# Patent

## Title
Multilayer polymer light-emitting diodes for solid state lighting applications

## Abstract

Multilayer polymer light-emitting diodes (PLEDs) are demonstrated using semiconducting polymers blended with organometallic emitters as the emissive layer and one or both of an electron transport layer and a hole transparent layer on the appropriate electron injection and hole injection sides of the emissive layer. The transport layers reduce energy potential gaps between the hole injection electrode and the emissive polymer and between the electron injection electrode and the emissive polymer. A solvent-processing based procedure for preparing these devices is also disclosed It uses nonpolar solvent-based solutions of emissive polymers to form the emissive layer and polar solvent-based solutions to form the transport layers to minimize etching and other undesirable interactions as the multiple layers are being laid down. Illumination quality white light can be obtained with stable Commission Internationale de l'Eclairage coordinates, stable color temperatures, and stable color rendering indices, all close to those of “pure” white light. These multilayer white light-emitting PLEDs are useful as backlights for liquid crystal displays and for solid state lighting applications.

## Background
CROSS-REFERENCE WITH RELATED APPLICATIONS
This present application is a continuation-in-part of application Ser. No. 10/680,084, filed on Oct 6, 2003 now U.S. Pat. No. 7,830,085.


FIELD OF THE INVENTION
This invention is in the field of organic polymer-based light-emitting diodes. More particularly this invention relates to multilayer polymer light-emitting diodes (PLEDs) that, in certain embodiments, emit white light that is useful for solid state lighting applications. This invention also pertains to methods for preparing these diodes.
BACKGROUND OF THE INVENTION
Polymer light-emitting diodes (PLEDs) which employ semiconducting polymers as emitting layers have been demonstrated. A wide range of colors of emission can be achieved by varying the materials present in the emitting layers. Blends of emitting polymers alone and together with organometallic emitters can be used to achieve additional color shades of emitted light including white light.
LEDs that emit white light are of interest and potential importance for use as back lights in active matrix displays (with color filters) and because they can be used for solid state lighting [A. J. Heeger, Solid State Commu., 1998. 107,673 & Rev. Modem Phys., 2001,73, 681; B. W. D'Andrade, S. R. Forrest, Adv. Mater., 2004, 16, 1585; R. H. Friend, R. W. Gymer, A. B. Holmes, J. H. Burroughes, R. N. Marks, C. Taliani, D. D. C. Bradley, D. A. Dos Santos, J. L. Bredas, M. J. Ögdlund, and. W. R. Salaneck, Nature, 1999, 397, 121]. In such applications, the fabrication of large-area devices and the use of low-cost manufacturing technology will be the major issues. The fabrication of PLEDs by processing the active materials from solution (e.g. by use of ink-jet printing or other printing technologies) promises to be less expensive than that of OLEDs (organic light-emitting diodes based on small molecules) where deposition of the active layers requires the use of vacuum technology [B. W. D'Andrade, S. R. Forrest, Adv. Mater., 2004, 16, 1585] Several approaches have been used to generate white light and light of other colors from OLEDs and PLEDs [J. Kido, H, Shionoya, K, Nagai, Appl. Phys. Lett., 1995, 67, 2281-2283; C. Zhang, A. J. Heeger, J. Appl. Phys., 1998, 84, 1579; Z. Shen, P. E. Burrows, V. Bulvić, S. R. Forrest, M. E. Thompson, Science, 1997, 276, 2009; Y. Hamada, T. Sano, H. Fujii, Y. Nishio, Jpn. J. Appl. Phys., 1996, 35, L1339; Y. Z. Wang, R. G. Sun, F. Meghdadi, G. Leising, A. J. Epstein, Appl. Phys. Lett., 1999, 74, 3613; M. Strukelj, R. H. Jordan, A. Dodabalapur, A.; J. Am. Chem. Soc., 1996, 118, 1213; B. W. D'Andrade, R. J. Holmes, and S. R. Forrest, Adv. Mater., 2004, 16, 624]. In the approaches in the articles listed above, the efficiency was modest and the lifetime was limited by that of the blue emitters [J. Kido, H, Shionoya, K, Nagai, Appl. Phys. Lett., 1995, 67, 2281; Y. Hamada, T. Sano, H. Fujii, Y. Nishio, Jpn. J. Appl. Phys., 1996, 35, L1339; Y. Z. Wang, R. G. Sun, F. Meghdadi, G. Leising, A. J. Epstein, Appl. Phys. Lett., 1999, 74, 3613; M. Strukelj, R. H. Jordan, A. Dodabalapur, A.; J. Am. Chem. Soc., 1996, 118, 1213; U. Scherf, E. J. W. List, Adv. Mater. 2002, 14, 477; S. Setayesh, D. Marsitzky, K. Müllen, Macromolecules, 2000, 33, 2016; X. Gong, P. Iyer, D. Moses, G. C. Bazan, A. J. Heeger, Adv. Func. Mater., 2003, 13, 325].
PLEDs fabricated with semiconducting polymers doped with organometallic emitters offer the additional promise of “plastic” electronics. Representative examples of such devices are described in U.S. application Ser. No. 10/680,084 filed Oct. 3, 2003. The emissive layers of PLEDs can be fabricated by casting polymers and blends from solution, thereby enabling relatively simple and low cost manufacturing processes [G. D. Müller, A. Falcou, N. Reckefuss, M. Roijhn, V. Wiederhimggg, P. Rudati, H. Frohne, O. Nuyken, H. Becker, K. Meerholz, Nature, 2003, 421, 829].
The fabrication techniques most favored for producing multilayer PLEDs include the use of sputtering and various vapor deposition methods to lay down inorganic layers such as high work function metal-metal oxide contacts (electrodes) and protective metallic overlayers. Solvent deposition methods such as spin-casting or printing successive layers from solution can be used to lay down organic polymer emissive layers as well as other layers in the devices. When multiple organic layers are present there can be problems with successive layers interacting. The solvent of a later layer can dissolve or disfigure (etch) a prior layer. It is often desirable to have each layer be smooth and coherent, thus this interaction can be destructive.
Light may be characterized by three quantities: the CIE (Commission Internationale de l'Eclairage) coordinates, the color temperature (CT) and the color rendering index (CRI). “Pure” white light has CIE coordinates of (0.333, 0.333), and is obtained by balancing the emission of the colors employed. For illumination applications, the CT needs to be equivalent to that of a blackbody source between 3000°K. and 7500°K. Average daylight has CT=6500°K., while a fluorescent lamp (warm white) has CT=3000°K. [R. W. G. Hunt, Measuring Color, 2nd Ed. Ellis Horwood, 1991]. The CRI is a numerical measure of how “true” colors look when viewed with the light source. CRI values range from 0 to 100, with 100 representing true color reproduction. Fluorescent lamps have CRI ratings between 60 and 99. Though a CIU value of at least 70 may be acceptable for certain applications, a preferred white light source will have a CRI of about 80 or higher. The demonstration of PLEDs which emit illumination quality white light with high brightness, high efficiency, suitable CT, high CRI and stable CIE coordinates is of importance to the future of solid state lighting.
STATEMENT OF THE INVENTION
We have now discovered an improvement in multilayer PLEDs that enhances their efficiency and facilitates their fabrication.
We have found that the addition of an electron transport layer and/or a hole transport layer adjacent to the emissive layer of a PLED improves the PLED's performance. We have further found that these additional layers can be incorporated into PLEDs by solvent processing techniques if the materials employed in these additional layers are differentially soluble in solvents which differ in polarity from the solvents used to dissolve and solvent process the emissive layer.
Thus, this invention can provide multilayer polymer light-emitting diodes (PLEDs) that in certain embodiment emit white light and are useful for solid state lighting applications. More specifically, the present invention can provide multilayer white PLEDs comprising semiconducting polymers blended with organometallic emitters as a relatively nonpolar solvent-soluble emissive layer, and relatively polar solvent-soluble organic materials (polymers or small molecules) as a hole injection/transport layer (HIL/HTL) and/or as an electron injection/transport layer (EIL/ETL); all layers preferably being cast from the corresponding solutions. The white emission of these preferred materials of the present invention can be used for backlights in liquid crystal displays (LCDs) and for solid state lighting applications. The white light is emitted from the polymer blend in a single emissive layer. The strategy developed in this invention enables the fabrication of multilayer white emitting PLEDs by casting the emissive polymer blends, HIL/HTL, and EIL/ETL from the corresponding solutions. This invention also enables the relatively simple fabrication of multilayer PLEDs which emit illumination quality light in all colors from blue to red and including white light. The methodology presented in this invention enables the relatively simple fabrication of multilayer PLEDs which emit illumination quality white light with high brightness, high efficiency, suitable color temperature, high color rendering index, and stable CIE (Commission Internationale de l'Eclairage) coordinates. The method for fabrication of multilayer PLEDs presented in this invention can be used for large-area multilayer displays and other large-area multilayer opto-electronic devices fabricated by casting the various layers from solution.
The devices of the present invention employ an emissive layer and at least one of a hole injection/transport layer (HIL/HTL) and an electron injection/transport layer (EIL/ETL) adjacent to the emissive layer. The benefits of the transport layers can be observed in devices which employ a single layer hole injection anode, in which case the hole transport layer may at times be referred to as a “hole injection/transport layer” or “HIL/HTL.” and also in devices which employ a bilayer anode with the second layer of the bilayer itself being a “hole injection layer.” In this second case, to avoid confusion, the transport layer is referred to simply as a “hole transport layer” or “HTL” and the art-known “hole injection layer” or “HIL” retains its usual name. The devices of the present invention employ relatively nonpolar solvent-soluble semiconducting polymers blended with organometallic emitters as their emissive layers and polar solvent (for example water and/or lower alkanol)-soluble polymers and small molecules as both HIL/HTL and EIL/ETL layers. The devices of the present invention can employ two or three luminescent emitters (represented in the Examples as Type I and Type II devices), in a single emissive region, rather than red, green and blue emission in different regions that appear white when averaged by the observer. More than three emitters can be used as well. The luminescent emitters can emit white light via fluorescence (from singlet states) or a combination of fluorescence (from singlet states) and phosphorescence (from triplet states). White light can be achieved from two or three luminescent emitters blended into a single material that forms a single emissive thin film layer through the combined emission from the host polymer (such as a conjugated polymer) and from the additional emitters such as green and red-emitting components blended into the host polymer. A single emissive layer comprising two or three or more emissive centers allows the fabrication of emitting PLEDs and especially white light-emitting PLEDs by solution processing.
The HIL/HTL and/or EIL/ETL layers provide a means to balance the electron and hole currents and increase the efficiency of the devices. Importantly, using polar solvent-soluble materials as both the HTL and ETL and less polar solvent-soluble materials as the emissive layer allows the fabrication of multilayer PLEDs that emit light with different colors within the visible spectrum, from blue to red and especially white by processing the various layers from solution. The strategy of the present invention enables the relatively simple fabrication of bright and efficient multilayer PLEDs, including white-emitting PLEDs that are characterized by a high color rendering index, suitable color temperature and desired CIE coordinates. Moreover, the color rendering index, color temperature and CIE coordinates from these multilayer electrophosphorescent PLEDs are insensitive to brightness, insensitive to the applied voltage and insensitive to the current density. Furthermore, the method for fabrication of multilayer PLEDs presented in this invention can be used for development of large-area displays comprising multilayer light-emitting diodes and other large-area multilayer opto-electronic devices processed from solution by printing technology.
One object of the present invention is to provide a method to produce multilayer PLEDs and especially white light-emitting PLEDs that exhibit high luminous efficiency, high external quantum efficiency and brightness adequate for applications in solid state lighting and as backlights for liquid crystal displays (LCDs).
Another object of the present invention is to produce high-performance multilayer PLEDs by using polar solvent-soluble polymers and small molecules as a hole injection/transporting layer and/or as an electron injection/transporting layer.
A third object of the present invention is to provide a technology which can be used for development of multilayer displays comprising light-emitting diodes and other multilayer opto-electronic devices processed from solution by printing technology.
Yet another object of the present invention is to produce multilayer white PLEDs that exhibit white light with high color rendering index, suitable color temperature and desired CIE coordinates.
A further object of the present invention is to utilize polar solvent-soluble polymers and small molecules as hole injection/transport layers and/or as electron injection/transport layers in PLEDs.
An additional object of the present invention is to produce multilayer white emitting PLEDs with stable color rendering index, stable color temperature and stable CIE coordinate all of which are insensitive to brightness, applied voltage and current density.
Yet another object of the present invention is to produce multilayer white light-emitting PLEDs that produce white emissions having CIE x, y-chromaticity coordinates close to the CIE coordinates of pure white light (0.333, 0.333).
An additional object of the present invention is to produce multilayer white light-emitting PLEDs that produce white emissions having color temperature close to the 6400°K. value characteristic of average daylight or close to the 4500°K. value characteristic of sunlight at solar altitude 20°.
A further object of the present invention is to produce multilayer white light-emitting PLEDs that produce white emission having color rendering indices in excess of 80.
Yet another object of the present invention is to produce multilayer white light-emitting PLEDs that produce white emission having color rendering indices in excess of 90.



