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The rapidly expanding demand for photovoltaics (PVs) requires stable, quick, and easy to manufacture solar cells based on socioeconomically and ecologically viable earth-abundant resources. Sb 2 S 3 has been a potential candidate for solar PVs and the efficiency of planar Sb 2 S 3 thin-film solar cells has witnessed a reasonable rise from 5.77% in 2014 to 8% in 2022. Herein, the aim is to bring new insight into Sb 2 S 3 solar cell research by investigating how the bulk and surface properties of the Sb 2 S 3 absorber and the current-voltage and deep-level defect characteristics of solar cells based on these films are affected by the ultrasonic spray pyrolysis deposition temperature and the molar ratio of thiourea to SbEX in solution. The properties of the Sb 2 S 3 absorber are characterized by bulk- and surface-sensitive methods. Solar cells are characterized by temperature-dependent current-voltage, external quantum efficiency, and deep-level transient spectroscopy measurements. In this paper, the first thin-film solar cells based on a planar Sb 2 S 3 absorber grown from antimony ethyl xanthate (SbEX) by ultrasonic spray pyrolysis in air are demonstrated. Devices based on the Sb 2 S 3 absorber grown at 200 °C, especially from a solution of thiourea and SbEX in a molar ratio of 4.5, perform the best by virtue of suppressed surface oxidation of Sb 2 S 3 , favorable band alignment, Sb-vacancy concentration, a continuous film morphology, and a suitable film thickness of 75 nm, achieving up to 4.1% power conversion efficiency, which is the best efficiency to date for planar Sb 2 S 3 solar cells grown from xanthate-based precursors. Our findings highlight the importance of developing synthesis conditions to achieve the best solar cell device performance for an Sb 2 S 3 absorber layer pertaining to the chosen deposition method, experimental setup, and precursors.

A comprehensive study of bulk molybdenum dichalcogenides is presented with the use of soft and hard X-ray photoelectron (SXPS and HAXPES) spectroscopy combined with hybrid density functional theory (DFT). The main core levels of MoS 2 , MoSe 2 , and MoTe 2 are explored. Laboratory-based X-ray photoelectron spectroscopy (XPS) is used to determine the ionization potential (IP) values of the MoX 2 series as 5.86, 5.40, and 5.00 eV for MoSe 2 , MoSe 2 , and MoTe 2 , respectively, enabling the band alignment of the series to be established. Finally, the valence band measurements are compared with the calculated density of states which shows the role of p-d hybridization in these materials. Down the group, an increase in the p-d hybridization from the sulfide to the telluride is observed, explained by the configuration energy of the chalcogen p orbitals becoming closer to that of the valence Mo 4d orbitals. This pushes the valence band maximum closer to the vacuum level, explaining the decreasing IP down the series. High-resolution SXPS and HAXPES core-level spectra address the shortcomings of the XPS analysis in the literature. Furthermore, the experimentally determined band alignment can be used to inform future device work., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Shell-isolated nanoparticles (SHINs) with a 37 nm gold core and an 11 nm tin dioxide (SnO 2 ) coating exhibited long-life Raman enhancement for 3 months and a wide pH stability of pH 2-13 in comparison with conventional SiO 2 -coated SHINs. Herein, Au-SnO 2 is demonstrated as a more durable SHIN for use in the technique Shell-Isolated Nanoparticles for Enhanced Raman Spectroscopy (SHINERS)., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

A newly reported compound, CuAgBiI 5 , is synthesized as powder, crystals, and thin films. The structure consists of a 3D octahedral Ag + /Bi 3+ network as in spinel, but occupancy of the tetrahedral interstitials by Cu + differs from those in spinel. The 3D octahedral network of CuAgBiI 5 allows us to identify a relationship between octahedral site occupancy (composition) and octahedral motif (structure) across the whole CuI-AgI-BiI 3 phase field, giving the ability to chemically control structural dimensionality. To investigate composition-structure-property relationships, we compare the basic optoelectronic properties of CuAgBiI 5 with those of Cu 2 AgBiI 6 (which has a 2D octahedral network) and reveal a surprisingly low sensitivity to the dimensionality of the octahedral network. The absorption onset of CuAgBiI 5 (2.02 eV) barely changes compared with that of Cu 2 AgBiI 6 (2.06 eV) indicating no obvious signs of an increase in charge confinement. Such behavior contrasts with that for lead halide perovskites which show clear confinement effects upon lowering dimensionality of the octahedral network from 3D to 2D. Changes in photoluminescence spectra and lifetimes between the two compounds mostly derive from the difference in extrinsic defect densities rather than intrinsic effects. While both materials show good stability, bulk CuAgBiI 5 powder samples are found to be more sensitive to degradation under solar irradiation compared to Cu 2 AgBiI 6 .

