Laser-induced bulk damage in various types of vitreous silica at 1064, 532, 355, and 266 nm: evidence of different damage mechanisms between 266-nm and longer wavelengths

Laser-induced-damage thresholds (LIDT's) with various types of vitreous silica at 1064, 532, 355, and 266 nm are investigated. At 1064 nm no difference in the LIDT was observed in any sample. At 1064-355 nm the wavelength dependence of the LIDT of synthetic fused silica (SFS) can be described well by the relation I(th) = 1.45lambda(0.43), where I(th) is the LIDT in J/cm(2) and lambda is the wavelength in nanometers. At 266 nm, however, LIDT's were smaller than half of the calculated value from the relation above. This difference can be explained by the damage mechanism; at 266 nm two-photon absorption-induced defects lower the LIDT as in the case of KrF-excimer-laser-induced defects, whereas at longer wavelengths the two-photon process does not occur. LIDT's of fused quartz (FQ) at 532 and 355 nm and that of SFS containing ~1000 ppm of Cl and no OH at 355 nm were a little lower than those of the other SFS's. This lower LIDT may be related to the absorption of metallic impurities in FQ and dissolved Cl(2) molecules in SFS. At 266 nm, on the other hand, LIDT's of FQ's were higher than those of most SFS's.     

Isotope selective near-resonant two-photon ionization of 41Ca isotope via the 4s11s 1S0 intermediate state

Isotope selective excitation of a 41Ca isotope using a near-resonant two-photon ionization scheme 4s2 1S0-->422.7924 nm,413.3685 nm4s11s 1S0-->514.5 nmCa+ has been proposed for using the 41Ca isotope in applications as a tracer in biomedical studies. The ionization efficiency and optical selectivity have been calculated for various powers of the excitation and ionization laser. Under the optimized excitation and ionization laser powers the ionization efficiency for the studied scheme is found to be 1.7x10(-4). The optical selectivity value is approximately 1.0x10(5) and both of these values are either comparable or slightly better than the earlier published work by our group. The overall ionization efficiency for the two-photon ionization scheme considering the throughput factor is 5x10(-3), which is 2 orders of magnitude higher than the stepwise excitation process. Therefore, the higher ionization efficiency of the process enables monitoring of the tracer isotope for longer durations. In combination with a mass spectrometer, an abundance sensitivity of approximately 10(10) can be obtained, which is adequate for biomedical applications.     

Wavelength dependence of repetitive-pulse laser-induced damage threshold in beta-BaB2O4

The dependence on wavelength of repetitive-pulse (10 Hz, 8-10 ns) laser-induced damage on beta barium metaborate (BBO) has been investigated. The thresholds of dielectric breakdown in bulk crystal have been found to be 0.3 GW/cm(2) at 266 nm, 0.9 GW/cm(2) at 355 nm, 2.3 GW/cm(2) at 532 nm, and 4.5 GW/cm(2) at 1064 nm. Results indicate two-photon absorption at 266 and 355 nm, which helps to produce an avalanche effect that causes breakdown at each of the four wavelengths tested. Neither the BBO refractive indices nor the absorption spectrum change until breakdown occurs.     

Analysis of dioxins by gas chromatography/resonance-enhanced multiphoton ionization/mass spectrometry using nanosecond and picosecond lasers

Dioxins in a soil sample were measured using gas chromatography/resonance-enhanced multiphoton ionization/time-of-flight mass spectrometry coupled with different types of laser sources. The fourth-harmonic emission (266 nm) of a nanosecond Nd:YAG laser (1 ns) provided low ionization efficiency, especially for highly chlorinated dioxins/dibenzofurans (CDDs/CDFs). The ionization efficiency was improved using the fourth-harmonic emission (266 nm) of a picosecond Nd:YAG laser (4 ps), due to shorter singlet excited-state lifetimes. It was, however, difficult to efficiently ionize hepta-CDD and octa-CDD/CDF, because of their shorter lifetimes, which were induced by stronger spin-orbit coupling that led to efficient relaxation of the excited molecule to triplet levels. The ionization efficiency was substantially improved using the fifth-harmonic emission (213 nm) of the picosecond Nd:YAG laser (4 ps), in which the analyte molecule that was relaxed to triplet levels was efficiently ionized using a photon with sufficient energy for ionization, although the pulse energy obtained at 213 nm was only one-third of the pulse energy obtained at 266 nm. The limits of detection achieved for 17 toxic polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDDs/PCDFs) were 0.41-45 pg. The analytical instrument developed in the present study performed sufficiently well for the practical trace analysis of dioxins in soil samples.     

