Patent Application
20120223635
1. Field of the Invention
Some embodiments relate to porous films, such as porous films for use in devices, such as light-emitting devices.
2. Description of the Related Art
Organic light-emitting devices (OLED) may be useful for incorporating into energy-efficient lighting equipment or devices. Unfortunately, the efficiency of OLEDs may be limited by both any inherent inefficiency in producing emitted light, and in the ability of emitted light to escape the device to provide lighting. The inability of emitted light to escape the device may also be referred to as trapping. Because of trapping, the efficiency of a device may be reduced to about 10-30% of the emissive efficiency. Light extraction may reduce trapping and thus substantially improve efficiency.
Some embodiments may include a porous film. A porous film may comprise: a non-polymeric organic compound having a refractive index in the range of about 1.1 to about 1.8; a plurality of irregularly arranged nanoprotrusions, nanoparticles, or aggregates thereof; and/or a plurality of voids having a total volume that is at least about 50% of the volume of the film, and at least about 10% of the plurality of voids have a longest dimension in the range of about 0.5 μm to about 5 μm. The porous film may have a thickness in the range of about 500 nm to about 20 microns; and/or the density of the porous film including the voids may be about 0.5 picograms/μm3 or less.
Some embodiments may include light-emitting device comprising: a porous film that may comprise: a first interface with a partially internally reflective layer in the light-emitting device, wherein a refractive index of the partially internally reflective layer may be higher than a refractive index of the porous film; a second interface with a substance that may have a refractive index that is lower than the refractive index of the porous film; and wherein the second interface may comprise a plurality of irregularly arranged nanoprotrusions or nanoparticles.
Some embodiments may include a light-emitting device comprising: a porous film that may be disposed over an anode or a cathode; wherein the porous film may have a refractive index that is lower than a refractive index of the anode and a refractive index of the cathode.
Some embodiments include a light-emitting device comprising: a light-emitting diode that may comprise: an anode; a cathode; an emissive layer that may be disposed between the anode and the cathode; and a porous film; wherein the porous film may be disposed on the anode or the cathode; or the light-emitting device may further comprises a transparent layer disposed between the anode and the porous film, or between the cathode and the porous film.
In some embodiments, the porous film may be prepared by a process comprising depositing an organic film; and heating the organic film at a temperature in the range of about 100° C. to about 290° C.
Some embodiments may include a light-emitting device comprising: a light-emitting diode comprising an porous film; wherein the porous film is disposed on an internally reflective layer selected from the group consisting of: an anode; a cathode; a transparent layer disposed between the anode and the porous film, or a transparent layer disposed between the cathode and the porous film; wherein a refractive index of the internally reflective layer is higher than a refractive index of the porous film; wherein the porous film may comprise a compound described herein.
These and other embodiments are described in detail herein.
The porous films described herein may be useful in a variety of devices involving the transmission of light from one layer to another, such as light-emitting diodes, photovoltaics, detectors, etc. In some embodiments, a porous film may provide efficient light outcoupling for organic light-emitting diodes for uses such as lighting. With some devices, light extraction from a substrate close to 90%, or possibly greater, may be achieved. The porous films may provide easy processing and potentially low cost improvement in device efficiency.
In some embodiments, the porous films described herein may improve efficiency of a device by reducing the amount of total internal reflection in a layer of the device. Total internal reflection may be a significant cause of trapping. When light passes from a high refractive index material to a low refractive index material, the light may be bent in a direction away from the normal angle to the interface. If light in a higher refractive index material encounters an interface with a lower refractive index material at an angle which deviates substantially from 90° the bending of the light may be greater than the angle at which the light approaches the interface, so that instead of passing out of the higher refractive index material, the light may be bent back into the higher refractive index material. This may be referred to as total internal reflection. Since air may have a lower refractive index than many materials, many interfaces between a device and air may suffer from loss due to total internal reflection. Furthermore, trapping due to total internal reflection may occur at any interface in a device where the light travels from a higher refractive index layer to a lower refractive index layer. Devices comprising porous films describe herein may have reduced total internal reflection or trapping and thus have improved efficiency.
In some embodiments, a porous film described herein may provide light scattering for a variety of devices that involve light passing from one material to another, including devices that absorb or emit light. Light scattering may be useful in a device to provide viewing angle color consistency, so that the color is substantially similar regardless of the angle from which light is viewed. Devices having no light scattering layer may emit light in such a way that the viewer observes a different color depending upon the angle from which the light is viewed.
In some embodiments, a porous film described herein may also be useful as a filter for a variety of devices that involve light passing from one material to another, including devices that absorb or emit light.
A porous film may include any film comprising a plurality of pores. For example, a porous film may comprise an irregularly oriented intermeshed nanostructure.
In some embodiments a porous film may be deposited on a transparent substrate, which may reduce the total internal reflection of light within the substrate.
In some embodiments, a porous film may comprise a first surface and a second surface, wherein the first surface has a coplanar area that is substantially greater than a coplanar area of the second surface. While “coplanar area” is a broad term, one way to determine the coplanar area of a surface may be to place the surface under consideration on a smooth flat surface, and measure the area of the surface that contacts the smooth flat surface.
A porous film may have a variety of structures. In some embodiments, a porous film may have a surface comprising a plurality of irregularly arranged protrusions, particles, or aggregates thereof. The protrusions or particles may be nanoprotrusions, including nanoprotrusions having one or more dimensions in the nanometer to micron range. For example, nanoprotrusions or nanoparticles may have: an average x dimension of about 400 nm, about 500 nm, about 1000 nm, about 1500 nm, about 2000 nm, about 2500 nm, about 3000 nm, or any value in a range bounded by, or between, any of these lengths; an average y dimension of about 50 nm, about 100 nm, about 300 nm, about 500 nm, about 700 nm, about 1000 nm, about 1200 nm, about 1500 nm, about 1800 nm, about 2000 nm, or any value in a range bounded by, or between, any of these lengths; and/or an average z dimension of about 10 nm, about 30 nm, about 50 nm, about 70 nm, about 90 nm, about 100 nm, or any value in a range bounded by, or between, any of these lengths. In some embodiments, at least one particle in the film, or average of the particles in the film, may have an x dimension, a y dimension, or a z dimension of about 5 nm, about 0.01 μm, about 0.02 μm, about 0.05 μm, about 0.1 μm, about 0.5 μm, about 1 μm, about 2 μm, about 5 μm, about 10 μm, about 20 μm, about 50 μm, about 100 μm, about 150 μm, about 200 μm, about 500 μm, about 1000 μm, or any length bounded by, or between, any of these values. In some embodiments, the nanoprotrusions or nanoparticles may have: an average x dimension in the range of about 400 nm to about 3000 nm, about 1000 nm to about 3000 nm, or about 2000 nm to about 3000 nm; an average y dimension in the range of about 100 nm to about 2000 nm, about 100 nm to about 1500 nm, or about 100 nm to about 1000 nm; and/or an average z dimension of about 10 nm to about 100 nm, about 30 nm to about 90 nm, or about 30 nm to about 70 nm. In some embodiments, at least one particle in the film, or average of the particles in the film, may have an x dimension, a y dimension, or a z dimension in the range of about 5 nm to about 1000 μm, about 0.02 μm to about 1 μm, or about 1 μm to about 200 μm.
In some embodiments, the protrusions, particles, or aggregates thereof may be substantially transparent or substantially translucent.
Although the particles, protrusions, or voids may be irregularly shaped, three dimensions, x, y, and z, may be quantified as depicted in
The three dimensional shapes of the particles or protrusions may be characterized by describing the shape of the particles or protrusions when viewed in a certain plane. For example, a particle or protrusion may be substantially rectangular, substantially square, substantially elliptical, substantially circular, substantially triagonal, substantially parallelogramatic, etc., when viewed in the two dimensions of the xy, xz, or yz plane. The particular shape need not be geometrically perfect, but need only be recognizable as reasonably similar to a known shape. The three dimensional shape of the particles or protrusions might also be characterized or described using other terms.
With respect to
The particle 210 may also be described as a nanoflake. The term “nanoflake” is a broad term that includes particles that are flake-like in shape and have any dimension in the nanometer to micrometer range. This may include particles that are relatively thin in one dimension (e.g. z) and have a relatively large area in another two dimensions (e.g. xy).
The larger area surface need only be identifiable, but does not need to be planar. For example, the larger area surface may be substantially in the xy plane, such as particle 210, but may also be curved or wavy, such that substantial portions of the surface are not in the plane.
The particle 210 may also be described as pseudoplanar. The term “pseudoplanar” is a broad term that includes particles that are essentially planar. For example, a pseudoplanar particle may have a z dimension that is relatively insignificant as compared to the xy area of the particle that is substantially in the xy plane.
In
With respect to any nanoflake or pseudoplanar particle or protrusion, including particle 210, particle 250, and the like, the ratio of the square root of the larger area or surface to a smallest dimension or a thickness normal to a point on the large surface (such as the ratio of the square root of an xy area to a z dimension), may be: about 3, about 5, about 10, about 20, about 100, about 1000, about 10,000, about 100,000, or any value in a range bounded by, or between, any of these ratios. In some embodiments, the ratio of the square root of the larger area or surface to a smallest dimension or a thickness normal to a point on the large surface may be about 3 to about 100,000, about 5 to about 1000, or about 1000 to about 10,000.
The outer edges of the particle may consist essentially of a plurality of linear edge portions.
