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Tris‐bidentate iridium(III) complexes used in organic light‐emitting diodes (OLEDs) are typically homoleptic or heteroleptic with three or two identical emissive ligands, respectively. Herein red phosphorescence emitting dendrimers composed of first generation biphenyl dendrons, 2‐ethylhexyloxy surface groups and an iridium(III) complex core with three, two or one emissive [4‐phenyl]−2‐[thiophen‐2‐yl]quinoline ligands are reported. The dendrimers have similar photoluminescence quantum yields (PLQYs) in solution (84–88%), neat film (23–25%) and when blended with tris(4‐carbazoyl‐9‐ylphenyl)amine (72–73%), enabling the effect of the number of emissive ligands on OLED performance to be determined. The external quantum efficiency (EQE) of OLEDs composed of neat dendrimer films increased with decreasing number of emissive ligands, with the device composed of the dendrimer having a single emissive ligand having an EQE of 9.2%, which is almost double that expected from a bottom emitting device and a film PLQY of 25 ± 3.6%. The emission is Lambertian and the higher‐than‐expected EQE is ascribed to alignment of the single emissive ligand being optimal for light‐outcoupling. The EQE of OLEDs containing the blend film also increased with decreasing emissive number of ligands (maximum EQE = 15.4%). [ABSTRACT FROM AUTHOR]

The performance of electronic and semiconductor devices is critically dependent on the distribution of guest molecules or atoms in a host matrix. One prominent example is that of organic light‐emitting diode (OLED) displays containing phosphorescent emitters, now ubiquitous in handheld devices and high‐end televisions. In such OLEDs the phosphorescent guest [normally an iridium(III)‐based complex] is typically blended into a host matrix, and charge injection and transport, exciton formation and decay, and hence overall device performance are governed by the distribution of the emissive guest in the host. Here high‐angle annular dark‐field scanning transmission electron microscopy (HAADF‐STEM) is used with depth sectioning to reconstruct the 3D distribution of emissive iridium(III) complexes, fac‐tris(2‐phenylpyridine)iridium(III) [Ir(ppy)3], blended into the amorphous host material, tris(4‐carbazoyl‐9‐ylphenyl)amine (TCTA), by resolving the position of each single iridium(III) ion. It is found that most Ir(ppy)3 complexes are clustered with at least one other, even at low concentrations, and that for films of 20 wt.% Ir(ppy)3 essentially all the complexes are interconnected. The results validate the morphology of blend films created using molecular dynamics simulations which mimic the evaporation film‐forming process and are also consistent with the experimentally measured charge transport and photophysical properties. [ABSTRACT FROM AUTHOR]

Solution-processing of organic light-emitting diode films has potential advantages in terms of cost and scalability over vacuum-deposition for large area applications. However, solution processed small molecule films can have lower overall device performance. Here, novel molecular dynamics techniques are developed to enable faster simulation of solvent evaporation that occurs during solution processing and give films of thicknesses relevant to real devices. All-atom molecular dynamics simulations are then used in combination with kinetic Monte Carlo transport modeling to examine how differences in morphology stemming from solution or vacuum film deposition affect charge transport and exciton dynamics in films consisting of light-emitting bis(2-phenylpyridine)(acetylacetonate)iridium(III) [Ir(ppy)2(acac)] guest molecules in a 4,4′-bis(N-carbazolyl)biphenyl host. While the structures of the films deposited from vacuum and solution were found to differ, critically, only minor variations in the transport properties were predicted by the simulations even if trapped solvent was present. [ABSTRACT FROM AUTHOR]

