Depositor and print head for depositing a non-emissive layer of graded thickness
20190386257 ยท 2019-12-19
Inventors
- William E. Quinn (Whitehouse Station, NJ, US)
- Gregory McGraw (Yardley, PA, US)
- Gregg Kottas (Ewing, NJ)
- Xin XU (Plainsboro, NJ, US)
- Julia J. Brown (Yardley, PA)
Cpc classification
H10K50/852
ELECTRICITY
H10K71/00
ELECTRICITY
H10K59/30
ELECTRICITY
H10K2101/80
ELECTRICITY
International classification
Abstract
Embodiments of the disclosed subject matter provide a depositor device having a first exhaust aperture and a second exhaust aperture, and a plurality of delivery apertures disposed between the first exhaust aperture and the second exhaust aperture. A first aperture of the plurality of delivery apertures may have a first length, and a second aperture of the plurality of delivery apertures may have a second length. The first length may be longer than the second length. The device may include a third aperture of the plurality of delivery apertures which may have a third length, where the second length may be longer that the third length. The plurality of delivery apertures of the device may include three or more delivery apertures having different lengths.
Claims
1. A depositor device comprising: a first exhaust aperture and a second exhaust aperture; and a plurality of delivery apertures disposed between the first exhaust aperture and the second exhaust aperture, wherein a first aperture of the plurality of delivery apertures has a first length, and a second aperture of the plurality of delivery apertures has a second length, and wherein the first length is longer than the second length.
2. The device of claim 1, further comprising: a first gas controller coupled to the first delivery aperture via a first manifold, and a second gas controller coupled to the second delivery aperture via a second manifold.
3. The device of claim 1, wherein a third aperture of the plurality of delivery apertures has a third length, and wherein the second length is longer that the third length.
4. The device of claim 3, further comprising: a third gas controller coupled to the third aperture via a third manifold.
5. The device of claim 3, wherein the first aperture is configured to deposit a first segment of film with a first length of between 0.3 and 3 mm which corresponds to a transport layer in a first-emitting device, wherein the second aperture is configured to deposit a second segment of film with a second length approximately 75% that of the first length which corresponds to a transport layer in a second-emitting device, and wherein the third aperture is configured to deposit a third segment of film with a third length approximately 55% that of the first length which corresponds to a transport layer in a third-emitting device.
6. (canceled)
7. The device of claim 1, wherein the plurality of delivery apertures are connected to a common delivery plenum.
8.-12. (canceled)
13. The device of claim 1, wherein the first aperture is divided into two parts to form a first aperture group, and wherein the second aperture is divided into two parts to form a second aperture group.
14. The device of claim 13, wherein the first aperture group has a first length and width, and the second aperture group has a second length and width, and wherein a first thickness of the first aperture is greater than a second thickness of the second aperture.
15. The device of claim 14, wherein a third aperture of the plurality of delivery apertures has a third length, wherein the second length is longer that the third length, and wherein the third aperture is divided into two parts to form a third aperture group.
16. The device of claim 15, wherein the third aperture has a third thickness, and wherein the second thickness of the second aperture is greater than the third thickness.
17. A depositor device comprising: a first exhaust aperture and a second exhaust aperture; and a plurality of delivery apertures disposed between the first exhaust aperture and the second exhaust aperture, wherein the plurality of delivery apertures extend through a membrane having variable thickness, wherein a first aperture of the plurality of delivery apertures passes through a portion of the membrane having a has a first thickness, and a second aperture of the plurality of delivery apertures passes through a portion of the membrane having a second thickness, and wherein the first thickness is less than the second thickness.
18. The device of claim 17, wherein the first aperture of the plurality of delivery apertures has a first width, and the second aperture of the plurality of delivery apertures has a second width, and wherein the first width is wider than the second width.
19. The device of claim 18, wherein a third aperture of the plurality of delivery apertures has a third width, and wherein the second width is wider that the third width.