Pseudo-parallelogramatic particles may have substantially right angles such as those depicted in
A particle or protrusion may be described as needlelike if it has a shape that is reasonably recognizable as similar to a shape of a needle.
A particle or protrusion may be described as fiber-shaped if it has a shape that is reasonably recognizable as similar to a shape of a fiber.
A particle or protrusion may be described as ribbon-shaped if it has a shape that is reasonably recognizable as similar to the shape of a ribbon. This may include particles or protrusions that have a flat rectangular surface that is elongated in one dimension and thin in another dimension. The ribbon shape may also be curved or twisted, so that the particle need not be substantially coplanar to be ribbon-shaped.
A particle or protrusion may be described as rod-shaped if it has a shape that is reasonably recognizable as similar to the shape of a rod. This may include particles or protrusions that are elongated in one dimension. A rod-shaped particle or protrusion may be substantially straight, or have some curvature or bending.
A particle or protrusion may be described as granular if the x, y, and z dimensions are similar, such as within an order of magnitude or one another.
A scale bar of 5 μm is indicated in the SEM, which may provide an indication of the size of the nanoparticles, nanoprotrusions, or voids of the film. This figure shows that a substantial number of particles or voids may have an x, y, and/or z dimension in the range of about 1 μm to about 20 μm. A substantial number of particles may also have a ratio of the square root of the xy area to the z dimension in the range of about 10 to about 100. For example, the particle circled in the figure appears to have a ratio:
of about 40, assuming that the length of the visible edge is about equal to the square root of the area. This method may be used for films such as the one depicted here, where, based upon other nanoflakes visible in the figure, the large area, or the xy area, is about equal to the length of one side viewed in the yz plane. Moreover, at least about 50%, about 70%, or about 90% of the particles on the surface may have a ratio of the square root of the xy area to the z dimension in the range of about 10 to about 1000.
A scale bar of 50 μm is indicated in the SEM of
A scale bar of 100 μm is indicated in the SEM of
A scale bar of 50 μm is indicated in the SEM of
A scale bar of 4 μm is indicated in the SEM of
A scale bar of 100 μm is indicated in the SEM of
A scale bar of 10 μm is indicated in the SEM of
A scale bar of 20 μm is indicated in the SEM of
A scale bar of 5 μm is indicated in the SEM of
A scale bar of 1 μm is indicated in the SEM of
A scale bar of 5 μm is indicated in the SEM of
A scale bar of 1 μm is indicated in the SEM of
A scale bar of 1 μm is indicated in the SEM of
A scale bar of 5 μm is indicated in the SEM of
A scale bar of 30 μm is indicated in the SEM of
A scale bar of 50 μm is indicated in the SEM of
A scale bar of 1 μm is indicated in the SEM of
A scale bar of 500 nm is indicated in the SEM of
A scale bar of 3 μm is indicated in the SEM of
A scale bar of 5 μm is indicated in the SEM of
A scale bar of 2 μm is indicated in the SEM of
A scale bar of 500 nm is indicated in the SEM of
A scale bar of 5 μm is indicated in the SEM of
A scale bar of 50 μm is indicated in the SEM of
A scale bar of 20 μm is indicated in the SEM of
A scale bar of 500 nm is indicated in the SEM of
A scale bar of 1 μm is indicated in the SEM of
A scale bar of 1 μm is indicated in the SEM of
A scale bar of 2 μm is indicated in the SEM of
A scale bar of 1 μm is indicated in the SEM of
A scale bar of 1 μm is indicated in the SEM of
A scale bar of 4 μm is indicated in the SEM of
A scale bar of 4 μm is indicated in the SEM of
A scale bar of 1 μm is indicated in the SEM of
A scale bar of 1 μm is indicated in the SEM of
A scale bar of 10 μm is indicated in the SEM of
A scale bar of 1 μm is indicated in the SEM of
A scale bar of 500 nm is indicated in the SEM of
A scale bar of 1 μm is indicated in the SEM of
A scale bar of 1 μm is indicated in the SEM of
A scale bar of 4 μm is indicated in the SEM of
A scale bar of 5 μm is indicated in the SEM of
A scale bar of 1 μm is indicated in the SEM of
A scale bar of 1 μm is indicated in the SEM of
A scale bar of 5 μm is indicated in the SEM of
A scale bar of 3 μm is indicated in the SEM of
A scale bar of 4 μm is indicated in the SEM of
A scale bar of 3 μm is indicated in the SEM of
A scale bar of 400 nm is indicated in the SEM of
Various shapes and dimensions are recited herein with respect to several examples of images and figures of associated with various examples of porous films. These shapes and dimensions are provided merely to help provide an understanding of the terminology used, and are not intended to be exhaustive descriptions for any particular example or figure. Thus, the omission of any particular term with respect to any particular example or figure does not suggest that the particular term does not apply to the particular example or figure.
In some embodiments, an angle between the plane of the individual nanostructures and the film may be any value between 0 and 90 degrees with equal probability and/or it may be that no particular angle is preferred. In other words, it may be that no particular general alignment or substantial orientation is exhibited by the nanostructures of this film.
The thickness of a porous film may vary. In some embodiments, a porous film may have a thickness in the nanometer to micro range. For example, the thickness of the film may be about 500 nm, about 0.1 μm, about 1 μm, about 1.3 μm, about 3 μm, or about 4 μm, about 5 μm about 7 μm, about 10 μm about 20 μm, about 100 μm, or any thickness in a range bounded by, or between, any of these values. In some embodiments, the thickness of the film may be about 500 nm to about 100 μm, about 0.1 μm to about 10 μm, or about 1 μm to about 5 μm.
A porous film may comprise a number of pores or voids. For example, a porous film may comprises a plurality of voids having a total volume that may be about 50%, about 70%, about 80%; about 85%, about 90%, about 95%, or about 99% of the volume of the film including the voids, or any percentage of total volume in a range bounded by, or between, any of these values. Thus, if the total volume of the voids is 50% of the volume of the film, 50% of the volume of the film is the material of the film and 50% of the volume of the film is the plurality of voids. In some embodiments, the porous film may comprise a plurality of voids having a total volume that may be about 50% to about 99%, about 70% to about 99%, about 80% to about 99%, or about 90% to about 99% of the volume of the film.
In some embodiments, a film may comprises a plurality of voids of a number and size such that the film may have a thickness that is about 2 times, about 10 times; up to about 50 times, or about 100 times, that of the thickness of a film of the same material which has no voids, or any thickness ratio in a range bounded by, or between, any of these values. For example, a film may have a thickness of about 5 μm when a film of the same material would have a thickness of 800 nm if the film had no voids. In some embodiments, the film may have a thickness that is in the range of about 2 times to about 100 times or about 2 to about 10 times that of the thickness of a film of the same material which has no voids.
The size of the voids may vary. The dimensions of a void may be quantified as described above for a particle or protrusion. In some embodiments, at least about 10% of the voids have a largest dimension, or an x dimension, of about 0.5 μm, about 1 μm, about 2 μm, about 3 μm, about 4 μm, about 5 μm, or any length in a range bounded by, or between, any of these values. In some embodiments, at least one void in the film, or an average of the voids in the film, may have an x dimension, a y dimension, or a z dimension of: about 5 nm, about 0.01 μm, about 0.02 μm, about 0.05 μm, about 0.1 μm, about 0.5 μm, about 1 μm, about 2 μm, about 5 μm, about 10 μm, about 20 μm, about 50 μm, about 100 μm, about 150 μm, about 200 μm, about 500 μm, about 1000 μm, or any length bounded by, or between, any of these values. In some embodiments, at least one void in the film, or an average of the voids in the film, may have an x dimension, a y dimension, or a z dimension in the range of about 0.01 μm to about 5 μm, about 0.01 μm to about 1 μm, about 0.01 μm to about 10 μm, about 0.01 μm to about 20 μm, about 0.01 μm to about 5 μm, about 0.02 μm to about 10 μm, about 0.05 μm to about 10 μm, about 0.1 μm to about 10 μm, about 0.1 μm to about 100 μm, about 0.1 μm to about 150 μm, about 0.1 μm to about 20 μm, about 0.1 μm to about 5 μm, about 0.5 μm to about 50 μm, about 1 μm to about 100 μm, about 1 μm to about 20 μm, about 1 μm to about 200 μm, about 1 μm to about 50 μm, about 1 μm to about 500 μm, about 10 μm to about 50 μm, about 10 nm to about 5 μm, about 2 μm to about 100 μm, about 20 μm to about 1000 μm, about 5 nm to about 5 μm, about 50 nm to about 2 μm, or about 50 nm to about 5 μm. The density of a porous film may vary, and may be affected by the voids, the material, and other factors. In some embodiments, the density of the film including the voids may be about 0.005 picograms/μm3, about 0.05 picograms/μm3, about 0.1 picograms/μm3, about 0.3 picograms/m3, about 0.5 picograms/μm3, about 0.7 picograms/μm3, about 0.9 picograms/μm3, or any density in a range bounded by, or between, any of these values. In some embodiments, the including the voids may be in the range of about: about 0.005 picograms/m3 to about 0.9 picograms/μm3, about 0.05 picograms/μm3 to about 0.7 picograms/μm3, or about 0.1 picograms/μm3 to about 0.5 picograms/p m3.
