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At least 1,063 records · Page 59

Light induced phase change in Cu{sub 2−x}Zn{sub 1.3}SnS{sub 4} thin films

Cu{sub 2}ZnSnS{sub 4} and its alloy based thin film solar cells have shown better photovoltaic performance under Cu-poor and Zn-rich conditions. However, the effect of Cu-stoichiometry on the coexistence of kesterite (KS), stannite and/or partially disordered kesterite (PD-KS) phases and their influence on photovoltaic performance is not clearly understood. Raman studies were carried out on Cu{sub 2−x}Zn{sub 1.3}SnS{sub 4} (x = 0, 0.3, and 0.5) thin films by changing the intensity of the incident laser beam. It was observed that both Cu-stoichiometry and incident laser beam intensity induce a disorder in the system. Disorder induced transformation of KS (I4{sup ¯}) to PD-KS (I4{sup ¯}2m) is explained by Raman studies.

36 MATERIALS SCIENCE↗

Nano-gold corking and enzymatic uncorking of carbon nanotube cups

Because of their unique stacked, cup-shaped, hollow compartments, nitrogen-doped carbon nanotube cups (NCNCs) have promising potential as nanoscale containers. Individual NCNCs are isolated from their stacked structure through acid oxidation and subsequent probe-tip sonication. The NCNCs are then effectively corked with gold nanoparticles (GNPs) by sodium citrate reduction with chloroauric acid, forming graphitic nanocapsules with significant surface-enhanced Raman signature. Mechanistically, the growth of the GNP corks starts from the nucleation and welding of gold seeds on the open rims of NCNCs enriched with nitrogen functionalities, as confirmed by density functional theory calculations. A potent oxidizing enzyme of neutrophils, myeloperoxidase (MPO), can effectively open the corked NCNCs through GNP detachment, with subsequent complete enzymatic degradation of the graphitic shells. Lastly, this controlled opening and degradation was further carried out in vitro with human neutrophils. In addition, the GNP-corked NCNCs were demonstrated to function as novel drug delivery carriers, capable of effective (i) delivery of paclitaxel to tumor-associated myeloid-derived suppressor cells (MDSC), (ii) MPO-regulated release, and (iii) blockade of MDSC immunosuppressive potential.

36 MATERIALS SCIENCE↗

Synthesis of graphene by cobalt-catalyzed decomposition of methane in plasma-enhanced CVD: Optimization of experimental parameters with Taguchi method

This article describes the significant roles of process parameters in the deposition of graphene films via cobalt-catalyzed decomposition of methane diluted in hydrogen using plasma-enhanced chemical vapor deposition (PECVD). The influence of growth temperature (700–850 °C), molar concentration of methane (2%–20%), growth time (30–90 s), and microwave power (300–400 W) on graphene thickness and defect density is investigated using Taguchi method which enables reaching the optimal parameter settings by performing reduced number of experiments. Growth temperature is found to be the most influential parameter in minimizing the number of graphene layers, whereas microwave power has the second largest effect on crystalline quality and minor role on thickness of graphene films. The structural properties of PECVD graphene obtained with optimized synthesis conditions are investigated with Raman spectroscopy and corroborated with atomic-scale characterization performed by high-resolution transmission electron microscopy and scanning tunneling microscopy, which reveals formation of continuous film consisting of 2–7 high quality graphene layers.

36 MATERIALS SCIENCE↗

Synthesis and Characterization of Silicon Nanowires by Electroless Etching

Silicon nanowires (SiNWs) were synthesized by two-step electroless etching of p-type Si (100) wafer and characterized by field emission scanning electron microscopy, UV–Vis spectroscopy, x-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and Raman spectroscopy. The vibrational signature at 1108 and 2087 cm{sup −1} confirmed SiNWs were passivated by both oxygen and hydrogen atoms. Raman peak at 517 cm{sup −1} indicated crystalline SiNWs with tailing toward redshift due to Fano effect. The Si(2p) and Si(2s) core orbital spectra of SiNWs were found at 99.8 and 150.5 eV, respectively. Moreover, the reflection of SiNWs is minimized to ~ 1 to 5% in the 650-nm wavelength.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

High pressure Raman spectroscopic studies of (p−chloroanilinium){sub 2}CuCl{sub 4}

(p−chloroanilinium){sub 2}CuCl{sub 4} has a corner shared layered structure of CuCl6{sup 4−} octahedra with p-chloroanilinium cation sandwiched between the layers. The CuCl{sub 6} octahedra are irregular due to Jahn-Teller distortion. We report our high pressure Raman results on this compound in the present manuscript. Our results indicate significant changes in Raman spectra at ∼ 3 GPa and ∼ 8 GPa. The changes at 3 GPa can be attributed to a reduction in puckering of the CuCl{sub 4}{sup 2−} layer and the transition at 8 GPa, which also leads to a colour change of this sample to deep red, could be due to delocalization of the eg electrons along with a reduction of the cooperative Jahn-Teller distortion in this layer. These changes were found to be reversible.

