Reversible Pressure-Induced Partial Phase Transition in Few-Layer Black Phosphorus.

The experimental identification of structural transitions in layered black phosphorus (BP) under mechanical stress is essential to extend its application in microelectromechanical (MEMS) devices under harsh conditions. High-pressure Raman spectroscopic analysis of BP flakes suggests a transition pressure at ∼4.2 GPa, where the BP's crystal structure progressively transforms from an orthorhombic to a rhombohedral symmetry (blue phosphorus, bP). The phase transition has been identified by observing a transition from blueshift to redshift of the in-plane characteristic Raman modes (B2g and Ag2) with increasing pressure. Recovery of the vibrational frequencies for all three characteristic Raman modes confirms the reversibility of the structural phase transition. First-principles calculations provide insight into the behavior of the Raman modes of BP under high pressure and reveal the mechanism responsible for the partial phase transition from BP to bP, corresponding to a metastable equilibrium state where both phases coexist.

Chemical insights into the formation of Cu2ZnSnS4 films from all-aqueous dispersions for low-cost solar cells.

Cu2ZnSnS4 (CZTS) shows great potential for photovoltaic application because of its non-toxic earth-abundant components and good optoelectronic properties. Combining low-cost and environmentally friendly routes would be the most favorable approach for the development of CZTS solar cells. In this context, development of Cu2ZnSnS4 (CZTS) films from all-aqueous CZTS nanocrystals inks represents an interesting challenge. Here, we have highlighted a condensation regulation by the alkali ion size observed in the alkali series Li+ < Na+ < K+ < Rb+ < Cs+, and demonstrated the chemical stability of Cu2ZnSnS4 surfaces in basic aqueous dispersions. Data such as optimal nanocrystal size, critical cracking thickness and average thickness to fabricate micron crack-free films from all-aqueous chalcogenide nanocrystals dispersions were determined. From these results, a proof of concept for the formation of a crack-free film of 2.2 µm formed from an all-aqueous CZTS nanocrystals ink is given. When employing low-cost materials, removal of carbon impurities represents another important challenge. With the objective to fabricate residue-free films, a specific annealing strategy is proposed involving a high temperature purification step under Se partial pressure. Carbon removal is thus achieved via the CSe2 gas formation, simultaneously to the amorphous domains crystallization as demonstrated by Raman spectroscopy. These source data favoring the formation of residue-free, crack-free, annealed films should assist the large scale development of CZTS solar cells from low-cost and environmentally friendly, all -aqueous inks.

Theoretical study of polyiodide formation and stability on monolayer and bilayer graphene.

The presence of polyiodide complexes have been reported several times when carbon-based materials were doped by iodine molecules, but their formation mechanism remains unclear. By using first-principles calculations that include nonlocal correlation effects by means of a van der Waals density functional approach, we propose that the formation of triiodide (I3(-)) and pentaiodide (I5(-)) is due to a large density of iodine molecules (I2) in interaction with a carbonaceous substrate. As soon as the concentration of surface iodine reaches a threshold value of 12.5% for a graphene monolayer and 6.25% for a bilayer, these complexes spontaneously appear. The corresponding structural and energetic aspects, electronic structures and vibrational frequencies support this statement. An upshift of the Dirac point from the Fermi level with values of 0.45 and 0.52 eV is observed for adsorbed complexes on graphene and intercalated complexes between two layers, respectively. For doped-graphene, it corresponds to a graphene hole density of around 1.1 × 10(13) cm(-2), in quantitative agreement with experiments. Additionally, we have studied the thermal stability at room temperature of these adsorbed ions on graphene by means of ab initio molecular dynamics, which also shows successful p-doping with polyiodide complexes.

Polaron Vibronic Progression Shapes the Optical Response of 2D Perovskites.

