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The addition of zinc complexes to the syntheses of indium phosphide nanocrystals (InP NCs) has become commonplace, due to their ability to alter and significantly improve observed optical properties. In this paper, the role of zinc complexes on the synthesis and observed properties of InP is carefully examined. Produced InP and InP:Zn2+ NCs are thoroughly characterized from both structural (core and surface) and optical perspectives over a wide range of Zn2+ compositions (0%–43% atomic content). We find no differences in the physical (NC size and polydispersity) and structural properties (crystallographic phase) of InP and InP:Zn2+ NCs. Optically, significant changes are observed when zinc is added to InP syntheses, including blueshifted absorption edges and maxima, increased quantum yields, and the near elimination of surface state emission. These improved optical properties result from surface passivation by zinc carboxylate moieties. Changes to the optical properties begin at zinc concentrations as low as 5%, demonstrating the high sensitivity of InP optical properties to exogenous species. [ABSTRACT FROM AUTHOR]

In this study, we investigate the effect of the inclusion of nitrogen in amorphous carbon thin films deposited by pulsed laser deposition, which results in stress induced modifications to the band structure and the concomitant changes to the electronic transport properties. The microstructural changes due to nitrogen incorporation were examined using electron energy-loss spectroscopy and Raman scattering. The band structure was investigated using spectroscopic ellipsometry data in the range of 1.5–5 eV, which was fitted to the Tauc Lorentz model parametrization and optical transmittance measurements. The dielectric constant evaluated using optical techniques was compared to that obtained with electrical measurements, assuming a Poole-Frenkel type conduction process based on the best fits to data. The electrical conduction mechanism is discussed for both low and high electric fields, in the context of the shape of the band density of states. By relating a wide range of measurement techniques, a detailed relationship between the microstructure, and the optical and the electrical structures of a-CNx films is obtained. From these measurements, it was found that, primarily, the change in density of the film, with increasing nitrogen pressure, affects the band structure of the amorphous carbon nitride. This is due to the fact that the density affects the stress in the film, which also impacts the localized states in the band gap. These results are supported by density of states measurements using scanning tunneling spectroscopy. [ABSTRACT FROM AUTHOR]

The surface of mixed transition metal sulfur TixTa1-xS2 has been studied both by X-ray photoelectron spectroscopy and scanning tunneling microscopy over the entire range of stoichiometry 0⩽x⩽1. For compositions close to the native materials, we highlight according to x an evolution between the existence of a charge density wave (TaS2) and the existence of structural defects (TiS2), interpreted as metal atoms vacancies or migration within the vacant sites of the structure. The results obtained by XPS and scanning probe microscopy for intermediate compositions (0.4⩽x⩽0.6) lead us to propose a model in ordered domains, separated by frontier zones where the metal distribution is random. These various interpretations, supported by our experimental results, find their origin from the different electronic characteristics of native materials and their evolution according to the composition. On the basis of model systems, we have undertaken band structure calculations (FP-LAPW method) in order to highlight specific interactions occurred in TixTa1-xS2 when x varies between 0.4 and 0.6. Those make it possible to rationalize some of our experimental data. [Copyright &y& Elsevier]

The scanning tunneling microscopy (STM) and atomic force microscopy (AFM) images of two model systems M1/4TiS2 (M=Fe, Ni) were interpreted on the basis of the partial electron density ρ(r,EF) and total electron density ρ(r) of a slab which consists of seven (0 0 1) M1/4TiS2 atomic layers. The geometrical structure of the slabs investigated was optimized. Electronic structure calculations were performed using the ab initio periodic LCAO-DFT method. The top sulfur plane (0 0 1) imaged gives a different answer depending both of the compounds considered and the scanning probe microscopic instrument used. Theoretical calculations have then been carried out in order to improve our knowledge of the surface electronic structure of these inserted compounds and attempts are made to rationalize the experimental data. A specific behavior of the surface electronic structure in comparison with the 3D compounds (depending on the guest specie inserted) is shown. [Copyright &y& Elsevier]

The effects of metal insertion (iron, cobalt and nickel) into 1T-CdI2-type TiS2 layered crystals, expressed as MxTiS2, have been studied by X-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy (STM) and band structure calculations (FLAPW method). The stoichiometry x=1/4 was chosen because of specific crystallographic features of the compounds studied. We focused our interest on the role played by chalcogen atoms. S 2p core spectra are found to depend strongly on their chemical surroundings (Ti or Ti and M) and on the guest metal. We imaged the top sulfur plane (001) for Fe1/4TiS2, Co1/4TiS2 and Ni1/4TiS2 and note that the results also depend on the compound considered. Theoretical calculations have been carried out in order to improve our knowledge of the electronic structure of M1/4TiS2 compounds and attempts are made to rationalize the experimental data. [Copyright &y& Elsevier]

