Investigating the Vibrational,Magnetic and Dielectric Properties,and Antioxidant Activity of Cerium Oxide Nanoparticles

Dielectric, magnetic and Raman measurements of cerium oxide nanoparticles obtained by the precipitation method are discussed. Morphological study was performed by scanning electron microscopy, confirming the formation of nanoparticles of 5–27 nm. The Raman spectra exhibited a strong band around 465 cm⁻¹, corresponding to the symmetrical stretching mode of the Ce-O8 vibrational unit. The nature of the room temperature ferromagnetism of cerium oxide nanoparticles was analyzed, taking into account the oxygen defects at the surface or interface of the nanoparticles. The evolution of dielectric constant, ε′, and dielectric loss, ε″ was studied as a function of frequency at different temperatures. Additionally, the variation of the electric conductivity versus temperature was investigated. Finally, complex impedance study of the cerium oxide nanoparticles was performed.     

Silver Cluster Interactions with Tyrosine: Towards Amino Acid Detection

Tyrosine (Tyr) is involved in the synthesis of neurotransmitters, catecholamines, thyroid hormones, etc. Multiple pathologies are associated with impaired Tyr metabolism. Silver nanoclusters (Ag NCs) can be applied for colorimetric, fluorescent, and surface-enhanced Raman spectroscopy (SERS) detection of Tyr. However, one should understand the theoretical basics of interactions between Tyr and Ag NCs. Thereby, we calculated the binding energy (E_b) between Tyr and Ag_n^q (n = 1–8; q = 0–2) NCs using the density functional theory (DFT) to find the most stable complexes. Since Ag NCs are synthesized on Tyr in an aqueous solution at pH 12.5, we studied Tyr⁻¹, semiquinone (SemiQ⁻¹), and Tyr⁻². Ag₃²⁺ and Ag₅⁺ had the highest E_b. The absorption spectrum of Tyr⁻² significantly red-shifts with the attachment of Ag₃²⁺, which is prospective for colorimetric Tyr detection. Ag₃²⁺ interacts with all functional groups of SemiQ⁻¹ (phenolate, amino group, and carboxylate), which makes detection of Tyr possible due to band emergence at 1324 cm⁻¹ in the vibrational spectrum. The ground state charge transfer between Ag and carboxylate determines the band emergence at 1661 cm⁻¹ in the Raman spectrum of the SemiQ⁻¹–Ag₃²⁺ complex. Thus, the prospects of Tyr detection using silver nanoclusters were demonstrated.     

Intramolecular Charge Transfer of Curcumin and Solvation Dynamics of DMSO Probed by Time-Resolved Raman Spectroscopy

Intramolecular charge transfer (ICT) of curcumin in dimethyl sulfoxide (DMSO) solution in the excited state was investigated by femtosecond electronic and vibrational spectroscopy. Excited-state Raman spectra of curcumin in the locally-excited and charge-transferred (CT) state of the S₁ excited state were separated due to high temporal (<50 fs) and spectral (<10 cm⁻¹) resolutions of femtosecond stimulated Raman spectroscopy. The ultrafast (0.6–0.8 ps) ICT and subsequent vibrational relaxation (6–9 ps) in the CT state were ubiquitously observed in the ground- and excited-state vibrational modes of the solute curcumin and the ν_CSC and ν_S=O modes of solvent DMSO. The ICT of curcumin in the excited state was preceded by the disruption of the solvation shells, including the breakage of hydrogen bonding between curcumin and DMSO molecules, which occurs at the ultrafast (20–50 fs) time scales.     

Single-step route to diamond-nanotube composite

Candle wax was used as a precursor for the production of a diamond-nanotube composite in a single step. The composite films were fabricated by sulfur-assisted hot-filament chemical vapor deposition technique. The morphology of the composite films was analyzed by scanning electron microscopy and transmission electron microscopy. Raman spectra of the films show characteristic diamond band at 1,332 cm⁻¹, D-band around 1,342 cm⁻¹, and graphitic G-band around 1,582 cm⁻¹. The electron energy-loss spectroscopy recorded at the carbon K-edge region shows signature features of diamond and carbon nanotube in the fabricated material. The ability to synthesize diamond-nanotube composites at relatively low temperatures by a single-step process opens up new possibilities for the fabrication of nanoelectronic devices.     

