Steady-state and transient ultraviolet resonance Raman spectrometer for the 193-270 nm spectral region

We describe a state-of-the-art tunable ultraviolet (UV) Raman spectrometer for the 193-270 nm spectral region. This instrument allows for steady-state and transient UV Raman measurements. We utilize a 5 kHz Ti-sapphire continuously tunable laser (approximately 20 ns pulse width) between 193 nm and 240 nm for steady-state measurements. For transient Raman measurements we utilize one Coherent Infinity YAG laser to generate nanosecond infrared (IR) pump laser pulses to generate a temperature jump (T-jump) and a second Coherent Infinity YAG laser that is frequency tripled and Raman shifted into the deep UV (204 nm) for transient UV Raman excitation. Numerous other UV excitation frequencies can be utilized for selective excitation of chromophoric groups for transient Raman measurements. We constructed a subtractive dispersion double monochromator to minimize stray light. We utilize a new charge-coupled device (CCD) camera that responds efficiently to UV light, as opposed to the previous CCD and photodiode detectors, which required intensifiers for detecting UV light. For the T-jump measurements we use a second camera to simultaneously acquire the Raman spectra of the water stretching bands (2500-4000 cm(-1)) whose band-shape and frequency report the sample temperature.     

Fiber-optic probes with improved excitation and collection efficiency for deep-UV Raman and resonance Raman spectroscopy

The ability of ultraviolet resonance Raman spectroscopy (UVRRS) to determine structural, environmental, and analytical information concerning low-concentration aqueous biomolecules makes it a powerful bioanalytical and biophysical technique. Unfortunately, its utility has been limited by experimental requirements that preclude in situ or in vivo studies in most cases. We have developed the first high-performance fiber-optic probes suitable for long-term use in pulsed UVRRS applications in the deep- UV (DUV, 205-250 nm). The probes incorporate recently developed improved ultraviolet (IUV) fibers that do not exhibit the rapid solarization and throughput decay that previously hampered the use of optical fibers for delivering pulsed, DUV light. A novel 90 degrees mirrored collection geometry is used to overcome the inner-filtering effects that plague flush-probe geometries. The IUV fibers are characterized with respect to their efficacy at transmitting pulsed, DUV laser light, and prototype probes are used to obtain pulsed UVRRS data of aromatic amino acids, proteins, and hormones at low concentrations with 205-240-nm pulsed excitation. Efficient probe geometries and fabrication methods are presented. The performance of the probes in examining resonance-enhanced Raman signals from absorbing chromophores is investigated, and the optimal excitation wavelength is shown to be significantly red-shifted from the maximum of the resonance Raman enhancement profile. Generally applicable procedures for determining optimal experimental conditions are also introduced.     

UV Raman studies on carbon nitride structures

Visible (514 nm) and deep UV (257 nm) Raman spectra of monoclinic tetracyanoethylene (tcne) are recorded at ambient conditions and also after laser heating at ambient pressure and at 40 GPa. Tetracyanoethylene (C₂(CN)₄) is a convenient precursor to synthesize hard C₃N₄ materials. At low incident laser powers the UV Raman spectra of virgin tcne resemble visible Raman spectra, and at higher powers there appear new, broad modes that increase in intensity as a function of laser power. When tcne is laser-heated at ambient pressure, there are two broad UV Raman peaks about 1,405 cm⁻¹ and 1,604 cm⁻¹ whereas visible laser Raman excitation results in too high a fluorescent background to show up any Raman modes. Raman spectrum of tcne laser heated at 40 GPa show broad peaks indicative of multiphase formation. The spectrum has additional modes at lower frequencies, and comparison with calculated Raman frequencies points to possible formation of α-C₃N₄.     

Stability and nonlinear optical properties of ZnO nanoparticles

Photoluminescence (PL) of ZnO nanoparticles of different surface states and sizes grown by several methods has been measured. The origin of luminescence and dependence of the luminescence spectrum shape and intensity on 325 nm excitation laser power are studied. Strong ultraviolet emission at 3.26 eV, weak violet emission around 3.12 eV and weak green emission at 2.40 eV have been observed in 16 nm nanoparticles capped by octylamine grown by non-hydrolytic method. The nanoparticles are stable under high power laser radiation and their PL intensity increases nonlinearly with an increasing laser power. As the nanoparticle size decreases to 12 nm, high power laser produces nonradiative centers which may quench the luminescence in a degree. Nanoparticles of 8 nm capped by PVP and uncapped nanoparticles of 14 nm are unstable and their luminescence depends on the excitation laser power. High power laser can quench O vacancy emission and enhance ultraviolet emission in PVP capped nanoparticles while vacancy emission can not be quenched in uncapped nanoparticles.     