The structures and band gaps of copper-zinc-tin selenosulfides (CZTSSe) are investigated for a range of anion compositions through experimental analysis and complementary first-principles simulations. The band gap was found to be extremely sensitive to the Sn-anion bond length, with an almost linear correlation with the average Sn-anion bond length in the mixed anion phase Cu 2 ZnSn(S x Se 1- x ) 4 . Therefore, an accurate prediction of band gaps using first-principles methods requires the accurate reproduction of the experimental bond lengths. This is challenging for many widely used approaches that are suitable for large supercells. The HSE06 functional was found to predict the structure and band gap in good agreement with the experiment but is computationally expensive for large supercells. It was shown that a geometry optimization with the MS2 meta-GGA functional followed by a single point calculation of electronic properties using HSE06 is a reasonable compromise for modeling larger supercells that are often unavoidable in the study of point and extended defects.

The improvement of antimony selenide solar cells by short-term air exposure is explained using complementary cell and material studies. We demonstrate that exposure to air yields a relative efficiency improvement of n-type Sb 2 Se 3 solar cells of ca. 10% by oxidation of the back surface and a reduction in the back contact barrier height (measured by J-V-T ) from 320 to 280 meV. X-ray photoelectron spectroscopy (XPS) measurements of the back surface reveal that during 5 days in air, Sb 2 O 3 content at the sample surface increased by 27%, leaving a more Se-rich Sb 2 Se 3 film along with a 4% increase in elemental Se. Conversely, exposure to 5 days of vacuum resulted in a loss of Se from the Sb 2 Se 3 film, which increased the back contact barrier height to 370 meV. Inclusion of a thermally evaporated thin film of Sb 2 O 3 and Se at the back of the Sb 2 Se 3 absorber achieved a peak solar cell efficiency of 5.87%. These results demonstrate the importance of a Se-rich back surface for high-efficiency devices and the positive effects of an ultrathin antimony oxide layer. This study reveals a possible role of back contact etching in exposing a beneficial back surface and provides a route to increasing device efficiency.

Making new van der Waals materials with electronic or magnetic functionality is a chemical design challenge for the development of two-dimensional nanoelectronic and energy conversion devices. We present the synthesis and properties of the van der Waals material Bi 4 O 4 SeCl 2 , which is a 1:1 superlattice of the structural units present in the van der Waals insulator BiOCl and the three-dimensionally connected semiconductor Bi 2 O 2 Se. The presence of three anions gives the new structure both the bridging selenide anion sites that connect pairs of Bi 2 O 2 layers in Bi 2 O 2 Se and the terminal chloride sites that produce the van der Waals gap in BiOCl. This retains the electronic properties of Bi 2 O 2 Se while reducing the dimensionality of the bonding network connecting the Bi 2 O 2 Se units to allow exfoliation of Bi 4 O 4 SeCl 2 to 1.4 nm height. The superlattice structure is stabilized by the configurational entropy of anion disorder across the terminal and bridging sites. The reduction in connective dimensionality with retention of electronic functionality stems from the expanded anion compositional diversity.

