Spectrophotometric Study of Luminol in Dimethyl Sulfoxide–Potassium Hydroxide

The spectrophotometric study of luminol (LH₂) in dimethyl sulfoxide (DMSO), DMSO-water solutions, and alkaline DMSO and DMSO-water solutions has been done, focusing on the effect of the KOH additon on LH₂ absorption and fluorescence properties. The absorption spectra indicate an acid-base equilibrium, and the luminol dianion (L^2–) formation at 3 × 10^–4 – 2.4 × 10^–3 M KOH. The decrease of the fluorescence intensity and the variation of the excitation spectra of LH₂-DMSO-KOH solutions with KOH concentration have been similarly explained. The acid-base process is reversible. The addition of HCl to the solution with 3.0 × 10^–3 M KOH leads to an increase of the fluorescence intensity to its highest value, observed in pure DMSO. The addition of HCl to the LH₂-DMSO solution leads to the decrease of the fluorescence intensity as a result of the LH⁺ ₃ cation formation. In LH₂-DMSO-water, the fluorescence band is shifted from 405 nm to 424 nm and increased in the intensity. In the presence of KOH (in LH₂-DMSO-water-KOH solution) a new band appears, with the maximum at 485 nm and the band at 405 nm decreased. The changes in fluorescence lifetimes also evidence the different chemical species formed.     

Absolute CH concentrations in low-pressure flames measured with laser-induced fluorescence

Laser-induced fluorescence in both theA–X andB–X band systems was used to measure absolute number densities of CH radicals in 40 Torr propane/air flames at temperatures near 1600 K. The fluorescence signal was calibrated against Rayleigh scattering in N₂ and Raman scattering in H₂. In a rich flame, = 1.15, the concentration at the peak of the CH distribution was 5.8 ± 1.5 ppm, or (1.4 ± 0.4) × 10¹² cm^–3, with independent values obtained using both band systems and calibration methods in good agreement. This result compares well with a prediction of 8 ppm from a kinetic model of this flame.     

Laser-fluorescence diagnostics for condensation in laser-ablated copper plasmas

We are investigating the thermodynamic conditions under which condensation occurs in laser ablated copper plasma plumes. The plasma is created by XeCl excimer laser ablation (308 nm, 300 mJ/pulse) at power densities from 500–1000 MW/cm² into backing pressures of helium in the range 0–50 torr. We use laser-induced fluorescence (LIF) to probe velocity and relative density of both atomic copper and the copper dimer molecule, Cu₂, which is formed during condensation onset. At low pressure (10 mtorr), the atomic Cu velocity peaks at approximately 2×10⁶ cm/s. Copper dimer time-of-flight data suggest that condensation onset occurs after the Cu atoms have slowed very significantly. Excitation scans of the Cu₂A-X (0,0) and (1,1) bands yield a rotational and vibrational temperature in the neighborhood of 300 K for all conditions studied. Such low temperatures support the theory that Cu₂ is formed under thermally and translationally cold conditions. Direct laser beam absorption is used to determine the number density of atomic copper. Typical densities attained with 5 torr of helium backing gas are 6–8×10¹³ cm^–3. Rayleigh scattering from particulate is easily observable under conditions favorable to particulate production.     

Optical emission diagnostics of laser-induced plasma for diamond-like film deposition

Optical emission from a laser-induced plasma plume is recorded during KrF excimer laser ablation of graphite in a gas mixture of Ar and H₂ (3%) for deposition of diamond-like thin films. At sub-GW/cm² laser intensities the spectrum is dominated by the bands of C₂ and CN. From the band intensities, the vibrational temperatures of both radicals are calculated to be 12–15×10³ K, and their concentrations are estimated to be 5×10¹⁴ cm^–3 and 2×10¹⁴ cm^–3, respectively.     