Fluorescence rejection in resonance Raman spectroscopy using a picosecond-gated intensified charge-coupled device camera

A Raman instrument was assembled and tested that rejects typically 98-99% of background fluorescence. Use is made of short (picosecond) laser pulses and time-gated detection in order to record the Raman signals during the pulse while blocking most of the fluorescence. Our approach uses an ultrafast-gated intensified charge-coupled device (ICCD) camera as a simple and straightforward alternative to ps Kerr gating. The fluorescence rejection efficiency depends mainly on the fluorescence lifetime and on the closing speed of the gate (which is about 80 ps in our setup). A formula to calculate this rejection factor is presented. The gated intensifier can be operated at 80 MHz, so high repetition rates and low pulse energies can be used, thus minimizing photodegradation. For excitation we use a frequency-tripled or -doubled Ti : sapphire laser with a pulse width of 3 ps; it should not be shorter in view of the required spectral resolution. Other critical aspects tested include intensifier efficiency as a function of gate width, uniformity of the gate pulse across the spectrum, and spectral resolution in comparison with ungated detection. The total instrumental resolution is 7 cm(-1) in the blue and 15 cm(-1) in the ultraviolet (UV) region. The setup allows one to use resonance Raman spectroscopy (RRS) for extra sensitivity and selectivity, even in the case of strong background fluorescence. Excitation wavelengths in the visible or UV range no longer have to be avoided. The effectiveness of this setup is demonstrated on a test system: pyrene in the presence of toluene fluorescence (lambda(exc) = 257 nm). Furthermore, good time-gated RRS spectra are shown for a strongly fluorescent flavoprotein (lambda(exc) = 405 nm). Advantages and disadvantages of this approach for RRS are discussed.     

High-energy picosecond near-vacuum ultraviolet pulses generated by sum-frequency mixing of an amplified Ti:sapphire laser

We demonstrate high-energy picosecond near-vacuum ultraviolet laser pulse generation. Frequency quadrupling is achieved by noncollinear sum-frequency mixing of the fundamental and the third harmonic of a two-stage Ti:sapphire amplifier in beta-BaB(2)O(4) crystal. UV pulses with energies of approximately 10 mJ tunable from 195 to 210 nm at a 10 Hz repetition rate are obtained.     

In situ measurement on ultraviolet dielectric components by a pulsed top-hat beam thermal lens

A simple and sensitive mode-mismatched thermal lens (TL) technique with a pulsed top-hat beam excitation and a near-field detection scheme is developed to measure in situ the thermoelastic and the thermooptical responses of ultraviolet (UV) dielectric coatings as well as bulk materials under excimer laser (193- or 248-nm) irradiations. Owing to its high sensitivity, the TL technique can be used for measurements at fluences far below the laser-induced damage threshold (LIDT). We report on the measurement of both linear and nonlinear absorption of the UV dielectric coatings and bulk materials as well as the investigation of time-resolved predamage phenomena, such as laser conditioning of highly reflective dielectric coatings and irradiation-induced changes of a coating's various properties. The pulsed TL technique is also a convenient technique for accurate measurement of the LIDT of dielectric coatings and for distinguishing different damage mechanisms: thermal-stress-induced damage or melting-induced damage.     

Capillary electrophoresis coupled on-line with ultraviolet resonance Raman spectroscopy

Capillary electrophoresis (CE) and resonance Raman spectroscopy (RRS) with excitation in the deep ultraviolet (UV) region (lambda(ex): 244 or 257 nm) were coupled on-line. The potential of this hyphenated technique, denoted as CE-UV-RRS, for analyte confirmation/identification purposes was explored with aromatic sulfonic acids and nucleotides as test compounds. Good-quality UV-RRS spectra could be recorded on-the-fly. Identification limits for the nucleotides were in the 10-125 microg/mL range. The RRS spectra showed sufficient characteristic features to enable analyte confirmation. In addition, the identification power of UV-RRS was studied with substituted pyrenes as model compounds. The compounds were distinguishable on the basis of their RRS spectra at 244 nm.     

Return flux budget of polychromatic laser guide stars

The polychromatic laser guide star (PLGS) is one of the solutions proposed to extend the sky coverage by large telescopes to 100% by enabling a complete knowledge of all perturbation orders of the wavefront. The knowledge of the tip-tilt is deduced from the monitoring of the chromatic components of the PLGS, from 330 nm to the visible or near infrared. Here we study the original scheme to create the PLGS by resonant excitation of the mesospheric sodium by two pulsed lasers (tens of kilohertz repetition rate, tens of watts average power, tens of nanoseconds pulse duration), at 589 and 569 nm, respectively. The efficiency of this process is investigated numerically by means of both Bloch equation and rate equation models. The influence of numerous laser parameters is studied. In the best case, having optimized all laser parameters, the return flux at 330 nm should not exceed 7x10(4) photons/s/m2 for 2x18 W laser average power at the mesosphere. This maximum is obtained for a modeless laser whose spot diameter corresponds to 4 times the diffraction limit. For a diffraction-limited spot, the return flux falls down to 4x10(4)photons/s/m2.     

