Low temperature synthesis and characterisation of lecontite, (NH4)Na(SO4)·2H20

Lecontite, (NH₄)Na(SO₄).2H₂O, was synthesised at room temperature in high purity compared to earlier work with a minor impurity of mascagnite, (NH₄)₂SO₄. Rietveld refinement of the XRD results confirmed the crystal structure and unit cell dimensions as published earlier. Raman and Infrared spectroscopy, in conjunction with factor group analysis, resulted in a complex pattern of overlapping sulphate, NH and OH modes. The NH modes υ₁ was observed around 2880 cm⁻¹, υ₂ around 1700 cm⁻¹ overlapping with water OH-bending modes, υ₃ around 3300 cm⁻¹ overlapping with water OH-stretching modes around 3023, 3185 and 3422 cm⁻¹, and υ₄ around 1432, 1447 and 1462 cm⁻¹. The sulphate group in the crystal structure displays a decrease in symmetry from T_d as evidenced by the activation of the ν₁ mode at 982 cm⁻¹ and the ν₂ mode around 452 cm⁻¹ in the Infrared spectrum. The υ₃ mode shows clear splitting in the infrared spectra with a strong band at 1064 cm⁻¹ accompanied by two shoulders at 1107 and 1139 cm⁻¹. The Raman spectra show three weak bands at 1068, 1109 and 1135 cm⁻¹ with a shoulder at 1155 cm⁻¹. Similar splitting was observed for the υ₄ mode around 611 and 632 cm⁻¹ in the Infrared and Raman spectra, respectively.     

Photoluminescence and Raman studies in swift heavy ion irradiated polycrystalline aluminum oxide

Polycrystalline aluminum oxide is synthesized by combustion technique and XRD studies of the sample revealed the α-phase. The synthesized sample is irradiated with 120 MeV swift Au⁹⁺ ions for the fluence in the range from 1 × 10¹¹ to 1 × 10¹³ ions cm⁻². A broad photoluminescence (PL) emission with peak at ∼ 447 nm and two sharp emissions with peak at ∼ 679 and ∼ 695 nm are observed in pristine when sample was excited with 326 nm. However, in the irradiated samples the PL intensity at ∼ 447, 679 and 695 nm decreases with increase in ion fluence. The α-Al₂O₃ gives rise to seven Raman modes with Raman intensity with peaks at ∼ 253, 396, 417, 546, 630, 842, 867 cm⁻¹ observed in pristine. The intensity of these modes decreases with increase in ion fluence. However, the Raman modes observed at lower fluences are found to disappear at higher fluence.     

Photochemical modification of single-walled carbon nanotubes using HPHMP photoinitiator for enhanced organic solvent dispersion

Photochemical modification of single-walled carbon nanotubes (SWCNTs) was carried out by covalent attachment of 2-propanol-2-yl radicals on the surface of SWCNTs, which were engendered by the photolysis of 1-[4-(2-Hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one (HPHMP) under ultraviolet (UV) light. Pristine single-walled carbon nanotubes (p-SWCNTs) were dispersed in acetone along with HPHMP photoinitiator. After that, the mixture was irradiated by UV light to generate the free radicals which were introduced onto the surface of SWCNTs. The modification of SWCNTs was supported by UV/visible spectroscopy, Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, thermal gravimetric analysis–mass spectrometry (TGA–MS), and transmission electron microscopy (TEM). UV/visible results revealed the loss of van Hove singularities due to covalent modification. The modification was further verified by FT-IR showing the signals at 3421 and 1100 cm⁻¹ due to stretching and bending of O–H group, respectively. Moreover, other peaks at 2927 and 2858 cm⁻¹ indicated the asymmetric and symmetric stretching modes of aliphatic C–H bond, respectively. Raman spectra illustrated that the intensity ratio of the tangential mode to the disorder mode (I _G/I _D), for modified SWCNTs (F-SWCNTs), decreased nearly four times than p-SWCNTs. TGA–MS also evidenced the signal corresponding to m/z 59 at 400 °C indicating the presence of 2-propanol-2-yl groups. TEM and dispersibility data demonstrated that the sidewall modification detached the bundled structure, enhanced the dispersion in common organic solvents and retained the original size of SWCNTs without hefty modification, which could cut or damage the nanotubes.     

