter material to non-radiative mode of surface plasmon polariton. The enhancement layer is provided no more than a threshold distance away from the organic emissive layer, wherein the emitter material has a total non-radiative decay rate constant and a total radiative decay rate constant due to the presence of the enhancement layer and the threshold distance is where the total non-radiative decay rate constant is equal to the total radiative decay rate constant. In some embodiments, the OLED further comprises an outcoupling layer. In some embodiments, the outcoupling layer is disposed over the enhancement layer on the opposite side of the organic emissive layer. In some embodiments, the outcoupling layer is disposed on opposite side of the emissive layer from the enhancement layer but still outcouples energy from the surface plasmon mode of the enhancement layer. The outcoupling layer scatters the energy from the surface plasmon polaritons. In some embodiments this energy is scattered as photons to free space. In other embodiments, the energy is scattered from the surface plasmon mode into other modes of the device such as but not limited to the organic waveguide mode, the substrate mode, or another waveguiding mode. If energy is scattered to the non-free space mode of the OLED other outcoupling schemes could be incorporated to extract that energy to free space. In some embodiments, one or more intervening layer can be disposed between the enhancement layer and the outcoupling layer. The examples for intervening layer(s) can be dielectric materials, including organic, inorganic, perovskites, oxides, and may include stacks and/or mixtures of these materials.
[0078] The enhancement layer modifies the effective properties of the medium in which the emitter material resides resulting in any or all of the following: a decreased rate of emission, a modification of emission line-shape, a change in emission intensity with angle, a change in the stability of the emitter material, a change in the efficiency of the OLED, and reduced efficiency roll-off of the OLED device. Placement of the enhancement layer on the cathode side, anode side, or on both sides results in OLED devices which take advantage of any of the above-mentioned effects. In addition to the specific functional layers mentioned herein and illustrated in the various OLED examples shown in the figures, the OLEDs according to the present disclosure may include any of the other functional layers often found in OLEDs.
[0079] The enhancement layer can be comprised of plasmonic materials, optically active metamaterials, or hyperbolic metamaterials. 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 includes at least one metal. In such embodiments the metal may include at least one of Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca alloys or mixtures of these materials, and stacks of these materials. In general, a metamaterial is a medium composed of different materials where the medium as a whole acts differently than the sum of its material parts. In particular, we define optically active metamaterials as materials which have both negative permittivity and negative permeability. Hyperbolic metamaterials, on the other hand, are anisotropic media in which the permittivity or permeability are of different sign for different spatial directions. Optically active metamaterials and hyperbolic metamaterials are strictly distinguished from many other photonic structures such as Distributed Bragg Reflectors (DBRs) in that the medium should appear uniform in the direction of propagation on the length scale of the wavelength of light. Using terminology that one skilled in the art can understand: the dielectric constant of the metamaterials in the direction of propagation can be described with the effective medium approximation. Plasmonic materials and metamaterials provide methods for controlling the propagation of light that can enhance OLED performance in a number of ways.
[0080] In some embodiments, the enhancement layer is provided as a planar layer. In other embodiments, the enhancement layer has wavelength-sized features that are arranged periodically, quasi-periodically, or randomly, or sub-wavelength-sized features that are arranged periodically, quasi-periodically, or randomly. In some embodiments, the wavelength-sized features and the sub-wavelength-sized features have sharp edges.
[0081] In some embodiments, the outcoupling layer has wavelength-sized features that are arranged periodically, quasi-periodically, or randomly, or sub-wavelength-sized features that are arranged periodically, quasi-periodically, or randomly. In some embodiments, the outcoupling layer may be composed of a first plurality of nanoparticles and in other embodiments the outcoupling layer is composed of a plurality of nanoparticles disposed over a material. In these embodiments the outcoupling may be tunable by at least one of varying a size of the first plurality of nanoparticles, varying a shape of the first plurality of nanoparticles, changing a material of the first plurality of nanoparticles, adjusting a thickness of the material, changing the refractive index of the material or an additional layer disposed on the first plurality of nanoparticles, varying a thickness of the enhancement layer, and/or varying the material of the enhancement layer. The first plurality of nanoparticles of the device may be formed from at least one of metal, dielectric material, semiconductor materials, an alloy of metal, a mixture of dielectric materials, a stack or layering of one or more materials, and/or a core of one type of material and that is coated with a shell of a different type of material. In some embodiments, the outcoupling 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. The first plurality of nanoparticles may have additional layer disposed over them. In some embodiments, the polarization of the emission can be tuned using the outcoupling layer. Varying the dimensionality and periodicity of the outcoupling layer can select a type of polarization that is preferentially outcoupled to air. In some embodiments the outcoupling layer also acts as an electrode of the device.
[0082] It is believed that the internal quantum efficiency (IQE) of fluorescent OLEDs can exceed the 25% spin statistics limit through delayed fluorescence. As used herein, there are two types of delayed fluorescence, i.e., P-type delayed fluorescence and E-type delayed fluorescence. P-type delayed fluorescence is generated from triplet-triplet annihilation (TTA).
[0083] On the other hand, E-type delayed fluorescence does not rely on the collision of two triplets, but rather on the thermal population between the triplet states and the singlet excited states. Compounds that are capable of generating E-type delayed fluorescence are required to have very small singlet-triplet gaps. Thermal energy can activate the transition from the triplet state back to the singlet state. This type of delayed fluorescence is also known as thermally activated delayed fluorescence (TADF). A distinctive feature of TADF is that the delayed component increases as temperature rises due to the increased thermal energy. If the reverse intersystem crossing rate is fast enough to minimize the non-radiative decay from the triplet state, the fraction of back populated singlet excited states can potentially reach 75%. The total singlet fraction can be 100%, far exceeding the spin statistics limit for electrically generated excitons.