Raman spectroscopy of single-wall boron nitride nanotubes

Single-wall boron nitride nanotubes samples synthesized by laser vaporization of a hexagonal BN target under a nitrogen atmosphere are studied by UV and visible Raman spectroscopy. We show that resonant conditions are necessary for investigating phonon modes of BNNTs. Raman excitation in the UV (229 nm) provides preresonant conditions, allowing the identification of the A1 tangential mode at 1370 cm(-1). This is 5 cm(-1) higher than the E(2g) mode in bulk h-BN. Ab initio calculations show that the lower frequency of bulk h-BN with respect to large diameter nanotubes and the single sheet of h-BN is related to a softening of the sp2 bonds in the bulk due to interlayer interaction.     

Generation of 224-nm radiation by stimulated Raman scattering of ArF excimer laser radiation in a mixture of H2 and D2

Raman shifting of tunable ArF excimer laser radiation in a mixture of H(2) and D(2) produces tunable radiation in the 224-nm region as a result of Stokes shifting the frequency of the fundamental radiation (193 nm) once in both H(2) and D(2). At a total pressure of 25 bars, a 19% H(2) in D(2) mixture is found to provide a maximum conversion efficiency (2.5%) to the 224-nm range. Both fundamental and 224-nm radiation were used to record laser-induced fluorescence excitation spectra of nitric oxide produced in an oxyacetylene flame. From the excitation spectra, we determined the tuning range of the 224-nm radiation to be 270 cm(-1) with a linewidth of 0.9 cm(-1), which is similar to the fundamental laser radiation. We derived the exact Raman shift of the generated radiation by comparing both excitation spectra which was found to be 7142.3(5) cm(-1).     

Ultraviolet native fluorescence detection in capillary electrophoresis using a metal vapor NeCu laser

Ultraviolet (UV) excitation for laser-induced native fluorescence (LINF) detection in capillary electrophoresis (CE) offers impressive performance figures of merit when assaying peptides containing tyrosine or tryptophan residues, catecholamines, indolamines, and a number of other classes of analytes with appreciable fluorescence when excited by UV radiation. One of the largest drawbacks of native fluorescence detection schemes in CE-LINF systems has been the expense and the complexity of the lasers required for excitation in the deep UV wavelength range of 200-300 nm. An improved "turnkey" NeCu laser operating at 248.6 nm interfaced to a sheath flow-based CE system obtains a performance similar to that of large frame frequency-doubled Ar ion lasers. The detection limits for serotonin and dopamine (27 nM and 8 microM, respectively, for approximately 3-nL injection) are similar to those obtained using a frequency-doubled Ar ion laser at 257 nm (21 nM and 8 microM, respectively). An example of the detection of serotonin-related analytes from a single-cell electropherogram demonstrates the performance of such a system for mass-limited measurements.     

ULTRA: A Unique Instrument for Time-Resolved Spectroscopy

We report the development of a high-sensitivity time-resolved infrared and Raman spectrometer with exceptional experimental flexibility based on a 10-kHz synchronized dual-arm femtosecond and picosecond laser system. Ultrafast high-average-power titanium sapphire lasers and optical parametric amplifiers provide wavelength tuning from the ultraviolet (UV) to the mid-infrared region. Customized silicon, indium gallium arsenide, and mercury cadmium telluride linear array detectors are provided to monitor the probe laser intensity in the UV to mid-infrared wavelength range capable of measuring changes in sample absorbance of ΔOD ~ 10(-5) in 1 second. The system performance is demonstrated for the time-resolved infrared, two-dimensional (2D) infrared, and femtosecond stimulated Raman spectroscopy techniques with organometallic intermediates, organic excited states, and the dynamics of the tertiary structure of DNA.     

Standoff detection of high explosive materials at 50 meters in ambient light conditions using a small Raman instrument

We have designed and demonstrated a standoff Raman system for detecting high explosive materials at distances up to 50 meters in ambient light conditions. In the system, light is collected using an 8-in. Schmidt-Cassegrain telescope fiber-coupled to an f/1.8 spectrograph with a gated intensified charge-coupled device (ICCD) detector. A frequency-doubled Nd : YAG (532 nm) pulsed (10 Hz) laser is used as the excitation source for measuring remote spectra of samples containing up to 8% explosive materials. The explosives RDX, TNT, and PETN as well as nitrate- and chlorate-containing materials were used to evaluate the performance of the system with samples placed at distances of 27 and 50 meters. Laser power studies were performed to determine the effects of laser heating and photodegradation on the samples. Raman signal levels were found to increase linearly with increasing laser energy up to approximately 3 x 10(6) W/cm2 for all samples except TNT, which showed some evidence of photo- or thermal degradation at higher laser power densities. Detector gate width studies showed that Raman spectra could be acquired in high levels of ambient light using a 10 microsecond gate width.     