Raman scattering studies of Mn-doped ZnO thin films deposited under pure Ar or Ar + N2 sputtering atmosphere

This paper investigates the anomalous and specific Raman modes present in Mn-doped ZnO thin films deposited using the magnetron co-sputtering method. To trace these peaks, we prepared Mn-doped ZnO films with different Mn concentrations by altering the sputtering power of the Mn target in a pure Ar or Ar + N₂ sputtering atmosphere. A broad band observed in the Raman spectra of heavily Mn-doped ZnO films ranges from 500 to 590 cm^− 1. This band involves the enhanced A₁ longitudinal mode and activated silent modes of ZnO, as well as a characteristic mode of Mn₂O₃. Four anomalous Raman peaks at approximately 276, 510, 645 and 585 cm^− 1 are present in pure and Mn-doped ZnO films deposited under the Ar + N₂ sputtering atmosphere. The peaks at 276 cm^− 1 and 510 cm^− 1 may originate from the complex defects of Zn_i-N_O and Zn_i-O_i, respectively, while the peak at approximately 645 cm^− 1 could be due to a complex defect of Zn_i coupled with both the N and Mn dopants. The results of this study suggest classifying the origins of anomalous and specific Raman peaks in Mn-doped ZnO films into three major types: structural disorder and morphological changes caused by the Mn dopant, Mn-related oxides and intrinsic host-lattice defects coupled with/without the N dopant.     

Raman active E2 modes in aluminum nitride films

The vibrational spectrum of AlN thin films has been studied in recent years by theoretical and experimental methods, but there is still a lack of full knowledge of the Raman shift of the active E₂ modes of this material. Early work by Carlone et al. [1] has indicated that the E₂ modes of AlN deposited on Si occur at frequencies of 303cm^-1 and 426cm^-1. In the present study, Raman spectra of AlN deposited by magnetron sputtering on polished Si, quartz and BK7 substrates and also the Raman spectrum of pure Si, were compared to show that these peaks can actually be assigned as Raman peaks of Si, instead of AlN Raman peaks. We show that the Raman lines at 240cm^-1 and 650cm^-1 are the true AlN E₂ Raman peaks in agreement with calculated and experimental works reported in the literature that indicate the occurrence of the low and high E₂ Raman modes of AlN in the ranges (228-252)cm^-1 and (631-665)cm^-1, respectively.     

Comparative microscopic and spectroscopic analysis of temperature-dependent growth of WO3 and W0.95Ti0.05O3 thin films

We present a comparative microscopic and spectroscopic study of the morphology and composition of WO₃ and W_0.95Ti_0.05O₃ thin films, grown by radio-frequency magnetron reactive sputtering at substrate temperatures varied from room temperature to 500 °C, using atomic force microscopy (AFM), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). With increasing growth temperature, the AFM results show increase in the average crystallite size and in the surface roughness for both undoped and doped samples. The AFM data, along with the Raman results, clearly indicate that for the given set of experimental conditions, higher growth temperatures are required to obtain crystalline Ti-doped WO₃ films than for WO₃ films. Also, the Raman results suggest a potential phase transformation from a monoclinic WO₃ structure to an orthorhombic, but more probably a tetragonal, configuration in the W_0.95Ti_0.05O₃ thin films. This remark is based on the observed shifting, with Ti doping, to lower frequencies of the Raman peaks corresponding to W–O–W stretching modes of WO₃ at 806 and 711 cm⁻¹ to 793 and 690 cm⁻¹, respectively. XPS data indicate that the doped material has a reduced WO_3−x stoichiometry at the surface, with the presence of W⁶⁺ and W⁵⁺ oxidation states; this observation could also be related to the existence of a different structural phase of this material, corroborating with the Raman measurements.     

