Bond Angle Disorder Research Articles

Weak oxidant fraction in the microwave plasma influencing the evolution of nanocrystalline-diamond–imbedded diamond–like carbon network at low temperatures and its orbital hybridization dependent wide optical band gaps

The diamond-like carbon (DLC) thin films having intrinsic nanocrystalline diamond (NCD) components were synthesized on bare glass substrates at 300 °C, employing a (C2H2/CO2/H2/) gas mixture in MW-PECVD. Relevant influence of the weak oxidant fraction [F = CO2/(CO2 + C2H2)] in the plasma on the specific hybridized constituents (sp3 and sp2) in the C-network, optical transmission characteristics of the film, and its accomplished degree of nanocrystallinity were investigated. A substantial segment of the NCD was achieved in the DLC matrix. An optimized diamond-phase component corresponding to the minimized bond angle disorder in the matrix was accounted from the manifestation of the maxima of IDia/IG and IDia/ID simultaneous to the minimum of ID/IG ratio in Raman response, along with an allied diamond peak appearing near 1332 cm−1. The optimal DLC film at F = 0.23 revealed a wide optical band gap (Eg) of ∼3.60 eV, ∼59% sp3-hybridized C component of the diamond phase, and a significant sp3/sp2 ratio of ∼2.1. The film microstructure seemed homogeneous with uniformly distributed NCDs of average diameter ∼7.5 nm and dominant 〈111〉 crystallographic orientation. The sp3/sp2 fraction in the film matrix has been correlated directly to the IDia/IG and IDia/ID, and inversely to ID/IG ratios of the Raman data. Atomic-O, including atomic-H, remains instrumental in chemical reactions, facilitating the etching of graphitic and a-C phases while preserving the superior sp3-hybridized NCD component growing uninterruptedly in the DLC network that subsists shielded from the high-energy ion impact within secondary plasma under the shadow mask.

Bifunctional hybrid magnetic colloidal clusters for efficient oil sludge recovery

Oil contamination of water bodies due to oil spills, industrial waste discharge, oil leaks, etc. poses a major threat to the quality of groundwater, soil, and living organisms. To combat this issue through effective environmental remediation, efficient and cost-effective materials and innovative strategies are required. Here, we report a novel bifunctional magnetic material for efficient oil sludge removal using superparamagnetic colloidal nanocrystal clusters(BSPM-CNC) of nickel ion doped iron oxide with a shell of nitrogen-activated carboxymethyl cellulose char. The BSPM-CNC is synthesized by using a single-step procedure using water as a solvent. The crystallite and cluster size were tuned by varying Ni2+ ion concentration, carboxymethyl cellulose, and urea ratio. The cluster size was found to increase, when the carboxymethyl cellulose and urea ratio was reduced, due to insufficient stabilization of the capping agent that allowed the formation of secondary structures. X-ray photoelectron spectroscopy results confirmed the presence of nitrogen in the shell because of the condensation of OH and carbonyl groups of CMC with amine groups of urea, sp2-type carbon, C-O/N and O-CO bonding states. Laser Raman spectra of the char showed two major bands G and D bands, originating from the sp2 bonds and sp2 microdomains of the bond angle disorder caused by the sp3 hybridizations, respectively. The BSPM-CNC was found to be very efficient for oil sludge removal, where an oil removal efficiency of ∼ 98% was achieved with a cluster loading of 16 mg/L. The mechanism of sorption of oil are π-π interaction between aromatic hydrocarbons and graphitic domains of BSPM-CNC, Lewis-acid base interaction between nitrogenous char and delocalized electron cloud, and absorption into the pores of clusters. Our new approach provides a new platform to produce magnetic nanoclusters for the efficient removal of oil pollutants.