36 MATERIALS SCIENCE↗

The role of TiO{sub 2} in the B{sub 2}O{sub 3}-Na{sub 2}O-PbO-Al{sub 2}O{sub 3} glass system

Optical and vibrational studies have been carried out on 60B{sub 2}O{sub 3}.(20-x)Na{sub 2}O.10PbO.10Al{sub 2}O{sub 3}:xTiO{sub 2} (x=0, 1, 2, 3, 4, and 5 mol%) glasses, in order to understand the role of TiO{sub 2} in the 60B{sub 2}O{sub 3}.20Na{sub 2}O.10PbO.10Al{sub 2}O{sub 3} glass matrix. The X-ray patterns reveal homogeneous glasses over the entire compositional range. The absorption spectra show that the energy of the optical band gap ({Delta}E{sub opt}) and Urbach's energy (E{sub U}) decreases as TiO{sub 2} content increases. The changes observed in the Raman and IR spectra are related to the BO{sub 4}{yields}BO{sub 3} back conversion effect and the appearance of 'loose' BO{sub 4}{sup -} groups. The data indicate that titanium ions act as a network modifier. - Graphical abstract: Behavior of the relative integrated intensity of the IR bands, Ar=A{sub 4}/A{sub 3}, as TiO{sub 2} content increases. A decrease of 45% of Ar indicates that the number of BO{sub 4} groups is decreasing due to the BO{sub 4}{yields}BO{sub 3} back conversion. Highlights: > The XRD data show the amorphous character of all measured glasses. > The optical absorption results evidenced possible change of the glass structure. > The Raman data have revealed some vibrational modifications. > The overall results indicate that titanium acts as a network modifier.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Glass–water interaction: Effect of high-valence cations on glass structure and chemical durability

Borosilicate glass is a durable solid, but it dissolves when in contact with aqueous fluids. The dissolution mechanism, which involves a variety of sequential reactions that occur at the solid-fluid interface, has important implications for the corrosion resistance of industrial and nuclear waste glasses. In this study, spectroscopic measurements, dissolution experiments, and Monte Carlo simulations were performed to investigate the effect of high–valence cations (HVC) on the mechanisms of glass dissolution under dilute and near-saturated conditions. Raman and NMR spectroscopy were used to determine the structural changes that occur in glass, specifically network formers (e.g., Al, Si, and B), with the addition of the HVC element hafnium in the Na2O–Al2O3–B2O3–HfO2–SiO2 system (e.g., Na/[Al+B] = 1.0 and HfO2/SiO2 from 0.0 to 0.42). Spectroscopic measurements revealed that increasing hafnium content decreases N4 (tetrahedral boron/total boron) and increases the amount of Si—O—Hf moieties in the glass. Results from flow–through experiments conducted under dilute and near–saturated conditions show a decrease of approximately 100× or more in the dissolution rate over the series from 0 to 20 mol% HfO2. Comparing the average steady-state rates obtained under dilute conditions to the rates obtained for near-saturated conditions reveals a divergence in the magnitude between the average steady state rates measured in these different conditions. The reason for this divergence was investigated more thoroughly using Monte Carlo simulations. Simulations indicate that the divergence in glass dissolution behavior under dilute and near-saturated conditions result from the stronger binding of Si sites that deposit on the surface from the influent when Hf is present in the glass. As a result, the residence time at the glass surface of these newly-formed Si sites is longer in the presence of Hf, which increases the density of anchor sites from which altered layers with higher Si densities can form. These results illustrate the importance of understanding solid–water/solid-fluid interactions by linking macroscopic reaction kinetics to nanometer scale interfacial processes.

