Growth morphology of {1 0 1} surfaces of l-arginine trifluoroacetate crystals investigated by AFM

Surface morphology of {1 0 1} surfaces of l-arginine trifluoroacetate (LATF) crystals have been investigated by atomic force microscopy (AFM). The dominant growth mechanism of the LATF crystals is the formation and expansion of dislocation spirals. Rectangular dislocation growth hillocks oriented with their longer sides in the [0 1 0] direction, which indicates the fast growth along this direction. Apart from that, typical step morphologies are presented and discussed on the basis of the observations.     

Some studies about the green and red light emitting structures in NaCl1−xBrx:Mn

In this work we present the results obtained from the luminescence spectra and X-ray diffraction as well as transmission electron microscopy, at room temperature on crystals of NaCl_1−xNaBr_x:MnCl₂:0.3% (x=0.00, 0.05, 0.25, and 0.50). The results suggest the existence of structures between the crystal planes (1 1 1) and (2 0 0), which may be associated with different types of Mn²⁺ arrangements, such as dipole complexes, octahedral and rhombohedral structures as well as other possible nanostructures that include mixtures of bromine/chlorine ions. These are responsible for the emission spectra of “as grown” crystals consisting of maxima around 500 nm and 600 nm. The green emission has been usually attributed to rhombohedral/tetrahedral symmetry sites; the present results point out that this is due to Mn–Cl/Br nanostructures with rhombohedral structure. On the other hand when the crystals are thermally quenched from 500 °C to room temperature the structures previously detected present changes. Only a red band appears around 620 nm if the samples are later annealed at 80 °C.     

Relationships between lattice energy and electronic polarizability of AB crystals

The correlations between the electronic polarizability, determined from Clausius-Mosotti equation based on dielectric constant ε, and the lattice energy density u have been established for A^NB^8-N crystals, such as the systems of rock salt crystals (group I-VII, II-VI) and tetrahedral coordinated crystals (group II-VI, III-V). For the A^NB^8-N crystals systems, our present conclusions suggest that lattice energy density u decreases exponentially with increasing electronic polarizability, and the normal mathematical expression between lattice energy density u and electronic polarizability is u = pα^q, p and q depend on the type of crystals. For the same cation binary A^NB^8-N crystals systems, curve fitting equations have been obtained, and the relevant squares of the correlation coefficient R² are larger than 0.99, which show all lattice energy density u are in good exponential relation with electronic polarizability. These empirical equations will give more information on calculating lattice energy or electronic polarizability. New data of lattice energy have been calculated on the above equation u = pα^q, and a good linear trend in the calculating values along with the Zhang’s values has been obtained.     

Optically excited secondary emission spectra of photonic crystals based on synthetic opals

The photonic dispersion, the group-velocity dispersion, the effective mass, refractive index, and the spectral distribution of the density of photonic states near the edge of the photonic stop band are numerically calculated in the one-dimensional model for photonic crystals based on synthetic opals. The fluorescence spectra of rhodamine 6G and 2,5-bis(2-benzoxazolyl)hydroquinone molecules infiltrated into a synthetic opal are measured. For both substances, it is observed that the spontaneous emission intensity in the range of the photonic stop band is appreciably suppressed. A blue shift of the fluorescence spectrum of rhodamine 6G molecules is revealed. Secondary emission of synthetic opals infiltrated with colloidal silver is observed in the Stokes range under excitation of opals by radiation at λ = 400 nm. The spectrum of the secondary emission is located in the range 450–590 nm, which contains the stop band and intervals near its edges.     

