A new sample environment for cryogenic nuclear resonance scattering experiments on single crystals and microsamples at P01, PETRA III

In order to carry out orientation dependent nuclear resonance scattering (NRS) experiments on small single crystals of e.g. iron proteins and/or chemical complexes but also on surfaces and other micrometer-sized samples a 2-circle goniometer including sample positioning optics has been installed at beamline P01, PETRA III, DESY, Hamburg. This sample environment is now available for all users of this beamline. Sample cooling is performed with a cryogenic gas stream which allows NRS measurements in the temperature range from 80 up to 400 K. In a first test this new sample environment has been used in order to investigate the orientation dependence of the nuclear inelastic scattering (NIS) signature of (i) a dinuclear iron(II) spin crossover (SCO) system and (ii) a hydrogen peroxide treated metmyoglobin single crystal.     

The sapphire backscattering monochromator at the Dynamics beamline P01 of PETRA III

We report on a high resolution sapphire backscattering monochromator installed at the Dynamics beamline P01 of PETRA III. The device enables nuclear resonance scattering experiments on Mössbauer isotopes with transition energies between 20 and 60 keV with sub-meV to meV resolution. In a first performance test with ¹¹⁹Sn nuclear resonance at a X-ray energy of 23.88 keV an energy resolution of 1.34 meV was achieved. The device extends the field of nuclear resonance scattering at the PETRA III synchrotron light source to many further isotopes like ¹⁵¹Eu, ¹⁴⁹Sm, ¹⁶¹Dy, ¹²⁵Te and ¹²¹Sb.     

Installation of an IR microscope at the nuclear resonance beamline ID18 of ESRF

An IR microscope has been installed at the beamline ID18 at the ESRF in Grenoble, France in order to obtain nuclear inelastic scattering (NIS) data and IR spectra simultaneously. This setup combines the advantages of both spectroscopic methods. The applicability of the installed setup to the study of the spin crossover (SCO) phenomenon in polynuclear iron complexes has been shown.     

A comparison of Raman scattering,resonance Raman scattering,and fluorescence from molecules adsorbed on silver island films

The enhancement of Raman scattering (RS), resonance Raman scattering (RRS), and fluorescence from molecules adsorbed on silver-island films is reported. A heirarchy of enhancements is found: 10⁵ for RS, 10³ for RRS, and 0.1–10 for fluorescence, depending on the quantum yield of the free molecule. Using the framework of the electromagnetic theory of surface-enhanced Raman scattering, generalized to treat molecular resonance phenomena, we develop a unified picture of the role of the surface plasmon resonances, and the surface-induced damping, in the light scattering processes. The observed heirarchy of enhancements is shown to have important spectroscopic consequences.     

Combined dielectric and plasmon resonance for giant enhancement of Raman scattering

Combined dielectric/metal resonators for colossal enhancement of inelastic light scattering are developed and their properties are investigated. It is shown that a record enhancement factor of 2 × 10⁸ can be obtained using these structures. The dielectric resonators are fabricated on Si/SiO₂ substrates where periodic arrays of square 10- to 200-nm-high dielectric pillars are produced via electron-beam lithography and plasma etching. The lateral size a of the pillars varies between 50 and 1500 nm, and their period in the array is 2a. To make a combined dielectric/metal resonator, a nanostructured layer of silver is deposited onto the fabricated periodic dielectric structure by thermal evaporation. It is established that, for a fixed height of the dielectric pillars, the Raman scattering enhancement factor experiences pronounced oscillations as a function of the period (and size) of the pillars. It is shown that these oscillations are determined by the modes of the dielectric resonator and governed by the relation between the excitation laser wavelength and the planar size of the dielectric pillars.     

Single‐crystal X‐ray diffraction and resonant X‐ray magnetic scattering at helium‐3 temperatures in high magnetic fields at beamline P09 at PETRA III

The resonant scattering and diffraction beamline P09 at PETRA III at DESY is equipped with a 14 T vertical field split‐pair magnet. A helium‐3 refrigerator is available that can be fitted inside the magnet's variable‐temperature insert. Here the results of a series of experiments aimed at determining the beam conditions permitting operations with the He‐3 insert are presented. By measuring the tetragonal‐to‐orthorhombic phase transition occurring at 2.1 K in the Jahn–Teller compound TmVO₄, it is found that the photon flux at P09 must be attenuated down to 1.5 × 10⁹ photons s^?1 for the sample to remain at temperatures below 800 mK. Despite such a reduction of the incident flux and the subsequent use of a Cu(111) analyzer, the resonant X‐ray magnetic scattering signal at the Tm L_III absorption edge associated with the spin‐density wave in TmNi₂B₂C below 1.5 K is intense enough to permit a complete study in magnetic field and at sub‐Kelvin temperatures to be carried out.     

