Chih-Hao Chang

Enhancing light outcoupling of organic light-emitting devices by locating emitters around the second antinode of the reflective metal electrode

Due to generally low conductivity and low carrier mobilities of organic materials, organic light-emitting devices (OLEDs) are typically optimized for light outcoupling by locating emitters around the first antinode of the metal electrode. In this letter, by utilizing device structures containing conductive doping, we investigate theoretically and experimentally the influences of the location of emitters relative to the metal electrode on OLED emission, and show that substantial enhancement in light outcoupling (1.2 times) or forward luminance (1.6 times) could be obtained by placing emitters around the second antinode instead of the first antinode. Depending on the detailed condition, the second-antinode device may also give more directed emission as often observed in strong-microcavity devices yet without suffering a color shift with viewing angles.

Iridium(III) Complexes of a Dicyclometalated Phosphite Tripod Ligand: Strategy to Achieve Blue Phosphorescence Without Fluorine Substituents and Fabrication of OLEDs†

Organic light-emitting diodes (OLEDs) based on heavy transition-metal complexes are playing a pivotal role in next generation of, for example, flat panel displays and solid-state lighting. The readily available, Os-, Pt-, and in particular Ir-based phosphorescence complexes grant superior advantage over fluorescent materials. This is mainly due to heavyatom-induced spin–orbit coupling, giving effective harvesting of both singlet and triplet excitons. However, tuning of phosphorescence over the entire visible spectrum still remains a challenge. Particularly, designing new materials to show higher energy, such as deep-blue emission—with an ideal CIEx,y coordinate (CIE = Commission Internationale de L Eclairage) of (0.14, 0.09)—encounters more obstacle than the progress made for obtaining green and red colors. Representative blue phosphors are a class of Ir complexes possessing at least one cyclometalated 4,6-difluorophenyl pyridine {(dfppy)H} ligand, known as FIrpic, FIr6, FIrtaz, and others. The majority of blue phosphors showed inferior color chromaticity with a sum of CIEx+y values being much greater than 0.3 or with single CIEy coordinate higher than 0.25. Such inferior chromaticity, in part, has been improved upon adoption of carbene-, triazolyl-, and fluorine-substituted bipyridine (dfpypy) based chelates. The above urgency prompted us to search for better and new blue phosphors. We produced a class of 2-pyridylazolate chelates possessing very large ligand-centered p–p* energy gap, as evidenced by the blue-emitting Os complexes. Subsequently, room-temperature blue phosphorescence was also visualized for the respective heteroleptic Ir complexes, particularly for those dubbed “nonconjugated” ancillary chelate(s). The nonconjugated ligands so far comprise a benzyl substituted pyrazole, an N-heterocyclic carbene, phosphines, and other ingenious molecular designs. Herein, we report the preparation of a novel class of heteroleptic Ir complexes by incorporation of tripodal, facially coordinated phosphite (or phosphonite), denoted as the P^C2 chelate, for serving as the ancillary, together with the employment of 2-pyridyltriazolate acting as blue chromophore. The reaction intermediate, which possesses an acetate chelate, was isolated and characterized to establish the synthetic pathway. The tridentate P^C2 ancillary chelate offers several advantages: 1) Good stabilization of complex and necessary long-term stability in application of for example, emitting devices. 2) The strong bonding of phosphorous donors is expected to destabilize the ligand field d–d excited state, thus minimizing its interference to the radiative process from the lower lying excited state. 3) P^C2 inherits profound and versatile functionality (see below) capable of fine-tuning the electronic character. As a result, highly efficient blue phosphorescence is attained with good OLED performance. Treatment of a mixture of [IrCl3(tht)3] (tht = tetrahydrothiophene) with an equimolar amount of triphenylphosphine (PPh3), triphenylphosphite {P(OPh)3}, and an excess of sodium acetate resulted in a high yield conversion (> 80%) into [Ir(P^C2)(PPh3)(OAc)] (1a); P^C2 = tripodal dicyclometalated phosphite (Scheme 1). Subsequent replacement of acetate in 1a with chelating 3-tert-butyl-5-(2-pyridyl)triazo-

Blue-emitting Ir(III) phosphors with 2-pyridyl triazolate chromophores and fabrication of sky blue- and white- emitting OLEDs