Synthesis, growth and characterization of novel second harmonic nonlinear chalcone crystal

Nonlinear optical (NLO) materials are useful in many of the industrial applications. New NLO chalcone derivative (2E)-3-[4-(methylsulfanyl)phenyl]-1-(4-nitrophenyl)prop-2-en-1-one (4N4MSP) crystals have been grown by slow evaporation technique at ambient temperature. The grown crystals were subjected to single crystal X-ray diffraction study. The crystal has noncentrosymmetric structure in the orthorhombic system with space group Aba2 and unit cell parameters a=14.0647(15) Å, b=33.738(4) Å and c=6.0039(6) Å. To confirm the presence of various functional groups in the compound, FT-IR spectrum was recorded. The crystal was subjected to TGA/DTA analysis to find its thermal stability. The grown crystals were characterized for their optical transmission and mechanical hardness. The second harmonic generation (SHG) efficiency of the crystal is obtained by classical powdered technique using Nd:YAG laser and its value is 28.57 times that of urea. The laser damage threshold for 4N4MSP crystal was determined using Q-switched Nd:YAG laser. The refractive index values for green and red wavelengths were measured by Brewster angle technique. The dielectric and electrical measurements were carried out to study the different polarization mechanism and conductivity of the crystal. Good thermal, mechanical, transmission and SHG response make it desirable for the NLO applications.     

Investigation of optical properties of annealed aluminum phthalocyanine derivatives thin films

Semiconducting molecular materials based on aluminum phthalocyanine chloride (AlPcCl) and bidentate amines have been successfully used to prepare thin films by using a thermal evaporation technique. The morphology of the deposited films was studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Studies of the optical properties were carried out on films deposited onto quartz and (1 0 0) monocrystalline silicon wafers and films annealed after deposition. The absorption spectra recorded in the UV–vis region for the as-deposited and annealed samples showed two absorption bands, namely the Q- and B-bands. In addition, an energy doublet in the absorption spectra of the monoclinic form at 1.81 and 1.99 eV was observed. A band-model theory was employed in order to determine the optical parameters. The fundamental energy gap (direct transitions) was determined to be within the 2.47–2.59 and 2.24–2.44 eV ranges, respectively, for the as-deposited and annealed thin films.     

Preparation and upconversion emission properties of TiO2 :Yb, Er inverse opals

Inverse opal photonic crystals of Y b³⁺, Er³⁺ co-doped TiO₂ (TiO₂:Yb, Er) were prepared by a self-assembly technique in combination with a sol-gel method. Upconversion (UC) luminescence properties of the inverse opals were investigated. The results show that photonic bandgap has significant influence on the upconversion emission of the TiO₂:Yb, Er inverse opal photonic crystals. Significant suppression of the upconversion emission was detected if the photonic bandgap overlapped with the Er³⁺ ions emission band.     

Deformation of single crystal sample using D-DIA apparatus coupled with synchrotron X-rays: In situ stress and strain measurements at high pressure and temperature

We present a technique for high pressure and high temperature deformation experiment on single crystals, using the Deformation-DIA apparatus at the X17B2 beamline of the NSLS. While deformation experiments on polycrystalline samples using D-DIA in conjunction with synchrotrons have been previously reported, this technical paper focuses on single crystal application of the technique. Our single crystals are specifically oriented such that only [1 0 0] slip or [0 0 1] slip in (0 1 0) plane is allowed. Constant applied stress (sigma <300 MPa) and specimen strain rates were monitored using in situ time-resolved X-ray diffraction and radiography imaging, respectively. Rheological properties of each activated slip system in the crystals can be revealed using this technique. In this paper, we describe the principle of sample preparation (e.g. [1 1 0]_c and [0 1 1]_c orientations) to activate specific slip systems (i.e. [1 0 0](0 1 0) and [0 0 1](0 1 0), respectively), stress measurement and procedures of the deformation experiments.     