Influence of temperature regimes of synthesis on the structure of glassy GeS2

The effect of synthesis temperature regimes on the structure and some physical properties of glassy germanium disulfide was examined using the methods of dilatometry and Raman scattering of light. It is concluded that the bond angle disorder increases and the formation of stronger Ge–S bonds in the tetrahedral structure depends on the increase in the synthesis temperature of glassy GeS2. Significant changes in the structural grid of glass also occur when the thermal history of the sample varies in the temperature interval of vitrification.

Enhanced dielectric and magnetic properties of magnetodielectric La2−xPrxCoMnO6 for spintronic applications

La2−xPrxCoMnO6 (x = 0.5, 1.0, 1.5 and 2.0) double perovskites were prepared via sol gel method. X-ray diffraction peak profile inveterate the nonexistence of impurity phases in the prepared system. Rietveld refinement suggested that ordered monoclinic (P21/n) phase exist along with disordered orthorhombic (Pbnm) and rhombohedral (R3c) structural phases. A decrease in unit cell volume and lattice parameters is observed with increase in Pr content which is in agreement with the difference in ionic radii of La and Pr ions. Morphological and compositional study using FESEM with EDX suggested that grain size lies in micrometer range and signifies the purity of developed samples. Dielectric constant as well as tangent loss exhibit dispersive behavior at lower frequencies and higher temperatures. The strong effect of bond angle, anti-site disorder and grain size is observed on dielectric properties. Due to large bond angle and large antisite disorder, LPCMO2 exhibited largest value of dielectric constant among all developed compositions. Cole-Cole plots proposed a non-Debye type relaxation and indicated NTCR (negative temperature coefficient of resistance) behavior for the synthesized compositions. Ac conductivity showed increasing tendency with rise in both frequency as well as temperature. Increase in dc conductivity with temperature proposed semiconducting behavior of prepared samples that can be explained on the basis of Thermal activation (TA) and Variable range hopping (VRH) models. The saturation magnetization (Ms) showed a strong correlation with bond angle, tilting of CoO6/MnO6 octahedra and grain size i.e. LPCMO2 is having largest Ms whereas lowest Ms is exhibited by LPCMO3 which may be due to variation in exchange interaction which strictly depends on bond angle and tilting of MO6 octahedra. Enhanced magnetic properties make these materials useful for spintronic devices and magnetic storage. Dielectric and magnetic properties of the prepared samples depend strongly on ˂Co-O-Mn˃ bond angle and have same variation tendency with Pr substitution which indicates coupling between these properties.

Characterization of low-loss hydrogenated amorphous silicon films for superconducting resonators

Superconducting resonators used in millimeter-submillimeter astronomy would greatly benefit from deposited dielectrics with a small dielectric loss. We deposited hydrogenated amorphous silicon films using plasma-enhanced chemical vapor deposition, at substrate temperatures of 100\deg C, 250\deg C and 350\deg C. The measured void volume fraction, hydrogen content, microstructure parameter, and bond-angle disorder are negatively correlated with the substrate temperature. All three films have a loss tangent below $10^{-5}$ for a resonator energy of $10^5$ photons, at 120 mK and 4-7 GHz. This makes these films promising for microwave kinetic inductance detectors and on-chip millimeter-submilimeter filters.

Characterization the microstructure and defects of matrix graphite irradiated with Xe ions

The matrix graphite of pebble fuel elements was irradiated with 1MeV Xe ions at room temperature to fluences of 5.8×1014ions/cm2 and 2.9×1015ions/cm2, respectively. The microstructure and defects of matrix graphite samples were characterized by using scanning electron microscopy (SEM), Raman spectroscopy and slow positron beam techniques. The SEM result reveals that hundred-nanometer sized pores appear at the surface after irradiation and the density of pore increases with fluence. Raman results show that D peak (1350cm−1) and G peak (1580cm−1) are broadened after irradiation. In addition, the G peak position shifts from 1580cm−1 to 1560cm−1 with the linewidth increases from 21cm−1 to 132cm−1, corresponding to the increase in bond-angle disorder as the matrix graphite transforms from microcrystalline to amorphous carbon(a-C). The slow positron beam study shows that the defects-trapped positron S parameter increases with fluence, suggesting that the vacancy-type defects concentration or size of open volume defects increases. The analysis of Raman and slow positron beam consistently conclude that the reason for the phase transition after irradiation is the increase in irradiation-induced vacancy defects accompanied by the overlap of disordered regions.