Spectroscopic Studies of R(+)-α-Lipoic Acid—Cyclodextrin Complexes

α-Lipoic acid (ALA) has a chiral center at the C6 position, and exists as two enantiomers, R(+)-ALA (RALA) and S(−)-ALA (SALA). RALA is naturally occurring, and is a cofactor for mitochondrial enzymes, therefore playing a major role in energy metabolism. However, RALA cannot be used for pharmaceuticals or nutraceuticals because it readily polymerizes via a 1,2-dithiolane ring-opening when exposed to light or heat. So, it is highly desired to find out the method to stabilize RALA. The purpose of this study is to provide the spectroscopic information of stabilized RALA and SALA through complexation with cyclodextrins (CDs), α-CD, β-CD and γ-CD and to examine the physical characteristics of the resultant complexes in the solid state. The RALA-CD structures were elucidated based on the micro fourier transform infrared (FT-IR) and Raman analyses. The FT-IR results showed that the C=O stretching vibration of RALA appeared at 1717 cm⁻¹ and then shifted on formation of the RALA-CD complexes. The Raman spectra showed that the S–S and C–S stretching vibrations for RALA at 511 cm⁻¹ (S–S), 631 cm⁻¹ (C–S) and 675 cm⁻¹ (C–S) drastically weakened and almost disappeared upon complexation with CDs. Several peaks indicative of O–H vibrations also shifted or changed in intensity. These results indicate that RALA and CDs form host-guest complexes by interacting with one another.     

Ultrafast Continuum IR Generation and Its Application in IR Spectroscopy

The spectral range of femtosecond time-resolved infrared spectroscopy is limited by the bandwidth of mid-IR pulses (100~400 cm⁻¹) generated from the combination of Ti:Sapphire amplifier, Optical Parametric Amplifier (OPA), and Difference Frequency Generation (DFG). To overcome this limitation, we implement a compact continuum mid-IR source producing ultrafast pulses that span the frequency range from 1000 to 4200 cm⁻¹ (from 10 to 2.4 μm), which utilize the mixing of fundamental, second-harmonic, and third-harmonic of 800 nm pulse in the air. After building an IR spectrometer with continuum IR and a monochromator, we found that the distortion of the measured IR spectrum originated from the contamination of higher-order diffraction. We used bandpass filters to eliminate the higher-order contributions and correct the measured IR spectrum. We further characterized the spectral properties of fundamental, second-harmonic, and third-harmonic fields after the plasmonic filamentation process, which helps to improve the efficiency of the continuum IR generation. Using the generated continuum IR pulses, we measured the IR absorption spectrum of a water–benzonitrile mixture, which was found to be consistent with the spectrum obtained with a commercial FT-IR spectrometer. The present work will be useful for the efficient generation of continuum IR pulses for IR pump-probe and two-dimensional IR spectroscopy experiments in the future.     

Raman Spectra and Ancient Life: Vibrational ID Profiles of Fossilized (Bone) Tissues

Raman micro-spectroscopy is a non-destructive and non-contact analytical technique that combines microscopy and spectroscopy, thus providing a potential for non-invasive and in situ molecular identification, even over heterogeneous and rare samples such as fossilized tissues. Recently, chemical imaging techniques have become an increasingly popular tool for characterizing trace elements, isotopic information, and organic markers in fossils. Raman spectroscopy also shows a growing potential in understanding bone microstructure, chemical composition, and mineral assemblance affected by diagenetic processes. In our lab, we have investigated a wide range of different fossil tissues, mainly of Mesozoic vertebrates (from Jurassic through Cretaceous). Besides standard spectra of sedimentary rocks, including pigment contamination, our Raman spectra also exhibit interesting spectral features in the 1200–1800 cm⁻¹ spectral range, where Raman bands of proteins, nucleic acids, and other organic molecules can be identified. In the present study, we discuss both a possible origin of the observed bands of ancient organic residues and difficulties with definition of the specific spectral markers in fossilized soft and hard tissues.     