Ir(ppy)3:CBP blends have been widely studied as the emissive layer in organic light emitting diodes (OLEDs), yet crucial questions about charge transport within the layer remain unaddressed. Recent molecular dynamics simulations show that the Ir(ppy)3 molecules are not isolated from each other, but at concentrations of as low as 5 wt. % can be part of connected pathways. Such connectivity raises the question of how the iridium(iii) complexes contribute to long-range charge transport in the blend. We implement a kinetic Monte Carlo transport model to probe the guest concentration dependence of charge mobility and show that distinct minima appear at approximately 10 wt. % Ir(ppy)3 due to an increased number of trap states that can include interconnected complexes within the blend film. The depth of the minima is shown to be dependent on the electric field and to vary between electrons and holes due to their different trapping depths arising from the different ionization potentials and electron affinities of the guest and host molecules. Typical guest-host OLEDs use a guest concentration below 10 wt. % to avoid triplet-triplet annihilation, so these results suggest that optimal device performance is achieved when there is significant charge trapping on the iridium(iii) complex guest molecules and minimum interactions of the emissive chromophores that can lead to triplet-triplet annihilation. [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]

Ligand substitution is often used for tuning the emission color of phosphorescent iridium(iii) complexes that are used in organic light-emitting diodes. However, in addition to tuning the emission color, the substituents can also affect the radiative and non-radiative decay rates of the excited state and hence the photoluminescence quantum yield. Understanding the substituent effect is therefore important for the design of new iridium(iii) complexes with specific emission properties. Using (time dependent) density functional methods, we investigate the substituent effect of n-propyl groups on the structure, emission color, and emission efficiency of fac-tris(1-methyl-5-phenyl-[1,2,4]triazolyl)iridium(iii) based phosphorescent complexes by comparing the calculated results for structural models with and without the n-propyl substituents. We find that attachment of the n-propyl groups increases the length of three Ir-N bonds, and although the emission color does not change significantly, the radiative and non-radiative rates do, leading to a prediction of enhanced blue phosphorescence emission efficiency. Furthermore, the calculations show that the attachment of the n-propyl groups leads to a larger activation energy to degradation and the formation of dark states. [ABSTRACT FROM AUTHOR]

Red‐emitting organic light‐emitting diodes (OLEDs) are important for displays and lighting, with the latter benefiting from solution processable materials, which would enable low embedded energy, scalable fabrication. Herein, the effect of annealing and phase separation on the performance of solution‐processed OLEDs incorporating a light‐emitting layer composed of the exciplex host, m‐MTDATA:OXD‐7, and a red phosphorescent light‐emitting dendrimer, Ir(tDCpq)3, is described. Solution‐processed OLEDs containing an annealed emissive layer with a low dendrimer concentration (2 wt%) are found to have the best performance, which is higher than the device in which the light‐emitting layer is not annealed. The improvement in the performance of the annealed device is ascribed to improved charge mobility within the emissive layer caused by phase separation of the OXD‐7. The OLEDs containing annealed m‐MTDATA:OXD‐7:(2 wt%) Ir(tDCpq)3 have maximum current, power, and external quantum efficiencies of 17.9 cd A−1, 19.4 lm W−1, and 14.8 ± 0.6%, respectively. The fact that the maximum external quantum efficiency (EQE) of 14.8% is larger than that expected based on the photoluminescence quantum yield (PLQY) and the normal out‐coupling efficiency of 20% from a bottom‐emitting device is determined to arise from the different pathways of exciton formation under photoexcitation and charge injection. [ABSTRACT FROM AUTHOR]

Tris(4‐carbazoyl‐9‐ylphenyl)amine (TCTA) is a commonly used host material for organic light‐emitting diodes (OLEDs). TCTA has poor solubility and hence to improve solubility the authors have synthesized first‐ and second‐generation TCTA‐based dendrimers with n‐propyl surface groups. These dendrimeric TCTA hosts have improved solubility and similar photophysical properties to TCTA. The hole mobility of solution‐processed TCTA is found to be an order of magnitude less than films formed by evaporation and similar to that of the two dendronized TCTAs (mobilities in the order of 10−5 cm2 V−1 s−1). The hole mobility in the films is found to decrease when a green emissive first‐generation light‐emitting dendrimer is blended with the host materials due to charge trapping on the emissive guest. In the case of the second‐generation host, there is evidence of a degree of phase separation in the film. Organic light‐emitting diodes are fabricated at guest concentrations corresponding to the maximum observed photoluminescence quantum yield (PLQY) and lowest hole mobility. It is found that the external quantum efficiency (EQE) does not always scale with the PLQY, leading to devices that have EQEs higher than expected based on the PLQY and outcoupling of light from a bottom emitting device. [ABSTRACT FROM AUTHOR]