The optical response of 2D layered perovskites is composed of multiple equally-spaced spectral features, often interpreted as phonon replicas, separated by an energy Δ ≃ 12 - 40 meV, depending upon the compound. Here the authors show that the characteristic energy spacing, seen in both absorption and emission, is correlated with a substantial scattering response above ≃ 200 cm-1 (≃ 25 meV) observed in resonant Raman. This peculiar high-frequency signal, which dominates both Stokes and anti-Stokes regions of the scattering spectra, possesses the characteristic spectral fingerprints of polarons. Notably, its spectral position is shifted away from the Rayleigh line, with a tail on the high energy side. The internal structure of the polaron consists of a series of equidistant signals separated by 25-32 cm-1 (3-4 meV), depending upon the compound, forming a polaron vibronic progression. The observed progression is characterized by a large Huang-Rhys factor (S > 6) for all of the 2D layered perovskites investigated here, indicative of a strong charge carrier - lattice coupling. The polaron binding energy spans a range ≃ 20-35 meV, which is corroborated by the temperature-dependent Raman scattering data. The investigation provides a complete understanding of the optical response of 2D layered perovskites via the direct observation of polaron vibronic progression. The understanding of polaronic effects in perovskites is essential, as it directly influences the suitability of these materials for future opto-electronic applications.

New probes based on carbon nano-cones for scanning probe microscopies.

All-graphenic carbon morphologies grown on individual carbon nanotubes (CNTs) consisting of short-fiber segments bearing sharp micro-/nano-cones at both ends were mounted as new probes for scanning probe microscopies (SPM). Three mounting procedures were tested, two based on focused ion and/or electron beam processes operated in scanning electron microscopes, and another based on an irradiation-free procedure under an optical microscope. The benefits and drawbacks of all the methods are described in details. The extent to which the structural integrity of the carbon material of the cones was affected by each of the mounting processes was also investigated using Raman spectroscopy and high-resolution transmission electron microscopy. The carbon cones were found to be sensitive to both ion and electron irradiation to an unusual extent with respect to structurally-close nano-objects such as multi-wall CNTs. This was assumed to be due to the occurrence of a large number of free graphene-edges at the cone surface. The suitability of such carbon cones as SPM probes is demonstrated, the characteristics of which make them potentially superior to Si-, diamond-, or CNT-probes.

Resonant laser-induced formation of double-walled carbon nanotubes from peapods under ambient conditions.

The selective excitation of fullerenes encapsulated in single-walled carbon nanotubes (SWCNTs) is carried out by irradiating them using a UV laser, the wavelength of which corresponds exactly to their maximum of absorption. Under such conditions, fullerenes strongly absorb the laser energy, open, and break, while the containing SWCNT merely acts as both a nanoreactor and a mold which is only weakly heated by the laser. The containing tube confines the fullerene fragments, promotes their reconstruction into an inner tube, and protects them from air oxidation. This leads to the overall formation of double-walled carbon nanotubes (DWCNTs). The transformation is found to strongly depend on the laser irradiance and dose. This proves that the related mechanism is a multiphoton photolysis, different from the previous heat-induced transformation attempts found in the literature, whether the heat is produced by means of a thermostat, infrared laser, or nonresonant UV laser. The actual peapod-to-DWCNT transformation is monitored by Raman spectroscopy and high-resolution transmission electron microscopy.

Texture, Nanotexture, and Structure of Carbon Nanotube-Supported Carbon Cones.

Graphene-based carbon micro-/nano-cones were prepared by depositing pyrolytic carbon onto individual carbon nanotubes as supports using a specific chemical vapor deposition process. They were investigated by means of high-resolution scanning electron microscopy, low-voltage aberration-corrected transmission electron microscopy, Raman spectroscopy, and molecular dynamics modeling. While the graphenes were confirmed to be perfect, the cone texture was determined to be preferably scroll-like, with the scroll turns being parallel to the cone axis. Correspondingly, many of the concentrically displayed graphenes (actually scroll turns) exhibit the same helicity vector. When radii of curvature are large enough, this could allow for coherent stacking to locally take place in spite of the lattice shift induced by the curvature. A particular care was taken on investigating the cone apexes, in which a specific type of graphene termination was observed, here designated as the "zip" defect. Calculations determined a plausible stable structure that such a defect type may correspond to. This defect was found to generate a very low Raman ID/ID' band ratio (1.5), for which physical reasons are proposed. Combining our results and that of the literature allowed proposing an identification chart for a variety of defects able to affect the graphene lattice or edges.

