Desorption of an organic conducting polymer by soft X-ray radiation created by a femtosecond laser

The possibility of the desorption of complicated molecular complexes by soft X rays resulting from a solid target irradiated by a single sharply focused femtosecond laser pulse with an energy of several millijoules has been experimentally demonstrated for polyaniline, which is an organic conducting polymer. X-ray desorption and photodesorption of polyaniline by femtosecond laser pulses have been compared using a time-of-flight mass spectrometer. The results provide the possibility of studying surfaces with spatial nanoresolution and high elemental (chemical) selectivity, as well as observing the photodesorption with a high temporal resolution.     

Analysis of infrared reflectivity of conducting polymers: example of camphor-sulphonic-acid-doped polyaniline

The reflectivity spectrum of a polyaniline CSA-doped in presence of m-cresol has been measured over the wide wavenumber range of 15- 9 000 cm ^-1 (0.002-1.1 eV) at room temperature. Experimental data compare well with similar experiments performed by another group. The conductivity spectrum of this conducting polymer has been deduced from the reflectivity spectrum by means of two methods, Kramers-Kronig transformation and best fit of an “extended Drude” model to the reflectivity spectrum. Whereas the deviation from Drude behavior was interpreted in terms of Anderson localization or by inhomogeneous disorder by other groups, it is shown here that a different model developed for conducting oxides that also exhibit non-Drude behavior, applies very well to this example of conducting polymer. Received 11 February 1999 and Received in final form 26 April 1999     

Polyaniline–Prussian blue hybrid: synthesis and magnetic behaviour

We report the synthesis of an organic–inorganic hybrid material composed of a conducting polyaniline (PANI) matrix and Prussian blue (PB) network, the latter formed in situ in the polymer matrix. The hybrid was prepared by treating FeCl₄ ^?-doped PANI with K₃Fe(CN)₆ unlike the previously reported method of potential cycling to obtain alternate layers of PANI and PB. Cyclic voltammetry and X-ray photoelectron spectroscopy investigations confirmed the formation of a network typical of PB inside the PANI matrix. Infrared spectroscopy points to the formation of an extended network between Fe in PANI matrix and Fe from K₃Fe(CN)₆. Magnetization studies of the hybrid material showed ferromagnetic ordering with a T _c of about 6?K.     

Compact, efficient diode-end-pumped Nd:GdVO4 slab continuous-wave 912-nm laser

A fiber-coupled laser-diode (LD) end-pumped Nd:GdVO₄ slab continuous-wave (CW) 912-nm laser and an LD bar end-pumped Nd:GdVO₄ slab CW 912-nm laser are both demonstrated in this paper. Using the fiber-coupled LD of end-pumped type, a highest CW 912-nm laser output power of 10.17 W is obtained with a high optical-to-optical conversion efficiency of 24.6% and a slope efficiency of 34.5%. The measured M² factors of beam quality in x and y directions are 5.3 and 5.1, respectively. Besides, an LD bar of end-pumped type is used to realize CW 912-nm laser output, which has the advantages of compactness and low cost. When the pump power is 38.8 W, the output power is 8.87 W and the measured M² factors of beam quality in x and y directions are 16 and 1.31, respectively. In order to improve the beam quality of the 912-nm laser at x direction, a new quasi-concentric laser resonator will be designed, and an LD bar end-pumped Nd:GdVO₄ slab high-power CW 912-nm TEM₀₀ laser will be realized in the future.     

Laser desorption studies using laser-induced fluorescence of large aromatic molecules

Pulsed laser desorption of non-volatile organic dye molecules paraterphenyl and tetra-t-butyl-p-quinquephenyl (QUI) was studied using gas phase ultraviolet laser induced fluorescence, following heating of a steel substrate by a pulsed 1.06-μm Nd:YAG laser. The fluorescence signal intensity is linear in concentration up to at least 30 monolayers and shows infrared power threshold behavior, as expected for evaporation, at ∼0.2 J/cm². Similar signal levels were also observed in air, with 532-nm heating, and using other metallic or dark black surfaces.     

Many-body effects in the formation of multiply charged ions in a strong laser field

Some of the many-body effects in the formation of multiply charged ions in a laser field have been taken into account: inelastic tunneling, collective tunneling, and magnetic moment projection relaxation of the atomic core. Strong fields with an intensity exceeding 10¹⁷ W cm⁻² are considered when the magnetic component of the laser field acts on the free motion of a photoelectron; therefore, the formation of multiply charged ions through rescattering becomes unlikely. Numerical calculations have been performed for Ar⁹⁺ … Ar¹³⁺, Kr¹⁹⁺ … Kr²³⁺, Rb¹⁰⁺, and Rb¹¹⁺ ions. A significant contribution of collective tunneling, which was not observed in weaker fields investigated previously, has been revealed. Allowance for collective tunneling is shown to reduce the intensity leading to saturation by more than 10%. In this case, the yield of multiply charged Rb ions changes by an order of magnitude, while the yield of multiply charged Ar and Kr ions changes by more than a factor of 2. Comparison with experimental data on the formation of argon ions under the action of a linearly polarized laser pulse is made.     