DETAILED DESCRIPTION OF THE INVENTION
Brief Description of the Drawings
This invention will be further described with reference being made to the drawings in which:
FIG. 1 shows the molecular structures of representative materials employed in the fabrication of devices of this invention including: poly(9,9-dioctylfluorene) (FFO); poly(9,9-dioctylfluorene) end-capped with 5-biphenyl-1,3,4-oxadiazole (PFO-ETM) (the electron-transport-moiety); poly(9,9-dioctylfluorene-co-fluorenone) with 1% fluorenone (PFO-F(1%)); tris (2,5-bis-2′-(9′,9′-dihexylfluorene) pyridine) iridium (III), Ir(HFP)3; poly(vinylcarbazole) sulfonic lithium (PVK-S03Li); and 4-(5-(4-tert-butylphenyl)-1,3,4-oxadiazole-2-yl)-biphenyl-4′-yl sulfonic sodium (t-Bu-PBD-S03Na);
FIG. 2 shows several representative device configurations in schematic cross-section;
FIG. 3 shows the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy levels of PFO-ETM, PVK-S03Li, t-Bu-PBD-S03Na and the work functions of PEDOT:PSS and Ba;
FIG. 4 shows the HOMO and LUMO energy levels of PFO-ETM, PFO-F (1%) and Ir (HFP)3;
FIG. 5 shows the electroluminescent spectra of the devices made with pure PFO-ETM, PFO-F (1%) and Ir(HFP)3 doped into PFO-ETM (Ir(HFP)3:PFO-ETM=1 wt.-%), as emissive layers;
FIG. 6 shows the electroluminescent spectra obtained from Type I electrophosphorescent PLEDs at different applied voltages;
FIG. 7 shows the electroluminescent spectra obtained from Type II electrophosphorescent PLEDs at different applied voltages;
FIG. 8 shows the CIE (193 1) chromaticity diagram, with coordinates corresponding to the emission from Type I devices (□□□) and Type II devices (∘∘∘) biased at different applied voltages. Also shown are the equi-energy point (E) for pure white light (0.333, 0.333) (▪) and the coordinates corresponding to color temperatures of 4000°K.(▴), 5000°K.(▾) and 6500°K.(●). The dotted line indicates different color temperatures; the dotted oval indicates the approximate area where the human eye perceives the color as white;
FIG. 9 shows the luminance versus applied voltage and current density versus applied voltage for Type I devices;
FIG. 10 shows the luminance versus applied voltage and current density versus applied voltage for Type II devices;
FIG. 11 shows the forward viewing external luminous efficiency (LEext) versus current density, J (mA/cm2) for devices with poly(3,4-ethylenedioxythophene):styrene sulfonic acid PEDOT:PSS as the HIL/HTL and t-Bu-PBD-SO3Na as the ETL, and for devices with PVK-SO3Li as the HTL and t-Bu-PBD-SO3Na as the ETL, respectively; and the forward viewing external power efficiency (PEext, 1 m/W) versus J (mA/cm2) for Type I devices;
FIG. 12 shows the forward viewing external luminous efficiency (LEext) versus current density, J (mA/cm2) for the devices with PEDOT:PSS as the HIL/HTL and t-Bu-PBD-SO3Na as the EIL/ETL, and for devices with PVK-SO3Li as the HIL/HTL and t-Bu-PBD-SO3Na as the EIL/ETL, respectively; and the forward viewing external power efficiency (PEext, 1 m/W) versus J (mA/cm2) for Type II devices;
FIG. 13 shows the total external luminous efficiency (LEtotal) and the total external power efficiency (PEtotal, 1 m/W) versus current density, J (mA/cm2) for Type I devices with PEDOT:PSS as the HIL, PVK-SO3 as the HTL and t-Bu-PBD-SO3Na as the EIL/ETL; and
FIG. 14 shows the total external luminous efficiency (LEtotal) and the total external power efficiency (PEtotal, 1 m/W) versus current density, J (mA/cm2) for Type II devices with PEDOT:PSS as the HIL and PVK-SO3Li as the HTL and t-Bu-PBD-SO3Na as the EIL/ETL.



