Synthetic Metals 140 (2004) 101104

Efcient blue-to-violet organic light-emitting diodes

Chengfeng Qiu, Haiying Chen, Man Wong*, Hoi S. Kwok
Department of Electrical and Electronic Engineering, Center for Display Research, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong Received 22 April 2002; received in revised form 27 January 2003; accepted 8 May 2003

Abstract Organic light-emitting diodes emitting in the range of 400 nm (violet) to 460 nm (blue) are reported. The basic device structure consists of indiumtin oxide/N,N0 -diphenyl-N,N0 -bis-(3-methylphenyl)-1,10 -biphenyl-4,40 -diamine (TPD)/2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP)/lithium uoride (LiF)/aluminum. Offset of the energy levels at the TPD/BCP interface favors blocking of holes on the TPD side of the interface. Voltage-induced color change is observed and explained in terms of a switching from emission dominated by interfacial exciplex-induced recombination at low applied bias to one dominated by bulk exciton-induced recombination at high applied bias. With the addition of copper(II) phthalocyanine (CuPc) as an anode buffer layer and tris-8-(hydroxyquinoline) aluminum (Alq3) as a cathode buffer layer, external quantum efciencies as high as 0.5% at blue emission and 0.4% at violet emission have been obtained. # 2003 Elsevier B.V. All rights reserved.
Keywords: Organic light-emitting diode; Violet light; Voltage-tunable emission; Exciplex

1. Introduction Organic light-emitting diodes (OLEDs) [1] are challenging liquid-crystals as an alternative at-panel display technology because of their relative merits of being self-emitting with a wider viewing angle, having a faster switching speed and being easier to manufacture because of their all solidstate nature. Using N,N0 -diphenyl-N,N0 -bis-(3-methylphenyl)-1,10 biphenyl-4,40 -diamine (TPD) as a hole transport layer and 4-dicyanomethylene-6-(p-dimethylaminostyryl)-2-methyl4H-pyran (DCM)-doped tris-8-(hydroxyquinoline) aluminum (Alq3) as an emission layer, Mori et al. [2] obtained voltage-tunable emission from red to green. Using two electron transport layers, Hamaguchi et al. [3] and Liu et al. [4] fabricated green-to-blue and red-to-orange voltage-tunable OLEDs. Kalinowski et al. fabricated an orangeto-greenish yellow voltage-tunable device by inserting a layer of red-emitting perylene-bis(2-phenyl) imide between an Alq3 electron transport layer and a magnesium cathode [5] and a red-to-blue device using a perylene-bis(2-phenyl) imide-doped TPD [6]. Despite the variety of voltage-tunable small-molecule OLEDs, their emissions are typically in the longer wave* Corresponding author. Tel.: 852-2358-7050; fax: 852-2358-1485. E-mail address: eemwong@ee.ust.hk (M. Wong).

length regime of the visible spectrum. In this paper, the fabrication and characterization of an efcient blue-to-violet emitting OLED using TPD as a hole transport layer and 2,9dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) as a hole-blocking [7,8] electron transport layer are reported. When the effective energy barriers against carrier injection are reduced by incorporating copper(II) phthalocyanine (CuPc) as an anode buffer layer [9] and Alq3 as a cathode buffer layer, efciencies as high as 0.5% at blue emission and 0.4% at violet emission have been obtained. A maximum luminance of greater than 2000 cd/m2 has been measured for the violet emission.

2. Materials and device fabrication Glass coated with 70 nm indiumtin oxide (ITO) was used as the starting substrate. The sequence of pre-cleaning prior to loading into the evaporation chamber consisted of ultrasonic detergent soak for 30 min, de-ionized (DI) water spray for 10 min, ultrasonic DI water soak for 30 min, oven bake-dry for 12 h and ultraviolet ozone illumination for 9 min [10]. The constituent organic layers for the OLEDs were deposited on the ITO glass substrates by thermal vacuum evaporation of commercial grade TPD, BCP, Alq3 and CuPc (Fig. 1) powder sources loaded in resistively heated eva-

0379-6779/$ see front matter # 2003 Elsevier B.V. All rights reserved. doi:10.1016/S0379-6779(03)00359-X

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Fig. 1. Molecule structures of the constituent organic materials used in OLED construction.

Fig. 2. LJV characteristics of type D and B devices.

poration cells. The base pressure in the evaporator was 8 mTorr. The deposition rates of the organic thin lms were 0.20.4 nm/s. While the ITO formed the anodes of the OLEDs, 0.1 nm lithium uoride (LiF) topped with 150 nm aluminum (Al) composite layers were used as the cathodes. The deposition rates of LiF and Al were 0.020.05 and 1 1.5 nm/s, respectively. Film thickness was determined in situ using a crystal monitor. Two types of 4 mm diameter OLEDs were fabricated using a set of shadow masks. These are type D devices without the electrode buffer layers: ITO (75 nm)/TPD (60 nm)/BCP (30 nm)/LiF (1 nm)/Al (150 nm), and type B devices with the electrode buffer layers: ITO (75 nm)/CuPc (20 nm)/TPD (40 nm)/BCP (30 nm)/Alq3 (30 nm)/LiF (1 nm)/Al (150 nm). The devices were characterized in room ambient and temperature without encapsulation. Electroluminescence (EL) intensity was measured using a Kollmorgen Instruments PR650 SpectraScan spectrophotometer and currentvoltage (IV) characteristics were measured using a Hewlett-Packard HP4145B semiconductor parameter analyzer. The 100 nm thick organic layers for measuring the photoluminescence (PL) and absorption spectra were deposited, respectively, on sapphire and on quartz substrates by thermal vacuum evaporation. Photoluminescence and absorption spectra of Alq3, BCP, TPD and a 4:1 co-evaporated mixture of BCP:TCP were measured. The excitation light for PL was obtained from a HeCd laser at a wavelength of 337 nm.

