The claimed invention was made by, on behalf of, and/or in connection with one or more of the following parties to a joint university corporation research agreement: Regents of the University of Michigan, Princeton University, University of Southern California, and the Universal Display Corporation. The agreement was in effect on and before the date the claimed invention was made, and the claimed invention was made as a result of activities undertaken within the scope of the agreement.
The present invention relates to techniques for fabricating light emitting devices such as OLEDs having a mixed-index layer, and devices such as organic light emitting diodes and other devices, including the same.
Opto-electronic devices that make use of organic materials are becoming increasingly desirable for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials. For example, the wavelength at which an organic emissive layer emits light may generally be readily tuned with appropriate dopants.
OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting. Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.
One application for phosphorescent emissive molecules is a full color display. Industry standards for such a display call for pixels adapted to emit particular colors, referred to as “saturated” colors. In particular, these standards call for saturated red, green, and blue pixels. Color may be measured using CIE coordinates, which are well known to the art.
One example of a green emissive molecule is tris(2-phenylpyridine) iridium, denoted Ir(ppy)3, which has the following structure:
In this, and later figures herein, we depict the dative bond from nitrogen to metal (here, Ir) as a straight line.
As used herein, the term “organic” includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic devices. “Small molecule” refers to any organic material that is not a polymer, and “small molecules” may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the “small molecule” class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. The core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a “small molecule,” and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.
As used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. Where a first layer is described as “disposed over” a second layer, the first layer is disposed further away from substrate. There may be other layers between the first and second layer, unless it is specified that the first layer is “in contact with” the second layer. For example, a cathode may be described as “disposed over” an anode, even though there are various organic layers in between.
As used herein, “solution processible” means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.
A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.
As used herein, and as would be generally understood by one skilled in the art, a first “Highest Occupied Molecular Orbital” (HOMO) or “Lowest Unoccupied Molecular Orbital” (LUMO) energy level is “greater than” or “higher than” a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IP) are measured as a negative energy relative to a vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (an EA that is less negative). On a conventional energy level diagram, with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A “higher” HOMO or LUMO energy level appears closer to the top of such a diagram than a “lower” HOMO or LUMO energy level.
As used herein, and as would be generally understood by one skilled in the art, a first work function is “greater than” or “higher than” a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a “higher” work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a “higher” work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.
More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.
According to an embodiment, a device such as an OLED includes a substrate; a mixed-index layer disposed above the substrate, which includes a first material and a second material having different refractive indices, the first and second materials being disposed in a periodic pattern such as a grid. An electrode may be disposed above the mixed-index layer, and one or more an organic emissive layers may be disposed above the electrode. A second electrode may be disposed above the organic emissive layer. The grid may be, for example, rectangular, triangular, hexagonal, or any other periodic and/or shape-filling grid pattern.
In embodiments, the grid may have a periodicity of 1-10 μm, and/or a line width of 0.1-5 μm. A material that makes up the grid line structure may have a refractive index within 0.1 of a refractive index of the first electrode. The difference between refractive indices of the materials in the mixed-index layer may be at least 0.1, at least 0.4, or any other suitable difference.
The refractive index of the host material may be in the range of about 1.0 to 3.0. The refractive index of the grid line material may be in the range of about 1.0 to 1.5. The mixed-index layer ma have a thickness of about 10 nm-2 μm, and/or it may be planar to within a tolerance of 0.1-2 nm.
In an embodiment, a device as disclosed herein may be fabricated by fabricating a mixed-index layer in a pattern over a substrate, which includes a high-index material and a low-index material; depositing a first electrode over the patterned mixed-index layer; depositing an organic emissive layer over the first electrode; and depositing a second electrode over the organic emissive layer. In an embodiment, fabrication of the mixed-index layer may include depositing a first high-index material in a layer over the substrate; removing the pattern from the first high-index material to form a patterned void; and depositing a second high-index material in a layer over the remaining first high-index material and over the patterned void. In an embodiment, fabrication of the mixed-index layer may include depositing a first high-index material over the substrate; removing the pattern from the first high-index material; depositing a low-index material over the high-index material and in the pattern. In some embodiments, the low-index material may be removed from above the remaining high-index material. Each technique may be used to fabricate each of the device structures and arrangements disclosed herein.
