Efficient and stable high energy organic light emitting devices (OLEDs) are a vital component of new generation general illumination solutions. However, large charge imbalances in the emissive layer of OLEDs lead to charge accumulation and subsequent side reactions which lowers the device efficiency and dramatically shortens operational lifetime. Radical changes in the way emitter materials are designed are needed to address this problem. Conventional approaches have only focused on color tuning; however, multi-functional emitter materials are needed to assist the transport of charge in the emissive layer. We have designed new organometallic iridium phosphorescent materials with bipolar charge transport properties to be used in high energy OLEDs and white light configurations. Theoretical data presented here indicates that these new emitter complexes would improve charge transport in the emissive layer.
Doped ZnO is one of the materials currently being considered in industrial applications as a possible
replacement for ITO as a transparent conducting oxide. The properties of doped ZnO anodes prepared at
Arkema Inc. are analyzed in 3D using high-throughput mapping tools. The 2D resistivities of the coatings
measured by 4-point probe compare well with the resistivity values calculated from the spectroscopic
ellipsometer measurements. It was found that the dependence of effective mass of doped ZnO on Hall-electron
concentration influences optically-calculated mobilities and electron concentrations. To study the
variation of the film properties along z-axis, the films are polished using mechanical planarization
technique. The electrical and crystallographic depth profiles for these films are studied by differential Hall-effect
and grazing-angle x-ray spectroscopy. The electron mobility increases continuously from the glass-film
interface (12 cm2/Vs) to the ZnO film surface (19 cm2/Vs). The electron concentration depth profile
has bell-like dependence with a maximum at 1.55 x 1021 cm-3. In addition to the increasing grain size, the
texture coefficients for the (002) reflection decrease and (103) reflection increase towards the air-film
interface. Examples of the applications of the doped ZnO anodes in the OLED structures suggest
improvement of external quantum efficiency with introduction of an Al2O3 undercoat.
We report an alternative, high-yielding synthesis for the known compound 2,4,6-tris(2′,4′-difluoro-[1,1′-biphenyl]-4-yl)-1,3,5-triazine (tris-(dFB)Tz). The energy of the lowest unoccupied molecular orbital (ELUMO) for tris-(dFB)Tz is estimated to be −3.5 eV from electrochemical measurements. The deep ELUMO of tris-(dFB)Tz affords a material with excellent electron acceptor characteristics for use in n-doped electron transport layers. Tris-(dFB)Tz shows a four order of magnitude increase in the number of carriers on doping with 8 wt. % Cs2CO3. Enhanced electron injection was also observed on doping with Cs2CO3, which eliminated the necessity for a separate LiF electron injection layer. Blue phosphorescent organic light-emitting devices (OLEDs) were fabricated using n-doped tris-(dFB)Tz electron transport layers. OLEDs with thick (700-Å) Cs2CO3-doped tris-(dFB)Tz electron transport layers had lower operating voltages than OLEDS with an undoped electron transport layer of bis(diphenylphosphoryl)dibenzothiophene (PO15), which has previously been used in low-voltage, high-efficiency OLEDs. The tris-(dFB)Tz results indicate that aromatic substituted triazines may be promising materials for use as electron acceptors in n-doped organic electronic systems.
We report the photophysical characterization, computational results, and device properties for ambipolar phosphine oxide-based host materials that were chemically functionalized to control the charge transport. We study the effects of structural modifications of phosphine oxide hosts on the charge balance in the emissive zone of organic light-emitting devices (OLEDs). Significant changes in charge transport within the emissive layer are observed upon introduction of functional groups, such as pyridine and carbazole, into the organic phosphine oxide host structure. We demonstrate that rational design of host materials allows for the control of charge balance in the emissive zone of OLEDs.
