APPLIED PHYSICS LETTERS 88, 183503 2006

Ultraviolet electroluminescence and blue-green phosphorescence using an organic diphosphine oxide charge transporting layer
P. E. Burrows, A. B. Padmaperuma, and L. S. Sapochak
Energy Science and Technology Directorate, Pacic Northwest National Laboratory, Richland, Washington 99352

P. Djurovich and M. E. Thompson

Department of Chemistry, University of Southern California, Los Angeles, California 90089

Received 16 November 2005; accepted 24 February 2006; published online 2 May 2006 We report electroluminescence at 338 nm from a simple bilayer organic light-emitting device OLED made using 4 , 4 -bis diphenylphosphine oxide biphenyl PO1 . In an OLED geometry, the material is preferentially electron transporting. Doping the PO1 layer with iridium III bis 4,6- di-uorophenyl -pyridinato-N,C2 picolinate FIrpic gives rise to electrophosphorescence with a peak external quantum efciency of 7.8% at 0.09 mA/ cm2 and 5.9% at 13 mA/ cm2. The latter current density is obtained at 6.3 V applied forward bias. 2006 American Institute of Physics. DOI: 10.1063/1.2193429 Most OLEDs with adequate efciency for display applications now utilize a composite emission layer consisting of a charge transporting host material doped with of a luminescent molecule. Achieving the highest possible quantum efciency requires the use of organic phosphorescence in order to harvest the triplet excitons formed as a result of the uncorrelated injection of electrons and holes. Excitons reach the dopant by Frster or Dexter energy transfer. Blue organic phosphorescence presents unique challenges since the triplet state of the host material must be higher than that of the blue phosphorescent dopant, otherwise energy transfer to quenching or lower energy longer wavelength sites will occur. Blue-green phosphorescent OLEDs were rst demonstrated using an endothermic energy transfer from a N , N -dicarbazolyl-4 , 4 -biphenyl CBP .1 The efciency of the endothermic transfer is limited. Increasing the host triplet energy is therefore important and has been accomplished by reducing the conjugation length of the host molecule2 or by using an electrically inert host and relying on a high doping level of the phosphor to carry the charge and emit light.3 A wide band gap, charge transporting host material is of interest to enable the efcient blue phosphorescent OLEDs at a lower voltage than is achievable using an inert matrix. Relatively few wide band gap electroluminescent EL materials have been published, limited to EL peaking at 405 410 nm from polysilane derivatives at 30 V,47 and in biphenyl derivatives peaking at 390 nm 10 V 8 and 372 nm 16 V .9 In this letter, we report EL at a peak wavelength of 338 nm from a wide band gap electron transporting organic material; 4 , 4 -bis diphenylphosphine oxide biphenyl PO1 . The observation of EL below 370 nm demonstrates the potential to develop a family of ultrawide band gap organic materials to function as charge conducting host layers for blue electrophosphorescent OLEDs. There are only a few examples reported of organophosphorus compounds used as the emitter in OLEDs.10,11 Triaryl phosphine oxide moieties have been incorporated into high performance polymers to impart high oxidative, thermal, and chemical stabilities,12 used as a polarizing group in nonlinear optical NLO polymers,13 and used as ancillary ligands in EL lanthanide complexes.14 More recently a Cs:phenyldipyrenylphosphine oxide layer was used as an electron transport layer in an OLED to improve electron injection properties through the formation of a charge transfer complex.15 However, studies of triaryl phosphine oxide materials as an active emissive and charge transporting layer in OLEDs, have not been reported. The photoluminescence spectrum of a 540 thick lm of PO1 grown by vacuum evaporation on a fused quartz substrate is illustrated in Fig. 1, peaking at 332 1 nm. The excitation wavelength was 270 nm from a xenon lamp. The phosphorescence spectrum, also shown in Fig. 1, was obtained from a frozen 2-methyltetrahydrofuran 2MeTHF glass at 77 K. From the optical data, the singlet and triplet exciton energies in PO1 are 4.11 and 2.72 eV, respectively. The radiative lifetime of the phosphorescence was measured to be 1.7 0.1 s, consistent with relatively weak spin-orbit coupling from the light P atom. The respective spectra are similar to those of the biphenyl chromophore,16 because the diphenylphosphine oxide groups prevent electron communication between the central biphenyl core and the outer phenyl groups in PO1 and polarize the biphenyl core resulting in high energy UV emission and high solution uorescence quantum efciency s = 0.73 vs quinine sulfate in 0.1 N H2SO4 .17 No measurable phosphorescence is observed in optically pumped thin lms at room temperature.

