Substitutional Impurities in PPV Crystals: An Intrinsic Donor-Acceptor System for High V(oc) Photovoltaic Devices

Defects are usually present in organic polymer films and are commonly invoked to explain the low efficiency obtained in organic-based optoelectronic devices. We propose that controlled insertion of substitutional impurities may, on the contrary, tune the optoelectronic properties of the underivatized organic material and, in the case studied here, maximize the efficiency of a solar cell. We investigate a specific oxygen-impurity substitution, the keto-defect -(CH(2)-C=O)- in underivatized crystalline poly(p-phenylenevinylene) (PPV), and its impact on the electronic structure of the bulk film, through a combined classical (force-field) and quantum mechanical (DFT) approach. We find defect states which suggest a spontaneous electron hole separation typical of a donor acceptor interface, optimal for photovoltaic devices. Furthermore, the inclusion of oxygen impurities does not introduce defect states in the gap and thus, contrary to standard donor-acceptor systems, should preserve the intrinsic high open circuit voltage (V(oc)) that may be extracted from PPV-based devices.

Associating biosensing properties with the morphological structure of multilayers containing carbon nanotubes on field-effect devices

The control of molecular architecture provided by the layer-by-layer (LbL) technique has led to enhanced biosensors, in which advantageous features of distinct materials can be combined. Full optimization of biosensing performance, however, is only reached if the film morphology is suitable for the principle of detection of a specific biosensor. In this paper, we report a detailed morphology analysis of LbL films made with alternating layers of single-walled carbon nanotubes (SWNTs) and polyamidoamine (PAMAM) dendrimers, which were then covered with a layer of penicillinase (PEN). An optimized performance to detect penicillin G was obtained with 6-bilayer SWNT/PAMAM LbL films deposited on p-Si-SiO(2)-Ta(2)O(5) chips, used in biosensors based on a capacitive electrolyte-insulator-semiconductor (EIS) and a light-addressable potentiometric sensor (LAPS) structure, respectively. Field-emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM) images indicated that the LbL films were porous, with a large surface area due to interconnection of SWNT into PAMAM layers. This morphology was instrumental for the adsorption of a larger quantity of PEN, with the resulting LbL film being highly stable. The experiments to detect penicillin were performed with constant-capacitance (Con Cap) and constant-current (CC) measurements for EIS and LAPS sensors, respectively, which revealed an enhanced detection signal and sensitivity of ca. 100 mV/decade for the field-effect sensors modified with the PAMAM/SWNT LbL film. It is concluded that controlling film morphology is essential for an enhanced performance of biosensors, not only in terms of sensitivity but also stability and response time. (C) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Application of abrupt cut-off models in the analysis of the capacitance spectra of conjugated polymer devices

In this paper, a detailed study of the capacitance spectra obtained from Au/doped-polyaniline/Al structures in the frequency domain (0.05 Hz-10 MHz), and at different temperatures (150-340 K) is carried out. The capacitance spectra behavior in semiconductors can be appropriately described by using abrupt cut-off models, since they assume that the electronic gap states that can follow the ac modulation have response times varying rapidly with a certain abscissa, which is dependent on both temperature and frequency. Two models based on the abrupt cut-off concept, formerly developed to describe inorganic semiconductor devices, have been used to analyze the capacitance spectra of devices based on doped polyaniline (PANI), which is a well-known polymeric semiconductor with innumerous potential technological applications. The application of these models allowed the determination of significant parameters, such as Debye length (approximate to 20 nm), position of bulk Fermi level (approximate to 320 meV) and associated density of states (approximate to 2x10(18) eV(-1) cm(-3)), width of the space charge region (approximate to 70 nm), built-in potential (approximate to 780 meV), and the gap states` distribution.

Low-Frequency Noise in Field-Effect Devices Functionalized With Dendrimer/Carbon-Nanotube Multilayers

Low-frequency noise in an electrolyte-insulator- semiconductor (EIS) structure functionalized with multilayers of polyamidoamine (PAMAM) dendrimer and single-walled carbon nanotubes (SWNT) is studied. The noise spectral density exhibits 1/f(gamma) dependence with the power factor of gamma approximate to 0.8 and gamma = 0.8-1.8 for the bare and functionalized EIS sensor, respectively. The gate-voltage noise spectral density is practically independent of the pH value of the solution and increases with increasing gate voltage or gate-leakage current. It has been revealed that functionalization of an EIS structure with a PAMAM/SWNTs multilayer leads to an essential reduction of the 1/f noise. To interpret the noise behavior in bare and functionalized EIS devices, a gate-current noise model for capacitive EIS structures based on an equivalent flatband-voltage fluctuation concept has been developed.

