Gang
Yu
a,
Fei
Ding
a,
Huibio
Wei
a,
Zifeng
Zhao
a,
Zhiwei
Liu
a,
Zuqiang
Bian
*a,
Lixin
Xiao
b and
Chunhui
Huang
a
aBeijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China. E-mail: bianzq@pku.edu.cn
bState Key Laboratory for Mesoscopic Physics, Department of Physics, Peking University, Beijing 100871, China
First published on 16th November 2015
We present highly efficient Tb(III)-based organic light-emitting diodes optimized by the subtle choice of bipolar hosts, adjacent layers and double emitting structures. By introducing di(9H-carbazol-9-yl)(phenyl)phosphine oxide (DCPPO) as the host for the first emitting layer, and 9-(4-tert-butylphenyl)-3,6-bis(diphenylphosphine oxide)-carbazole (DPPOC) for the second emitting layer for Tb(PMIP)3 (PMIP stands for 1-phenyl-3-methyl-4-isobutyryl-pyrazol-5-one), the excitons can be well confined within the double-emitting layer. When 4,4′,4′′-tris(N-carbazolyl)triphenylamine (TCTA) and tris-[3-(3-pyridyl)mesityl]borane (3TPYMB) with high triplet energy levels are used as a hole transporting layer (HTL) and an electron transporting layer (ETL), respectively, the optimized device reaches a maximum efficiency of 52 lm W−1, 57 cd A−1, i.e. a maximum external quantum efficiency (EQE) of 15%. At a practical brightness of 100 cd m−2 (4.6 V) the efficiency remains at around 20 lm W−1, 30 cd A−1.
Since 1990, a number of studies based on Tb(III)-based OLEDs have been reported. The maximum luminance has been improved from 7 cd m−223 to more than 2000 cd m−2,34,35 and the maximum efficiency has risen to 36 cd A−1, 16 lm W−1. At a practical brightness of 100 cd m−2, the best efficiency was 15.7 cd A−1.35
In the reported work,35 pure Tb(PMIP)3 (PMIP stands for 1-phenyl-3-methyl-4-isobutyryl-pyrazol-5-one) acting as the first emitting layer in the device was demonstrated to be most important for the green electroluminescence with the high efficiency. Without the first Tb(PMIP)3 layer, the emission of NPB (N,N′-diphenyl-N,N′-bis(1-naphthyl)-1,10-diphenyl-4,4′-diamine) was observable at high current density while the mono-emitting layer is as thick as 60 nm in the device ITO/NPB/Tb(PMIP)3(DPPOC) (DPPOC stands for 9-(4-tert-butylphenyl)-3,6-bis(diphenylphosphine oxide)-carbazole)/BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline)/Alq3 (tris(8-hydroxyquinoline))/Mg0.9Ag0.1. When pure Tb(PMIP)3 was introduced between the hole-transporting layer (HTL) and the emitting layer (EML), a thickness of 20 nm was required to completely eliminate the emission from NPB in the device ITO/NPB/Tb(PMIP)3/Tb(PMIP)3(DPPOC)/BCP/Alq3/Mg0.9Ag0.1.
Now, we have further improved the electroluminescence (EL) efficiency based on triplet confinement by the subtle choice of adjacent layers, balancing the carrier transport by using a new first emitting layer. When 4,4′,4′′-tris(N-carbazolyl)triphenylamine (TCTA) and tris-[3-(3-pyridyl)mesityl]borane (3TPYMB) with high triplet energy levels are used as a HTL and an electron transporting layer (ETL), respectively, the device ITO/MoO3 (1 nm)/TCTA:MoO3 (20%) (20 nm)/TCTA (15 nm)/Tb(PMIP)3:DCPPO (dicarbazolylphenylphosphine) (1:1) (10 nm)/Tb(PMIP)3:DPPOC (1:1) (10 nm)/3TPYMB (50 nm)/LiF (1 nm)/Al (100 nm) reaches a maximum efficiency of 52 lm W−1, 57 cd A−1, i.e. a maximum external quantum efficiency (EQE) of 15%. At a practical brightness of 100 cd m−2 (4.6 V) the efficiency remains at around 20 lm W−1, 30 cd A−1, which renews a record for Tb(III)-based OLEDs.