Radical concentration measurements in hydrocarbon diffusion flames

Absolute OH· concentrations and relative H-atom and O-atom profiles have been measured in a laminar, co-flowing methane/air diffusion flame burning at atmospheric pressure. Laser absorption and laser-induced fluorescence methods were used to probe the A ² X ²II_itransition in OH·. The maximum OH· concentration is found to be 1.8±0.2 ×10¹⁶ cm^–3 (mole fraction =5.0×10^–3) at a temperature of 2080 K, which is twice the value calculated assuming local total equilibrium but less than half that predicted from partial equilibrium (O₂+H₂ 2OH·). Multiphoton ionization (2+1 process at 243 nm) has been used to detect H atoms, while laser-induced fluorescence at 845 nm excited by two-photon absorption at 226 nm was employed to observe O atoms. In both cases it was found that low photon intensities (2×10⁸W/cm²) and a retroreflected beam, Doppler-free geometry was required in order to avoid the photolytic production of the species of interest. For all of the concentration profile data it is necessary to correct the raw signals for variations in collisional quenching. In the case of the multiphoton ionization measurements the variation in electron detection sensitivity as a function of flame position must be accounted for as well. Establishing absolute H-atom and O-atom concentrations is discussed in terms of partial equilibrium considerations and detailed flame structure calculations.Formerly the National Bureau of Standards     

Environmental influence on the IR fluorescence of Xe<Subscript>2</Subscript><Superscript>*</Superscript> molecules in electron beam excited Ar–Xe mixture at high density

We report new measurements of the near infrared (NIR) Xe₂^* excimer fluorescence in an electron–beam–excited Ar (90%)–Xe (10 %) mixture at room temperature. Previous measurements up to a density N≈2×10²⁶ m^-3 discovered a broad excimer fluorescence band at ≈7800 cm^-1, whose center is red–shifted by increasing N [A.F. Borghesani, G. Bressi, G. Carugno, E. Conti, D. Iannuzzi, J. Chem. Phys. 115, 6042 (2001)]. The shift has been explained by assuming that the energy of the optical active electron in the molecule is shifted by the density–dependent Fermi shift and by accounting for the solvation effect due to the environment. We have extended the density range up to N≈6×10²⁶ m^-3, confirming the previous measurements and extending the validity of the interpretative model. A detailed analysis of the width of the fluorescence band gives a value of 2.85 nm for the size of the investigated excimer state. Such a large value lends credibility to the validity of the proposed explanation of the experimental findings.     

Molecular Dynamics of Biological Probes by Fluorescence Correlation Microscopy with Two-Photon Excitation

We report on the application of fluorescence correlation microscopy under two-photon excitation of fluorophores of biological interest: FITC–dextran (MW, from 20 to 150 kDa), green fluorescent protein (MW, 27 kDa), and fluorescein (MW, 330 Da). Under these experimental conditions, the translational diffusion coefficients of these molecules in aqueous solutions derived from the fluorescence intensity autocorrelation function were determined for the first time and were found to be 24 × 10^–7, 8.2 × 10^–7, and 3 × 10^–7 cm² s^–1 for 150-kDa FITC–dextran, green fluorescent protein, and fluorescein, respectively. These results are discussed in connection with previously reported results obtained by different methods. The great sensibility of the system has been applied to single-molecule detection of the smaller fluorophore, fluorescein.     

XeCl-laser-generated ablation products from a nitrogen-rich polymer studied by laser-ionization mass spectrometry

Laser-ionization time-of-flight mass spectrometry has been used to probe laser-ablation products from a nitrogen-rich polymer at a wavelength of 308 nm. The ablation products at a laser fluence of 150 mJ/cm² showed, similar to 532 nm ablation studied previously [18], two strong peaks due to neutral species that were assigned to C⁺ and CN⁺, as well as several weak peaks that were assigned to CH⁺, HCN⁺, HCNH⁺, H_nN–CN⁺ (n=1–3), and H₂N–C=N–CN⁺ or H₂N–C=N–CN⁺. The ablation products at 870 mJ/cm² revealed, in addition to a broad signal due to ionic products generated directly by the ablation laser, several peaks due to neutral products that were assigned to C⁺, C ₂ ⁺ , C ₃ ⁺ , CN⁺, HCN⁺, HCNH⁺, and NCCN⁺. The most probable flight velocities for major neutral products are 5.7×10⁴ cm/s at 150 mJ/cm² and 2.3–2.7×10⁴ cm/s at 870 mJ/cm². The results at a laser fluence of 150 mJ/cm² support the finding that the translational energy of the tragments has importance for the collision-induced product generation in the laser plume, as suggested earlier [18]. Furthermore, the product generation at 870 mJ/cm² is interpreted by the ejection of small neutral and ionic fragments, and subsequent reactions among the fragments.     

