Raman Spectroscopy Research Articles

Bio-ultrasonic synthesis of tin oxide quantum dots: effect of bio-carbon and their UV photocatalytic activity

An ecofriendly synthesis is realized to elaborate tin oxide quantum dots (SnO2 -QDs) using the plant aqueous extract of Aloe Barbadensis Miller (Aloe Vera) and SnCl4.5H2O at room temperature as a biological solvent and a precursor respectively. The effect of Aloe Vera extract concentration on the properties of SnO2-QDs has been studied. Morphological and structural properties of the as synthesized nanoparticles have been characterized using field effect-scanning electron microscopy (FE-SEM) and x-ray diffraction (XRD). The chemical composition of the nanoparticles was studied by Raman, energy dispersive x-ray (EDX) and Fourier transformation infra-red (FTIR) spectroscopy. The optical properties were investigated by UV–Vis spectrophotometer. The x-ray diffraction analysis showed that all samples have a tetragonal rutile structure, with an estimated crystal size closed to the exciton Bohr radius, indicating a strong confinement of the carriers in the material. The crystallite size of SnO2-QDs nanoparticles decreases as Aloe Vera plant extract concentration increases. The formation of SnO2-QDs and the presence of graphitic carbon in samples were confirmed by Raman spectroscopy, EDX analysis and Fourier transformation infra-red (FTIR) spectroscopy. The blue shift in absorption is the most likely due to the quantum confinement effect. An Ostwald-repining growth model based on the concept of surface energy has been proposed to explain the kinetic growth of SnO2 QDs. The photocatalytic activities of the as-prepared powders were confirmed by the fast and efficient degradation of methylene blue (MB).

Bio-synthesis, purification and structural analysis of Cyclosporine-A produced by Tolypocladium inflatum with valorization of agro-industrial wastes

Cyclosporine A (CyA) holds significant importance as a strategic immunosuppressive drug for organ transplant patients. In this study, we aimed to produce pure and cost-effective Cyclosporine A (CyA) by fermenting a culture medium containing dairy sludge, using Tolypocladium inflatum PTCC 5253. Following the fermentation stage, ethyl acetate extraction and fast protein liquid chromatography were employed for sample purification. The initial evaluation of the effectiveness of CyA obtained from these processes was performed through bioassay, wherein the antimicrobial clear zone diameter was found to be larger compared to the sample obtained from the fermentation culture. The concentration of CyA was determined using high-performance liquid chromatography, yielding values of 334 mg/L, 456 mg/L, and 578 mg/L for the fermented, extracted, and purified samples, respectively. Further analysis utilizing liquid chromatography tandem mass spectrometry (LC/MS/MS) confirmed a purity of 91.9% and proper agreement with the standard sample based on the ion intensity of Z/m 1205. To validate the structure of CyA, nuclear magnetic resonance spectroscopy, Fourier-transform infrared (FT-IR), and Raman spectroscopy were employed. X-ray diffraction and differential scanning calorimetry analyses demonstrated that the purified CyA exhibited a crystal structure similar to the standard sample, characterized by two broad peaks at 2θ = 9° and 20°, and comparable glass transition temperatures (57–68 °C for the purified sample; 53–64 °C for the standard sample). Dynamic light scattering analysis confirmed a uniform particle size distribution in both the purified and standard samples. The zeta potentials of the purified and standard samples were determined to be − 25.8 ± 0.16 and − 23.63 ± 0.12 mV, respectively. Our results demonstrate that dairy sludge can serve as a suitable culture medium for the production of (CyA).