Mixed ionic-electronic conductors (MIECs) that display high oxide ion conductivity (σ o ) and electronic conductivity (σ e ) constitute an important family of electrocatalysts for a variety of applications including fuel cells and oxygen separation membranes. Often MIECs exhibit sufficient σ e but inadequate σ o . It has been a long-standing challenge to develop MIECs with both high σ o and stability under device operation conditions. For example, the well-known perovskite oxide Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3- δ (BSCF) exhibits exceptional σ o and electrocatalytic activity. The reactivity of BSCF with CO 2 , however, limits its use in practical applications. Here, the perovskite oxide Bi 0.15 Sr 0.85 Co 0.8 Fe 0.2 O 3- δ (BiSCF) is shown to exhibit not only exceptional bulk transport properties, with a σ o among the highest for known MIECs, but also high CO 2 tolerance. When used as an oxygen separation membrane, BiSCF displays high oxygen permeability comparable to that of BSCF and much higher stability under CO 2 . The combination of high oxide transport properties and CO 2 tolerance in a single-phase MIEC gives BiSCF a significant advantage over existing MIECs for practical applications., (© 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The earth-abundant semiconductor Cu 3 BiS 3 (CBS) exhibits promising photovoltaic properties and is often considered analogous to the solar absorbers copper indium gallium diselenide (CIGS) and copper zinc tin sulfide (CZTS) despite few device reports. The extent to which this is justifiable is explored via a thorough X-ray photoemission spectroscopy (XPS) analysis: spanning core levels, ionization potential, work function, surface contamination, cleaning, band alignment, and valence-band density of states. The XPS analysis overcomes and addresses the shortcomings of prior XPS studies of this material. Temperature-dependent absorption spectra determine a 1.2 eV direct band gap at room temperature; the widely reported 1.4-1.5 eV band gap is attributed to weak transitions from the low density of states of the topmost valence band previously being undetected. Density functional theory HSE06 + SOC calculations determine the band structure, optical transitions, and well-fitted absorption and Raman spectra. Valence band XPS spectra and model calculations find the CBS bonding to be superficially similar to CIGS and CZTS, but the Bi 3+ cations (and formally occupied Bi 6s orbital) have fundamental impacts: giving a low ionization potential (4.98 eV), suggesting that the CdS window layer favored for CIGS and CZTS gives detrimental band alignment and should be rejected in favor of a better aligned material in order for CBS devices to progress.

Multinary lithium oxides with the rock salt structure are of technological importance as cathode materials in rechargeable lithium ion batteries. Current state-of-the-art cathodes such as LiNi 1/3 Mn 1/3 Co 1/3 O 2 rely on redox cycling of earth-abundant transition-metal cations to provide charge capacity. Recently, the possibility of using the oxide anion as a redox center in Li-rich rock salt oxides has been established as a new paradigm in the design of cathode materials with enhanced capacities (>200 mAh/g). To increase the lithium content and access electrons from oxygen-derived states, these materials typically require transition metals in high oxidation states, which can be easily achieved using d 0 cations. However, Li-rich rock salt oxides with high valent d 0 cations such as Nb 5+ and Mo 6+ show strikingly high voltage hysteresis between charge and discharge, the origin of which is uninvestigated. In this work, we study a series of Li-rich compounds, Li 4+ x Ni 1- x WO 6 (0 ≤ x ≤ 0.25) adopting two new and distinct cation-ordered variants of the rock salt structure. The Li 4.15 Ni 0.85 WO 6 (x = 0.15) phase has a large reversible capacity of 200 mAh/g, without accessing the Ni 3+ /Ni 4+ redox couple, implying that more than two-thirds of the capacity is due to anionic redox, with good cyclability. The presence of the 5d 0 W 6+ cation affords extensive (>2 V) voltage hysteresis associated with the anionic redox. We present experimental evidence for the formation of strongly stabilized localized O-O single bonds that explain the energy penalty required to reduce the material upon discharge. The high valent d 0 cation associates localized anion-anion bonding with the anion redox capacity.