An embedded interfacial network stabilizes inorganic CsPbI3 perovskite thin films.

The black perovskite phase of CsPbI3 is promising for optoelectronic applications; however, it is unstable under ambient conditions, transforming within minutes into an optically inactive yellow phase, a fact that has so far prevented its widespread adoption. Here we use coarse photolithography to embed a PbI2-based interfacial microstructure into otherwise-unstable CsPbI3 perovskite thin films and devices. Films fitted with a tessellating microgrid are rendered resistant to moisture-triggered decay and exhibit enhanced long-term stability of the black phase (beyond 2.5 years in a dry environment), due to increasing the phase transition energy barrier and limiting the spread of potential yellow phase formation to structurally isolated domains of the grid. This stabilizing effect is readily achieved at the device level, where unencapsulated CsPbI3 perovskite photodetectors display ambient-stable operation. These findings provide insights into the nature of phase destabilization in emerging CsPbI3 perovskite devices and demonstrate an effective stabilization procedure which is entirely orthogonal to existing approaches.

International amphibian micronucleus standardized procedure (ISO 21427-1) for in vivo evaluation of double-walled carbon nanotubes toxicity and genotoxicity in water.

Considering the important production of carbon nanotubes (CNTs), it is likely that some of them will contaminate the environment during each step of their life cycle. Nevertheless, there is little known about their potential ecotoxicity. Consequently, the impact of CNTs on the environment must be taken into consideration. This work evaluates the potential impact of well characterized double-walled carbon nanotubes (DWNTs) in the amphibian larvae Xenopus laevis under normalized laboratory conditions according to the International Standard micronucleus assay ISO 21427-1:2006 for 12 days of half-static exposure to 0.1-1-10 and 50 mg L(-1) of DWNTs in water. Two different endpoints were carried out: (i) toxicity (mortality and growth of larvae) and (ii) genotoxicity (induction of micronucleated erythrocytes). Moreover, intestine of larvae were analyzed using Raman spectroscopy. The DWNTs synthetized by catalytic chemical vapor deposition (CCVD) were used as produce (experiment I) and the addition of Gum Arabic (GA) was investigated to improve the stability of the aqueous suspensions (experiment II). The results show growth inhibition in larvae exposed to 10 and 50 mg L(-1) of DWNTs with or without GA. No genotoxicity was evidenced in erythrocytes of larvae exposed to DWNTs, except to 1 mg L(-1) of DWNTs with GA suggesting its potential effect in association with DWNTs at the first nonacutely toxic concentration. The Raman analysis confirmed the presence of DWNTs into the lumen of intestine but not in intestinal tissues and cells, nor in the circulating blood of exposed larvae.

Intense Raman D Band without Disorder in Flattened Carbon Nanotubes.

Above a critical diameter, single- or few-walled carbon nanotubes spontaneously collapse as flattened carbon nanotubes. Raman spectra of isolated flattened and cylindrical carbon nanotubes have been recorded. The collapse provokes an intense and narrow D band, despite the absence of any lattice disorder. The curvature change near the edge cavities activates a D band, despite framework continuity. Theoretical calculations based on Placzek approximation fully corroborate this experimental finding. Usually used as a tool to quantify defect density in graphenic structures, the D band cannot be used as such in the presence of a graphene fold. This conclusion should serve as a basis to revisit materials comprising structural distortion where poor carbon organization was concluded on a Raman basis. Our finding also emphasizes the different visions of a defect between chemists and physicists, a possible source of confusion for researchers working in nanotechnologies.

Optimizing metal-support interphase for efficient fuel cell oxygen reduction reaction catalyst.