Selective imaging of active pharmaceutical ingredients in powdered blends with common excipients utilizing two-photon excited ultraviolet-fluorescence and ultraviolet-second order nonlinear optical imaging of chiral crystals

Second order nonlinear optical imaging of chiral crystals (SONICC) and two-photon excited fluorescence measurements [both autofluorescence and two-photon excited UV-fluorescence (TPE-UVF)] were assessed for the selective detection of APIs relative to common pharmaceutical excipients. Active pharmaceutical ingredients (APIs) compose only a small percentage of most tabulated formulations, yet the API distribution within the tablet can affect drug release and tablet stability. Complementary measurements using either UV-SONICC (266 nm detection) or TPE-UVF were shown to generate signals >50-fold more intense for a model API (griseofulvin) than those produced by common pharmaceutical excipients. The combined product of the measurements produced signals >10(4)-fold greater than the excipients studied. UV-SONICC or TPE-UVF produced greater selectivity than analogous measurements with visible-light detection, attributed to the presence of aromatic moieties within the API exhibiting strong one and two photon absorption at ~266 nm. Complementary SONICC and fluorescence measurements allowed for the sensitive detection of the three-dimensional distribution of tadalafil within a Cialis tablet to a depth of >140 μm.     

Analysis of water contaminants and natural water samples using two-step laser mass spectrometry

The applicability of two-step laser mass spectrometry (L2MS) to the analysis of water contaminants and environmental water samples is demonstrated. First, the ionization characteristics of a selection of naphthyl and carbamate pesticides and of phenol were determined. The ion signal of all compounds increased with ionization laser pulse energy, within the investigated range (20-200 microJ). Ion yields relative to an internal standard, benz[alanthracene, reached 30% for naphthyl pesticides ionized at 225 nm and 2-8% at 266 nm. At 266 nm, similar relative ion yields were found for phenol. Carbamate pesticides showed lower relative ion yields at all wavelengths, by a factor of approximately 10-100, but higher relative ion yields, on the order of 1%, were obtained when using short (ps) laser pulses for ionization. These data allow one to estimate the detection limits of these analytes in a variety of matrixes once they are known for one of the compounds. Second, the quantitative analysis of carbaryl, phenol, and polycyclic aromatic hydrocarbons in rainwater is demonstrated. The aqueous samples were frozen to permit direct L2MS analysis of organic pollutants without tedious sample preparation. Detection limits were in the low-microgram per liter concentration range and recoveries of phenol from spiked rainwater samples were above 90%. The specific advantages are exemplified with the investigation of dynamic washout processes of atmospheric organic pollutants with a resolution of 0.01 mm of precipitation.     

On-line concentration by analyte adsorption and subsequent laser desorption in supersonic jet spectrometry

A narrow capillary, the tip of which was restricted to form a supersonic jet, was employed for sample introduction in time-of-flight mass spectrometry. The analyte was adsorbed at the tip of the capillary, due to a temperature decrease by the Joule-Thomson effect. Then, the analyte was desorbed using a pulsed laser emitting at 532 nm, and was entrained into a carrier gas. The analyte in the jet was subsequently ionized using a pulsed laser emitting at 266 nm. The duration of the analyte passing through the ionization region was 5.4 mm in length (9 micros in time), and the signal intensity was enhanced 310-fold. This technique can also improve selectivity by controlling the nozzle temperature, since volatile compounds are not trapped at the tip of the capillary and then are not concentrated in the jet. In this approach, the analyte can be injected in a pulsed mode into a vacuum without using a complicated mechanical valve even at a repetition rate of >1 kHz from the nozzle heated at a temperature of >300 degrees C.     