Semiconducting 2D materials, such as SnS 2 , hold immense potential for many applications ranging from electronics to catalysis. However, deposition of few-layer SnS 2 films has remained a great challenge. Herein, continuous wafer-scale 2D SnS 2 films with accurately controlled thickness (2 to 10 monolayers) are realized by combining a new atomic layer deposition process with low-temperature (250 °C) postdeposition annealing. Uniform coating of large-area and 3D substrates is demonstrated owing to the unique self-limiting growth mechanism of atomic layer deposition. Detailed characterization confirms the 1T-type crystal structure and composition, smoothness, and continuity of the SnS 2 films. A two-stage deposition process is also introduced to improve the texture of the films. Successful deposition of continuous, high-quality SnS 2 films at low temperatures constitutes a crucial step toward various applications of 2D semiconductors., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The earth-abundant material CuSbS 2 (CAS) has shown good optical properties as a photovoltaic solar absorber material, but has seen relatively poor solar cell performance. To investigate the reason for this anomaly, the core levels of the constituent elements, surface contaminants, ionization potential, and valence-band spectra are studied by X-ray photoemission spectroscopy. The ionization potential and electron affinity for this material (4.98 and 3.43 eV) are lower than those for other common absorbers, including CuIn x Ga (1-x) Se 2 (CIGS). Experimentally corroborated density functional theory (DFT) calculations show that the valence band maximum is raised by the lone pair electrons from the antimony cations contributing additional states when compared with indium or gallium cations in CIGS. The resulting conduction band misalignment with CdS is a reason for the poor performance of cells incorporating a CAS/CdS heterojunction, supporting the idea that using a cell design analogous to CIGS is unhelpful. These findings underline the critical importance of considering the electronic structure when selecting cell architectures that optimize open-circuit voltages and cell efficiencies.

Layered two-anion compounds are of interest for their diverse electronic properties. The modular nature of their layered structures offers opportunities for the construction of complex stackings used to introduce or tune functionality, but the accessible layer combinations are limited by the crystal chemistries of the available anions. We present a layered three-anion material, Bi 4 O 4 Cu 1.7 Se 2.7 Cl 0.3 , which adopts a new structure type composed of alternately stacked BiOCuSe and Bi 2 O 2 Se-like units. This structure is accessed by inclusion of three chemically distinct anions, which are accommodated by aliovalently substituted Bi 2 O 2 Se 0.7 Cl 0.3 blocks coupled to Cu-deficient Bi 2 O 2 Cu 1.7 Se 2 blocks, producing a formal charge modulation along the stacking direction. The hypothetical parent phase Bi 4 O 4 Cu 2 Se 3 is unstable with respect to its charge-neutral stoichiometric building blocks. The complex layer stacking confers excellent thermal properties upon Bi 4 O 4 Cu 1.7 Se 2.7 Cl 0.3 : a room-temperature thermal conductivity (κ) of 0.4(1) W/mK was measured on a pellet with preferred crystallite orientation along the stacking axis, with perpendicular measurement indicating it is also highly anisotropic. This κ value lies in the ultralow regime and is smaller than those of both BiOCuSe and Bi 2 O 2 Se. Bi 4 O 4 Cu 1.7 Se 2.7 Cl 0.3 behaves like a charge-balanced semiconductor with a narrow band gap. The chemical diversity offered by the additional anion allows the integration of two common structural units in a single phase by the simultaneous and coupled creation of charge-balancing defects in each of the units.

Surface effects strongly dominate the intrinsic properties of semiconductor nanowires (NWs), an observation that is commonly attributed to the presence of surface states and their modification of the electronic band structure. Although the effects of the exposed, bare NW surface have been widely studied with respect to charge carrier transport and optical properties, the underlying electronic band structure, Fermi level pinning, and surface band bending profiles are not well explored. Here, we directly and quantitatively assess the Fermi level pinning at the surfaces of composition-tunable, intrinsically n-type InGaAs NWs, as one of the prominent, technologically most relevant NW systems, by using correlated photoluminescence (PL) and X-ray photoemission spectroscopy (XPS). From the PL spectral response, we reveal two dominant radiative recombination pathways, that is, direct near-band edge transitions and red-shifted, spatially indirect transitions induced by surface band bending. The separation of their relative transition energies changes with alloy composition by up to more than ∼40 meV and represent a direct measure for the amount of surface band bending. We further extract quantitatively the Fermi level to surface valence band maximum separation using XPS, and directly verify a composition-dependent transition from downward to upward band bending (surface electron accumulation to depletion) with increasing Ga-content x(Ga) at a crossover near x(Ga) ∼ 0.2. Core level spectra further demonstrate the nature of extrinsic surface states being caused by In-rich suboxides arising from the native oxide layer at the InGaAs NW surface.