20. The device of claim 19, wherein the first aperture is configured to deposit a first segment of film with a first aperture width of between 10 m to 50 m, wherein the second aperture is configured to deposit a second segment of film with a second aperture width approximately 100% to 150% that of the first width, and wherein the third aperture is configured to deposit a third segment of film with a third aperture width approximately 100% to 200% that of the first width.
21. The device of claim 20, wherein the first segment of film is deposited over a first color filter, the second segment of film is deposited over a second color filter, and the third segment of film is disposed over a third color filter.
22. The device of claim 21, wherein a first plurality of emissive layers are deposited over the first segment of film, a second plurality of emissive layers are deposited over the second segment of film, and a third plurality of emissive layers are deposited over the third segment of film.
23. (canceled)
24. The device of claim 20, further comprising a fourth delivery aperture configured to deposit a fourth segment of film, with a fourth aperture width approximately 50% to 200% that of the first width.
25. The device of claim 24, wherein a first emissive layer is deposited over the first segment of film, a second emissive layer is deposited over the second segment of film, a third emissive layer is deposited over the third segment of film, and a fourth emissive layer is deposited over the fourth segment of film.
26.-27. (canceled)
28. A depositor device comprising: a first exhaust aperture and a second exhaust aperture; and a plurality of delivery aperture subunits disposed between the first exhaust aperture and the second exhaust aperture, wherein a first subunit of the plurality of delivery aperture subunits is configured to deposit a film of uniform thickness across a width of a pixel, wherein a second subunit of the plurality of delivery aperture subunits is configured to deposit a film of the same material as the first subunit of uniform thickness over the width of the two subpixels of the pixel with longer wavelength emission, while not adding to the material thickness over the subpixel with shorter wavelength emission, and wherein a third subunit of the plurality of delivery aperture subunits is configured to deposit a film of uniform thickness of the subpixel with the longest wavelength emission, while leaving the other two subpixels unchanged.
29. The device of claim 28, further comprising: a first gas controller coupled to a first delivery aperture of the first subunit via a first manifold; a second gas controller coupled to a second delivery aperture of the first subunit via a second manifold; and a third gas controller coupled to a third delivery aperture of the first subunit via a third manifold.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
[0047] 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.
[0048] 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.
[0049] More recently, OLEDs having emissive materials that emit light from triplet states (phosphorescence) have been demonstrated. Baldo et al., Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices, Nature, vol. 395, 151-154, 1998; (Baldo-I) and Baldo et al., Very high-efficiency green organic light-emitting devices based on electrophosphorescence, Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) (Baldo-II), are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference.
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[0051] More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F.sub.4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. 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.
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[0053] The simple layered structure illustrated in
[0054] 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
[0055] 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.
[0056] 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.
[0057] Devices fabricated in accordance with embodiments of the invention can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices such as discrete light source devices or lighting panels, etc. that can be utilized by the end-user product manufacturers. Such electronic component modules can optionally include the driving electronics and/or power source(s). Devices fabricated in accordance with embodiments of the invention can be incorporated into a wide variety of consumer products that have one or more of the electronic component modules (or units) incorporated therein. A consumer product comprising an OLED that includes the compound of the present disclosure in the organic layer in the OLED is disclosed. Such consumer products would include any kind of products that include one or more light source(s) and/or one or more of some type of visual displays. Some examples of such consumer products include 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, mobile phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, micro-displays (displays that are less than 2 inches diagonal), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screen, and a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 C to 30 C, and more preferably at room temperature (20-25 C), but could be used outside this temperature range, for example, from 40 C to 80 C.
[0058] The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.
[0059] In some embodiments, the OLED has one or more characteristics selected from the group consisting of being flexible, being rollable, being foldable, being stretchable, and being curved. In some embodiments, the OLED is transparent or semi-transparent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes.
[0060] In some embodiments, the OLED further comprises a layer comprising a delayed fluorescent emitter. In some embodiments, the OLED comprises a RGB pixel arrangement or white plus color filter pixel arrangement. In some embodiments, the OLED is a mobile device, a hand held device, or a wearable device. In some embodiments, the OLED is a display panel having less than 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a display panel having at least 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a lighting panel.