Effect of deposition voltage on the microstructure of electrochemically deposited hydrogenated amorphous carbon films

Hydrogenated amorphous carbon (a-C:H) films were deposited on Si substrates by electrolysis in a methanol solution at ambient pressure and a low temperature (50 °C), using various deposition voltages. The influence of deposition voltage on the microstructure of the resulting films was analyzed by visible Raman spectroscopy at 514.5 nm and X-ray photoelectron spectroscopy (XPS). The contents of sp³ bonded carbon in the various films were obtained by the curve fitting technique to the C1s peak in the XPS spectra. The hardness and Young’s modulus of the a-C:H films were determined using a nanoindenter. The Raman characteristics suggest an increase of the ratio of sp³/sp² bonded carbon with increasing deposition voltage. The percentage of sp³-bonded carbon is determined as 33–55% obtained from XPS. Corresponding to the increase of sp³/sp², the hardness and Young’s modulus of the films both increase as the deposition voltage increases from 800 V to 1600 V.     

The Influence of UV Light on Photodegradation of Acetylsalicylic Acid

Photodegradation of the aqueous solutions of acetylsalicylic acid, in the absence (ASA) and the presence of excipients (ASE), is demonstrated by the photoluminescence (PL). A shift of the PL bands from 342 and 338 nm to 358 and 361–397 nm for ASA and ASE in solid state and as aqueous solutions was reported. By exposure of the solution of ASA 0.3 M to UV light, a decrease in the PL band intensity was highlighted. This behavior was revealed for ASA in the presence of phosphate buffer (PB) having the pH equal to 6.4, 7, and 8 or by the interaction with NaOH 0.3 M. A different behavior was reported in the case of ASE. In the presence of PB, an increase in the intensity of the PL band of ASE simultaneously with a change of the ratio between the intensities of the bands at 361–364 and 394–397 nm was highlighted. The differences between PL spectra of ASA and ASE have their origin in the presence of salicylic acid (SAL). The interaction of ASE with NaOH induces a shift of the PL band at 405–407 nm. Arguments for the reaction of ASA with NaOH are shown by Raman scattering and FTIR spectroscopy.     

Monitoring of molybdenum H-ZSM5 catalyst preparation by in situ ultraviolet Raman spectroscopy

In situ ultraviolet Raman spectroscopy was used to follow the preparation of Mo/H-ZSM5 catalysts by thermal treatment of a physical mixture of MoO₃ and H-ZSM5. The Raman spectra recorded from 300 to 1800 cm^–1 during the thermal treatment showed that MoO₃ spread over the zeolite support to form dispersed molybdenum oxide species. Curve-fitting analysis of the overall spectral profile for the samples after treatment at 600°C in O₂ showed the presence of three spectral components at 962, 868 and 815 cm^–1. The band at 815 cm^–1 was assigned to the zeolite support. The most intense band at 962 cm^–1 could be attributed to terminal Mo=O groups of isolated tetrahedrally coordinated monomers and the weaker band at 868 cm^–1 to bridging Mo–O–Mo groups of dimeric species. These last two assignments are not definitive and may be due to other unique structures of oxides of molybdenum on the zeolite framework.     