Novel Li2−2xK2xPbP2O7 glass system: Synthesis, thermal, structural and dielectric properties

Novel Li2−2xK2xPbP2O7 system (x = 0, 0.2, 0.4, 0.6, 0.8, and 1 mol%) was synthesized through the conventional melt-quenching method. The amorphous and crystalline characteristics of the resulting compounds were investigated using X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The study assessed the effect of potassium doping on thermal parameters, including glass transition temperature (Tg), crystallization temperature (Tc), and overall thermal stability. The findings reveal that the stability does not consistently follow a single pattern with K2O doping. Notably, the Li1.6K0.4PbP2O7 glass exhibits the greatest stability. The addition of K2O led to a reduction of the density and an increase in the molar volume of the system. These observations align with FTIR results, which reveal that introducing additional potassium ions results in longer bond lengths and weaker bonds. The spectroscopic study was supported by Raman spectroscopy. Post-annealing XRD analysis revealed the presence of distinct crystalline phases that differed according to the K2O content The structure of the various phosphate groups in the synthesized materials after annealing was also analyzed using Fourier Transform Infrared (FTIR) spectroscopy. Moreover, dielectric studies were conducted over a range of frequencies, and the presence of the relaxation phenomenon as well as the influence of potassium content on dielectric features have been evidenced.

Gaining insights into the responses of individual yeast cells to ethanol fermentation using Raman tweezers and chemometrics

Saccharomyces cerevisiae is the most common microbe used for the industrial production of bioethanol, and it encounters various stresses that inhibit cell growth and metabolism during fermentation. However, little is currently known about the physiological changes that occur in individual yeast cells during ethanol fermentation. Therefore, in this work, Raman spectroscopy and chemometric techniques were employed to monitor the metabolic changes of individual yeast cells at distinct stages during high gravity ethanol fermentation. Raman tweezers was used to acquire the Raman spectra of individual yeast cells. Multivariate curve resolution-alternating least squares (MCR-ALS) and principal component analysis were employed to analyze the Raman spectra dataset. MCR-ALS extracted the spectra of proteins, phospholipids, and triacylglycerols and their relative contents in individual cells. Changes in intracellular biomolecules showed that yeast cells undergo three distinct physiological stages during fermentation. In addition, heterogeneity among yeast cells significantly increased in the late fermentation period, and different yeast cells may respond to ethanol stress via different mechanisms. Our findings suggest that the combination of Raman tweezers and chemometrics approaches allows for characterizing the dynamics of molecular components within individual cells. This approach can serve as a valuable tool in investigating the resistance mechanism and metabolic heterogeneity of yeast cells during ethanol fermentation.

Comparative study of iodine-doped and undoped pyrrole grafting with plasma on poly (glycerol sebacate) scaffolds and its human dental pulp stem cells compatibility.

This study addresses the morphological and chemical characterization of PGS scaffolds after (6, 12, 18, 24, and 30 min) residence in undoped pyrrole plasma (PGS-PPy) and the evaluation of cell viability with human dental pulp stem cells (hDPSCs). The results were compared with a previous study that used iodine-doped pyrrole (PGS-PPy/I). Analyses through SEM and AFM revealed alterations in the topography and quantity of deposited PPy particles. FTIR spectra of PGS-PPy scaffolds confirmed the presence of characteristic absorption peaks of PPy, with higher intensities observed in the nitrile and -C≡C- groups compared to PGS-PPy/I scaffolds, while raman spectra indicated a lower presence of polaron N+ groups. On the other hand, PGS scaffolds modified with PPy exhibited lower cytotoxicity compared to PGS-PPy/I scaffolds, as evidenced by the Live/Dead assay. Furthermore, the PGS-PPy scaffolds at 6 and 12 min, and particularly the PGS-PPy/I scaffold at 6 min, showed the best results in terms of cell viability by the fifth day of culture. The findings of this study suggest that undoped pyrrole plasma modification for short durations could also be a viable option to enhance the interaction with hDPSCs, especially when the treatment times range between 6 min and 12 min.