DESCRIPTION OF PREFERRED EMBODIMENTS
Nomenclature and Abbreviations
In this description of this invention a variety of chemical compounds will be referred to. Some of the compounds being named are depicted in FIG. 1.
In addition, the following abbreviations will be employed.

    
    
        CIE Commission Internationale de l'Eclairage
        CT color-rendering index
        EIL/ETL electron injection-transport layer
        ETM electron-transport layer
        HIL/HTL hole injection-transport layer
        HIL hole injection layer
        HTL hole transport later
        HFP 9,9-dihexylfluorene pyridine
        HOMO highest occupied molecular orbital
        ITO indium tin oxide
        Ir(HFP)3 tris 2,5-bis-2′(9′,9′ dihexylfluorene) pyridine iridium (III)
        LCD liquid crystal display
        LUMO lowest unoccupied molecular orbital
        MEH-PPV poly[2-methoxy-5-(2-ethyl-hexyloxy)-1,4-phenylenevinylene
        MBL-PPV poly[5-methoxy-2-(4-sulfobutoxy)-1,4-phenylenevinylene
        OLED organic-light-emitting diode
        PLED polymer light emitting diode
        PPV poly(phenylenevinylene)
        PFO poly(9,9-dioctylfluorene)
        PFO-ETM poly(9,9-dioctylfluorene) endcapped with electro-transport-moiety for example, poly(9,9-dioctylfluorene) endcapped with 5-biphenyl-1,3,4 oxadiazole
        PFO-F poly(9,9-dioctyfluorene)-fluorenone
        t-Bu PBD-SO3Na 4-(5-(4-tert-butylphenyl)-1,3,4-oxasiazole-2-yl)biphenyl-4′-yl sulfonic sodium
        PVK poly(vinylcarbazole)
        PVK-SO3Na poly(vinylcarbazole) sulfonic sodium
        PVK-SO3Li poly(vinylcarbazole) sulfonic lithium
        PEDOT: SSS poly(3,4-ethylenedioxythophene): styrene sulfonic acid
        poly(BT[PD-Si-PFCB) poly(bis)tetraphenyldiamino)biphenyl-perfluorocyclobutane
        THF tetrahydrofuran
        DMSO dimethyl sulfoxide
        DMF dimethylformamide

Definitions

    
    