[0084] E-type delayed fluorescence characteristics can be found in an exciplex system or in a single compound. Without being bound by theory, it is believed that E-type delayed fluorescence requires the luminescent material to have a small singlet-triplet energy gap (AES-T). Organic, non-metal containing, donor-acceptor luminescent materials may be able to achieve this. The emission in these materials is often characterized as a donor-acceptor charge-transfer (CT) type emission. The spatial separation of the HOMO and LUMO in these donor-acceptor type compounds often results in small AES-T. These states may involve CT states. Often, donor-acceptor luminescent materials are constructed by connecting an electron donor moiety such as amino- or carbazole-derivatives and an electron acceptor moiety such as N-containing six-membered aromatic ring.
[0085] Devices fabricated in accordance with embodiments of the invention can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices such as discrete light source devices or lighting panels, etc. that can be utilized by the end-user product manufacturers. Such electronic component modules can optionally include the driving electronics and/or power source(s). Devices fabricated in accordance with embodiments of the invention can be incorporated into a wide variety of consumer products that have one or more of the electronic component modules (or units) incorporated therein. A consumer product comprising an OLED that includes the compound of the present disclosure in the organic layer in the OLED is disclosed. Such consumer products would include any kind of products that include one or more light source(s) and/or one or more of some type of visual displays. Some examples of such consumer products include a flat panel display, a curved display, a computer monitor, a medical monitor, a television, a billboard, a light for interior or exterior illumination and/or signaling, a heads-up display, a fully or partially transparent display, a flexible display, a rollable display, a foldable display, a stretchable display, a laser printer, a telephone, a cell phone, tablet, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a micro-display that is less than 2 inches diagonal, a 3-D display, a virtual reality or augmented reality display, a vehicle, an automotive display, video walls comprising multiple displays tiled together, a theater or stadium screen, and a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 C to 30 C, and more preferably at room temperature (20-25 C), but could be used outside this temperature range, for example, from 40 C to 80 C.
[0086] The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.
[0087] In some embodiments, the OLED has one or more characteristics selected from the group consisting of being flexible, being rollable, being foldable, being stretchable, and being curved. In some embodiments, the OLED is transparent or semi-transparent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes.
[0088] In some embodiments, the OLED further comprises a layer comprising a delayed fluorescent emitter. In some embodiments, the OLED comprises a RGB pixel arrangement or white plus color filter pixel arrangement. In some embodiments, the OLED is a mobile device, a hand held device, or a wearable device. In some embodiments, the OLED is a display panel having less than 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a display panel having at least inch diagonal or 50 square inch area. In some embodiments, the OLED is a lighting panel.
[0089] In some embodiments of the emissive region, the emissive region further comprises a host.
[0090] In some embodiments, the compound can be an emissive dopant. In some embodiments, the compound can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence), triplet-triplet annihilation, or combinations of these processes.
[0091] The OLED disclosed herein can be incorporated into one or more of a consumer product, an electronic component module, and a lighting panel. The organic layer can be an emissive layer and the compound can be an emissive dopant in some embodiments, while the compound can be a non-emissive dopant in other embodiments.
[0092] The organic layer can also include a host. In some embodiments, two or more hosts are preferred. In some embodiments, the hosts used maybe a) bipolar, b) electron transporting, c) hole transporting or d) wide band gap materials that play little role in charge transport. In some embodiments, the host can include a metal complex. The host can be an inorganic compound.
Combination with Other Materials
[0093] The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.
[0094] Various materials may be used for the various emissive and non-emissive layers and arrangements disclosed herein. Examples of suitable materials are disclosed in U.S. Patent Application Publication No. 2017/0229663, which is incorporated by reference in its entirety.
Conductivity Dopants:
[0095] A charge transport layer can be doped with conductivity dopants to substantially alter its density of charge carriers, which will in turn alter its conductivity. The conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor may also be achieved. Hole-transporting layer can be doped by p-type conductivity dopants and n-type conductivity dopants are used in the electron-transporting layer.
HIL/HTL:
[0096] A hole injecting/transporting material to be used in the present invention is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material.
EBL:
[0097] An electron blocking layer (EBL) may be used to reduce the number of electrons and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies, and or longer lifetime, as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and or higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in EBL contains the same molecule or the same functional groups used as one of the hosts described below.
Host:
[0098] The light emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as light emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. Any host material may be used with any dopant so long as the triplet criteria is satisfied.