The refractive index of the material of the porous film may vary. In some embodiments, the refractive index of the material of the porous film may be greater than or equal to that of the substrate. In some embodiments, a refractive index of an anode, a refractive index of a cathode, a refractive index of a transparent layer between an anode and a porous layer, and/or a refractive index of a transparent layer between a cathode and a porous layer, may be higher than a refractive index of a porous layer. For example, the refractive index may be about 1.1, about 1.5, about 1.7, about 1.8, or any refractive index in a range bounded by, or between, any of these values. In some embodiments, the refractive index may be in the range of about 1.1 to about 1.8, about 1.1 to about 1.7, or about 1.1 to about 1.5.
In some embodiments, at least 1, at least 50% or at least 90% of the particles, the protrusions, or the voids of a porous film may have an x, y, and/or z dimension in the range of: about 0.01 μm to about 5 μm, about 0.01 μm to about 1 μm, about 0.01 μm to about 10 μm, about 0.01 μm to about 20 μm, about 0.01 μm to about 5 μm, about 0.02 μm to about 10 μm, about 0.05 μm to about 10 μm, about 0.1 μm to about 10 μm, about 0.1 μm to about 100 μm, about 0.1 μm to about 150 μm, about 0.1 μm to about 20 μm, about 0.1 μm to about 5 about 0.5 μm to about 50 μm, about 1 μm to about 100 μm, about 1 μm to about 20 μm, about 1 μm to about 200 μm, about 1 μm to about 50 μm, about 1 μm to about 500 μm, about 10 μm to about 50 μm, about 10 nm to about 5 μm, about 2 μm to about 100 μm, about 20 μm to about 1000 μm, about 5 nm to about 5 μm, about 50 nm to about 2 μm, or about 50 nm to about 5 μm.
A porous film may be prepared by depositing an organic film on a surface, such as a substrate. For example, the deposition may be vapor deposition, which may be carried out under high temperature and/or high vacuum conditions; or the porous film may be deposited by drop casting or spin casting. In some embodiments, the material may be deposited on a substantially transparent substrate. Deposition and/or annealing conditions may affect the characteristics of the film.
The rate of deposition of the material on a surface may vary. For example, the organic film may be deposited at a rate of: about 0.1 Å/sec, about 0.2 Å/sec, about 1 Å/sec, about 10 Å/sec, about 20 Å/sec, about 60 Å/sec, about 100 Å/sec, about 500 Å/sec, about 1000 Å/sec, or any value in a range bounded by, or between, any of these deposition rates. In some embodiments, the organic film may be deposited at a rate in the range of about 0.1 Å/sec to about 1000 Å/sec, about 1 Å/sec to about 100 Å/sec, or about 2 Å/sec to about 60 Å/sec.
The material may be deposited onto a variety of surfaces to form a porous film or an organic film. For some devices, the material may be deposited onto an anode, a cathode, or a transparent layer.
An organic film that has been deposited on a surface may be further treated by heating or annealing. The temperature of heating may vary. For example, an organic film may be heated at a temperature of about 80° C., about 100° C., about 110° C., about 120° C., about 130° C., about 150° C., about 180° C., about 200° C., about 240° C., about 260° C., about 290° C., or any temperature in a range bounded by, or between, any of these values. In some embodiments, an organic film may be heated at a temperature in the range of about 100° C. to about 290° C., about 100° C. to about 260° C., about 80° C. to about 240° C., about 80° C. to about 200° C., about 200° C. to about 260° C., or about 200° C. to about 240° C.
The time of heating may also vary. For example, an organic film may be heated for about 5 minutes, about 15 minutes, about 30 minutes, about 60 minutes, about 2 hours, about 5 hours, about 10 hours, about 20 hours, or any amount of time in a range bounded by, or between, any of these values. In some embodiments, an organic film may be heated from about 5 minutes to about 20 hours, about 4 minutes to about 2 hours, or about 5 minutes to about 30 minutes. In some embodiments, a material may be heated at about 100° C. to about 260° C. for about 5 minutes to about 30 minutes.
A porous film or an organic film may comprise a material that includes a non-polymeric organic compound, and may comprise an optionally substituted aromatic ring. In some embodiments, a porous film or an organic film may comprise at least one of the compounds below:
Other compounds that may be useful in porous films or organic films include any compound described in one of the following documents: U.S. Provisional Application No. 61/221,427, filed Jun. 29, 2009, which is incorporated by reference herein in its entirety; U.S. patent application Ser. No. 12/825,953, filed Jun. 29, 2010, which is incorporated by reference herein its entirety; U.S. Provisional Patent Application No. 61/383,602, filed Sep. 16, 2010, which is incorporated by reference herein in its entirety; U.S. Provisional Application No. 61/426,259, filed Dec. 22, 2010; the U.S. Patent Provisional Application No. 61/449,001, filed on Mar. 3, 2011 under the title SUBSTITUTED BIPYRIDINES FOR USE IN LIGHT-EMITTING DEVICES” by inventor Shijun Zheng, which is incorporated by reference herein in its entirety; and the U.S. Patent Provisional Application No. 61/449,034, filed on Mar. 3, 2011 under the title COMPOUNDS FOR POROUS FILMS IN LIGHT-EMITTING DEVICES” by inventors Shijun Zheng and Jensen Cayas, which is incorporated by reference herein in its entirety.
In some embodiments a porous film may comprise COMPOUND-2 and may have a density of about 80% and/or a thickness greater than about 4 μm. In some embodiments, COMPOUND-2 may be heated at about 110° C. and/or heating may be carried out for about 60 min.
In some embodiments a porous film may comprise COMPOUND-3 and may have a thickness of about 1.3 μm. In some embodiments, COMPOUND-3 may be heated at about 180° C. and/or heating may be carried out for about 15 minutes.
Table 1 below describes the materials and process used to prepare the films depicted in
Generally, a porous film may be deposited on at least part of a surface of a layer in a device to provide an outcoupling or a scattering effect. For outcoupling, a porous film may deposited on at least part of a surface of any partially internally reflective layer, including any layer that may both internally reflect light and allow light to pass through the partially internally reflective layer to an adjacent layer, such as an emissive layer, an anode, a cathode, any transparent layer, etc. In some embodiments, a transparent layer may be disposed between the anode and the film, the cathode and the film, etc.
A light-emitting device comprising a porous film may have a variety of configurations. For example, a light emitting device may include an anode, a cathode and an emissive layer disposed between the anode and cathode.
With respect to the devices described herein, if a first layer is “disposed over” a second layer, the first layer covers at least a portion of the second layer, but optionally allows one or more additional layers to be positioned between the two layers. If a first layer is “disposed on” a second layer, the first layer makes direct contact with at least a portion of the second layer. For simplicity, in any situation where the “disposed over” is used herein, it should be understood to mean “disposed over or disposed on.”
With reference to
The OLED 5410 that is suitable for the devices described above generally comprises an emissive layer 5425 disposed between an anode 5560 and a cathode 5510. Other layers, such as an electron-transport layer, a hole-transport layer, an electron-injection layer, a hole-injection layer, an electron-blocking layer, a hole-blocking layer, additional emissive layers, etc., may be present between the emissive layer 5425, and the anode 5560 and/or the cathode 5510. With reference to
In some embodiments, an outcoupling film or porous layer 5430 described herein may be disposed over the anode 5560 or the cathode 5510, so that light passes through the anode or the cathode, any intervening layers (if present), and through the outcoupling film or porous layer 5430. In some embodiments, a transparent substrate or a glass substrate may be disposed between the anode 5560 and the porous layer 5430, or between the cathode 5510 and the porous layer 5430. In some embodiments, the porous layer 5430 is disposed on the transparent substrate. The transparent substrate is disposed on the anode 5560 if the light is emitted from the OLED through the anode 5560. In other embodiments, the transparent substrate is disposed on the cathode 5510 when the light is emitted from the OLED through the cathode 5510.
In some embodiments, additional layers may be present between the emissive layer 5425 and the anode 5560 or between the emissive layer 5425 and the cathode 5510. With reference to
In some embodiments, the anode may be reflective and the light may be emitted from the cathode 5510 side. With reference to
In some embodiments, the light may be emitted through a transparent anode 5560. With reference to
An anode may be a layer comprising a conventional material such as a metal, a mixed metal, an alloy, a metal oxide or a mixed-metal oxide, a conductive polymer, and/or an inorganic material such as carbon nanotube (CNT). Examples of suitable metals include the Group 1 metals, the metals in Groups 4, 5, 6, and the Group 8-10 transition metals. If the anode layer is to be light-transmitting, metals in Group 10 and 11, such as Au, Pt, and Ag, or alloys thereof; or mixed-metal oxides of Group 12, 13, and 14 metals, such as indium-tin-oxide (ITO), indium-zinc-oxide (IZO), and the like, may be used. In some embodiments, the anode layer may be an organic material such as polyaniline. The use of polyaniline is described in “Flexible light-emitting diodes made from soluble conducting polymer,” Nature, vol. 357, pp. 477-479 (11 Jun. 1992). Examples of suitable high work function metals and metal oxides include but are not limited to Au, Pt, or alloys thereof; ITO; IZO; and the like. In some embodiments, the anode layer can have a thickness in the range of about 1 nm to about 1000 nm.