Monitoring the Simultaneous Implantation of Ti and Tb Cations to a Sacrificial Template and the Sol-Gel Synthesis of Tb-Doped TiO2 (Anatase) Hollow Spheres and Their Transition to Rutile Phase

Tb-doped TiO₂ (anatase) micro-hollow spheres (HSs) with nano-shells, in the range 0.00–3.00 at.% Tb, were successfully synthesized by a simultaneous chemical implantation route of both Ti and Tb cations from chlorides to a poly-styrene (PST)-co-poly-divinyl benzene (PDVB) sacrificial template, followed by controlled hydrolysis and polycondensation reactions. After water addition to the mixture of the precursors with the template, a decrease in the intensity and a shift to lower wavenumbers of the C=O absorption band in the IR spectra can indicate not only the anchoring of Ti and Tb ions to the carbonyl group of the template but also the hydrolysis of the implanted precursors. This latter process can involve a proton attack on the Ti–Cl, Tb–Cl and C=O bonds, the occupation of a vacant site by a water molecule, and then the dissociation of the dangling Ti–Cl, Tb–Cl ligands and C=O bonds. It gives rise to Ti_1−xTb_x[(OH)_4−uCl_v]@PST–PDVB and Ti_1−xTb_x[(OH)_4−y]@PST–PDVB complexes (x = 0.00, 0.0012, 0.0170 and 0.030). Finally, polycondensation of these species leads to Ti_1−xTb_xO_2−w′@PST–PDVB compounds. After subsequent thermal removal at 550 °C of the template, the IR bands of the core (template) totally vanished and new bands were observed in the 400–900 cm⁻¹ region which can be attributed to the metalloxane bondings (M–O, M’–O, M–O–M, M–O–M’ and/or M’–O–M’, being M and M’ = Ti and Tb, respectively, i.e., mainly vibration modes of anatase). Then, micron-sized HSs of TiO₂ and Tb-doped-TiO₂ (anatase) were obtained with nano-shells according to field emission gun scanning electron microscopy (FEG-SEM) and transmission electron microscopy (TEM) observations. Furthermore, X-ray photoelectron spectroscopy (XPS) measurements confirmed the presence of Tb⁴⁺ (38.5 and 41.2% for 1.70 and 3.00 at.% Tb, respectively) in addition to Tb³⁺ in the resulting HSs, with increasing Tb⁴⁺ content with both Tb doping and higher calcination temperatures. Then, these HSs can be considered as rare earth (RE) co-doped systems, at least for 1.70 and 3.00 at.% Tb contents being the transition to rutile phase favored by Tb doping for those compositions. Finally, diffusion of Tb from the inner parts to the surface of the HSs with the calcination treatments was also observed by XPS.     

Design and Synthesis of Novel Raman Reporters for Bioorthogonal SERS Nanoprobes Engineering

Surface-enhanced Raman spectroscopy (SERS) exploiting Raman reporter-labeled nanoparticles (RR@NPs) represents a powerful tool for the improvement of optical bio-assays due to RRs’ narrow peaks, SERS high sensitivity, and potential for multiplexing. In the present work, starting from low-cost and highly available raw materials such as cysteamine and substituted benzoic acids, novel bioorthogonal RRs, characterized by strong signal (10³ counts with FWHM < 15 cm⁻¹) in the biological Raman-silent region (>2000 cm⁻¹), RRs are synthesized by implementing a versatile, modular, and straightforward method with high yields and requiring three steps lasting 18 h, thus overcoming the limitations of current reported procedures. The resulting RRs’ chemical structure has SH-pendant groups exploited for covalent conjugation to high anisotropic gold-NPs. RR@NPs constructs work as SERS nanoprobes demonstrating high colloidal stability while retaining NPs’ physical and vibrational properties, with a limit of detection down to 60 pM. RR@NPs constructs expose carboxylic moieties for further self-assembling of biomolecules (such as antibodies), conferring tagging capabilities to the SERS nanoprobes even in heterogeneous samples, as demonstrated with in vitro experiments by transmembrane proteins tagging in cell cultures. Finally, thanks to their non-overlapping spectra, we envision and preliminary prove the possibility of exploiting RR@NPs constructs simultaneously, aiming at improving current SERS-based multiplexing bioassays.     

