Laser action studies of φ-conjugated polymer microcavities

Unidirectional laser emission was observed from φ-conjugated polymer microcavities with spiral geometry, and from microdisks containing line defects. For both type of cavities directionality contrast of the laser emission was found to be ̃ 10, with far-field lateral divergence angle of ̃ 15°. No significant increase in the laser threshold intensity was observed compared with simple microdisk cavities. In addition we also studied the emission spectra of microring polymer lasers fabricated on nylon microfibers upon application of uniaxial stress with strain up to ̃ 12%. Substantial change in the laser emission spectrum was observed when stress was applied; showing enhanced optical sensitivity to stress larger than the changes induced in the emission spectrum caused by the microfiber diameter change. We explain the enhanced sensitivity to stress as due to the induced change in the polymer refractive index dispersion, in particular at the laser emission wavelength (̃ 635 nm). ©2008 IEEE

Studies of polymer microring lasers subject to uniaxial stress

The emission spectra of microring lasers fabricated from π -conjugated polymer films casted on nylon microfibers with diameters in the range of 35-90 μm were studied upon application of uniaxial stress with strain up to ∼12%. The laser emission spectra substantially change with the applied stress, showing enhanced sensitivity to stress over changes induced in the fiber diameter alone. This is explained as due to the induced change in the polymer refractive index spectrum upon stress, causing an unexpected increase in the refractive index dispersion and, consequently, also in the effective refraction index for lasing at emission wavelengths. © 2007 American Institute of Physics

Unidirectional laser emission from π-conjugated polymer microcavities with broken symmetry

We report unidirectional laser emission from π-conjugated polymer microcavities with broken symmetry geometries such as spiral and microdisk containing a "line defect," in comparison with plain microdisk cavity having isotropic emission. We found that the laser emission directionality contrast ratio is 8-10 and far field lateral divergence angle is 12°-15° for both broken symmetry geometries, with no significant increase in the laser threshold intensity. Fourier transform analysis of the laser emission spectra shows that unlike microdisks with line defect, the variation of light trajectories in the spiral microcavities leads to less defined laser modes. © 2007 American Institute of Physics

Apparent phonon side band modes in pi-conjugated systems: polymers, oligomers and crystals

The emission spectra of many pi-conjugated polymers and oligomers contain side-band replicas with apparent frequencies that do not match the Raman active mode frequencies. Using a time dependent model we show that in such many mode systems, the increased damping of the time dependent transition dipole moment correlation function results in an effective elimination of the vibrational modes from the emission spectrum; subsequently causing the appearance of a regularly spaced progression at a new apparent frequency. We use this damping dependent vibrational reshaping to quantitatively account for the vibronic structure in the emission spectra of pi-conjugated systems in the form of films, dilute solutions and single crystals. In particular, we show that by using the experimentally measured Raman spectrum we can account in detail for the apparent progression frequencies and their relative intensities in the emission spectrum.Comment: Presented in "Optical Probes 2005", Bangalore, Indi

Optical and Transport Studies of Single Molecule Tunnel junctions based on Self-Assembled Monolayers

We have fabricated a variety of novel molecular tunnel junctions based on self-assembled-monolayers (SAM) of two-component solid-state mixtures of molecular wires (1,4 methane benzene-dithiol; Me-BDT with two thiol anchoring groups), and molecular insulator spacers (1-pentanethiol; PT with one thiol anchoring group) at different concentration ratios, r of wires/spacers, which were sandwiched between two metallic electrodes such as gold and cobalt. FTIR spectroscopy and surface titration were used, respectively to verify the formation of covalent bonds with the electrodes, and obtain the number of active molecular wires in the device. The electrical transport properties of the SAM devices were studied as a function of (i) r-value, (ii) temperatures, and (iii) different electrodes, via the conductance and differential conductance spectra. The measurements were used to analyze the Me-BDT density of states near the electrode Fermi level, and the properties of the interface barriers. We measured the Me-BDT single molecule resistance at low bias and gold electrodes to be 6x10^9 Ohm. We also determine the energy difference, D between the Me-BDT HOMO level and the gold Fermi level to be about 1.8 eV. In addition we also found that the temperature dependence of the SAM devices with r < 10^-4 is much weaker than that of the pure PT device (or r = 0), showing a small interface barrier.Comment: 32 pages 10 fugure