The materials are listed in Scheme 1. The device structures are listed as follows:
Device A: ITO/MoO3 (1 nm)/NPB (35 nm)/Tb(PMIP)3:DPPOC (1:1) (20 nm)/Alq3 (40 nm)/LiF (1 nm)/Al (100 nm)
Device B: ITO/MoO3 (1 nm)/TCTA (35 nm)/Tb(PMIP)3:DPPOC (1:1) (20 nm)/TPBi (40 nm)/LiF (1 nm)/Al (100 nm)
Device C: ITO/MoO3 (1 nm)/TCTA (35 nm)/Tb(PMIP)3:DPPOC (1:1) (20 nm)/3TPYMB (40 nm)/LiF (1 nm)/Al (100 nm)
Device D: ITO/MoO3 (1 nm)/TCTA (35 nm)/Tb(PMIP)3:DCPPO (1:1) (10 nm)/Tb(PMIP)3:DPPOC (1:1) (10 nm)/3TPYMB (40 nm)/LiF (1 nm)/Al (100 nm)
Device E: ITO/MoO3 (1 nm)/TCTA:MoO3 (20%) (20 nm)/TCTA (15 nm)/Tb(PMIP)3:DCPPO (1:1) (10 nm)/Tb(PMIP)3:DPPOC (1:1) (10 nm)/3TPYMB (50 nm)/LiF (1 nm)/Al (100 nm)
V on [V] | V 100 [V] | L max [cd m−2] | LEmax [cd A−1] | LE100 [cd A−1] | EQEmax [%]c | EQE100 [%]c | EQE500 [%]d | PEmax [lm W−1] | PE100 [lm W−1] | CIE100 [x, y] | |
---|---|---|---|---|---|---|---|---|---|---|---|
a At 100 cd m−2. b Corresponding driving voltage is listed in the bracket. c Calculated using Matlab according to the emission spectra and current-luminance relativity. d At 500 cd m−2. | |||||||||||
A | 4.7 | 7.9 | 3823 (17) | 7.9 | 5.6 | 2.6 | 1.9 | 1.5 | 5.0 | 2.2 | 0.27, 0.51 |
B | 3.8 | 5.3 | 2592 (14) | 32 | 23 | 8.2 | 6.3 | 3.4 | 25 | 13 | 0.30, 0.62 |
C | 4.0 | 6.6 | 1672 (14) | 44 | 25 | 11.6 | 6.6 | 2.9 | 35 | 12 | 0.32, 0.62 |
D | 4.1 | 6.4 | 2438 (15) | 48 | 28 | 12.5 | 7.4 | 3.4 | 34 | 14 | 0.31, 0.62 |
E | 3.4 | 4.6 | 2784 (10) | 57 | 30 | 14.8 | 7.7 | 3.2 | 52 | 20 | 0.32, 0.62 |
To root out the emission of NPB, the HTL was replaced with TCTA (T1 = 2.7 eV)38 for the remaining improved devices, and an alternative ETL was chosen from TPBi and 3TPYMB with higher T1 values of 2.6 eV39 and 2.95 eV,40 respectively. Device B with TPBi displayed a dramatic efficiency rise compared to device A with a four-fold maximum luminous efficiency and five-fold maximum power efficiency. Pure Tb(III) emission was realized at practical brightness with the efficiency of 23 cd A−1, 13 lm W−1. This could be mainly attributed to TCTA and TPBi's higher T1 than NPB and Alq3 (2.0 eV),39 respectively. In lanthanide complex electroluminescence, the S1 state of the ligand transferred to the triplet energy levels through intersystem crossing, and then to the excited state of the Ln ions and released as f–f relaxation. In some cases, higher energy levels may be excited by the ligand but nonradiative relaxations occur from these higher energy levels until the energy has decayed to the emitting levels where visible radiation originates.41 Triplet confinement can be a crucial factor when generated excitons' energy was transferring to the central Ln ions. If adjacent layers had lower T1 levels, the energy could transfer to the adjacent layers and relax as non-radiative transition (Fig. 1). Due to better electron mobility and suitable LUMO levels, device B showed a lower turn-on voltage of 3.8 V and a faster current rise (Fig. 2a). To be noted, the LUMO level of TCTA is 0.2 eV higher than NPB, which can block some electron when compared to NPB. This is a positive effect for avoiding exciton recombination in the HTL, and indeed no emission of the HTL was found at practical luminance. However, these devices all showed large efficiency roll-off especially at high luminance (Table 1). This efficiency roll-off is probably caused by the long luminescence lifetime of Tb(PMIP)3. The luminescence lifetime of co-deposited film of Tb(PMIP)3:DPPOC (1:1) was as long as 764 μs (Fig. S2, ESI†). Two quenching mechanisms of triplet–triplet and polaron–triplet annihilation are suggested to be the main negative effect.42