Raman and surface-enhanced Raman scattering of a series of size-separated polyynes

Solutions of hydrogen-capped polyynes were prepared by laser ablation of graphite powder in n-hexane and subjected to size separation by high-performance liquid chromatography. Solutions of size-selected polyynes C_nH₂ (n = 8–16) were investigated by normal Raman (NR) and surface-enhanced Raman scattering (SERS) spectroscopy. A main band appearing in the 2000–2200 cm⁻¹ region of the NR spectra showed a systematic downward shift as the chain length increased. The observed NR bands were assigned to Raman-active CC stretching vibrational modes by comparison with calculations based on density functional theory. Raman bands observed in SERS spectra were very broad and located at frequencies lower than the NR bands. A systematic band shift with increasing chain length was also observed for one of the bands. This band was thus assigned to a counterpart of the strong band in the NR spectra. These results made it possible to assign the origins of previously reported SERS bands of mixed polyyne solutions.     

Using Synchrotron Radiation-Based Infrared Microspectroscopy to Reveal Microchemical Structure Characterization: Frost Damaged Wheat vs. Normal Wheat

This study was conducted to compare: (1) protein chemical characteristics, including the amide I and II region, as well as protein secondary structure; and (2) carbohydrate internal structure and functional groups spectral intensities between the frost damaged wheat and normal wheat using synchrotron radiation-based Fourier transform infrared microspectroscopy (SR-FTIRM). Fingerprint regions of specific interest in our study involved protein and carbohydrate functional group band assignments, including protein amide I and II (ca. 1774–1475 cm⁻¹), structural carbohydrates (SCHO, ca. 1498–1176 cm⁻¹), cellulosic compounds (CELC, ca. 1295–1176 cm⁻¹), total carbohydrates (CHO, ca. 1191–906 cm⁻¹) and non-structural carbohydrates (NSCHO, ca. 954–809 cm⁻¹). The results showed that frost did cause variations in spectral profiles in wheat grains. Compared with healthy wheat grains, frost damaged wheat had significantly lower (p < 0.05) spectral intensities in height and area ratios of amide I to II and almost all the spectral parameters of carbohydrate-related functional groups, including SCHO, CHO and NSCHO. Furthermore, the height ratio of protein amide I to the third peak of CHO and the area ratios of protein amide (amide I + II) to carbohydrate compounds (CHO and SCHO) were also changed (p < 0.05) in damaged wheat grains. It was concluded that the SR-FTIR microspectroscopic technique was able to examine inherent molecular structure features at an ultra-spatial resolution (10 × 10 μm) between different wheat grains samples. The structural characterization of wheat was influenced by climate conditions, such as frost damage, and these structural variations might be a major reason for the decreases in nutritive values, nutrients availability and milling and baking quality in wheat grains.     

Constructing Morphologically Tunable Copper Oxide-Based Nanomaterials on Cu Wire with/without the Deposition of Manganese Oxide as Bifunctional Materials for Glucose Sensing and Supercapacitors

Morphologically tunable copper oxide-based nanomaterials on Cu wire have been synthesized through a one-step alkali-assisted surface oxidation process for non-enzymatic glucose sensing. Subsequently, copper oxide-based nanomaterials on Cu wire as a supporting matrix to deposit manganese oxide for the construction of heterostructured Mn-Cu bimetallic oxide architectures through spontaneous redox reaction in the KMnO₄ solution for supercapacitors. Field emission scanning electron microscopy (FESEM), field emission transmission electron microscopy (FETEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) confirmed that morphological and phase transformation from Cu(OH)₂ to CuO occurred in copper oxide-based nanomaterials on Cu wire with different degrees of growth reaction. In non-enzymatic glucose sensing, morphologically tunable copper oxide-based nanomaterials owned the high tunability of electrocatalytically active sites and intrinsic catalytic activity to meet efficient glucose electrooxidation for obtaining promoted non-enzymatic glucose sensing performances (sensitivity of 2331 μA mM⁻¹ cm⁻² and the limit of detection of 0.02 mM). In the supercapacitor, heterostructured Mn–Cu bimetallic oxide-based nanomaterials delivered abundant redox-active sites and continuous conductive network to optimize the synergistic effect of Mn and Cu redox species for boosting the pseudo-capacitance performance (areal capacitance value of 79.4 mF cm⁻² at 0.2 mA cm⁻² current density and capacitance retention of 74.9% after 1000 cycles). It concluded that morphologically tunable copper oxide-based nanomaterials on Cu wire with/without deposition of manganese oxide could be good candidates for the future design of synergistic multifunctional materials in electrochemical techniques.     