Modeling of the atomic structure and electronic properties of amorphous GaN1−xAsx

Chemically ordered 250-atom models for amorphous GaN1−xAsx alloys in the concentration range of 0.17<x<0.75 have been studied with density functional theory simulations, starting with initial continuous random network structures. The analysis of network topology has been achieved by examining partial-pair correlation functions, bond angle distributions, ring statistics and average coordination numbers. The electronic properties of amorphous GaN1−xAsx alloys have been estimated by means of electronic density states (EDOS) and inverse participation ratios (IPR). Our calculations indicate that the introduction of As into GaN reduces the bond angle disorder. According to our ring analysis the 250atom a-GaN1−xAsx model has a disordered tetrahedral characteristic confirming the fact that continuous random network (CRN) can provide an ideal initial structure. The study of EDOS and IPR proves that the bandgap of a-GaN1−xAsx gets narrower with increasing As concentration, which is in good agreement with the experimental results and the band anti-crossing model.

Excess Specific Heat in Evaporated Amorphous Silicon

The specific heat C of e-beam evaporated amorphous silicon (a-Si) thin films prepared at various growth temperatures T(S) and thicknesses t was measured from 2 to 300 K, along with sound velocity v, shear modulus G, density n(Si), and Raman spectra. Increasing T(S) results in a more ordered amorphous network with increases in n(Si), v, G, and a decrease in bond angle disorder. Below 20 K, an excess C is seen in films with less than full density where it is typical of an amorphous solid, with both a linear term characteristic of two-level systems (TLS) and an additional (non-Debye) T3 contribution. The excess C is found to be independent of the elastic properties but to depend strongly on density. The density dependence suggests that low energy glassy excitations can form in a-Si but only in microvoids or low density regions and are not intrinsic to the amorphous silicon network. A correlation is found between the density of TLS n0 and the excess T3 specific heat c(ex) suggesting that they have a common origin.

Detailed Micro Raman Spectroscopy Analysis of Doped Silicon Thin Film Layers and Its Feasibility for Heterojunction Silicon Wafer Solar Cells

Hydrogenated doped silicon thin films deposited using RF (13.56 MHz) PECVD were studied in detail using micro Raman spectroscopy to investigate the impact of doping gas flow, film thickness, and substrate type on the film characteristics. In particular, by deconvoluting the micro Raman spectra into amorphous and crystalline components, qualitative and quantitative information such as bond angle disorder, bond length, film stress, and film crystallinity can be determined. By selecting the optimum doped silicon thin film deposition conditions, and combining our p-doped and n-doped silicon thin films in different heterojunction structures, we demonstrate both (i) an efficient field effect passivation and (ii) further improvement to c-Si/a-Si:H(i) interface defect density with observed improvement in implied open-circuit voltage VOC and minority carrier lifetimes across all injections levels of interest. In particular, the heterojunction structure (a-Si:H(p)/a-Si:H(i)/c-Si(n)/a-Si:H(i)/a-Si:H(p)) demonstrates a minority carrier lifetime of 2.4 ms at an injection level of 1015 cm-3, and a high implied open-circuit voltage of 725 mV. Simulation studies reveal a strong dependence of the interface defect density Dit on the heterojunction silicon wafer solar cell performance, affected by the deposition conditions of the overlying doped silicon thin film layers. Using our films, and a fitted Dit of 5 × 1010 cm-2·eV-1, we demonstrate that a solar cell efficiency of ~22.5% can be potentially achievable.