Since TPBi's T1 is almost equivalent to the 5D4 level of Tb(III), not high enough to efficiently avoid energy dissipation, 3TPYMB with T1 as high as 2.95 eV was introduced as the ETL to fabricate device C. The maximum efficiency could reach 44 cd A−1. The turn-on voltage rose a little to 4.0 V, and 6.6 V was required to reach 100 cd m−2, which could be ascribed to 3TPYMB's deeper LUMO and lower electron-mobility than TPBi.39
When TCTA acted as the HTL, pure green emission of Tb(III) with the CIE coordinates of (0.32, 0.62) was realized at a few hundred cd m−2, but a small peak at around 400 nm rose at high luminance (Fig. 2d), which can be assigned to emission from TCTA.43 The intensity of the TCTA peak at high luminance can reveal the location of the exciton recombination area, corresponding to the NPB emission in device A. DPPOC with two DPPO groups increases the electron-mobility of the emitting layer, resulting in the recombination zone near the interface between the HTL and the EML (Fig. 3a). Therefore, another host dicarbazolylphenylphosphine oxide (DCPPO) with two carbazole groups was introduced in a double-emitting-layer device D, ITO/MoO3 (1 nm)/TCTA (35 nm)/Tb(PMIP)3:DCPPO (1:1) (10 nm)/Tb(PMIP)3:DPPOC (1:1) (10 nm)/3TPYMB (40 nm)/LiF (1 nm)/Al (100 nm). DCPPO has a high T1 of 3.0 eV,36 high enough to transfer to Tb(PMIP)3. Pure characteristic emission of Tb(III) can be realized (Fig. 4c and Fig. S1, ESI†). The EL performance of device C–E are shown in Fig. 4. The TCTA emission at high luminance was almost eliminated in device D, which revealed that the excitons were well-confined within the EML (Fig. 3b and 4d) due to the hole-transporting ability of the first EML. As a result, device D showed a maximum efficiency of 48 cd A−1, 34 lm W−1. We successfully controlled the charge balance and exciton recombination by bipolar host and adjacent materials.44 With the p-doped TCTA layer (TCTA:MoO3, 20 wt%) and thickness modification of 3TPYMB, device E showed a turn-on voltage as low as 3.4 V, a faster current rise, a maximum efficiency of 57 cd A−1, 52 lm W−1 and an EQE of 15%. The relative lower driving voltage and faster current rise could mainly be attributed to the better carrier mobility of p-doped TCTA. Even at a luminance of 100 cd m−2, the efficiency remained at 30 cd A−1, 20 lm W−1, which is the best result of Tb(III)-complex electroluminescence reported so far. We also tested the lifetime of device E. Unfortunately, the LT50 of device E at an initial luminance of 800 cd m−2 is only 19.1 minutes (Fig. S3, ESI†). This can be translated to a LT50 at 100 cd m−2 of only 10.8 h using the formula LT50(L1) = LT50(L0)*(L0/L1)1.7.45 The instability of the β-diketonate ligand could be the main reason for the short lifetime of the device.46–48 Further exploration of stable ligands for lanthanide luminescent complexes is under progress in our group.
Fig. 3 Exciton recombination zone at high luminance of the single-emitting structure (a) and double-emitting structure (b). |
Footnote |
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c5tc02944a |
This journal is © The Royal Society of Chemistry 2016 |