The development of cost-effective and highly-efficient electro-catalysts is essential for the advancement of proton exchange membrane fuel cells (PEMFC). We present a novel nitrogen-sulphur co-doped carbon nanotubes-few layer graphene1D-2D hybrid support formed by partially exfoliating multiwall carbon nanotubes (PECNT), to improve interface bonding to catalyst nanoparticles. Detailed Raman spectroscopy and STEM-EDS analyses demonstrate that active sites on the co-doped hybrid support ensure both uniform distribution and improved bonding of the catalyst nanoparticles to the support. Electrochemical studies show that Pt nanoparticles decorated on nitrogen-sulphur co-doped PECNT (Pt/NS-PECNT) have higher electrochemical active surface area and mass activity accompanied by low H2O2 formation and improved positive half-wave potential, as compared to those decorated on co-doped rGO-incorporated PECNT hybrid structure (Pt/NS-(rGO-PECNT)). Fuel cell measurements demonstrate a higher power density for our novel (Pt/NS-PECNT) electro-catalyst when compared to both Pt/NS-(rGO + PECNT), and commercial Pt/C electro-catalyst. We demonstrate in this work that the interconnectivity between Pt-nanoparticles and the dopant or defect sites on the support play a crucial role in enhancing the ORR activity, fuel cell performance, and durability of the catalyst.

Molecular nature of breakdown of the folic acid under hydrothermal treatment: a combined experimental and DFT study.

Using a combination of experimental Raman, FTIR, UV-VIS absorption and emission data, together with the corresponding DFT calculations we propose the mechanism of modification of the folic acid specifically under the hydrothermal treatment at 200 °C. We established that folic acid breaks down into fragments while the pteridine moiety remains intact likely evolving into 6-formylpterin with the latter responsible for the increase in fluorescence emission at 450 nm. The results suggest that hydrothermal approach can be used for production of other purpose-engineered fluorophores.

Indirect tail states formation by thermal-induced polar fluctuations in halide perovskites.

Halide perovskites possess enormous potential for various optoelectronic applications. Presently, a clear understanding of the interplay between the lattice and electronic effects is still elusive. Specifically, the weakly absorbing tail states and dual emission from perovskites are not satisfactorily described by existing theories based on the Urbach tail and reabsorption effect. Herein, through temperature-dependent and time-resolved spectroscopy on metal halide perovskite single crystals with organic or inorganic A-site cations, we confirm the existence of indirect tail states below the direct transition edge to arise from a dynamical Rashba splitting effect, caused by the PbBr6 octahedral thermal polar distortions at elevated temperatures. This dynamic effect is distinct from the static Rashba splitting effect, caused by non-spherical A-site cations or surface induced lattice distortions. Our findings shed fresh perspectives on the electronic-lattice relations paramount for the design and optimization of emergent perovskites, revealing broad implications for light harvesting/photo-detection and light emission/lasing applications.

Author Correction: Indirect tail states formation by thermal-induced polar fluctuations in halide perovskites.

The original version of this article incorrectly listed the present address of Bo Wu as 'Present address: Institute of Electronic Paper Displays, South China Academy of Advanced Optoelectronics, South China Normal University, Guangzhou, Guangdong Province 510006, China'. This is the author's primary affiliation. This has been corrected in both the PDF and HTML versions of the article.

Characterisation and in vivo ecotoxicity evaluation of double-wall carbon nanotubes in larvae of the amphibian Xenopus laevis.

Because of their outstanding properties, carbon nanotubes (CNTs) are being assessed for inclusion in many manufactured products. Due to their massive production and growing number of potential applications, the impact of CNTs on the environment must be taken into consideration. The present investigation evaluates the ecotoxicological potential of double-walled carbon nanotubes (DWNTs) in the amphibian larvae Xenopus laevis at a large range of concentrations in water (from 10 to 500 mgL(-1)). Acute toxicity and genotoxicity were analysed after 12 days of static exposure in laboratory conditions. Acute toxicity was evaluated according to the mortality and the growth of larvae. The genotoxic effects were analysed by scoring the micronucleated erythrocytes of the circulating blood of larvae according to the International Standard micronucleus assay. Moreover, histological preparations of larval intestine were prepared after 12 days of exposure for observation using optical and transmission electron microscopy (TEM). Finally, the intestine of an exposed larva was prepared on a slide for analyse by Raman imaging. The results showed no genotoxicity in erythrocytes of larvae exposed to DWNTs in water, but acute toxicity at every concentration of DWNTs studied which was related to physical blockage of the gills and/or digestive tract. Indeed, black masses suggesting the presence of CNTs were observed inside the intestine using optical microscopy and TEM, and confirmed by Raman spectroscopy analysis. Assessing the risks of CNTs requires better understanding, especially including mechanistic and environmental investigations.

