Production of defects in ZBLAN, ZBLAN : Tm3+ and ZBLAN : Cr3+ glasses by ultra-short pulses laser interaction

In this work we have studied pure and thulium- and chromium-doped ZBLAN glasses irradiated by ultra-short laser pulses. A Ti:sapphire CPA system was used, producing a 500 Hz train of pulses, centered at 830 nm, with 375 mu J of energy and 50 fs of duration (FWHM). The beam was focused by a 20 Him lens, producing a converging beam with a waist of 12 pin. The absorption spectra before and after laser irradiation were obtained showing production of color centers in pure, thulium-doped and chromium-doped ZBLAN glasses. A damage threshold of 9.56 TW/cm(2) was determined for ZBLAN. (C) 2007 Elsevier Ltd. All rights reserved.

Time-of-flight two-photon photoemission spectromicroscopy with femtosecond laser radiation

Time-of-flight photoemission spectromicroscopy was used to measure and compare the two-photon photoemission (2PPE) spectra of Cu and Ag nanoparticles with linear dimensions ranging between 40 nm and several 100 nm, with those of the corresponding homogeneous surfaces. 2PPE was induced employing femtosecond laser radiation from a frequency-doubled Ti:sapphire laser in the spectral range between 375 nm and 425 nm with a pulse width of 200 fs and a repetition rate of 80 MHz. The use of a pulsed radiation source allowed us to use a high-resolution photoemission electron microscope as imaging time-of-flight spectrometer, and thus to obtain spectroscopic information about the laterally resolved electron signal. Ag nanoparticle films have been deposited on Si(111) by electron-beam evaporation, a technique leading to hemispherically-shaped Ag clusters. Isolated Cu nanoparticles have been generated by prolonged heating of a polycrystalline Cu sample. If compared to the spectra of the corresponding homogeneous surfaces, the Cu and Ag nanoparticle spectra are characterized by a strongly enhanced total 2PPE yield (enhancement factor up to 70), by a shift (about 0.1 eV) of the Fermi level onset towards lower final state energies, by a reduction of the work function (typically by 0.2 eV) and by a much steeper increase of the 2PPE yield towards lower final state energies. The shift of the Fermi level onset in the nanoparticle spectra has been explained by a positive unit charge (localized photohole) residing on the particle during the time-scale relevant for the 2PPE process (few femtoseconds). The total 2PPE yield enhancement and the different overall shape of the spectra have been explained by considering that the laser frequency was close to the localized surface plasmon resonance of the Cu and Ag nanoparticles. The synchronous oscillations induced by the laser in the metal electrons enhance the near-zone (NZ) field, defined as the linear superposition of the laser field and the field produced in the vicinity of the particles by the forced charge oscillations. From the present measurements it is clear that the NZ field behavior is responsible for the 2PPE enhancement and affects the 2PPE spatial and energy distribution and its dynamics. In particular, its strong spatial dependence allows indirect transitions through real intermediate states to take place in the metal clusters. Such transitions are forbidden by momentum conservation arguments and are thus experimentally much less probable on homogeneous surfaces. Further, we investigated specially tailored moon-shaped small metal nanostructures, whose NZ field was theoretically predicted, and compared the calculation with the laterally resolved 2PPE signal. We could show that the 2PPE signal gives a clear fingerprint of the theoretically predicted spatial dependence of the NZ field. This potential of our method is highly attractive in the novel field of plasmonics.

Entwicklung des Laserionenquellen und -fallenprojekts LIST für Ultraspurendetektion und Grundlagenforschung

Die vorliegende Dissertation beschreibt die Realisation des neuartigen Konzepts der Laserionenquellenfalle für die on-line Produktion exotischer Nuklide und für den Nachweis von Spurenisotopen in Proben mit starken Isobarenkontaminationen. Ziel dieser Entwicklung ist eine wesentliche Steigerung der Isobarenselektivität einer herkömmlichen Laserionenquelle, sowie die Erzeugung zeitlich kontrollierter Ionenpulse mit hervorragender Strahlqualität. Es konnte die prizipielle Funktionsfähigkeit des Systems in Kombination mit einem Titan:Saphir-Lasersystem für die Elemente Gallium, Calcium und Nickel demonstriert und Ionenpulse mit einer minimalen Pulslänge von 1 µs erzeugt werden. Nach ersten Abschätzungen ist die Effizienz des Systems etwa einen Faktor 2500 geringer als die einer herkömmlichen Laserionenquelle. Der zweite Teil der Arbeit beschäftigt sich mit dem spurenanalytischen Nachweis von 99-Tc, mit dem Ziel, das Verhalten von 99-Tc in der Umgebung eines möglichen Endlagers für nukleare Abfälle studieren zu können. Hier wurden erste Studien mit dem kurzlebigen Isomer 99m-Tc zur Wechselwirkung von Tc(VII) mit Huminsäure und Kaolinit durchgeführt. Für den Einsatz der Laserionenquellenfalle in der Ultraspurenanalyse, wurde ein effizientes Anregungsschema für Titan:Saphir-Laser entwickelt und 99-Tc in einer herkömmlichen Ionenquelle nachgewiesen. Der letzte Teil der Arbeit beschreibt Machbarkeitsstudien zum Aufbau einer Laserionenquelle auf Basis eines Titan:Sahphir-Lasersystems, die parallel zu oben genannten Entwicklungen am Oak Ridge National Laboratory durchgeführt wurden. Im Rahmen dieser Messungen wurden Anregungsschemata für die resonante Anregung und Ionisation von Kupfer und Palladium für Titan:Saphir-Laser getestet. Dabei konnte zum ersten Mal frequenzvervierfachtes Laserlicht in einer Laserionenquelle eingesetzt werden. Am ORNL wurden Studien zur Zeitstruktur von Laserionenpulsen, sowie Emittanzmessungen von Laser- und Oberflächenionenstrahlen durchgeführt werden.

Point-by-point inscription of 250 nm period structure in bulk fused silica by tightly focused femtosecond UV pulses

By conducting point-by-point inscription in a continuously moving slab of pure fused silica at the optimal depth (170νm depth below the surface), we have fabricated a 250nm period nanostructure with 30nJ, 300fs, 1kHz pulses from a frequency-tripled Ti:sapphire laser. This is the smallest value for the inscribed period yet reported, and has been achieved with radical improvement in the quality of the inscribed nanostructures in comparison with previous reports.

Point-by-point inscription of 250-nm-period structure in bulk fused silica by tightly-focused femtosecond UV pulses: experiment and numerical modeling

By conducting point-by-point inscription in a continuously moving slab of a pure fused silica at the optimal depth (170 μm depth below the surface), we have fabricated a 250-nm-period nanostructure with 30 nJ, 300 fs, 1 kHz pulses from frequency-tripled Ti:sapphire laser. This is the smallest value for the inscribed period yet reported, and has been achieved with radical improvement in the quality of the inscribed nanostructures in comparison with previous reports. The performed numerical modeling confirms the obtained experimental results.

Quantum dot-based terahertz photoconductive antennas

We present novel Terahertz (THz) emitting optically pumped Quantum Dot (QD) photoconductive (PC) materials and antenna structures on their basis both for pulsed and CW pumping regimes. Full text Quantum dot and microantenna design - Presented here are design considerations for the semiconductor materials in our novel QD-based photoconductive antenna (PCA) structures, metallic microantenna designs, and their implementation as part of a complete THz source or transceiver system. Layers of implanted QDs can be used for the photocarrier lifetime shortening mechanism[1,2]. In our research we use InAs:GaAs QD structures of varying dot layer number and distributed Bragg reflector(DBR)reflectivity range. According to the observed dependence of carrier lifetimes on QD layer periodicity [3], it is reasonable to assume that electron lifetimes can be potentially reduced down to 0.45ps in such structures. Both of these features; long excitation wavelength and short carriers lifetime predict possible feasibility of QD antennas for THz generation and detection. In general, relatively simple antenna configurations were used here, including: coplanar stripline (CPS); Hertzian-type dipoles; bow-ties for broadband and log-spiral(LS)or log-periodic(LP)‘toothed’ geometriesfor a CW operation regime. Experimental results - Several lasers are used for antenna pumping: Ti:Sapphire femtosecond laser, as well as single-[4], double-[5] wavelength, and pulsed [6] QD lasers. For detection of the THz signal different schemes and devices were used, e.g. helium-cooled bolometer, Golay cell and a second PCA for coherent THz detection in a traditional time-domain measurement scheme.Fig.1shows the typical THz output power trend from a 5 um-gap LPQD PCA pumped using a tunable QD LD with optical pump spectrum shown in (b). Summary - QD-based THz systems have been demonstrated as a feasible and highly versatile solution. The implementation of QD LDs as pump sources could be a major step towards ultra-compact, electrically controllable transceiver system that would increase the scope of data analysis due to the high pulse repetition rates of such LDs [3], allowing real-time THz TDS and data acquisition. Future steps in development of such systems now lie in the further investigation of QD-based THz PCA structures and devices, particularly with regards to their compatibilitywith QD LDs as pump sources. [1]E. U. Rafailov et al., “Fast quantum-dot saturable absorber for passive mode-locking of solid-State lasers,”Photon.Tech.Lett., IEEE, vol. 16 pp. 2439-2441(2004) [2]E. Estacio, “Strong enhancement of terahertz emission from GaAs in InAs/GaAs quantum dot structures. Appl.Phys.Lett., vol. 94 pp. 232104 (2009) [3]C. Kadow et al., “Self-assembled ErAs islands in GaAs: Growth and subpicosecond carrier dynamics,” Appl. Phys. Lett., vol. 75 pp. 3548-3550 (1999) [4]T. Kruczek, R. Leyman, D. Carnegie, N. Bazieva, G. Erbert, S. Schulz, C. Reardon, and E. U. Rafailov, “Continuous wave terahertz radiation from an InAs/GaAs quantum-dot photomixer device,” Appl. Phys. Lett., vol. 101(2012) [5]R. Leyman, D. I. Nikitichev, N. Bazieva, and E. U. Rafailov, “Multimodal spectral control of a quantum-dot diode laser for THz difference frequency generation,” Appl. Phys. Lett., vol. 99 (2011) [6]K.G. Wilcox, M. Butkus, I. Farrer, D.A. Ritchie, A. Tropper, E.U. Rafailov, “Subpicosecond quantum dot saturable absorber mode-locked semiconductor disk laser, ” Appl. Phys. Lett. Vol 94, 2511 © 2014 IEEE.