Heteroleptic Ir(III) complexes with 3-tert-butyl-5-(2-pyridyl)-1,2,4-triazolate chromophore (bptz) and cyclometalating benzyldiphenylphosphine (bdp) or phenyl diphenylphosphinite (pdpit) ancillary (i.e. [Ir(bptz)2(bdp)] (1) and [Ir(bptz)2(pdpit)] (2)) are synthesized upon treatment of [IrCl3(tht)3] (tht = tetrahydrothiophene) with the relevant phosphine, followed by the addition of 2 equiv. of bptz chelate at elevated temperature. Their photophysical properties in solution were measured, along with the characteristics detected as dopants in thin solid films. For application, organic light emitting diodes (OLEDs) were also fabricated using 1 and 2 as dopants, achieving respective maximum efficiencies of 17.8% (44.8 cd A−1 and 46.3 lm W−1) and 9.1% (22.8 cd A−1 and 23.6 lm W−1). In addition, sky blue iridium complex 1 was used with red osmium complex [Os(bpftz)2(PPhMe2)2] (3) to fabricate phosphorescent OLEDs with a sophisticated red/blue/red emitting layer architecture, attaining a stable warm white color with CIE coordinates of (0.397, 0.411). This white OLED attained an electroluminescence efficiency of up to 18.1%, 39.6 cd A−1, and 35.7 lm W−1 for the forward direction.

Phosphorescent OLEDs assembled using Os(II) phosphors and a bipolar host material consisting of both carbazole and dibenzophosphole oxide

We report on the synthesis of a new series of Os(II) complexes (1–3) functionalized with 2-pyridyl (or 2-isoquinolyl) pyrazole chelates, together with a new diphosphine, 1,2-bis(phospholano)benzene chelate (pp2b). The resulting Os(II) complexes are fully characterized and their structural versus spectroscopic properties have been comprehended by absorption/emission together with computational approaches. The inherent electron richness, restricted rotational barrier and good steric hindrance of pp2b lead to the production of both orange and red phosphorescence with high quantum efficiency. For exploring these Os(II) based OLEDs, we also synthesized a bipolar material 5-[4-(carbazo-9-yl)phenyl] dibenzophosphole-5-oxide (CzPhO), possessing both carbazole donor and dibenzophosphole oxide acceptor. Successful fabrication of OLEDs using complexes 1 and 3 as the dopant and either 4,4′-N,N′-dicarbazolebiphenyl (CBP) or CzPhO as host is reported. For comparison, the CBP and CzPhO devices with 1 as the emitter showed peak efficiencies EQE of 10.9%, ηL of 21.7 cd A−1, and ηp of 11.9 lm W−1, and EQE of 14.3%, ηL of 34.8 cd A−1, and ηp of 45.2 lm W−1, respectively.

Efficient White OLEDs Employing Phosphorescent Sensitization

We have investigated white-emitting organic light-emitting devices (WOLEDs) making use of both blue-phosphor-sensitized orange-red fluorescence and the residual blue phosphorescence. By carefully adjusting the concentrations the phosphor and the fluorophore in the emitting layer and choosing the carrier-transport layers in the device structure, WOLEDs containing a single phosphor-sensitized emitting layer (type-I devices) can give colors close to the equal-energy white (0.33, 0.33), CRI up to 75, and efficiencies up to (10%, 23 cd/A, 13.4lm/W). Furthermore, by doping a green phosphor into the poorly emitting electron-transport layer (type-II devices) to recycle excitons formed there, the EL efficiencies can be further enhanced up to (12.1%, 35.3 cd/A, 23.9lm/W). In both types of devices, the phosphor sensitization reduces population of triplet excitons in the emitting region and substantially mitigates the efficiency roll-off with the driving current or brightness that is often observed in all-phosphor OLEDs. At the brightness of 1000 cd/m2, both types of devices retain quantum and cadmium per ampere (cd/A) efficiencies similar to their peak values

Heteroleptic Ir(III) phosphors with bis-tridentate chelating architecture for high efficiency OLEDs

A bis-tridentate iridium complex represented by a formula (I): where R3 to R8, R21 to R23, R9, R10, X1, X2, and X3 are as defined in the specification.

Os(II) metal phosphors bearing tridentate 2,6-di(pyrazol-3-yl)pyridine chelate: synthetic design, characterization and application in OLED fabrication

Treatment of 2,6-di(5-trifluoromethylpyrazol-3-yl)pyridine (pz2py)H2 with Os3(CO)12 affords a mononuclear Os(II) complex [Os(pz2py)(CO)2(H2O)] (1) in excellent yield. Ligand substitution reactions were next executed to identify products with good photoluminescence at both fluid and solid states at RT. Therefore, substitutions with phosphorus donors such as PPh2Me and 2,6-bis(diphenylphosphinomethyl) pyridine (P2N), and nitrogen donors such as pyridine, 2,2′-bipyridine (bpy) and 2,2′:6′,2′′-terpyridine (tpy), afforded products with formula [Os(pz2py)(PPh2Me)2(CO)] (2), [Os(pz2py)(P2N)] (3), [Os(pz2py)(CO)2(py)] (4), [Os(pz2py)(CO)(bpy)] (5) and [Os(pz2py)(CO)(tpy)] (6). The single crystal X-ray structural analyses were executed on 1, 2, 3 and 6 to reveal the bonding of pz2py chelate as well as the structural effect imposed by the phosphorus and/or nitrogen donor groups. The photophysical properties were studied and discussed using the results of DFT and TDDFT calculations. For application, fabrication and analysis of organic light emitting diodes (OLEDs) were also carried out. OLEDs using 2 as a dopant exhibited an intense yellow emission with a maximum efficiency of 18.3%, 61.0 cd A−1, and 53.8 lm W−1, which are higher than those of most reported devices with greenish yellow/yellow emitters. Moreover, dopant 2 was combined with a red emitting dopant Os(bpftz)2(PPhMe2)2 (7) and two different sky-blue phosphors FIrpic and Ir(bptz)2(bdp) (8) to fabricate white OLEDs (WOLEDs). Device W1 achieved the highest efficiency of 18.0%, 33.9 cd A−1, and 31.2 lm W−1 while the maximized efficiency of device W2 was 15.3%, 29.3 cd A−1, and 27.0 lm W−1. Both devices showed stable warm-white emissions with a wide luminance range. In addition, device W2 exhibited a higher CRI of 84.2 with a low CCT of 2675 K at 103 cd m−2, making it a potential candidate for domestic lighting.