Giant Electron-Phonon Coupling and Deep Conduction Band Resonance in Metal Halide Double Perovskite.

The room-temperature charge carrier mobility and excitation-emission properties of metal halide perovskites are governed by their electronic band structures and intrinsic lattice phonon scattering mechanisms. Establishing how charge carriers interact within this scenario will have far-reaching consequences for developing high-efficiency materials for optoelectronic applications. Herein we evaluate the charge carrier scattering properties and conduction band environment of the double perovskite Cs2AgBiBr6 via a combinatorial approach; single crystal X-ray diffraction, optical excitation and temperature-dependent emission spectroscopy, resonant and nonresonant Raman scattering, further supported by first-principles calculations. We identify deep conduction band energy levels and that scattering from longitudinal optical phonons- via the Fröhlich interaction-dominates electron scattering at room temperature, manifesting within the nominally nonresonant Raman spectrum as multiphonon processes up to the fourth order. A Fröhlich coupling constant nearing 230 meV is inferred from a temperature-dependent emission line width analysis and is found to be extremely large compared to popular lead halide perovskites (between 40 and 60 meV), highlighting the fundamentally different nature of the two "single" and "double" perovskite materials branches.

Enlightening the ultrahigh electrical conductivities of doped double-wall carbon nanotube fibers by Raman spectroscopy and first-principles calculations.

Highly aligned, packed, and doped carbon nanotube (CNT) fibers with electrical conductivities approaching that of copper have recently become available. These fibers are promising for high-power electrical applications that require light-weight, high current-carrying capacity cables. However, a microscopic understanding of how doping affects the electrical conductance of such CNT fibers in a quantitative manner has been lacking. Here, we performed Raman spectroscopy measurements combined with first-principles calculations to determine the position of the average Fermi energy and to obtain the temperature of chlorosulfonic-acid-doped double-wall CNT fibers under high current. Due to the unique way in which double-wall CNT Raman spectra depend on doping, it is possible to use Raman data to determine the doping level quantitatively. The correspondence between the Fermi level shift and the carbon charge transfer is derived from a tight-binding model and validated by several calculations. For the doped fiber, we were able to associate an average Fermi energy shift of ∼-0.7 eV with a conductance increase by a factor of ∼5. Furthermore, since current induces heating, local temperature determination is possible. Through the Stokes-to-anti-Stokes intensity ratio of the G-band peaks, we estimated a temperature rise at the fiber surface of ∼135 K at a current density of 2.27 × 108 A m-2 identical to that from the G-band shift, suggesting that thermalization between CNTs is well achieved.

Carbon nanotube ecotoxicity in amphibians: assessment of multiwalled carbon nanotubes and comparison with double-walled carbon nanotubes.

The potential impact of industrial multiwalled carbon nanotubes (MWNTs) was investigated under normalized laboratory conditions according to the International Standard micronucleus assay ISO 21427-1 for 12 days of half-static exposure to 0.1, 1, 10 and 50 mg/l of MWNTs in water. Three different end points were carried out for 12 days of exposure: mortality, growth inhibition and micronuclei induction in erythrocytes of the circulating blood of larvae. Raman spectroscopy analysis was used to study the presence of carbon nanotubes in the biological samples. Considering the high diversity of carbon nanotubes according to their different characteristics, MWNTs were analyzed in Xenopus larvae, comparatively to double-walled carbon nanotubes used in a previous study in similar conditions. Growth inhibition in larvae exposed to 50 mg/l of MWNTs was evidenced; however, no genetoxicity (micronucleus assay) was noticed, at any concentration. Carbon nanotube localization in the larvae leads to different possible hypothesis of mechanisms explaining toxicity in Xenopus.