Atmospheric effects on the thermally induced sintering of nanoparticulate gold films

Gold (Au) films were formed by sintering of Au nanoparticles (NPs) under gas flows of air, oxygen (O₂), nitrogen (N₂), or N₂ bubbled through formic acid (FA/N₂). The microstructure changes of the Au nanoparticulate films were studied when different atmospheres were applied. The Au film sintered under FA/N₂ showed the progressive agglomeration and grain growth with porosity in the film, while the film sintered under N₂ had NPs without participating grain growth. A necking between NPs was observed in the film, however, unnecked NPs were still found. The Au film sintered under O₂ atmosphere showed the NPs agglomeration with various sizes up to 50 nm. X-ray characteristic peaks of the (111)-preferred orientation were observed in all samples. All samples showed N–H stretching at 3200–3300 cm⁻¹ regardless of sintering atmosphere. Hydrocarbon chains (C–H) at 2850–3000 cm⁻¹ were detected in the film sintered under N₂. For the Au film sintered under O₂, C–H stretching at 2850–3000 cm⁻¹, C–H deformation at 1350–1470 cm⁻¹, and C–O stretching at 1200–1300 cm⁻¹ were observed. C–O stretching at 1600–1700 cm⁻¹ was observed for the film sintered under FA/N₂ atmosphere. The electrical resistance of the film was related with microstructures and organic residual materials left in the film. Even though either porosity or carbon residues were observed in the film, the sintering of NPs in FA/N₂ or N₂ showed the sheet resistance comparable to that of electroplated one.     

Visible photoluminescence of hydrothermal synthesized Sn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ni<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>2</Subscript> nanostructures

Sn_1−x Ni _x O₂ nanostructures such as nanocubes, nanospheres and hollow spheres were synthesized by a simple hydrothermal method. Room temperature photoluminescence spectra of the as-synthesized samples display a strong yellow emission at about 600 nm and a weak blue emission at about 430 nm. The as-prepared and annealed Sn_1−x Ni _x O₂ (x = 0, 0.01, 0.02, 0.04) were characterized by X-ray diffraction, field emission scanning electron microscopy, Raman spectrum, UV–Vis absorption spectra, and room temperature photoluminescence spectra. By investigating the relationship between the Raman band centered at 560 cm⁻¹ and the photoluminescence of the samples, we suggest that the broad yellow emission and weak blue emission primarily originate from singly ionized oxygen vacancies and tin interstitials, respectively.     

Influence of sputtering power on the physical properties of magnetron sputtered molybdenum oxide films

Thin films of molybdenum oxide were formed on glass and silicon substrates by sputtering of molybdenum target under various sputtering powers in the range 2.3–6.8 W/cm², at a constant oxygen partial pressure of 2 × 10⁻⁴ mbar and substrate temperature 523 K employing DC magnetron sputtering technique. The effect of sputtering power on the core level binding energies, chemical binding configurations, crystallographic structure, surface morphology and electrical and optical properties was systematically studied. X-ray photoelectron spectroscopic studies revealed that the films formed at sputtering powers less than 5.7 W/cm² were mixed oxidation states of Mo⁵⁺ and Mo⁶⁺. The films formed at 5.7 W/cm² contained the oxidation state Mo⁶⁺ of MoO₃. Fourier transform infrared spectra contained the characteristic optical vibrations. The presence of a sharp absorption band at 1,000 cm⁻¹ in the case of the films formed at 5.7 W/cm² was also conformed the existence of α-phase MoO₃. X-ray diffraction studies also confirmed that the films formed at sputtering powers less than 5.7 W/cm² showed the mixed phase of α-and β-phase of MoO₃ where as at sputtering power of 5.7 W/cm² showed single phase α-MoO₃. The electrical conductivity of the films increased from 8 × 10⁻⁶ to 1.2 × 10⁻⁴ Ω⁻¹ cm⁻¹, the optical band gap decreased from 3.28 to 3.12 eV and the refractive index decreased from 2.12 to 1.94 with the increase of sputtering power from 2.3 to 6.8 W/cm², respectively.     