Studies of vibrational relaxation in CDF3 following intense laser excitation

The V-T/R relaxation time of CDF₃ was measured studying the laser-induced infrared fluorescence emitted by vibrationally excited CDF₃. Following excitation by the 10R(12) line of a TEA CO₂ laser infrared fluorescence has been detected without spectral resolution in the 1100–700 cm^–1 range. A decay rate of 28.8 ms^–1 Torr^–1 was obtained for pure CDF₃ when it is excited with a fluence of 390 mJ/cm². Measurements have also been made in the presence of different bath gases (He, Ne, Ar, Xe, and CHF₃).     

Spectroscopic studies of laser-produced plasmas formed in CO and CO2 using 193, 266, 355, 532 and 1064 nm laser radiation

The wavelength dependence of laser-produced breakdown in air, CO and CO₂ has been studied using the four Nd:YAG harmonics (266 nm, 355 nm, 532 nm and 1064 nm) and the ArF-excimer laser (193 nm). Breakdown thresholds at these wavelengths are reported for air, CO and CO₂. A significant reduction in the breakdown thresholds for both CO and CO₂ is apparent when comparing 193 nm with the four Nd:YAG harmonics. This reduction is attributed to the resonance-enhanced two-photon ionization of metastable carbon atoms generated in the laser focus at the ArF-laser wavelength. In addition to reporting breakdown thresholds, the laser-produced plasmas in CO and CO₂ are characterized in terms of plasma temperatures and electron densities which are measured by time-resolved emission spectroscopy. Electron densities range from 9 × 10¹⁷ cm^–3 to 1 × 10₁₇ cm^–3. Excitation temperatures range from 22 000 K at 0.2 µs to 11 000 K at 2 µs. Ionization temperatures range from 22 000 K at 0.1 µs to 16 000 K at 2 µs. Evidence is presented to indicate that, like ArF-laser-produced plasmas, Nd:YAG-laser-produced plasmas formed in CO and CO₂ are in or near a state of Local Thermodynamic Equilibrium (LTE) soon after their formation.     

Shallow acceptor population and free hole concentration in Si: In and Si:Ga with IR-photoexcitation

Hall measurements at low temperaturesT<50 K have been performed on Si:In (N _In10¹⁷ cm^–3) and Si:Ga (N _Ga10¹⁸ cm^–3) with infrared photoexcitation of holes into the valence band. It is shown in quantitative agreement with a theoretical model that the population of shallow acceptors, e.g. B and Al, which are present as impurities in concentrations ofN _B,Al10¹²-10¹⁴ cm^–3 strongly affects the photoexcited hole concentration. Photo-Hall measurements can, therefore, serve as a tool for the determination of low impurity acceptor concentrations in the case of high In- or Ga-doping. Hole capture coefficientsB _In=6×10^–4 (T/K)^–1,8 cm³ s^–1 andB _Ga=2×10^–4 (T/K)^–1 cm³ s^–1 have been determined.     

Nonlinear Optical Characteristics of BSO and BGO Photorefractive Crystals in Visible and Infrared Ranges

Nonlinear refraction, nonlinear absorption and optical limiting in photorefractive crystals Bi₁₂SiO₂₀(BSO) and Bi₁₂GeO₂₀(BGO) at the wavelengths of 1064 and 532 nm were investigated. It was shown that both BSO and BGO crystals possess by positive nonlinear refraction in two investigated spectral ranges (n ₂ ^BSO=(2.5 ± 0.5)× 10^–12 esu, n ₂ ^BGO=(6.3 ± 1.3)× 10^–12 esu at equals 1064 nm; n ₂ ^BSO=(4.4 plusmn; 0.9)× 10^–12 esu, n ₂ ^BGO=(7.4 ± 1.5)× 10^–12 esu at = 532 nm). The nonlinear absorption was due to three-photon absorption at the wavelength of 1064 nm ( ⁽³⁾ _BSO=(2.5 ± 0.8)× 10^–20cm³W^–2, ⁽³⁾ _BSO=(4.4 ± 1.3)× 10^–20cm³W^–2) and two-photon absorption at the wavelength of 532 nm ( ⁽²⁾ _BSO=(2 ± 0.4)× 10^–9cm W^–1, ⁽²⁾ _BGO=(3.7 ± 0.7)× 10^–9cm W^–1).     