EML:
[0099] EML can comprise a phosphorescent or fluorescent emitter. Phosphorescence generally refers to emission of a photon with a change in electron spin, i.e., the initial and final states of the emission have different multiplicity, such as from T1 to S0 state. Ir and Pt complexes currently widely used in the OLED belong to phosphorescent emitters. In some embodiments, if an exciplex formation involves a triplet emitter, such exciplex can also emit phosphorescent light. On the other hand, fluorescent emitters generally refer to emission of a photon without a change in electron spin, such as from S1 to S0 state. Fluorescent emitters can be delayed fluorescent or non-delayed fluorescent emitters. Depending on the spin state, fluorescent emitter can be a singlet emitter or a doublet emitter, or other multiplet emitter. It is believed that the internal quantum efficiency (IQE) of fluorescent OLEDs can exceed the 25% spin statistics limit through delayed fluorescence. There are two types of delayed fluorescence, i.e., P-type and E-type delayed fluorescence. P-type delayed fluorescence is generated from triplet-triplet annihilation (TTA). On the other hand, E-type delayed fluorescence does not rely on the collision of two triplets, but rather on the thermal population between the triplet states and the singlet excited states. Thermal energy can activate the transition from the triplet state back to the singlet state. This type of delayed fluorescence is also known as thermally activated delayed fluorescence (TADF). E-type delayed fluorescence characteristics can be found in an exciplex system or in a single compound. Without being bound by theory, it is believed that TADF requires a compound or an exciplex having a small singlet-triplet energy gap (AES-T) less than or equal to 300, 250, 200, 150, 100, or 50 meV. There are two major types of TADF emitters, one is called donor-acceptor type TADF, the other one is called multiple resonance (MR) TADF. Often, donor-acceptor single compounds are constructed by connecting an electron donor moiety such as amino- or carbazole-derivatives and an electron acceptor moiety such as N-containing six-membered aromatic ring. Donor-acceptor exciplex can be formed between a hole transporting compound and an electron transporting compound. The examples for MR-TADF include a highly conjugated boron-containing compounds. In some embodiments, the reverse intersystem crossing time from T1 to S1 of the delayed fluorescent emission at 293K is less than or equal to 10 microseconds. In some embodiments, such time can be greater than 10 microseconds and less than 100 microseconds.
[0100] In some embodiments, the emissive dopant can be a phosphorescent or fluorescent material. In some embodiments, the non-emissive dopant can also be a phosphorescent or fluorescent material. In some embodiments, the OLED may comprise an additional compound selected from the group consisting of a fluorescence material, a delayed fluorescence material, a phosphorescent material, and combination thereof.
[0101] In some embodiments, the phosphorescent material is an emitter which emits light within the OLED. In some embodiments, the phosphorescent material does not emit light within the OLED. In some embodiments, the phosphorescent material energy transfers its excited state to another material within the OLED. In some embodiments, the phosphorescent material participates in charge transport within the OLED. In some embodiments, the phosphorescent material is a sensitizer, and the OLED further comprises an acceptor. In some embodiments, the phosphorescent emitter and the acceptor both emit light within the OLED.
[0102] In some embodiments, the fluorescence material or the delayed fluorescence material is an emitter which emits light within the OLED. In some embodiments, the fluorescence material or the delayed fluorescence material does not emit light within the OLED. In some embodiments, the fluorescence material or the delayed fluorescence material energy transfers its excited state to another material within the OLED. In some embodiments, the fluorescence material or the delayed fluorescence material participates in charge transport within the OLED. In some embodiments, the fluorescence material or the delayed fluorescence material is a sensitizer, and the OLED further comprises an acceptor.
HBL:
[0103] A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies and/or longer lifetime as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and or higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and or higher triplet energy than one or more of the hosts closest to the HBL interface.
ETL:
[0104] An electron transport layer (ETL) may include a material capable of transporting electrons. The electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.
Charge Generation Layer (CGL)
[0105] In tandem or stacked OLEDs, the CGL plays an essential role in the performance, which is composed of an n-doped layer and a p-doped layer for injection of electrons and holes, respectively. Electrons and holes are supplied from the CGL and electrodes. The consumed electrons and holes in the CGL are refilled by the electrons and holes injected from the cathode and anode, respectively; then, the bipolar currents reach a steady state gradually. Typical CGL materials include n and p conductivity dopants used in the transport layers.
[0106] Organic light emitting devices (OLEDs) are becoming widely adopted in display and other light-generating applications. However, the devices fundamentally face several challenges, including maximizing the number of photons that are coupled into free space, and enhancing stability and efficiency for light emitting devices, particularly blue light emitting devices. Typical OLED device, that are top or bottom emitting, utilize at least one electrode that also functions as a mirror. This electrode reflects light so that the device emits only from a single side, maximizing the efficiency of light that can be collected. However, since the electrode is metallic, the emitters in the emissive layer of the OLED can couple to the electrode and generate surface plasmons. These surface plasmons have a large in-plane momentum and cannot be directly recovered to photons in free space, leading to a lowering of the efficiency of the OLED. Embodiments of the disclosed subject matter may include low-loss OLEDs which utilize the Mie scattering of nanoparticles to outcouple the light and nonmetallic electrodes to avoid the losses associated with metallic electrodes. In some embodiments, these devices have increased efficiency over that of typical devices which have a metal-based electrode. In some embodiments, the overall efficiency of the device may be similar or lower than metal-based OLEDs, but angular dependence and/or emission shape may be improved when compared to OLEDs containing a metal electrode.
[0107] Embodiments of the disclosed subject matter provide low-loss OLEDs, which utilizes high-refractive index dielectric particles to outcouple the EL (electroluminescence) emission from the OLEDs. The low-loss OLEDs may provide enhanced external quantum efficiency (EQE) for both horizontal and vertical aligned dipoles. In some embodiments, the OLEDs may have minimal Purcell enhancement. However, the device may be driven at lower current and thereby increase the overall device stability even without a Purcell enhancement. In some embodiments, to reduce the ohmic loses due to metal electrodes, non-metallic electrodes or multilayer stack with thin layers of metallic and nonmetallic conducting layers may be used for the electrodes. An array of high-index, low loss dielectric particles disposed on one or both transparent conducting electrodes may be used to outcouple the emissive layer of the OLED from the device.