Magnetoresistance and spin transport in organic semiconductor devices

The study of electron-spin transport through nonmagnetic spacer materials sandwiched in between ferromagnetic electrodes is an extremely active eld, because of the rich physics involved and the important applications in the area of magnetic sensors.1 If the spin diffusion length is larger than or comparable to the distance between the electrodes, the current through such sandwich structures can depend strongly on the mutual orientation of the magnetizations of the electrodes, which is called the spin valve effect. Switching of this orientation by an external magnetic eld, B, can then lead to a strong dependence of the current on B, an effect called giant magnetoresistance (GMR).2,3 This effect can be used in magnetic sensors, e.g., in reading magnetic information in hard disks

Spectroscopic studies of photoexcitations in regioregular and regiorandom polythiophene films

Optical probe techniques were used to study the steady state and transient dynamics of charged and neutral photoexcitations in thin films of poly(3-hexyl thiophene)s with regioregular order, which form self-assembled lamellae structures with increased interchain interactions and regiorandom order that preserve a chain-like morphol. In regiorandom polythiophene films intrachain excitons with correlated photoinduced absorption and stimulated emission bands are the primary photoexcitations; they give rise to a moderately strong photoluminescence band, and long-lived triplet excitons and intrachain charged polarons. In regioregular polythiophene films, the primary photoexcitations are excitons with much larger interchain component; this results in lack of stimulated emission, vanishing intersystem crossing, and a weak photoluminescence band. The long-lived photoexcitations in regioregular polythiophene films are interchain excitons and delocalized polarons (DP) within the lamellae, with small relaxation energy. The DP species were thoroughly studied as a function of the alkyl side group of the polymer backbone, film deposition conditions, and solvents, at high hydrostatic pressure. The quantum interference between the low energy absorption band of the DP species and a series of photoinduced IR active vibrations, which give rise to antiresonances that are superimposed on the electronic absorption band were studied and explained by a Fano-type interference mechanism, using the amplitude mode mode

Time-Resolved Microwave Measurements of the Polarizability of Photoexcitations on Conjugated Polymer Chains

Changes as small as 1 ppm in the real and imaginary components of the complex permittivity resulting from flash photoexcitation of dilute solutions of (pi) -bond conjugated oligomers and polymers can be measured with nanosecond time resolution using the time-resolved microwave conductivity technique. The results provide information on the extent of delocalization of singlet and triplet state photoexcitations. Data are presented for oligomeric and polymeric derivatives of phenylene vinylene, paraphenylene and thiophene. For the polymers excess polarizability volumes, (Delta) Vp, of the singlet exciton of 2000, 180 and 570 angstroms3 are found, respectively. (Delta) Vp for the triplet exciton of the polythiophene derivative is found to be only 25 angstroms3

Time-resolved microwave measurements of the polarizability of photoexcitations on conjugated polymer chains

Changes as small as 1 ppm in the real and imaginary components of the complex permittivity resulting from flash photoexcitation of dilute solutions of (pi) -bond conjugated oligomers and polymers can be measured with nanosecond time resolution using the time-resolved microwave conductivity technique. The results provide information on the extent of delocalization of singlet and triplet state photoexcitations. Data are presented for oligomeric and polymeric derivatives of phenylene vinylene, paraphenylene and thiophene. For the polymers excess polarizability volumes, (Delta) Vp, of the singlet exciton of 2000, 180 and 570 angstroms3 are found, respectively. (Delta) Vp for the triplet exciton of the polythiophene derivative is found to be only 25 angstroms3