In this research, the hafnium titanate oxide thin films, Ti x Hf 1- x O₂, with titanium contents of x = 0, 0.25, 0.9, and 1 were deposited on germanium substrates by atomic layer deposition (ALD) at 300 °C. The approximate deposition rates of 0.2 Å and 0.17 Å per cycle were obtained for titanium oxide and hafnium oxide, respectively. X-ray Photoelectron Spectroscopy (XPS) indicates the formation of GeO x and germanate at the interface. X-ray diffraction (XRD) indicates that all the thin films remain amorphous for this deposition condition. The surface roughness was analyzed using an atomic force microscope (AFM) for each sample. The electrical characterization shows very low hysteresis between ramp up and ramp down of the Capacitance-Voltage (CV) and the curves are indicative of low trap densities. A relatively large leakage current is observed and the lowest leakage current among the four samples is about 1 mA/cm² at a bias of 0.5 V for a Ti 0.9 Hf 0.1 O₂ sample. The large leakage current is partially attributed to the deterioration of the interface between Ge and Ti x Hf 1- x O₂ caused by the oxidation source from HfO₂. Consideration of the energy band diagrams for the different materials systems also provides a possible explanation for the observed leakage current behavior.

We report that the internal quantum efficiency for hydrogen generation in spherical, Pt-decorated CdS nanocrystals can be tuned by quantum confinement, resulting in higher efficiencies for smaller than for larger nanocrystals (17.3% for 2.8 nm and 11.4% for 4.6 nm diameter nanocrystals). We attribute this to a larger driving force for electron and hole transfer in the smaller nanocrystals. The larger internal quantum efficiency in smaller nanocrystals enables a novel colloidal dual-band gap cell utilising differently sized nanocrystals and showing larger external quantum efficiencies than cells with only one size of nanocrystals (9.4% for 2.8 nm particles only and 14.7% for 2.8 nm and 4.6 nm nanocrystals). This represents a proof-of-principle for future colloidal tandem cell.

Crystalline and quasicrystalline allotropes of Pb are formed by evaporation on the fivefold surface of the icosahedral (i) Ag-In-Yb quasicrystal under ultra-high vacuum. Lead grows in three dimensional quasicrystalline order and subsequently forms fivefold-twinned islands with the fcc(111) surface orientation atop of the quasicrystalline Pb. The islands exhibit specific heights (magic heights), possibly due to the confinement of electrons in the islands. We also study the adsorption behavior of C60 on the two allotropes of Pb. Scanning tunneling microcopy reveals that a high corrugation of the quasicrystalline Pb limits the diffusion of the C60 molecules and thus produces a disordered film, similar to adsorption behavior of the same molecules on the clean substrate surface. However, the sticking coefficient of C60 molecules atop the Pb islands approaches zero, regardless of the overall C60 coverage.

Quasicrystals are materials with long-range ordering but no periodicity. We report scanning tunneling microscopy (STM) observations of quasicrystalline molecular layers on 5-fold quasicrystal surfaces. The molecules adopt positions and orientations on the surface consistent with the quasicrystalline ordering of the substrate. Carbon-60 adsorbs atop sufficiently separated Fe atoms on icosahedral Al-Cu-Fe to form a unique quasicrystalline lattice, whereas further C60 molecules decorate remaining surface Fe atoms in a quasi-degenerate fashion. Pentacene (Pn) adsorbs at 10-fold symmetric points around surface-bisected rhombic triacontahedral clusters in icosahedral Ag-In-Yb. These systems constitute the first demonstrations of quasicrystalline molecular ordering on a template.

Scanning tunneling microscopy and x-ray photoemission spectroscopy on a polygrain icosahedral (i-) Al–Pd–Re quasicrystal (QC) show the formation of the twofold surfaces with symmetry and composition expected from the bulk. The predominant occurrence of the twofold surface on the polygrain i-QC having random grain orientation, as well as preferential formation of terrace edges, kinks and voids along the twofold axes, consistently indicates that the twofold surface, which has the highest atomic density, is the most stable among all the crystallographic planes.