The efficiency and stability of blue organic light emitting devices (OLEDs) continue to be a primary roadblock to
developing organic solid state white lighting. For OLEDs to meet the high power conversion efficiency goal, they
will require both close to 100% internal quantum efficiency and low operating voltage in a white light emitting
device.1 It is generally accepted that such high quantum efficiency, can only be achieved with the use of
organometallic phosphor doped OLEDs. Blue OLEDs are particularly important for solid state lighting. The simplest
(and therefore likely the lowest cost) method of generating white light is to down convert part of the emission from a
blue light source with a system of external phosphors.2 A second method of generating white light requires the
superposition of the light from red, green and blue OLEDs in the correct ratio. Either of these two methods (and
indeed any method of generating white light with a high color rendering index) critically depends on a high efficiency
blue light component.3
Conductivity doping of charge transporting layers is becoming increasingly attractive for improving power efficiency in
OLEDs. However, the number of commercially available organic molecular p-dopants is limited. The electron
acceptor 2,3,5,6-tetrafluoro-7,7,8,8,-tetracyanoquinodimethane (F4-TCNQ) is the most utilized p-dopant. F4-TCNQ can
be used as a dopant for most hole transporting materials (HTM), but it is very volatile, which makes it difficult for
vacuum processing, and has a low sticking coefficient. Here we present the design of novel anchored molecular dopants
based on the TCNQ core. We first review how the reduction potential of TCNQ core is affected by substitution with
alkyl groups of different electronic properties. Electron donating groups have negative effect on the reduction potential
of the acceptor. However, attaching electron withdrawing groups such as halogens counteracts the effect of electron
donating groups. Using gas phase theoretical calculations we determined that trifluorinated TCNQ can be anchored
through a σ-coupled alkyl chain to an inert molecular anchor without sacrificing the electron affinity.
Organic light emitting devices (OLEDs) are projected to provide a
low-cost, long-lived, and efficient wide area lighting
solution if challenges in reliability, cost, and efficiency can be overcome. Development of new transparent conducting
oxides (TCOs) that do not contain indium for use as the anode in bottom-emitting OLEDs can lead to cost savings and provide longer device lifetimes. Indium-free TCOs need to meet or exceed performance targets including high
conductivity and visible light transmission, acceptable stability and, for blue or white OLEDs, a high work function to
match the deep HOMO of the hole transport material. In this work, we report results from our efforts to scale up sputter deposition on large area substrates (up to hundreds of cm2) of a
Ga-doped ZnO TCO having a composition identified
using combinatorial methods. We present the results of initial
scale-up efforts and evaluate relevant properties for these
films. Finally, we have incorporated these materials in the production of OLEDs, and show performance comparisons
between devices fabricated on the scaled-up GZO and commercial indium tin oxide (ITO). The results demonstrate that
we are able to generate substrates with the appropriate work function to reduce the operating voltage of blue
phosphorescent OLEDs compared to commercial ITO. This work
function-HOMO energy matching leads to more efficient charge injection into the device hole transport layer.
Phosphine oxide substitution of small molecules with high triplet exciton energies allows development of vacuum
sublimable, electron transporting host materials for blue OLEDs. Heteroaromatic building blocks (carbazole,
dibenzofuran and dibenzothiophene) with ET ~ 3 eV were incorporated into phosphine oxide (PO) structures. External
quantum efficiencies (EQEs) at lighting brightness (i.e., 800 cd/m2) reached as high as 9.8% at 5.2V for OLEDs using
the heteroaromatic PO hosts doped with the sky blue phosphor, iridium(III)bis(4,6-(di-fluorophenyl)-pyridinato-N,C2,)
picolinate (FIrpic). Comparing device properties at a similar current density (i.e., J = 13 mA/cm2) showed the
dibenzothiophene-bridged PO compound exhibits the highest EQEs and lowest operating voltages at all phosphor dopant
levels. These results are explained with respect to the effects of the inductive phosphine oxide substituents on
electrochemical, photophysical and electroluminescence properties of the substituted heteroaromatic building blocks.
High efficiency small molecule organic light emitting devices (OLEDs) based on light emission from an
electrophosphorescent dopant dispersed in an organic host matrix are well known. Achieving blue phosphorescent
OLEDs is particularly challenging because the host triplet energy should ideally be > 2.8 eV to prevent back-transfer of
energy from the dopant to the host matrix resulting in loss of efficiency. A design strategy for developing new host
materials with high triplet energies by using phosphine oxide (P=O) moieties as points of saturation in order to build
sublimable, electron transporting host materials starting from small, wide bandgap molecular building blocks (i.e.,
biphenyl, phenyl, naphthalene, octafluorobiphenyl, and N-ethylcarbazole) is described. Electrophosphorescent OLEDs
using the organic phosphine oxide compounds as host materials for the sky blue organometallic phosphor,
iridium(III)bis(4,6-(di-fluorophenyl)-pyridinato-N,C2,) picolinate (FIrpic) give maximum external quantum efficiencies
of ~ 8% and maximum luminance power efficiencies up to 25 lm/W.