Is the unfolding of the group discussion off-pattern? Improving coordination support in educational forums using mobile devices

A forum is a valuable tool to foster reflection in an in-depth discussion; however, it forces the course mediator to continually pay close attention in order to coordinate learners` activities. Moreover, monitoring a forum is time consuming given that it is impossible to know in advance when new messages are going to be posted. Additionally, a forum may be inactive for a long period and suddenly receive a burst of messages forcing forum mediators to frequently log on in order to know how the discussion is unfolding to intervene whenever it is necessary. Mediators also need to deal with a large amount of messages to identify off-pattern situations. This work presents a piece of action research that investigates how to improve coordination support in a forum using mobile devices for mitigating mediator`s difficulties in following the status of a forum. Based on summarized information extracted from message meta-data, mediators consult visual information summaries on PDAs and receive textual notifications in their mobile phone. This investigation revealed that mediators used the mobile-based coordination support to keep informed on what is taking place within the forum without the need to log on their desktop computer. (C) 2009 Elsevier Ltd. All rights reserved.

Novel electroluminescent devices containing Eu(3+)-(2-acyl-1,3-indandionate) complexes with TPPO ligand

Fabrication and electroluminescent properties of devices containing europium complexes of general formula [Eu(ACIND)(3)(TPPO)(2)], where ACIND, 2-acyl-1,3-indandionate ligands: and TPPO, triphenylphosphine oxide. as emitter layers are discussed. The double-layer devices based on these complexes present the following configurations: device 1: ITO/TPD/[Eu(AlND)(3)(TPPO)(2)]/Al: device 2: ITO/TPD/[Eu(ISOV-IND)(3)(TPPO)(2)]/Al and device 3: ITO/TPD/[Eu(BIND)(3)(TPPO)(2)]/Al, where AlND, 2-acetyl-1,3-indandionate; ISOVIND, 2-isovaleryl-1,3-indandionate; and BIND, 2-benzoyl-1,3-indandionate, respectively. These devices exhibited photo and electroluminescent emissions. An important characteristic presented by devices is that their electroluminescent (EL) spectra, in the region of (5)D(0) -> (7)F(J) (J = 0, 1, 2, 3 and 4) transitions of Eu(3+) ion, show profiles that are different from photoluminescent (PL) ones. In addition to narrow bands arising from intraconfigurational-4f(6) transitions, devices 1 and 2 also exhibited a broad band with maximum at around 500 nm which is assigned to electrophosphorescence from the indandionate ligands. On the other hand, EL spectra of device 3 present only narrow bands from (5)D(0) -> (7)F(J) transitions. [Eu(ACIND)(3)(TPPO)(2)] complexes are promising candidates to prepare efficient organic light-emitting devices (OLEDs) when compared with those containing Eu(3+)-complexes of aliphatic beta-diketonate anions. (C) 2009 Elsevier B.V. All rights reserved.

Development of Highly Selective Enzymatic Devices Based on Deposition of Permselective Membranes on Aligned Nanowires

We describe a simple and efficient strategy to fabricate enzymatic devices based on the deposition of glucose oxidase on aligned and highly oriented CoNiMo metallic nanowires. CoNiMo nanowires with an average diameter of 200 nm and length of 50 mu m were electrodeposited on Au-covered alumina substrates via electrodeposition, using alumina membranes as templates. Enzyme-modified electrodes were fabricated via enzyme immobilization using a cross-linker. To minimize nonspecific reactions in the presence of interfering agents, a permselective membrane composed of poly(vinylsulfonic acid) and polyamidoamine dendrimer was deposited via electrostatic interaction. The formation of hydrogen peroxide as a product of the enzymatic reaction was monitored at low overpotential, 0.0 V (vs Ag/AgCl). The detection limit was estimated at 22 mu M under an applied potential of 0.0 V. The apparent Michaelis-Menten constant determined from the Lineweaver-Burke plot was 2 mM.