Unexpected weakened formation of disinfection byproducts and enhanced production of halates by cupric oxide during chlorination of peptide-bound aspartic acid

Under the condition that the residual chlorine is guaranteed, the biofilm still thrives in drinking water distribution systems through secreting a large number of extracellular polymeric substances (EPS), in which protein components are the primary precursor of disinfection byproducts (DBPs), mostly in the form of combined amino acids. The aim of this study is to investigate the action of CuO on the formation of halates (XO3−, ClO3− and BrO3−) and DBPs (trihalomethanes, THMs; haloacetonitriles, HANs) with aspartic acid tetrapeptide (TAsp) as protein surrogate. The presence of CuO promoted the self-decay rather than TAsp-induced decay of oxidants, resulting in an increase in XO3− yield and a decrease in DBPs yield. It was CuO-induced weaker production of cyanoacetic acid and 3-oxopropanoic acid that induced the decreased yields of HANs and THMs, respectively. The FTIR and Raman spectra indicate a weak complexation between CuO and TAsp. Given this, the CuO-HOX/OX− complexes were inferred to be reactive to HOX/OX− but less reactive to TAsp. The study helps to better understand the formation of XO3− and DBPs during the chlorination of EPS, and propose precise control strategies when biofilm boosts in water pipes.

Synthesis and structural characterization of a hydrated sodium–caesium tetracosatungstate(VI), Na5Cs19[W24O84]·21H2O

Crystal formation of pentasodium nonadecacesium tetracosatungstate(VI) heneikosahydrate, Na5Cs19[W24O84]·21H2O, was successfully achieved by the conversion of [H2W12O42]10− through the addition of excess Cs+. The crystal structure comprising the toroidal isopolyoxidometalate is presented, as well as its Raman spectrum. Na5Cs19(H2O)21W24O84 crystallizes in the rhombohedral space group R\overline{3} with an obverse centering. The title compound represents the addition of a new member to the isopolytungstate family with mixed alkali counter-ions and contains rarely observed five-coordinate tungsten(VI) atoms in the [W24O84]24− anion (site symmetry C 3i ) arising from the conversion mediated by Cs+ counter-ions.

Exploring photocurrent effects as a function of CdS shell in ultrasmall quantum dots

In this study, we report the photocurrent effects in CdSe/CdS ultrasmall quantum dots (USQDs). The photocurrent effects can be observed when photons with energy higher than the band gap energy illuminate the USQDs, generating of charge carries. Here we use two types of USQDs to analyze these effects: CdSe and CdSe/CdS core/shell. The Raman spectrum was used to confirm the presence or absence of the shell. The CdSe USQDs exhibited a photocurrent effect consistent with the pattern typically observed in semiconductor materials. The sample exhibited a rise time of 1.26 s when the light was turned on and a decay time of 0.70 s when the light was turned off, reaching a maximum current value of 12.90 pA. However, an overshoot phenomenon was observed in the CdSe/CdS USQDs when the light was turned off. This effect is related to the accumulation of charge carriers that appear when the USQDs are subjected to an electric field and the presence of light. Thus, this accumulation caused by the potential barrier formed by the shell is released when the light is turned off. The sample exhibited a rise time of 2.28 s when the light was turned on and a decay time of 2.59 s when the light was turned off, reaching a maximum current value of 70.51 pA. Therefore, we have demonstrated that it is possible to explore the photocurrent effects in CdSe/CdS USQDs.

Noncollinear Electric Dipoles in a Polar Chiral Phase of CsSnBr3 Perovskite.

Polar and chiral crystal symmetries confer a variety of potentially useful functionalities upon solids by coupling otherwise noninteracting mechanical, electronic, optical, and magnetic degrees of freedom. We describe two phases of the 3D perovskite, CsSnBr3, which emerge below 85 K due to the formation of Sn(II) lone pairs and their interaction with extant octahedral tilts. Phase II (77 K < T < 85 K, space group P21/m) exhibits ferroaxial order driven by a noncollinear pattern of lone pair-driven distortions within the plane normal to the unique octahedral tilt axis, preserving the inversion symmetry observed at higher temperatures. Phase I (T < 77 K, space group P21) additionally exhibits ferroelectric order due to distortions along the unique tilt axis, breaking both inversion and mirror symmetries. This polar and chiral phase exhibits second harmonic generation from the bulk and pronounced electrostriction and negative thermal expansion along the polar axis (Q22 ≈ 1.1 m4 C-2; αb = -7.8 × 10-5 K-1) through the onset of polarization. The structures of phases I and II were predicted by recursively following harmonic phonon instabilities to generate a tree of candidate structures and subsequently corroborated by synchrotron X-ray powder diffraction and polarized Raman and 81Br nuclear quadrupole resonance spectroscopies. Preliminary attempts to suppress unintentional hole doping to allow for ferroelectric switching are described. Together, the polar symmetry, small band gap, large spin-orbit splitting of Sn 5p orbitals, and predicted strain sensitivity of the symmetry-breaking distortions suggest bulk samples and epitaxial films of CsSnBr3 or its neighboring solid solutions as candidates for bulk Rashba effects.

