Photophysics of conjugated polymers: interplay between Forster energy migration and defect concentration in shaping a photochemical funnel in PPV

Recent single molecule experiments have suggested the existence of a photochemical funnel in the photophysics of conjugated polymers, like poly[2-methoxy-5-(2'-ethylhexyl)oxy-1,4-phenylenevinylene] (MEH-PPV). The funnel is believed to be a consequence of the presence of conformational or chemical defects along the polymer chain and efficient non-radiative energy transfer among different chromophore segments. Here we address the effect of the excitation energy dynamics on the photophysics of PPV. The PPV chain is modeled as a polymer with the length distribution of chromophores given either by a Gaussian or by a Poisson distribution. We observe that the Poisson distribution of the segment lengths explains the photophysics of PPV better than the Gaussian distribution. A recently proposed version of an extended particle-in-a-box' model is used to calculate the exciton energies and the transition dipole moments of the chromophores, and a master equation to describe the excitation energy transfer among different chromophores. The rate of energy transfer is assumed to be given here, as a first approximation, by the well-known Forster expression. The observed excitation population dynamics confirms the photochemical funneling of excitation energy from shorter to longer chromophores of the polymer chain. The time scale of spectral shift and energy transfer for our model polymer, with realistic values of optical parameters, is in the range of 200-300 ps. We find that the excitation energy may not always migrate towards the longest chromophore segments in the polymer chain as the efficiency of energy transfer between chromophores depends on the separation distance between the two and their relative orientation.

Relation between Tc and hole concentration in superconducting cuprates

The superconducting transition temperature, Tc, of several series of cuprates shows a nonlinear dependence on the hole concentration, nh, determined by chemical titrations. The tc becomes maximum when nh is in the 0.12-0.15 range in cuprates containing a single Cu-O layer and around 0.2 in cuprates containing two Cu-O layers.

Thermodynamics of Phosphorus and Sulphur Removal during Basic Oxygen Steelmaking

Removal of impurity elements from hot metal is essential in basic oxygen steelmaking. Oxidation of phosphorus from hot metal has been studied by several authors since the early days of steelmaking. Influence of different parameters on the distribution of phosphorus, seen during the recent work of the authors, differs somewhat from that reported earlier. On the other hand, removal of sulphur during steelmaking has drawn much less attention. This may be due to the magnitude of desulphurisation in oxygen steelmaking being relatively low and desulphurisation during hot metal pre-treatment or in the ladle furnace offering better commercial viability Further, it is normally accepted that sulphur is removed to steelmaking slag in the form of sulphide only However, recent investigations have indicated that a significant amount of sulphur removed during basic oxygen steelmaking can exist in the form of sulphate in the slag under oxidising conditions. The distribution of sulphur during steelmaking becomes more important in the event of carry-over of sulphur-rich blast-furnace slag, which increases sulphur load in the BOF. The chemical nature of sulphur in this slag undergoes a gradual transition from sulphide to sulphate as the oxidative refining progresses.

Quasichemical equations for oxygen and sulphur in liquid binary alloys

An equation has been derived for predicting the activity coefficient of oxygen or sulphur in dilute solution in binary alloys, based on the quasichemical approach, where the metal atoms and the oxygen atoms are assigned different bond numbers. This equation is an advance on Alcock and Richardson's earlier treatment where all the three types of atoms were assigned the same coordination number. However, the activity coefficients predicted by this new equation appear to be very similar to those obtained through Alcock and Richardson's equation for a number of alloy systems, when the coordination number of oxygen in the new model is the same as the average coordination number used in the earlier equation. A second equation based on the formation of “molecular species” of the type XnO and YnO in solution is also derived, where X and Y atoms attached to oxygen are assumed not to make any other bonds. This equation does not fit experimental data in all the systems considered for a fixed value of n. Howover, if the strong oxygen-metal bonds are assumed to distort the electronic configuation around the metal atoms bonded to oxygen and thus reduce the strength of the bonds formed by these atoms with neighbouring metal atoms by approximately a factor of two, the resulting equation is found to predict the activity coefficients of oxygen that are in good agreement with experimental data in a number of binary alloys.

A study of measures of population density and of concentration of fishing effort in the fishery for yellowfin tuna, Neothunnus macropterus, in the Eastern Tropical Pacific Ocean, from 1951 to 1956

ENGLISH: This study shows how the catch and effort statistics, from 1951 to 1956, of the fishery for yellowfin tuna, Neothunnus macropterus, in the Eastern Tropical Pacific Ocean, have been used to compute: (i) two indices of average population density; (ii) an index of concentration of effort on areas of greatest density of available yellowfin. These three indices were then used to determine: (i) quarterly and annual variation in each of them; (ii) the relationship between the two indices of density; (iii) the relationship of each of the indices to the number of exploited one-degree rectangles. To remove extreme sampling variation at low levels of effort, the data from all one-degree rectangles subjected to less than five logged days' fishing in a quarter were eliminated, and the computations were repeated for comparison with those of the original data. SPANISH: Este estudio da a conocer cómo las estadísticas sobre la pesca y el esfuerzo de pesca de la pesquería del atún aleta amarilla, Neothunnus macropterus, en el Océano Pacífico Oriental Tropical, durante 1951 a 1956, han servido para computar: (i) dos índices del promedio de la densidad de la población; (ií) un índice de la concentración del esfuerzo en las áreas de mayor densidad de atún aleta amarilla disponible. Estos tres índices han sido luego usados para determinar: (i) la variación trimestral y anual en cada uno de ellos; (ií) la relación entre los dos índices de densidad; (iii) la relación de cada uno de los índices con el número de rectángulos de un grado explotados. Para evitar la extrema variación del muestreo a bajos niveles de esfuerzo, se eliminaron los datos de todos los rectángulos de un grado sujetos a menos de cinco días de actividad pesquera durante un trimestre según los registros de los cuadernos de bitácora, y las computaciones se repitieron para compararlas con las de los datos originales.