Second-harmonic generation in the thermal/electrical poling (100−x)GeS2·x(0.5Ga2S3·0.5CdS) chalcogenide glasses

Utilizing Maker fringe (MF) method, second-harmonic generation (SHG) has been observed within the GeS₂-Ga₂S₃-CdS pseudo-ternary glasses through thermal/electrical poling technique. The SHG phenomenon was considered to be the result of breakage of the glassy macroscopic isotropy originated from the reorientations of dipoles during the thermal/electrical poling process. Under the same poling condition conducted with 5 kV and 280 °C for 30 min, the maximum value of second-order nonlinear susceptibility χ⁽²⁾ of the poled (100−x)GeS₂·x(0.5Ga₂S₃·0.5CdS) glasses was obtained to be ≈4.36 pm/V when the value of x is equal to 30. Nonlinear dependence of χ⁽²⁾ on compositions of these glasses can be well explained according to the theory related to the reorientation of dipoles.     

Optical and magneto-optical spectra of europium-doped strontium tetraborate single crystals

Optical absorption, luminescence, magnetic circular dichroism and Faraday rotation spectra of Sr_0.95Eu_0.05B₄O₇ single crystals are studied. The crystal field parameter for europium ions is found to be equal to 790 cm⁻¹. Excitation spectrum of luminescence strongly differs from that of low-doped polycrystalline strontium tetraborate. The Verdet constant in the ultraviolet is comparable to that of terbium gallium garnet in the visible.     

Spatially controlled dissolution of Ag nanoparticles in irradiated SiO2 sol-gel film

In this paper, we report the spatially controlled dissolution of silver nanoparticles in irradiated SiO₂ sol-gel films. The Ag nanoparticles have been formed in the sol-gel solution before the film deposition by adding Triton and ascorbic acid and also after the film deposition using a heat treatment at 700 °C for few minutes or at 550 °C for 6 h in reducing atmosphere. Using a spectrometer, a new view white light interferometer and a micro-thermal analyzer, we demonstrate that the silver nanoparticles can be dissolved using a continuous black ray UV lamp or with a near-infrared (NIR) femtosecond laser, due to a significantly increase in the local temperature. We confirm that the micro-thermal analyzer can be used as a new tool to study the dissolution of metallic nanoparticles in thin film if located at the surface of the films.     

Insulating state of Na clusters and their metallic transition in low-silica X zeolite

Optical and magnetic properties are investigated for low-silica X (LSX) zeolite loaded with Na metals at various loading densities. In LSX, β-cages with the inside diameter of ∼7 Å are arrayed in a diamond structure and the supercages with that of ∼13 Å are formed among them. When the average number of guest Na atoms per β cage, n, is smaller than ∼2, optical reflectance shows a peak at ∼2.5 eV. This corresponds to the 1s-1p transition of the cluster formed in β cage. At n>2, this peak disappears and several strong peaks are seen at 1-3 eV. The oscillator strength increases with n. They can be attributed to surface-plasmon-like excitations of the Na clusters formed in supercages. At n≤10, clear absorption tails with energy gaps are observed at near IR region indicating insulating states. However, when n is increased up to ∼12, a clear Drude reflection suddenly appears in the IR region, indicating that an insulator-to-metal transition abruptly occurs. This dramatic change of the electronic state may be caused by the successive connection between adjacent clusters in supercages due to some special arrangement of Na⁺ ions as well as the delocalized wave function of electrons at high Na-loading density.     

Influence of vapor transport equilibration on Raman spectra of Er:LiNbO3 crystals