Abstract: The performance of organic light‐emitting diodes (OLEDs) can change when they are subjected to thermal stress after manufacture. The effect of heat on OLED film stacks is studied, in which the emissive layer (EML) comprises either a phosphorescent iridium(III) dopant blended in a host at different concentrations or materials with alkyl substituents to increase the steric bulk of the host and/or dopant. Neutron reflectometry with in situ photoluminescence measurements shows that interdiffusion between the emissive and hole transport layers within the films occurs on thermal annealing. Interdiffusion occurs independent of dopant concentration or steric bulk of the EML components. Importantly, when held at relatively low temperatures, the EML materials are found to only partially diffuse into an adjacent charge transport layer. The movement of materials is found to correlate with the change in luminescence from the hole transport material and an initial enhancement of the emission from the iridium(III) dopant. The results provide an explanation for the burn‐in often observed for OLEDs as well as the need to change the driving characteristics over time to ensure that pixels can be held at the requisite brightness. [ABSTRACT FROM AUTHOR]

The effect of varying the emitter concentration on the structural properties of an archetypal phosphorescent blend consisting of 4,4′-bis( N-carbazolyl)biphenyl and tris(2-phenylpyridyl)iridium(III) has been investigated using non-equilibrium molecular dynamics (MD) simulations that mimic the process of vacuum deposition. By comparison with reflectometry measurements, we show that the simulations provide an accurate model of the average density of such films. The emitter molecules were found not to be evenly distributed throughout film, but rather they can form networks that provide charge and/or energy migration pathways, even at emitter concentrations as low as ≈5 weight percent. At slightly higher concentrations, percolated networks form that span the entire system. While such networks would give improved charge transport, they could also lead to more non-radiative pathways for the emissive state and a resultant loss of efficiency. [ABSTRACT FROM AUTHOR]

Two new heteroleptic Pt(II) complexes bearing an n-hexyloxy substituted phenyllepidine-based ligand and either a picolinate (pic) or acetylacetonate (acac) coligand are synthesized for use in organic light-emitting field-effect transistors (LEFETs). Both compounds are obtained in good yields via a short and straightforward synthetic route. It is found that while both Pt(II) complexes show good chemical stability and solubility, the coligand affects the photoluminescence quantum yield and crystal packing of the complexes. Although aggregate induced phosphorescence enhancement is not observed, it is found that high concentrations of the emitters in a poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] host lead to improved charge injection in hybrid LEFETs. LEFETs with area emission, high ON/OFF ratios (>106) and mobilities (≈1.3 cm2 V−1 s−1), and external quantum efficiencies of up to 0.1% at the highest brightness of 855 cd m−2 are demonstrated. [ABSTRACT FROM AUTHOR]

Dendrimers have proved to be successful materials for solution-processable phosphorescent organic light emitting diodes (OLEDs). Recently we have been investigating poly(dendrimer)s with improved viscosity for ink-jet printing applications. In this work we present three phosphorescent side-chain copolymers comprised of a poly(styrene) backbone, carbazole charge transporting units, and iridium(iii) complexes containing no dendrons (simple complex), a single dendron attached to two of the ligands, or doubly dendronised complexes with two dendrons added to the ligands. In addition to their charge transporting capability the copolymer structure incorporating carbazole units can also prevent aggregation of the chromophores, as evidenced by there being only one emissive environment in time-resolved luminescence. We report high external quantum efficiencies of 11.0% (37.3 cd A−1) at 100 cd m−2 and 8.3 V for devices made with the neat copolymers. The best performance is achieved by blending the doubly dendronised copolymer with 50 wt% of 4,4′-bis(N-dicarbazolyl)biphenyl (CBP) which results in 14.7% EQE (48.3 cd A−1) at 100 cd m−2 and 9.3V. [ABSTRACT FROM AUTHOR]