A cathode may be a layer including a material having a lower work function than the anode layer. Examples of suitable materials for the cathode layer include those selected from alkali metals of Group 1, Group 2 metals, Group 12 metals including rare earth elements, lanthanides and actinides, materials such as aluminum, indium, calcium, barium, samarium and magnesium, and combinations thereof. Li-containing organometallic compounds, LiF, and Li2O may also be deposited between the organic layer and the cathode layer to lower the operating voltage. In some embodiments a cathode may comprise AI, Ag, Mg, Ca, Cu, Mg/Ag, LiF/Al, CsF, CsF/Al or alloys thereof. In some embodiments, the cathode layer can have a thickness in the range of about 1 nm to about 1000 nm.
A transparent electrode may include an anode or a cathode through which some light may pass. In some embodiments, a transparent electrode may have a relative transmittance of about 50%, about 80%, about 90%, about 100%, or any transmittance in a range bounded by, or between, any of these values. In some embodiments, a transparent electrode may have a relative transmittance of about 50% to about 100%, about 80% to about 100%, or about 90% to about 100%.
An emissive layer may be any layer that can emit light. In some embodiments, an emissive layer may comprise an emissive component, and optionally, a host. The device may be configured so that holes can be transferred from the anode to the emissive layer and/or so that electrons can be transferred from the cathode to the emissive layer. If present, the amount of the host in an emissive layer may vary. For example, the host may be about 50%, about 60%, about 90%, about 97%, or about 99% by weight of the emissive layer, or may be any percentage in a range bounded by, or between, any of these values. In some embodiments, the host may be about 50% to about 99%, about 90% to about 99%, or about 97% to about 99% by weight of the emissive layer.
In some embodiments, Compound 10 may be the host in an emissive layer.
The amount of an emissive component in an emissive layer may vary. For example, the emissive component may be about 0.1%, about 1%, about 3%, about 5%, about 10%, or about 100% of the weight of the emissive layer, or may be any percentage in a range bounded by, or between, any of these values. In some embodiments, the emissive layer may be a neat emissive layer, meaning that the emissive component is about 100% by weight of the emissive layer, or alternatively, the emissive layer consists essentially of emissive component. In some embodiments, the emissive component may be about 0.1% to about 10%, about 0.1% to about 3%, or about 1% to about 3% by weight of the emissive layer.
The emissive component may be a fluorescent and/or a phosphorescent compound. In some embodiments, the emissive component comprises a phosphorescent material. Some non-limiting examples of emissive compounds may include: PO-01, bis-{2-[3,5-bis(trifluoromethyl)phenyl]pyridinato-N,C2′}iridium(III)-picolinate, bis(2-[4,6-difluorophenyl]pyridinato-N,C2′)iridium(III)picolinate, bis(2-[4,6-difluorophenyl]pyridinato-N,C2′)iridium(acetylacetonate), Iridium(III)bis(4,6-difluorophenylpyridinato)-3-(trifluoromethyl)-5-(pyridine-2-yl)-1,2,4-triazolate, Iridium(III)bis(4,6-difluorophenylpyridinato)-5-(pyridine-2-yl)-1H-tetrazolate, bis[2-(4,6-difluorophenyl)pyridinato-N,C2′]iridium(III)tetra(1-pyrazolyl)borate, Bis[2-(2′-benzothienyl)-pyridinato-N,C3′]iridium(III)(acetylacetonate); Bis[(2-phenylquinolyl)-N,C2′]iridium(III)(acetylacetonate); Bis[(1-phenylisoquinolinato-N,C2′)]iridium(III)(acetylacetonate); Bis[(dibenzo[f,h]quinoxalino-N,C2′)iridium(III)(acetylacetonate); Tris(2,5-bis-2′-(9′,9′-dihexylfluorene)pyridine)iridium(III); Tris[1-phenylisoquinolinato-N,C2′]iridium(III); Tris-[2-(2′-benzothienyl)-pyridinato-N,C3′]iridium(III); Tris[1-thiophen-2-ylisoquinolinato-N,C3′]iridium(III); and Tris[1-(9,9-dimethyl-9H-fluoren-2-yl)isoquinolinato-(N,C3′)iridium(III)), Bis(2-phenylpyridinato-N,C2′)iridium(III)(acetylacetonate) [Ir(ppy)2(acac)], Bis(2-(4-tolyl)pyridinato-N,C2′)iridium(III)(acetylacetonate) [Ir(mppy)2(acac)], Bis(2-(4-tert-butyl)pyridinato-N,C2′)iridium(III)(acetylacetonate) [Ir(t-Buppy)2(acac)], Tris(2-phenylpyridinato-N,C2′)iridium(III) [Ir(ppy)3], Bis(2-phenyloxazolinato-N,C2′)iridium(III)(acetylacetonate) [Ir(op)2(acac)], Tris(2-(4-tolyl)pyridinato-N,C2′)iridium(III) [Ir(mppy)3], Bis[2-phenylbenzothiazolato-N,C2′]iridium(III)(acetylacetonate), Bis[2-(4-tert-butylphenyl)benzothiazolato-N,C2′]Iridium(III)(acetylacetonate), Bis[(2-(2′-thienyl)pyridinato-N,C3′)]iridium(III) (acetylacetonate), Tris[2-(9.9-dimethylfluoren-2-yl)pyridinato-(N,C3′)]iridium(III), Tris[2-(9.9-dimethylfluoren-2-yl)pyridinato-(N,C3′)]iridium(III), Bis[5-trifluoromethyl-2-[3-(N-phenylcarbzolyl)pyridinato-N,C2′]iridium(III)(acetylacetonate), (2-PhPyCz)2Ir(III)(acac), etc.
The thickness of an emissive layer may vary. In some embodiments, an emissive layer may have a thickness in the range of about 1 nm to about 150 nm or about 200 nm.
A hole-transport layer may comprise at least one hole-transport material. Examples of hole-transport materials may include: an aromatic-substituted amine, a carbazole, a polyvinylcarbazole (PVK), e.g. poly(9-vinylcarbazole); polyfluorene; a polyfluorene copolymer; poly(9,9-di-n-octylfluorene-alt-benzothiadiazole); poly(paraphenylene); poly[2-(5-cyano-5-methylhexyloxy)-1,4-phenylene]; a benzidine; a phenylenediamine; a phthalocyanine metal complex; a polyacetylene; a polythiophene; a triphenylamine; copper phthalocyanine; 1,1-Bis(4-bis(4-methylphenyl)aminophenyl)cyclohexane; 2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline; 3,5-Bis(4-tert-butyl-phenyl)-4-phenyl[1,2,4]triazole; 3,4,5-Triphenyl-1,2,3-triazole; 4,4′,4′-tris(3-methylphenylphenylamino)triphenylamine (MTDATA); N,N′-bis(3-methylphenyl)N,N′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (TPD); 4,4′-bis[N-(naphthyl)-N-phenyl-amino]biphenyl (α-NPD); 4,4′,4″-tris(carbazol-9-yl)-triphenylamine (TCTA); 4,4′-bis[N,N′-(3-tolyl)amino]-3,3′-dimethylbiphenyl (HMTPD); 4,4′-N,N′-dicarbazole-biphenyl (CBP); 1,3-N,N-dicarbazole-benzene (mCP); Bis[4-(p,p′-ditolyl-amino)phenyl]diphenylsilane (DTASi); 2,2′-bis(4-carbazolylphenyl)-1,1′-biphenyl (4CzPBP); N,N′N″-1,3,5-tricarbazoloylbenzene (tCP); N,N′-bis(4-butylphenyl)-N,N′-bis(phenyl)benzidine; a combination thereof; or any other material known in the art to be useful as a hole-transport material.
An electron-transport layer may comprise at least one electron-transport material. Examples of electron-transport materials may include: 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD); 1,3-bis(N,N-t-butyl-phenyl)-1,3,4-oxadiazole (OXD-7), 1,3-bis[2-(2,2′-bipyridine-6-yl)-1,3,4-oxadiazo-5-yl]benzene; 3-phenyl-4-(1′-naphthyl)-5-phenyl-1,2,4-triazole (TAZ); 2,9-dimethyl-4,7-diphenyl-phenanthroline (bathocuproine or BCP); aluminum tris(8-hydroxyquinolate) (Alq3); and 1,3,5-tris(2-N-phenylbenzimidazolyl)benzene; 1,3-bis[2-(2,2′-bipyridine-6-yl)-1,3,4-oxadiazo-5-yl]benzene (BPY-OXD); 3-phenyl-4-(1′-naphthyl)-5-phenyl-1,2,4-triazole (TAZ),2,9-dimethyl-4,7-diphenyl-phenanthroline (bathocuproine or BCP); and 1,3,5-tris[2-N-phenylbenzimidazol-z-yl]benzene (TPBI). In some embodiments, the electron transport layer may be aluminum quinolate (Alq3), 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD), phenanthroline, quinoxaline, 1,3,5-tris[N-phenylbenzimidazol-z-yl]benzene (TPBI), a derivative or a combination thereof, or any other material known in the art to be useful as an electron-transport material.
