VUV F<Subscript>2</Subscript> laser ablation of sodium chloride

We report an investigation of the ablation of NaCl crystals at the 157-nm wavelength of the F₂ laser where there is very strong excitonic absorption. Probe-beam deflection and etch-rate measurements show that the interaction is characterised by a low ablation threshold (∼80 mJ cm^-2) and a capability for controllable material removal at the nanometer level. Scanning electron microscopy of the exposed surfaces show this to be microscopically smooth but with fine cracks present. It is demonstrated that micron-scale features can be formed in NaCl using 157-nm laser ablation, a result attributed to the strongly localised optical and thermal nature of the interaction. The results are discussed within the framework of a thermal vaporisation model. Received: 29 May 2002 / Accepted: 17 July 2002 / Published online: 4 November 2002 RID="*" ID="*"Corresponding author. Fax: +44-1482/465606, E-mail: p.e.dyer@hull.ac.uk     

Raman scattering by Hg<Subscript>2</Subscript>F<Subscript>2</Subscript> polycrystals

The Raman spectra of Hg₂F₂ polycrystals are experimentally measured for the first time. The spectra of Hg₂F₂ are interpreted using X-ray diffraction analysis and group-theoretical treatment. The results obtained are discussed in comparison with the spectra of Hg₂Hal₂ crystals.     

Thermodynamic properties and structure of oxyfluorides Rb<Subscript>2</Subscript>KMoO<Subscript>3</Subscript>F<Subscript>3</Subscript> and K<Subscript>2</Subscript>NaMoO<Subscript>3</Subscript>F<Subscript>3</Subscript>

According to the results of calorimetric and structural studies, the Fm{ie1202-1}m phase in K₂NaMoO₃F₃ remains stable at least to 100 K. No ferroelectric transformation assumed earlier has been revealed in a series of Rb₂KMoO₃F₃ samples prepared using various technologies. Only a phase transition of nonferroelectric origin has been observed near 195 K, and its thermodynamic characteristics have been determined. An analysis of the stability of the cubic structure of molybdenum fluorine-oxygen elpasolites-cryolites has been performed in the framework of the hypothesis on strengths of interatomic bonds. The barocaloric effect in Rb₂KMoO₃F₃ has been estimated.     

Spectral characteristics of a Yb-doped Y<Subscript>2</Subscript>O<Subscript>3</Subscript> ceramic laser

We report the experimental observation of random wavelength emission and intensity-dependent central-wavelength shift in a diode-pumped Yb³⁺-doped Y₂O₃ ceramic laser. We show experimentally that, like conventional lasers, the emission of the laser has fixed well-defined transverse modes; however, its instantaneous emission wavelengths change randomly with time. The central wavelength of the laser emission also shifts with the intracavity light intensity. A model was developed to describe the spectral behavior of Yb³⁺-doped lasers. We show that the observed random wavelength emission and central lasing wavelength shift of the laser could be well explained based on the strong reabsorption of light in the gain medium. PACS 42.55.Rz; 42.60.Mi; 42.55.Xi     

Silicon isotope separation utilizing infrared multiphoton dissociation of Si<Subscript>2</Subscript>F<Subscript>6</Subscript> irradiated with two-frequency CO<Subscript>2</Subscript> laser lights

Silicon isotope separation has been performed utilizing the infrared multiphoton dissociation (IRMPD) of Si₂F₆ irradiated with two-frequency CO₂ laser lights. The two-frequency excitation method improved the separation efficiency by keeping the high enrichment factors. For example, Si₂F₆ with the ²⁸Si fraction of 99.4% was obtained at 40.0% dissociation of Si₂F₆ after the simultaneous irradiation of 100 pulses with 966.23 cm^-1 photons (0.089 J/cm²) and 954.55 cm^-1 photons (0.92 J/cm²), while 1000 pulses were needed to obtain 99.0% of ²⁸Si at 27.2% dissociation in the case of single frequency irradiation at 954.55 cm^-1 (0.92 J/cm²). The single-step enrichment factors of ²⁹Si and ³⁰Si increased with increasing Si₂F₆ pressure. The reason for this enhancement has been discussed in terms of the rotational and vibrational relaxations by collisions with ambient gases. PACS 42.62.Cf; 82.30.Lp; 82.50.Bc     