On Liangzhu Culture Tremolite-Tempered Pottery: Social complexity, logistical networks and cross-craft interaction in Neolithic China

This investigation delves into the utilization of tremolite, a rare mineral, as a pottery temper for cooking vessels of the late Neolithic lower Yangtze Liangzhu culture. Raman spectroscopy analysis of 165 mineral-tempered pottery sherds from the Dazemiao site revealed that tremolite was the predominant tempering material for tripods (ding), whereas a mixture of feldspar and quartz was used for open-topped vats (da-kou-gang). SEM images indicate that the tremolite temper exhibits relatively coarse fiber structure, corresponding to one of the nephrite materials used for the Liangzhu jade. It is suggested that the Liangzhu miners reallocated materials according to nephrite quality, formulating different product lines, including different types of jade objects and pottery temper. Additionally, the utilization of tremolite temper persisted throughout the entire Liangzhu culture. The presence of tremolite-tempered pottery in regions without indigenous tremolite mines necessitated robust logistical networks for the transportation of these bulky materials. The tremolite temper not only reconfirms the strong ‘jade culture’ of Liangzhu, but also provides evidence of extensive socio-economic exchanges between different geographical regions on the Yangtze River delta.

In situ single-cell spontaneous Raman spectroscopy differentiates tumor-associated macrophages

The analysis of in situ single cells in tissue is crucial for the study of tumors. However, simultaneous analysis of multiple biomolecules for single cells by fluorescence immunohistochemistry is challenging. Spontaneous Raman spectroscopy provides biochemical fingerprints of individual cells in a label-free and nondestructive manner, yet it is not well applied to single cells in tissue. Here, we develop an in situ single-cell spontaneous Raman spectroscopy (SRS) system that can localize a single cell in tissue with fluorescence imaging, while obtaining the single-cell Raman spectra for molecular analysis. Our system is verified by measuring the standard polystyrene beads of different sizes. Measurements of in situ single macrophages in clinical cancerous and para-cancerous tissues are then performed. By using discriminant analysis, it is shown that CD68+ macrophages in cancerous and para-cancerous tissues are classified with an accuracy of 98.3 %. The molecular content of single macrophages in tissue is analyzed by using multivariate curve resolution-alternating least squares method. We find that the lipid content of tumor-associated macrophages in cancerous tissues is higher while both the contents of protein and nucleic acid are lower than those in para-cancerous tissues, which is challenging to achieve by conventional immunohistochemistry. Our in situ single-cell SRS system has the capability for the obtaining of molecular information of a localized single cell in tissue, which may find potential applications for clinical cancer diagnosis.

Oxide-Encapsulated Silver Electrocatalysts for Selective and Stable Syngas Production from Reactive Carbon Capture Solutions.