The surface of Ni1/4TiS2 was investigated by X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM). Electronic calculations were performed using the ab initio Hartree–Fock program crystal. The XPS results (chemical shift of core peaks) are satisfactorily accounted for through a Mulliken population analysis. Concerning the STM results, we imaged the top sulfur plane (0 0 1) and interpret the data on the basis of the partial electron density of a slab which consist of seven (0 0 1) Ni1/4TiS2 layers. It was found that the bright spots in experimental STM images correspond to sulfur atoms in a single metallic environment (Ti atoms). Beside higher electronic density, these atoms are highlighted because of their proximity to the tip compared with sulfur atoms in a double environment (Ti and Ni). [Copyright &y& Elsevier]

Abstract: Supported molybdenum-sulfide nanoparticles are known catalysts for petroleum hydrodesulfurization as well as for electrochemical hydrogen evolution. In this study, we investigate molybdenum-sulfide nanoparticles supported on Au(111) using X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM), aiming to correlate spectroscopically determined chemical states with atomically resolved nanostructure. The results of this study allow us to conclude the following: (1) the XPS results from our model system are in good agreement with previously published results on supported MoS2 for industrial applications, validating in part the fidelity of the model system; (2) STM reveals that catalytically active, crystalline MoS2 nanoparticles exhibiting the well-known metallic edge state are only present after a post-deposition annealing step in the synthesis procedure, without which the particles exhibit amorphous shapes and incomplete sulfidation; and (3) the sulfided nanoparticles are found to be stable in air at room temperature. [Copyright &y& Elsevier]

Supported metal single atom catalysis is a dynamic research area in catalysis science combining the advantages of homogeneous and heterogeneous catalysis. Understanding the interactions between metal single atoms and the support constitutes a challenge facing the development of such catalysts, since these interactions are essential in optimizing the catalytic performance. For conventional carbon supports, two types of surfaces can contribute to single atom stabilization: the basal planes and the prismatic surface; both of which can be decorated by defects and surface oxygen groups. To date, most studies on carbon-supported single atom catalysts focused on nitrogen-doped carbons, which, unlike classic carbon materials, have a fairly well-defined chemical environment. Herein we report the synthesis, characterization and modeling of rhodium single atom catalysts supported on carbon materials presenting distinct concentrations of surface oxygen groups and basal/prismatic surface area. The influence of these parameters on the speciation of the Rh species, their coordination and ultimately on their catalytic performance in hydrogenation and hydroformylation reactions is analyzed. The results obtained show that catalysis itself is an interesting tool for the fine characterization of these materials, for which the detection of small quantities of metal clusters remains a challenge, even when combining several cutting-edge analytical methods., (© 2024 Wiley-VCH GmbH.)

II-V semiconductor nanocrystals such as Cd 3 P 2 and Zn 3 P 2 have enormous potential as materials in next-generation optoelectronic devices requiring active optical properties across the visible and infrared range. To date, this potential has been unfulfilled due to their inherent instability with respect to air and moisture. Core-shell system Cd 3 P 2 /Zn 3 P 2 is synthesized and studied from structural (morphology, crystallinity, shell diameter), chemical (composition of core, shell, and ligand sphere), and optical perspectives (absorbance, emission-steady state and time resolved, quantum yield, and air stability). The improvements achieved by coating with Zn 3 P 2 are likely due to its identical crystal structure to Cd 3 P 2 (tetragonal), highlighting the key role crystallographic concerns play in creating cutting edge core-shell NCs.

The quest of exploring alternative materials for the replacement of toxic cadmium- and lead-based quantum dots (QDs) is necessary for envisaging a sustainable future but remains highly challenging. Tackling this issue, we present the synthesis of Zn3P2 nanocrystals (NCs) of unprecedented quality. New, reactive zinc precursors yield highly crystalline, colloidally stable particles, exhibiting oxide-free surfaces, size tunability and outstanding optical properties relative to previous reports of zinc phosphide QDs.

Understanding the modification of the graphene's electronic structure upon doping is crucial for enlarging its potential applications. We present a study of nitrogen-doped graphene samples on SiC(000) combining angle-resolved photoelectron spectroscopy, scanning tunneling microscopy and spectroscopy and X-ray photoelectron spectroscopy (XPS). The comparison between tunneling and angle-resolved photoelectron spectra reveals the spatial inhomogeneity of the Dirac energy shift and that a phonon correction has to be applied to the tunneling measurements. XPS data demonstrate the dependence of the N 1s binding energy of graphitic nitrogen on the nitrogen concentration. The measure of the Dirac energy for different nitrogen concentrations reveals that the ratio usually computed between the excess charge brought by the dopants and the dopants' concentration depends on the latter. This is supported by a tight-binding model considering different values for the potentials on the nitrogen site and on its first neighbors.

Many potential applications of graphene require either the possibility of tuning its electronic structure or the addition of reactive sites on its chemically inert basal plane. Among the various strategies proposed to reach these objectives, nitrogen doping, i.e., the incorporation of nitrogen atoms in the carbon lattice, leads in most cases to a globally n-doped material and to the presence of various types of point defects. In this context, the interactions between chemical dopants in graphene have important consequences on the electronic properties of the systems and cannot be neglected when interpreting spectroscopic data or setting up devices. In this report, the structural and electronic properties of complex doping sites in nitrogen-doped graphene have been investigated by means of scanning tunneling microscopy and spectroscopy, supported by density functional theory and tight-binding calculations. In particular, based on combined experimental and simulation works, we have systematically studied the electronic fingerprints of complex doping configurations made of pairs of substitutional nitrogen atoms. Localized bonding states are observed between the Dirac point and the Fermi level in contrast with the unoccupied state associated with single substitutional N atoms. For pyridinic nitrogen sites (i.e., the combination of N atoms with vacancies), a resonant state is observed close to the Dirac energy. This insight into the modifications of electronic structure induced by nitrogen doping in graphene provides us with a fair understanding of complex doping configurations in graphene, as it appears in real samples.