FIG. 1. Photoluminescence spectra of PO1; a room temperature solution in CH2Cl2, b room temperature 540 thick lm on quartz, c 77 K in 2MeTHF glass, d 77 K in 2MeTHF glass delayed by 300 s after the excitation pulse.

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FIG. 2. EL spectra of CuPc /PO1 bilayer devices at various PO1 thicknesses; a 270, b 430, c 540, and d 810 . The broken line shows the transmission of the glass+ ITO+ CuPc layers for which the data are corrected.

FIG. 3. EL spectra of CuPc/TPD/PO1 at various PO1 thicknesses; a 270, b 430, c 540, and d 810 . Dotted line e shows the EL spectrum of a PO1 layer doped with 33% by mass of TPD.

A simple OLED structure was grown on glass, precoated with ITO 15 / sq . The devices consisted of a 200 thick lm of copper phthalocyanine CuPc followed by a 200 800 thick lm of PO1. Cathodes consisting of a 6 thick lm of LiF, immediately followed by a 1000 thick layer of Al were deposited by thermal evaporation through a stencil mask. With the exception of the Al, which was evaporated from an Al-wrapped W wire, all layers were deposited from bafed Ta boat sources. With the cathode biased negative with respect to the anode, EL in the UV 330 350 nm depending on layer thickness was measured at a low voltage 13 mA/ cm2 injected current at 3.1 7.6 V using a PO1 layer thickness of 270 810 , respectively . The EL spectra, shown in Fig. 2, closely resemble the uorescence measured from PO1 thin lms with small shifts as a function of layer thickness due to weak microcavity effects.18 A weak longer wavelength tail is observed from 400 to 500 nm, which we speculate is due either to aggregates or PO1 electrophosphorescence. This tail is not observed in room temperature photoluminescence experiments either in solution or in thin lm suggesting that excimer emission does not play a role. Table I shows the device operating voltage at 13 mA/ cm2 injected current
TABLE I. Summary of PO1 device operating voltage Vop and external quantum efciency QE . Both are reported at 13mA/ cm2 forward current injection which represents 200 cd/ cm2 brightness. For the phosphorescent doped devices, the peak QE is also given which is typically at 10 20 cd/ m2. Structure PO1 thickness 270 430 540 810 270 430 540 810 600 Vop 3.1 4.3 5.3 7.6 4.0 4.8 6.9 11.5 9.6 QEop 0.008 0.032 0.044 0.016 0.053 0.074 0.091 0.079 0.20

CuPc/PO1

CuPc/TPD/PO1 CuPc/TPD/ PO1:33%TPD/PO1

Phosphorescent OLEDs 5% FIrpic 10% FIrpic 20% FIrpic 7.0 6.7 6.3 2.5 4.5 peak 5.0 6.2 peak 5.9 7.8 peak

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and the external quantum efciency, measured using a 1 cm2 Si photodetector placed behind the OLED. The data are corrected for absorption in the glass substrate, the ITO layer and the CuPc also shown in Fig. 2 , which becomes signicant at wavelengths 350 nm. No further corrections are made for light waveguided in the organic thin lms or the substrate.19 No light was observed when the cathode was biased positively with respect to the anode, nor from a bilayer device consisting of a 400 thick layer of PO1 capped with a 400 thick layer of tris 8-hydroxyquinoline aluminum III . Both these observations suggest that PO1 preferentially transports electrons and blocks holes in an OLED geometry. Indeed, the low observed quantum efciency in all these devices is partially ascribed to a lack of electron connement in the bilayer structure, since CuPc is also a good electron conductor.20 Furthermore, a high barrier to hole injection into PO1 is consistent with electronic structure calculations, which predict a substantial lowering of the PO1 highest occupied molecular orbital HOMO energy by 1.7 eV compared to the corresponding hole transporting diamine structure 4 , 4 -bis diphenylamine biphenyl DDB . The calculated HOMO energy B3LYP/ 6-31+ G* of geometry optimized PO1 and DDB are 6.69 and 4.98 eV, respectively.21 The corresponding calculated lowest unoccupied molecular orbital LUMO energies of PO1 and DDB are 1.77 and 1.20 eV, respectively. Whereas the increased band gap of PO1 is therefore attributed primarily to the lowering of the HOMO, a somewhat lower LUMO energy for PO1 is also consistent with a reversible reduction potential found in the solution at 2.33 V versus ferrocenium/ ferrocene and suggests that PO1 can also serve as an effective electron transport material. Whether PO1 is an n- or p-type charge transport material, however, cannot be determined from these simple OLED structures and will be the subject of future studies. To improve electron connement in the PO1 layer, a second set of devices was fabricated consisting of, in sequence, a 200 thick layer of CuPc, a 50 thick layer of 4 , 4 -bis N- m-tolyl -N-phenyl-amino biphenyl TPD , and various thicknesses of PO1, again capped with a LiF:Al cathode. Electroluminescent spectra are shown in Fig. 3. Both the external quantum efciency QE Table I of the EL and the operating voltage were signicantly larger than in the simple bilayer devices, suggestive of improved carrier connement due to the blocking of electrons by the thin TPD layer, however, the UV EL became dominated by a longer