[0108] In some embodiments, the electrodes may be a thin layer of indium tin oxide (ITO), fluorine doped tin oxide (FTO), indium doped zinc oxide (IZO), Aluminum Zinc Oxide (AZO), indium-doped cadmium oxide, barium stannate, carbon nanotubes, graphene, multilayer graphene, single layer graphene, graphene oxide, metallic nano particle or nanowire impregnated materials, as well as conductive polymers such as polyacetylene, polypyrrole, polyindole, polyaniline, Poly(p-phenylene vinylene), poly(3-alkylthiophenes), (poly(3,4-ethylenedioxythiophene)), and the like.
[0109] In some embodiments, a composite material that may include one or more polymers, oxide materials, carbon-based compounds, and the like with nano-sized metallic particles or nano wires may be used as the electrode. In some embodiments, the electrodes may include a plurality of layers of conducting materials (e.g., such as those described above), or without a thin metallic layer. In some embodiments, when a metallic layer is used in the electrode the EML layer will be placed at least 75 nm away from the metal layer to minimize the plasmon loss owing to the excitation of plasmon modes. In some embodiments, the thickness of the metallic layer may be at least 2 nm but not more than 10 nm to ensure light transmission through the electrode. The total thickness of the transparent conducting electrode may be between 10 to 200 nm, and more preferably between to less than 50 nm.
[0110]
[0111] As used throughout, in-plane may be defined as a plane horizontal to the substrate, and/or any other layer that is disposed horizontally on the substrate. As used throughout, out-of-plane may be defined as a plane perpendicular to the substrate, and/or any other layer that is disposed horizontally on the substrate.
[0112] In an embodiment where there is an array in the vertical direction, there may be a dielectric layer between multiple nanoparticle layers. The dielectric layer may not be needed in the arrangement shown in
[0113] In an embodiment, the bottom of the nanoparticle layer to the top of the emissive layer is not more than 50 nm. In an embodiment, this 50 nm distance may include a dielectric gap directly underneath the nanoparticle layer. In an embodiment, nanoparticles in the nanoparticle layer may sit almost directly on top of the layer below the nanoparticle layer, for example on top of an emissive layer. In an embodiment, nanoparticle in the nanoparticle layer may sit on top of a dielectric gap, as noted above.
[0114]
[0115] Each nanoparticle may be at least 50 nm, at least 150 nm, at least 300 nm, and/or at least 500 nm in distance for the largest out-of-plane direction. As shown in
[0116] In a first embodiment, the shortest edge-to-edge spacing may be a horizontal in-plane distance between to any adjacent nanoparticle. In the first embodiment, this distance (i.e., distance B as shown in
[0117] In a second embodiment, the shortest edge-to-edge spacing may be a distance to any adjacent nanoparticle in any plane. In the second embodiment, this distance (i.e., distance A as shown in
[0118]
[0119] Each nanoparticle may be at least 50 nm, at least 150 nm, at least 300 nm, and/or at least 500 nm in distance for the largest out-of-plane direction. As shown in
[0120] A center-to-center interparticle spacing of the first plurality of nanoparticles in any ordered direction may be less than 300 nm, less than 400 nm, less than 500 nm, and/or less than 600 nm. As shown in
[0121] When nanoparticles are manufactured, it is well known and understood that each nanoparticle is not identical and there are manufacturing variances between individual nanoparticles. For example, nanoparticle spheres may be produced that have an average diameter of 100 nm with a standard deviation 5 nm. In this example, the coefficient of variation is 5%. In another example, nanoparticle cubes may be produced that an average length of each side of 100 nm with a standard deviation of 5 nm. In this example, the coefficient of variation is 5%. In an embodiment, any distance of a nanoparticle may be used to define the nanoparticle. For example, radius or diameter of a sphere, height of a cone, side of a cube, length of a rectangle, width of a rectangle, and the like.
[0122] In an embodiment, a first nanoparticle is sized differently from a second nanoparticle when the average size of the first particle is different than one standard deviation of the average size of the second particle. In an alternative embodiment, a first nanoparticle is sized differently from a second nanoparticle when the average size of the first particle is different than two standard deviation of the average size of the second particle. In yet another alternative embodiment, a first nanoparticle is sized differently from a second nanoparticle when the average size of the first particle is different than any number of standard deviation of the average size of the second particle.
[0123] In an embodiment, a first nanoparticle is sized differently from a second nanoparticle when the average size of the first particle is different than one coefficient of variation of the average size of the second particle. In an alternative embodiment, a first nanoparticle is sized differently from a second nanoparticle when the average size of the first particle is different than two coefficient of variation of the average size of the second particle. In yet another alternative embodiment, a first nanoparticle is sized differently from a second nanoparticle when the average size of the first particle is different than any number of coefficient of variation of the average size of the second particle.
[0124] Similarly, when nanoparticles are manufactured, it is well known and understood that each nanoparticle shape is not identical and there are manufacturing variances between individual nanoparticles. Therefore, while all nanoparticles may be a sphere, for example, they are not all identical spheres, and there may be a difference sphericity between one or more of the nanoparticles. Similarly, while all nanoparticles may be a cone, for example, they are not all identical cones, and there may be a different conicity between one or more conical nanoparticles. There may be one or remnant and/or waste particles that may be distributed amongst a layer of nanoparticles that result from the forming of the nanoparticles. For example, there may be remnant and/or waste particles that are differently sized and/or shaped that are distributed amongs a layer, matrix, and/or other arrangement of spherical nanoparticles. In an embodiment, a first nanoparticle is a different shape nanoparticle than a second nanoparticle when the devices disclosed herein perform differently utilizing the first nanoparticle versus the second nanoparticle.