Quasicrystals, materials with aperiodic long-range order, have been found in intermetallics, soft materials such as colloids and supermolecules, and also in two-dimensional monolayer films. Here we present the first example of three-dimensional growth of a single-element quasicrystalline film. Using a hitherto unexplored template, the icosahedral Ag-In-Yb quasicrystal, and various experimental techniques combined with theoretical calculations of adsorption energies, we find that lead atoms deposited on the surface occupy the positions of atoms in the rhombic triacontahedral cluster, the building block of the substrate, and thus grow in layers with different heights and adsorption energies. We show that the adlayer-adlayer interaction is crucial for stabilizing this epitaxial quasicrystalline structure. The finding opens an avenue for further investigation of the impact of the aperiodic atomic order over periodic order on the physical and chemical properties of materials.

The growth of Bi on Ag(111) induces different surface structures, including (√3 × √3)R30° surface alloy, Bi-(p × √3) overlayer and Bi(110) thin film, as a function of increasing Bi coverage. Here we report the study of electronic states of these structures using core level and valence band photoemission spectroscopy at room temperature. The sp-derived Shockley surface state on Ag(111) is rapidly quenched upon deposition of Bi, due to the strong variation of the in-plane surface potential in the Ag(2)Bi surface alloy. The Bi 4f core levels of the (√3 × √3)R30° alloy and Bi(110) thin film are shifted to lower binding energy by ~0.6 eV and ~0.3 eV compared with the Bi bulk value, respectively. Mechanisms inducing the core level shifts are discussed as due to a complex superposition of several factors. As Bi coverage increases and a Bi(110) overlayer forms on Ag(111), a new state is observed at ~0.9 ML arising from electronic states localized at the Ag-Bi interface. Finally the change of work function as a function of coverage is discussed on the basis of a charge transfer model.

The development of chemical functionalization techniques for diamond nanocrystallites opens up ways with a view to altering their solubility in different solvents, improve interfacial adhesion of nanodiamonds with a composite matrix in new materials, and provide new possibilities for the modification of the electronic properties of nanodiamond crystallites. In this work, we present results on the chemical functionalization of nanodiamonds by amino groups using ammonia as a nitrogenation agent. Nanodiamond material used was formed by the detonation technique with average crystallite sizes of 4-5 nm. The final materials and intermediates products were characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). Chemical functionalization of nanodiamonds by amino groups could enable the preparation of new nylon nano-composite materials. Presence of surface amino groups could alter pH of nanodiamond colloids towards basic values and improve colloidal stability of nanodiamond suspensions at pH close to 7. This could enable syntheses of new drug delivery systems based on nanodiamonds.

Carbon nanotubes (CNTs) have been introduced recently as a novel carrier system for both small and large therapeutic molecules. CNTs can be functionalized (i.e., surface engineered) with certain functional groups in order to manipulate their physical or biological properties. In addition to the ability of CNTs to act as carriers for a wide range of therapeutic molecules, their large surface area and possibility to manipulate their surfaces and physical dimensions have been exploited for use in the photothermal destruction of cancer cells. This paper paper will discuss the therapeutic applications of CNTs with a major focus on their applications for the treatment of cancer.

The deposition of 1/3 of a monolayer of Pb on Ag(111) leads to the formation of PbAg(2) surface alloy with a long range ordered (√3 × √3)R30° superstructure. A detailed analysis of this structure using low-energy electron diffraction (LEED) I-V measurements together with density functional theory (DFT) calculations is presented. We find strong correlation between experimental and calculated LEED I-V data, with the fit between the two data sets having a Pendry's reliability factor of 0.21. The Pb atom is found to replace one top layer Ag atom in each unit cell, forming a substitutional PbAg(2) surface alloy, as expected, with the Pb atoms residing approximately 0.4 Å above the Ag atoms due to their size difference. DFT calculations are in good agreement with the LEED results., (© 2011 IOP Publishing Ltd)

We have performed an experimental structure determination of the ordered p(sqrt[3] x sqrt[3])R30 degrees structures of chlorine and iodine on Au{111} using low-energy electron diffraction (LEED). Despite great similarities in the structure of the underlying substrate, which shows only minor deviations from the bulk positions in both cases, chlorine and iodine are found to adsorb in different adsorption sites, fcc and hcp hollow sites, respectively. The experimental Au-Cl and Au-I bond lengths of 2.56 and 2.84 A are close to the sums of the covalent radii, supporting the view that the bond is essentially covalent in nature; however, they are significantly shorter than predicted theoretically.

