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The charge carrier mobility in tris(4‐carbazoyl‐9‐ylphenyl)amine (TCTA), a host and hole transport material typically used in organic light‐emitting diodes (OLEDs), is measured using charge carrier electrical injection metal–insulator–semiconductor charge extraction by linearly increasing voltage (i‐MIS‐CELIV). By employing the injection current i‐MIS‐CELIV method, charge transport at time scales shorter than the transit times typically observed in standard MIS‐CELIV is measured. The i‐MIS‐CELIV technique enables the experimental measurement of unequilibrated and pretrapped charge carriers. Through a comparison of injection and extraction current transients obtained from i‐MIS‐CELIV and MIS‐CELIV, it is concluded that hole trapping is negligible in evaporated neat films of TCTA within the time‐scales relevant to the operational conditions of optoelectronic devices, such as OLEDs. Furthermore, photocarrier generation in conjunction with i‐MIS‐CELIV (photo‐i‐MIS‐CELIV) to quantify the properties of charge injection from the electrode to the semiconductor of the MIS devices is utilized. Based on the photo‐i‐MIS‐CELIV measurements, it is observed that the contact resistance does not limit the injection current at the TCTA/molybdenum oxide/silver interface. Therefore, when TCTA is employed as the hole transport/electron‐blocking layer in OLEDs, it does not significantly reduce the injection current and remains compatible with the high injection current densities required for efficient OLED operation. [ABSTRACT FROM AUTHOR]

We report the development of light-emitting dendrimers with heteroleptic or homoleptic iridium(III) complexes at the core, with one, two, or three first- or second-generation biphenyl-based dendrons attached to the 2-phenylpyridyl ligand that is involved in the emission of light. The 5-phenyl-1-methyl3-n-propyl-1H-1,2,4-triazole co-ligand was not dendronised and was not involved in the emission process. The dendrimers with two emissive ligands were found to have the highest solution photoluminescence quantum yields (PLQYs) which were greater than 90% independent of the dendrimer generation. The second-generation dendrimers were all found to have higher neat film PLQYs than their first-generation counterparts due to the increased shielding of the emissive core by the dendrons and surface groups. The maximum external quantum efficiencies of devices made from the neat film and a guest:host blend of the second-generation dendrimer with two emissive ligands were found to be the highest (7.5% and 15.8%, respectively), which was attributed to a balance between the interactions required for charge transport and minimising those that lead to non-radiative processes. Thus, we have demonstrated that combining dendrimer generation and number of emissive dendronised ligands is a viable strategy for optimising light-emitting dendrimer OLED performance. [ABSTRACT FROM AUTHOR]

A series of solution-processable green emitting dendronised bis-tridentate iridium(III) complexes composed of [2,6-diimidazolylidene]benzene and the dianionic ligand, 2-[3-(trifluoromethyl)-1H-pyrazol-5-yl]-6-[4-(trifluoromethyl)phenyl]pyridine, have been synthesised to investigate the role of surface groups (t-butyl versus 2-ethylhexyloxy) and dendron generation (first versus second) on the photoluminescent (PL) and electroluminescent (EL) properties of the dendrimers. The dendrimers exhibited similar solution photoluminescent quantum yields (PLQYs) in toluene (60–70%) independent of the surface groups and dendrimer generation. In contrast, the PLQY values of the second-generation dendrimers were significantly higher than those with the first-generation dendrons in the neat film due to the higher generation dendrons providing more effective encapsulation of the emissive cores. When the dendrimers were blended at a concentration of 2 mol% in tris[4-carbazoyl-9-ylphenyl]amine (TCTA) the PLQYs increased but were still below the values measured in solution suggesting that the dendrimers were not evenly distributed throughout the host. Emission from the guest and host in the 2 mol% blends provided evidence for uneven distribution of the guest and inefficient energy transfer from the host to the dendrimers. The difference in encapsulation of the cores by the dendrons also affected charge transport in the neat films. In the case of the second-generation dendrimer with 2-ethylhexyloxy groups, the hole mobility was <10−8 cm2 V−1 s−1, which was an order of magnitude lower than for the less sterically encumbered dendrimers. Simple two-layer organic light-emitting diodes (OLEDs) with a solution-processed light-emitting layer were prepared. The best of the host-free devices exhibited a maximum external quantum efficiency (EQE) of 13.4%. The devices with the dendrimers blended with TCTA had more uniform EQEs of 12.2% to 13.5%, which are amongst the highest reported for solution-processed OLEDs containing a bis-tridentate iridium(III) complex emitter. Finally, it was found that devices containing the dendrimer with the t-butyl surface groups had greater stability. [ABSTRACT FROM AUTHOR]