Raman spectra of as-grown and vapor transport equilibration (VTE) treated Er:LiNbO₃ crystals, which have different cut orientations (X-cut and Z-cut), different Er-doping levels (Er:(0.2, 0.4 and 2.0 mol%)LiNbO₃) and different VTE durations (80, 120, 150 and 180 h), were recorded at room temperature in the wavenumber range 50-1000 cm⁻¹ by using backward scattering geometry. The spectra were attributed on the basis of their spectral features and the previous experimental work and the most recent theoretical progress in lattice dynamics on pure LiNbO₃. In comparison with the pure crystal the most remarkable effect of Er-doping on the Raman spectrum is observed for the E(TO₉) mode. It does not appear at 610 cm⁻¹ as the pure crystal, but locates at 633 cm⁻¹. In addition, the doping also results in the lowering of the Raman phonon frequency, the broadening of the Raman linewidth and the changes of the relative Raman intensity of some peaks. The VTE treatment results in the narrowing of the linewidth, the recovery of the lowered phonon frequency and the further changes of relative Raman intensity. The narrowing of Raman linewidth indicates that the VTE processing has brought these crystals closer to stoichiometric composition. The VTE treatment has induced the formation of a precipitate ErNbO₄ in the high-doped Er(2.0%):LiNbO₃ crystals whether X- or Z-cut. For these precipitated crystals, besides above linewidth and phonon frequency features, they also display more significant Raman intensity changes compared with those not precipitated crystals. In addition, a slight mixing between A₁(TO) and E(TO) spectra is also observed for these precipitated crystals. Above doping and VTE effects on Raman spectra were quantitatively or qualitatively correlated with the characteristics of the crystal structure and phonon vibrational system.     

Micromechanical and thermal behaviour of gel grown pure- and sodium-modified copper tartrate crystals

Results regarding micromechanical characteristics of gel grown pure- and sodium-modified copper tartrate crystals, bearing composition CuC₄H₄O₆·3H₂O, (Cu)_0.77(Na)_0.23C₄H₄O₆·3H₂O and (Cu)_0.65(Na)_0.35C₄H₄O₆·H₂O, as obtained on using indentation induced hardness testing technique are reported. Thermal behaviour of these crystals in the temperature ranging from room temperature (∼25 °C) to about 600 °C is also reported. Pure copper tartrate crystals are found to be thermally more stable than the sodium-modified ones. Dependence of Vickers’ hardness number H_v on load ranging from 0.049 to 2.94 N on two different planes for all the three compositions is analyzed. It is shown that after initial rise in the value of H_v, the same achieves saturation at a load of 0.49 N. Modification of copper tartrate crystal by introducing sodium in its lattice brings about a change in the micromechanical characteristics. The saturation value of H_v decreases with increase in the concentration of sodium ions. The results on (0 0 1) and (1 1 1) planes for both pure and modified copper tartrate crystals suggest hardness anisotropy. Relative difference of hardness between the two planes and yield strength for both pure and modified copper tartrate crystals is worked out. The experimental results are analyzed for applicability of Meyer’s law and Proportional Specimen Resistance Model. It is suggested that the experimental results indicating reverse ISE phenomenon may be explained in terms of the existence of a distorted zone near the crystal-medium interface. The integral method of Coats and Redfern approximation applied to the thermoanalytical data suggests “Random Nucleation Model” for the reaction kinetics of these crystals. Non-isothermal kinetic parameters such as activation energy, frequency factor and order of reaction are calculated.     

Template-directed self-organized silica beads on square and Penrose-like patterns

Since a decade photonic band gap research is expanding quickly and especially with self-assembled silica beads, called opals. However, a lot of problems are arising in their preparation, in particular the difficulty to produce large frequencies band gaps in common (periodic) silica photonic materials. To solve this problem quasiperiodic opals are known to be good candidates. Actually, the high degree of isotropy and the high homogeneity of Penrose tilings make them a good way to generate complete photonic band gaps. The aim of our group is to elaborate quasiperiodic photonic crystals by directed-assembly (dip-coating) on Penrose-like patterned surfaces (through electron beam lithography). We will briefly present the different elaboration steps of our opals. Thus, the patterning methods and the dip-coating system will be discussed with our recent results in dip-coated photonic crystals.     