[0125] In an embodiment, the layers may be stacked so at least a portion of a nanoparticle in the top layer is above a corresponding nanoparticle in the bottom layer. In an embodiment, the layers may be stacked so the nanoparticle in the top layer is offset from a corresponding nanoparticle in the bottom layer (i.e., having no overlap).
[0126]
[0127] The EQE enhancement may depend on the scattering efficiency of the dielectric particles. Unlike the metal particles, where the excitations are mostly electric resonances, the dielectric particles may excite both electric and magnetic mode resonances. This may provide efficient control over the light scattering, and may optimize the intensity in a forward or backward direction, and/or in steering the beam in arbitrary direction. Since the radiation of the dipole emitters may be affected by the surrounding medium, an enhancement in the Purcell factor may be expected with the dielectric nanoparticle as the outcoupling layer.
[0128] The scattering efficiency of the dielectric particles may depend on the particle size, shape, and/or the material refractive index. For particle size comparable to the wavelength of the light, the scattering efficiency may be estimated based on Mie's theory. The enhanced light outcoupling may be achieved by direct coupling of EL emission (i.e., emission by the emissive layer (EL)) to the Mie scattering modes of the nanoparticles. To enable strong coupling of EL emission to the Mie scattering modes of the nanoparticles, the EML layer may be disposed closer to the outcoupling layer such that distance from the top of the EML layer to the bottom of the outcoupling layer is within 1/10 of the peak emission wavelength of the emitter. In some embodiments, coupling between the Mie scattering modes and at least some of the EML layer may occur at longer distances, up to of the peak emission wavelength of the emitter. One difference between at least some embodiments of the disclosed subject matter and other OLEDs containing dielectric nanoparticles is the direct coupling of the emitters in the EML to the Mie modes of the dielectric particles. In OLEDs using dielectric nanoparticles without direct coupling to the Mie modes, the emitter first generates or emits a photon which later is scattered by the Mie modes of the dielectric nanoparticles. Conversely, in embodiments of the disclosed subject matter, the emission event of the photon from the emitter involves the Mie mode of the particles directly. For this reason, proximity between the EML and the dielectric nanoparticles is preferred. Since the scattering efficiency increases with refractive index, materials with high index of refraction are preferred. Additionally, materials with lower light absorption in the visible region may be used. Some high index materials, which may be used for preparing the nano-sized particles may include silicon, silicon nitride, boron nitride, silicon carbide, carbon, diamond, zinc sulfide, zinc selenide, germanium, zinc telluride, potassium niobate, titanium oxide, antimony oxide, niobium pentoxide, tantalum pentoxide, vanadium oxide, vanadium pentoxide, gallium phosphate, bismuth oxide, gallium arsenide, and/or aluminum gallium.
[0129] Arbitrary-shaped particles with preferred spectral characteristics in single or multiparticle configurations such as dimers, trimers, and the like as shown in
[0130] To demonstrate the enhancement in the outcoupling efficiency of the proposed low-loss OLEDs, the EQEs of OLED devices were simulated using single or multiple dielectric particles of different shapes and sizes for outcoupling. The simulations were performed by finite difference time domain (FDTD) method using Ansys Lumerical FDTD solutions. Different layers of the OLED devices were rendered into a computational volume of 4 m4 m1 m by their refractive index values and were enclosed within the perfectly matched layers (PML) in all directions to match the open boundary conditions. A single dipole emitter in vertical or horizonal orientation with broad emission spectrum covering the entire visible region (450-750 nm), placed 20 nm away from a 50 nm thick ITO electrode that acts as the emissive layer. That is, the simulations were performed with a 70 nm distance between the emissive layer and the nanoparticles. We used a 75 nm thick non absorbing dielectric layer with refractive index of 1.7 to model the host medium. The simulations were performed with and without high index particles above the ITO layer. The light emission in the far field were recorded using two power monitors placed 300 nm above the particle and 250 nm below the bottom of the OLED stack, which were used to calculate the top emission (TE) and bottom emission (BE) EQEs of the device respectively. The computational volume was discretized with a non-uniform index adjusted rectangular mesh with a resolution of 34 mesh cells per wavelength. Additionally, a mesh override region with 1 nm resolution was used for high index dielectric particles to minimize the computational error. The Purcell enhancement was estimated by calculating the power emitter by the dipole using a box of monitors surrounding the emitter normalized to the free space emission power.
[0131]
[0132] Additionally, the scattering properties can be further modified by assembling multiple particles in the form of dimers, trimers etc. as illustrated in
[0133]
[0134] That is, the plots in
[0135]
[0136]
[0137] The simulation results shown in
[0138]
[0139] In some embodiments, a periodic array of high index dielectric particles may be used as the outcoupling layer as shown in
[0140] In some embodiments, the periodic structures of dielectric materials will be fabricated on the electrode layer, example of
[0141] In some embodiments, periodic arrays of dielectric particles with tapered ends may be used, as shown in
[0142] The arrays of high index particles on electrodes may be prepared by the various top-down and bottom-up approaches such as lithography-based techniques, multi photon absorption photopolymerization of the resins with or without nanoparticle inclusions using a focused laser beam, nanosphere lithography, directed self-assembly based methods using particles prepared by chemical synthesis or photopolymerization, or the like.