Design, construction, and applications of a high-resolution terahertz time-domain spectrometer

This thesis reports on the design, construction, and initial applications of a high-resolution terahertz time-domain ASOPS spectrometer. The instrument employs asynchronous optical sampling (ASOPS) between two Ti:sapphire ultrafast lasers operating at a repetition rate of approximately 80 MHz, and we thus demonstrate a THz frequency resolution approaching the limit of that repetition rate. This is an order of magnitude improvement in resolution over typical THz time-domain spectrometers. The improved resolution is important for our primary effort of collecting THz spectra for far-infrared astronomy. We report on various spectroscopic applications including the THz rotational spectrum of water, where we achieve a mean frequency error, relative to established line centers, of 27.0 MHz. We also demonstrate application of the THz system to the long-duration observation of a coherent magnon mode in a anti-ferromagnetic yttrium iron oxide (YFeO3) crystal. Furthermore, we apply the all-optical virtual delay line of ASOPS to a transient thermoreflectance experiment for quickly measuring the thermal conductivity of semiconductors.

Design and Applications of a Decade-Spanning Terahertz Frequency Comb Spectrometer: Doppler-limited Rotational Spectroscopy of Methanol and Methanol-OD

This thesis details the design and applications of a terahertz (THz) frequency comb spectrometer. The spectrometer employs two offset locked Ti:Sapphire femtosecond oscillators with repetition rates of approximately 80 MHz, offset locked at 100 Hz to continuously sample a time delay of 12.5 ns at a maximum time delay resolution of 15.6 fs. These oscillators emit continuous pulse trains, allowing the generation of a THz pulse train by the master, or pump, oscillator and the sampling of this THz pulse train by the slave, or probe, oscillator via the electro-optic effect. Collecting a train of 16 consecutive THz pulses and taking the Fourier transform of this pulse train produces a decade-spanning frequency comb, from 0.25 to 2.5 THz, with a comb tooth width of 5 MHz and a comb tooth spacing of ~80 MHz. This frequency comb is suitable for Doppler-limited rotational spectroscopy of small molecules. Here, the data from 68 individual scans at slightly different pump oscillator repetition rates were combined, producing an interleaved THz frequency comb spectrum, with a maximum interval between comb teeth of 1.4 MHz, enabling THz frequency comb spectroscopy.

The accuracy of the THz frequency comb spectrometer was tested, achieving a root mean square error of 92 kHz measuring selected absorption center frequencies of water vapor at 10 mTorr, and a root mean square error of 150 kHz in measurements of a K-stack of acetonitrile. This accuracy is sufficient for fitting of measured transitions to a model Hamiltonian to generate a predicted spectrum for molecules of interest in the fields of astronomy and physical chemistry. As such, the rotational spectra of methanol and methanol-OD were acquired by the spectrometer. Absorptions from 1.3 THz to 2.0 THz were compared to JPL catalog data for methanol and the spectrometer achieved an RMS error of 402 kHz, improving to 303 kHz when excluding low signal-to-noise absorptions. This level of accuracy compares favorably with the ~100 kHz accuracy achieved by JPL frequency multiplier submillimeter spectrometers. Additionally, the relative intensity performance of the THz frequency comb spectrometer is linear across the entire decade-spanning bandwidth, making it the preferred instrument for recovering lineshapes and taking absolute intensity measurements in the THz region. The data acquired by the Terahertz Frequency Comb Spectrometer for methanol-OD is of comparable accuracy to the methanol data and may be used to refine the fit parameters for the predicted spectrum of methanol-OD.