Synthesis,crystal growth and characterisation of 2-aminomethylpyridinium picrate (2-ampp)-a charge transfer molecular complex and organic nonlinear optical material

Single crystals of 2-aminomethylpyridinium picrate (2-AMPP) were grown by slow evaporation-solution growth technique at room temperature. The cell and structural parameters of the grown crystal were determined by single crystal X-ray diffraction analysis. The characteristic functional groups in the compound were identified from Fourier transform infrared spectroscopy. The transmission and absorption spectra of this crystal show that the lower cut-off wavelength lies at 360 nm. Thermal analysis was performed to study the thermal stability of the grown crystal. The powder second harmonic generation efficiency of the grown crystal measured by Kurtz technique is 2 times efficient than potassium dihydrogen orthophosphate (KDP). Vicker's microhardness test showed that the hardness value increases with increasing the applied load up to 50 g. The dielectric measurements of the compound in the frequency region from 50 Hz to 5 MHz showed that the material has lesser defects and can be used for optical application.     

Upconversion luminescence of Er/Yb-codoped natrium-germanium-bismuth glasses

The absorption and upconversion fluorescence spectra of a series of Er³⁺/Yb³⁺-codoped natrium-germanium-bismuth glasses have been studied. The transition probabilities, excited state lifetimes, and the branching ratios have been predicted for Er³⁺ based on the Judd-Ofelt theory. At room temperature, an upconversion efficiency of 6.1×10⁻² has been obtained for the green emission from the glass with 0.5 wt% Er₂O₃ and 3.0 wt% Yb₂O₃ pumped by 980 nm radiation with an intensity of 270 W/cm². And the “standardized” efficiency for green upconversion light is higher than that reported in lead-germanate, lead-tellurite-germanate, and silicate glasses. The results indicate that the Er³⁺/Yb³⁺-codoped natrium-germanium-bismuth oxide glass may be a potential material for developing upconversion optic devices.     

Synthesis and characterization of porous silicon layers for 1D photonic crystal application

In this paper, we studied the optical and physical properties of electrochemically prepared porous silicon layers. The atomic force microscopy analysis showed that the etching depth, pore diameter and surface roughness increase as the etching time increased from 30 to 50 mA/cm². By tuning two current densities J₁ = 50 mA/cm² and J₂ = 30 mA/cm², two samples of 1D porous silicon photonic crystals were fabricated. The layered structure of 1D photonic crystals has been confirmed by scanning electron microscopy measurement which showed white and black strips of two distinct refractive index layers. Finally, the measured reflectance spectra of 1D porous silicon photonic crystals were compared with simulated results.     

Linear and nonlinear optical susceptibilities of orthorhombic rare earth molybdates RE2(MoO4)3

The dielectric responses (i.e. the refractive indices and the second order nonlinear susceptibilities) of all orthorhombic rare earth molybdates have been studied on the basis of the relationship between dielectric responses and the average atomic number of constituent atoms of crystals. Both the linear and second order nonlinear optical responses at 1.064 μm decrease with increasing atomic number from La to Lu.     

Stimulated Raman scattering of light in artificial opal filled by water

We investigate stimulated scattering of light in globular photonic crystals infiltrated by water. Excitation of stimulated scattering of light is realized using powerful ultrashort (70 ps) laser pulses with an energy of 35 mJ and a frequency repetition of 15 Hz. We use the second-harmonic generation (532 nm) of the master oscillator and amplifier with a wavelength of 1064 nm. The photonic crystals under study are artificial opals filled by water or ethanol. We characterize the sample structures employing an electronic microscope along with the fiber-optics reflectance-spectroscopy technique. Photonic crystals have a stop band near the spectral positions of the exciting line (532 nm) and the first satellite of stimulated Raman scattering of light in water (649 nm). We observe a substantial reduction of the threshold of stimulated Raman scattering of light in water-infiltrated artificial-opal matrices in comparison with that of pure water. Such a reduction is explained as the result of a sharp increase in the photonic density of states near the stop-band edges of investigated photonic crystals. The reduction in the threshold of stimulated Raman scattering of light in water-infiltrated artificial-opal matrices opens up the opportunity to observe stimulated Raman scattering in numerous water media, including water solutions, biological and medical samples, heavy waters, and others.