We report the design, syntheses, structure-property relationships, and applications of alternating copolymers containing heteroaromatic rings. Polymers with different structures were synthesized by Suzuki couplings of 1,4-phenyldiboronic acid with various dibromoarenes. The effect of heteroatoms was studied by comparing polymers containing biphenyl, bipyridine, bithiazole, or thienyl moieties. The changes in the polymer structure led to changes in singlet and triplet energies, absorption and emission properties, as well as energy transfer parameters. The effect of polymer structure on absorption maxima, emission properties, excimer formation, aggregate formation, as well as singlet and triplet energies were studied. Alternating copolymers of bipyridyl moieties gave rise to blue-emitting polymers with emission maxima at 410nm, where as the use of bithiazole moieties red-shifted the emission. All of these polymers can be used in polymer light-emitting devices as the emitting layers, where thienyl containing polymers can be used as hole transport layers. The polymers transferred energy efficiently to Coumarins and europium complexes, allowing for their potential use in longer wavelength emitting applications. The ability of bipyridine containing polymers for use as metal ion sensors was studied.
Energy transfer studies were performed with polyphenylene-type polymers as the donating species and a series of organic dyes as the acceptors. The polymers were synthesized via Suzuki coupling of 2,5-didecyloxyphenyl-1,3-bisboronic acid with a corresponding dihaloarene. Coupling with 1,4-dibromobenzene produced a para-only polymer, while 3,5-dibromoethylbenzoate produced a polymer with alternating para- and meta-linkages. Several Coumarins served as singlet acceptors, while some porphyrins were used as triplet acceptors. Photophysical data and energy transfer parameters are presented.
Novel complexes based on a europium(III) core surrounded by three β-diketonate ligands were synthesized. The diketonates were synthesized by condensations of ethyl-2-pyrazinecarboxylate with various aromatic ketones. The metal centered emissions of the europium complexes as well as the ligand centered emission of the gadolinium complexes were studied. The complexes based on gadolinium were studied to establish the singlet and triplet energy levels of the ligands. These europium complexes were used to harvest energy from conjugated polymers. PPP-type polymers with bipyridine moieties and terpyridine pendant groups were studied initially. The europium complex attached to the bipyridine and terpyridine moieties facilitated energy transfer from polymer to europium. A novel class of polymers with a β-diketonate pendant group was synthesized and studied. Each of the polymers were synthesized via Suzuki coupling of 1,4-phenylbisboronic acid with a dibromoarenecarboxylate. Ethyl 3,5-dibromobenzoate was used in the polymerization to synthesize alternating copolymers of phenyl groups. These polymers were then reacted with 2-acetylthiophene to obtain polymers with β-diketonate pendant groups. The photophysics of these polymers and their lanthanide complexes were determined.
We report the design, synthesis, and spectroscopic characterization of polyphenylene-type polymers that can be used to sensitize europium complexes. Although benzophenone is widely studied and characterized, polybenzophenones have not been widely used in photophysical studies. The properties of poly(4'-methyl-2,4-benzophenone) (MB), poly(4'-methyl-2,5-benzophenone) (PB) and poly[2,2'-bipyridine-5,5'-diyl(2,5-didecoxy-1,4-phenylene)] (PBP) are described in this paper. All three polymers have backbones that are similar to polyphenylene. PBP has a bipyridine unit that alternates with a phenyl ring. Benzophenone rings are polymerized with para or meta linkages in PB and MB, respectively. All three polymers have similar emission maxima at 430 nm, but PBP has a higher quantum efficiency of emission. The polymers studied in this paper proved to be of lower energy than what is needed to sensitize many europium complexes. In almost all of the lanthanide complexes the ligands played a major role in the emission properties. This was elaborated in studies done previously. Europium chelates of the two different ligands: di(2-thienoyl)methane (DTM) and di(2-naphthoyl)methane (DNM) proved to be of comparable energies with the polymers studied. Results showed that energy transfer did occur between the polymers and the europium chelates, but the energy transfer was not 100% because residual emission from the polymers was detected.
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