A simple way of tuning the emission color in solution processed phosphorescent organic light emitting diodes is demonstrated. For each color a single emissive spin-coated layer consisting of a blend of three materials, a fac-tris(2-phenylpyridyl)iridium (III) cored dendrimer (Ir–G1) as the green emitter, a heteroleptic [bis(2-phenylpyridyl)-2-(2′-benzo[4,5-α]thienyl)pyridyl]iridium (III) cored dendrimer [Ir(ppy)2btp] as the red emitter, and 4,4′-bis(N-carbazolyl) biphenyl (CBP) as the host was employed. By adjusting the relative amount of green and red dendrimers in the blends, the color of the light emission was tuned from green to red. High efficiency two layer devices were achieved by evaporating a layer of electron transporting 1,3,5-tris(2-N-phenylbenzimidazolyl)benzene (TPBI) on top of the spin-coated emissive layer. A brightness of 100 cd/m2 was achieved at drive voltages in the range 5.3–7.3 V. The peak external efficiencies at this brightness ranged from 31 cd/A (18 lm/W) to 7 cd/A (4 lm/W). [ABSTRACT FROM AUTHOR]

Abstract: We describe a phosphorescent green solution-processable iridium(III) complex containing poly(dendrimer), where the polymer character enhances compatibility with ink-jet printing techniques while the dendritic structure improves solid-state performance. The poly(dendrimer) shows an increased viscosity in chlorobenzene solutions of 1.1mPas at 25mg/ml concentration relative to a simple first generation dendrimer. The poly(dendrimer) has a photoluminescence quantum yield of 15% in a neat film which increases to 52%, accompanied by an increase in radiative rate, when the material is blended with 4,4′-bis(N-carbazolyl)-2,2′-biphenyl (CBP). Blending with poly(styrene) results in a slightly decreased efficiency of 13%, showing the importance of choosing compatible materials when blending the poly(dendrimer). Organic light emitting diodes were fabricated containing the poly(dendrimer) and these had a 5.1% external quantum efficiency. [Copyright &y& Elsevier]

Solution-processed monochrome and white organic light-emitting diodes (OLEDs) that have a light-emitting layer composed of a 4,4′,4″-tris(carbazol-9-yl)triphenylamine (TCTA) and (5-terphenyl-1,3-phenylene)bis(diphenylphosphine oxide) (POPH) exciplex host and soluble blue, green and/or red phosphorescent dendrimers have been fabricated and characterised. The OLED performance characteristics were found to be scan dependent, with the first scans having large external quantum efficiencies (EQEs) at low luminance, with subsequent scans showing stable performance. The monochrome (blue, green and red) films were found to have high photoluminescence quantum yields, relatively balanced hole and electron mobilities, and the OLEDs had stable EQEs of between 9 and 12% at 100 cd m−2 over multiple scans. The blue, green and red emissive materials were blended with the exciplex host, with their ratio tuned to achieve white emission. The optimal blend ratio provided white OLEDs that had EQEs of 11.7% and 10.6% at 100 cd m−2 and 1000 cd m−2, respectively. The best balance of 1931 Commission Internationale d'Eclairage (CIE) coordinates (0.40,0.40), Colour Rendering Index (70), and Delta uv (0.003) was achieved for an OLED with the light-emitting layer containing the blue, green and red dendrimers in a ratio of 20.0:0.4:0.8 wt%. A feature of the white OLEDs was the stability of the CIE coordinates, with a change of only (0.013,0.005) between a luminance of 100 cd m−2 and 4000 cd m−2. [Display omitted] • A common exciplex host composed for solution processed blue, green, red and white emissive OLEDs. • Monochrome light-emitting dendrimer:exciplex host blend films have relatively balanced hole and electron mobilities. • Monochrome OLEDs with external quantum efficiencies of up to 22.5%. • White emitting OLEDs external quantum efficiencies of 10.6% at 1000 cd m−2 • White OLEDs with stable CIE coordinates across a broad range of luminance. [ABSTRACT FROM AUTHOR]