Environmental Molecular Sciences Laboratory↗

Spin-squeezing-induced enhancement of the sensitivity of an atomic clock using coherent population trapping

The coherent population trapping (CPT) effect is used for making compact atomic clocks. There are two types of CPT clocks: the one in which the Raman beams are applied continuously and the one in which two CPT pulses separated by a dark period are applied (Ramsey scheme). It is obvious that the technique of spin squeezing can only be applied to the Ramsey CPT clock to enhance the sensitivity. However, it is not apparent how to adapt to the CPT clock the protocols for the microwave clock using one-axis-twist squeezing (OATS), since the Ramsey CPT clock is not trivially equivalent to the Ramsey microwave clock. In this paper, we show explicitly how to adapt two protocols using OATS, namely, the Schrödinger cat state protocol (SCSP) and the generalization thereof, and the echo squeezing protocol (ESP), to the CPT clock. The ESP magnifies the phase shift by a factor of N / e , while the SCSP magnifies the phase shift by a factor of N / 2 , making it able to achieve a higher sensitivity in the presence of excess noise.

Li, Jinyang↗

Pressure effect on the electronic, structural, and vibrational properties of layered 2 H - MoTe 2

Layered molybdenum dichalchogenides differ from the classic example of bilayer graphene with their unique electronic properties: the application of pressure can continuously tune electronic structure since the band gap is controlled by delicate interlayer interaction. In this work, we have performed measurements of Raman scattering, synchrotron x-ray diffraction, electrical conductivity, and Hall coefficient combined with density functional theory calculations to synthetically study the pressure effect on $2H$-MoTe 2 . Both the experiments and calculations consistently demonstrate that MoTe2 undergoes a semiconductor-to-metallic (S-M) transition above 10 GPa. Unlike MoS 2 , the S-M transition is driven by the gradual tunability of electric structure and band gap without structural transition. The applied pressure also effectively enhances conductivity and carrier concentration while reducing the mobility, which makes MoTe 2 more suitable for applications than most other transition-metal dichalchogenides and allows it to be applied in strain-modulated optoelectronic devices.

36 MATERIALS SCIENCE↗

Probing electronic lifetimes and phonon anharmonicities in high-quality chemical vapor deposited graphene by magneto-Raman spectroscopy

We present a magneto-Raman study on high-quality single-layer graphene grown by chemical vapor deposition (CVD) that is fully encapsulated in hexagonal boron nitride by a dry transfer technique. By analyzing the Raman D, G, and 2D peaks, we find that the structural quality of the samples is comparable with state-of-the-art exfoliated graphene flakes. From B-field dependent Raman measurements, we extract the broadening and associated lifetime of the G peak due to anharmonic effects. Furthermore, we determine the decay width and lifetime of Landau level (LL) transitions from magneto-phonon resonances as a function of laser power. At low laser power, we find a minimal decay width of 140 cm{sup −1} highlighting the high electronic quality of the CVD-grown graphene. At higher laser power, we observe an increase of the LL decay width leading to a saturation, with the corresponding lifetime saturating at a minimal value of 18 fs.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Thermal and structural stability of single- and multi-walled carbon nanotubes up to 1800 °C in Argon studied by Raman spectroscopy and transmission electron microscopy

Graphical abstract: Display Omitted Highlights: ► Structural stability of carbon nanotubes up to 1800 °C in Argon (∼0.05 MPa). ► Thorough TEM and Raman spectroscopy of as received and heat treated CNTs. ► Analyses on the extent of structural changes during high temperature exposure. ► Discussion on safe upper temperature limit for practical use of SWCNTs and MWCNTs. -- Abstract: Effect of high temperature exposure (up to 1800 °C) on morphology of single- and multi-walled carbon nanotubes in Argon atmosphere has been studied using Raman spectroscopy and transmission electron microscopy. Although, as received nanotubes contained irregular graphene layers and other structural defects, microscopic observations revealed that heat treatment in Argon reduced the defect density and helped proper alignment of graphene layers. Raman spectra of as received and heat treated nanotubes strongly reinforced the microscopic observations. While, D-band to G-band intensity ratio in Raman spectra of 1800 °C heat treated multiwalled nanotubes reduced by ∼43% over as received one, this ratio for heat treated singlewalled nanotubes was ∼27% lower than that of the untreated specimen. Present study suggested that although, multiwalled nanotubes were structurally stable up to 1800 °C in an inert atmosphere having only a few nano-scale defects, singlewalled nanotubes suffered considerable damage at 1800 °C due to much thinner dimension than the former.