According to an embodiment, a first device comprising a first organic light emitting device is also provided. The first organic light emitting device can include an anode, a cathode, and an organic layer, disposed between the anode and the cathode. The organic layer can include a mixed-index layer providing a buried grid as disclosed herein. The first device can be a consumer product, an organic light-emitting device, and/or a lighting panel.
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.
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.
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”), which 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.
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 F4-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. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.
The simple layered structure illustrated in
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
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.
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.
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. 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 flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, cell phones, tablets, phablets, personal digital assistants (PDAs), laptop computers, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays, vehicles, a large area wall, theater or stadium screen, or 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.
To increase the efficiency of OLED devices, it is often desirable to use wavelength- and viewing angle-independent means to efficiently outcouple light out of the device. Conventional OLEDs fabricated on glass substrates can emit only about 20% light into viewable “air modes” due to internal reflection from the glass modes into the air. Many techniques and structures may be used to outcouple glass modes, such as using scattering layers, roughening the substrate surface, using large hemispherical lenses, and the like. In some cases, an efficient technique to outcouple light is the use of microlens arrays placed on the outer surface of the device. This method often relies on stamped hemispherical microlenses, typically 5-10 μm in diameter, and often made from polymers that are attached to the rear surface of the OLEDs. The use of microlenses is wavelength and viewing angle independent, and generally can couple 1.7-2.0 times more light into air modes than a flat glass substrate.
An addition, often more difficult challenge is to couple out the waveguide modes from the OLED active region into the glass substrate or air. Conventional techniques to do so include scattering layers, including roughening the interface between a transparent anode and the underlying glass, the use of high index spheres deposited on the glass prior to covering them with an electrode material, and the use of a low index grid (LIG) arranged within the OLED, between the electrode and the other OLED layers. When coupled with microlenses to extract light from the glass modes, this technique may result in a total outcoupling enhancement of over two times the outcoupling, commonly observed in OLEDs on a flat glass substrate.
For example, a white light emitting OLED (WOLED) based on electrophosphorescence with a luminance efficiency of 50 lm/W on glass would be expected to have an efficiency of 115 lm/W using a device structure including a LIG and a microlens sheet. While the LIG employs relatively easy to achieve pattern resolutions (typically 1-5 μm), and hence is also wavelength and angle independent while being inexpensive to fabricate, the fact that the grid must be fabricated within the OLED active region may result in undesirable effects. For example, the grid typically creates non-emissive regions within each OLED, and can give rise to sports and other nonuniformities in the OLED structure and emission due to the irregularity of the effective substrate surface on which the ° LED must be deposited. Such defects may occur because typically the LIG is about 100 nm high above the substrate, which is approximately the same thickness as the OLED itself. Finally, since some of the device area that lies over the grid is nonemissive, a device including a LIG requires a higher current density to achieve the same brightness as a conventional device, although this drawback may marginally impact the ultimate light output enhancement due to the higher outcoupling of the LIG.
Disclosed herein are systems and devices that allow for outcoupling of waveguide modes that are as effective as the LIG in extracting these modes, without the disadvantages previously described. As described herein, a “buried grid” (BG) may be used, in which a grid formed from two materials with different indices of refraction is disposed outside an OLED device, such as below a lower electrode. A buried grid as described herein may be formed, for example, using a combination of imprint lithography followed by simple lamination of a polymer sheet onto its surface. The structure may be completely buried, i.e., below the electrode, providing a base onto which electrode material such as ITO and subsequent OLED active layers may then be deposited, thus avoiding non-emissive regions and surface features that occur in a conventional LIG design.
In some embodiments, an additional overlayer 340 may be disposed above die grid layer 350, as described in further detail herein. For example, a thin, high-index layer, such as a polymer sheet, may be applied or laminated onto the surface of the grid, leaving voids over each narrow grid line.