3. Results and discussion Typical luminance (L)current density (J)V characteristics of the two types of devices are shown in Fig. 2. Since both hole and electron injection efciencies are improved with the incorporation of the electrode buffer layers, the

power efciency of type B device is clearly higher because of both higher luminance current efciency (dened as the ratio of L to J) and lower threshold voltage for L and J. Typical voltage-dependent EL spectra of type D and B devices are shown in Fig. 3a and b, respectively. For a type D device biased at 10 V, a spectral peak can be observed at a wavelength (l) of 466 nm (blue). As the spectral intensity decreases with decreasing l, a minor plateau can be seen at l  400 nm (violet). With increasing bias, the major peak shifts to shorter l from 466 nm and the intensity at 400 nm increases. At a bias of 16 V, the peak shifts to 420 nm, equivalent to a deep blue emission. A respective external quantum efciency (x) and maximum power efciency (Zp) of 0.4% and 0.3 lm/W have been obtained for blue. The corresponding numbers for violet were x  0:2% and Zp 0:08 lm/W for violet. A maximum luminance of 360 cd/m2 has been measured. For a type B device biased at 10 V, similar spectral peak and plateau can be observed at l  466 and 400 nm, respectively. With increasing bias, the major peak shifts to a shorter l. At a bias of 16 V, the peak shifts to 400 nm, though the intensity at 420 nm is still strong. A respective external quantum efciency (x) and maximum power efciency (Zp) of 0.5% and 0.5 lm/W have been obtained for blue. The corresponding numbers for violet were x  0:4% and Zp 0:2 lm/W for violet. A maximum luminance of 2010 cd/m2 has been measured. The energy-level diagram of a type B device is shown in the inset in Fig. 4a [7,11]. Because of the lower highestoccupied molecular orbital (HOMO) of the electron-transporting BCP compared to that of the hole-transporting TPD, holes drifting through the TPD are blocked on the TPD side of the TPD/BCP interface. Similarly, because of the higher lowest-unoccupied molecular orbital (LUMO) of TPD, electrons are blocked on the BCP side of the TPD/BCP interface. The energy barrier against electron injection is

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Fig. 3. Normalized EL spectra of (a) type D and (b) type B OLEDs. Voltage-induced spectral shifts are clearly visible. Shown in insets are the relative EL spectra before normalization and the corresponding device structures.

Fig. 4. (a) PL spectra of TPD, BCP, Alq3 and a 4:1 mixture of BCP:TPD on sapphire. The energy-level diagram of a type B device is shown in the inset. (b) Absorption spectra of TPD, BCP, and a 4:1 mixture of BCP:TPD on quartz.

smaller than that against hole injection at the TPD/BCP interface. The photoluminescence spectra of Alq3, BCP, TPD and a 4:1 co-evaporated mixture of BCP:TCP are summarized in Fig. 4a. PL peaks are observed for Alq3 at 520 nm, for BCP in the ultraviolet range and for TPD at 420 and 400 nm. Therefore, it is possible to identify TPD as being responsible for the EL emission at 420 and 400 nm. The PL spectrum of the BCP:TPD mixture peaks at 452 nm, a wavelength signicantly longer than the peak locations of pure BCP or TPD. This peak, the closest that can be attributed to the EL emission at 466 nm, is attributed to exciplex recombination [12] associated with the LUMO and HOMO of BCP and

TPD, respectively. Compared to the absorption spectra of pure TPD and BCP shown in Fig. 4b, no new absorption peaks were observed on the BCP:TPD mixture. This is further evidence that the PL emission attributed to exciplex is not induced by any aggregate type effects. Lastly, the most likely cause of the relative red-shift of the EL peak from the PL peak is microcavity effect [13]. It is presently proposed that the emission at 466 nm is associated with exciplex emission at the TPD/BCP interface (inset of Fig. 4a). At low applied bias, both the injection of carriers across the interface and their drift in the bulk of the transport layers are limited. Exciplex emission dominates, involving the excited state of BCP and the ground state of TPD. As the applied bias is increased, more electrons than holes are injected across the interface because of the smaller

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energy barrier against electron injection. Exciton formation in the bulk of TPD and their subsequent recombination become dominant. This explains shifting of the emission peaks to 420 and 400 nm at higher applied bias. Such voltage-induced switching of exciplex (yellow) to exciton (green) dominated emission has been observed in OLEDs involving a different set of constituent materials [14].

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4. Conclusion Efcient blue-to-violet voltage-tunable organic light-emitting diodes, with quantum efciencies of 0.4 and 0.2%, respectively, for blue and violet, have been fabricated and characterized. With the incorporation of electrode buffer layers, the efciency can be further improved to, respectively, 0.5% for blue and 0.4% for violet. The voltage-controlled emission has been explained in terms of a switching from interfacial emission dominated by exciplex recombination to bulk emission dominated by exciton recombination.

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Acknowledgements This research was supported by a grant from the Research Grants Council of the Hong Kong Special Administrative Region. References

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