In this description of this invention and in the claims, at times reference is made to solvents as being “polar” or “nonpolar” and reference is made to a material being “differentially soluble” or having “differential solubility” in “polar” or “nonpolar” solvents.
Solvent polarity is defined herein in accord with the teachings of Christian Reichart, Solvents and Solvent Effects in Organic Chemistry, VCH Publishers 2nd ed., 1988. Reichart provides values for relative polarity ranging from a high of 1.000 for water to a low of 0.006 for cyclohexane. Using these relative polarity values, a “polar solvent” is defined to be a solvent having a relative polarity of from 0.400 to 1.000. Such solvents include, for example, water, glycerin, ethylene glycol, methanol, diethylene glycol, ethanol; the propanols, acetonitrile, dimethyl sulfoxide (DMSO) and dimethylformamide (DMF) and mixtures thereof. Water, lower alkanols (C1-C3) and mixtures thereof are preferred polar solvents.
A “nonpolar solvent” is defined to be a solvent having a relative polarity of from 0.006 to about 0.300. Such solvents include, for example, cyclohexane, pentane, hexane, heptane; carbon tetrachloride, xylene toluene, benzene, diethyl ether, methyl-tert-butyl-ether (MTBE), dioxane, tetrahydrofuran (THF), ethyl acetate, glyme, diglyme and chloroform. C6-C8 hydrocarbons and especially benzene and toluene are preferred nonpolar solvents.
In the processing of this invention various materials are said to be “differentially soluble” in a “polar” solvent or a “nonpolar” solvent. This means, at its most general, that the material is more soluble in one family of solvents than the other. Preferably “differential solubility” implies in that a material is at least 150% and more preferably at least 200% and most preferably at least 300% as soluble in one family as in the other.
Device Configurations
As shown as “A” in FIG. 2, PLEDs of the prior art have been made up of a semiconducting luminescent emitter layer 115 contacted with a low work function electron injection electrode 113 and a high work function hole injection electrode 118. As shown in “A,” PLEDs are supported on a substrate 119 which provides mechanical strength and commonly contain a passivation layer 112 to mechanically and chemically protect the electrode on the side away from the support. The positions of support 119 and passivation layer 112, relative to the hole injection electrode 118 and electron injection electrode 113 are most commonly as depicted in FIG. 2. One could reverse these positions if desired and put the electron injection electrode on the support without departing from the spirit of the invention. Similarly, in describing the invention and its advantages, at times references to these “support 119” and “protective outer layer 112” layers may be omitted for simplicity.
As also shown in FIG. 2 at “B,” the prior art further contemplated PLEDs which included a bilayer anode made up of an organic hole injection layer 117 located between the hole injection electrode 118 and the emissive layer 115. This bilayer anode hole injection configuration is known [D. Braun and A. Heeger, Appln. Phys. Lett., 119, 58, 1982].
FIG. 2, at 10, 11 and 12, depicts three configurations for devices of this invention in which one or two additional “transport” layers 114 and 116 are present. When two “transport” layers are present they are on opposite sides of the emissive layer 115 (see 10). When one “transport” layer is present it can be on the electron injection side of layer 115 as EIL/ETL 114 (see 11) or on the hole injection side of layer 115 as HTL 116 (see 12). We have obtained best results when both of EIL/ETL and HTL are present.
It should be kept in mind that the bilayer anode hole injection electrode of prior art B in FIG. 2 includes an organic hole injection layer 117. In embodiment 13, hole injection layer is combined with the hole transport layer as a single HIL/HTL organic layer 120.
These individual layers will next be described.
The Emissive Layer (115)
The emissive layer 115 shown in FIG. 2 comprises a blend (mixture) of one or more emitting polymers (or copolymers) with one or more organometallic emitters. Preferred emitting polymers are generally conjugated. Preferred examples include devices made from PFO or poly(9,9-dioctylfluorene) end-capped with 5-biphenyl-1,3,4-oxadiazol (PFO-ETM) blended with tris (2,5-bis-2′-(9′,9′-dihexylfluorene)pyridine) iridium (III), (Ir(HFP)3) and devices made from blends of PFO-ETM with poly(9,9-dioctylfluorene-co-fluorenone) with 1% fluorenone (PFO-F(1%)) and Ir(HFP)3. FIG. 1 shows the molecular structures of PFO-ETM, PFO-F(1%) and Ir(HFP)3. The synthesis of PFO-ETM has been reported in the scientific literature (X. Gong, W. L. Ma, J. C. Ostrowski, K. Bechgaad, G. C. Bazan, D. Moses, A. J. Heeger, S. Xiao, Adv. Func. Mater., 2004, 14,393]. Other emitting polymers and especially blue-emitting polymers can also be used in the practice of the invention. The synthesis of Ir(HFP)3 has been reported in the scientific literature [J. C. Ostrowski, M. R. Robinson, A. J. Heeger and G. C. Bazan, Chem. Commun., 2002, 7, 784]. The synthesis of PFO-F(1%) was also reported [X. Gong, D. Moses and A. J. Heeger, Synth. Met. 2004, 141, 17]. Ir(HFP)3 is representative of the useful organometallic emitters which are complexes and compounds having Ir, Pr, Os, Ru or Au or the like as a center atom.
High-performance PLEDs based on PFO-ETM as host and organometallic emitters as guests have been previously demonstrated. [X. Gong, W. L. Ma, J. C. Ostrowski, K. Bechgaad, G. C. Bazan, D. Moses, A. J. Heeger, S. Xiao, Adv. Func. Mater., 2004, 14, 393; X. Gong, J. C. Ostrowski, D. Moses, G. C. Bazan, A. J. Heeger, M. S. Liu, A. K-Y. Jen, Adv. Mat. 2003,15,45; X. Gong, J. C. Ostrowski, D. Moses, G. C. Bazan, A. J. Heeger, J. Poly. Sci. Poly. Phys., 2003, 41, 2691].
The polymer materials used in these emissive layers commonly show differential solubility in nonpolar solvents, such as hydrocarbon solvents.
The materials described herein as preferred are preferred in settings where white light emission is desired. The polymers such as PFO-ETM themselves are blue-emitting materials. The organometallic emitter and the other host polymers can produce emissions which result in a white overall emission.
The Electron Injection/Transport Layer (114)
The electron injection/transport layer (EIL/ETL), typically 20 to 30 nm thick, is cast from solution onto the top surface of emissive layer 115 as shown in FIG. 2. The electron injection/transport layer is fabricated from a semiconducting organic polymer material with a relatively large electron affinity; i.e. with a lowest unoccupied molecular orbital (LUMO) close in energy to that of the bottom of the π*-band of the luminescent polymer in the emissive layer, for example within about 1 eV. Preferably the EIL/ETL is fabricated from a material having a LUMO closer to the LUMO of the emissive layer than the work function of the low work function electron injection electrode. Examples include t-Bu-PBD SO3Na [T. J. Boyd, R. R. Schrock, Macromolecules, 1999, 32, 6608]. This layer is cast from a polar solvent-based solution such as an aqueous and/or lower alkanol solution.
The Hole Transport Layer (116)
The hole transport layer (HTL), typically 20 to 30 nm thick, is cast from solution onto the top surface of hole injection layer 117. If the hole injection electrode is a single layer anode 118 which does not have a layer 117, then the layer 116 will be deposited directly in electrode 118 as an HIL/HTL as will explained. The hole injection/transport layer is fabricated from a semiconducting organic polymer material with a relatively small ionization potential; i.e., with highest occupied molecular orbital (HOMO) close in energy to that of the top of the n-band of the luminescent polymer in the emissive layer, for example within about 1 eV. Preferably the HTL is fabricated from a material having a HOMO closer to the HOMO of the emissive layer than the work function of the hole injection electrode. Examples include PVK-S03Li [S. Wang, Z. Zeng, S. Yang, L.-T. Weng, P. C. L. Wong, K. Ho, Macromolecules, 2000, 33, 3232. This layer is cast from a polar solvent-based solution such as an aqueous and/or lower alkanol solution.
The devices of the invention may include a bilayer anode. One layer of a bilayer anode is generally referred to as a “Hole Injection Layer” or “HIL.” If such a layer is present, then this layer 116 will be referred to as a “Hole Transport Layer” or “HTL.” If a separate Hole Injection Layer is not present then layer 116 can serve both functions and can be referred to as a “Hole Injection Transport Layer” or “HIL/HTL.”
The Optional Hole Injection Layer (117)
When a hole injection layer 117 is present to provide a bilayer anode, it is typically 20 to 30 nm thick and is cast from solution onto the electrode 118. Examples of materials used in layer 117 include semiconducting organic polymers such as PEDOT:PSS cast from a polar (aqueous) solution or the precursor of poly(BTPD-Si-PFCB) [S. Liu, X. Z. Jiang, H. Ma, M. S. Liu, A. K.-Y. Jen, Macro., 2000, 33, 3514; X. Gong, D. Moses, A. J. Heeger, S. Liu and A. K.-Y. Jen, Appl. Phys. Lett., 2003, 83, 183]. PEDOT:PSS is preferred. On the other hand, by using poly(BTPD-Si-PFCB) as hole injection layer, many processing issues existing in PLEDs, brought about by the use of PEDOT:PSS, such as the undesirable etching of emissive polymers, undesirable etching of ITO electrodes, and the formation of micro-shorts can be avoided [G. Greczynski, Th. Kugler and W. R. Salaneck, Thin Solid Films, 1999, 354, 129; M. P. de Jong, L. J. van Ijzendoorn, M. J. A. de Voigt, Appl. Phys. Lett. 2000, 77, 2255].