Generation of lower and higher harmonics in different plasma media with small <Emphasis Type="Italic">Z</Emphasis>

The generation of lower (third) and higher harmonics of femtosecond laser radiation in plasmas produced by laser ablation of different targets with a small atomic number Z (B, Be, Li) has been investigated. The high (10⁻³) efficiency of third-harmonic generation was observed in plasma produced on the boron surface. Efficient third-harmonic generation was also observed in beryllium plasma using femtosecond pulses of Ti:sapphire laser radiation (λ = 790 nm) and its second harmonic (395 nm). We could tune the higher harmonics generation spectrum by tuning the crystal converter when using 395-nm radiation to be converted. It is shown that, in plasmas formed on targets with small Z, the conversion efficiency and limiting generated harmonic order depend on the delay between the ablation pulse and the pulse to be converted.     

Enhanced soft X-ray emission from carbon nanofibers irradiated with ultra-short laser pulses

A comparative experimental study of the X-ray emission in the water-window spectral region has been performed using carbon nanofibers (CNFs) of different sizes and graphite plate targets, irradiated with ultra-short (Ti:sapphire) laser pulses. More than an order of magnitude enhancement in the X-ray yield is observed from CNFs of 60-nm diameter with respect to graphite targets. The X-ray emission from CNFs of 160-nm diameter was also high. The integrated X-ray yield of these carbon-based targets scales with the laser intensity (I _L) as I_L ^{~ 1.3-1.4}I_{\mathrm{L}}^{\sim 1.3-1.4} in the intensity range of 4×10¹⁶–4×10¹⁷ W/cm². The effect of the laser pulse duration on the X-ray emission from the CNFs was also studied by varying the pulse duration from 45 fs up to 3 ps at a constant fluence of 2×10⁴ J/cm². The optimum laser pulse duration for maximum X-ray emission increases with the diameter of the CNFs used. The results are explained from physical considerations of heating and hydrodynamic expansion of the CNF plasma in which resonance field enhancement takes place while passing through two times the critical density. The results add to the efforts towards achieving an efficient low-cost water-window X-ray source for microscopy.     

Effect of the wavelength dependence of the emissivity on inferred soot temperatures measured by spectrally resolved laser-induced incandescence

Flame-generated soot was heated using a pulsed laser, and temperatures of the irradiated soot were inferred by fitting the Planck function to spectrally resolved laser-induced incandescence with the temperature as an adjustable parameter. The effect of the wavelength dependence of the emissivity on the inferred temperatures of the irradiated soot was studied using selected expressions for the soot emissivity in the fit. Depending upon the choice of the functional form of the emissivity, the maximum temperature reached by the soot during the laser pulse was calculated to span a range of 341 K (3475–3816 K) at a 1064-nm laser fluence of 0.1 J/cm² and 456 K (4115–4571 K) at a 1064-nm laser fluence of 0.4 J/cm² with a 1σ standard deviation about the mean of ∼25 K. Comparison of the present results with temperature measurements from previous studies suggests that the emissivity may depend on flame conditions and that further investigation on the subject is needed. The use of two-color or spectrally resolved LII to infer the soot temperature during or after laser heating requires a careful characterization of the wavelength dependence of the emissivity. The spread in temperature leads to large uncertainties regarding the physico-chemical processes occurring at the surface of the soot during the laser heating.     

Rb atomic absorption line reference for single Sr+ laser cooling systems

85 Rb, 5s²S_1/2(F”=2)→6p²P_1/2(F’=2,3) absorption resonance with the ⁸⁸Sr⁺, 5s²S_1/2→5p²P_1/2 transition is exploited to provide a simple, effective frequency reference for a laser cooling/fluorescence excitation source applied to single Sr⁺ ions. A modulation-free frequency stabilization system has been designed which uses the differential signal from two frequency-displaced beams traversing a Rb cell and which probe the Doppler-broadened Rb S–P lineshape at microwatt power levels. The method is applied to frequency lock a 422-nm frequency-doubled diode laser system that is used for excitation of a single ⁸⁸Sr⁺ ion. Stable, long-term laser cooling and fluorescence are achieved using the frequency-stabilized 422-nm source resulting in observed ion confinement times without adjustment of over 8 h, together with an improvement in single-ion loading efficiency. Received: 12 February 1998     