Laser mass spectrometry as on-line sensor for industrial process analysis: process control of coffee roasting

The objective of the project is to develop on-line, real-time, and noninvasive process control tools of coffee roasting that help deliver a consistent and high-quality coffee aroma. The coffee roasting process was analyzed by direct injection of the roaster gas into a time-of-flight mass spectrometer and ionized either by resonance enhanced multiphoton ionization (REMPI) at 266 and 248 nm or vacuum ultraviolet single-photon ionization (VUV-SPI) at 118 nm. The VUV ionization scheme allows detecting mainly the most volatile and abundant compounds of molecular mass below 100 m/z, while REMPI ionizes mainly aromatic compounds of molecular mass larger than 100 m/z. Combining the compounds ionized by resonant and single-photon ionization, approximately 30 volatile organic compounds are monitored in real time. Time-intensity profiles of 10 important volatile coffee compounds were discussed in connection with their formation chemistry during roasting. Applying multivariate statistics (principle component analysis) on time-intensity traces of nine volatile coffee compounds, the roasting degree could be traced as a consistent path in the score plot of the two most significant principle components (including 68% of the total variance), for a range of roasting temperatures (200-250 degrees C).     

Limitations arising from two-photon absorption of solvent in pulsed-laser thermal lens detection: determination of the two-photon absorption coefficient of ethanol at 266 nm

Two-photon absorption of the solvent under pulsed-laser excitation at 266 nm produces a high background thermal lens signal interfering with the analyte signal. Discrimination of both solvent and analyte signals along with calibration of the photothermal response has allowed the determination of the two-photon absorption coefficient of ethanol. The obtained value, 3.0x10(-10) cm W-1, is close to the literature values obtained from transmittance measurements using picosecond or femtosecond laser pulses.     

Monitoring O3 with solar-blind Raman lidars

The benefits of retrieving ozone concentration profiles by a use of a single Raman signal rather than the Raman differential absorption lidar (DIAL) technique are investigated by numerical simulations applied either to KrF- (248 nm) or to quadrupled Nd:YAG- (266 nm) based Raman lidars, which are used for both daytime and nighttime monitoring of the tropospheric water-vapor mixing ratio. It is demonstrated that ozone concentration profiles of adequate accuracy and spatial and temporal resolution can be retrieved under low aerosol loading by a single Raman lidar because of the large value of the ozone absorption cross section both at 248 nm and at 266 nm. Then experimental measurements of Raman signals provided by the KrF-based lidar operating at the University of Lecce (40 degrees 20'N, 18 degrees 6'E) are used to retrieve ozone concentration profiles by use of the Raman DIAL technique and the nitrogen Raman signal.     

Optical parametric properties of ultraviolet-pumped cesium lithium borate crystals

We report the optical parametric properties of cesium lithium borate (CLBO) crystals pumped by UV radiation of the fourth-harmonic generation at 266 nm and the third-harmonic generation at 355 nm of a picosecond Nd:YAG laser. A special optical design was used to avoid damage to the optical elements by the UV-pumped beam at 266 nm. The optical parametric generator (OPG)/optical parametric amplifier (OPA) of the 266-nm-pumped CLBO covers the tuning range from 347 nm in the UV to 1137 nm in the near IR. The 355-nm-pumped CLBO OPG/OPA, on the other hand, is tunable from 447 to 1725 nm. The experimental tuning curves for each CLBO OPG/OPA were measured and compared with the theoretical tuning curves. With a double-pass OPG configuration and a pumping intensity of approximately 6 GW/cm2, the maximum conversion efficiency, including both the signal and the idler, was approximately 11% for the 266-nm-pumped CLBO and is greater than 16% for the 355-nm-pumped CLBO without taking into account the surface losses from the uncoated elements. The bandwidth of this double-pass CLBO OPG at various wavelengths was measured and compared with other optical parametric systems. Because of the small angular dispersion of CLBO, the bandwidth of the OPG and OPA systems is exceptionally narrow, especially for the 266-nm-pumped system. Without the use of any dispersion element, the bandwidth of the 266-nm-pumped system can be as narrow as 0.22 nm at wavelengths far from the degenerate point. Comparison between the experimental bandwidth and the theoretical calculation shows that the bandwidth of the UV-pumped CLBO OPG/OPA is limited mainly by the divergence of the pump beam.     