It will be noted that the advantages of using an emissive layer made of polymers differentially soluble in nonpolar solvents with transfer layers made of materials differentially soluble in polar solvents also are achieved when the optional hole injection layer is made of materials differentially soluble in polar solvents. This means that in embodiment 13 of FIG. 2 where a single hole injection/transport layer 120 is employed, it is advantageously differentially soluble in a polar solvent to achieve the desired processing advantages. The materials in this layer 120 can essentially duplicate the materials in layer 117 and layer 116, if desired.
The High Work Function Electrode (118)
The high work function hole injection electrode is typically a transparent conductive metal-metal oxide or sulfide material such as indium-tin oxide (ITO) with resistivity of 20 ohm/square or less and transmission of 89% or greater @ 550 nm. Other materials are available such as thin, transparent layers of gold or silver. A “high work function” in this context is generally considered to be a work function of about 4.5 eV or greater. This electrode is commonly deposited on the solid support 112 by thermal vapor deposition, electron beam evaporation, RF or Magnetron sputtering, chemical deposition or the like. These same processes can be used to deposit the low work-function electrode 113 as well. The principal requirement of the high work function electrode is the combination of a suitable work function, low resistivity and high transparency.
The Low Work Function Electrode (113)
The low work function electrode 113 serves as an electron injection contact. It is typically made of a low work function metal or alloy placed on the opposite side of the active emissive polymeric layer 115 from electrode 118. Low work function metals in the context of the present invention include materials with a work function of about 4.3 eV or less and are known in the art to include, for example Ba, Ca, Mg, In and Th. They are often accompanied by a layer of stable metal such as Ag, Au, Al or the like. This serves as a protection layer on top of reactive materials such as Ba, Ca, Tb. Other low work function (low ionization potential) conducting materials can be used in place of a conventional metal as the electron injection contact. The thickness of the electron injection electrode film is not critical and can be adjusted to achieve the desired surface resistance (surface resistance or sheet resistance is defined as the resistivity divided by the thickness) and can typically vary in the range of from significantly less than 100 Å to about 2000 Å or more. These materials are generally laid down as thin films with the techniques set out in the description of electrode 118.
The Support (119)
The various active layers 113-118 and passivation layer 112 are usually supported by a solid substrate 119. This can be a rigid material such as plastic, glass, silicon, ceramic or the like or a flexible material such as a flexible plastic as well. This support may be transparent (as is the support shown in FIG. 2) in which case the light can be emitted through it and through the transparent electrode 118. Alternatively, the support can be non-transparent, in which case the transparent electrode 118, through which light is emitted, is on the surface of the emissive layer away from the support.
The Passivation Layer (112)
The passivation (protection) layer on the cathode is commonly made up of a stable metal that is typically thermally deposited in vacuum onto the top surface of the low work function metal cathode. Useful metals for the passivation layer are known in the art and include, for example, Ag and Al and the like. The thickness of the passivation layer is not critical and can be adjusted to achieve the desired surface resistance (surface resistance or sheet resistance is defined as the resistivity divided by the thickness) and can vary in the range of from few hundred Angstroms to more than one thousand Angstroms.
Fabrication Methods
The PLEDs of this invention may be fabricated using techniques known in the art, such as solution casting, screen printing, contact printing, precursor polymer processing, melt-processing, and the like to lay down the emissive polymer blend layer 115, hole injection layer 117 and the one or two transport layers 114 and 116. Sputtering, evaporation and the like may be used to lay down the electrode materials in layers 113 and 118 and the passivation materials in layer 112.
In a preferred embodiment, the present invention provides a method for obtaining efficient electrophosphorescent PLEDs by solution processing. The PLED is built up with successive layers as described above. In a most typical embodiment the first of the organic layers, hole injection layer 117 of the bilayer electrode is deposited on a transparent metal/metal oxide electrode 118 itself present on the substrate 119. Layer 117 is cast or printed onto the electrode as a solution. The solvent is removed by evaporation and the next layer in the sequence, hole transport layer 116, is cast onto the previously-deposited layer 117, again as a solution and again with the solvent being removed by evaporation. Next the emissive layer 115 is cast from solution. This solution contains the luminescent polymers and the organometallic emitters that make up the emissive layer. Solvent is removed and the next layer, electron transport layer 114 is deposited as a solution which is dried and overcoated by vacuum depositing electron injection electrode 113 followed by passivation layer 112. In this embodiment it is advantageous if the layers which bound the emissive layers are differentially soluble in a more polar solvent such as water or a relatively polar organic liquid such as a 1 to 3 carbon alkanol, that is methanol, ethanol, propanol or isopropanol or a blend of water and such alkanol and if the solution of luminescent polymers blended with organometallic emitters from which layer 115 is formed is formed in a suitable relatively nonpolar solvent such as a relatively nonpolar organic solvent, especially a relatively nonpolar hydrocarbon or the like. This prevents these successive layers from disrupting, etching and dissolving one another.
By processing the emissive layer and the one or two transport layers from solutions, and particularly solutions in a less polar solvent for the emissive layer and in more polar solvents for the transport layers, the emitted light can be tuned by varying the concentrations. Thus, by processing from solution, efficient white light with stable CIE coordinates, high CRI values and stable color temperature can be achieved from electrophosphorescent PLEDs.
This invention provides white electrophosphorescent PLEDs which have high brightness, stable CIE coordinates close to CIE coordinates (0.333, 0.333) of pure white light, high CRI values and stable color temperature. And more importantly, the white electrophosphorescent PLEDs described herein have CIE coordinates, CIU values and color temperatures that are insensitive to brightness, applied voltages and applied current density.
High brightness, stable CIE coordinates close to those of pure white light (0.333, 0.333) high CRI values, and stable color temperature are critical parameters for light sources that are useful for solid state lighting applications [D. B. Judd and G. Wyszelki, Color in Business, Science and Industry, 3th ed. (John Wiley & Sons) 1975, pp. 91-388; G. Wyszelki and W. S. Stiles, Color Science, 2nd ed. (Wiley, New York) 1982, pp. 117-2321. Thus by processing all active layers from the solutions, high brightness, stable CIE coordinates close to (0.333, 0.333), high CRI values and stable color temperature are obtainable from multilayer white emitting PLEDs. Therefore, this invention discloses a method for obtaining high performance multilayer white PLEDs; a method which is useful for solid state lighting applications.
Mechanism for Generating White Light
The mechanism for achieving white light from the Type I PLEDs of this invention can be described with reference to the representative emissive layer made up of an Ir(HFP)3: PFO-ETM blend. In this case the mechanism involves hole trapping on the Ir(HFP)3 followed by electron trapping on the Ir(HFP)3+ cation [X. Gong, J.C. Ostrowski, D. Moses, G. C. Bazan, and A. J. Heeger, Appl. Phys. Lett., 2002, 81, 3711]. In this representative white emitting PLEDs, a portion of the injected holes (from ITO/PEDOT:PSS or poly(BTPD-Si-PFCB) and electrons (from the Ca/Ag or Ba/Al) recombine on the PFO-ETM main chain to produce blue and/or green light, [X. Gong, P. Iyer, D. Moses, G. C. Bazan, A. J. Heeger, Adv. Func. Mater., 2003, 13, 325]. Another portion of injected holes and electrons are trapped by Ir(HFP)3 with subsequent emission of red light from the triplet of Ir(HFP)3 [X. Gong, J. C. Ostrowski, D. Moses, G. C. Bazan, A. J. Heeger, M. S. Liu, A. K-Y. Jen, Adv. Mat. 2003, 15, 45; X. Gong, J. C. Ostrowski, D. Moses, G. C. Bazan, A. J. Heeger, J. Poly. Sci. Poly. Phys. 2003, 41, 2691; X. Gong, J. C. Ostrowski, D. Moses, G. C. Bazan, and A. J. Heeger, Appl. Phys. Lett., 2002, 81,3711].
