Efficiency of extrinsic and intrinsic charge-carrier photogeneration processes obtained from the steady-state photocurrent action spectra of poly(p-phenylene vinylene) derivatives

The efficiency of the charge-carrier photogeneration processes in poly(2,5-bis(3',7'-dimethyl-octyloxy)-1,4-phenylene vinylene) (OC(1)OC10-PPV) has been analyzed by the spectral response of the photocurrent of devices in ITO/polymer/Al structures. The symbatic response of the photocurrent action spectra of the OC1OC10-PPV devices, obtained for light-excitation through the ITO electrode and for forward bias, has been fitted using a phenomenological model which considers that the predominant transport mechanism under external applied electric field is the drift of photogenerated charge-carriers, neglecting charge-carrier diffusion. The proposed model takes into account that charge-carrier photogeneration occurs via intermediate stages of bounded pairs (excitonic states), followed by dissociation processes. Such processes result in two different contributions to the photoconductivity: The first one, associated to direct creation of unbound polaron pairs due to intrinsic photoionization; and the second one is associated to secondary processes like extrinsic photoinjection at the metallic electrodes. The results obtained from the model have shown that the intrinsic component of the photoconductivity at higher excitation energies has a considerably higher efficiency than the extrinsic one, suggesting a dependence on the photon energy for the efficiency of the photogeneration process.Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP

Exciton Diffusion in Polyfluorene Copolymer Thin Films: Kinetics, Energy Disorder and Thermally Assisted Hopping

A series of {(9,9-dioctylfluorene)(0.7-x)-(dibenzothiophene-S,S-dioxide)(0.3)-[4,7-b is(2-thienyl)-2,1,3-benzothiadiazole](x)} (PFS30-TBTx), where x represents the minor percentage of the red emitter 4,7-bis(2-thienyl)-2,1,3-benzothiadiazole (TBT) randomly incorporated into the copolymer backbone, is investigated in order to follow the energy transfer from PFS30, to TBT moieties. The emission of the donor poly[(9,9-dioctylfluorene)(0.7)-(dibenzothiophene-S,S-dioxide)(0.3) identified by PFS30 and peaking at 450 nm, is clearly quenched by the presence of the red TBT chromophore emitting at 612 nm, with an isoemissive point observed when the spectra are collected as a function of temperature. A plot of the ratio between the TBT and PFS30, emissions as a function of the reciprocal of temperature gives a clear linear trend between 290 and 200 K, with an activation energy of 20 meV and showing a turn over to a non-activated regime below 200 K. Picosecond time-resolved fluorescence decays collected at the PFS30 and TBT emission wavelengths, show a decay of the PFS30, emission and a fast build-in, followed by a decay, of the TBT emission, confirming that the population of the TBT excited state occurs during the PFS30 lifetime(similar to 600 ps). The population of the TBT excited state occurs on a time regime around 150 ps at 290 K, showing an energy barrier of 20 meV that turns over to a non-activated regime below 200 K in clear agreement with the steady-state data. The origin of the activation barrier is attributed to the presence of physical and energetic disorder, affected by fast thermal fluctuations that dynamically change the energy landscape and control the exciton migration through the polymer density of states

Analysis of the Al-PANI interfaces by complex impedance spectroscopy

This paper describes a new approach to improve the analysis of surface modification of free-standing semiconducting polymer films emerged from the interfacial interaction between aluminium electrode and HCl-doped polyaniline (PANI) films. The Al-PANI-Al structure was prepared by casting PANI/N-methyl-2-pirrolidone onto a glass substrate and then being sandwiched between Al electrodes after immersion in HCl aqueous solutions and then dried. The Al-polymer interface was investigated by means of complex impedance spectroscopy in the frequency domain on HCl-doped PANI films. The dc conductivity of the interfacial layer between the Al and PANI surface exposed to air during the film processing is higher than those obtained with Al and PANI surface exposed to glass. Raman spectroscopy data confirm this evidence. Here, it is speculated that some dissociated chlorine and aluminium-salt-containing species have contributed as ionic carriers increasing the electrical conductivity of the polymer bulk, and by the formation of an Al(2)O(3) thin layer between the Al and PANI films. An equivalent circuit model considering the influence of Al-PANI reactions on the electrical behaviour of the Al-PANI-Al structure was proposed. Additionally, it was demonstrated that the impedance spectroscopy facilitates the identification of interface modification in the Al-PANI-Al films.Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP

New Boron(III) Blue Emitters for All-Solution Processed OLEDs: Molecular Design Assisted by Theoretical Modeling

Luminescent boron(III) complexes have recently been employed as emitters in organic light-emitting diodes (OLEDs) with reasonable success. They are easy to prepare and sufficiently stable to be used in such devices, being of great interest as a simple molecular emissive layer. Although emitters for this class with all colors have already been reported, highly efficient and stable blue emitters for applications in solution processed devices still pose a challenge. Here, we report the design, synthesis, and characterization of new boron complexes based on the 2-(benzothiazol-2-yl)phenol ligand (HBT), with different donor and acceptor groups responsible for modulating the emission properties, from blue to red. The molecular design was assisted by calculations using our newly developed formalism, where we demonstrate that the absorption and fluorescence spectra can be successfully predicted, which is a powerful technique to evaluate molecular photophysical properties prior to synthesis. In addition, density functional theory (DFT) enables us to understand the molecular and electronic structure of the molecules in greater detail. The molecules studied here presented fluorescence efficiencies as high as Φ = 0.88 and all solution processed OLEDs were prepared and characterized under an ambient atmosphere, after dispersion in the emitting layer. Surprisingly, even considering these rather simple experimental conditions, the blue emitters displayed superior properties compared to those in the present literature, in particular with respect to the stability of the current efficiency

Mechanical power of ventilation is associated with mortality in critically ill patients: an analysis of patients in two observational cohorts

Abstract Purpose Mechanical power (MP) may unify variables known to be related to development of ventilator-induced lung injury. The aim of this study is to examine the association between MP and mortality in critically ill patients receiving invasive ventilation for at least 48 h. Methods This is an analysis of data stored in the databases of the MIMIC–III and eICU. Critically ill patients receiving invasive ventilation for at least 48 h were included. The exposure of interest was MP. The primary outcome was in-hospital mortality. Results Data from 8207 patients were analyzed. Median MP during the second 24 h was 21.4 (16.2–28.1) J/min in MIMIC-III and 16.0 (11.7–22.1) J/min in eICU. MP was independently associated with in-hospital mortality [odds ratio per 5 J/min increase (OR) 1.06 (95% confidence interval (CI) 1.01–1.11); p = 0.021 in MIMIC-III, and 1.10 (1.02–1.18); p = 0.010 in eICU]. MP was also associated with ICU mortality, 30-day mortality, and with ventilator-free days, ICU and hospital length of stay. Even at low tidal volume, high MP was associated with in-hospital mortality [OR 1.70 (1.32–2.18); p < 0.001] and other secondary outcomes. Finally, there is a consistent increase in the risk of death with MP higher than 17.0 J/min. Conclusion High MP of ventilation is independently associated with higher in-hospital mortality and several other outcomes in ICU patients receiving invasive ventilation for at least 48 h

Mechanical power of ventilation is associated with mortality in critically ill patients: an analysis of patients in two observational cohorts

Purpose: Mechanical power (MP) may unify variables known to be related to development of ventilator-induced lung injury. The aim of this study is to examine the association between MP and mortality in critically ill patients receiving invasive ventilation for at least 48&nbsp;h. Methods: This is an analysis of data stored in the databases of the MIMIC\u2013III and eICU. Critically ill patients receiving invasive ventilation for at least 48&nbsp;h were included. The exposure of interest was MP. The primary outcome was in-hospital mortality. Results: Data from 8207 patients were analyzed. Median MP during the second 24&nbsp;h was 21.4 (16.2\u201328.1) J/min in MIMIC-III and 16.0 (11.7\u201322.1) J/min in eICU. MP was independently associated with in-hospital mortality [odds ratio per 5&nbsp;J/min increase (OR) 1.06 (95% confidence interval (CI) 1.01\u20131.11); p = 0.021 in MIMIC-III, and 1.10 (1.02\u20131.18); p = 0.010 in eICU]. MP was also associated with ICU mortality, 30-day mortality, and with ventilator-free days, ICU and hospital length of stay. Even at low tidal volume, high MP was associated with in-hospital mortality [OR 1.70 (1.32\u20132.18); p &lt; 0.001] and other secondary outcomes. Finally, there is a consistent increase in the risk of death with MP higher than 17.0&nbsp;J/min. Conclusion: High MP of ventilation is independently associated with higher in-hospital mortality and several other outcomes in ICU patients receiving invasive ventilation for at least 48&nbsp;h