Two-photon ionization of composite molecules as a method of simulating particle tracks by means of N2 laser radiation

The simulation of tracks of charged particles by means of the two-photon ionization of organic molecules with the ionization potential I_i < 7.36 induced by radiation from pulsed laser on molecular nitrogen (λ = 337 nm). It is shown that an injection o f saturated vapours of N, N, N′, N′-tetramethyl-p-phenylenediamine, N, N′-dipropylaniline, α-naphthylamine and other compound into the working gas of the detector makes it possible to imitate tracks of particles of any ionizing power by means of a serial N₂ laser LGI-21 (pulse power up to 6 kW). The kinematics of the two-photon ionization and the relation between the reaction cross section and the characteristics of the molecule are considered.     

Negative ion formation in laser ion mobility increment spectrometer

A new method is proposed and implemented, according to which small concentrations of organic compounds in the atmosphere are measured by combining the ion mobility increment spectrometer and laser ionization. The experimental setup makes use of the pulsed fourth-harmonic radiation of a YAG:Nd³⁺ laser (λ = 266 nm). At high intensities (q ∼ 10⁷ W/cm²) of laser radiation, ion spectra with reactant peaks are observed, which are identical to the spectra obtained with traditional sources of ionization by corona discharge and β radiation. The ion spectra obtained at low laser radiation intensities (q ∼ 10⁵ W/cm²) are free of background and reactant peaks, which ensures the high selectivity of the analysis. It is concluded that the mechanism of negative ion formation from the molecules of nitro compounds can change depending on the intensity of ionizing laser radiation.     

A two-color three-photon ionization scheme for the efficient and selective ionization of a chlorinated aromatic hydrocarbon

A two-color three-photon ionization scheme, for the efficient and selective ionization of a chlorinated aromatic hydrocarbon that has an ionization potential higher than the two-photon energy of the laser used for excitation, is described. In this technique, an ultraviolet (UV) laser, i.e., the second harmonic emission of a fundamental (VIS) laser, is used for excitation and a UV and VIS laser for the subsequent two-photon ionization from the electronic excited state. A sample of o-chlorophenol was used as a model compound to demonstrate the advantage of this technique. The signal in supersonic jet/resonance-enhanced multiphoton ionization/mass spectrometry was increased approximately 4 times by the introduction of the VIS beam, when the polarization was adjusted to be parallel to the UV beam. Thus, the two-color three-photon (2UV+VIS) ionization scheme is more sensitive than one-color three-photon (3UV) ionization. The merits of this method over other ionization schemes such as two-color two-photon (UV(1)+UV(2)) ionization are discussed in terms of sensitivity and selectivity in spectrometric analysis.     

Selective multiphoton ionization of coplanar polychlorobiphenyls using 266-nm laser emission by gas chromatography/mass spectrometry

Polychlorinated biphenyls (PCBs), used as a heat exchange oil (Kanechlor, KC-300), can be measured by gas chromatography combined with multiphoton ionization mass spectrometry (GC/MPI-MS). Several compounds, e.g., 4,4'-dichlorobiphenyl and 3,4,4'-trichlorobiphenyl, have nearly the same retention time but can be selectively determined by MPI-MS. Coplanar PCBs are more efficiently ionized using the fourth harmonic emission of a Nd:YAG laser (266 nm), compared to noncoplanar PCBs. Thus, the approach reported herein may be useful in the selective as well as the sensitive analysis of toxic PCBs, contained in old transformers and capacitors that have been mandated by the government to be properly disposed of within 10 years in Japan.     

GaAs:Mn nanowires grown by molecular beam epitaxy of (Ga,Mn)as at MnAs segregation conditions

GaAs:Mn nanowires were obtained on GaAs(001) and GaAs(111)B substrates by molecular beam epitaxial growth of (Ga,Mn)As at conditions leading to MnAs phase separation. Their density is proportional to the density of catalyzing MnAs nanoislands, which can be controlled by the Mn flux and/or the substrate temperature. After deposition corresponding to a 200 nm thick (Ga,Mn)As layer the nanowires are around 700 nm long. Their shapes are tapered, with typical diameters around 30 nm at the base and 7 nm at the tip. The wires grow along the 111 direction, i.e., along the surface normal on GaAs(111)B and inclined on GaAs(001). In the latter case they tend to form branches. Being rooted in the ferromagnetic semiconductor (Ga,Mn)As, the nanowires combine one-dimensional properties with the magnetic properties of (Ga,Mn)As and provide natural, self-assembled structures for nanospintronics.     