Xe2Cl fluorescence and absorption in self-sustained discharge XeCl lasers

Fluorescence at 490 nm from the triatomic excimer Xe₂Cl^* has been investigated to determine the 308 nm absorption due to this species in an x-ray preionized, self-sustained gas discharge XeCl laser. The dependence of Xe₂Cl^* density on laser intensity (at 308 nm), buffer gas and Xe and HCl partial pressures has been determined for discharges with a peak electrical power deposition of 2.5 GWl^–1. Xe₂Cl^* absorption is estimated to reach 0.6% cm^–1 under non-lasing conditions but decreases to a non-saturable 0.2% cm^–1 for intracavity laser intensity>1 MW cm^–2. XeCl^* and Xe₂Cl^* fluorescence intensities were found to be a similar for both helium and neon buffer gases but laser output was a factor of two greater with a neon buffer.     

Relaxation oscillations and damping factors of 1.3 μm In(Ga)As/GaAs quantum-dot lasers

In(Ga)As/GaAs quantum-dot (QD) lasers with emission wavelength at 1295 nm at room temperature are fabricated. The laser active region contains a threefold stack of QD layers with surface dot density of 4.56 × 10¹⁰ cm^–2. The laser structure is aluminum-free with InGaP as cladding layers. Threshold current density of a narrow stripe laser of 8 m wide and 3.5 mm long is 152.5 A/cm². The highest relaxation oscillation frequency measured at room temperature is 1.8 GHz, corresponding to a modulation bandwidth of 2.8 GHz due to the small damping factor. From the above measurement, the differential gain and gain compression factor were extracted to be 4.3 × 10^–16 cm² and 3.4 × 10 ^–17 cm ³, respectively. Using these parameters, the maximum modulation bandwidth f _{3 dB max} is estimated as 7.9 GHz.     

Optical and transport properties of δ-doped pseudomorphic AlGaAs/InGaAs/GaAs structures

We investigate the effects of spacer layer thickness on the optical and transport properties of the n-type-doped pseudomorphic Al_0.30Ga_0.70As/In_0.15Ga_0.85As / GaAs structures. A-doped AlGaAs/InGaAs/GaAs structure with a 6nm spacer layer yields a sheet carrier concentration of 1.5×10¹² cm^–2 at 77K with electron mobility of 6.4×10³ cm²/Vs, 3.11×10⁴ cm²/Vs, and 3.45×10⁴ cm²/Vs at room temperature, 77 and 20K, respectively. The effects of the different scattering mechanisms on luminescence linewidth and electron mobility have also been discussed.     

UV-CVD deposited SiNH films on InP: Optimization of the physico-chemical and interface properties

High quality silicon nitride films are deposited at low temperature on InP substrates by direct photolysis at 185 nm of a NH₃-SiH₄ gas mixture. The composition of the films is measured by nuclear analysis. The thickness and refractive index are obtained by ellipsometry at 632.8 nm. As-deposited and post annealed samples are electrically characterized: quasi-static I(V) at 5×10^–4 Hz and C(V) characteristics at 1 MHz are performed on InP MIS diodes structures in order to optimize bulk and interface properties. At 250° C and 4 Torr, it is found that the highest critical field (measured for a leakage current density of 10^–9 A/cm²) is obtained for the injected ratio [SiH₄]/[NH₃]=2%. For these conditions, the film is stoichiometric, the critical field is 4 MV/cm and the resistivity is 6×10¹⁵ cm. The interface state density (N _ss) on InP is deduced from Terman analysis. The annealing conditions and the surface cleaning of InP have been optimized in order to reduce the N _ss which is, for our best conditions, as low as 2×10¹¹ eV^–1 cm^–2.     