Electrolysis of bicarbonate-containing CO2 capture solutions is a promising approach towards achieving low-cost carbon-neutral chemicals production. However, the parasitic bicarbonate-mediated hydrogen evolution reaction (HER) and electrode instability in the presence of trace impurities remain major obstacles to overcome. This work demonstrates that the combined use of titanium dioxide (TiO2) overlayers with the chelating agent ethylene diamine tetra-acetic acid (EDTA) significantly enhances the selectivity and stability of Ag-based electrocatalysts for bicarbonate electrolysis. The amorphous TiO2 overlayers suppress the HER by over 50% at potentials more negative than -0.7 V vs. RHE, increasing the CO faradaic efficiency (FE) by 33% (relative). In situ surface-enhanced Raman spectroscopy (SERS) measurements reveal the absence of near-surface bicarbonate species and an abundance of CO2 reduction intermediates at the Ag|TiO2 buried interface, suggesting that the overlayers suppress HER by blocking bicarbonate ions from reaching the buried active sites. In accelerated degradation tests with 5 ppm of Fe(III) impurity, the addition of EDTA allows stable CO production with >47% FE, while the electrodes rapidly deactivate in the absence of EDTA. This work highlights the use of TiO2 overlayers for enhancing the CO:H2 ratio while simultaneously protecting electrocatalysts from impurities likely to be present in "open" carbon capture systems.

Silver-decorated three-dimensional ZnO nanoflowers enhancing the electromagnetic coupling for ultrasensitive SERS detection of multi-pesticide residues

—The development of sensitive analytical methods is of prime importance for the detection of pesticide residues on the surfaces of fruits and vegetables at extremely low concentrations. Here, we synthesized Ag-decorated three-dimensional ZnO nanoflowers (ZnO@Ag) composed of ultrathin nanosheets as surface-enhanced Raman spectroscopy (SERS) substrates. Combined with the finite-difference time-domain (FDTD) method, it is proven that the ultrathin nanosheets greatly improve the electromagnetic coupling between the two metal nanoparticles due to the high refractive index of ZnO and generate new “hot spots”. The nanosheets also endow the incident light with multiple reflections to motivate the local electromagnetic field. The substrate presents high sensitivity and the enhancement factor was as high as 2.98 × 107 utilizing R6G as probe molecules. The detection concentration of thiram and malachite green (MG) solutions can reach 10−10 M and 10−9 M, respectively. For the real-life sample assays, the substrate can simultaneously detect the two pesticides on apple skin with high sensitivity. The research also reveals the importance of semiconductors toward the local electromagnetic field enhancement in noble metal-semiconductor substrates, benefiting the realization of highly sensitive SERS substrates and the wide application of the SERS technology in real-world scenarios.

Evolution of radiation-induced damage in nuclear graphite – A comparative structural and microstructural study

Graphite, as a material for high-temperature gas-cooled reactors (HTGR), will be exposed to harsh environment. The stability of graphite structure under irradiation is of a key importance for efficiency, reliability and security of the Generation IV nuclear reactors. Three types of nuclear grade graphite were subjected to irradiation in this research – two commercially manufactured (IG-110 and NBG-17) and the laboratory's in-home material (NCBJ). The samples were exposed to 150 keV Ar+ and He+ ions bombardment at 400 °C with fluences ranging from 1E12 to 2E17 ion/cm2 in order to simulate in-reactor conditions. For analysis of the level of structure damage, type of created defects and crystallite size changes under ion irradiation ex-situ Raman spectroscopy was used. The methodology of spectra fitting was developed. Furthermore, SEM observation of irradiated materials was performed. Results showed structural degradation of materials by the means of amorphisation: slight at a low fluence level, rising rapidly at higher irradiation values. Furthermore, stronger structural disorder was found in the materials irradiated with heavier Ar+ ions than with lighter He+. Microstructural evolution of the nuclear graphites aligned with the structural deterioration in its stepwise character.

Preparation of waterborne anti-counterfeiting ink based on dual luminescent nanohybrids of bacterial cellulose nanocrystals and lanthanide‑nitrogen co-modified GQDs

