Electromodulated photoinduced absorption : A new spectroscopy in π- conjugated polymer/C60 blends

Optical Science, Engineering and Instrumentation '97, 1997, San Diego, CA, United StatesMartin Liess, Paul A. Lane, Zakya H. Kafafi, M. Hamaguchi, Masanori Ozaki, Katsumi Yoshino, and Z. Valy Vardeny "Electromodulated photoinduced absorption: a new spectroscopy in π-conjugated polymer/C60 blends", Proc. SPIE 3142, Fullerenes and Photonics IV, (1 November 1997). DOI: https://doi.org/10.1117/12.29335

A theoretical investigation of the low lying electronic structure of poly(p-phenylene vinylene)

The two-state molecular orbital model of the one-dimensional phenyl-based semiconductors is applied to poly(p-phenylene vinylene). The energies of the low-lying excited states are calculated using the density matrix renormalization group method. Calculations of both the exciton size and the charge gap show that there are both Bu and Ag excitonic levels below the band threshold. The energy of the 1Bu exciton extrapolates to 2.60 eV in the limit of infinite polymers, while the energy of the 2Ag exciton extrapolates to 2.94 eV. The calculated binding energy of the 1Bu exciton is 0.9 eV for a 13 phenylene unit chain and 0.6 eV for an infinite polymer. This is expected to decrease due to solvation effects. The lowest triplet state is calculated to be at ca. 1.6 eV, with the triplet-triplet gap being ca. 1.6 eV. A comparison between theory, and two-photon absorption and electroabsorption is made, leading to a consistent picture of the essential states responsible for most of the third-order nonlinear optical properties. An interpretation of the experimental nonlinear optical spectroscopies suggests an energy difference of ca. 0.4 eV between the vertical energy and ca. 0.8 eV between the relaxed energy, of the 1Bu exciton and the band gap, respectively.Comment: LaTeX, 19 pages, 7 eps figures included using epsf. To appear in Physical Review B, 199

Theory of excited state absorptions in phenylene-based π\pi-conjugated polymers

Within a rigid-band correlated electron model for oligomers of poly-(paraphenylene) (PPP) and poly-(paraphenylenevinylene) (PPV), we show that there exist two fundamentally different classes of two-photon A$_g$ states in these systems to which photoinduced absorption (PA) can occur. At relatively lower energies there occur A$_g$ states which are superpositions of one electron - one hole (1e--1h) and two electron -- two hole (2e--2h) excitations, that are both comprised of the highest delocalized valence band and the lowest delocalized conduction band states only. The dominant PA is to one specific member of this class of states (the mA$_g$). In addition to the above class of A$_g$ states, PA can also occur to a higher energy kA$_g$ state whose 2e--2h component is {\em different} and has significant contributions from excitations involving both delocalized and localized bands. Our calculated scaled energies of the mA$_g$ and the kA$_g$ agree reasonably well to the experimentally observed low and high energy PAs in PPV. The calculated relative intensities of the two PAs are also in qualitative agreement with experiment. In the case of ladder-type PPP and its oligomers, we predict from our theoretical work a new intense PA at an energy considerably lower than the region where PA have been observed currently. Based on earlier work that showed that efficient charge--carrier generation occurs upon excitation to odd--parity states that involve both delocalized and localized bands, we speculate that it is the characteristic electronic nature of the kA$_g$ that leads to charge generation subsequent to excitation to this state, as found experimentally.Comment: Revtex4 style, 2 figures inserted in the text, three tables, 10 page

Linear and nonlinear optical properties of the conjugated polymers PPV and MEH-PPV

We have used absorption and electroabsorption spectroscopy to investigate the electronic structure of poly(para-phenylene vinylene) (PPV) and poly (2-methoxy, 5-(2'-(ethyl)hexyloxy)-p-phenylene vinylene) (MEH-PPV). In particular we examine the often used assumption that the electronic structure of PPV and its dialkoxy substituted derivatives are essentially the same. The absorption spectrum of PPV consists of three peaks, while that of MEH-PPV has four peaks. We discuss the controversial origin of the extra peak as well as evidence for Davydov splitting effects in the absorption spectrum of PPV. The analysis of the nonlinear spectra shows further differences between the two materials. First, the binding energy of the 1B(u) exciton for PPV is some 0.1 eV higher than for MEH-PPV. Second, the peak value of Im{chi((3))(-omega;0,0,omega)} for PPV is approximately 40 times higher than that of MEH-PPV. We also found that the sum-over-states modeling of the electroabsorption spectra indicates that the transition dipole moment between the mA(g) and nB(u) states is of opposite sign in the two polymers. [S0163-1829(99)02523-0]