Femtosecond-pulse laser ablation of human corneas

A femtosecond pulse laser in the visible spectral region shows promise as a potentially new powerful corneal sculpting tool. It combines the clinical and technical advantages of visible wavelengths with the high ablation quality observed with nanosecond-pulse excimer lasers at 193 nm. A femtosecond and a nanosecond dye laser with pulse durations of 300 fs and 7 ns, and centre wavelengths at 615 nm and 600 nm, respectively, both focused to an area of the order of 10^–5 cm², have been applied to human corneal ablation. Nanosecond laser pulses caused substantial tissue disruption within a 30–100 m range from the excision edge at all fluences above the ablation threshold of F _th60 J cm^–2 (I _th9 GW cm^–2). Completely different excisions are produced by the femtosecond-pulse laser: high quality ablations of the Bowman membrane and the stroma tissue characterised by damage zones of less than 0.5 m were observed at all fluences above ablation threshold of F _th1 J cm^–2 or I _th3 TW cm^–2 (3×10¹² W cm^–2). The transparent cornea material can be forced to absorb ultrashort pulses of extremely high intensity. The fs laser generates its own absorption by a multiphoton absorption process.     

Characterization of ammonia two-photon laser-induced fluorescence for gas-phase diagnostics

Two-photon laser-induced fluorescence (LIF) of ammonia (NH₃) with excitation of the C′-X transition at 304.8 nm and fluorescence detection in the 565 nm C′-A band has been investigated, targeting combustion diagnostics. The impact of laser irradiance, temperature, and pressure has been studied, and simulation of NH₃-spectra, fitted to experimental data, facilitated interpretation of the results. The LIF-signal showed quadratic dependence on laser irradiance up to 2 GW/cm². Stimulated emission, resulting in loss of excited molecules, is induced above 10 GW/cm², i.e., above irradiances attainable for LIF imaging. Maximum LIF-signal was obtained for excitation at the 304.8 nm bandhead; however, lower temperature sensitivity over the range 400–700 K can be obtained probing lines around 304.9 nm. A decrease in fluorescence signal was observed with pressure up to 5 bar absolute and attributed to collisional quenching. A detection limit of 800 ppm, at signal-to-noise ratio 1.5, was identified for single-shot LIF imaging over an area of centimeter scale, whereas for single-point measurements, the technique shows potential for sub-ppm detection. Moreover, high-quality NH₃-imaging has been achieved in laminar and turbulent premixed flames. Altogether, two-photon fluorescence provides a useful tool for imaging NH₃-detection in combustion diagnostics.     

Formation of thermally stable low-resistance Ti/W/Au ohmic contacts on n-type GaN

A Ti(12 nm)/W(20 nm)/Au(50 nm) metallization scheme has been investigated for obtaining thermally stable low-resistance ohmic contacts to n-type GaN (4.0×10¹⁸ cm^-3). It is shown that the current–voltage (I–V) characteristics of the samples are abnormally dependent on the annealing temperature. For example, the samples that were annealed at temperatures below 750 °C for 1 min in a N₂ ambient show rectifying behavior. However, annealing the samples at temperatures in excess of 850 °C results in linear I–V characteristics. The contact produces a specific contact resistance as low as 8.4×10^-6 Ω cm² when annealed at 900 °C. It is further shown that the contacts are fairly thermally stable even after annealing at 900 °C; annealing the samples at 900 °C for 30 min causes insignificant degradation of the electrical and structural properties. Based on glancing angle X-ray diffraction and Auger electron microscopy results, the abnormal temperature dependence of the ohmic behavior is described and discussed. PACS 72.80.Ey; 73.40.Cg; 73.20.At; 79.60Bm; 73.40.Gk     

Sensitive detection of H2 molecules by two-photon excited laser-induced fluorescence

The sensitive detection of H₂ molecules was demonstrated by means of twophoton excited laser-induces fluorescence spectroscopy with a narrow-band ArF excimer laser. A detection limit of 2×10¹⁴ cm^–3 was obtained with an excitation power of 150 kW. This is already comparable with that obtained by the coherent anti-Stokes Raman scattering (CARS). This technique was successfully applied to measure a spatial distribution of H₂ in a town-gas burner.