A hole-injection layer may include any material that can inject electrons. Some examples of hole-injection materials may include an optionally substituted compound selected from the following: a polythiophene derivative such as poly(3,4-ethylenedioxythiophene (PEDOT)/polystyrene sulphonic acid (PSS), a benzidine derivative such as N,N, N′,N′-tetraphenylbenzidine, poly(N,N′-bis(4-butylphenyl)-N,N′-bis(phenyl)benzidine), a triphenylamine or phenylenediamine derivative such as N,N′-bis(4-methylphenyl)-N,N′-bis(phenyl)-1,4-phenylenediamine, 4,4′,4″-tris(N-(naphthylen-2-yl)-N-phenylamino)triphenylamine, an oxadiazole derivative such as 1,3-bis(5-(4-diphenylamino)phenyl-1,3,4-oxadiazol-2-yl)benzene, a polyacetylene derivative such as poly(1,2-bis-benzylthio-acetylene), a phthalocyanine metal complex derivative such as phthalocyanine copper (CuPc), a combination thereof, or any other material known in the art to be useful as a hole-injection material. In some embodiments, hole-injection materials, while still being able to transport holes, may have a hole mobility substantially less than the hole mobility of conventional hole-transport materials.
A variety of methods may be used to provide a porous film layer to a light-emitting device.
A coupling medium may be any material that has a similar refractive index to the glass substrate and may be capable of causing the glass substrate to be affixed to the OLED, such as by adhesion. Examples may include a refractive index matching oil or double sticky tape. In some embodiments, a glass substrate may have refractive index of about 1.5, and a coupling medium may have refractive index of about 1.4. This may allow light to come through the glass substrate and the coupling medium without light loss.
In some embodiments, the material of the porous film may be deposited directly on the OLED. An optional heating step may also be carried out on the deposited material to provide a porous film.
In some embodiments, the heating temperature may be sufficiently low that the performance of the OLED is not adversely affected to a degree that is unacceptable. In some embodiments wherein the material of the porous film comprises COMPOUND-1, annealing (i.e., heating step) may not be necessary.
A light-emitting device may further comprise an encapsulation or protection layer to protect the porous film element from environmental damage, such as damage due to moisture, mechanical deformation, etc. For example, a protective layer may be placed in such a way as to provide a protective barrier between the porous film and the environment.
While there may be many ways to encapsulate or protect a porous film,
If present, an electron injection layer may be in a variety of positions in a light-emitting device, such as any position between the cathode layer and the light emitting layer. In some embodiments, the lowest unoccupied molecular orbital (LUMO) energy level of the electron injection material(s) is high enough to prevent it from receiving an electron from the light emitting layer. In other embodiments, the energy difference between the LUMO of the electron injection material(s) and the work function of the cathode layer is small enough to allow the electron injection layer to efficiently inject electrons into the emissive layer from the cathode. A number of suitable electron injection materials are known to those skilled in the art. Examples of suitable electron injection materials may include but are not limited to, an optionally substituted compound selected from the following: LiF, CsF, Cs doped into electron transport material as described above or a derivative or a combination thereof.
If present, a hole-blocking layer may be in a variety of positions in a light-emitting device, such as any position between the cathode and the emissive layer. Various suitable hole-blocking materials that can be included in the hole-blocking layer are known to those skilled in the art. Suitable hole-blocking material(s) include but are not limited to, an optionally substituted compound selected from the following: bathocuproine (BCP), 3,4,5-triphenyl-1,2,4-triazole, 3,5-bis(4-tert-butyl-phenyl)-4-phenyl-[1,2,4]triazole, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 1,1-bis(4-bis(4-methylphenyl)aminophenyl)-cyclohexane, etc, and combinations thereof.
If present, an exciton-blocking layer may be in a variety of positions in a light-emitting device, such as in any position between the emissive layer and the anode. In some embodiments, the band gap energy of the material(s) that comprise exciton-blocking layer may be large enough to substantially prevent the diffusion of excitons. A number of suitable exciton-blocking materials that can be included in the exciton-blocking layer are known to those skilled in the art. Examples of material(s) that can compose an exciton-blocking layer include an optionally substituted compound selected from the following: aluminum quinolate (Alq3), 4,4′-bis[N-(naphthyl)-N-phenyl-amino]biphenyl (α-NPD), 4,4′-N,N′-dicarbazole-biphenyl (CBP), and bathocuproine (BCP), and any other material(s) that have a large enough band gap to substantially prevent the diffusion of excitons.
To a mixture of 5-bromonicotinic acid (10 g) in thionyl chloride (25 ml) was added anhydrous DMF (0.5 ml). The whole was refluxed overnight. After cooling to room temperature (RT), the excess thionyl chloride was removed under reduced pressure. A white solid (11 g) was obtained, which was used for the next step without further purification.
A mixture of 5-bromonicotinoyl chloride (7.5 g, 33 mmol), 2-bromoaniline (5.86 g, 33 mmol) and triethylamine (14 ml, 100 mmol) in anhydrous dichloromethane (100 ml) was stirred under argon overnight. The resulting mixture was worked up with water and extracted with dichloromethane (200 ml×2). The organic phase was collected and dried over Na2SO4. After the organic phase was concentrated to 150 ml, white crystalline solid was crashed out. Filtration and washing with hexanes gave a white solid (10.0 g, 85% yield).
A mixture of 5-bromo-N-(2-bromophenyl)nicotinamide (3.44 g, 9.7 mmol), CuI (0.106 g, 0.56 mmol), Cs2CO3 (3.91 g, 12 mmol) and 1,10-phenanthroline (0.20 g, 1.12 mmol) in anhydrous 1,4-dioxane (50 mL) was heated at 100° C. overnight. After cooling to RT, the mixture was poured into ethyl acetate (200 ml), then washed with water. The aqueous phase was extracted with ethyl acetate (200 ml×2), and the organic phase was collected and dried over Na2SO4, purified by flash chromatography (silica gel, hexanes/ethyl acetate 3:1) to give a light yellow solid (2.0 g, 75% yield).
Compound-1:
A mixture of 2-(5-bromopyridin-3-yl)benzo[d]oxazole (550 mg, 2 mmol), potassium acetate (600 mg, 6.1 mmol), bis(pinacolato)diboron (254 mg, 1 mmol) and [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium (73 mg, 0.1 mmol) in DMSO was degassed and heated at 90° C. under argon atmosphere overnight. After cooling, the whole was poured into water, filtration gave a solid which was washed with isopropanol, methylene chloride. A white solid was obtained (250 mg, 64% yield) as product Compound-1.
A mixture of 3-bromobenzoyl chloride (10.0 g, 45.6 mmol), 2-bromoaniline (7.91 g, 46 mmol), Cs2CO3 (30 g, 92 mmol), CuI (0.437 g, 2.3 mmol) and 1,10-phenanthroline (0.829 g, 4.6 mmol) in anhydrous 1,4-dioxane (110 ml) was heated at 120° C. for 8 h. After cooling to RT, the mixture was poured into ethyl acetate (300 ml), worked up with water (250 ml). The aqueous solution was extracted with dichloromethane (300 ml). The organic phase was collected, combined, and dried over Na2SO4. Purification by a short silica gel column (hexanes/ethyl acetate 3:1) gave a solid which was washed with hexanes to give a light yellow solid (9.54 g, 76% yield).
A mixture of 2-(3-bromophenyl)benzo[d]oxazole (2.4 g, 8.8 mmol), bis(pinacolato)diboron (2.29 g, 9.0 mmol), [1,1′-Bis(diphenylphosphino)ferrocene]dichloropalladium (0.27 g, 0.37 mmol), and potassium acetate (2.0 g, 9.0 mmol) in anhydrous 1,4-dioxane (50 mL) was degassed, then heated at 80° C. overnight. After cooling to RT, the mixture was poured into ethyl acetate (100 ml). After filtration, the solution was absorbed on silica gel and purified by flash chromatography (hexanes/ethyl acetate 4:1) to give a white solid (2.1 g in 75% yield).
Compound-2:
A mixture of 3,5-dibromopyridine (0.38 g, 1.6 mmol), 2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[d]oxazole (1.04 g, 3.1 mol), Pd(PPh3)4 (0.20 g, 0.17 mmol) and potassium carbonate (0.96 g, 7.0 mmol) in dioxane/water (40 ml/8 ml) was degassed and heated at 90° C. overnight under argon. After cooling to RT, the precipitate was filtered and washed with methanol to give a white solid (0.73 g, in 95% yield).
1,3-dibromobenzene (2.5 g, 10.6 mmol), bis(pinacolato)diboron (6.0 g, 23.5 mmol), Pd(dppf)2Cl2 (0.9 g, 1.2 mmol), and potassium acetate (7.1 g, 72.1 mmol) were dissolved in 50 mL of 1,4-dioxane. The reaction mixture was degassed with argon and then heated to 85° C. under argon for 18 hours. The reaction mixture was filtered and an extraction was performed in ethyl acetate. The organic phase was washed with water and brine. The extract was dried over sodium sulfate, filtered, and concentrated. The resulting residue was purified by a silica gel column with 1:9 ethyl acetate:hexanes as the eluent. The solvents were removed and the product was recrystallized from dichloromethane/methanol to yield the product as an off-white solid (3.008 g, 86% yield).
To a mixture of 5-bromonicotinic acid (10 g) in thionyl chloride (25 ml) was added anhydrous DMF (0.5 ml). The whole was heated to reflux for overnight. After cooled to RT, the excess thionyl chloride was removed under reduced pressure. A white solid (11 g) was obtained, which was used for the next step without further purification.
A mixture of 5-bromonicotinoyl chloride (7.5 g, 33 mmol), 2-bromoaniline (5.86 g, 33 mmol) and triethylamine (14 mL, 100 mmol) in anhydrous dichloromethane (100 ml) was stirred under argon overnight. The resulting mixture was worked up with water and extracted with dichloromethane (200 mL×2). The organic phase was collected and dried over Na2SO4. After concentrated to 150 mL, white crystalline solid was crashed out. Filtration and washing with hexanes gave a white solid (10.0 g, 85% yield).