36 MATERIALS SCIENCE↗

Phase transition in two-dimensional monolayer (1L)-molybdenum disulfide induced by atomic S-basal plane gliding via synchrotron X-ray monochromatic beam radiation for superior electronic performance

Here, in this work, we report a novel approach to reduce the channel resistance by inducing a phase transition behavior from 2H to 1T in a monolayer MoS 2 (1L-MoS 2 ) by a synchrotron X-ray monochromatic beam (mono-beam) radiation. The effects of the biphase structure by the mono-beam on the 1L-MoS2 film were investigated using Raman spectra, photoluminescence (PL) spectra, scanning tunneling microscopy, and scanning tunneling spectroscopy, respectively. Through material characterization, we identified that the lateral sliding of S-vacancies along the S-plane in the 1L-MoS 2 is the key reason for the origin of unidirectional phase transition. The precise phase engineering triggered by the mono-beam radiation process allows the realization of field-effect transistors (FET) with 2X improvement in mobility toward a high on/off ratio (~10 8 ) and a near-ideal subthreshold swing of ~88 mV per decade. The validity of the phase engineering could be further extended for its application as a memory device, exhibiting a gate tunable conduction modulation behavior and a high resistance ratio of ~10 2 at a gate bias of 5 V with endurance of ~100 cycles. Furthermore, an artificial neural network using the synaptic weight update with accuracy of ~93 % was achieved.

36 MATERIALS SCIENCE↗

Impact of deposition conditions on the crystallization kinetics of amorphous GeTe films

The speed at which phase change memory devices can operate depends strongly on the crystallization kinetics of the amorphous phase. To better understand factors that affect the crystallization rate, we have investigated in this paper crystallization of GeTe films as a function of their deposition temperatures and deposition rates, using X-ray synchrotron radiation and Raman spectroscopy. As-deposited films were found to be fully amorphous under all conditions, even though films deposited at higher temperatures and lower rates experienced lower effective quench rates. Non-isothermal transformation curves show that the apparent crystallization temperature of GeTe films decreases with increasing deposition temperature and decreasing deposition rate. It was found that this correlates with a decrease in the activation energy for nucleation (calculated using Kissinger’s analysis), while the activation energy for crystal growth remained unaffected. Finally, from Raman spectroscopy measurements, it was found that increasing the deposition temperature or decreasing the deposition rate, and therefore the effective quench rate, reduces the number of homopolar Te–Te bonds and thereby reduces the barrier to crystal nucleation.

36 MATERIALS SCIENCE↗

Theory of time-resolved Raman scattering in correlated systems: Ultrafast engineering of spin dynamics and detection of thermalization

Ultrafast characterization and control of many-body interactions and elementary excitations are critical to understanding and manipulating emergent phenomena in strongly correlated systems. In particular, spin interaction plays an important role in unconventional superconductivity, but efficient tools for probing spin dynamics, especially out of equilibrium, are still lacking. To address this question, we develop a theory for nonresonant time-resolved Raman scattering, which can be a generic and powerful tool for nonequilibrium studies. We also use exact diagonalization to simulate the pump-probe dynamics of correlated electrons in the square-lattice single-band Hubbard model. Different ultrafast processes are shown to exist in the time-resolved Raman spectra and dominate under different pump conditions. For high-frequency and off-resonance pumps, we show that the Floquet theory works well in capturing the softening of bimagnon excitation. By comparing the Stokes and anti-Stokes spectra, we also show that effective heating dominates at small pump fluences, while a coherent many-body effect starts to take over at larger pump amplitudes and frequencies on resonance to the Mott gap. In conclusion, time-resolved Raman scattering thereby provides the platform to explore different ultrafast processes and design material properties out of equilibrium.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Ammonia sensing properties of V-doped ZnO:Ca nanopowders prepared by sol–gel synthesis

V-doped ZnO:Ca nanopowders with different V loading were prepared by sol–gel synthesis and successive drying in ethanol under supercritical conditions. Characterization data of nanopowders annealed at 700 °C in air, revealed that they have the wurtzite structure. Raman features of V-doped ZnO:Ca samples were found to be substantially modified with respect to pure ZnO or binary ZnO:Ca samples, which indicate the substitution of vanadium ions in the ZnO lattice. The ammonia sensing properties of V-doped ZnO:Ca thick films were also investigated. The results obtained demonstrate the possibility of a fine tuning of the sensing characteristics of ZnO-based sensors by Ca and V doping. In particular, their combined effect has brought to an enhanced response towards NH{sub 3} compared to bare ZnO and binary V-ZnO and Ca-ZnO samples. Raman investigation suggested that the presence of Ca play a key role in enhancing the sensor response in these ternary composite nanomaterials. - Graphical abstract: V-doped ZnO:Ca nanopowders prepared by sol–gel synthesis possess enhanced sensing characteristics towards NH{sub 3} compared to bare ZnO. - Highlights: • V-doped ZnO:Ca nanopowders with different V loading were prepared by sol–gel synthesis. • Raman features of V-doped ZnO:Ca samples indicate the substitution of V ions in the ZnO lattice. • Combined effects of dopants have brought to an enhanced response to NH{sub 3} compared to ZnO. • Ca play a key role in enhancing the sensor response of ternary V-doped ZnO:Ca composites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