[0143] In some embodiments, a thin layer of high index material may be placed on the electrode layer. In some embodiments, the device may have a thin transparent layer on top of the nanoparticle layer. In some embodiments, the dielectric particle arrays may be fabricated on the second electrode. A first or second layer may be disposed on top of the nanoparticle outcoupling layer in some embodiments. The nanoparticle outcoupling layer may be formed by first forming a thin film and then utilizing subtractive etching methods to form the nanoparticles. In other embodiments, the nanoparticles may be formed through another synthesis method and then deposited on the substrate. The nanoparticles are formed on the OLED substrate by physical vapor deposition in some embodiments.
[0144] In some embodiments, the device may have a first side and a second side, and the emission of light may come from the first side of the device. In some embodiments, a highly reflective layer may be placed on the second side of the device to direct the emission to the first side of the device. The first electrode may be replaced with a thick metal layer to reflect the light to the first side of the device, with the emissive layer dispose at least 75 nm from the metallic electrode to minimize the metallic loss according to embodiments of the disclosed subject matter. The thickness of the metal layer may be at least 50 nm, and preferably about 200 nm to ensure near unity reflectivity from the layer. In some embodiments, a distributed Bragg reflector (DBR) stack may be used to reflect the light from the second side of the device. The DBR stack may have at least 2-3 pairs of layers, more preferably 10 pairs of layers, and preferably not more than 20 pairs of layer due to the time required to manufacture the DBR. The number of pairs may depend on the refractive index difference between high and low index material layers. In some embodiments, the transparent electrode layer may be deposited directly to the emissive layer to enhance the Purcell or the efficiency of the device.
[0145] In some embodiments, the refractive index of the nanofeatures responsible for outcoupling is at least 1.9, more preferably at least 2.1, and most preferably more than 2.5. In some embodiments, the nanoparticles may be composed of materials that have minimal absorption in the spectral range of outcoupling. This may prevent any loss due to absorption when the nanoparticle scatters energy out of the OLED. In some embodiments, the absorption of the nanoparticle may be tuned to a specific value which may modify the electric and magnetic dipolar resonances and change their relationship at various wavelengths of emission.
[0146] In some embodiments, the high dielectric nanoparticle outcoupling layer may be adjacent to a metallic electrode. The high dielectric nanoparticle outcoupling layer may be adjacent to the electrode, and the nanoparticles are arranged to dimers, trimers, or higher-level units in some embodiments. For all the embodiments described above, the overall thickness of the OLED stack having a plurality of layers may range between 50-600 nm. The thickness of the emissive layer may be at least 0.2 nm and not more than 75 nm, and may located preferably not more than 500 nm from the transparent electrode on which the nanoparticles forming the outcoupling layer will be fabricated. The nanoparticles may be disposed on the second electrode, which may be the transparent electrode. More preferably, the emissive layer may be within 10-200 nm from the transparent electrode on which the nanoparticles forming the outcoupling layer will be fabricated. The dimensions of the particles in-plane to the transparent electrode may range between 200-800 nm, and more preferably within 400-600 nm. The out-of-plane dimensions of the particle may range between 25-600 nm, and more preferably within 75-200 nm.
[0147] In some of the embodiments described above in connection with
[0148] The organic emissive layer of the device may have a thickness that is at least 0.2 nm, but not more than 75 nm. In some embodiments, the organic emissive layer of the device is disposed from the second electrode by at least 10 nm, at least 100 nm, at least 300 nm, and/or at least 600 nm. The OLED may be a stack having a plurality of layers, and a thickness of the stack is 50-600 nm.
[0149] The first plurality of nanoparticles of the nanoparticle layer of the device may be disposed in an outcoupling layer disposed over the second electrode. In some embodiments, at least some of the nanoparticles of the device may be integrated with the second electrode. The arrangement of the nanoparticles in the nanoparticle layer of the device may result in an external quantum efficiency (EQE) of at least 15%. The nanoparticles of the nanoparticle layer may include at least one nanoparticle having a Mie scattering efficiency of 2-8 based. The Mie scattering efficiency value may be based on a size of the nanoparticles, a shape of the nanoparticles, and/or a material refractive index of the nanoparticles. For example, a refractive index of the first plurality of nanoparticles may be at least 1.9, at least 2.1, at least 2.5, and/or less than 3.5. The arrangement of the first plurality of nanoparticles may result in an external quantum efficiency (EQE) of at least 30%, of at least 50% or the like.
[0150] The nanoparticles of the nanoparticle layer may include silicon, silicon nitride, boron nitride, silicon carbide, carbon, diamond, zinc sulfide, zinc selenide, germanium, zinc telluride, potassium niobate, titanium oxide, antimony oxide, niobium pentoxide, tantalum pentoxide, vanadium oxide, vanadium pentoxide, gallium phosphate, bismuth oxide, gallium arsenide, and/or aluminum gallium. The dielectric material of the first plurality of nanoparticles may absorb not more than 50% of the light energy in a spectral range of outcoupling. In some embodiments, the dielectric material of the first plurality of nanoparticles may absorb not more than 20% of the light energy in a spectral range of outcoupling.
[0151] The first plurality of nanoparticles may have a single configuration or may have multiparticle configurations. For example, the multiparticle configurations may include dimers, trimers, and/or higher-level units (e.g., units that include a pluarlity of levels). The nanoparticles in these arrangements may be configured to output a non-Lambertian emission. The device may be configured to emit at least 60%, at least 70%, and/or at least 80% of the light through one side of the device side where the nanoparticles are disposed.