A mixture of 5-bromo-N-(2-bromophenyl)nicotinamide (3.44 g, 9.7 mmol), CuI (0.106 g, 0.56 mmol), Cs2CO3 (3.91 g, 12 mmol) and 1,10-phenanthroline (0.20 g, 1.12 mmol) in anhydrous 1,4-dioxane (50 ml) was heated at 100° C. overnight. After cooling to RT, the mixture was poured into ethyl acetate (200 ml), then washed with water. The aqueous phase was extracted with ethyl acetate (200 ml×2), and the organic phase was collected and dried over Na2SO4, purified by flash chromatography (silica gel, hexanes/ethyl acetate 3:1) to give a light yellow solid (2.0 g, 75% yield).
Compound-3:
A mixture of 1,3-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene (0.63 g, 1.92 mmol), 2-(5-bromopyridin-3-yl)benzo[d]oxazole (1.05 g, 3.83 mmol), Pd(PPh3)4 (0.219 g, 0.19 mmol) and potassium carbonate (1.1 g, 8 mmol) in dioxane/water (30 ml/6 ml) was degassed and heated at 85° C. overnight under argon. After cooling to RT, the precipitate was filtered and washed with methanol (300 ml×3) and dried under vacuum to give a white solid (0.88 g, 98% yield).
A mixture of 4-bromobenzoylchloride (4.84 g, 22 mmol), 2-bromoaniline (3.8 g, 22 mmol), CuI (0.21 g, 1.1 mmol), Cs2CO3 (14.3 g, 44 mmol) and 1,10-phenanthroline (0.398 g, 2.2 mmol) in anhydrous 1,4-dioxane (80 ml) was degassed and heated at about 125° C. under argon overnight. The mixture was cooled and poured into ethyl acetate (−200 ml) and filtered. The filtrate was absorbed on silica gel, purified by column chromatography (hexanes/ethyl acetate 4:1), and precipitated by hexanes to give a white solid (5.2 g, in 87% yield).
A mixture of X1 (4.45 g, 16 mmol), bis(pinacolate)diborane (4.09 g, 16.1 mmol), anhydrous potassium acetate (3.14 g, 32 mmol) and Pd(dppf)Cl2 (0.48 g, 0.66 mmol) in anhydrous 1,4-dioxane (80 ml) was degassed and heated at about 85° C. for about 48 hours under argon. After cooling to RT, the mixture was poured into ethyl acetate (−200 ml) and filtered. The filtrate was absorbed on silica gel and purified by column chromatography (hexanes/ethyl acetate, 4:1) to give a white solid (4.15 g, in 81% yield).
Di-p-tolylamine (6.0 g, 30.4 mmol), 4,4′-dibromobiphenyl (23.7 g, 76.0 mmol), sodium tert-butoxide (7.26 g, 91.2 mmol), and [1,1-bis(diphenylphosphino)ferrocene]palladium(11)dichloride (Pd(dppf)Cl2) (666 mg, 0.912 mmol, 3 mol %) were added to anhydrous toluene (about 250 ml) and degassed in argon for about 30 minutes. The resulting mixture was heated at about 80° C. for about 6 hours, after which a TLC analysis indicated that most of the di-p-tolylamine was consumed. After being cooled to RT, the mixture was poured into saturated aqueous sodium bicarbonate and extracted with 2 portions of ethyl acetate. The organic layers were pooled and washed with water and brine, then dried over MgSO4. After filtration, the extract was concentrated to dryness on a rotary evaporator, and then loaded onto silica gel. A flash column (gradient of 100% hexane to 1% methylene chloride in hexane) resulted in 9.4 g (72%) of a white solid confirmed by 1H NMR in CDCl3.
Compound-4:
A mixture of X2 (0.66 g, 2.05 mmol), compound 22 (0.80 g, 1.87 mmol), Na2CO3 (0.708 g, 6.68 mmol) and Pd(PPh3)4 (0.065 g, 56.1 mmol) in THF/H2O (10 mL/6 mL) was degassed and heated at 80° C. overnight under argon atmosphere. After cooling, the mixture was poured into dichloromethane (100 ml) and washed with water (2×200 ml) and brine (100 ml). Organic phase was collected, dried over Na2SO4, then purified by flash chromatography (silica gel, hexanes/ethyl acetate 40:1 to 9:1) to give a solid (0.936 g, in 93% yield).
A mixture of (4-(diphenylamino)phenyl)boronic acid (1.5 g, 5.19 mmol), 4-iodo-1-bromobenzene (1.33 g, 4.71 mmol), Na2CO3 (1.78 g, 16.8 mmol) and Pd(PPh3)4 (0.163 g, 0.141 mmol) in THF/H2O (28 mL/17 mL) was degassed and heated at reflux overnight under argon atmosphere. After cooling, the mixture was poured into dichloromethane (150 mL), then washed with water (2×150 mL) and brine (100 mL). The organic phase was dried over Na2SO4, purified with flash column chromatography (silica gel, hexanes/ethyl acetate 50:1) then recrystallized in dichloromethane/methanol to afford a white solid (1.64 g, in 87% yield).
Compound-5:
A mixture of X3 (1.40 g, 3.5 mmol), compound 10 (1.52 g, 3.85 mmol), Na2CO3 (1.32 g, 12.5 mmol) and Pd(PPh3)4 (121 mg, 0.105 mmol) in THF/H2O (21 ml/12.5 ml) was degassed and heated to reflux overnight under an argon atmosphere. After cooling to RT, the mixture was poured into dichloromethane (150 ml), then washed with water (150 ml) and brine (150 ml). The organic phase was dried over Na2SO4, absorbed on silica gel, and purified with flash column chromatography (hexane/ethyl acetate 5:1 to 2:1, then dichoromethane as eluent). Product was collected and recrystallized from acetone/hexanes to give a solid (1.69 g). It was recrystallized again in dichoromethane/ethyl acetate to give a solid (1.4 g, 68% yield).
A mixture of 4-(diphenylamino)phenylboronic acid (7.00 g, 24.2 mmol), 5-bromo-2-iodopyridine (7.56 g, 26.6 mmol), tetrakis(triphenylphosphine)palladium(0) (1.40 g, 1.21 mmol), Na2CO3 (9.18 g, 86.6 mmol), H2O (84 mL) and THF (140 mL) was degassed with argon for 1.5 h while stirring. The stirring reaction mixture was then maintained under argon at 80° C. for 19 h. Upon confirming consumption of the starting material by TLC (SiO2, 19:1 hexanes-EtOAc), the reaction was cooled to RT and poured over EtOAc (500 mL). The organics were then washed with sat. NaHCO3, H2O and brine, dried over MgSO4, filter and concentrated in vacuo. The crude product was purified via flash chromatography (SiO2, 2:1 hexanes-dichloromethane) to afford compound 1 (9.54 g, 98%) as a light yellow, crystalline solid.
A mixture of 1 (6.00 g, 15.0 mmol), bis(pinacolato)diboron (4.18 g, 16.4 mmol), [1,1′-bis(diphenylphosphino)-ferrocene]dichloropalladium(11) (0.656 g, 0.897 mmol), potassium acetate (4.40, 44.9 mmol) and anhydrous 1,4-dioxane (90 mL) was degassed with argon for 50 min while stirring. The stirring reaction mixture was then maintained under argon at 80° C. for 67 h. Upon confirming consumption of the starting material by TLC (SiO2, 4:1 hexanes-acetone), the reaction was cooled to RT, filtered, and the filtrant washed copiously with EtOAc (ca. 200 mL). The organics were then washed with sat. NaHCO3, H2O, sat. NH4Cl and brine, dried over MgSO4, filtered and concentrated in vacuo. The crude was then taken up in hexanes (ca. 300 mL), the insolubles filtered off and the filtrate concentrated to yield 2 (6.34 g, 95%) as a yellow foam, which was carried forward without further purification.
A mixture of 2-aminothiophenol (5.01 g, 40.0 mmol), 5-bromo-2-formylpyridine (7.44 g, 40.0 mmol) and ethanol (40 mL) was heated to reflux (100° C.) while open to the atmosphere for 3 days. Upon confirming consumption of the starting materials by TLC (SiO2, 29:1 hexanes-acetone), the reaction was cooled to RT, the resulting mixture filtered, and the filtrant washed copiously with ethanol to afford 9 (5.62 g, 48%) as an off-white solid.
A mixture of 9 (3.05 g, 7.59 mmol), 2 (3.40 g, 7.59 mmol), tetrakis(triphenylphosphine)palladium(0) (0.438 g, 0.379 mmol), Na2CO3 (7.42 g, 70.0 mmol), H2O (70 mL) and THF (115 mL) was degassed with argon for 1.25 h while stirring. The stirring reaction mixture was then maintained under argon at 80° C. for 65 h. Upon confirming consumption of the starting materials by TLC (SiO2, CH2Cl2), the reaction was cooled to RT and poured over CH2Cl2 (400 mL). The organics were then washed with sat. NaHCO3, H2O and brine, dried over MgSO4, filter and concentrated in vacuo. Purification of the crude product via flash chromatography (SiO2, 100% CH2Cl2 to 49:1 CH2Cl2-acetone) provided Compound-6 (3.98 g, 82%) as a yellow solid.