Effect of bond angle and dihedral angle disorder on diamagnetic susceptibility of tetrahedrally coordinated amorphous semiconductors

We study the effect of bond angle and dihedral angle disorder on the diamagnetic susceptibility (χ) of a model amorphous semiconductor by adopting a linear combination of hybrids formalism. We have constructed orthormal basis states for the disorder network by introducing distortion in bond angles and dihedral angles. We have used the disorder basis states in the expression for χ and adopted suitable averaging techniques to obtain χ in terms of disorder parameters, which shows interesting results.

Amorphous to crystalline phase transition in pulsed laser deposited silicon carbide

SiC thin films were grown on Si (1 0 0) substrates by excimer laser ablation of a SiC target in vacuum. The effect of deposition temperature (up to 950 °C), post-deposition annealing and laser energy on the nanostructure, bonding and crystalline properties of the films was studied, in order to elucidate their transition from an amorphous to a crystalline phase. Infra-red spectroscopy shows that growth at temperatures greater than 600 °C produces layers with increasingly uniform environment of the Si–C bonds, while the appearance of large crystallites is detected, by X-ray diffraction, at 800 °C. Electron paramagnetic resonance confirms the presence of clustered paramagnetic centers within the sp 2 carbon domains. Increasing deposition temperature leads to a decrease of the spin density and to a temperature-dependent component of the EPR linewidth induced by spin hopping. For films grown below 650 °C, post-deposition annealing at 1100 °C reduces the spin density as a result of a more uniform Si–C nanostructure, though large scale crystallization is not observed. For greater deposition temperatures, annealing leads to little changes in the bonding properties, but suppresses the temperature dependent component of the EPR linewidth. These findings are explained by a relaxation of the stress in the layers, through the annealing of the bond angle disorder that inhibits spin hopping processes.

Amorphization of carbon materials studied by X-ray photoelectron spectroscopy

X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy have been applied to investigate amorphization processes by ion irradiation for various carbons, including highly oriented pyrolytic graphite (HOPG), isotropic graphite, glassy carbon (GC) and C60. It is found that the asymmetry of the XPS C 1s line increases as the irradiation dose increases. The origin of the asymmetry appeared on the C 1s line is discussed. We conclude that the asymmetry of the C 1s line does not relate to the increase in the size of a graphitic layer, but relates to structural disorders, such as a bond angle disorder.

RAMAN SCATTERING STUDIES ON THE STRUCTURAL PROPERTIES OF PULSED LASER DEPOSITED AMORPHOUS CARBON NITRIDE THIN FILMS

Raman scattering analysis revealed that the structure of carbon films prepared by pulsed laser deposition (PLD) at room temperature is predominantly amorphous and the structure of amorphous carbon nitride ( a-CN x) thin films can be changed with varying substrate temperatures (ST) from 20°C to 500°C. The deposited a-CN x films are composed of C – N , C ≡ N and C – O bonded materials and the C – N and C ≡ N bonds are increased with ST. We have found that no other obvious peaks can be distinguished in the range 900–2300 cm-1 in which several peaks always appear in a-CN x films. The spectra were deconvoluted into Raman D and G peaks and the structural parameters are determined. The upward shifts of the Raman G peak towards 1592 cm-1 shows the evidence of a progressive formation of crystallites in a-CN x films upon increase of ST. While the upward shifts of the Raman D peak towards 1397 cm-1 have been related to the decrease of bond-angle disorder and sp3 tetrahedral bonding in its structure. Raman FWHM and I D /I G also indicate that N incorporation with increase of ST caused an increase in the number and/or size of graphitic domains in the a-CN x films.

