Chi‐Chung Kwok

Photophysical Properties and OLED Applications of Phosphorescent Platinum(II) Schiff Base Complexes

The syntheses, crystal structures, and detailed investigations of the photophysical properties of phosphorescent platinum(II) Schiff base complexes are presented. All of these complexes exhibit intense absorption bands with lambda(max) in the range 417-546 nm, which are assigned to states of metal-to-ligand charge-transfer ((1)MLCT) (1)[Pt(5d)-->pi*(Schiff base)] character mixed with (1)[lone pair(phenoxide)-->pi*(imine)] charge-transfer character. The platinum(II) Schiff base complexes are thermally stable, with decomposition temperatures up to 495 degrees C, and show emission lambda(max) at 541-649 nm in acetonitrile, with emission quantum yields up to 0.27. Measurements of the emission decay times in the temperature range from 130 to 1.5 K give total zero-field splitting parameters of the emitting triplet state of 14-28 cm(-1). High-performance yellow to red organic light-emitting devices (OLEDs) using these platinum(II) Schiff base complexes have been fabricated with the best efficiency up to 31 cd A(-1) and a device lifetime up to 77 000 h at 500 cd m(-2).

Robust Phosphorescent Platinum(II) Complexes Containing Tetradentate O^N^C^N Ligands: Excimeric Excited State and Application in Organic White‐Light‐Emitting Diodes

The bright white lights: A series of highly robust platinum(II) complexes supported by tetradentate O N C N ligands with high emission quantum yields (0.72-0.93) and high T(d) (>400 °C) have been synthesized. Among the complexes, that shown in the figure has strong excimer emission attributed to the monomer triplet excited state with a localized structure. The application of this low band-gap material on single-dopant organic or polymer white-light-emitting diodes (WOLED) is highlighted.

Efficient Red Electroluminescent Devices with Sterically Hindered Phosphorescent Platinum(II) Schiff Base Complexes and Iridium Complex Codopant

Sterically hindered platinum(II) Schiff base complexes were prepared. Complex 4, which displays red emission with a quantum yield of 0.29 in a thin film and a self-quenching rate constant of 1×10(-7) dm(3) mol(-1)  s(-1), was used to fabricate organic light-emitting diodes with single or double emissive layers (EMLs). An iridium(III) complex with a wide band gap was codoped into the electron-dominant EML to act as a deep electron trapper, and red-light-emitting devices with the highest current, power, and external quantum efficiencies of 20.43 cd A(-1) 18.33 Lm W(-1), and 11.7%, respectively, were fabricated. A high current efficiency and EQE of up to 14.69 cd A(-1) and 8.3%, respectively, were achieved at a high brightness of 1000 cd m(-2). The significant delay of efficiency roll-off is attributed to the bulky 3D structure of the norbornene moiety at the periphery of the Schiff base ligand of 4 and to the new device design strategy. The fabricated device had a projected lifetime (LT50) of 18,000 h.

Phosphorescent Cyclometalated Iridium(III) Complexes That Contain Substituted 2-Acetylbenzo[b]thiophen-3-olate Ligand for Red Organic Light-Emitting Devices

We report the synthesis of a new class of thermally stable and strongly luminescent cyclometalated iridium(III) complexes 1-6, which contain the 2-acetylbenzo[b]thiophene-3-olate (bt) ligand, and their application in organic light-emitting diodes (OLEDs). These heteroleptic iridium(III) complexes with bt as the ancillary ligand have a decomposition temperature that is 10-20 % higher and lower emission self-quenching constants than those of their corresponding complexes with acetylacetonate (acac). The luminescent color of these iridium(III) complexes could be fine-tuned from orange (e.g., 2-phenyl-6-(trifluoromethyl)benzo[d]thiazole (cf3 bta) for 4) to pure red (e.g., lpt (Hlpt=4-methyl-2-(thiophen-2-yl)quinolone) for 6) by varying the cyclometalating ligands (C-deprotonated C^N). In particular, highly efficient OLEDs based on 6 as dopant (emitter) and 1,3-bis(carbazol-9-yl)benzene (mCP) as host that exhibit stable red emission over a wide range of brightness with CIE chromaticity coordinates of (0.67, 0.33) well matched to the National Television System Committee (NTSC) standard have been fabricated along with an external quantum efficiency (EQE) and current efficiency of 9 % and 10 cd A(-1) , respectively. A further 50 % increase in EQE (>13 %) by replacing mCP with bis[4-(6H-indolo[2,3-b]quinoxalin-6-yl)phenyl]diphenylsilane (BIQS) as host for 6 in the red OLED is demonstrated. The performance of OLEDs fabricated with 6 (i.e., [(lpt)2Ir(bt)]) was comparable to that of the analogous iridium(III) complex that bore acac (i.e., [(lpt)2 Ir(acac)]; 6a in this work) [Adv. Mater.- 2011, 23, 2981] fabricated under similar conditions. By using ntt (Hnnt=3-hydroxynaphtho[2,3-b]thiophen-2-yl)(thiophen-2-yl)methanone) ligand, a substituted derivative of bt, the [(cf3bta)2Ir(ntt)] was prepared and found to display deep red emission at around 700 nm with a quantum yield of 12 % in mCP thin film.