To address the growing challenge of counterfeit prevention, this study developed a novel anti-counterfeiting ink system based on bacterial cellulose nanocrystals (BCNC) and lanthanide (Er, Yb)‑nitrogen (N) co-dropped graphene quantum dots (GQDs), which exhibited both photoluminescence (PL) and upconversion photoluminescence (UCPL) fluorescent properties as well as excellent rheological characteristics. The Er/Yb/N-GQDs with positive charges were synthesized by a one-step hydrothermal method and subsequently assembled with negatively charged BCNC through electrostatic self-assembly to fabricate a novel nanohybrid, Er/Yb/N-GQDs-BCNC. Raman spectroscopy results indicated an enhancement in the graphitization of GQDs due to lanthanide modification. The TEM results demonstrated a homogeneous distribution of Er/Yb/N-GQDs on BCNC, while XRD, FTIR, and XPS analyses confirmed their physical binding, thus validating the successful synthesis of novel nanohybrids. Then, Er/Yb/N-GQDs-BCNC was introduced into PVA waterborne ink and exhibited dual anti-counterfeiting properties by emitting blue fluorescence at Em 440 nm under Ex 370 nm and green fluorescence at Em 550 nm under Ex 980 nm. Furthermore, the incorporation of BCNC significantly enhanced the thixotropic behavior and yield stress of the PVA waterborne ink. This enhancement made the dual anti-counterfeiting fluorescent ink more suitable for diversified applications on different devices and various substrates, thus providing a novel approach for convenient and rapid information encryption and high security anti-counterfeiting.

Influence of ZnO and Pr6O11 incorporation on the structural, thermal, optical, mechanical, and magnetic properties of calcium lithium borate glasses

A new glass of calcium lithium borate with the chemical formula (62.75-x)B2O3 + 20CaO + 0.25Pr6O11 + 17Li2O + xZnO, where x = 0, 2.5, 5, 10, 20 (mol%) have been prepared by conventional melt-quenching process. The amorphous character has been confirmed by the very short-range ordering structural matrices demonstrated through X-ray diffraction.The Raman spectra of the prepared glass revealed an enhancement of host lattice distortions. Differential scanning calorimetry (DSC) estimated the glass transition temperature (Tg), the onset temperature of crystallization (Tc), and the melting temperature (Tm). The glass transition decreased from 441 °C to 431 °C with increasing ZnO content up to 10 mol%. The criteria of glass samples up to 10 % ZnO have higher strength, rigidity and higher level of thermal stability. The physical quantities as density, molar volume, inter-atomic distance, polaron radius, packing density, and oxygen packing density were calculated. The glass density increases while the molar volume decreases with ZnO content. The optical properties of glasses were investigated using UV–Vis spectrophotometer. The addition of ZnO enhances the light absorption in UV–Vis. The results of the calculated direct and indirect optical band gaps decrease from 3.663 eV to 3.233 eV for and from 3.167 eV to 2.648 eV for direct and indirect transitions respectively with the increment of ZnO addition. Additionally, the dispersion energy and static refractive index clearly increase while the oscillator energy declines. The Makishima-Mackenzie’s (M−M) method was employed to ascertain mechanical parameters, including elastic moduli, and Poisson’s ratio. The study revealed an enhancement to the mechanical properties as the content of ZnO increased. Vibrating sample magnetometer (VSM) was used to investigate the magnetic properties of the prepared glass and all samples exhibited a ferromagnetic behavior. The incorporation of ZnO act as glass modifier controlling their physical, optical and mechanical properties making the investigated glasses suitable for various applications.

W-rich zircons from the granite in the Hukeng tungsten deposit, South China: Genesis and exploration significance

South China is endowed with copious hydrothermal tungsten ore deposits, which are generally suggested to be associated with highly fractionated granites. However, the mechanism of tungsten enrichment and mineralization during magmatic-hydrothermal processes is not clear. Here, we clearly identified W-rich zircons (up to several thousand ppm) from the granite in the Hukeng tungsten deposit in South China. W-rich zircons are generally dark in cathodoluminescence images with irregular cracks, cavities and blurry oscillatory zones. They also show high contents of U, Nb, REEs, and high W/Gd ratios, which are not possible to be produced only by magma differentiation. Raman spectra of zircons indicate that these W-rich zircons have experienced different degrees of metamictization. Thus, these W-rich zircons should be crystallized from the late magma and subsequently altered by W-rich magmatic-hydrothermal fluids. W-rich zircons record the activity of W-rich ore-forming fluids which were exsolved from the granitic magma. We suggested that the W/Gd ratios of > 0.2 of zircons can be used as an indicator to estimate the W mineralization potential of a granite. This study provides a new pathway for using zircon to record tungsten mineralization processes and to guide tungsten ore prospecting.