Luminescence and electronic excitations in KBe<Subscript>2</Subscript>BO<Subscript>3</Subscript>F<Subscript>2</Subscript> crystals

This paper reports on a study of the dynamics of electronic excitations in KBe₂BO₃F₂ (KBBF) crystals by low-temperature luminescent vacuum ultraviolet spectroscopy with nanosecond time resolution under photoexcitation by synchrotron radiation. The first data have been obtained on the kinetics of photoluminescence (PL) decay, time-resolved PL spectra, time-resolved PL excitation spectra, and reflection spectra at 7 K; the estimation has been performed for the band gap E _g = 10.6−11.0 eV; the predominantly excitonic mechanism for PL excitation at 3.88 eV has been identified; and defect luminescence bands at 3.03 and 4.30 eV have been revealed. The channels of generation and decay of electronic excitations in KBBF crystals have been discussed.     

Actively mode-locked Tm-Ho:LiYF<Subscript>4</Subscript> and Tm-Ho:BaY<Subscript>2</Subscript>F<Subscript>8</Subscript> lasers

We report on the generation of mode-locking pulse trains with high average output powers from diode-pumped Tm-Ho:LiYF₄ and Tm-Ho:BaY₂F₈ lasers emitting at around 2 μm. The highest output power of 365 mW was obtained with the Tm-Ho:YLF₄ laser, whereas the shortest pulse duration of 120 ps and the widest tunability range of 59 nm was achieved with the Tm-Ho:BaY₂F₈ laser. PACS 42.55.Xi; 42.60.Fc; 42.72.Ai; 42.55.Rz; 42.70.Hj     

Spin dynamics in LiCu<Subscript>2</Subscript>O<Subscript>2</Subscript> and NaCu<Subscript>2</Subscript>O<Subscript>2</Subscript> low-dimensional helical magnets

Comprehensive NMR investigation of low-frequency spin dynamics of LiCu₂O₂ (LCO) and NaCu₂O₂ (NCO) low-dimensional helical magnets in the paramagnetic state has been carried out for the first time. Temperature dependences of the spin–lattice relaxation rate and anisotropy on various LCO/NCO nuclei have been determined at various orientations of single crystals in an external magnetic field. The spatial asymmetry of spin fluctuations in LCO multiferroic has been discovered. The quantitative analysis of the anisotropy of spin–lattice relaxation in LCO/NCO has allowed estimating the contributions of individual neighboring Cu²⁺ ions to the transferred hyperfine field on Li⁺(Na⁺) ions.     

Charge carrier mobility in crystals of the Pb<Subscript>0.67</Subscript>Cd<Subscript>0.33</Subscript>F<Subscript>2</Subscript> superionic conductor

The frequency (ν = 10^?1–10⁷ Hz) dependences σ(ν) of the conductivity of single crystals of the Pb_0.67Cd_0.33F₂ superionic conductor with the fluorite-type structure (CaF₂) in the temperature range of 132–395 K have been studied. The dependences σ(ν) have been discussed in the framework of the hopping relaxation of ionic carriers, which are mobile anions F^?. From experimental curves σ(ν), the direct-current (dc) conductivity σ_dc and the average charge carrier hopping frequency ν_h have been determined. This has made it possible to calculate the charge carrier mobility μ_mob and charge carrier concentration n _mob in these crystals. At room temperature (293 K), the electrical parameters are σ_dc = 1.6 × 10^?4 S/cm, ν_h = 2.7 × 10⁷ Hz, μ_mob = 2.0 × 10^?7 cm²/(s V), and n _mob = 5.1 × 10²¹ cm^?3.     

Effect of deuteration on the thermal properties and structural parameters of the (NH<Subscript>4</Subscript>)<Subscript>2</Subscript>WO<Subscript>2</Subscript>F<Subscript>4</Subscript> oxyfluoride

The thermal properties and structure of (ND₄)₂WO₂F₄ crystals are investigated. It is established that deuteration does not lead to a change in the symmetry of the initial phase Cmcm but considerably decreases the extent of its disordering, which, in turn, brings about a substantial decrease in the phase transition entropy. Apart from the anomalies associated with phase transitions characteristic of the protonic compound, the heat capacity exhibits two additional anomalies. Analysis of the phase diagram of the deuterated crystal reveals a triple point at a pressure p = 0.18 GPa, which is predicted for (NH₄)₂WO₂F₄ at about 0.7 GPa.     