Near-infrared excited Raman optical activity

Measurements of near-infrared scattered circular polarization Raman optical activity (SCP-ROA) are presented using laser excitation at 780 nm for samples of S-(-)-alpha-pinene and L-alanyl-L-alanine. These are the first measurements of ROA outside the blue-to-green visible region between 488 and 532 nm. Comparison of Raman and ROA intensities measured with excitation at 532 and 780 nm demonstrate that the expected frequency to the fourth-power dependence for Raman scattering and the corresponding fifth-power dependence for ROA are observed. It can be concluded that, to within this frequency dependence, the same level of efficiency of Raman and ROA measurements using commercial instrumentation with 532 nm excitation is maintained with the change to near-infrared excitation at 780 nm.     

Investigation of optical fibers for gas-phase, ultraviolet laser-induced-fluorescence (UV-LIF) spectroscopy

We investigate the feasibility of transmitting high-power, ultraviolet (UV) laser pulses through long optical fibers for laser-induced-fluorescence (LIF) spectroscopy of the hydroxyl radical (OH) and nitric oxide (NO) in reacting and non-reacting flows. The fundamental transmission characteristics of nanosecond (ns)-duration laser pulses are studied at wavelengths of 283 nm (OH excitation) and 226 nm (NO excitation) for state-of-the-art, commercial UV-grade fibers. It is verified experimentally that selected fibers are capable of transmitting sufficient UV pulse energy for single-laser-shot LIF measurements. The homogeneous output-beam profile resulting from propagation through a long multimode fiber is ideal for two-dimensional planar-LIF (PLIF) imaging. A fiber-coupled UV-LIF system employing a 6 m long launch fiber is developed for probing OH and NO. Single-laser-shot OH- and NO-PLIF images are obtained in a premixed flame and in a room-temperature NO-seeded N(2) jet, respectively. Effects on LIF excitation lineshapes resulting from delivering intense UV laser pulses through long fibers are also investigated. Proof-of-concept measurements demonstrated in the current work show significant promise for fiber-coupled UV-LIF spectroscopy in harsh diagnostic environments such as gas-turbine test beds.     

Ultrafast Solar‐Blind Ultraviolet Detection by Inorganic Perovskite CsPbX3 Quantum Dots Radial Junction Architecture

Inorganic CsPbX₃ (X = Cl, Br, I, or hybrid among them) perovskite quantum dots (IPQDs) are promising building blocks for exploring high performance optoelectronic applications. In this work, the authors report a new hybrid structure that marries CsPbX₃ IPQDs to silicon nanowires (SiNWs) radial junction structures to achieve ultrafast and highly sensitive ultraviolet (UV) detection in solar‐blind spectrum. A compact and uniform deployment of CsPbX₃ IPQDs upon the sidewall of low‐reflective 3D radial junctions enables a strong light field excitation and efficient down‐conversion of the ultraviolet incidences, which are directly tailored into emission bands optimized for a rapid photodetection in surrounding ultrathin radial p‐i‐n junctions. A fast solar‐blind UV detection has been demonstrated in this hybrid IPQD‐NW detectors, with rise/fall response time scales of 0.48/1.03 ms and a high responsivity of 54 mA W^?1@200 nm (or 32 mA W^?1@270 nm), without the need of any external power supply. These results pave the way toward large area manufacturing of high performance Si‐based perovskite UV detectors in a scalable and low‐cost procedure.     

UV resonance Raman detection and quantitation of domoic acid in phytoplankton

Cultures of the phytoplankton diatom, Pseudonitzschia multiseries, have been harvested under controlled growth conditions ranging from late logarithmic to late stationary phase (17-58 days). The amount of domoic acid (DA) present in the growth media and in the homogenized cells has been determined by HPLC. Defined samples of media, homogenized cells, whole cells, and whole cells in media have been laser excited at 251 nm for the purpose of selectively exciting intense UV resonance Raman spectra from DA in the samples. Neither media nor cell component spectra from algae seriously interfere with DA spectra. The spectral cross sections for the dominant 1652-cm-1 mode of DA have been determined for 242-, 251-, and 257-nm excitation. Maximum sensitivities are achieved with 251-nm excitation because cross sections for DA are a maximum, and interference from other algal components becomes very small. DA concentrations that have been determined with 251-nm excitation by resonance Raman methods correlate closely with values determined independently with HPLC, especially at higher DA concentrations. The UV resonance Raman analysis of DA in phytoplankton algae is shown to be very sensitive and quantitative as well as rapid and nonintrusive.