A resonance tracking method for stable operation of a near-field scanning optical microscope in liquid environment

We report on the novel design of the near-field scanning optical microscope (NSOM) which operates in liquid environment. A resonance tracking digital scanning method is applied to compensate the resonance shift due to the evaporation of the liquid in the atmospheric pressure. By this method, stable operation of NSOM system is demonstrated by showing topographic images of the metallic grating embedded in liquid environment.     

Raman scattering in crystalline fluorosilicate hexahydrates of iron and manganese at a phase transition

The work reports a Raman scattering study of FeSiF₆·6H₂O and MnSiF₆·6H₂O crystals within the 2–340 K temperature range. The crystals are ordered at low temperatures. Phase transition-induced changes in the spectra have been observed. An analysis of the number and polarization of the Raman lines has permitted determination of the symmetry of the high-and low-symmetry phases. A possible mechanism of the phase transition is proposed. Fiz. Tverd. Tela (St. Petersburg) 39, 929–939 (May 1997)     

Raman scattering as a probe of phonon confinement and surface optical modes in semiconducting nanowires

Raman scattering is shown to be an effective probe of optical and surface optical phonons in highly crystalline semiconducting nanowires (SNWs). We show that the confinement model of Richter et al. well describes the nanowire diameter dependence of the asymmetric broadening of the one-phonon band in Si nanowires observed at ∼520 cm^-1. We also show that the use of high laser flux (∼0.1 mW/μm²) leads to a second mechanism that can asymmetrically broaden the 520 cm^-1 Raman band. This broadening has nothing to do with confinement, and can qualitatively be understood in terms of inhomogeneous laser heating. A model is presented that supports this explanation. The production of SNWs via the vapor–liquid–solid growth mechanism leads, in many cases, to an instability in the nanowire diameter or cross-sectional area. In the second part of this review, we show that this instability activates the surface optical (SO) phonon Raman scattering. Examples of this phenomenon are shown for GaP and ZnS nanowires. The former and latter have, respectively, cylindrical and rectangular cross sections. We show that the cross-sectional shape of the nanowire is important for a quantitative analysis of these SO modes. PACS 78.67.-n; 78.67.Lt; 78.30.-j; 78.30.Fs; 72.10.Di     

Inversion of absorption and scattering at plasmon resonance in nanoparticles with a metallic sheath

Numerical simulation of the optical properties of spherical nanostructures comprising an absorbing (amplifying) insulating core and a metallic sheath is carried out under the conditions of plasmon resonance. A decrease in the absorption by the core is shown to increase the cross sections of absorption and scattering by the nanostructure in the plasmon resonance spectral range. If the core exhibits amplification, an extra resonance arises, causing a change in the dependence of the absorption cross section on the amplification factor. Conditions for such a resonance to appear are considered.     

Advantages of a synchrotron bending magnet as the sample illuminator for a wide‐field X‐ray microscope

In this paper the choice between bending magnets and insertion devices as sample illuminators for a hard X‐ray full‐field microscope is investigated. An optimized bending‐magnet beamline design is presented. Its imaging speed is very competitive with the performance of similar microscopes installed currently at insertion‐device beamlines. The fact that imaging X‐ray microscopes can accept a large phase space makes them very well suited to the output characteristics of bending magnets which are often a plentiful and paid‐for resource. There exist opportunities at all synchrotron light sources to take advantage of this finding to build bending‐magnet beamlines that are dedicated to transmission X‐ray microscope facilities. It is expected that demand for such facilities will increase as three‐dimensional tomography becomes routine and advanced techniques such as mosaic tomography and XANES tomography (taking three‐dimensional tomograms at different energies to highlight elemental and chemical differences) become more widespread.     

Development of a laser-based Raman scattering system for identifying and quantifying major gas species

The construction of a laser-based Raman scattering system for identifying major gas species and quantifying their partial pressures is described. The system incorporates a pulsed laser to minimize the background luminescence. The results obtained at room temperature for N₂ at (365·80·5) nm and for O₂ at (355·80·5) nm are presented.     