Efficient red organic electroluminescent devices by doping platinum(II) Schiff base emitter into two host materials with stepwise energy levels

In this work, organic electroluminescent (EL) devices with double light-emitting layers (EMLs) having stepwise energy levels were designed to improve the EL performance of a red-light-emitting platinum(II) Schiff base complex. A series of devices with single or double EML(s) were fabricated and characterized. Compared with single-EML devices, double-EML devices showed improved EL efficiency and brightness, attributed to better balance in carriers. In addition, the stepwise distribution in energy levels of host materials is instrumental in broadening the recombination zone, thus delaying the roll-off of EL efficiency. The highest EL current efficiency and power efficiency of 17.36 cd/A and 14.73 lm/W, respectively, were achieved with the optimized double-EML devices. At high brightness of 1000 cd/m², EL efficiency as high as 8.89 cd/A was retained.

Efficient Color-Tunable Copper(I) Complexes and Their Applications in Solution-Processed Organic Light-Emitting Diodes

A series of dppnc- and neocuproine-based CuI complexes (dppnc=7,8-bis(diphenylphosphino)-7,8-dicarba-nido-undecaborate) are synthesized and the emission color of these CuI complexes can be tuned from green to deep red via rational modification of the neocuproine ligand structure. The molecular structures of the emissive CuI complexes, Cu(dppnc)-G (green emitting), Cu(dppnc)-Y (yellow emitting), and Cu(dppnc)-R (red emitting), are characterized and their electronic structures and related transition properties are elucidated by photo-physical and computational (density functional theory) studies. The calculation results suggest that thermally activated delayed fluorescence (TADF) is the emission mechanism for these CuI complexes. Efficient solution-processed green-, yellow-, and red-emitting OLEDs are fabricated based on the emissive complexes as the dopants. High external quantum efficiency (EQE) of 15.20 % and current efficiency of 48.15 cd A-1 at 1000 cd m-2 are achieved in the green-emitting device with Cu(dppnc)-G. A maximum EQE of 10.17 %, CIE coordinates of (0.61, 0.38) and a maximum electroluminescent peak of 631 nm are achieved in the red device based on Cu(dppnc)-R.

Phosphorescent Platinum(II) Complexes for White Organic Light-Emitting Diode Applications

The applications of phosphorescent platinum(II) complexes in white organic light-emitting diode (WOLED) are discussed. White electroluminescence formed by complementary colors mixing has been achieved by employing phosphorescent platinum(II) complexes as dopants. The approach is to mix triplet monomer emissions of the platinum(II) dopant complexes at orange-red region with a blue-emitting component or, alternatively, to mix the emissions from both monomer and aggregate states of the same platinum(II) complex in the blue-green (λ max~480nm) and orange-red (λ max~600nm) regions. Platinum(II) material-based WOLEDs could be fabricated from both thermal deposition and solution process, since polymeric WOLED materials could be prepared by incorporating platinum(II) complexes in polymer backbone. The WOLEDs fabricated from platinum(II) complexes exhibit good Commission Internationale de l’Eclairage, color-rendering index, and device efficiency, which may find potential applications for solid-state lighting.

Luminescent Coordination and Organometallic Complexes for OLEDs

Applications of platinum(II) complexes were mainly focused on anti-cancer drug (such as cisplatin – cis -(NH 3 ) 2 PtCl 2 ) and catalysis (such as Karstedt’s catalyst – H 2 PtCl 6 ) before the 1980s. The weakly luminescent or nonemissive nature of the contemporary platinum(II) complexes in solutions at ambient temperature limited the development of phosphorescent platinum(II) complexes for optoelectronics applications. This predicament was overcome by a panel of platinum(II) complexes bearing diimine ligand reported by Maestri et al. in 1985. Following this work, research activity concerning the design and photophysical studies of emissive platinum(II) complexes began booming and many high-performance phosphorescent organic light-emitting diodes (P-OLEDs) fabricated with phosphorescent platinum(II) complexes were reported in the last decade. This chapter describes the history and the basic theory of emissive platinum(II) complexes, including the development of different ligand systems for application in OLEDs.