In the Type II PLEDs, such as those made from the blends of Ir(HFP)3:PFO-F(1%):PFO-ETM, injected holes and electrons recombine by two processes; direct recombination on the main chain (PFO-ETM) to produce blue and/or green emission in parallel with electron and hole trapping on the fluorenone units and on the Ir(HFP)3 followed by radiative recombination, with green light from PFO-F (1%) [X. Gong, D. Moses and A. J. Heeger, Synthe. Met., 2004, 141, 171 and red light from the triplet excited state of Ir(HFP)3 [X. Gong, J. C. Ostrowski, D. Moses, G. C. Bazan, A. J. Heeger, M. S. Liu, A. K-Y. Jen, Adv. Mat. 2003, 15, 45; X. Gong, J. C. Ostrowski, D. Moses, G. C. Bazan, A. J. Heeger, J. Poly. Sci. Poly. Phys. 2003, 41, 2691; X. Gong, J. C. Ostrowski, M. R. Robinson, D. Moses, G. C. Bazan, and A. J. Heeger, Adv. Mat., 2002, 14, 581; X. Gong, J. C. Ostrowski, D. Moses, G. C. Bazan, and A. J. Heeger, Appl. Phys. Lett., 2002, 81, 3711].
Approaching Balanced Charge Injection and Transport in White PLEDs
The performance improvements attained by the addition of the hole transport layer and the electron transport layer can be explained by reference to FIGS. 3 and 4. FIG. 3 presents the energy levels of the top of the π-band (highest occupied molecular orbital, HOMO) and the bottom of the π*-band (lowest unoccupied molecular orbital, LUMO) of poly(9,9-dioctylfluorene) end-capped with 5-biphenyl-1,3,4-oxadiazol(PFO-ETM), poly(vinylcarbazole) sulfonic lithium (PVK-SO3Li) and 4-(5-(4-tert-butylphenyl)-1,3,4-oxadiazole-2-yl)-biphenyl-4′-yl sulfonic sodium (t-Bu-PBD-SO3Na) and the work functions of barium (Ba) and poly(3,4-ethylene dioxythiophene): poly(styrene sulfonic acid) (PED0T:PSS). FIG. 4 shows the corresponding energy levels of PFO-ETM, tris (2,5-bis-2′-(9′,9′-dihexylfluorene) pyridine) iridium (111), Ir(HFP)3, and fluorenone.
The HOMO energy level of PVK-SO3Li, at −5.75 eV, is well aligned with the HOMO energy level of PFO-ETM, at −5.80 eV, implying a nearly ohmic contact for hole injection from PVK-So3Li to PFO-ETM. The LUMO of t-Bu-PBD-SO3Na, at −2.60 eV, is −0.10 eV higher than the work function of barium, at −2.70 eV. However, even this small electron injection barrier will be reduced by the formation of an interface dipole layer at the Ba/t-Bu-PBD-SO3Na interface [X. Gong, P. Iyer, D. Moses, G. C. Bazan, A. J. Heeger, Adv. Func. Mater., 2003, 13, 325; A. Rajagopal, C. I. Wu, A. Kahn, J. Appl. Phys., 1998, 83, 2649; S. T. Lee, X. Y. Hou, M. G. Mason, C. W. Tang, Appl. Phys. Lett., 1998, 72, 1593]. Therefore, the use of PVK-SO3Li as the hole injection/transport layer from the anode to the emissive polymer layer and t-Bu-PBD-SO3Na as the electron injection/transport layer from the cathode to the emissive polymer layer results in improved transport and high performance white light-emitting PLEDs (see FIGS. 9-14 for results demonstrating this).
In addition, the HTL and ETL block the transport of the electrons and holes, respectively, at the interface between the semiconducting emissive polymer layer and the HTL and/or ETL, thereby enhancing the probability of radiative recombination within the emissive layer. As a result, higher values of luminous efficiency, power efficiency and luminance are achieved (see FIGS. 11 and 12).
Solid State Lighting
For solid state lighting applications, one should include the light emitted through the surface and edge of the glass/ITO substrate when calculating the total efficiency [H. A. E. Keitz, “Light Calculations and Measurements,” 2nd Edition, Macmillan and Co Ltd, 1971; A. D. Ryer, “Light Measurement Handbook.” International Light Inc., 1998]. Assuming typical values for the refractive indices of the glass (n=1.5), IT0 (n=1.8-2.0) and polymer (n=1.6-1.8), the critical angle, θ, between the direction of the light emitted in the polymer layer and the substrate surface normal is  ̃36° at the air-polymer interface and  ̃62° at the glass-polymer interfaces [B. W. D'Andrade, R. J. Holmes, and S. R. Forrest, Adv. Mater., 2004, 16, 624; M. H. Lu, J. C. Sturm, J. Appl. Phys., 2002, 91, 595; J. Kido, Y. Lizurni, Appl. Phys. Lett., 1998, 73, 2721; N.C. Greenham, R. H. Friend, and D. D. C. Bradley, Adv. Mater., 1994, 6, 491]. Light incident on the interface at an angle greater than the critical angle will be totally internally reflected within the glass/ITO and then waveguided within the device. Although some of the guided light escapes by scattering, the remainder is either partially absorbed within the device or coupled out at the edges of the glass/ITO substrate. Theoretically, the fraction of light emitted in the forward direction is 1/(2n2) of the total where n is the index of refraction of emitter layer [N. C. Greenham, R. H. Friend, and D. D. C. Bradley, Adv. Mater., 1994, 6, 491]. More detailed optical modeling predicted (3⁄4n2) as the fraction emitted in the forward direction [J. S. Kim, P. H. Ho, N. C. Greenham, and R. H. Friend, J. Appl. Phys., 2000, 88, 1073]. Through a series of experiments using an integrating sphere, Cao et al. demonstrated that the measured reduction factor is approximately a factor of 2-2.5 less than the theoretical value, (2n2)≈6 (assuming n=1.7 for emitted layer); i.e. closer to 4n2/3≈3.85 [Y. Cao, I. D. Parker, G. Yu, C. Zhang, and A. J. Heeger, Nature, 1999, 397, 414]. Forrest and colleagues have obtained similar results; in the small device approximation, they found that the total LE is larger by a factor of 1.7 ̃-2.4 than observed in the forward viewing direction [B. W. D'Andrade, S. R. Forrest, Adv. Mater., 2004, 16, 1585; B. W. D'Andrade, R. J. Holmes, and S. R. Forrest, Adv. Mater., 2004, 16,624].
EXAMPLES
Example 1
Synthesis of PVK-SO3Li: The sulfonation of PVK was performed by a procedure described in the literature [S. Wang, Z. Zeng, S. Yang, L.-T. Weng, P. C. L. Wong, K. Ho, Macromolecules, 2000, 33, 3232]. The degree of sulfonation of PVK was about 28%. The sulfonated PVK was dissolved in a minimum amount of hot ethanol, and the resulting solution was cooled down to room temperature. To this solution was added excess EtOLi solution in ethanol and white precipitate was formed. The precipitate was collected by filtration, washed with cooled ethanol and dried under vacuum to obtain the lithium salt PVK-SO3Li.
Example 2
Synthesis of t-Bu-PBD-SO3Na: t-Bu-PBD-SO3H was synthesized by a procedure described in the literature [T. J. Boyd, R. R. Schrock, Macromolecules, 1999, 32, 6608]. A concentrated solution of t-Bu-PBD-SO3H in water/THF(v/v 6:1) was added into a salt brine to afford a white precipitate. The precipitate was extracted into ethanol and the ethanol was removed to obtain the desired sodium salt t-Bu-PBD-SO3Na.
Example 3
Three stock solutions, PFO-ETM, PFO-F (1%) and Ir(HFP)3 were prepared by dissolving 50 mg PFO-ETM, 20 mg PFO-F (1%) and 5 mg Ir(HFP)3 into 1 ml toluene, respectively. The resulting 0.5 wt.-% Ir(HFP)3 solution was diluted to 0.05 wt.-% Ir(HFP)3. The mixtures were stirred overnight at 65° C. and then cooled to room temperature.
This example demonstrates that the emissive materials used in the practice of this invention are soluble in common nonpolar organic solvents.
Example 4
Preparation of Type I solution: 2.4 μl of a solution of 0.05 wt.-% Ir(HFP)3 in toluene and 400 μl of a solution of 5 wt.-% PFO-ETM in toluene were added into 197.6 μl of pure toluene.
Preparation of Type II solution: 19.2 μl of a solution of 0.05 wt.-% Ir(HFP)3 in toluene and 400 μl of a solution of wet.-% PFO-ETM in toluene were added into 180.8 μl of pure toluene.
This example demonstrates that solutions of the emissive materials can be made in nonpolar organic solvent at desired concentrations by blending conjugated polymers with organometallic emitters.
Example 5
A solution of 0.5 wt.-% PVK-S033Li in ethanol was prepared.
A solution of 0.5 wt.-% t-Bu-PBD-S03Na in ethanol was prepared.
This example demonstrates that solutions of PVK-S03Li and t-Bu-PBD-SO3Na can be made at desired concentrations in polar solvents.
Example 6
A PVK-S03Li solution prepared according to Example 5 was spin-cast at 5000 rpm in nitrogen atmosphere onto a preformed hole injection layer of PEDOT:PSS and thereafter baked at about 85° C. in a vacuum oven for 24 hours to yield a hole transport layer 116 on top of a hole injection layer 117. Alternative hole transport layers 116 can be used such as, for example, poly(BTPD-Si-PFCB).
Example 7
Type I and Type II solutions prepared according to Example 4 were spin-cast at 2000 rpm in nitrogen atmosphere onto PVK-S03Li layers 116 prepared according to Example 6, and thereafter baked at 65° C. in a nitrogen atmosphere for 20 minutes to yield a variety of emissive layers 115 on hole transport layers 116.
Example 8
t-Bu-PBD-SO3Na solution prepared according to Example 5 was spin-cast at 5000 rpm in nitrogen atmosphere onto the emissive layer 115 and thereafter baked at about 95° C. in vacuum oven for 24 hours to yield a representative electron transport layer 114 on emissive layer 115.
Example 9
A Ba electrode 113 (for electron injection) was formed with a thickness of approximate 100 angstroms onto the t-Bu-PBD-S03Na layer 114 and then a protective Al over layer 112 was deposited with a thickness of approximate 2000 angstroms by vapor deposition at 10−6 Torr. [X. Gong, J. C. Ostrowski, M. R. Robinson, D. Moses, G. C. Bazan, and A. J. Heeger, Adv. Mat. 2002, 14, 581; X. Gong, J. C. Ostrowski, D. Moses, G. C. Bazan, A. J. Heeger, M. S. Liu, A. K-Y. Jen, Adv. Mat. 2003, 15, 45].
Ca or other low work function metals (and their alloys) can be used for the electron injection layer 113.