Investigation of structural properties of amorphous carbon nitride thin films prepared by xenon cloride pulsed laser deposition of camphoric carbon precursor

Raman scattering analysis revealed that the structure of carbon (C) films prepared by pulsed laser deposition at room temperature is predominantly amorphous and the structure of amorphous C nitride (a-CN x ) films can be changed with varying substrate temperatures (ST) from 20 to 500 °C. The deposited a-CN x films are composed of C-N, C-N and C-O bonded materials and the C-N and C=N bonds are increased with ST. We have found no other obvious peaks can be distinguished in the range 900 to 2300 cm−1 in which several peaks always appear in a-CN x films. The spectra were deconvoluted into Raman D and G peaks and the structural parameters are determined. The upward shifts of Raman G peak towards 1592 cm−1 shows the evidence of a progressive formation of crystallites in a-CN x films upon increase of ST. While, the upward shifts of Raman D peak towards 1397 cm−1 have been related to the decreased of bond-angle disorder and sp3 tetrahedral bonding in its structure. Raman FWHM and IDIG also indicate that N incorporation with increased of ST caused an increase in the number and/or size of graphitic domains in the a-CN x films.

RAMAN SCATTERING STUDIES ON THE STRUCTURAL PROPERTIES OF PULSED LASER DEPOSITED AMORPHOUS CARBON NITRIDE THIN FILMS

Raman scattering analysis revealed that the structure of carbon (C) films prepared by pulsed laser deposition at room temperature is predominantly amorphous and the structure of amorphous C nitride ( a-CN x) films can be changed with varying substrate temperatures (ST) from 20 to 500°C. The deposited a-CN x films are composed of C–N , C≡N and C–O bonded materials and the C–N and C≡N bonds are increased with ST. We have found no other obvious peaks that can be distinguished in the range of 900 to 2300 cm-1 in which several peaks always appear in a-CN x films. The spectra were deconvoluted into Raman D and G peaks and the structural parameters were determined. The upward shifts of Raman G peak towards 1592 cm-1 show evidence of a progressive formation of crystallites in a-CN x films upon increase of ST, while the upward shifts of Raman D peak towards 1397 cm-1 have been related to the decrease of bond-angle disorder and sp 3 tetrahedral bonding in its structure. Raman FWHM and I D /I G also indicate that N incorporation with increase of ST caused an increase in the number and/or size of graphitic domains in the a-CN x films.

Raman spectroscopic investigations of activated carbon materials

Raman spectra of activated carbon materials have been investigated by a peak-deconvolution technique. It has been found as a result of our fitting trials that four Gaussians and a linear background are necessary and enough to reproduce the spectral data throughout our experiment, with a pair of relatively sharp peaks at about 1600 cm−1 and about 1350 cm−1, namely G1 and D1, and a pair of relatively broad peaks around 1560 cm−1 and 1340 cm−1, namely G2 and D2. From the characteristic behavior of these paired peaks, it has been concluded that the structure of activated carbon materials is schematically classified into two parts. The former part, represented by sharp G1 and G2 peaks, arises from winding short basal planes with bond angle order, while the latter, by broad G2 and D2 peaks, sp2 clusters like a-Cs with bond angle disorder. We have found the peak intensity ratio of G2 to G1, the I(G1)/I(G2) ratio, as a useful parameter expressing the relative content of the disorder part to the order part in the activated carbons, revealing the structural changes induced by anneal or activations. Since the changes of fitting parameters including the I(G2)/I(G1) ratio were completely opposite for H2O and KOH activation, it has been clarified that the part with bond angle disorder is selectively removed or become ordered by H2O activation, whereas induced by KOH activation, though both activation methods yield similar surface area.

A Model to Interpret the Raman Spectra of Disordered, Amorphous and Nanostructured Carbons

ABSTRACTRaman spectroscopy is a very popular, non-destructive tool for the structural characterisation of carbons. Raman scattering from carbons is always a resonant process, in which those configurations whose band gaps match the excitation energy are preferentially excited. The Raman spectra of carbons do not follow the vibration density of states, but consist of three basic features, the G and D peaks around 1600 and 1350 cm-1 and an extra T peak, for UV excitation, at ∼980–1060 cm-1. TheRaman spectra at any wavelength depend on 1) clustering of the sp2 phase, 2)bond length and bond angle disorder, 3) presence of sp2 rings or chains, and 4) the sp2/sp3 ratio. It will be shown how the basic features of the Raman spectra vary by rationalising them within a three-stage model of order of carbons. It is shown how the three-stage model can account for the vast range of experimental data available for Raman experiments at any excitation wavelength. This model can also account for apparently contradictory trends reported in literature, since the clustering of the sp2 phase and the sp3 to sp2 conversion are separately treated.