Deposition of crystalline C3N4 films via microwave plasma chemical vapour deposition

Crystalline carbon nitride films have been synthesized on polycrystalline Ni substrates by a microwave plasma chemical vapour deposition technique, using a mixture of N₂, CH₄ and H₂ as precursor. Scanning electron microscopy shows that the film consisted of perfect crystals of short and long hexagonal bars, tetragonal bars and irregular particles. From the X-ray photoelectron spectroscopy (XPS) data, a maximum N/C ratio of 1.0 was achieved in the films. The XPS spectra of the film typically showed three peaks in the C 1s core spectrum (centered at 284.78, 285.94, and 287.64 eV) and two peaks in the N 1s core level spectrum (centered at 398.35 and 400.01 eV). This indicates that there are two types of C–N bonds; N is bonded to sp²- or sp³-coordinated C atoms in the as-deposited film. The X-ray diffraction pattern indicates that the film is composed of α-, β-, pseudocubic, graphitic C₃N₄ and an unidentified phase. A series of intense sharp Raman peaks were observed in the range of 100–1500 cm^− 1. These peaks match well with the calculated Raman frequencies of α- and β-C₃N₄, revealing the formation of α- and β-C₃N₄ phase.     

Formation of nanoscale tungsten oxide structures and colouration characteristics

In this work, pH dependent evolution of tungsten oxide (WO₃) nanostructures is being reported along with physical characteristics. The synthesis was carried out via an inexpensive solvothermal cum chemical reduction route, with sodium tungstate (Na₂WO₄) and cetyl trimethyl ammonium bromide (C₁₉H₄₂NBr) as main reactants. The X-ray diffraction, together with transmission electron microscopic studies have revealed formation of regular polyhedral nanocrystalline structures and fractals as one goes from higher pH (= 5·5) to lower pH (= 2) values. The average crystallite size, as calculated through Williamson–Hall plots, was varied within 2·8–6·8 nm for different pH samples. Fourier transform infrared spectroscopy reveals in-plane bending vibration δ (W–OH), observable at ∼1630 cm^− 1 and strong stretching ν (W–O–W) located at ∼814 cm^− 1. Raman spectroscopy has divulged WO₃ Raman active optical phonon modes positioned at ∼717 and 805 cm^− 1. The thermochromic and photochromic properties of the nanoscale WO₃ sample prepared at pH = 5·5, are also highlighted.     

Raman temperature dependence analysis of carbon-doped titanium dioxide nanoparticles synthesized by ultrasonic spray pyrolysis technique

Carbon-doped titanium dioxide nanoparticles were prepared by ultrasonic spray pyrolysis technique using titanium tetra-ethoxide as a precursor and glucose as a dopant. The as-synthesized nanoparticles were then characterized using high resolution transmission electron microscopy for the structural properties and temperature dependence Raman spectroscopy for the optical properties. High resolution transmission electron microscopy analysis shows that the ultrasonic synthesized carbon-doped titanium dioxide nanoparticles have an interplanar d-spacing of 0.352 nm, a value close to 0.374 nm of the pure undoped anatase titanium dioxide (bulk). The fast Fourier transform (FFT) of the selected electron diffraction images, of the selected areas, display the fact that only the main diffraction (reflection) plane of Miller indices (101) in titanium dioxide is responsible for diffraction pattern. Raman spectroscopy confirms the titanium dioxide polymorph to be anatase with the intense phonon frequency at 153 cm⁻¹ blue-shifted from 141 cm⁻¹ due to both carbon doping and particle size decrease. The temperature dependence analysis of the spectra shows an initial linear dependence of the Raman shift for the E _g(1) mode at 152.7 cm⁻¹ with increase in temperature up to a critical temperature 450 °C, after which we observe a decrease with increase in temperature. The other Raman modes [B _1g and E _g(3)] exhibit a different temperature dependence in that the B _1g displays a somewhat sinusoidal behavior and the E _g(3) mode shows a linear decrease of Raman shift with an increase in temperature. Temperature dependence analysis of peak width for the E _g(1) indicates the peak width of the as prepared nanoparticle to be 20 cm⁻¹ which is far much larger than that for single crystal of 7 cm⁻¹ at room temperature.     