High-density optical data storage with one-photon and two-photon near-field fluorescence microscopy

A spatially localized photochemical reaction induced by near-field femtosecond laser pulses is demonstrated on a nanometer scale and used for high-density optical data storage. Recorded domains down to 120 and 70 nm are obtained with one-photon and two-photon excitation, respectively. It is shown that the local-field confinement that is due to the quadratic dependence of two-photon excitation on light intensity has the potential to increase the near-field optical storage density.     

On-Line Emission Analysis of Polycyclic Aromatic Hydrocarbons down to pptv Concentration Levels in the Flue Gas of an Incineration Pilot Plant with a Mobile Resonance-Enhanced Multiphoton Ionization Time-of-Flight Mass Spectrometer

A newly developed, mobile laser mass spectrometer (resonance-enhanced multiphoton ionization - time-of-flight mass spectrometer, REMPI-TOFMS) was applied to on-line measurements at a waste incineration pilot plant. REMPI-TOFMS combines the optical selectivity of resonance-enhanced multiphoton ionization with a time-of-flight mass analysis to give a two-dimensional analytical method. Special care was taken to build up a sampling and inlet system suitable for on-line measurements of large, semivolatile polycyclic aromatic hydrocarbons (PAHs). An effusive molecular beam inlet in combination with a fixed frequency UV laser (Nd:YAG at 266 nm or KrF excimer at 248 nm) was used. Under these conditions, many different PAHs can be ionized selectively from the complex flue gas matrix. For example, the achieved detection limit for naphthalene is in the 10 parts-per-trillion by volume (pptv) concentration range. Calibration was performed by using external concentration standards supplied in low ppbv concentrations. The instrumentation is sufficiently robust to be operated under industrial conditions at incineration plants, for instance. The REMPI mass spectra can be acquired at 5-50 Hz. Time profiles of the concentrations of different PAHs in the flue gas were monitored with a time resolution of 200 ms. Significant variations in the concentration profile of several PAHs up to mass 276 amu (e.g., benzo[ghi]perylene) and methylated PAHs have been observed while combustion parameters were changing. In summary, it was demonstrated that laser mass spectrometry (REMPI-TOFMS) enables a real-time on-line trace analysis of combustion flue gases or industrial process gases.     

Identification of impurities in phenylacetylene by species-selected mass-analyzed threshold ionization spectroscopy

Two-color resonant two-photon mass-analyzed threshold ionization (MATI) spectroscopy was used to identify styrene impurities in a commercial phenylacetylene sample. With the mass-gating setup, the recorded MATI spectra are free of contamination from molecules of different mass. Analysis of these spectra gives information on the precise adiabatic ionization and the active cation vibrations, which can be used as fingerprints for the identification of molecular ions.     

Imaging of droplets and vapor distributions in a diesel fuel spray by means of a laser absorption-scattering technique

The droplets and vapor distributions in a fuel spray were imaged by a dual-wavelength laser absorption-scattering technique. 1,3-dimethylnaphthalene, which has physical properties similar to those of Diesel fuel, strongly absorbs the ultraviolet light near the fourth harmonic (266 nm) of a Nd:YAG laser but is nearly transparent to the visible light near the second harmonic (532 nm) of a Nd:YAG laser. Therefore, droplets and vapor distributions in a Diesel spray can be visualized by an imaging system that uses a Nd:YAG laser as the incident light and 1,3-dimethylnaphthalene as the test fuel. For a quantitative application consideration, the absorption coefficients of dimethylnapthalene vapor at different temperatures and pressures were examined with an optical spectrometer. The findings of this study suggest that this imaging technique has great promise for simultaneously obtaining quantitative information of droplet density and vapor concentration in Diesel fuel spray.