The growth of Bi on a pseudomorphic Bi monolayer on the fivefold surface of the icosahedral Al-Pd-Mn quasicrystal has been investigated using low energy electron diffraction and scanning tunnelling microscopy. Initially randomly oriented pseudocubic islands are formed with a preference for an even number of layers. Subsequently a morphological transformation takes place to hexagonal Bi islands, which align along high symmetry directions of the substrate. The Bi flux is found to have a strong effect on which island structure is preferred. When C(60) is adsorbed on the three different allotropes of Bi present in this system, hexagonal C(60) islands are formed in each case. On the pseudocubic and hexagonal islands, the C(60) islands are aligned with the substrate. We discuss the energetic, kinetic and geometrical factors which influence the morphological transformation referred to above.

Enantio-specific interactions on intrinsically chiral or chirally modified surfaces can be identified experimentally via comparison of the adsorption geometries of similar nonchiral and chiral molecules. Information about the effects of substrate-related and intermolecular interactions on the adsorption geometry of glycine, the only natural nonchiral amino acid, is therefore important for identifying enantio-specific interactions of larger chiral amino acids. We have studied the long- and short-range adsorption geometry and bonding properties of glycine on the intrinsically chiral Cu{531} surface with low-energy electron diffraction, near-edge X-ray absorption fine structure spectroscopy, X-ray photoelectron spectroscopy, and temperature-programmed desorption. For coverages between 0.15 and 0.33 ML (saturated chemisorbed layer) and temperatures between 300 and 430 K, glycine molecules adsorb in two different azimuthal orientations, which are associated with adsorption sites on the {110} and {311} microfacets of Cu{531}. Both types of adsorption sites allow a triangular footprint with surface bonds through the two oxygen atoms and the nitrogen atom. The occupation of the two adsorption sites is equal for all coverages, which can be explained by pair formation due to similar site-specific adsorption energies and the possibility of forming hydrogen bonds between molecules on adjacent {110} and {311} sites. This is not the case for alanine and points toward higher site specificity in the case of alanine, which is eventually responsible for the enantiomeric differences observed for the alanine system.

Diamond nanoparticle (DN)-coated CNTs were synthesized using a cationic surfactant-assisted sonochemical method. The as-prepared DN coated CNTs were characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The results show that the DNs were coated on the outer wall surface of CNTs. The DN-coated CNTs were infused in Nylon-6 polymer through a melt extrusion process to form nanocomposite fibers that were tested for their tensile properties. The ultimate tensile strength is found to be 363 MPa for DN/CNTs/Nylon-6 single fibers as compared to 240 MPa for neat Nylon-6 single fibers. These results were also compared with Nylon-6 fibers infused with pristine CNTs and pristine DNs.

Controlling the electronic structure of carbon nanotubes (CNTs) is of great importance to various CNT based applications. Herein the electronic fine structure of single-walled carbon nanotube films modified with 4-nitrophenyl groups, produced following reaction with 4-nitrobenzenediazonium tetrafluoroborate, was investigated for the first time. Various techniques such as x-ray and ultra-violet photoelectron spectroscopy, and near edge x-ray absorption fine structure studies were used to explore the electronic structure, and the results were compared with the measured electrical resistances. A reduction in number of the pi electronic states in the valence band consistent with the increased resistance of the functionalized nanotube films was observed.

We have determined the structure of a complex rhodium carbonyl chloride [Rh(CO)2Cl] molecule adsorbed on the TiO2(110) surface by the normal incidence x-ray standing wave technique. The data show that the technique is applicable to reducible oxide systems and that the dominant adsorbed species is undissociated with Rh binding atop bridging oxygen and to the Cl found close to the fivefold coordinated Ti ions in the surface. A minority geminal dicarbonyl species, where Rh-Cl bond scission has occurred, is found bridging the bridging oxygen ions forming a high-symmetry site.