A mixture of carbazole (6.30 g, 37.7 mmol), 1-bromo-4-iodobenzene (15.99 g, 56.52 mmol), copper powder (4.79 g, 75.4 mmol), K2CO3 (20.83 g, 150.7 mmol) and anhydrous DMF (100 mL) was degassed with argon for 1 h while stirring. The stirring reaction mixture was then maintained under argon at 130° C. for 42 h. Upon confirming consumption of the starting material by TLC (SiO2, 4:1 hexanes-dichloromethane), the mixture was cooled to RT, filtered, the filtrant washed copiously with EtOAc (ca. 200 mL) and the resulting filtrate concentrated in vacuo. Purification of the crude product by flash chromatography (SiO2, hexanes) afforded 4 (11.7 g, 96%) as a pale yellow solid.
A mixture of 4 (11.64 g, 36.12 mmol), bis(pinacolato)diboron (19.26 g, 75.85 mmol), [1,1′-bis(diphenylphosphino)-ferrocene]dichloropalladium(11) (1.59 g, 2.17 mmol), potassium acetate (10.64, 108.4 mmol) and anhydrous 1,4-dioxane (200 mL) was degassed with argon for 2 h while stirring. The stirring reaction mixture was then maintained under argon at 80° C. for 67 h. Upon confirming consumption of the starting material by TLC (SiO2, hexanes), the mixture was cooled to RT, filtered through a short silica gel plug and the filtrant washed copiously with EtOAc (ca. 400 mL). The organics were then washed with sat. NaHCO3, H2O and brine, dried over MgSO4, filtered and concentrated in vacuo. Purification of the crude product via flash chromatography (SiO2, 7:3 to 1:1 hexanes-dichloromethane) provided 5 (10.8 g, 81%) as a colorless solid.
Following the procedure for 1, 5 (4.84 g, 13.1 mmol), 5-bromo-2-iodopyridine (3.72 g, 13.1 mmol), tetrakis(triphenylphosphine)palladium(0) (0.757 g, 0.655 mmol), Na2CO3 (4.97 g, 46.9 mmol), H2O (45 mL) and THF (75 mL) yielded 6 (4.73 g, 90%) as a colorless solid after flash chromatography (SiO2, 1:1 hexanes-dichloromethane) and subsequent trituration with EtOAc.
Following the procedure for 2, 6 (6.22 g, 15.6 mmol), bis(pinacolato)diboron (4.35 g, 17.1 mmol), [1,1′-bis(diphenylphosphino)-ferrocene]dichloropalladium(11) (0.684 g, 0.935 mmol), potassium acetate (4.59, 46.7 mmol) and anhydrous 1,4-dioxane (93 mL) yielded 7 (6.55 g, 94%) as a brownish gray solid.
A mixture of 7 (0.841 g, 1.89 mmol), 9 (0.549 g, 1.89 mmol), tetrakis(triphenylphosphine)palladium(0) (109 mg, 94.2 μmol). Na2CO3 (1.59 g, 15.0 mmol), H2O (15 mL) and THF (25 mL) was degassed with argon for 20 min while stirring. The stirring reaction mixture was then maintained under argon at 80° C. for 18 h. Upon confirming consumption of the starting materials by TLC (SiO2, CH2Cl2), the mixture was cooled to RT and poured over CHCl3 (300 mL). The organics were then washed with sat. NaHCO3, H2O and brine, dried over MgSO4, filtered and concentrated in vacuo. Purification of the crude product via flash chromatography (SiO2, 100% CH2Cl2 to 49:1 CH2Cl2-acetone) provided Compound-7 (0.72 g, 72%) as a light yellow solid.
Following the procedure for Compound-7, a mixture of 7 (0.868 g, 1.95 mmol), 10 (0.535 g, 1.95 mmol) (which is made following the same procedure as of for 9), tetrakis(triphenylphosphine)palladium(0) (112 mg, 97.2 μmol), Na2CO3 (1.59 g, 15.0 mmol), H2O (15 mL) and THF (25 mL) yielded Compound-8 (0.81 g, 81%) as a white solid after flash chromatography (SiO2, 100% CH2Cl2 to 19:1 CH2Cl2-acetone).
To a mixture of 2-aminothiophenol (500 mg, 3.99 mmol) and 5-bromo-3-pyridinecarboxaldehyde (743 mg, 3.99 mmol) was added ethanol (10 mL). The mixture was then heated to reflux (100° C.) overnight under ambient air. After cooling, the mixture was dried under vacuum then redissolved in methylene chloride (100 ml). Solution was washed with water (100 ml) and brine (50 ml), and dried over sodium sulfate. The crude material was run through a plug of silica (16% ethyl acetate in hexanes), and precipitated from methanol to give 564 mg of the material in 49% yield.
1,3-dibromo-5-methylbenzene (5.0 g, 20.0 mmol), bis(pinacolato)diboron (11.3 g, 44.4 mmol), Pd(dppf)Cl2 (1.6 g, 2.2 mmol), and potassium acetate (13.3 g, 136.0 mmol) were dissolved in 75 ml of 1,4-dioxane. The reaction mixture was degassed with argon and then heated to 85° C. under argon for 18 hours. The reaction mixture was filtered and an extraction was performed in ethyl acetate. The organic phase was washed with water and brine, then dried over magnesium sulfate, filtered, and concentrated. The resulting residue was purified by a silica gel column with 1:4 ethyl acetate:hexanes as the eluent to yield the product as an off-white solid (0.399 g, 58% yield).
Compound-9:
A mixture of 2,2′-(5-methyl-1,3-phenylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (0.747 g, 2.17 mmol), 2-(5-bromopyridin-3-yl)benzo[d]thiazole (1.39 g, 4.77 mmol), Pd(PPh3)4 (0.165 g, 0.143 mmol) and potassium carbonate (1.81 g, 17.0 mmol) in THF/water (30 ml/17 ml) was degassed and heated at reflux (85° C.) overnight under argon. After cooling to RT, the mixture was filtered and the solid was washed with water, methanol and THF. The solid was collected and the filtrate was added to water (150 ml) and extracted with dichloromethane (150 ml×2). The organic solution was dried over Na2SO4 and loaded on silica gel, purified by flash column using hexanes/acetone (4:1 to 3:1). The desired fraction was collected and combined with the solid from the first filtration. The solid was washed with hot dichloromethane, filtered and washed with methanol to afford 0.91 g product in 82% yield.
Compound-10 3,5-di([1,1′-biphenyl]-3-yl)pyridine:
A mixture of 3,5-dibromopyridine (1.235 g, 5.215 mmol), [1,1′-biphenyl]-3-ylboronic acid (2.169 g, 10.95 mmol), tetrakis(triphenylphosphine)palladium(0) (0.362 g, 0.313 mmol), Na2CO3 (2.544 g, 24.00 mmol), H2O (24 mL) and THF (40 mL) was degassed with argon for 43 min while stirring. The reaction mixture was then maintained under argon at 80° C. while stirring until TLC (SiO2, 7:3 hexanes-ethyl acetate) confirmed consumption of the starting material (4 days). Upon completion, the reaction was cooled to RT and poured over dichloromethane (ca. 250 mL). The organics were then washed with H2O and brine, dried over MgSO4, filter and concentrated in vacuo. Purification of the crude product via flash chromatography (SiO2, 100% dichloromethane) yielded compound-10 (1.38 g, 69%) as an off-white solid.
A mixture of 5-bromonicotinoyl chloride (13.46 g, 61.04 mmol), 2-bromoaniline (10.00 g, 58.13 mmol), Cs2CO3 (37.88 g, 116.3 mmol), CuI (0.554 g, 2.907 mmol), 1,10-phenanthroline (1.048 g, 5.813 mmol) and anhydrous 1,4-dioxane (110 mL) was degassed with argon for 1 h while stirring. The reaction mixture was then maintained under argon at 120° C. while stirring until TLC (SiO2, 1:1 hexanes-dichloromethane) confirmed consumption of the starting material (48 h). Upon cooling to RT, dichloromethane (ca. 200 mL) was added to the reaction, the mixture filtered, the filtrant washed copiously with dichloromethane (ca. 200 mL) and ethyl acetate (ca. 200 mL) and the filtrate concentrated in vacuo. Purification of the crude product via flash chromatography (SiO2, 100% dichloromethane to 29:1-dichloromethane:acetone) afforded 2-(5-bromopyridin-3-yl)benzo[d]oxazole (7.32 g, 46%) as a light brown crystalline solid.
A mixture of 2-(5-bromopyridin-3-yl)benzo[d]oxazole (7.119 g, 25.88 mmol), bis(pinacolato)diboron (7.229 g, 28.47 mmol), [1,1′-Bis(diphenylphosphino)ferrocene]dichloropalladium (0.947 g, 1.294 mmol), potassium acetate (7.619 g, 77.63 mmol) and anhydrous 1,4-dioxane (150 mL) was maintained under argon at 100° C. while stirring until TLC (SiO2, 9:1 dichloromethane:acetone) confirmed consumption of the starting material (3 days). Upon cooling to RT, dichloromethane (ca. 300 mL) was added to the reaction, the mixture filtered and the filtrant washed with dichloromethane (ca. 100 mL). The fitrate was then washed with sat. NaHCO3, H2O and brine, dried over MgSO4, filter and concentrated in vacuo. The crude product was purified by filtration from hot hexanes and the resulting filtrate concentrated to yield 2-(5-bromopyridin-3-yl)benzo[d]oxazole (6.423 g, 77%) as an orangish-brown solid via recrystallization.