Optical studies of phase transitions in the (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>Ti(O<Subscript>2</Subscript>)F<Subscript>5</Subscript> crystal

Polarization-optical study of twinning and measurements of the Raman spectra and birefringence in oxyfluoride (NH₄)₃Ti(O₂)F₅ were carried out over the temperature range 90–350 K. Phase transitions were detected at temperatures T ₀₁ = 266 K (second-order transition) and T ₀₂ = 225 K (first order). It is assumed that the crystal symmetry is changed as follows: Fm3m ? I4/mmm ? I4/m. Anomalies of the spectral parameters are established in the frequency range of internal vibrations of ammonium ions and Ti(O₂)F₅ complexes. An analysis of the results shows that the transition at T ₀₁ is likely due to small shifts of the tetrahedral groups from their position on the triad axis and that the transition at T ₀₂ is due to fluorine-oxygen ordering of Ti(O₂)F₅ complexes.     

Vibrational spectra of disordered oxyfluoride (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>WO<Subscript>3</Subscript>F<Subscript>3</Subscript>

Comparative analysis of the IR absorption and Raman scattering spectra of a polycrystalline sample of perovskite-type oxyfluoride (NH₄)₃WO₃F₃ has been performed in the frequency range 370–4000 cm^?1 at temperatures from 92 to 303 K, including the transition between the orientationally disordered cubic and low-symmetry phases. The conformation of WO₃F₃ octahedral groups is established and transitional anomalies of the internal modes of these groups and ammonium ions are revealed. Comparative analysis of the IR and Raman spectra suggests that the phase transition under study is mainly related to the ordering of octahedral groups and formation of W-O…H-N hydrogen bonds.     

Upconversion excitations in Pr<Superscript>3+</Superscript>-doped BaY<Subscript>2</Subscript>F<Subscript>8</Subscript> crystal

We report the orange-to-blue and infrared-(IR)-to-blue wavelengths upconversion luminescence in Pr³⁺:BaY₂F₈ crystals. Mechanism of the orange light upconversion into blue ³P₀ state emission was confirmed to be energy transfer between two Pr³⁺ ions in the ¹D₂ state. IR-to-blue upconversion has only been observed under two different color IR pumping. The first resonant step was the ³H₄→¹G₄ ground state absorption transition, and the second resonant transition was the excited state absorption from the ¹G₄ to ¹I₆ and ³P_J levels. A comparison of the efficiency of the IR-to-blue upconversion in several praseodymium activated host is presented and discussed. A model of the IR pumped upconversion praseodymium blue laser is presented and the population inversion conditions are calculated.     

Structural changes during phase transitions and the critical and noncritical order parameters in the (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>Nb(O<Subscript>2</Subscript>)<Subscript>2</Subscript>F<Subscript>4</Subscript> crystal

The structures of two phases of the (NH₄)₃Nb(O₂)₂F₄ crystal, namely, the parent cubic phase and the most distorted low-temperature phase, have been determined from data of an X-ray diffraction experiment performed for a powder sample. The profile and structural parameters have been refined according to the procedure implemented in the DDM program. The results obtained have been discussed with invoking the group-theoretical analysis of the complete order parameter condensate, which takes into account the critical and noncritical atomic displacements and allows the interpretation of the obtained experimental data. It has been found that the most probable sequence of structural transformations occurring in the crystal can be schematically represented in the following form:

High resolution patterning of sapphire by F<Subscript>2</Subscript>-laser ablation

The ablation behavior of single crystalline sapphire with nanosecond laser pulses at 157 nm wavelength is investigated. Ablation rates of about 10 to 100 nm/pulse are obtained at fluences ranging from 1 to 9 J/cm². At moderate fluences, incubation behavior is observed, i.e. ablation starts after material modification by a number of laser pulses. The ablation can be utilized to fabricate sapphire micro-optics. The capability of creating lenses or gratings on the tip of sapphire fibers is demonstrated. Multilevel diffractive optical elements and high resolution gratings with 1 μm period are fabricated on planar sapphire substrates.