Trends in nitrate-nitrogen, nitrite-nitrogen and phosphorus concentration in Ebonyi river, Nigeria

A baseline study of the limnological integrity of Ebonyi River, a tropical lotic system in south-eastern Nigeria was conducted between September 2006 and February 2008 to assess its potential in enhancing fisheries production for the benefit of the rural poor, who depend on the resources of the river for survival. The parameters measured were nitrate-nitrogen, nitrite-nitrogen and phosphate-phosphorus. Results show that nitrate varied between 40.43mg/L in September 2006 and 1.73mg/L in December 2007, Showing significant difference (P<0.01) among months. The values recorded for nitrites varied between 0.2mg/L in September 2006 and 0.4mg/L in February 2008, showing significant (P<0.01) variation among months. Values recorded for phosphorus was highest (0.05mg/L) in the month of October 2006 while the least mean value (0.32mg/L) was recorded in the month of May 2007 and showed significant (p<0.01) variation in monthly means. It was concluded that the values of the measured parameters falls within tolerable range for enhanced fisheries development in the area. KEYWORDS: Limnology, Tropical, River, Monthly, Mean, Variation

High quantum efficiency and high concentration erbium-doped silica glasses fabricated by sintering nanoporous glasses

A new method was used to prepare erbium-doped high silica (SiO2% > 96%) glasses by sintering nanoporous glasses. The concentration of erbium ions in high silica glasses can be considerably more than that in silica glasses prepared by using conventional methods. The fluorescence of 1532 nm has an FWHM (Full Wave at Half Maximum) of 50 nm, wider than 35 nm of EDSFA (erbium-doped silica fiber amplifer), and hence the glass possesses potential application in broadband fiber amplifiers. The Judd-Ofelt theoretical analysis reflects that the quantum efficiency of this erbium-doped glass is about 0.78, although the erbium concentration in this glass (6 x 103) is about twenty times higher than that in silica glass. These excellent characteristics of Er-doped high silica glass will be conducive to its usage in optical amplifiers and microchip lasers.

Ni(Pt)-silicide contacts on CMOS devices: Impact of substrate nature and Pt concentration on the phase formation

Ni silicides used as contacts in source/drain and gate of advanced CMOS devices were analyzed by atom probe tomography (APT) at atomic scale. These measurements were performed on 45 nm nMOS after standard self-aligned silicide (salicide) process using Ni(5 at.% Pt) alloy. After the first annealing (RTA1), δ-Ni2Si was the only phase formed on gate and source/drain while, after the second annealing (RTA2), two different Ni silicides have been formed: NiSi on the gate and δ-Ni2Si on the source and drain. This difference between source/drain and gate regions in nMOS devices has been related to the Si substrate nature (poly or mono-crystalline) and to the size of the contact. In fact, NiSi seems to have difficulties to nucleate in the narrow source/drain contact on mono-crystalline Si. The results have been compared to analysis performed on 28 nm nMOS where the Pt concentration is higher (10 at.% Pt). In this case, θ-Ni2Si is the first phase to form after RTA1 and NiSi is then formed at the same time on source (or drain) and gate after RTA2. The absence of the formation of NiSi from δ-Ni 2Si/Si(1 0 0) interface compared to θ-Ni2Si/Si(1 0 0) interface could be related to the difference of the interface energies. The redistributions of As and Pt in different silicides and interfaces were measured and discussed. In particular, it has been evidenced that Pt redistributions obtained on both 45 and 28 nm MOS transistors correspond to respective Pt distributions measured on blanket wafers. © 2013 Elsevier B.V. All rights reserved.

Raman scattering study of vibrational modes and hole concentration in GaxMn1-xSb

The Raman scattering study of vibrational modes and hole concentration in a ferromagnetic semiconductor Ga1-xMnxSb grown by Mn ion implantation, deposition and post-annealing has been presented. The experiments are performed both in implanted and unimplanted regions before and after etching the samples. The Raman spectra measured from the unimplanted region show only GaSb-like phonon modes. On the other hand, the spectra measured from the implanted region show additional phonon modes approximately at 115, 152, 269, 437 and 659 cm(-1). The experimental results demonstrate that the extra modes are associated with surface defects, crystal disorder and blackish layer that is formed due to Mn ion implantation, deposition and annealing processes. Furthermore, we have determined the hole concentration as a function of laser probing position by modeling the Raman spectra using coupled mode theory. The contributions of GaSb-like phonon modes and coupled LO-phonon plasmon mode are taken into consideration in the model. The hole-concentration-dependent CLOPM is resolved in the spectra measured from the implanted and nearby implanted regions. The hole concentrations determined by Raman scattering are found to be in good agreement with those measured by the electrochemical capacitance-voltage technique.