Facile mechano-chemical synthesis and enhanced photocatalytic performance of Cu2ZnSnS4 nanopowder

In the present study, Cu₂ZnSnS₄ (CZTS) powder was synthesized by the mechano-chemical method from its elemental constituents. X-ray diffraction (XRD), Energy-dispersive X-ray spectroscopy (EDS), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and diffusion reflectance spectroscopy (DRS) were used for characterization of structural, morphological and optical properties. XRD result confirmed that a highly crystalline CZTS phase corresponding to the kesterite structure was formed after 50 h ball milling. Raman analysis confirmed the existence of single phase CZTS without any other phases. FESEM and TEM images reveal the irregular CZTS nanoparticles with an average size of 90 nm. The elemental mapping of the CZTS nanopowder showed the uniform distribution in agreement with the stoichiometry. DRS result showed a band gap value of 1.53 eV. XPS result revealed the oxidation states as Cu⁺, Zn²⁺, Sn⁴⁺ and S²⁻. The photocatalytic activity of CZTS has been investigated through photodegradation of methylene blue (MB) and methyl orange (MO) dyes solution with different concentrations under visible light irradiation. Although the CZTS decomposed MO only 81% until 210 min, the MB solution was completely photodegraded after 100 min. A kinetic study by Langmuir-Hinshelwood (L-H) model indicated about 3.7 times faster degradation of MB than MO and also higher adsorption capacity for MB by CZTS. Furthermore, the prepared CZTS was reusable and can be repeatedly used for the removal of dyes from aqueous solutions.     

Preparation of a Z-Type g-C3N4/(A-R)TiO2 Composite Catalyst and Its Mechanism for Degradation of Gaseous and Liquid Ammonia

In this study, an (A-R)TiO₂ catalyst (ART) was prepared via the sol–gel method, and g-C₃N₄ (CN) was used as an amendment to prepare the g-C₃N₄/(A-R)TiO₂ composite catalyst (ARTCN). X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, N₂ adsorption–desorption curves (BET), UV–Vis diffuse absorption spectroscopy (UV–Vis DRS), and fluorescence spectroscopy (PL) were used to evaluate the structure, morphology, specific surface area, optical properties, and photocarrier separation ability of the catalysts. The results showed that when the modifier CN content was 0.5 g, the dispersion of the ARTCN composite catalyst was better, with stronger light absorption performance, and the forbidden band width was smaller. Moreover, the photogenerated electrons in the conduction band of ART transferred to the valence band of CN and combined with the holes in the valence band of CN, forming Z-type heterostructures that significantly improved the efficiency of the photogenerated electron-hole migration and separation, thus increasing the reaction rate. Gaseous and liquid ammonia were used as the target pollutants to investigate the activity of the prepared catalysts, and the results showed that the air wetness and initial concentration of ammonia had a great influence on the degradation of gaseous ammonia. When the initial concentration of ammonia was 50 mg/m³ and the flow rate of the moist air was 0.9 mL/min, the degradation rate of gaseous ammonia by ARTCN-0.5 reached 88.86%, and it had good repeatability. When the catalytic dose was 50 mg and the initial concentration of NH₄⁺ was 100 mg/L, the degradation rate of liquid ammonia by ARTCN-0.5 was 71.60% after 3 h of reaction, and small amounts of NO₃⁻ and NO₂⁻ were generated. The superoxide anion radical (·O₂⁻) and hydroxyl radical (·OH) were the main active components in the photocatalytic reaction process.     