An electrode layer 330, such as a layer of ITO, may be disposed over the substrate surface and the grid. Additional OLED layers may then be disposed above the electrode 330, such as one or more organic layers 320, an electrode 310 such as a cathode, and other layers as are used in conventional devices. When combined with microlenses disposed below the substrate 360, a buried grid device as shown in
The geometry of the grid may be defined by the grid line width w, the grid height h, and the grid periodicity P as shown. In some embodiments, the grid may have a periodicity dictated by or selected based upon the wavelength of light emitted by the device. For example, as described in further detail herein, it may be preferred for the grid to have a periodicity larger than the wavelength of light emitted by the device. Thus, for a device that emits in the visual wavelength, a grid periodicity of at least 1 μm, or in the range of 1-10 μm may be preferred. The grid line width may be in the range of 0.1-5 μm. The grid may have any geometry, which may be selected based upon fabrication constraints, the desired physical geometry of the device, expected outcoupling, or any other factor. In general, space-filling grid geometries may be preferred. Example geometries suitable for use with a buried grid as disclosed herein include rectangular, triangular, and hexagonal, as well as any regular lattice or any other repeated pattern. More generally, it may be preferred for the materials in the mixed-index layer to be arranged in a periodic pattern, i.e., a repeated arrangement of the materials across the mixed-index layer that is regular and consistent throughout the layer, though in some embodiments the pattern may be different in one direction than in another, parallel to the electrode, across the layer, such as where a rectangular grid is used.
The grid height h may be selected based upon the desired physical structure of the resulting device, though it may be preferred for the grid to be relatively small so as to remain in relative proximity to the bottom electrode. For example, it may be preferred for the mixed-index layer, and thus the grid, to have a grid height of not more than about 10 nm-2 μm.
In some embodiments, it may be preferred for the mixed-index layer to be relatively smooth, to have minimal or no protrusions or indentations across the surface of the layer. For example, it may be preferred for the mixed-index layer to have a planar surface closest to the electrode to a tolerance of at least 0.1-2 nm. That is, it may be preferred for the layer to have no protrusions or indentations that vary by more than 0.1-2 nm from the average surface of the layer. One way to determine the size of such protrusions or indentations is to measure the distance from the bottom of the layer, adjacent to the substrate, to the relevant point on the far surface of the layer.
The refractive indices of each material in the mixed-index layer may be selected independently. In some embodiments, it may be preferred to have a relatively large difference between the host and grid material indices. For example, it may be preferred for the difference to be at least 0.1, 0.2, 0.3, 0.4, or more. Similarly, it may be preferred for the grid material to have a relatively low index, such as 1.0, 1.0-1.5, or 1.0-3.0. Although lower indices may be preferred, in some embodiments any grid index may be used, though it may still be desirable for the grid index to be less than the index of the host material.
As previously described, additional layers such as organic layers 440 and an electrode 450 may be disposed over the bottom electrode 430, i.e., farther away from the substrate. Thus, the mixed-index grid layer may be disposed between the substrate 410 and the bottom electrode 430. In some embodiments, a microlens sheet 460 or other additional outcoupling structure may be disposed within, adjacent to, or fabricated as a part of the substrate 410 to provide further outcoupling from glass to air modes.
Various techniques may be used to fabricate the devices and structures disclosed herein. Referring to
Typical pattern geometries, such as those used in the calculations in
To fabricate a device structure as shown in
In an embodiment, an interlayer may be deposited onto the surface of the mixed-index buried grid layer, as shown in
A bottom electrode may then be fabricated over the mixed-index grid layer, such as by sputtering ITO or any other suitable electrode material to form the bottom contact of the device. Additional OLED layers may be fabricated using any suitable conventional technique over the bottom electrode.
Additional outcoupling layers or structures, such as a polymer microlens array also may be fabricated on the free glass surface as previously described with respect, to
One particular advantage of the use of a buried grid as disclosed herein may be that the substrate is first prepared, and then may be provided to an OLED manufacturer who can apply conventional OLED manufacturing processes without modification. That is, organic layer deposition, electrode deposition, protective layers, and other conventional OLED processing techniques may be applied to a substrate that includes a mixed-index grid layer as described herein. In addition, the buried grid may not change the appearance of the OLE) compared to devices without a buried grid. For example, the OLED may retain a “mirror” finish if there are no intervening polarizers or other optical structures between the viewer and, the device itself.
Another example calculation of the increase in outcoupling (assuming microlens arrays are place on the substrate on the surface opposite from the OLED) as a function of the indices of refraction of the grid material and “host” material (i.e., the material disposed between the grid lines in the multi-index layer) is shown in
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.
This application claims priority to U.S. Provisional Patent Application Ser. No. 61/909,351, filed Nov. 26, 2013, the entire contents of which is incorporated herein by reference.
This application was made with government support under Contract No. DE-SC0001013 awarded by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, as part of the Center for Energy Nanoscience, Energy Frontier Research Center. The government may have certain rights in this invention.
Number | Date | Country | |
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61909351 | Nov 2013 | US |