EPR and photoluminescence properties of combustion-synthesized ZnAl<Subscript>2</Subscript>O<Subscript>4</Subscript>:Cr<Superscript>3+</Superscript> phosphors

An efficient red emitting ZnAl₂O₄:Cr³⁺ powder phosphor material was prepared at furnace temperatures as low as 500 °C by using the combustion method. The prepared powders were analyzed by X-ray diffraction and scanning electron microscopy techniques. The optical properties were studied using photoluminescence technique. The EPR spectra exhibit an intense resonance signal at g = 3.74 which is attributed to Cr³⁺–Cr³⁺ pairs, and the weak resonance signal of at g = 1.97 is attributed to Cr³⁺ single ion transition. The spin population (N) has been evaluated as a function of temperature. The excitation spectrum exhibits two broad bands in the visible region which are characteristic of Cr³⁺ ions in octahedral symmetry and the emission spectrum exhibits zero-phonon line frequencies along with vibronic frequencies. The crystal field parameter (Dq) and Racah parameters (B and C) have been evaluated and discussed.     

Raman spectroscopy determination of carrier concentration in <Emphasis Type="Italic">n</Emphasis>-In<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ga<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>As epitaxial films

We have studied in detail the coupled phonon-plasmon mode Raman spectra of n-In _x Ga_{1 − x} As with n in the range 10¹⁷ to 10¹⁹ cm⁻³. The results indicate that the behavior of the high-frequency mode L ₊ can be described in terms of coupled modes in the Drude approximation. The proposed theory and experimental data are used to estimate the carrier concentration in the solid solution and its composition.     

Oxygen isotope shifts of the Raman modes of YBa2Cu3O7−x

Raman scattering experiments have been carried out on sintered pellets of YBa₂Cu₃ ¹⁶O_7−x and YBa₂Cu₃ ¹⁸O_7−x obtained both by gas exchange and by growth with substituted oxides. The frequencies of the modes at 340, 435 and 502 cm⁻¹, which involve motion of the oxygen atoms and which shift significantly upon oxygen isotope substitution, have been measured for several sets of samples. The measured frequency shifts indicate that the isotope exchange on the O(2) and O(3) sites is more complete than the exchange on the O(4) site. The 502 cm⁻¹ line of the¹⁸O samples is observed to be broadened and this is attributed to¹⁸O-¹⁶O disorder on the O(4) sites. The results are discussed with reference to previous measurements of site activation energies and models for the exchange mechanism.     

Spectroscopic studies of TeO<Subscript>2</Subscript>–ZnO–Er<Subscript>2</Subscript>O<Subscript>3</Subscript> glass system

Series of glass based on the (80 − x)TeO₂–20ZnO–(x)Er₂O₃ system (0.5 mol% ≤ x ≤ 2.5 mol%) has successfully been made by melt quenching technique. The optical properties of glass have been investigated by means of IR and Raman spectroscopy. It is observed that as the Er₂O₃ content is being increased, the sharp IR absorption peaks are consistently shifted from 650 to 672 cm⁻¹ while the Raman shift intensity around 640–670 cm⁻¹ is decreases but increases around 720–740 cm⁻¹. It is found out that both phenomenons are related to the structural changes between the stretching vibration mode of TeO₄ tbp and TeO₃ tp, and bending vibration mode of Te–O bonds in the glass linkages.     