The overlayer 112 can be made using any inert metal, for example, silver or gold.
Examples 6-9 together demonstrate that multilayer PLEDs can be fabricated by solution processing the organic layers.
Example 10
FIG. 5 shows the electroluminescent spectra obtained from devices made from pure PFO-ETM, PFO-F (1%) and Ir(HFP)3 doped into PFO-ETM (at a concentration of Ir(HFP)3:/PFO-ETM=1 wt. %). The strong green emission from “blue-emitting” PFO-ETM results from fluorenone defects generated during device fabrication/operation [x. Gong, P. Iyer, D. Moses, G. C. Bazan, A. J. Heeger, Adv. Func. Mater., 2003, 13, 325]. The broad green emission from PFO-F (1%) originates from excitation energy transfer in the copolymer from the PFO-ETM majority component to the fluorenone minority component. [X. Gong, D. Moses and A. J. Heeger, Synthe. Met. 2004, 141, 17]. The red emission with maximum at 600 nm and a shoulder at 620 is the Ir(HFP)3 triplet emission. [X. Gong, J. C. Ostrowski, D. Moses, G. C. Bazan, A. J. Heeger, M. S. Liu, A. K-Y. Jen, Adv. Mat. 2003, 15, 45; J. C. Ostrowski, M. R. Robinson, A. J. Heeger and G. C. Bazan, Chem. Commun., 2002, 7, 784].
Example 11
FIG. 6 shows the electroluminescent spectra obtained from Type I devices at different applied voltages. White light was generated from two components, PFO-ETM and Ir(HFP)3; both blue and green from PFO-ETM [X. Gong, P. Iyer, D. Moses, G. C. Bazan, A. J. Heeger, Adv. Func. Mater., 2003, 13, 325] and red from Ir(HFP)3.
Example 12
FIG. 7 shows the electroluminescent spectra obtained from Type II devices at different applied voltages. In this white light PLED, PFO-F (1%) was added into the PFO-ETM:Ir(HFP)3 blends to fine-tune the color distribution. Therefore, white light was generated by Type II devices from three components, PFO-ETM, PFO-F (1%) and Ir(HFP)3; blue and green from PFO-ETM [X. Gong, P. Iyer, D. Moses, G. C. Bazan, A. J. Heeger, Adv. Func. Mater., 2003, 13, 325] and red from Ir(HFP)3, green from PFO-F (1%) [X. Gong, D. Moses, and A. J. Heeger, Synthe. Met. 2004, 141, 171 and red from Ir(HFP)3.
Example 13
The CIE coordinates, CT and CRI were quantitatively evaluated from the electroluminescence spectra obtained in Example 12 [G. Wyszelki and W. S. Stiles, Color Science, 2nd ed. (Wiley, New York) 1982; D. B. Judd and G. Wyszecki, Color in Business, Science and Industry, 3rd ed. (John Wiley & Sons) 1975].
Example 14
FIG. 8 shows the 1931 CIE chromaticity diagram, with coordinates corresponding to the emission from electrophosphorescent PLEDs: data points are shown for both Type I devices (open squares) and Type II devices (open circles) biased at different applied voltages. For Type I devices, the CIE coordinates shift from (0.328, 0.334) at J=0.10 mA/cm2 to (0.296, 0.290) at J=33 mA/cm2; For Type II devices, the CIE coordinates shift from (0.380, 0.400) at J=0.2 mA/cm2; to (0.346, 0.368) at J=115 mA/cm2. All are very close to the CIE coordinates for pure white light, (0.333, 0.333). The stability of the CIE coordinates as a function of applied voltage is much better than reported previously for white PLEDs/OLEDs [J. Kido, H, Shionoya, K, Nagai, Appl. Phys. Lett., 1995,67,2281; Y. Hamada, T. Sano, H. Fujii, Y. Nishio, Jpn. J. Appl. Phys., 1996, 35, L1339; M. Strukelj, R. H. Jordan, A. Dodabalapur, A.; J. Am. Chem. Soc., 1996,118, 1213; B. W. D'Andrade, R. J. Holmes, and S. R. Forrest, Adv. Mater., 2004, 16, 624; Kido, H. Hongawa, K. Okuyama and K. Nagai, Appl. Phys. Lett. 1994, 64, 815; Y. Z. Wang, R. G. Sun, F. Meghdadi, G. Leising, A. J. Epstein, Appl. Phys. Lett., 1999, 74, 3613].
Example 15
Type I devices have CT  ̃6400°K. (see FIG. 8), very close to the CT of average daylight (6500°K.), [R. W. G. Hunt, Measuring Color, 2nd Ed. Ellis Horwood, 1991] and CRI=92. Type II devices have CT  ̃4500°K. (see FIG. 4), very close to the CT of sunlight at solar altitude 20° (4700°K.) [R. W. G. Hunt, Measuring Color, 2nd Ed. Ellis Horwood, 1991], and CRI=86 (all values insensitive to J). The specific concentrations used in the Type I and Type II devices were chosen for example only; the CIE coordinates can be changed continuously by changing the composition of the blends. In FIG. 8, the dotted line indicates different color temperatures; the dotted oval indicates the approximate area where the human eye perceives the color as white.
Example 16
FIG. 9 shows the luminance (L) versus voltage (V) and current-density (J) versus voltage (V) characteristics for Type I devices. All devices turn on at approximately 6 V, which is  ̃1 V higher than the devices without PVK-SO3Li, due to the larger film thickness. Type I devices have Lmax≈2.4 104 cd/m2 at 25 V.
Example 17
FIG. 10 shows the luminance (L) versus voltage (V) and current-density (J) versus voltage (V) characteristics for Type II devices. All devices turn on at approximately 6 V, which is  ̃1 V higher than the devices without PVK-SO3Li, due to the larger film thickness. Type II devices have Lmax≈2.4×104 cd/m2 at 25 V.
Example 18
FIG. 11 shows the forward viewing external luminous efficiency (LEext) versus current density, J (mA/cm2) for Type I devices with PEDOT:PSS as the HIL/HTL, t-Bu-PBD-S03Na as the ETL, and PVK-S03Li as the HTL and t-Bu-PBD-S03Na as the ETL, respectively; and the forward viewing external power efficiency (PEext, lm/W) versus J (mA/cm2).
For display applications, a Lambertian intensity profile was assumed; the forward viewing efficiencies, LEext and PEext shown in FIG. 11, were measured with the following results: [K. Müllen, Editor, Electroluminescence-from Synthesis to Devices, Wiley-VCH, 2005 (in press). Type I devices have LEext=10.4 cd/A, L=2391 cd/m2 and PEext=3 lm/W at J=23 mA/cm2 (V=11 V); Note that even at J=200 mA/cm2, the Type I devices have L=19500 cd/m2, LEext=9.5 cd/A and PEext=2 lm/W. The LEext and PEext at 200 mA/cm2 are significantly higher than any reported previously for white OLEDs and PLEDs [J. Kido, H, Shionoya, K, Nagai, Appl. Phys. Lett., 1995, 67, 2281; C. Zhang, A. J. Heeger, J. Appl. Phys., 1998, 84, 1579; Z. Shen, P. E. Burrows, V. Bulvić, S. R. Forrest, M. E. Thompson, Science, 1997, 276, 2009; Y. Hamada, T. Sano, H. Fujii, Y. Nishio, Jpn. J. Appl. Phys., 1996, 35, L1339; Y. Z. Wang, R. G. Sun, F. Meghdadi, G. Leising, A. J. Epstein, Appl. Phys. Lett., 1999, 74, 3613; M. Strukelj, R. H. Jordan, A. Dodabalapur, A.; J. Am. Chem. Soc., 1996, 118, 1213; B. W. D'Andrade, R. J. Holmes, and S. R. Forrest, Adv. Mater., 2004, 16, 6241.
As shown in FIG. 11, the LEext from white PLEDs with t-Bu-PBD-SO3Na as is higher than that without t-Bu-PBD-SO3Na. Similarly, the LEext from white PLEDs with both PVK-SO3Na as HTL and t-Bu-PBD-SO3Na as ETL are higher than that with only t-Bu-PBD-SO3Na as ETL. Therefore, these results demonstrate that white PLEDs comprising HTL and ETL which reduce the energy barriers for hole and electron injection have the highest LEext and PEext and, correspondingly, the highest L at a given J.
Example 19
FIG. 12 shows the forward viewing external luminous efficiency (LEext) versus current density, J (mA/cm2) for Type II devices with PED0T:PSS as the HIL/HTL, t-Bu-PBD-SO3Na as the ETL, and PVK-SO3Li as the HTL and t-Bu-PBD-SO3Na as the ETL, respectively; and the forward viewing external power efficiency (PEext/lm/W) versus J (mA/cm2).
The measurement approach of Example 18 was repeated LEext=7.2 cd/A, L=882 cd/m2 and PEext=1.5 lm/W at J=12 mA/cm2 (V=15 V). Note that even at J=200 mA/cm2, Type II devices have L=9600 cd/m2, LEext=4.8 cd/A and PEext=0.65 lm/W. Again, the LEext and PEext at 200 mA/cm2 are significantly higher than any reported previously for white OLEDs and PLEDs.
Moreover, as shown in FIG. 12, the LEext from white Type II PLEDs with t-Bu-PBD-SO3Na as ETL is higher than that without t-Bu-PBD-SO3Na. Similarly, the LEext from white PLEDs with both PVK-SO3Na as HTL and t-Bu-PBD-SO3Na as ETL are higher than that only with t-Bu-PBD-SO3Na as ETL.
Example 20
For solid state lighting applications, a Lambertian intensity profile was assumed; the total external luminous efficiency (LEtotal) and power efficiency (PEtotal) were measured with the results shown in FIGS. 13 and 14: [N/. C. Greenham, R. H. Friend, and D. D. C. Bradley, Adv. Mater., 1994, 6, 491-494; J. S. Kim, P. H. Ho, N. C. Greenham, and R. H. Friend, J. Appl. Phys., 2000, 88, 1073; Y. Cao, I. D. Parker, G. Yu, C. Zhang, and A. J. Heeger, Nature, 1999, 397, 414; Commission International de l'Éclairage: Measurement of LEDs, CIE publication 127; B. W. D'Andrade, S. R. Forrest, Adv. Mater., 2004, 16, 1585; B. W. D'Andrade, R. J. Holmes, and S. R. Forrest, Adv. Mater., 2004, 16, 624; K. Mullen, Edited, Electroluminescence-from Synthesis to Devices, Wiley-VCH, 2005 (in press); M. H. Lu, J. C. Sturm, J. Appl. Phys., 2002, 91, 5951.
FIG. 13 shows the total external luminous efficiency (LEtotal,) and the total external power efficiency (PEtotal, lm/W) versus current density J (mA/cM2) for Type I devices with PEDOT:PSS as the HIL, PVK-SO3Li as the HTL and t-Bu-PBD-SO3Na as the EIL/ETL.
FIG. 14 shows the total external luminous efficiency (LEtotal) and the total external power efficiency (PEtotal, MW) versus current density J (mA/cm2) for Type II devices with PEDOT:PSS as the HIL and PVK-SO3Li as the HTL and t-Bu-PBD-SO3Na as the EIL/ETL. As reflected in these Figures, Type I devices have LEtotal=21 cd/A and PEtotal=6 lm/W at J=23 mA/cm2 and Type 11 devices have LEtotal=16 cd/A and PEtota=3 lm/W at J=12 mA/cm2.