[0152] The nanoparticles of the device may include two or more materials, each having materials of a different refractive index, that are homogeneously or inhomogeneously distributed within the outcoupling layer, where at least one of the two or more materials creates the difference of at least 1.0 between the refractive index of the at least one of the two or more materials and the surrounding medium. The nanoparticles may be shaped as a cube, a cylinder, a sphere, a spheroid, a parallelopiped shape, a rod-shape, a star-shape, a pyramidal shape, an amorphous shape, and/or a multi-faceted three-dimensional object. There may be differences between at least two of the first plurality of nanoparticles. These differences may include sizes, shapes, and/or indices of refraction.
[0153] The nanoparticles of the device may be configured in a periodic array, such as shown in
[0154] The device may include a second plurality of nanoparticles having a dielectric material that is disposed over the first plurality of nanoparticles that are disposed over the second electrode. A first layer may be disposed over the first plurality of nanoparticles, and a second layer disposed over the second plurality of nanoparticles.
[0155] The device may include a transparent layer disposed on the first plurality of nanoparticles. The transparent layer may be a layer that allows at least 50%, at least 70%, at least 80%, and/or at least 90% of light emitted from an emissive layer of the OLED to pass through. The transparent layer may include a dielectric material having a refractive index less than 1.2, less than 1.5, less than 2, less than 2.5, and/or less than 3. The effective refractive index of the transparent layer may be less than the ranges detailed here, as the layer thickness can be less than the particle height, and the index difference of 1 with particle material may still be satisfied.
[0156] The device may include a transparent dielectric layer, which may have a thickness at least 2 nm but not more than 50 nm minus a thickness of the electrode. The transparent dielectric layer may be disposed between the second electrode and the nanoparticle layer. A refractive index of the dielectric material may be less than 1.2, less than 1.5, less than 2, and/or less than 2.5.
[0157] The device may have a first side and a second side. The first electrode may include a reflective metal layer to reflect light to the first side of the device. The second electrode may be a transparent layer, and the nanoparticle layer is disposed over the transparent layer. The organic emissive layer may be disposed at least 75 nm from the reflective metal layer. A thickness of the reflective metal layer may be at least 50 nm, at least 100 nm, at least 150 nm, at least 200 nm, and/or less than 300 nm. In some embodiments, light may be emitted from both the first side and the second side. A thickness of the second electrode may be 10-20 nm, 20-50 nm, and/or 50-100 nm.
[0158] The device may include a reflective layer and/or partially reflective layer disposed on the first side or the second side of the device to direct emission of light from the device. The partially reflective or reflective layer may have a reflectivity of at least 40%, at least 50%, at least 70%, and/or at least 90%.
[0159] The device may include a distributed Bragg reflector (DBR) stack disposed to reflect light from a second side of the device. The substrate may have a first side and a second side, and the DBR stack may be disposed on the first side and/or the second side of the substrate. An OLED stack may be disposed on the first side of the substrate. In some embodiments, the DBR may be disposed on the first side of the substrate, and the OLED may be disposed on the DBR. The DBR stack may include at least 2 pair of layers, at least three pairs of layer, at least 5 pairs of layers, at least 10 pairs of layers, and/or not more than 20 pairs of layers. The number of pairs of layers may be based on a refractive index difference between a first index material layer and a second index material layer. The first index material and second index material may form a pair. The first index material may be made of one material type with particular index value and second index material will be made of different material with index value different from first index material. The first index material layer may be a high index of at least 1.6, at least 2, at least 2.3, and/or less than 3.5, and the second material index layer may be a low index of less than 1.2, and/or less than 1.6.
[0160] The first electrode and/or the second electrode may be a transparent electrode, where the nanoparticles may be disposed on the second electrode. An in-plane dimension of the nanoparticles may be 200-400 nm, 400-600 nm, and/or 600-800 nm, where the in-plane dimension is in a plane that is horizontal to the substrate. A distance in an out-of-plane dimension between the nanoparticles may be 25-75 nm, 75-200 nm, 200-400 nm, and/or 400-600 nm, where the out-of-plane dimension is in a plane perpendicular to the substrate.
[0161] An in-plane dimension of the nanoparticles may be between 200-400 nm, 400-600 nm, and/or 600-800 nm, where the in-plane dimension is in a plane that is horizontal to the substrate. A distance of an out-of-plane dimension between the nanoparticles may be 25-75 nm, 75-200 nm, 200-400 nm, and/or 400-600 nm, where the out-of-plane dimension is in a plane perpendicular to the substrate.
[0162] The first electrode and/or the second electrode of the device may include indium tin oxide, fluorine doped tin oxide, indium doped zinc oxide, Aluminum Zinc Oxide, indium-doped cadmium oxide, barium stannate, carbon nanotubes, graphene, multilayer graphene, single layer graphene, graphene oxide, metallic nano particle or nanowire impregnated materials, as well as conductive polymers such as polyacetylene, polypyrrole, polyindole, polyaniline, Poly(p-phenylene vinylene), and/or poly(3-alkylthiophenes), (poly(3,4-ethylenedioxythiophene)).
[0163] The first electrode and/or the second electrode of the device may include polymers, oxide materials, nano-sized metallic nanoparticles, and/or metal nanowires. The first electrode and/or the second electrode may include a multilayer that is indium tin oxide, fluorine doped tin oxide, indium doped zinc oxide, aluminum zinc oxide, indium-doped cadmium oxide, barium stannate, carbon nanotubes, graphene, multilayer graphene, single layer graphene, graphene oxide, metallic nanoparticle or nanowire impregnated materials, polyacetylene, polypyrrole, polyindole, polyaniline, Poly(p-phenylene vinylene), and/or poly(3-alkylthiophenes), (poly(3,4-ethylenedioxythiophene)). The first electrode and/or the second electrode may include a metal layer having a thickness of 2-5 nm and/or 6-10 nm. The organic emissive layer may be disposed at least 75 nm from the metal layer.
