Jesse R. Salem

Degradation and failure of MEH‐PPV light‐emitting diodes

Light‐emitting diodes made with poly(2‐methoxy‐5(2′‐ethyl)hexoxy‐phenylenevinylene) (MEH‐ PPV) using indium‐tin‐oxide (ITO) as anode and Ca as cathode have been examined as they age during operation in a dry inert atmosphere. Two primary modes of degradation are identified. First, oxidation of the polymer leads to the formation of aromatic aldehyde, i.e., carbonyl which quenches the fluorescence. The concomitant chain scission results in reduced carrier mobility. ITO is identified as a likely source of oxygen. The second process involves the formation of localized electrical shorts which do not necessarily cause immediate complete failure because they can be isolated by self‐induced melting of the surrounding cathode metal. We have not identified the origin of the shorts, but once they are initiated, thermal runaway appears to accelerate their development. The ultimate failure of many MEH‐PPV devices occurs when the regions of damaged cathode start to coalesce.

Mechanism for bistability in organic memory elements

We demonstrate that the resistive switching phenomenon observed in organic semiconductor layers containing granular metal particles conforms to a charge storage mechanism described by Simmons and Verderber [Proc. R. Soc. A 391, 77 (1967)]. The space-charge field due to the stored charge inhibits further charge injection from the electrodes. The equilibrium current–voltage curve is N shaped and the low and high resistance states are obtained by applying voltage close to the local maximum and minimum, respectively.

Increased brightness and lifetime of polymer light-emitting diodes with polyaniline anodes

Abstract The properties of light-emitting diodes based on poly(2-methoxy,5-(2′-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV) with indium-tin oxide (ITO) anodes are compared with those in which a layer of polyaniline (PAni) is coated between the ITO and the emissive polymer. It is found that the PAni injection layer yields higher current, brighter emission and a lower rate of degradation than ITO. The electrical behavior is discussed in terms of bulk and contact current limitation. The improvement in degradation is attributed to reduced oxidation as the PAni layer provides a barrier for the passage of oxygen out of the oxide. In addition, improvement in microscopic short formation indicates planarization of the anode interface by the PAni film.

C60 Rotation in the Solid State: Dynamics of a Faceted Spherical Top

The rotational dynamics of C60 in the solid state have been investigated with carbon-13 nuclear magnetic resonance (13C NMR). The relaxation rate due to chemical shift anisotropy (1/9T1CSA1) was precisely measured from the magnetic field dependence of T1, allowing the molecular reorientational correlation time, τ, to be determined. At 283 kelvin, τ = 9.1 picoseconds; with the assumption of diffusional reorientation this implies a rotational diffusion constant D = 1.8 x 1010 per second. This reorientation time is only three times as long as the calculated τ for free rotation and is shorter than the value measured for C60 in solution (15.5 picoseconds). Below 260 kelvin a second phase with a much longer reorientation time was observed, consistent with recent reports of an orientational phase transition in solid C60. In both phases τ showed Arrhenius behavior, with apparent activation energies of 1.4 and 4.2 kilocalories per mole for the high-temperature (rotator) and low-temperature (ratchet) phases, respectively. The results parallel those found for adamantane.

Scandium clusters in fullerene cages.

The production and spectroscopic characterization of fullerene-encapsulated metal-atom clusters is reported. In particular, both solution and solid-state electron paramagnetic resonance (EPR) spectra of Sc3C82 have been obtained. ScC82 also gives an EPR spectrum, but Sc2Cn species—the most abundant metallofullerenes in the mass spectrum—are EPR-silent even though Sc2 is EPR-active in a rare-gas matrix at 4.2 K. The results suggest that the three scandium atoms in Sc3C82 form an equilateral triangle—as was previously suggested for Sc3 molecules isolated in a cryogenic rare-gas matrix. The spectrum of ScC82 has features similar to those found earlier for LaC82 and YC82, suggesting that it can also be described as a +3 metal cation within a -3 fullerene radical anion. An implication of this work is that production of macroscopic quantities of clustercontaining fullerenes may make possible the fabrication of exotic new structures with regular arrays of metal-atom clusters isolated in fullerene molecules, resulting in a new type of host/guest nanostructured material.

Photovoltaic measurement of the built-in potential in organic light emitting diodes and photodiodes

We measure the voltage at which the current under illumination in poly[2-methoxy, 5-(2-ethylhexoxy)-1,4-phenylene vinylene] based light emitting diodes is equal to the dark current. At low temperatures, this voltage, which we term the “compensation” voltage, is found to be equal to the built-in potential, as measured with electroabsorption on the same diode. Diffusion of thermally injected charges at room temperature, however, shifts the compensation voltage to lower values. A model explaining this behavior is developed and its implications for the operation of organic light emitting diodes and photovoltaic cells are briefly discussed.

Superconducting Tl-Ca-Ba-Cu-O thin films with zero resistance at temperatures of up to 120 K

We have prepared superconducting Tl‐Ca‐Ba‐Cu‐O thin films on a variety of substrates with transition temperatures as high as ≂120 K, confirmed by sharp onsets of substantial Meissner and shielding signals at the same temperatures. The properties of the films are found to depend sensitively on the post‐annealing conditions. Highly textured c‐axis‐oriented films comprised mostly of Tl2Ca1Ba2Cu2Ox, Tl1Ca2Ba2Cu3Ox, and Tl2Ca2Ba2Cu3Ox were synthesized by varying the annealing procedure with corresponding maximum superconducting transition temperatures of ≂100, 110, and 120 K, respectively.

Multiple species of La@C82 and Y@C82. Mass spectroscopic and solution EPR studies

Abstract Two dominant electron paramagnetic resonance (EPR) hyperfine patterns for both La and Y fullerenes have been identified and linked to the mass spectroscopic (MS) peaks of La@C 82 and Y@C 82 , respectively, as also observed by Suzuki. Additionally, lower intensity La@C n EPR multiplets are identified which have not, as yet, been correlated with specific MS peaks. The intensity ratios of the two dominant EPR multiplets depend on various parameters such as solvent and temperature, suggesting the species possess different chemical properties.

High Tc YBa2Cu3O7−x thin films on Si substrates by dc magnetron sputtering from a stoichiometric oxide target

Thin films of YBa2Cu3O7−x were deposited on Si substrates at 600–700 °C by dc magnetron sputtering from a stoichiometric oxide target. Resistivity measurement results indicate that these films are superconducting with a zero resistance Tc as high as 76 K, without further high‐temperature post‐annealing treatments. These films give both core and valence‐band x‐ray photoemission, and x‐ray diffraction spectra similar to those for superconducting films prepared with a high‐temperature post‐annealing step. No significant diffusion of Si from the substrate into the film was detected for the films deposited at 650 °C or lower, according to depth profiles obtained using secondary ion mass spectrometry.

Hole limited recombination in polymer light-emitting diodes

By comparing the quantum efficiencies of light emission in a series of poly[2-methoxy-5(2′ethyl)hexoxy-phenylenevinylene] diodes with calcium cathodes and various anode metals, we show that, in all cases electrons are the majority carrier and recombination is limited by hole injection. These conclusions are confirmed by the examination of a second series of samples in which alkanethiol barrier layers of varying thickness, are deposited on a gold anode. The highest external quantum efficiency was achieved in these experiments using a clean, semitransparent gold anode. We suggest that electron and hole injection rates play the primary role in determining current balance and that mobilities play a minor role.