MoS 2 Nanoplatelets on Hybrid Core-Shell (HyCoS) AuPd NPs for Hybrid SERS Platform for Detection of R6G

In this work, a novel hybrid SERS platform incorporating hybrid core-shell (HyCoS) AuPd nanoparticles (NPs) and MoS 2 nanoplatelets has been successfully demonstrated for strong surface-enhanced Raman spectroscopy (SERS) enhancement of Rhodamine 6G (R6G). A significantly improved SERS signal of R6G is observed on the hybrid SERS platform by adapting both electromagnetic mechanism (EM) and chemical mechanism (CM) in a single platform. The EM enhancement originates from the unique plasmonic HyCoS AuPd NP template fabricated by the modified droplet epitaxy, which exhibits strong plasmon excitation of hotspots at the nanogaps of metallic NPs and abundant generation of electric fields by localized surface plasmon resonance (LSPR). Superior LSPR results from the coupling of distinctive AuPd core-shell NP and high-density background Au NPs. The CM enhancement is associated with the charge transfer from the MoS 2 nanoplatelets to the R6G. The direct contact via mixing approach with optimal mixing ratio can effectively facilitate the charges transfer to the HOMO and LUMO of R6G, leading to the orders of Raman signal amplification. The enhancement factor (EF) for the proposed hybrid platform reaches ~10 10 for R6G on the hybrid SERS platform.

36 MATERIALS SCIENCE↗

Spatiotemporal distribution of chemical signatures exhibited by Myxococcus xanthus in response to metabolic conditions

Myxococcus xanthus is a common soil bacterium with a complex life cycle, which is known for production of secondary metabolites. However, little is known about the effects of nutrient availability on M. xanthus metabolite production. In this study, we utilize confocal Raman microscopy (CRM) to examine the spatiotemporal distribution of chemical signatures secreted by M. xanthus and their response to varied nutrient availability. Here, ten distinct spectral features are observed by CRM from M. xanthus grown on nutrient-rich medium. However, when M. xanthus is constrained to grow under nutrient-limited conditions, by starving it of casitone, it develops fruiting bodies, and the accompanying Raman microspectra are dramatically altered. The reduced metabolic state engendered by the absence of casitone in the medium is associated with reduced, or completely eliminated, features at 1140 cm –1 , 1560 cm –1 , and 1648 cm –1 . In their place, a feature at 1537 cm –1 is observed, this feature being tentatively assigned to a transitional phase important for cellular adaptation to varying environmental conditions. In addition, correlating principal component analysis heat maps with optical images illustrates how fruiting bodies in the center co-exist with motile cells at the colony edge. While the metabolites responsible for these Raman features are not completely identified, three M. xanthus peaks at 1004, 1151, and 1510 cm –1 are consistent with the production of lycopene. Thus, a combination of CRM imaging and PCA enables the spatial mapping of spectral signatures of secreted factors from M. xanthus and their correlation with metabolic conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantum size effects and tunable visible photoluminescence in a-Si:H/nc-Si:H superlattices

Quantum size effects are commonly observed in semiconductor nanocrystals and quantum dots. Here, we demonstrate unexpected quantum size effects in an unusual bulk system with multiple interfaces, consisting of alternating layers of nanocrystalline silicon (nc-Si:H) and amorphous silicon (a-Si:H) material thin films. The nc-Si:H layers consist of silicon nanocrystals embedded in an amorphous matrix, with an amorphous-crystalline interface separating the two structures. Plasma-enhanced chemical vapor deposition was utilized to grow nanocrystalline-amorphous silicon superlattices with a varying thickness of the nanocrystalline layer. Strong visible photoluminescence at room temperature was deconvoluted into individual peaks. As the nanocrystalline silicon layer thickness was increased from 5 to 20 nm, the photoluminescence spectra red-shifted with the emission wavelength varying as d 2 (d is the size of the nanocrystallites), the characteristic signature underlying quantum size effects. The size d of the nanocrystals was estimated by the measured shift of the Raman peak, and could be tuned by varying the thickness of the nc-Si:H layers. High resolution transmission electron microscopy show nanocrystals with a narrow size distribution, in an amorphous matrix. We also observe long wavelength photoluminescence from interfacial states that leads to persistent photconductivity. In conclusion nanocrystalline-amorphous superlattices offer a unique pathway for synthesizing embedded nanocrystals with controlled sizes and photonic signatures.

36 MATERIALS SCIENCE↗