Abstract: By using phosphorescent emitters, organic light emitting displays can be up to four times more efficient than those of fluorescent materials. Full colour displays based on phosphorescent materials have not been achieved thus far due to the poor efficiency of blue phosphorescent emitters. We show that there is a correlation between non-radiative decay of phosphorescence and vibrational coupling for related blue emissive materials containing similar iridium(III) complex chromophores. The materials had solution photoluminescence quantum yields (PLQYs) of up to 55% at room temperature with Commission Internationale de l’Eclairage co-ordinates of (0.155, 0.16). Stronger vibrational coupling was found to lead to an increased non-radiative decay rate and decreased PLQY. The activation energy for non-radiative decay was found to depend on the environment with the non-radiative decay rate being decreased when the emissive materials were placed in a solid host. [Copyright &y& Elsevier]

Phosphorescent poly(dendrimers) with a norbornene-derivedbackbonehave been synthesized using ring-opening metathesis polymerizationwith the Grubbs III catalyst. The dendrimers are comprised of a heterolepticiridium(III) complex core with two 2-phenylpyridyl ligands and a phenyltriazolylligand, biphenyl-based dendrons, and 2-ethylhexyloxy surface groups.The phenyltriazolyl ligand provides the attachment point to the polymerbackbone, and the two poly(dendrimers) differ in the number of dendronsattached to the 2-phenylpyridyl ligands. The poly(dendrimer) withone and two dendrons per ligand are termed mono- and doubly dendronized.The mono- and doubly dendronized poly(dendrimers) were found to haverelatively narrow polydispersities, around 1.4, viscosities approachingthose required for inkjet printing, and could be solution processedto form thin films. The dendrons played an important role in controllingthe photophysical properties of the materials. The parent homopolymerwith the same iridium(III) complex but no dendrons attached to theligands had a solution photoluminescence quantum yield (PLQY) of 48%.The solution PLQY was found to increase with increasing number ofdendrons with the mono- and doubly dendronized materials having solutionPLQYs of 65% and 71%, respectively. The increase in PLQY is due todecreased intrachain interchromophore interactions. A similar trendwas observed in the solid state with the parent, mono-, and doublydendronized polymers having film PLQYs of 2%, 44%, and 58%, respectively,demonstrating that both intra- and interchain interactions are controlledby the dendrons. [ABSTRACT FROM AUTHOR]

Abstract: A uniform dispersion of highly soluble phosphorescent dendrimer emitters is achieved by blending with a polymer host poly(9-vinylcarbazole) (PVK) containing N,N′-diphenyl-N,N′-(bis(3-methylphenyl)-[1,1-biphenyl]-4,4′-diamine (TPD) and 2-(4-biphen-4′-yl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD). No visible aggregation or self-quenching was observed for guest-to-host weight ratios of up to 33:67. The dendrimers contain a fac-tris(2-phenylpyridyl)iridium(III) [Ir(ppy)3] core, first generation biphenyl-based dendrons, and 2-ethylhexyloxy surface groups. The guest–host blend is used for all solution processed organic light-emitting diodes. A maximum external and current efficiency of 10.2% and 38cd/A (at 5V and a brightness of 50cd/m2), and a maximum brightness of 27,000cd/m2 (at 14.5V), were obtained when a CsF/Al cathode was used. Blade coating was used to fabricate a multi-layer structure that also contained an electron-transport layer. The device that had a LiF/Al cathode had a maximal efficiency of 40cd/A corresponding to an external quantum efficiency of 10.8% (at 5V and a brightness of 19cd/m2). The maximum brightness of the second device was 17,840cd/m2 at 14V. [Copyright &y& Elsevier]