Electroluminescent devices based on rare-earth tetrakis beta-diketonate complexes

In this paper the synthesis, photo luminescence and electroluminescence investigation of the novel tetrakis beta-diketonate of rare-earth complexes such as M[Eu(dbM)(4)] and M[Tb(acac)(4)] with a variety of cationic ligands, M=Li(+), Na(+) and K(+) have been investigated. The emission spectra of the Eu(3+) and Tb(3+) complexes displayed characteristic narrow bands arising from intraconfigurational transitions of trivalent rare-earth ions and exhibited red color emission for the Eu(3+) ion ((5)D(0) -> F(J), J=0-6) and green for the Tb(3+) ion ((5)D(4) -> (7)F(J), J = 6-0). The lack of the broaden emission bands arising from the ligands suggests the efficient intramolecular energy transfer from the dbm and acac ligands to Eu(3+) and Tb(3+) ions, respectively. In accordance to the expected, the values of PL quantum efficiency (eta) of the emitting (5)D(0) state of the tetrakis(beta-diketonate) complexes of Eu(3+) were higher compared with those tris-complexes. Therefore, organic electroluminescent (EL) devices were fabricated with the structure as follows: indium tin oxide (ITO)/hole transport layer (HTL) NPB or MTCD/emitter layer M[RE(beta-diketonate)(4)] complexes)/Aluminum (Al). All the films were deposited by thermal evaporation carried out in a high vacuum environment system. The OLED light emission was independent of driving voltage, indicating that the combination of charge carriers generates excitons within the M[RE(beta-diketonate)(4)] layers, and the energy is efficiently transferred to RE(3+) ion. As a best result, a pure red and green electroluminescent emission was observed from the Eu(3+) and Tb(3+) devices, confirmed by (X,Y) color coordinates. (C) 2008 Elsevier B.V. All rights reserved.

Polymeric electro-mechanic devices applied to antibiotic-controlled release

Polymeric electroactive blends formed by electropolymerized aniline inside a non-conductive polyacrylamide porous matrix were already shown as suitable materials for the electrocontrolled release of model compounds like safranin. In this paper the intermolecular interactions between the two components of the blend are put in evidence by Raman spectroscopy measurements. Also, in situ optical microscopy was used to follow changes occurring in the polyaniline/polyacrylamide blend during pyrocathecol violet release tests. These two sets of experiments show the possibility of controlling electrochemically the release of both, safranin (a cation) and pyrocathecol violet (an anion) and allow to infer a release mechanism based on the electromechanical properties of the blends explaining the dependence of the release kinetics on the applied potential. Tetracycline release curves for different potentials and pHs are shown and the obtained profiles are in agreement with those expected for a device acting as an electrochemically driven pump due to the artificial muscle properties of the conducting phase of the blends. (c) 2007 Elsevier B.V. All rights reserved.

Electrical and optical properties of poly(2-dodecanoylsulfanyl-p-phenylenevnylene) and its application in electroluminescent devices

We describe the optical and electrical characterization of a poly(p-phenylenevinylene) derivative: poly(2-dodecanoylsulfanyl-p-phenylenevinylene) (12COS-PPV). The electrical characterization was carried out on devices with the FTO\PEDOT:PSS\12COS-PPV/Al structure. Positive charge carrier mobility mu(h) of similar to 1.0 x 10(-6) cm(2) V(-1) s(-1) and barrier height phi of similar to 0.1 eV for positive charge carrier injection at the PEDOT:PSS/12COS-PPV interface were obtained using a thermionic injection model. FTO\PEDOT:P55\12COS-PPV/Ca devices exhibited green-yellow electroluminescence with maximum emission at lambda = 540 nm.

Automatic devices for monitoring environmentally induced auto-oxidative degradation of artistic materials in conservation sites

This paper describes an automatic device for in situ and continuous monitoring of the ageing process occurring in natural and synthetic resins widely used in art and in the conservation and restoration of cultural artefacts. The results of tests carried out under accelerated ageing conditions are also presented. This easy-to-assemble palm-top device, essentially consists of oscillators based on quartz crystal resonators coated with films of the organic materials whose response to environmental stress is to be addressed. The device contains a microcontroller which selects at pre-defined time intervals the oscillators and records and stores their oscillation frequency. The ageing of the coatings, caused by the environmental stress and resulting in a shift in the oscillation frequency of the modified crystals, can be straightforwardly monitored in this way. The kinetics of this process reflects the level of risk damage associated with a specific microenvironment. In this case, natural and artificial resins, broadly employed in art and restoration of artistic and archaeological artefacts (dammar and Paraloid B72), were applied onto the crystals. The environmental stress was represented by visible and UV radiation, since the chosen materials are known to be photochemically active, to different extents. In the case of dammar, the results obtained are consistent with previous data obtained using a bench-top equipment by impedance analysis through discrete measurements and confirm that the ageing of this material is reflected in the gravimetric response of the modified quartz crystals. As for Paraloid B72, the outcome of the assays indicates that the resin is resistant to visible light, but is very sensitive to UV irradiation. The use of a continuous monitoring system, apart from being obviously more practical, is essential to identify short-term (i.e. reversible) events, like water vapour adsorption/desorption processes, and to highlight ageing trends or sudden changes of such trends. (C) 2007 Elsevier B.V. All rights reserved.