[0164] The second electrode of the device may be a metallic electrode, and the nanoparticle layer may be disposed over the metallic electrode. The first plurality of nanoparticles of the nanoparticle layer may be configured as dimers, trimers, and/or a plurality of levels of units to be configured to output a non-Lambertian emission. The organic emissive layer of the device may a first surface positioned over a second surface, the metallic electrode of the device may have a first surface positioned over a second surface, and the distance from the first surface of the organic emissive layer to a second surface of the metallic electrode is at least one selected from the group consisting of: less than 10 nm, less than 15 nm, less than 20 nm, less than 30 nm, and less than 40 nm. The metallic electrode of the device may have one or more metallic layers of silver, one or more metallic layers of aluminum, and/or one or more metallic layers of gold. A distance between the first surface and the second surface of the metallic electrode may be less than 20 nm, less than 30 nm, and/or less than 50 nm. The organic emissive layer may have a thickness that is less than 1 nm, less than 2 nm, less than 5 nm, and/or less than 10 nm. The organic emissive layer of the device may have a first surface positioned over a second surface, the metallic electrode of the device may have a first surface positioned over a second surface, and a distance from the first surface of the organic emissive layer to the second surface of the nanoparticle layer may be at least 20 nm, at least 30 nm, at least 40 nm, and/or at least 50 nm. A dielectric layer may be disposed between the metallic electrode and the nanoparticle layer that has a thickness that is less than 10 nm, less than 5 nm, and/or at least 2 nm. A refractive index of the dielectric layer may be at least 1.5, at least 1.75, at least 2, at least 2.5, and/or greater than 2.5.
[0165] In this mode of light outcoupling, the emitter may couple to the surface plasmon modes of the metallic electrode and the light may be outcoupled through the hybrid plasmonic dielectric modes. For efficient coupling of the emissive layer (EL) to the surface plasmon modes of the electrodes, the emissive layer may be disposed closer to the metallic electrode. The distance from the top of the emissive layer (e.g., the first surface of the emissive layer) to the bottom of the metallic electrode may be less than 10 nm, less than 15 nm, less than 20 nm, less than 30 nm and/or less than 40 nm. Metallic layers of silver, aluminum, or gold having a thickness less than 20 nm, less than 30 nm or less than 50 nm may be used as metallic electrodes. The emissive layer may have a thickness less than 1 nm, less than 2 nm, less than 5 nm and/or less than 10 nm. The distance from the top of the emissive layer (e.g., the first surface of the emissive layer) to the bottom of the nanoparticle layer (e.g., the second surface of the nanoparticle layer) may be at least 20 nm, at least 30 nm, at least 40 nm, or at least 50 nm. In some embodiments, a dielectric layer having a thickness that is less than 10 nm, less than 5 nm, or at least 2 nm may be disposed between the metallic electrode and nano particle layer. The refractive index of dielectric layer may be at least 1.5, at least 1.75, at least 2, at least 2.5, or greater than 2.5.
[0166] The substrate of the device may be a transparent material. The device may have a first side and a second side, where the first and second electrode are transparent, and light is output from the first and second sides of the device.
[0167] According to an embodiment, a consumer electronic device may include a device may include an organic light emitting device (OLED) having a substrate, a first electrode disposed over the substrate, a second electrode disposed over the first electrode, and an organic emissive layer disposed between the first electrode and the second electrode, where the organic emissive layer may have a first surface positioned over a second surface. A nanoparticle layer may be disposed over the organic emissive layer, and the nanoparticle layer may have a first surface that is positioned over a second surface. The nanoparticle layer may include a plurality of nanoparticles comprising a dielectric material, and a surrounding medium. A distance from the second surface of the nanoparticle layer to the first surface of the organic emissive layer may not be more than 50 nm, and there may be a difference of at least 1.0 between a refractive index of the dielectric material and the surrounding medium.
[0168] The device may be a flat panel display, a curved display, a computer monitor, a medical monitor, a television, a billboard, a light for interior or exterior illumination and/or signaling, a heads-up display, a fully or partially transparent display, a flexible display, a rollable display, a foldable display, a stretchable display, a laser printer, a telephone, a cell phone, tablet, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a micro-display that is less than 2 inches diagonal, a 3-D display, a virtual reality or augmented reality display, a vehicle, an automotive display, video walls comprising multiple displays tiled together, a theater or stadium screen, and a sign.
[0169] In some embodiments, a device may include an organic light emitting device (OLED) having a substrate, a first electrode disposed over the substrate, a second electrode disposed over the first electrode, and an organic emissive layer disposed between the first electrode and the second electrode. The organic emissive layer may have a first surface positioned over a second surface, and the nanoparticle layer may have a first surface that is positioned over a second surface. A nanoparticle layer may be disposed over the organic emissive layer. The nanoparticle layer may include a plurality of nanoparticles comprising a dielectric material, and a surrounding medium. The organic emissive layer may directly couple to the Mie scattering modes of the plurality of nanoparticles. A distance from the second surface of the nanoparticle layer to the first surface of the organic emissive layer may be not more than , not more than , and/or not more than 1/10 of a peak emission wavelength capable of being emitted by the organic emissive layer. Direct coupling may include coupling to the grating modes of the nanoparticle lattices for the ordered nanoparticle arrays, and the like.
[0170] It is understood that the various embodiments described herein are by way of example only, and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. The present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting.