Processing of C<Subscript>60</Subscript> thin films by Matrix-Assisted Pulsed Laser Evaporation (MAPLE)

Thin films of fullerenes (C₆₀) were deposited onto silicon using matrix-assisted pulsed laser evaporation (MAPLE). The deposition was carried out from a frozen homogeneous dilute solution of C₆₀ in anisole (0.67 wt%), and over a broad range of laser fluences, from 0.15 J/cm² up to 3.9 J/cm². MAPLE has been applied for deposition of fullerenes for the first time and we have studied the growth of thin films of solid C₆₀. The fragmentation of C₆₀ fullerene molecules induced by ns ablation in vacuum of a frozen anisole target with C₆₀ was investigated by matrix-assisted laser desorption/ionization (MALDI). Our findings show that intact fullerene films can be produced with laser fluences ranging from 0.15 J/cm² up to 1.5 J/cm².     

Comparative Raman study of the Ti complex Cp2Ti(η2-C60) · C6H5CH3 and TixC60 films

Raman spectra from the first Ti fullerene complex Cp ₂Ti(η²-C₆₀) · C₆H₅CH₃ are presented. Compared to spectra of pure C₆₀, the spectra of the Ti complex exhibit a number of new peaks due to the symmetry lowering for C₆₀. The A _g(2) mode is downshifted by 12 cm⁻¹ compared to C₆₀, which corresponds to a charge transfer of one electron per Ti-C₆₀ bond. This value (6 cm⁻¹ for one transferred electron) is identical to the downshift of the A _g(2) mode in alkali metal fullerides with ionic bonding. The spectra of Cp ₂Ti(η²-C₆₀) · C₆H₅CH₃ were compared to the spectra of evaporated Ti_xC₆₀ films. The A _g(2) mode in Ti₄C₆₀ showed a downshift of about 25 cm⁻¹ compared to pure C₆₀, which corresponds to a charge transfer of one electron per Ti atom; this is similar to the ionic alkali metal fullerides and different from η²-C₆₀-type bonding. From Fizika Tverdogo Tela, Vol. 44, No. 3, 2002, pp. 483–485. Original English Text Copyright ? 2002 by Talyzin, Jansson, Usatov, Burlakov, Shur, Novikov. This article was submitted by the authors in English.     

CO2-laser isotope separation of tritium with pentafluoroethane-T (C2TF5)

Isotope separation of tritium by CO₂ laser-induced multiphoton dissociation (MPD) of C₂TF₅ is reported for the first time. The MPD spectrum obtained for C₂TF₅ comprised a broad peak at about 940 cm^–1 where C₂HF₅ was nearly transparent. The unimolecular dissociation of C₂TF₅ was induced with much lower laser fluence than that for CTF₃, another working molecule we proposed for laser isotope separation of tritium. The mechanisms and kinetics of the dissociation of C₂TF₅ and C₂HF₅ were investigated under various experimental conditions: laser frequency, pulse energy, pulse duration, tritium concentration, sample pressure, buffer gas pressure and irradiation geometry. Single-step separation factors exceeding 500 were achieved with the most efficientP(20) line in 00^o–10^o0 transition at 944.2 cm^–1.     

Electronic properties of C60 single crystals doped with lithium by electrodiffusion

Diffusion of lithium cations in C₆₀ single crystals driven by electric field has been detected and studied. A novel technique for fullerene crystal doping based on injection of ions through a “superionic crystal/C₆₀ single crystal” heterojunction has been suggested. It has been found that lithium doping of C₆₀ single crystals brings about an ESR signal, and this signal as a function of time has been investigated. The electronic conductivity in Li_xC₆₀ crystals has a nonmetallic nature. Reflection spectra measured in the IR band have shown that the reflectivity due to free electrons gradually decreases with time, which correlates with the evolution of signals due to ESR and microwave conductivity. Lithium doping of crystals increases the oscillator strength of the T _1u (4) vibrational mode and shifts it to lower frequencies (from 1429 cm⁻¹ to 1413 cm⁻¹), which indicates that one electron is present at the C₆₀ molecule, and this fact may be treated as evidence that the LiC₆₀ phase is generated in a C₆₀ crystal. Zh. éksp. Teor. Fiz. 116, 1706–1722 (November 1999)     

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.     

Sensitive intracavity photoacoustic measurements with a CO2 waveguide laser

A photoacoustic intracavity configuration is presented; a resonant photoacoustic cell excited in its first longitudinal mode is placed inside the cavity of a CO₂ waveguide laser. Due to the high laser power and the sharp intracavity focus, saturation effects occur in the excitation and relaxation process of absorbing C₂H₄ molecules. A more optimal configuration is applied to measure the C₂H₄ emission of several Rumex species. A detection sensitivity of 6 ppt (parts per trillion) C₂H₄ is reached, equivalent to a minimal detectable absorption of 1.8×10^–10 cm^–1.     

Solution‐Based Phototransformation of C60 Nanorods: Towards Improved Electronic Devices

A modified liquid–liquid interface precipitation synthesis of C₆₀ nanorods, effects and opportunities following an in situ photochemical transformation in the liquid state, and an electronic characterization using a field‐effect transistor (FET) geometry are reported. The nanorods feature a high aspect ratio of ≈10³ and a notably small average diameter of 172 nm. Interestingly, it is found that a decreased nanorod diameter appears to correlate with distinctly improved electronic properties, and an average electron mobility of 0.30 cm² V^?1 s^?1, as measured in a FET geometry, is reported for as‐grown nanorods, with the peak value being an impressive 1.0 cm² V^?1 s^?1. A photoexposure using green laser light (λ = 532 nm) is demonstrated to result in the formation of a polymer‐C₆₀ shell encapsulating a monomer‐C₆₀ bulk; such photo‐transformed nanorods exhibit an electron mobility of 4.7 × 10^?3 cm² V^?1 s^?1. It is notable that the utilized FET geometry only probes the polymer‐C₆₀ nanorod surface shell, and that the monomer‐C₆₀ bulk is anticipated to exhibit a higher mobility. Importantly, photoexposed nanorods can be conveniently processed as a stabile dispersion in common hydrophobic solvents, and this finding is attributed to the insoluble character of the polymer‐C₆₀ shell.     

Study of opto-mechanical characteristics of interaction of ultrashort laser pulses with polymer materials

The opto-mechanical characteristics, such as the specific mechanical recoil momentum, the specific impulse, and the energy efficiency, of the laser ablation of flat polymer targets ((C₂F₄) _n , (CH₂O) _n ) have been determined experimentally for the first time for the case of excitation with femtosecond pulses (τ ∼ 45–70 fs) of UV-IR (λ ∼ 266, 400, 800 nm) laser radiation (I ₀ up to 10¹⁵ W/cm²) under normal atmospheric and vacuum (p ∼ 10⁻⁴ mbar) conditions. The efficiency of mechanical recoil momentum generation is analyzed for various regimes of the laser irradiation.     

纳秒激光诱导C60分子碎裂中轻碎片离子C+n(n＜30)的产生机理研究

采用飞行时间质谱计测量了纳秒激光诱导C₆₀分子碎裂中轻碎片离子C⁺_n(n≤11)的初始平均动能,结果显示轻碎片离子具有相同的初始平均动能(约为0.34eV),并且该动能在一定范围内不随激光通量的变化而明显改变.结合前人的实验结果,对纳秒激光诱导C₆₀分子碎裂中轻碎片离子C⁺_n(n＜30)的主要产生模式作了新的阐述,即C< 关键词： 飞行时间质谱计 轻碎片离子 笼形结构塌陷 初始动能     

Theory for the ultrafast dynamics of excited clusters: interplay between elementary excitations and atomic structure

We present a theoretical study of the short-time relaxation of clusters in response to ultrafast excitations using femtosecond laser pulses. We analyze the excitation of different types of clusters (Hg_n, Ag_n, Si_n, C₆₀ and Xe_n) and classify the relaxation dynamics in three different regimes, depending on the intensity of the exciting laser pulse. For low-intensity pulses (I<10¹² W/cm²) we determine the time-dependent structural changes of clusters upon ultrashort ionization and photodetachment. We also study the laser-induced non-equilibrium fragmentation and melting of Si_n and C₆₀ clusters, which occurs for moderate laser intensities, as a function of the pulse duration and energy. As an example for the case of high intensities (I>10¹⁵ W/cm²), the explosion of clusters under the action of very intense ultrashort laser fields is described. Received: 26 November 1999 / Published online: 2 August 2000     

Selective optothermal detection of NO2 and H2O with a frequency-tuned CO waveguide laser

The results are reported of the CO-laser optothermal (OT) detection of impurity gases when their absorption spectra overlap with those of an interfering gas. The influence of the latter was avoided using low gas pressures corresponding to a maximum of the OT sensitivity. Frequency tuned in the 5.2–6.3 m wavelength range, ¹²C¹⁶O and ¹³C¹⁶O waveguide lasers were used. The fine frequency tuning at 490 MHz was achieved for 150 laser transitions of both molecules. The OT sensitivity was estimated by NO₂ detection in the presence of water vapor. The minimal detectable concentration proved to be 60 ppb at P _19–18(14) transition of a ¹²C¹⁶O laser for NO₂ and 75 ppb on P _12–11(13) transition of a ¹³C¹⁶O laser for H₂O.     