Acoustic CO2 Gas Sensor Based on Phase Difference Measurement

In this research, an acoustic sensor has been successfully built to measure the concentration of CO2 gas in a mixture of gases (N2 and CO2). The nitrogen and carbon dioxide gases used are ultra-high purity (UHP) gas. The measurement parameter used is the speed of sound by utilizing the phase shift between ultrasonic wave signals that are sent and received continuously. The acoustic method in this research is by using the speaker as an ultrasonic wave transmitter, and the microphone as an ultrasonic wave receiver emitted by the speaker on the gas medium. This acoustic phase shift method is very sensitive to be used to determine the speed of sound on a gas medium. From the sensor testing, the sensor has good linearity in detecting changes in CO2 concentration in the gas mixture. The sensor test results have been validated theoretically and obtained an RMS error of 3.36 (3.36% with a maximum concentration of 100%), this proves that the work of the sensor is in accordance with the theory. In addition to theoretical validation, the work of the sensor has also been validated by looking at the direct relationship between sensor input and output through the inverse function, and an RMS error of 3.51 (3.51% with a maximum concentration of 100%) is obtained. From the overall results obtained, the acoustic CO2 gas sensor that is built can detect changes in CO2 concentrations in the gas mixture accurately, fabrication of the sensor is easy to do, and the costs required in the manufacturing process are cheap

Electrochemical, morphological and microstructural characterization of carbon film resistor electrodes for application in electrochemical sensors

The electrochemical and microstructural properties of carbon film electrodes made from carbon film electrical resistors of 1.5, 15, 140 [Omega] and 2.0 k[Omega] nominal resistance have been investigated before and after electrochemical pre-treatment at +0.9 V vs SCE, in order to assess the potential use of these carbon film electrodes as electrochemical sensors and as substrates for sensors and biosensors. The results obtained are compared with those at electrodes made from previously investigated 2 [Omega] carbon film resistors. Cyclic voltammetry was performed in acetate buffer and phosphate buffer saline electrolytes and the kinetic parameters of the model redox system Fe(CN)63-/4- obtained. The 1.5 [Omega] resistor electrodes show the best properties for sensor development with wide potential windows, similar electrochemical behaviour to those of 2 [Omega] and close-to-reversible kinetic parameters after electrochemical pre-treatment. The 15 and 140 [Omega] resistor electrodes show wide potential windows although with slower kinetics, whereas the 2.0 k[Omega] resistor electrodes show poor cyclic voltammetric profiles even after pre-treatment. Electrochemical impedance spectroscopy related these findings to the interfacial properties of the electrodes. Microstructural and morphological studies were carried out using contact mode Atomic Force Microscopy (AFM), Confocal Raman spectroscopy and X-ray diffraction. AFM showed more homogeneity of the films with lower nominal resistances, related to better electrochemical characteristics. X-ray diffraction and Confocal Raman spectroscopy indicate the existence of a graphitic structure in the carbon films.http://www.sciencedirect.com/science/article/B6THY-4S7BD8R-1/1/06dc918640a4700879aa96e50ac04a8

Optical studies of electric fields in poly(2-methoxy-5-ethyl(2(')-hexyloxy) para-phenylene vinylene) light-emitting diodes

We report electroabsorption studies of poly(2-methoxy-5-ethyl(2(')-hexyloxy) para-phenylene vinylene) light-emitting diodes. An electric field develops during operation which opposes the field of the applied bias. The counter field builds up within 5 s of turning on the device, increases in magnitude with the operating voltage, and decays exponentially with a time constant between 15 and 32 s. We attribute the counter field to bulk carrier traps and discuss its relevance to the increase of the turn-on voltage as organic light-emitting diodes degrade. (c) 1999 American Institute of Physics. [S0003-6951(99)01224-3]