Achieving three-peak white organic light-emitting devices using wavelength-selective mirror electrodes

We report an effective approach based on wavelength-selective mirrors for implementing three-peak white-emitting organic light-emitting devices (OLEDs). Such three-peak white OLEDs have electroluminescence spectra matching better with the transmission spectra of typical color filters and thus give much enhanced color gamut for full-color OLED display applications. The wavelength-selective mirror uses the metal/dielectric stack that is compatible with the OLED fabrication.

Near infrared-emitting tris-bidentate Os(II) phosphors: control of excited state characteristics and fabrication of OLEDs

A series of four Os(II) complexes bearing (i) chromophoric diimine ligands (N^N), such as 2,2′-bipyridine (bpy) and substituted 1,10-phenanthrolines, (ii) dianionic bipz chelate ligands derived from 5,5′-di(trifluoromethyl)-2H,2′H-3,3′-bipyrazole (bipzH2), and (iii) bis(phospholano)benzene (pp2b) as the third ancillary ligand completing the coordination sphere were synthesized. X-ray diffraction studies confirm the heteroleptic tris-bidentate coordination mode. These Os(II) complexes [Os(N^N)(bipz)(pp2b)], N^N = bpy (3), phenanthroline (4), 3,4,7,8-tetramethyl-1,10-phenanthroline (5) and 4,7-diphenyl-1,10-phenanthroline (6), display near infrared (NIR) emission between 717 nm and 779 nm in the solid state at RT. On the basis of hybrid-DFT and TD-DFT calculations, the emissions are assigned to metal-to-ligand charge transfer transitions (3MLCT) admixed with small ligand-to-ligand charge transfer (3LLCT) contributions. Successful fabrication of organic light emitting diodes (OLEDs) using Os(II) complex 5 as the dopant and either tris(8-hydroxyquinoline) aluminum (Alq3) or 3,3′,5,5′-tetra[(m-pyridyl)-phen-3-yl]-biphenyl (BP4mPy) as the host is reported. These OLEDs were measured with emission maxima at 690 nm and extending into the NIR, with peak power efficiencies of up to 0.13 lm W−1 and external quantum efficiencies of up to 2.27%.

Enhancing device efficiencies of solid-state white light-emitting electrochemical cells by employing waveguide coupling

Solid-state white light-emitting electrochemical cells (LECs) have received intense scientific attention owing to their potential applications in display and lighting. Although device efficiencies of white LECs have been significantly improved in recent years, further improvements are still required for their practical applications. In this work, we demonstrate the enhancement of device efficiencies of white LECs by employing waveguide coupling. Two transparent photoresist (TPR) layers doped with TiO2 nanoparticles (NPs) are inserted between the indium tin oxide (ITO) layer and the glass substrate. By tuning the doping concentration of 25 nm TiO2 NPs in the upper TPR layer to adjust the refractive index, effective waveguide coupling between the ITO layer and the lower TPR layer can be achieved. Since the lower TPR layer contains 250 nm TiO2 NPs, electroluminescence (EL) outcoupled from the ITO layer can be scattered and redirected into the forward direction. Furthermore, the EL trapped in the glass substrate can also transmit into the lower TPR layer and then is scattered to the forward direction. When the EL trapped in the ITO layer and the glass substrate can be effectively recycled into the forward direction, the peak external quantum efficiency and power efficiency obtained in white LECs employing waveguide coupling are up to 19.4% and 34.1 lm W−1, respectively. These efficiencies are among the highest reported for white LECs and thus confirm that waveguide coupling would be useful for realizing highly efficient white LECs. In addition to the enhanced device efficiencies, improved color migration of EL spectra, which is desired for lighting applications, can be obtained in white LECs with scattering waveguide layers since EL of different angles can be mixed in the forward direction.