Efficient and low cost devices for solar energy conversion: Efficiency and stability of some natural-dye-sensitized solar cells

Dye-sensitized solar cells, named by us Dye-Cells, are one of the most promising devices for solar energy conversion due to their reduced production cost and low environmental impact, especially those sensitized by natural dyes. The efficiency and stability of devices based on natural sensitizers such as mulberry (Morus alba Lam), blueberry (Vaccinium myrtillus Lam), and jaboticaba`s skin (Mirtus cauliflora Mart) were investigated. Dye-Cells prepared with aqueous mulberry extract presented the highest P(max) value (1.6 mW cm(-2)) with J(sc) = 6.14 mA cm(-2) and V(oc) = 0.49 V, Photoelectrochemical parameters of 16 cm(2) active area devices sensitized by mulberry dye were constant for 14 weeks of continuous evaluation. Moreover, the cell remained stable even after 36 weeks with a fairly good efficiency. Therefore, mulberry dye opens up a perspective of commercial feasibility for inexpensive and environmentally friendly Dye-Cells. (C) 2009 Elsevier B.V. All rights reserved.

All solid-state electrochromic devices with gelatin-based electrolyte

6 x 8cm(2) electrochromic devices (ECDs) with the configuration K-glass/EC-layer/electrotype/ion-storage (IS) layer/K-glass, have been assembled using Nb2O5:Mo EC layers, a (CeO2)(0.81)-TiO2 IS-layer and a new gelatin electrolyte containing Li+ ions. The structure of the electrolyte is X-ray amorphous. Its ionic conductivity passed by a maximum of 1.5 x 10(-5) S/CM for a lithium concentration of 0.3g/15ml. The value increases with temperature and follows an Arrhenius law with an activation energy of 49.5 kJ/mol. All solid-state devices show a reversible gray coloration, a long-term stability of more than 25,000 switching cycles (+/- 2.0 V/90 s), a transmission change at 550 nm between 60% (bleached state) and 40% (colored state) corresponding to a change of the optical density (Delta OD = 0. 15) with a coloration efficiency increasing from 10cm(2)/C (initial cycle) to 23cm(2)/C (25,000th cycle). (c) 2007 Elsevier B.V. All rights reserved.

Development of Electrochromic Devices

Electrochromic devices (ECD) are systems of considerable commercial interest due to their controllable transmission, absorption and/or reflectance. For instance, these devices are mainly applied to glare attenuation in automobile rearview mirrors and also in some smart windows that can regulate the solar gains of buildings. Other possible applications of ECDs include solar cells, small-and large-area flat panel displays, frozen food monitoring and document authentication also are of great interest. Over the past 20 years almost 1000 patents and 1500 papers in journals and proceedings have been published with the keyword ""electrochromic windows"". Most of these documents report on materials for electrochromic devices and only some of them about complete systems. This paper describes the first patents and some of the recent ones on ECDs, whose development is possible due to the advances in nanotechnology.

Simple telemedicine for developing regions: Camera phones and paper-based microfluidic devices for real-time, off-site diagnosis

This article describes a prototype system for quantifying bioassays and for exchanging the results of the assays digitally with physicians located off-site. The system uses paper-based microfluidic devices for running multiple assays simultaneously, camera phones or portable scanners for digitizing the intensity of color associated with each colorimetric assay, and established communications infrastructure for transferring the digital information from the assay site to an off-site laboratory for analysis by a trained medical professional; the diagnosis then can be returned directly to the healthcare provider in the field. The microfluidic devices were fabricated in paper using photolithography and were functionalized with reagents for colorimetric assays. The results of the assays were quantified by comparing the intensities of the color developed in each assay with those of calibration curves. An example of this system quantified clinically relevant concentrations of glucose and protein in artificial urine. The combination of patterned paper, a portable method for obtaining digital images, and a method for exchanging results of the assays with off-site diagnosticians offers new opportunities for inexpensive monitoring of health, especially in situations that require physicians to travel to patients (e.g., in the developing world, in emergency management, and during field operations by the military) to obtain diagnostic information that might be obtained more effectively by less valuable personnel.