## Claims

1. In an organic polymer-based light-emitting device comprising an electron injection electrode and a hole injection electrode on opposite sides of an emissive layer, the emissive layer comprising at least one luminescent first semiconducting polymer capable of fluorescent emission serving as host to at least one admixed phosphorescent emitter capable of phosphorescent emission, the improvement comprising at least one of:
an organic electron transport layer comprising a second semiconducting polymer disposed between the electron injection electrode and the emissive layer and having a lowest unoccupied molecular orbital close in energy to the bottom of the Π* band of the luminescent polymer; and
an organic hole transport layer comprising a third semiconducting polymer disposed between the hole injection electrode and the emissive layer and having a highest occupied molecular orbital close in energy to the top Π band of the luminescent polymer.

2. The light-emitting device of claim 1 comprising an electron transport layer.

3. The light-emitting device of claim 2 wherein the second semiconducting polymer has a lowest unoccupied molecular orbital having an energy level between the bottom of the Π* band of the luminescent polymer and the work function of the electron injection electrode.

4. The light-emitting device of claim 1 comprising a hole transport layer.

5. The light-emitting device of claim 4 wherein the third semiconducting polymer has a highest occupied molecular orbital having an energy level between the top Π band of the luminescent polymer and the work function of the hole injection electrode.

6. The light-emitting device of claim 1 wherein the hole injection electrode is a bilayer electrode itself comprising a high work function electrode and an organic hole injection layer between the high work function electrode and the emissive layer.

7. The light-emitting device of claim 1 wherein the emissive layer comprises a conjugated polymer.

8. The light-emitting device of claim 1 wherein the emissive layer comprises a single phosphorescent emitter and wherein the first semiconducting polymer serves as host to the phosphorescent emitter.

9. The light-emitting device of claim 1 wherein the emissive layer comprises two or more phosphorescent emitters and wherein the first semiconducting polymer serves as common host to the two or more phosphorescent emitters.

10. A multilayer organic polymer-based light-emitting device comprising in layer order one to another: a low work function electrode, an organic polymer-based electron injection/transport layer, an emissive layer comprising a semiconducting organic polymer and at least one phosphorescent emitter, an organic polymer-based hole transport layer, and a high work function electrode.

11. The light-emitting device of claim 10 additionally comprising a substrate and a protective layer, one of which is positioned adjacent to the low work function electrode and the other of which is positioned adjacent to the high work function electrode, and at least one of which is transparent to at least a portion of light produced in the emissive layer.

12. The light-emitting device of claim 10 wherein the emissive layer comprises a semiconducting polymer differentially soluble in nonpolar solvents and the transport layers each comprise a polymer differentially soluble in polar solvents.

13. The light-emitting device of claim 10 wherein the emissive layer comprises a conjugated polymer.

14. The light-emitting device of claim 10 wherein the emissive layer additionally comprises a single phosphorescent emitter and wherein the semiconducting polymer serves as host to the phosphorescent emitter.

15. The light-emitting device of claim 10 wherein the emissive layer additionally comprises two or more phosphorescent emitters and wherein the semiconducting polymer serves as common host to the two or more phosphorescent emitters.

16. The light-emitting device of claim 10, wherein the emissive layer comprises: a. at least one organic polymeric fluorescent emitter, and b. at least one phosphorescent emitter in intimate admixture as a single emissive region; and wherein the emission from the at least one organic polymeric fluorescent emitter is higher in photon energy than the emission from the at least one phosphorescent emitter, and wherein the combined emission of the at least one organic polymeric fluorescent emitter and the at least one phosphorescent emitter sufficiently spans the visible spectrum to give a white emission.

17. The A multilayer organic polymer-based light-emitting device comprising in layer order one to another: a low work function electrode, an organic polymer-based electron injection/transport layer, an emissive layer comprising a semiconducting organic polymer and at least one phosphorescent emitter, an organic polymer-based hole transport layer, and a high work function electrode;
wherein the high work function electrode is a bilayer electrode itself comprising a high work function layer and an organic polymer-based hole injection layer between the high work function layer and the hole transport layer.

18. In an organic polymer-based white light-emitting device comprising an electron injection electrode and a hole injection electrode on opposite sides of an emissive layer, the emissive layer comprising at least one luminescent first semiconducting polymer capable of fluorescent emission serving as host to at least one admixed phosphorescent emitter capable of phosphorescent emission, wherein the device, at J=200 mA/cm2, L equal to at least about 10000 cd/m2, LEext equal to at least about 10 cd/A and PEext equal to at least about 2 lm/W.

19. The light-emitting device of claim 18, wherein the device comprises an emissive layer comprising a single phosphorescent emitter.

20. The white light-emitting device of claim 19 having a color temperature of about 6400°K.

21. The white light-emitting device of claim 18 being a Type II device, wherein the device comprises an emissive layer comprising two or more phosphorescent emitters.

22. The white light-emitting device of claim 18 emitting light having a color rendering index in excess of 80.

23. The white light-emitting device of claim 21 having a color temperature of about 4700°K.

24. The white light-emitting device of claim 22 fabricated as a multilayer device by sequential solution processing and being suitable for solid state light applications.

25. The white light-emitting device of claim 22 having, at J=23 mA/cm2, luminance equal to at least about 20000 cd/m2, LEtotal equal to at least about 20 cd/A and PEtotal equal to at least about 6 lm/W and being suitable for solid state light applications.

26. In an organic polymer-based light-emitting device comprising an electron-injection layer and a hole-injection layer on opposite sides of an emissive layer, the emissive layer comprising at least one luminescent first semiconducting polymer capable of fluorescent emission serving as host to at least one admixed phosphorescent emitter capable of phosphorescent emission, the improvement comprising at least one of an organic electron transport layer comprising a second semiconducting polymer disposed between the electron injection layer and the emissive layer and having a lowest unoccupied molecular orbital close in energy to the bottom of the Π band of the luminescent polymer an organic hole transport layer comprising a third semiconducting polymer disposed between the hole injection layer and the emissive layer and having a highest occupied molecular orbital close in energy to the top Π band of the luminescent first semiconducting polymer, said first semiconducting polymer being differentially soluble in a first solvent and at least one of said second and third semiconducting polymers being differentially soluble in a second solvent, said first and second solvents differing in polarity from one another.

27. The light-emitting device of claim 26 wherein the first solvent is less polar than the second solvent.

28. The light-emitting device of claim 27 wherein the first solvent comprises a liquid hydrocarbon and the second solvent comprises a lower alkanol.

29. A method for fabricating a light-emitting device of claim 26 which comprises laying down the emissive layer as a solution in said first solvent and evaporating the first solvent and laying down the at least one of the electron transport layer and the hole transport layer as a solution in said second solvent and evaporating the second solvent.

30. The method of claim 29 wherein the solvent evaporating is completed for a first layer before a second layer is laid down.

31. The method of claim 29 comprising laying down both an electron transport layer and a hole transport layer and wherein the hole transport layer is laid down first, followed by the emissive layer and thereafter followed by the electron transport layer.

32. The method of claim 31 wherein the solvent for the emissive layer solution is a more nonpolar solvent and wherein the solvent for the electron transport layer solution is the same or different than the solvent for the hole transport layer solution with the solvents for the transport layer solutions being more polar than the solvent for the emissive layer.

33. The method of claim 32 wherein the solvent for the emissive layer comprises a nonpolar hydrocarbon and wherein the solvents for the transport layers comprise a lower alkanol.