Fac -tris[2-phenylpyridinato- C 2 , N ]iridium(III) [Ir(ppy) 3 ] is a well-known phosphorescent material for organic light-emitting diodes (OLEDs) and while uniform thin films can be formed using evaporation under high vacuum, it is not sufficiently soluble to enable it to be processed from solution. Ir(ppy) 3 -cored dendrimers with solubilizing surface groups can be processed from solution to form good quality neat or guest:host blends, even when the host has relatively poor solubility. In this manuscript, we report the effect of adding different solubilizing surface groups, namely 2-ethylhexyloxy, n -propyl or t -butyl to first generation dendrons attached to the Ir(ppy) 3 core on the optoelectronic properties of neat and blend films with tris(4-carbazoyl-9-ylphenyl)amine (TCTA). The different dendrons were found to have minimal effect on the photoluminescence spectra and efficiency of energy transfer from the host to the guest in the blend films. The hole mobility of neat films of the solution-processed Ir(ppy) 3 -cored dendrimer films was around 10−6 cm2 V−1 s−1, which was an order of magnitude less than Ir(ppy) 3 films formed by evaporation. Blending the dendrimers with TCTA at a concentration of 11 mol% (the concentration of the highest film photoluminescence quantum yield) led to an order of magnitude decrease in the hole mobility compared to the neat films. However, despite the relatively low mobilities, simple two-layer OLEDs composed of a blend light-emitting layer and an electron transporting layer were found to reach a maximum EQE of 11.1% at a luminance of 1000 cd m−2 for a film with a PLQY of 60%. [Display omitted] • Ir(ppy)3-cored dendrimers with solubilising surface groups are solution processed. • Good quality guest:host blend films formed with poorly soluble TCTA host. • Dendron type was found to have minimal effect on the host to guest energy transfer. • Charge mobility in dendrimer:TCTA blends less than in neat film. • Simple two-layer OLEDs had maximum EQEs of 11.1% at a luminance of 1000 cd m-2. [ABSTRACT FROM AUTHOR]

Abstract: A convergent procedure has been developed for the preparation of fac-tris(2-phenylpyridyl)iridium(III) cored dendrimers with first- and second-generation dendrons that each contain one and two carbazole units, respectively. The carbazole moieties are both an electroactive moiety and a branching unit in the dendron. The photoluminescence quantum yields of neat films of the first- and second-generation dendrimers were 48±5% and 39±4%, respectively. These values are substantially higher than for equivalent first- and second-generation dendrimers with phenyl moieties at the branching points of the dendrons instead of the carbazole units. The improved solid state luminescent properties can be attributed to the increased steric demand of the carbazole unit relative to the phenyl ring, which reduces more effectively the intermolecular interactions that cause the cores to be less emissive. Electrochemical experiments showed that both the core of the dendrimers and the dendrons were electroactive. Thin film hole mobilities of the first-generation dendrimer with the carbazolyl branching units in the dendrons were found to be higher than the equivalent dendrimer with biphenyl branching units across a range of fields. [Copyright &y& Elsevier]

Iridium-based phosphorescent dendrimers have shown much promise as highly efficient light emitting materials for organic light emitting diodes (OLEDs). Here we report the effects of modifying the chemical structure on the emissive and charge transport properties of Ir(ppy)3 based electrophosphorescent dendrimers. We investigate a novel para linked first generation (G1) iridium dendrimer. This material is compared to G1 and G2 meta linked dendrimers. We show that by blending these dendrimers into a CBP host, high external quantum efficiencies of over 10% and luminous efficiencies of 27 lm/W can be achieved. [Copyright &y& Elsevier]

The article discusses the use of the specific luminescence properties of phosphorescent transition metal complexes to monitor intramolecular vibrational redistribution (IVR) and cooling. The IVR manifests itself as a photoluminescence decay. The addition of dendrons to the phosphorescent core opens up new channels for the dissipation of vibrational energy.