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.     

Electron-impact ionization and dissociation of C<Subscript>2</Subscript>D<Superscript>+</Superscript>

Absolute cross sections for electron-impact single ionization, dissociative excitation and dissociative ionization of the ethynyl radical ion (C₂D⁺)^+) have been measured for electron energies ranging from the corresponding reaction thresholds to 2.5 keV. The animated crossed electron-ion beam experiment is used and results have been obtained for the production of C₂D²⁺, C²⁺, C₂⁺_2^+ , CD⁺, C⁺ and D⁺. The maximum of the cross section for single ionization is found to be (2.01 ± 0.02) × 10^-17 cm², at the incident electron energy of 105 eV. Absolute total cross sections for the various singly charged fragments production are observed to decrease by a factor of almost three, from the largest cross-section measured for C⁺, over C₂⁺_2^+ and CD⁺ down to that of D⁺. The maxima of the cross sections are obtained to be (14.5 ± 0.5) × 10^-17 cm² for C₂⁺_2^+, (12.1 ± 0.1) × 10^-17 cm² for CD⁺, (27.7 ± 0.2) × 10^-17 cm² for C⁺ and (11.1 ± 0.8) × 10^-17 cm² for D⁺. The smallest cross section is measured to be (1.50 ± 0.04) × 10^-18 cm² for the production of the doubly charged ion C²⁺. Individual contributions for dissociative excitation and dissociative ionization are determined for each singly-charged product. The cross sections are presented in closed analytic forms convenient for implementation in plasma simulation codes. Kinetic energy release distributions of dissociation fragments are seen to extend from 0 to 6 eV for the heaviest fragment C₂⁺_2^+, up to 11.0 eV for CD⁺, 14.2 eV for C⁺ and 11.2 eV for D⁺ products.     

Infrared-microwave two-photon spectroscopy with13C16O2 and12C18O2 lasers of the ν2-band of ammonia

A tunable microwave frequency was added to, or subtracted from fixed frequency¹³C¹⁶O₂ and¹²C¹⁸O₂ laser lines using the nonlinearity of molecular absorptions. In this way the frequency of 30 transitions of the ν₂-band of ammonia were measured with an accuracy of ±0.0005 cm⁻¹. A further four transitions were measured with an accuracy of ±0.0001 cm⁻¹ by saturating the two-photon transition and observing the Lamb dip. For laser lines up to 11 GHz off-resonant with in frared transitions Doppler-limited signals were observed with microwave power densities of only 10 mW/cm² using a wide-band intracavity cell.     

Ultrafast motion of liquids C2H4Cl2 and C2H4Br2 studied with a femtosecond laser

Transient optical Kerr effect of liquids C₂H₄Cl₂ and C₂H₄Br₂ is investigated, for the first time to our knowledge, with a femtosecond (fs) probe laser delayed with respect to a coherent fs pump laser. Coherent coupling and electronic Kerr signals are observed around zero delay when pump and probe overlap. Persisting after the pump-probe overlap are Kerr signals arising from the torsional and other intramolecular vibrations of the trans and gauche conformations; Kerr signals arising from the intermolecular motion are also observed. Vibrational quantum interference is only observed in liquid C₂H₄Br₂ and the related beats data are fitted with the torsional vibrations, 91 cm⁻¹ (gauche) and 132 cm⁻¹ (trans), and the CCBr angle-bending vibrations, 231 cm⁻¹ (gauche) and 190 cm⁻¹ (trans), with dephasing times, 0.45 ps, 0.45 ps, 2 ps, and 1.5 ps, respectively. These vibrational frequencies agree with those obtained in the frequency-domain. That no vibrational mode is observed for C₂H₄Cl₂ might be attributed to ineffective Raman-pumping. Kerr signals observed after the pump-probe overlap are Fourier transformed to give the spectra of the intermolecular motion and the vibrational spectrum, which agrees with the one observed in the infrared absorption and/or Raman scattering heretofore.     