Grain boundaries in epitaxial graphene on the SiC(0001̅) substrate are studied using scanning tunneling microscopy and spectroscopy. All investigated small-angle grain boundaries show pronounced out-of-plane buckling induced by the strain fields of constituent dislocations. The ensemble of observations determines the critical misorientation angle of buckling transition θc = 19 ± 2°. Periodic structures are found among the flat large-angle grain boundaries. In particular, the observed θ = 33 ± 2° highly ordered grain boundary is assigned to the previously proposed lowest formation energy structural motif composed of a continuous chain of edge-sharing alternating pentagons and heptagons. This periodic grain boundary defect is predicted to exhibit strong valley filtering of charge carriers thus promising the practical realization of all-electric valleytronic devices.

Using scanning tunnelling microscopy and spectroscopy, we investigated the atomic and electronic structure of nitrogen-doped single walled carbon nanotubes synthesized by chemical vapor deposition. The insertion of nitrogen in the carbon lattice induces several types of point defects involving different atomic configurations. Spectroscopic measurements on semiconducting nanotubes reveal that these local structures can induce either extended shallow levels or more localized deep levels. In a metallic tube, a single doping site associated with a donor state was observed in the gap at an energy close to that of the first van Hove singularity. Density functional theory calculations reveal that this feature corresponds to a substitutional nitrogen atom in the carbon network.

Prior to the implementation of multi-walled carbon nanotubes in microelectronic devices, investigating their electronic structure down to the nanometer scale is necessary. In that prospect, we used scanning tunneling microscopy (STM) to study the detailed atomic scale structure of double-walled carbon nanotubes, each comprising two rolled monolayers of graphene. Atomically resolved STM images usually displayed a motif and periodicity similar to that found in graphite but, on selected regions, atomically resolved motifs with a clearly defined superstructure were observed. This phenomenon has been reported previously but without a suitable explanation. We discuss the origin of this behavior in terms of modified stacking sequences due to the mismatch in registry between the chiral angles of the inner and the outer shells, associated with the interaction between the two carbon monolayers. These phenomena must be taken into account for the realization of lateral interference devices based on carbon nanotubes or graphene layers.

The atomic and electronic structure of a twisted and collapsed double-walled carbon nanotube was characterized using scanning tunneling microscopy and spectroscopy. It was found that the deformation opens an electronic band gap in an otherwise metallic nanotube, which has major ramifications on the use of carbon nanotubes for electronic applications. Fundamentally, the importance of the intershell interaction in this double-walled carbon nanotube points to the potential of a reversible metal-semiconductor junction, which can have device applications, as well as a caution in the design of semiconductor components based on carbon nanotubes. Lattice registry effects between the two neighboring walls evidenced by atomically resolved images confirm earlier first principle calculations indicating that the helicity influences the collapsed structure and show excellent agreement with the predicted twisted-collapse mode.

We report the electrical characterization of single-walled carbon nanotubes (SWCNTs) trapped between two electrodes by dielectrophoresis (DEP). At high frequency, SWCNTs collected by DEP are expected to be of metallic type. Indeed current-voltage (I-V) measurements for devices made at 10 MHz show high values of conductivity and exhibit metallic behavior with linear and symmetric electrical features attributed to ohmic conduction. At low frequency, SWCNTs attracted by DEP are expected to be of semiconducting nature. Devices made at 10 kHz behave as semiconductors and demonstrate nonlinear and rectifying electrical characteristics with conductivities many orders of magnitude below the sample resulting from high-frequency immobilization of SWCNTs. Conducting atomic force microscopy (C-AFM) and current density calculation results are presented to reinforce results obtained by I-V measurements which clearly show type separation of SWCNTs after DEP experiments.

Evidence for modified electronic structure in double-walled carbon nanotubes with respect to their individual inner and outer constituent single-walled nanotubes is provided by scanning tunneling microscopy and spectroscopy experiments. The contribution originating from the inner tube to the local density of states of the double-walled system was identified in agreement with previous theoretical calculations. Consequently, the chiral index for the inner tube was extracted based on the additional van Hove singularities present in the experimental tunneling spectra.

The growth of carbon nanotubes from Ni catalysts is reversed and observed in real time in a transmission electron microscope, at room temperature. The Ni catalyst is found to be Ni3C and remains attached to the nanotube throughout the irradiation sequence, indicating that C most likely diffuses on the surface of the catalyst to form nanotubes. We calculate the energy barrier for saturating the Ni3C (2-13) surface with C to be 0.14 eV, thus providing a low-energy surface for the formation of graphene planes.