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FIG. 4. The device structure is CuPc 200 / -NPD 200 /TCTA 60 / FIrpic doped PO1 200 /PO1 200 /LiF 6 /Al 1000 . TCTA is 4 , 4 , 4 -tris carbazol-9-yl -triphenylamine and -NPD is N , N -diphenylN , N -bis 1-naphthol 1 , 1 -biphenyl-4 , 4 diamine.

coupled with small rotational barriers about the P-aryl bonds creates a high propensity for crystallization in PO1, which we expect will be reduced via substitution of more rigid bridges and outer group structures. In conclusion, we have demonstrated singlet UV EL and efcient, low voltage blue-green electrophosphorescence from an OLED containing an electron transporting organic phosphine oxide compound doped with a blue organometallic phosphor. These studies of PO1 demonstrate that organic phosphine oxide materials can function as wide band gap electron transporting host materials for blue electrophosphorescent devices and provide low operating voltages even without conductivity doping. The authors acknowledge nancial support from the U.S. Department of Energy/Building Technologies SolidState Lighting Program, PNNL LDRD program, and P.D. and M.E.T. acknowledge support from Universal Display Corporation. We also thank Dr. Kim Ferris for theoretical calculations. Pacic Northwest National Laboratory PNNL is operated by the Battelle Memorial Institute for the U.S. Department of Energy DOE under Contract No. DE-AC0676RLO 1830.
C. Adachi, R. C. Kwong, P. Djurovich, V. Adamovich, M. A. Baldo, M. E. Thompson, and S. R. Forrest, Appl. Phys. Lett. 79, 2082 2001 . 2 R. J. Holmes, S. R. Forrest, Y.-J. Tung, R. C. Kwong, J. J. Brown, S. Garon, and M. E. Thompson, Appl. Phys. Lett. 82, 2422 2003 . 3 R. J. Holmes, B. W. DAndrade, S. R. Forrest, X. Ren, J. Li, and M. E. Thompson, Appl. Phys. Lett. 83, 3818 2003 . 4 C.-H. Yuan, S. Hoshino, S. Toyoda, H. Suzuki, M. Fujiki, and N. Matsumoto, Appl. Phys. Lett. 71 3326 1997 . 5 S. Hoshino, K. Furukawa, K. Ebata, C.-H. Yuan, and H. Suzuki, J. Appl. Phys. 88, 2892 2000 . 6 S. Hoshino, K. Ebata, and K. Furukawa, J. Appl. Phys. 87, 1968 1999 . 7 H. Suzuki, S. Hoshino, C.-H. Yuan, M. Fujiki, S. Toyoda, and N. Matsumoto, Thin Solid Films 331, 64 1998 . 8 L. Zou, V. Savvateev, J. Booher, C.-H. Kim, and J. Shinar, Appl. Phys. Lett. 79, 2282 2001 . 9 H. Zhang, B. Yang, Y. Zheng, G. Yang, L. Ye, Y. Ma, X. Chen, G. Cheng, and S. Liu, J. Phys. Chem. B 108, 9571 2004 . 10 A. B. Padmaperuma, G. Schmett, D. Fogarty, N. Washton, S. Nanayakkara, L. S. Sapochak, K. Ashworth, L. Madrigal, B. Reeves, and C. S. Spangler, Mater. Res. Soc. Symp. Proc. 621, Q3.9.1 2000 . 11 C. Fave, T.-Y. Cho, M. Hissler, C.-W. Chen, T.-Y. Luh, C.-C. Wu, and R. Rau, J. Am. Chem. Soc. 125, 9254 2003 . 12 K. A. Watson, F. L. Palmieri, and J. W. Connell, Macromolecules 35, 4968 2002 . 13 K. L. Kott, C. M. Whitaker, and R. J. McMahon, Chem. Mater. 7, 426 1995 . 14 X.-C. Gao, H. Cao, C.-H. Huang, B.-G. Li, K. Ibrahim, F.-Q. Liu, and S. Umitani, Chem. Phys. Lett. 297, 530 1998 . 15 T. Oyamoad, H. Sasabe, C. Adachi, S. Murase, and T. Tominaga, Appl. Phys. Lett. 86, 033503 2005 . 16 H. V. Taylor, A. L. Allred, and B. M. Hoffman, J. Am. Chem. Soc. 95, 3215 1973 . 17 S. I. Klink, G. A. Hebbink, L. Grave, P. G. B. Oude Alink, F. C. J. M. Van Veggel, and M. H. V. Werts, J. Phys. Chem. A 106, 3681 2002 . 