Electron paramagnetic resonance spectral studies on natural sapphire

EPR study of both blue and green sapphire samples confirms the presence of Cr(III) in four different octahedral sites. The g (1.98) value is the same but D values differ for the two the samples. The EPR spectra suggest that the blue sapphire contains more chromium than the green sapphire. No Fe(III) impurity was noted in the EPR spectrum.

Raman spectroscopic study of the antimonate mineral lewisite (Ca,Fe,Na)2(Sb,Ti)2O6(O,OH)7

The mineral lewisite, (Ca,Fe,Na)2(Sb,Ti)2O6(O,OH)7 an antimony bearing mineral has been studied by Raman spectroscopy. A comparison is made with the Raman spectra of other minerals including bindheimite, stibiconite and roméite. The mineral lewisite is characterised by an intense sharp band at 517 cm-1 with a shoulder at 507 cm-1 assigned to SbO stretching modes. Raman bands of medium intensity for lewisite are observed at 300, 356 and 400 cm-1. These bands are attributed to OSbO bending vibrations. Raman bands in the OH stretching region are observed at 3200, 3328, 3471 cm-1 with a distinct shoulder at 3542 cm-1. The latter is assigned to the stretching vibration of OH units. The first three bands are attributed to water stretching vibrations. The observation of bands in the 3200 to 3500 cm-1 region suggests that water is involved in the lewisite structure. If this is the case then the formula may be better written as Ca, Fe2+, Na)2(Sb, Ti)2(O,OH)7 •xH2O.

Raman spectroscopic study of the arsenite minerals leiteite ZnAs2O4 , reinerite Zn3(AsO3)2 and cafarsite Ca5(Ti,Fe,Mn)7(AsO3)12.4H2O

The selected arsenite minerals leiteite, reinerite and cafarsite have been studied by Raman spectroscopy. DFT calculations enabled the position of AsO22- symmetric stretching mode at 839 cm-1, the antisymmetric stretching mode at 813 cm-1, and the deformation mode at 449 cm-1 to be calculated. The Raman spectrum of leiteite shows bands at 804 and 763 cm-1 assigned to the As2O42- symmetric and antisymmetric stretching modes. The most intense Raman band of leiteite is the band at 457 cm-1 and is assigned to the ν2 As2O42- bending mode. A comparison of the Raman spectrum of leiteite is made with the arsenite minerals reinerite and cafarsite.

Raman spectroscopic study of the uranyl titanate mineral betafite (Ca,U)2(Ti,Nb)2O6(OH) –Effect of Metamictization

Raman spectra of the uranyl titanate mineral betafite were obtained and related to the mineral structure. A comparison is made with the spectra of uranyl oxyhydroxide hydrates. Observed bands are attributed to the (UO2)2+ stretching and bending vibrations, U-OH bending vibrations, H2O and (OH)- stretching, bending and libration modes. U-O bond lengths in uranyls and O-H…O bond lengths are calculated from the wavenumbers assigned to the stretching vibrations. Raman bands of betafite are comparable with those of the uranyl oxyhydroxides. The mineral betafite is metamict as is evidenced by the intensity of the UO stretching and bending modes being of lower intensity than expected and with bands that are significantly broader.

The effect of metamictization on the Raman spectroscopy of the uranyl titanate mineral davidite (La,Ce)(Y,U,Fe2+)(Ti,Fe3+)20(O,OH)38

Raman spectra of the uranyl titanate mineral davidite-(La) (La,Ce)(Y,U,Fe2+)(Ti,Fe3+)20(O,OH)38 were analysed and related to the mineral structure. Observed bands are attributed to the TiO and (UO2)2+ stretching and bending vibrations, U-OH bending vibrations, H2O and (OH)- stretching, bending and libration modes. U-O bond lengths in uranyls and O-H…O bond lengths are calculated from the wavenumbers assigned to the stretching vibrations. Raman bands of davidite-(La) are in harmony with those of the uranyl oxyhydroxides. The mineral davidite-(La) is metamict as is evidenced by the intensity of the UO stretching and bending modes being of lower intensity than expected and with bands that are significantly broader.