Visualization of the spatio-temporal structure of a pulsed photoelectron beam formed by femtosecond laser radiation

A method based on an original electron microscope created for investigating photoelectron beams is presented. It ensures a nanometer spatial resolution and picosecond time resolution. Electrons appearing when a metal needle is irradiated by femtosecond laser pulses are transmitted through a dielectric microcapillary and are subjected to a ponderomotive potential created by femtosecond laser radiation focused near the capillary tip. The position-sensitive detection scheme allows for the detection of the spatial profile of a photo-electron beam with a magnification of K ≅ 4 × 10⁴. The time structure of the photoelectron beam is visualized by scanning the delay time between laser pulses irradiating the needle and a laser pulse focused near the capillary tip.     

Photovoltaic activity in a ZnSe/PEO–chitosan blend electrolyte junction

Thin films of ZnSe and PEO–chitosan blend polymer doped with NH₄I and iodine crystals were prepared to form the two sides of a semiconductor electrolyte junction. ZnSe was electrodeposited on indium tin oxide (ITO) conducting glass. The polymer is a blend of 50 wt% chitosan and 50 wt% polyethylene oxide. The polymer blend was complexed with ammonium iodide (NH₄I), and some iodine crystals were added to the polymer–NH₄I solution to provide the I⁻/I³⁻redox couple. The room temperature ionic conductivity of the polymer electrolyte is 4.32 × 10⁻⁶ S/cm. The polymer film was sandwiched between the ZnSe semiconductor and an ITO glass to form a ZnSe/polymer electrolyte/ITO photovoltaic cell. The open circuit voltage (V _oc) of the fabricated cells ranges between 200 to 400 mV and the short circuit current between 7 to 10 μA.     

Self-assembled organic monolayers as high-resolution resists in rapid nonlinear processing with single femtosecond laser pulses

Femtosecond laser patterning of alkanethiol monolayers on gold-coated silicon substrates at λ=800 nm, τ<30 fs and ambient conditions has been investigated. Single-pulse processing allows one to selectively remove the organic coating. Subsequently, pattern transfer into the gold film via wet etching in ferri-/ferrocyanide solution is achieved. As demonstrated, burr-free patterning can be carried out over an extremely wide range of laser pulse fluences from above 2 J/cm² down to 0.5 J/cm². Moreover, at low fluences, sub-wavelength processing down to λ/5 is feasible. In particular, at a 1/e laser spot diameter of about 1 μm, holes with diameters of 160 nm and step edges below 80 nm are fabricated. These results emphasize the prospects of organic monolayers as high-resolution resists in rapid nonlinear femtosecond laser processing.     

Quasi-point incoherent ArF<Superscript>∗</Superscript> excimer emission source at 193 nm using a laser-produced plasma

We have demonstrated proof-of-principle of an incoherent ArF^∗ emission source with a quasi-point emission geometry using a laser-produced plasma in an Ar/F₂/He/Ne mixed gas. The VUV emission characteristics, such as the emission size, were dependent on those of the plasma-initiating laser. The average emission power was 10 μW at a repetition rate of 10 Hz at 193 nm. The average power conversion efficiency of the 193-nm emission from the plasma-initiating Nd:YAG laser was 6.3×10⁻⁶. The average emission power at 193 nm was proportional to that of the plasma-initiating laser, indicating the scaling of the emission source.     

Structural and ionic conductivity studies on proton conducting polymer electrolyte based on polyvinyl alcohol

An attempt has been made to prepare a new proton conducting polymer electrolyte based on polyvinyl alcohol (PVA) doped with NH₄NO₃ by solution casting technique. The complex formation between polymer and dissociated salt has been confirmed by X-ray diffraction analysis. The ionic conductivity of the prepared polymer electrolyte has been found by ac impedance spectroscopic analysis. The highest ionic conductivity has been found to be 7.5 × 10⁻³ Scm⁻¹ at ambient temperature for 20 mol% NH₄NO₃-doped PVA with low activation energy (~0.19 eV). The temperature-dependent conductivity of the polymer electrolyte follows an Arrhenius relationship, which shows hopping of ions in the polymer matrix.     