Specific Mycoparasite-Fusarium Graminearum Molecular Signatures in Germinating Seeds Disabled Fusarium Head Blight Pathogen’s Infection

Advances in Infrared (IR) spectroscopies have entered a new era of research with applications in phytobiome, plant microbiome and health. Fusarium graminearum 3-ADON is the most aggressive mycotoxigenic chemotype causing Fusarium head blight (FHB) in cereals; while Sphaerodes mycoparasitica is the specific Fusarium mycoparasite with biotrophic lifestyle discovered in cereal seeds and roots. Fourier transform infrared (FTIR) spectroscopy analyses depicted shifts in the spectral peaks related to mycoparasitism mainly within the region of proteins, lipids, also indicating a link between carbohydrates and protein regions, involving potential phenolic compounds. Especially, S. mycoparasitica contributes to significant changes in lipid region 3050–2800 cm⁻¹, while in the protein region, an increasing trend was observed for the peaks 1655–1638 cm⁻¹ (amide I) and 1549–1548 cm⁻¹ (amide II) with changes in indicative protein secondary structures. Besides, the peak extending on the region 1520–1500 cm⁻¹ insinuates a presence of aromatic compounds in presence of mycoparasite on the F. graminearum root sample. Monitoring shift in improved seed germination, fungus-fungus interface through scanning electron microscopy (SEM) and confocal laser scanning microscopy (CLSM), and FTIR molecular signatures combined with principal component analysis (PCA) proved useful tools to detect an early mycoparasitism as a vital asset of the preventive biocontrol strategy against plant pathogens.     

The role of pressure on thin amorphous carbon films deposited using microwave surface wave plasma CVD

We report the effects of gas composition pressure (GCP) on the optical, structural and electrical properties of thin amorphous carbon (a-C) films grown on p-type silicon and quartz substrates by microwave surface wave plasma chemical vapor deposition (MW SWP CVD). The films, deposited at various GCPs ranging from 50 to 110 Pa, were studied by UV/VIS/NIR spectroscopy, atomic force microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and current–voltage characteristics. The optical band gap of the a-C film was tailored to a relatively high range, 2.3–2.6 eV by manipulating GCPs from 50 to 110 Pa. Also, spin density strongly depended on the band gap of the a-C films. Raman spectra showed qualitative structured changes due to sp³/sp² carbon bonding network. The surfaces of the films are found to be very smooth and uniform (RMS roughness < 0.5 nm). The photovoltaic measurements under light illumination (AM 1.5, 100 mW/cm²) show that short-circuit current density, open-circuit voltage, fill factor and photo-conversion efficiency of the film deposited at 50 Pa were 6.4 μA/cm², 126 mV, 0.164 and 1.4 × 10^− 4% respectively.     

Synthesis of graphene paper from pyrolyzed asphalt

A new technique for the synthesis of large sheets (>10 cm²) of multi-layered graphene is presented. The condensation onto a heated surface (≈650 °C) of fumes from the thermal decomposition of asphalt in a ceramic crucible produces carbon films with a metallic sheen. Heating was done by a Fisher burner (natural gas/air) flame and the crucible was covered but exposed to laboratory atmosphere. These films were determined to be multi-layered graphene by scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy (XPS), Raman and infrared spectroscopy and X-ray diffraction. XPS indicates that the films are primarily sp² hybridized carbon with small amounts of sp³ C–H and C–O or C–N functionalities. Based on the D band shift (1593 cm⁻¹) and the ratio of D band to G band (1354 cm⁻¹) of 0.93, the Raman spectrum also indicates that the material is sp² C with some nanocrystalline features. The infrared spectrum exhibits A_1U (868 cm⁻¹) and E_1U (1599 cm⁻¹) stretching of the intralayer bonds of graphene. This form of chemical vapor deposition may be a scalable to give much larger surface areas. Furthermore, the process does not require metal substrates. Deposition onto silica nanosprings and diatomites is demonstrated.