Comparison of the Raman detection limit for IRS- and CARS-spectroscopy at excitation near molecular one-photon resonance

The nonlinear Raman methods IRS and CARS are compared according to the signal detectability at excitation of molecules under the condition of one-photon resonance. At one photon resonance it is the background contribution resulting from the scattering molecules themselves that determines the maximum attainable signal to noise ratio. These contributions acting for IRS and CARS respectively are compared. The essential difference between IRS and CARS results from a 3rd order saturation contribution to IRS, which may mask the IRS Raman signal near exact resonance while it does not contribute to CARS. This gives to CARS the preference before IRS at resonance excitation. The situation for IRS with respect to background is similar to that of spontaneous Raman scattering, where the resonance fluorescence — corresponding to the saturation contribution at IRS — masks the resonance Raman signal.     

Observations of wavefront reproduction by stimulated Brillouin and Raman scattering as a function of pump power and waveguide dimensions

Experimental investigations have been made of wavefront reproduction (WFR) by backward stimulated Raman scattering (SRS) and backward stimulated Brillouin scattering (SBS) in CS₂ and C₇H₆O using a linearly polarized ruby pump at λ=0.694 μm. The studies were carried out as a function of the length and cross-section of the optical waveguide and the pump power at the input to the nonlinear medium; curves showing the percentage of nonreproduced backscattered radiation versus power into the waveguide are presented. In all of the cases studied the degree of reproduction by SBS was higher than that by SRS and the efficiency of WFR for both SBS and SRS improved as the pump power into the waveguide was increased, the bore diameter of the lightpipe decreased, and the length of active media decreased.     

Development of a high speed imaging microscope and new software for nuclear track detector analysis

Automated digital imaging optical microscopy is widely used for diagnostic applications in the health care and biology fields and for routine inspection in industrial applications such as semiconductor fabrication. These applications require the imaging of large areas at high speed in order to obtain sufficient data for image processing with good statistics. Track detector analysis also benefits from the rapid acquisition of large areas on the detector surface. We have developed a new microscope system, the HSP-1000, for high speed image acquisition that uses a line sensor camera in place of a traditional CCD camera. Continuous, automatic focusing of the microscope is achieved by means of an optical pick-up system that provides fast feedback for control of distance between the objective and the image surface. Using transmitted light illumination, the microscope is able to digitize a area at resolution in . As a result of continuous stage motion and continuous focusing, we have attained image acquisition speeds that are 50–100 times faster than conventional CCD-based microscope systems. In this paper, we describe a number of aspects of the microscope system including the use of the line sensor and the automatic focus system.     

Investigation of the orientational ordering and anisotropy of the local field in a nematic liquid crystal based on resonance Raman scattering spectra

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 53, No. 3, pp. 437–443, September, 1990.     

Stimulated Raman scattering in carbon dioxide and a measurement of time for V-T energy transfer

A weak Q-switched ruby laser (1 MW, 40 nsec, 0.015 cm^-1 linewidth) was focused into a cell (CO₂, 50 atm). The spectrum of the total output energy (40–50 MW, 25 nsec) was studied. In addition to powerful Brillouin scattering, the first stimulated Raman Stokes line of CO₂ (10 MW) and the first three anti-Stokes Raman lines were observed for the first time in pure CO₂. It was also possible to obtain coherent Raman excitation in a second CO₂ cell for pressure down to 3 atm. This last experimental result has been applied to the measurement of the time for V-T transfer in CO₂.     

Highly reproducible tip‐enhanced Raman scattering using an oxidized and metallized silicon cantilever tip as a tool for everyone

We have successfully improved the reproducibility of tip‐enhancement effect on metallized silicon cantilever tips for characterization of carbon nanotubes. Plasmon resonance tuning relative to an excitation wavelength is crucial for efficient tip‐enhancement, which is accomplished by thermal oxidization and subsequent metallization of commercial silicon tips. Because of the change of the refractive index of the tip from silicon to silicon dioxide, the plasmon resonance of the silver‐coated tip is blue‐shifted showing an enormous enhancement at 532 nm excitation. Highly reproducible tips exhibit an enhancement factor of >100 with a 100% yield. Because the tips are fabricated from commercially available silicon cantilever tips in a simple and robust way, our approach provides an important step of ‘tip‐enhanced Raman spectroscopy for everyone’. Copyright © 2012 John Wiley & Sons, Ltd.