[0061] In some embodiments of the emissive region, the emissive region further comprises a host.
[0062] In some embodiments, the compound can be an emissive dopant. In some embodiments, the compound can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence), triplet-triplet annihilation, or combinations of these processes.
[0063] The OLED disclosed herein can be incorporated into one or more of a consumer product, an electronic component module, and a lighting panel. The organic layer can be an emissive layer and the compound can be an emissive dopant in some embodiments, while the compound can be a non-emissive dopant in other embodiments.
[0064] The organic layer can also include a host. In some embodiments, two or more hosts are preferred. In some embodiments, the hosts used maybe a) bipolar, b) electron transporting, c) hole transporting or d) wide band gap materials that play little role in charge transport. In some embodiments, the host can include a metal complex. The host can be an inorganic compound.
Combination with Other Materials
[0065] The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.
[0066] Various materials may be used for the various emissive and non-emissive layers and arrangements disclosed herein. Examples of suitable materials are disclosed in U.S. Patent Application Publication No. 2017/0229663, which is incorporated by reference in its entirety.
Conductivity Dopants:
[0067] A charge transport layer can be doped with conductivity dopants to substantially alter its density of charge carriers, which will in turn alter its conductivity. The conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor may also be achieved. Hole-transporting layer can be doped by p-type conductivity dopants and n-type conductivity dopants are used in the electron-transporting layer.
HIL/HTL:
[0068] A hole injecting/transporting material to be used in the present invention is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material.
EBL:
[0069] An electron blocking layer (EBL) may be used to reduce the number of electrons and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies, and or longer lifetime, as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and or higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in EBL contains the same molecule or the same functional groups used as one of the hosts described below.
Host:
[0070] The light emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as light emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. Any host material may be used with any dopant so long as the triplet criteria is satisfied.
HBL:
[0071] A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies and/or longer lifetime as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and or higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and or higher triplet energy than one or more of the hosts closest to the HBL interface.
ETL:
[0072] An electron transport layer (ETL) may include a material capable of transporting electrons. The electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.
Charge Generation Layer (CGL)
[0073] In tandem or stacked OLEDs, the CGL plays an essential role in the performance, which is composed of an n-doped layer and a p-doped layer for injection of electrons and holes, respectively. Electrons and holes are supplied from the CGL and electrodes. The consumed electrons and holes in the CGL are refilled by the electrons and holes injected from the cathode and anode, respectively; then, the bipolar currents reach a steady state gradually. Typical CGL materials include n and p conductivity dopants used in the transport layers.
[0074] The thickness of the functional layers may be varied in different color subpixels of an OLED display to create a microcavity with optimal outcoupling at a desired emission wavelength from each subpixel type. Embodiments of the disclosed subject matter provide a modified Delivery-Exhaust-Confinement (DEC) type OVJP depositor to print a common charge transport layer of graded thickness over a pixel comprised of multiple monochromatic OLED subpixels of different color. The disclosed subject matter may provide delivery aperture groups fluidly coupled to a common delivery channel such that one or more of the aperture groups has a different hydrodynamic resistance from the others. The deposition rates generated by each delivery aperture group may be different, and may provide a printed film with graded thickness. This film may provide the different thicknesses of a charge transport layer desired for each subpixel. Depositors may be arranged in linear arrays for mass-printing.
[0075] Embodiments of the disclosed subject matter improve an OVJP process, such as disclosed in U.S. Patent Publn. No. 2014/065750, which may be used to deposit a non-emissive layer shared between different colored segments a multicolor OLED array so that the layer is of different thickness in different segments of the array. This may optimize the optical microcavity created by each segment to outcouple the peak emission wavelength of that segment.