18 V. Blovic, V. B. Khaln, G. Gu, P. E. Burrows, D. Z. Garbuzov, and S. R. Forrest, Phys. Rev. B 58, 3730 1998 . 19 S. R. Forrest, D. D. C. Bradley, and M. E. Thompson, Adv. Mater. Weinheim, Ger. 15, 1043 2003 . 20 T. Yasuda and T. Tsutsui, Chem. Phys. Lett. 402, 395 2005 . 21 It is understood that electronic structure calculations for a particular molecule is dependent on the basis set used and often differ signicantly from experimental measurements, however, it has been shown that calculations for a series of molecules accurately predict trends within the series as interpreted here, see, e.g., P. Marsal, I. Avilov, D. A. da Silva Filho, J. L. Brdas, and D. Beljonne, Chem. Phys. Lett. 392, 521 2004 . 22 American Dye Source, Inc., Quebec, Canada.
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wavelength peak at 480 500 nm. A further small peak at 405 nm was ascribed to the exciton recombination in the TPD layer. Indeed, thicker layers of TPD resulted in predominately TPD EL, indicating that PO1 behaves as an effective hole blocking layer. The longer wavelength emission is consistent with a recombination from a TPD-PO1 exciplex. This was conrmed by doping 33% by mass of TPD into the PO1 layer, which yielded the EL also shown in Fig. 3 and summarized in Table I. To demonstrate the potential of PO1 as a host material for blue electrophosphorescence, we made a third series of devices using the shortest wavelength commercially available phosphorescent dopant, iridium III bis 4,6- diuorophenyl -pyridinato-N, C2 picolinate FIrpic 22 doped at various concentrations into PO1. The as-purchased FIrpic was further puried by temperature gradient sublimation before use. The device structure was modied from the published work using an inert, tetraaryl silane-based host matrix.3 In our devices, we expect the PO1 matrix to support electron conduction, while holes are injected and transported directly onto the FIrpic dopant. The quantum efciency and operating voltage of this series of devices is shown in Fig. 4. Using 20% FIrpic in PO1, we obtain a peak quantum efciency of 7.8% at 0.09 mA/ cm2 18 cd/ m2 and 3.9 V and 5.9% at 13 mA/ cm2 and 6.3 V at a brightness of 1920 cd/ m2. These data correspond to efciencies of 20.8 and 15.8 cd/ A, respectively. Assuming approximately Lambertian emission into steradians, the maximum and bright luminous efciencies are 19.7 and 7.9 lm/ W, respectively. While the measured quantum efciencies are comparable to those obtained using inert host materials, the operating voltage is signicantly lower and is, furthermore, less dependent on the dopant molecule concentration. The emission spectra from all except the lowest doping ratio showed only FIrpic emission indicating complete energy transfer to the phosphorescent dopant. The 5% doped device spectrum contained a small amount of NPD and TCTA emission, suggesting both poor hole injection into the doped PO1 layer in this device and weak electron connement. This conrms that holes are injected onto FIrpic rather than into the PO1 HOMO. We have not performed lifetime testing on devices appropriately encapsulated for long operating lifetimes, however, unencapsulated devices show visible crystallization after 24 h of storage in N2. Although the glass transition temperature of PO1 is 90 C, the polar P v O moieties

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