Charge transport measurement using the Metal-Insulator-Semiconductor Charge Extraction by Linearly Increasing Voltage (MIS-CELIV) technique is a promising method for determining charge mobility in organic semiconductors because of its ability to study electron and hole mobilities independently. However, MIS-CELIV measurements have a number of parameters that can potentially affect the calculated mobility. There are only a few reports on MIS-CELIV being used to determine the charge mobility for materials typically used in organic light-emitting diodes (OLEDs), and the impact of each of the MIS-CELIV experimental parameters on the mobility is presently unknown. We find that the pulse duration, injection time, maximum voltage, offset voltage, and external load resistance have different levels of influence on the calculated mobility. Using the hole transporting OLED host material, tris(4-carbazoyl-9-ylphenyl)amine (TCTA), we show that having an injection time sufficient to fully charge the insulator layer, a pulse duration comparable to the transit time, and an external circuit time constant much smaller than the transit time is required to give a mobility relevant to an OLED. The optimized MIS-CELIV parameters led to the measurement having a similar current density and electric field to that of an operational OLED. Under these conditions, the hole mobility of TCTA was determined to be 2.90 ± 0.07 × 10−4 cm2 V−1 s−1, which is similar to that measured using time-of-flight techniques. Using inappropriate experimental parameters could lead to an underestimation of the mobility by an order of magnitude. Simulations of the MIS-CELIV measurements verified the effect the different parameters played in determining the charge mobility. [ABSTRACT FROM AUTHOR]

Dual emission light‐emitting dendrimers composed of phosphorescent fac‐tris[2‐phenylpyridyl]iridium(III) [Ir(ppy)3] cores and thermally activated delayed fluorescence‐based (TADF‐based) dendrons have been prepared. The TADF‐based dendrons are designed to have green or blue emission. The dendrimers show solvatochromism, with the emission switching between phosphorescence and TADF depending on the medium in which the measurement is undertaken. Time‐dependent photoluminescence (PL) spectra measurements show that the TADF dendrons can act as an energy pool for emission from the phosphorescent core. The PL quantum yields (PLQYs) are found to be strongly dependent on the dielectric constant of the solvent, ranging from as high as 76% to as low as 0.3%. Neat films of the dendrimers are found to have relatively balanced hole and electron mobilities of order 10–6 cm2 V–1 s–1, with bilayer organic light‐emitting diodes (OLEDs) containing neat emissive layers having a maximum external quantum efficiency (EQE) of 4.7% for a film having a PLQY of 12%. Finally, the solution processed OLEDs fabricated using 0.4 mol% of the dendrimers blended with 9‐[3‐(9H‐carbazol‐9‐yl)phenyl]‐9H‐carbazole‐3‐carbonitrile result in green emission with maximum EQEs of 9.8% and 15.1% for the dendrimers with green and blue emissive TADF dendrons, respectively. [ABSTRACT FROM AUTHOR]

Phosphorescent emissive materials in organic light‐emitting diodes (OLEDs) manufactured using evaporation are usually blended with host materials at a concentration of 3–15 wt% to avoid concentration quenching of the luminescence. Here, experimental measurements of hole mobility and photoluminescence are related to the atomic level morphology of films created using atomistic nonequilibrium molecular dynamics simulations mimicking the evaporation process with similar guest concentrations as those used in operational test devices. For blends of fac‐tris[2‐phenylpyridinato‐C2,N]iridium(III) [Ir(ppy)3] in tris(4‐carbazoyl‐9‐ylphenyl)amine (TCTA), it is found that clustering of the Ir(ppy)3 (surface of the molecules within ≈0.4 nm) in the simulated films is directly relatable to the experimentally‐measured hole mobility. Films containing 1–10 wt% of Ir(ppy)3 in TCTA have a mobility of up to two orders of magnitude lower (≈10−6 cm2 V−1 s−1) than the neat TCTA film, which is consistent with the Ir(ppy)3 molecules acting as hole traps due to their smaller ionization potential. Comparison of the simulated film morphologies with the measured photoluminescence properties shows that for luminescence quenching to occur, the Ir(ppy)3 molecules have to have their ligands partially overlapping. Thus, the results show that the effect of guest interactions on charge transport and luminescence are markedly different for OLED light‐emitting layers. [ABSTRACT FROM AUTHOR]