Synthesis of functional diamond-like carbon nanocomposite films containing titanium dioxide nanoparticles

Synthesis of diamond-like carbon (DLC) films with UV-induced-hydrophilicity function was studied by inductively-coupled plasma (ICP) chemical vapor deposition. Titanium tetraisopropoxide (TTIP) and oxygen gases were employed as the precursors to deposit diamond-like nanocomposite films containing titanium dioxide (TiO₂) nanoparticles. X-ray diffraction and high-resolution transmission electron microscopy revealed that TiO₂ nanocrystallites were formed in the DLC films when oxygen concentration was higher than TTIP concentration during deposition. The DLC nanocomposite film was hydrophobic without ultraviolet (UV) irradiation, and became highly hydrophilic under UV irradiation, exhibiting the self-cleaning effect. A very broad peak centered at 1580 cm^− 1 was observed in the Raman spectra confirming the formation of DLC films. The hardness of the film was about 8 GPa with a stress of 3 GPa. ICP was essential in forming the photocatalytic TiO₂ nanoparticles in the DLC matrix.     

Local vibrational modes of N<Subscript>2</Subscript>−O<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> defects in Cz-Silicon

In this paper we investigate N₂−O _n defect complexes in Czochralski silicon (Cz-Si) by means of local density functional theory. We consider the N₂O and the N₂O₂ defect and determine their structural, electronic and vibrational properties. The calculated local vibrational modes of the N₂O defect are in good agreement with the experiment. Furthermore the calculated binding energy matches very well with the experimental estimate. Motivated by recent experimental work, where several new absorption lines in IR absorbance spectra were observed, we present first principle studies on the ground state configuration, binding energy and local vibrational modes of the N₂O₂ defect and make a tentative assignment to the experimentally observed lines at 1018 and 810 cm⁻¹.     

Large-scale electrochemical synthesis of SnO2 nanoparticles

Tin oxide nanoparticles were synthesized by electrochemical oxidation of a tin metal sheet in a non-aqueous electrolyte containing NH₄F. The as-prepared nanoparticles were then thermally annealed at 700 °C for 6 h. The resulting particles were characterized by a variety of experimental techniques, including X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), Raman, UV-visible, and photoluminescence (PL) spectroscopy. The XRD patterns clearly showed that the amorphous phase of the as-synthesized SnO₂ particles was transformed into a rutile-type crystalline structure after thermal treatment; and from the line broadening of the XRD peaks, the average size of the annealed particles was found to be 15.4, 12.5, 11.8 nm for the particles initially synthesized at 20, 30, and 40 V, respectively. Consistent results were also observed in HRTEM measurements which showed clear crystalline lattice fringes of the calcined nanoparticles, as compared to the featureless profiles of the as-produced counterparts. In Raman spectroscopic studies, three dominant peaks were observed at 480, 640, and 780 cm⁻¹ which were ascribed to the E_1g, A_1g, and B_2g Raman active vibration modes, respectively, and the wavenumbers of these peaks blue-shifted with decreasing particle size. Additionally, a broad strong emission band was observed in room-temperature photoluminescence measurements.     

Effect of microwave power and C2 emission intensity on structural and surface properties of nanocrystalline diamond films

Nanocrystalline diamond (NCD) films are synthesized using microwave plasma enhanced chemical vapour deposition technique at 2 × 10⁴ Pa and 600 °C with microwave power of 600-1600 W. Deposition is carried out on n-type (100) silicon wafer with Ar/H₂/CH₄ gas mixtures. The film properties are analyzed using micro Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy and atomic force microscopy. Raman spectra show two predominant peaks centered around 1335 cm⁻¹ and 1560 cm^− 1 and two humps around 1160 cm^− 1 and 1450 cm^− 1, respectively. FTIR spectra show C:H stretching modes around 3000 cm^− 1. XRD patterns show a peak at 44° (2θ). In situ diagnostic of plasma is carried out using Optical Emission Spectroscopy. It has been observed that C₂ dimer plays an important role in the nucleation of diamond crystals during NCD film deposition and the emission intensity of C₂ can be adjusted by varying the microwave power. It has also been observed that the structural properties like growth rate, surface morphology and grain size of the growing film are dependent on the C₂ intensity during deposition.