High-Pressure Induced Continuous Structural Evolution of Kagome Antiferromagnet MgMn3(OH)6Cl2: A Structural Analogue to Quantum Spin Liquid Herbertsmithite.

MgMn3(OH)6Cl2 serves readily as the classical Heisenberg kagome antiferromagnet lattice spin frustration material, due to its similarity to herbertsmithite in composition and crystal structure. In this work, nanosheets of MgMn3(OH)6Cl2 are synthesized through a solid-phase reaction. Low-temperature magnetic measurements revealed two antiferromagnetic transitions, occurring at ∼8 and 55 K, respectively. Utilizing high-pressure synchrotron radiation X-ray diffraction techniques, the topological structural evolution of MgMn3(OH)6Cl2 under pressures up to 24.8 GPa was investigated. The sample undergoes a second-order structural phase transition from the rhombohedral phase to the monoclinic phase at pressures exceeding 7.8 GPa. Accompanying the disappearance of the Fano-like line shape in the high-pressure Raman spectra were the emergence of new Raman active modes and discontinuities in the variations of Raman shifts in the high-frequency region. The phase transition to a structure with lower symmetry was attributed to the pressure-induced enhancement of cooperative Jahn-Teller distortion, which is caused by the mutual substitution of Mn2+ ions from the kagome layer and Mg2+ ions from the triangular interlayer. High-pressure ultraviolet-visible absorption measurements support the structural evolution. This research provides a robust experimental approach and physical insights for further exploration of classical geometrical frustration materials with kagome lattice.

Surface morphology and associated high temperature evolution of copper covered with vapor deposited graphene

Copper (Cu) has been widely used as a conductor in the field of information-transport applications due to its high electrical conductivity. However, it is susceptible to high-temperature surface oxidation. In this work, we examined in detail about the effect of vapor-deposited graphene (Gr) coatings on the high-temperature evolution of Cu surfaces. Both morphology/chemical characterizations and electrical conductivity revealed significantly enhanced resistance to surface evolution, especially at temperatures below 300 °C, for Cu with Gr compared to pure Cu counterparts. Theoretical calculations suggested that the enhanced high-temperature stability of Gr/Cu was mainly attributed to the high energy barrier resistance of defects-containing Gr formation. Moreover, this barrier resistance weakened when the temperature approached 400 °C, leading to the formation of more defect-containing Gr, as confirmed by both quasi-static and statistical results of Raman spectra. The present findings may provide further insights into the surface protective mechanisms of Gr coatings on metals.

Microstructure evolution of carbon films, grown by physical vapor deposition, when substrate temperature is increased

We study how the increases of substrate temperature influence the structural properties of carbon films deposited by physical vapor deposition (PVD) techniques. We installed and adapted a heating system inside the deposition chamber, which can reach temperatures as high as 700 °C. Here we develop an experimental setup that allows us to obtain large films of the desired material on any substrate, with deposition times of the order of a minute. The characterization is based mainly on the analysis of the Raman spectra, where the evolution of the G and D peaks corresponding to the material in its amorphous phase is observed. With the increase of substrate temperature, the sp2 zones grow. A displacement to the right of the G peak and an increase in the ID/IG ratio is seen. At 700 °C a 2D zone at a frequency greater than 2000 cm−1 appears. Four Lorentzian-shaped bands are necessary to account for the peaks at this zone, whose centers correspond to different combinations of first-order ones. This shows that we are transitioning from an amorphous to a carbon phase with more ordered or graphitic zones and that we are near the crystallization point. This opens the path to produce structures similar to graphene using this method of deposition. The Tauc gap energy ratio decreases as temperature increases indicating that there is a graphitization of the sample. Transmission FTIR study is carried out at some of the intermediate temperatures, determining the type of bond at low frequencies. These bonds are consistent with the ones of the hydrogenated amorphous carbon (a-C:H) structure.