A mixture of 2-(5-bromopyridin-3-yl)benzo[d]oxazole (2.000 g, 6.208 mmol), 3,5-dibromopyridine (0.7003 g, 2.956 mmol), tetrakis(triphenylphosphine)palladium(0) (0.205 g, 0.177 mmol), Na2CO3 (3.18 g, 30.0 mmol), H2O (15 mL) and THF (25 mL) was degassed with argon for 27 min while stirring. The reaction mixture was then maintained under argon at 85° C. for 16 h. Upon cooling to RT, the reaction mixture was filtered and the filtrant washed copiously with H2O and methanol to provide Compound-11 (1.36 g, 99%) as an off-white solid.
A mixture of 3-bromobenzoyl chloride (6.005 g, 27.36 mmol), 2-bromoaniline (4.707 g, 27.36 mmol), Cs2CO3 (17.83 g, 54.73 mmol), CuI (0.261 g, 1.37 mmol), 1,10-phenanthroline (0.493 g, 2.74 mmol) and anhydrous 1,4-dioxane (50 mL) was degassed with argon at 40° C. for 30 min while stirring. The reaction mixture was then maintained under argon at 120° C. while stirring until TLC (SiO2, 4:1 hexanes-ethyl acetate) confirmed consumption of the starting material (24 h). Upon cooling to RT, the mixture was filtered and the filtrant washed copiously with ethyl acetate (ca. 350 mL). The filtrate was then washed with sat. NaHCO3, H2O and brine, dried over MgSO4, filter and concentrated in vacuo. Purification of the crude product via flash chromatography (SiO2, 4:1-hexanes:ethyl acetate) afforded 2-(3-bromophenyl)benzo[d]oxazole (7.50 g, 100%) as an off-white solid.
A mixture of 2-(3-bromophenyl)benzo[d]oxazole (7.500 g, 27.36 mmol), bis(pinacolato)diboron (7.296 g, 28.73 mmol), [1,1′-Bis(diphenylphosphino)ferrocene]dichloropalladium (1.001 g, 1.368 mmol), potassium acetate (6.176 g, 62.93 mmol) and anhydrous 1,4-dioxane (71 mL) was degassed with argon at 40° C. for 37 min while stirring. The reaction mixture was then maintained under argon at 100° C. while stirring until TLC (SiO2, 2:1 hexanes-dichloromethane) confirmed consumption of the starting material (21 h). Upon cooling to RT, the mixture was filtered and the filtrate washed copiously with ethyl acetate (ca. 700 mL). The filtrate was then washed with sat. NaHCO3, H2O and brine, dried over MgSO4, filter and concentrated in vacuo. Purification of the crude product via flash chromatography (SiO2, 9:1-dichloromethane:hexanes to 19:1-dichloromethane:acetone) afforded 2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[d]oxazole (6.76 g, 77%)
3,3″-bis(benzo[d]oxazol-2-yl)-1,1′:3′,1″-terphenyl (Compound-12). A mixture of 2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[d]oxazole (2.25 g, 7.01 mmol), 1,3-diiodobenzene (1.101 g, 3.337 mmol), tetrakis(triphenylphosphine)palladium(0) (0.193 g, 0.167 mmol), Na2CO3 (2.555 g, 24.11 mmol), H2O (24 mL) and THF (40 mL) was degassed with argon for 33 min while stirring. The reaction mixture was then maintained under argon at 80° C. while stirring until TLC (SiO2, 9:1 hexanes-acetone) confirmed consumption of the starting material (22 h). Upon completion, the reaction was cooled to RT and poured over dichloromethane (ca. 350 mL). The resulting mixture was then filtered, the filtrate washed with sat. NaHCO3, H2O and brine, dried over MgSO4, filter and concentrated in vacuo. Purification of the crude product via flash chromatography (SiO2, 19:1-dichloromethane:hexanes to 100% dichloromethane) yielded compound-12 (0.98 g, 63%) as a light yellow solid.
I-V-L characteristics were taken with a Keithley 2400 SourceMeter and Newport 2832-C power meter and 818 UV detector.
OLED A 6401 was prepared according to the schematic shown in
Although the layers of a device such as OLED A may comprise a variety of materials, in OLED A the cathode 6460 was LiF/AI, the electron-transport layer 6450 was TPBI, the emissive layer 6440 comprised about 5% PO-01 as emitter and Compound-10 as a host, the hole-transport layer 6430 was α-NPD, the hole-injection layer 6420 was PEDOT, the anode 6410 was ITO, and the transparent substrate 6400 was glass.
OLED A was prepared by the following procedure. The PEDOT hole injection layer was spin-coated on top of a pre-cleaned ITO/glass, followed by vacuum deposition of the 30 nm-thick α-NPD hole-transport layer at a deposition rate of about 1 Å/s. The emissive layer was added by co-deposition of yellow emitter PO-01 and host Compound-10 at a deposition rate of about 0.05 and about 1 Å/s, respectively, to form an emissive layer having a thickness of about 30 nm. Then TPBI was deposited at about 1 Å/s to a thickness of about 30 nm. LiF was deposited on top of ETL at 0.1 Å/s deposition rate to a thickness of about 1 nm, followed by the deposition of Al at 2 Å/s rate to a thickness of about 100 nm. The base vacuum of the chamber was about 3×10−7 torr.
Device B 6501 was prepared according to the schematic shown in
Device B was prepared by the same procedure as Device A except that a 50-nm thickness α-NPD layer was deposited on the outer surface of the glass substrate at a deposition rate of about 2 Å/s under a vacuum of about 4×10−7 torr.
Device C 6701 was prepared according to the schematic shown in
Device C was prepared by the same procedure as Device A, except that a 600 nm-thick layer of COMPOUND-9 was deposited on top of the outer-face of the glass substrate at a deposition rate of about 2 Å/s under a vacuum of about 4×10−7 torr.
Device D 7000 was prepared according to the schematic shown in
Device D was prepared by the same procedure as Device A, except that a 600 nm-thick layer of COMPOUND-2 was deposited on the outer surface of the glass substrate. The thickness was determined by a thickness sensor installed near the deposition source that records deposition rate. The thickness obtained by the thickness sensor relies upon the assumption that the film is dense. The material was deposited at a rate that corresponded to about of 2 Å/s of dense material under a vacuum of about 4×10−7 torr. SEM and thickness measurements showed that the deposited COMPOUND-2 layer is highly porous, and has a thickness of about 3 μm, which is about 5 times the thickness of a nonporous film.
The power efficiency of a device similar to Device D was obtained with varying thickness of the COMPOUND-2 layer.
The light extraction efficiency from the transparent substrate by the porous film was determined by the following method. The experimental setup is depicted in
The power efficiency of OLED A 6401 was obtained with only air 6405 between the glass substrate 6410 of the OLED device A and the surface of the light-detection sensor 6407 (Si photo diode), as shown in the left side of
OLED A was then immersed in an oil 6403 with an index of refraction of about 1.5, which is the same as the index of refraction of the transparent substrate. The oil 6403 filled the entire gap between the device 6401 and the light detection sensor 6407 (Si-photo diode), so all the light trapped within the glass passes through the glass-oil interface. Thus, the Si-photo diode detector receives the amount of light it would in the ideal case of 100% light extraction.
COMPOUND-3 was deposited on a glass substrate. A photograph of the film on the substrate is indicated as slide 1 in
COMPOUND-3 was also deposited on a glass substrate and then heated at about 200° C. for about 5 minutes. A photograph of this heated film is indicated as slide 2 in
COMPOUND-3 was also deposited on a glass substrate and then heated at about 200° C. for about 30 minutes. A photograph of this heated film is indicated as slide 5 in
COMPOUND-3 was also deposited on a glass substrate and then heated at about 240° C. for about 5 minutes. A photograph of this heated film is indicated as slide 6 in
COMPOUND-3 was also deposited on a glass substrate and then heated at about 300° C. for about 5 minutes. This appears to have caused a substantial amount of the film to evaporate. A photograph of this heated film is indicated as slide 7 in
Films prepared as described above were coated onto the exterior surface of the transparent substrate of OLED A and the power efficiency was measured as a function of luminance, as shown in
COMPOUND-2 was coated on a polyethylene terephthalate (PET) flexible substrate through vacuum deposition by the same method as the COMPOUND-2 layer on the Device D to form a layer having a thickness of about 6 um. The substrate with the coating was heated at 110° C. for 1 hour.
The coated flexible substrate was coupled to OLED A using the refractive index matching oil to obtain Device E.
As described with respect to
An encapsulation or protection layer was added to Device F as follows to provide Device G: an epoxy resin was applied around the edge of the light scattering layer, which upon curing built a gap between the transparent substrate and the encapsulation/protection layer that is another transparent cover glass.
Although the claims have been described in the context of certain preferred embodiments and examples, it will be understood by those skilled in the art that the scope of the claims extend beyond the specifically disclosed embodiments to other alternative embodiments and/or uses and obvious modifications and equivalents thereof.
The present application claims priority under 35 U.S.C. §119 (e) to U.S. Provisional Application No. 61/449,032 filed on Mar. 3, 2011, the disclosures of which is incorporated by reference herein in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| 61449032 | Mar 2011 | US |