Two-color photoionization spectroscopy of uranium in a U–Ne hollow cathode discharge tube

A U–Ne hollow cathode discharge tube is used as a source of uranium atomic vapors as well as a photoelectron/photoion detector for carrying out two-color three-photon photoionization spectroscopy of uranium. Using the uranium excitation transition 0 cm⁻¹ (⁵L ₆ ⁰ ) → 16 900.38 cm⁻¹ (⁷M₇) at 591.5-nm laser wavelength as a first step transition and scanning the wavelength of a second laser from 558 to 568 nm, high-lying odd-parity atomic levels of uranium are studied in the energy region 34 500–34 813 cm⁻¹. All the expected 21 odd-parity atomic levels identified by various researchers in this region are observed in a single spectrum, demonstrating the high sensitivity achieved therein. In addition to this, we have identified eight autoionization resonances of uranium starting from its odd-parity atomic level at 33 801.06 cm⁻¹ pumped by two-photon excitation. Four out of these eight autoionization resonances are observed for the first time.     

Primary solid state batteries

Low - cost, easily fabricated dry cells were constructed by gluing a composite conducting material or a metal sulphide on magnesium or aluminium foils, using a solid electrolyte made from polyvinyl - pyrolidone. Composite conducting materials consisted of polypyrrole and polyaniline incorporated into an inorganic or polymer matrix or cupric oxide incorporated into a styrene - butadiene copolymer matrix. The efficiency, energy densities and voltage values of the cells were in the range 0.5 – 18.3 mWh cm⁻³, 9 – 339 wh kg⁻¹ and 0.5 – 2.0 V, respectively. The energy densities of the cells were up to seventeen times more than the energy density of the PbO₂ -H₂SO₄ - Pb multiple charge / discharge system and up to ten times more than the energy density of the nickel / cadmium rechargeable cell. A dry cell composed solely from polymers was constructed with cell voltage 0.25 – 0.50 V and efficiency ranging from 0.07 to 0.13 mWh cm⁻³ ten times lower than other commercial cells. Paper presented at the 1st Euroconference on Solid State Ionics, Zakynthos, Greece, 11–18 Sept. 1994     

Neodymium concentration dependence of 0.94-, 1.06- and 1.34-μm laser emission and of heating effects under 809- and 885-nm diode laser pumping of Nd:YAG

Laser emission in the 0.94-, 1.06- and 1.34-micron ranges in diluted and concentrated Nd:YAG crystals longitudinally pumped by a 885-nm diode laser on the ⁴ I _9/2→⁴ F _3/2 transition is investigated. Continuous-wave operation at watt level in all these wavelength ranges is demonstrated with a 1.0-at. % Nd:YAG crystal; however, the laser performance is impeded by the low pump absorption efficiency. Improved output power and overall efficiency were obtained with a highly doped 2.5-at. % Nd:YAG crystal: 5.5 W at 1.06 μm and 3.8 W at 1.34 μm with 0.38 and 0.26 efficiencies, respectively. Comparative results with traditional pumping at 809 nm into the highly absorbing ⁴ F _5/2 level are presented, showing the advantage of the direct ⁴ F _3/2 pumping. The influence of the lasing wavelength and of the Nd concentration on the thermal effects induced by the optical pumping in the laser material is discussed. A clear relation between the heat generated in the Nd:YAG crystals in lasing and non-lasing regimes, a function of the Nd doping, is demonstrated. PACS 42.55.Rz; 42.60.By; 42.60.Da     

Electronic non-equilibrium conditions at C60–pentacene heterostructures

The electronic structure of vacuum-sublimed layered organic heterostructures of pentacene (PEN) and fullerene (C₆₀) on conducting polymer substrates was investigated using ultraviolet photoelectron spectroscopy (UPS). The conditions at the PEN/C₆₀interface changed from thermodynamic non-equilibrium (i.e. the onset of the PEN highest occupied molecular orbital above the substrate Fermi-energy) for thin PEN coverages on C₆₀ to thermodynamic equilibrium for thicker PEN coverages (i.e. Fermi-level pinning of PEN). This finding is attributed to a coverage-dependent pinhole connection of PEN through the C₆₀ layer with the substrate. The experiments demonstrate the importance of organic thin film morphology for UPS measurements to assess the energy level alignment at organic/organic heterointerfaces.     

Reduced absorption of neon-like bromine X-ray laser radiation in helium

We have measured the absorption of the 19.47-nm neon like bromine (J=2–1) X-ray laser line in low-pressure helium. The experiment was motivated by the coincidence of this line with the low-absorption wing of an autoionizing transition in helium. We observe that, with 1 mbar of helium, the continuum background and another bromine X-ray laser line at 19.82 nm are strongly reduced, enhancing the relative strength of the 19.47-nm laser line. Increasing the helium pressure to 1.5 mbar makes the continuum virtually disappear, resulting in an almost monochromatic emission of the X-ray laser line. An estimate of the absorption cross section for the 19.47-nm line is given as ≈3.9×10^-19 cm² and for the nearby continuum as 0.9–1.3×10^-18 cm². Received: 8 March 1999 / Revised version: 26 April 1999 / Published online: 11 August 1999