A comparative study of the energy migration and energy transfer in highly doped Nd:YAG single crystal

The donor-donor (D-D) energy migration interaction parameter C_DD in high-concentration Nd³⁺-doped YAG laser crystal is estimated, for the first time, by using the Yokota-Tanimoto (Y-T) model and the spectral overlap model (SOM) of Kushida. Firstly, the experimental luminescence decay curves of ⁴F_3/2 state of Nd³⁺ ions in YAG laser crystal at room temperature for 2.0 and 3.0 at% Nd³⁺ concentrations reported by Mao are fitted successfully by using the Y-T model and the parameter C_DD is obtained to be 1.50×10⁻³⁹ cm⁶/s. Secondly, the parameter C_DD is also directly calculated by using the SOM of Kushida: C_DD is calculated to be 2.73×10⁻³⁹ cm⁶/s. By comparing the energy migration interaction parameter C_DD and the donor-acceptor (D-A) energy transfer interaction parameter C_DA (1.794×10⁻⁴⁰ cm⁶/s), it is concluded that energy migration rate between Nd³⁺ ions in YAG laser crystal was about 11 times larger than energy transfer rate, and that energy migration would play a very important role in high-concentration Nd³⁺ -doped YAG laser crystal.     

Rovibrational constants for the ground state and ν8 = 1 state of ethylene-d3 (C2HD3) by high-resolution FTIR spectroscopy

The Fourier transform infrared (FTIR) spectrum of the ν₈ fundamental band of ethylene-d₃ (C₂HD₃) was recorded with a unapodized resolution of 0.0063 cm⁻¹ in the wavenumber region of 840–980 cm⁻¹. By assigning and fitting a total of 738 infrared transitions using a Watson’s A-reduced Hamiltonian in the I^r representation, rovibrational constants for the upper state (ν₈ = 1) up to all five quartic centrifugal distortion terms were derived for the first time. The root-mean-square (rms) deviation of the fit was 0.00076 cm⁻¹. The ground state rovibrational constants of C₂HD₃ were also determined for the first time by a fit of 450 combination-differences from the present infrared measurements, with rms deviation of 0.00075 cm⁻¹. Local frequency perturbations were not detected in the C-type ν₈ band of C₂HD₃ which is centred at 918.73199 ± 0.00007 cm⁻¹.     

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.     

Detection of C2H2 and HCl using mid-infrared degenerate four-wave mixing with stable beam alignment: towards practical in situ sensing of trace molecular species

A stable and convenient optical system to realize the forward phase-matching geometry for degenerate four-wave mixing (DFWM) is demonstrated in the mid-infrared spectral region by measuring DFWM signals generated in acetylene (C₂H₂) and hydrogen chloride (HCl) molecules by probing the fundamental ro-vibrational transitions. IR laser pulses tunable from 2900 cm^?1 to 3350 cm^?1 with a 0.025 cm^?1 linewidth were obtained using a laser system composed of an injection seeded Nd:YAG laser, a dye laser, and a frequency mixing unit. At room temperature and atmospheric pressure, a detection limit of 35 ppm (～ 9.5×10¹⁴ molecules/cm³) for C₂H₂ was achieved in a gas flow of a C₂H₂/N₂ mixture by scanning the P(11) line of the (010(11)⁰)–(0000⁰0⁰) band. The detection limit of the HCl molecule was measured to be 25 ppm (～6.8×10¹⁴ molecules/cm³) in the same environment by probing the R(4) line. The dependences of signal intensities on molecular concentrations and laser pulse energies were demonstrated using C₂H₂ as the target species. The variations of the signal line shapes with changes in the buffer gas pressures and laser intensities were recorded and analyzed. The experimental setup demonstrated in this work facilitates the practical implementation of in situ, sensitive molecular species sensing with species-specific, spatial and temporal resolution in the spectral region of 2.7–3.3 μm (3000–3700 in cm^?1), where various molecular species important in combustion have absorption bands.     

Experimental study of optical gas-dynamic processes of polymeric material ablation by ultrashort laser pulses

Optical gas-dynamic processes occurring in polymeric targets ((CH₂O) _n , (C₂F₄) _n ) exposed to ultrashort laser pulses (τ _0.5 ∼ 45 − 70 fs; λ _I,II,III = 266, 400, 800 nm; and E/S ∼ 0.1 − 40 J/cm² at r ₀ ∼ 20 μm) were studied under normal conditions and in vacuum (p ∼ 10⁻² Pa). The dynamics of the mass flow from the target surface (m′ ∼ 10⁻⁵ − 10⁻⁴ g/J) was studied and the spectral-energy thresholds of laser ablation, the electron density distribution (n _e ∼ 10¹⁴ − 10¹⁸ cm⁻³), the mass-averaged velocity of the material flow from the target surface (∼ 10³ m/s), and the chemical composition and average temperature in the near-surface plasma formation (T ∼ 5000 K) were determined using interference microscopy, emission spectroscopy, and shadowgraphy.