Quantification of polyimide carbonization after laser ablation

Polyimide was irradiated with a XeCl excimer laser (308 nm) and the ablated area and its surrounding were studied using transmission electron microscopy (TEM) and confocal Raman microscopy. Ring-like structures surrounding the ablated area were detected at all fluences. At fluences lower than 250 mJ/cm−2 the formation of conical structures was observed within the irradiated area. The width of the rings increases with fluence and only slightly with the number of pulses. The rings consist mainly of polycrystalline carbon with a relatively high bond angle disorder, with thickness decreasing radially from the crater edge. The thickness of the deposited carbon was determined from TEM analysis and calculated from the intensity ratios of Raman bands assigned to carbon and polyimide using a two layer model. Comparing the two results an estimate of the absorption coefficient of the deposited carbon could be obtained. On top of the cone structures carbon was detected with a higher degree of crystallinity and lower bond angle disorder as compared to the material deposited outside the crater. With energy dispersive x-ray analysis, calcium could be detected on top of the cones. Therefore, it can be assumed that the Ca impurities are causing the cone structures. The higher crystallinity of the carbon inside the irradiated area is probably due to a tempering-like process on top of the Ca compound which is heated upon laser irradiation or to a mixture of growth mechanisms similar to the ones suggested for the formation of carbon nanotubes on metal particles and carbon nanohorns without metal catalysis.

Structural and optoelectronic properties of amorphous and microcrystalline silicon deposited at low substrate temperatures by RF and HW CVD

AbstractThe structural and optoelectronic properties of silicon thin films prepared by hot wire chemical vapor deposition and radio frequency plasma enhanced chemical vapor deposition are studied in the range of substrate temperatures (Tsub)from 100 °C to 25 °C. The defect density, structure factor and bond angle disorder of amorphous silicon films (a-Si:H) deposited by both techniques are strongly improved by the use of hydrogen dilution. Correlation of these structural properties with important optoelectronic properties, such as photo-to-dark conductivity ratio, is made. Microcrystalline silicon (μc-Si:H) is obtained using HW with a large crystalline fraction for hydrogen dilutions above 85% independently of Tsub. The deposition of μc-Si:H by RF requires increasing the hydrogen dilution and shows decreasing crystalline fraction as Tsub is decreased. The properties of the low Tsub films are compared to those of samples produced at 175 °C and 250 °C in the same reactors.

Ab initiomolecular-dynamics study of liquidGeSe2

The structural, vibrational, and electronic properties of liquid GeSe${}_{2}$ are investigated using ab initio molecular dynamics. The static structure factor $S(Q)$ and the pair-correlation functions of our model are in good agreement with experiment. We find many similarities between the topology of the liquid and the glass state. In addition we introduce a way of characterizing the intermediate-range order of liquid and glassy GeSe${}_{2}$ through fourfold and sixfold rings. The overall vibrational density of states is found to be consistent with Raman experiments. The intensity of the low-frequency modes, splitting of the ${A}_{1}$ and ${A}_{1c}$ peaks, and the decrease in the intensity of the high-frequency modes are all reproduced. The electronic density of states is determined and compared to our results for glassy GeSe${}_{2}$. We find that an increase in Se bond length and bond-angle disorder significantly broadens the conduction band. The time-dependent behavior of the electronic eigenvalues is examined and transient events are observed in which an electronic state crosses the optical gap. The structural configurations which produce states in the optical gap are determined using an ab initio molecular-dynamics approach and are found to be in agreement with experimental photoluminescence and electron-spin-resonance data. We also find that a linear relationship exists between the root mean square of the thermal fluctuations of an electronic eigenvalue in time and its localization.