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[0077] An alternate approach may be to adjust the thickness of one of the organic layers, usually the hole transport layer. The thickness of the hole transport layer may have little effect on the electronic properties of the device within certain limits, so its thickness may be selected to optimize microcavity effects. Deposition of organic thin films may be typically an additive process, so etching may not be used. A method of accurately depositing an organic thin film of varying thickness in specific locations on the substrate may be selected. Organic vapor jet printing is a spatially selective and scalable organic thin film deposition process that may be able to deposit a charge transport layer of graded thickness over the substrate of a large area multicolor OLED array. The near total isolation between print zones that is provided by OVJP may not be needed when printing hole transport material to generate devices with microcavities of different thicknesses. A few angstroms of cross-talk between zones of graded thickness may have negligible effect if the same material is printed in each zone. Embodiments of the disclosed subject matter may provide an OVJP depositor that is configured to deposit multiple thicknesses of a transport layer of the different color subpixels of a multicolor OLED array.
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[0082] Embodiments of the disclosed subject matter may minimize the non-uniformity within each thickness gradation, both to maintain an optimal microcavity effect and for consistent device electronic properties. The delivery aperture printing each gradation may be divided into a cluster of multiple apertures referred to as an aperture group. Apertures in a group may print the same feature with the same gradation of thickness, but the apertures may be sized and distributed to provide a uniform organic flux onto the substrate.
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[0086] As shown in connection with
[0087] The first aperture of the device may be configured to deposit a first segment of film with a first length of between 0.3 and 3 mm which corresponds to a transport layer in a first-emitting device. The second aperture may be configured to deposit a second segment of film with a second length approximately 75% that of the first length, which corresponds to a transport layer in a second-emitting device. The third aperture may be configured to deposit a third segment of film with a third length approximately 55% that of the first length which corresponds to a transport layer in a third-emitting device. In some embodiments, the lengths of the first second and third apertures may be relative to each other, and the absolute lengths may depend on the configuration of each aperture. For example, the first aperture may have a length of x, the second aperture may have a length of 0.8x, and the third aperture may have a length of 0.6x. In some embodiments, a blue hole transport layer (HTL) may be 1000 (e.g., for the blue subpixel 603 shown in
[0088] In embodiments of the disclosed subject matter, the plurality of delivery apertures of the device may be connected to a common delivery plenum. A delivery channel of the device may carry organic vapor entrained in a delivery gas stream to the plurality of delivery apertures.
[0089] The device may include a first exhaust channel and a second exhaust channel, where the first exhaust channel is coupled to the first exhaust aperture (e.g., exhaust apertures 401 shown in
[0090] The device may include a first transverse channel and a second transverse channel (e.g., transverse channels 505 shown in
[0091] The first aperture of the device may be divided into two parts to form a first aperture group, and the second aperture may be divided into two parts to form a second aperture group (e.g., the aperture groups configured to print thin film gradations of a greater thickness 701, and an intermediate thickness 702, as shown in
[0092] The distribution of organic flux from a depositor onto a substrate may be controlled, and the thickness profile of the layer of non-emissive organic material grown on a substrate. The conductivity of delivery apertures within an array may be varied to achieve a desired flux profile. Two operations by which this can be achieved are illustrated in
[0093] The width of apertures 904 may be varied instead of their length, as shown by the substrate side of the depositor depicted in
[0094] Apertures may be distributed along a printing direction 1001 as illustrated in
[0095] In some embodiments, such as shown in
[0096] The emissive layer (EML) to be disposed may alternatively be an orange EML, a yellow EML, a blue-green EML, a sky-blue EML, or a violet EML. Such EMLs may include a single species of light emitting material, or they may include a mixture of light emitting materials. In some embodiments, an EML with a mixture of light emitting materials may emit white light. Examples of pixel designs with such EMLs are shown in
[0097] Display designs typically have red, green, and blue light emitted by separate subpixels, but some display architectures may include subpixels that emit light that is not of a primary additive color. Microcavities may be optimized for these subpixels as well.
[0098] Emissive layers may overlap in devices with a polychromatic emission spectrum to form stacked devices such as in the example device shown in
[0099] 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.