Silver nanoparticles/graphene oxide (AgNPs/GO) nanocomposites were prepared in a solution of AgNO3 and GO. The GO serves not only as a reductant but also as a substrate to support the as-reduced silver nanoparticles. The reducibility of GO was investigated by analyzing the influence factors such as pH, duration, the reaction temperature, and the weight ratio of AgNO3 and GO in the AgNP/GO nanocomposite mixture, which were evaluated by the UV–vis absorption spectroscopy. The results demonstrated that Ag nanoparticles with an average diameter of 5–10 nm were uniformly dispersed on the surface of GO nanosheets under the optimum synthesis conditions of pH between 8 and 11, weight ratio of AgNO3 and GO between 55 % and 60 %, and at 80 °C for 6 h. Moreover, the obtained AgNPs/GO nanocomposites exhibit good electrocatalytic activity for the reduction of p-nitrophenol to 4-(hydroxyamino) phenol.
PTCDI molecules were evaporated onto a Ag/Si(111)√3×√3 surface and studied using scanning tun-resolution STM images are used to identify the delicate molecule/molecule and molecule/substrate interactions and the shapes of the molecular orbitals. The results show that the substrate/molecule interaction strongly modifies the electronic configuration of the molecules as their orbital shapes are quite different at 1 and 2 monolayer (ML) coverage. Simple models of molecular HOMO/LUMO levels and intermolecular hydrogen-bondings have been made for 1 and 2 ML PTCDI coverages to explain the STM images. Changes due to the interaction with the substrate are also found in ARUPS as extra states above the regular HOMO level at 1 ML PTCDI coverage. The ARUPS data also show that the electronic structure of the substrate remains unchanged after the deposition of molecules as the dispersion of the substrate related bands is unchanged. The changes in electronic structure ofthe molecules are discussed based on aHOMO/LUMO split.
3,4,9,10-perylene tetracarboxylic diimide molecules were evaporated onto a Ag/Si(111)-√3 x √3 surface and studied using photoelectron spectroscopy and near edge X-ray absorption fine structure (NEXAFS). All core levels related to the imide group of the molecules showed a partial shift to lower binding energies at low coverages. In NEXAFS spectra, the first transitions to the unoccupied states were weaker at low coverages compared to thicker films. Also, extra states in the valence band between the regular highest occupied molecular orbital and the Fermi level were found at low coverages. These changes were explained by two types of molecules. Due to charge transfer from the surface, these two types have different interactions between the imide group and the substrate. As a result, one type has a partially filled lowest unoccupied molecular orbital while the other type does not.
Perylene tetracarboxylic diimide molecules were evaporated onto a Sn/Si(111)-2 root 3 x 2 root 3 surface and studied using scanning tunneling microscopy (STM) and low energy electron diffraction. At low coverages, single molecules are locked into specific adsorption geometries, which are investigated in detail using high resolution STM. The electronic structure of these individual molecules was studied using bias dependent STM images. The molecules form 1D rows that become more common with increasing coverages. Possible intermolecular O center dot center dot center dot H interactions within the rows have been identified. At around half of a monolayer (ML), the rows of molecules interact with each other and form a commensurate 4 root 3 x 2 root 3 reconstruction. In a complete monolayer, several structures emerge as molecules fill in the space between the 4 root 3 x 2 root 3 stripes. Possible intermolecular interactions within the 1 ML structures have been discussed. At coverages above 1 ML, the growth is characterized by island growth, where the molecules are arranged according to the canted structure within the layers.
3,4,9,10-perylene tetracarboxylic diimide molecules were evaporated onto a Ag/Si(111)-root 3 x root 3 surface and studied by scanning tunneling microscopy/spectroscopy and low energy electron diffraction (LEED). The growth mode was characterized as layer-by-layer growth with a single molecular unit cell in a short range order. The growth of the first two monolayers involves a molecule/substrate superstructure and a molecule/molecule superstructure. At higher coverages, the molecules in each layer were found to align so that unit cells are on top of each other. The experimentally obtained LEED pattern is described as a combination of patterns from the molecular unit cell and the molecule/substrate superstructure. The electronic structure was found to be strongly dependent on the film thickness for the first few layers: Several extra states are found at low coverages compared to higher coverages resulting in a very small pseudo gap of 0.9 eV for the first layer, which widens up to 4.0 eV for thicker films.
The surface morphology and electronic structure of hexagonal ZnO nanoplates have been studied by Atomic Force Microscopy (AFM) and Scanning Tunneling Microscopy (STM). It was found that these nanoplates are terminated by their polar (0001) surfaces. The AFM investigation was performed in the ambient conditions with the nanocrystals “as grown”. Surprisingly, the AFM images of the top surfaces revealed an interesting triangular reconstruction, which was earlier observed only after cycles of sputtering and annealing of the ZnO(0001) surface in Ultra High Vacuum (UHV) systems. The surface atomic and electronic structures of these nanoplates have been further studied by STM and Scanning Tunneling Spectroscopy (STS) in UHV. The STM images also showed a triangular structure with single atomic steps. In addition, a 2x2 surface reconstruction has been observed with high resolution STM. This reconstruction agrees well with the recently proposed model that involves the removal of 1/4 of the topmost Zn atoms on the ZnO(0001) surface.
ZnO nanocrystals distributed by spin-coating on SiO2/Si surfaces were annealed in UHV and studied in situ by synchrotron radiation based X-ray Photoelectron Spectroscopy. Changes in chemical composition and electronic structure of ZnO nanocrystal surfaces were found with increasing annealing temperatures. Annealing at 650 °C reduces the surface contaminant levels without any observed de-composition of ZnO. After annealing at 700 °C an initial de-composition of ZnO together with further reduction of contaminants was observed. As a result, 650 °C is found to be the optimal annealing temperature for thermal cleaning of ZnO nanocrystals. Chemical changes and induced point defect formation cause changes in the band structure of the ZnO/SiO2/Si system. An upward band bending of 0.7 eV on the surfaces of the ZnO nanocrystals was found after annealing at 300 °C. The bands on the surfaces of ZnO nanocrystals gradually bend downwards with increasing annealing temperatures. A downward band bending of 1.4 eV is the result after annealing at 750 °C for 1 h. This large downward band bending is explained as due to the change in balance of oxygen vacancies and zinc vacancies on the surfaces of ZnO nanocrystals.
In this article we report our findings on the electronic structure of the Li induced Ge(1 1 1)–3 × 1reconstruction as determined by angle-resolved ultraviolet photoelectron spectroscopy (ARUPS) and core-level spectroscopy using synchrotron radiation. The results are compared to the theoretical honeycomb-chain-channel (HCC) model for the 3 × 1reconstruction as calculated using density functional theory (DFT). ARUPS measurements were performed in both the and directions of the 1 × 1 surface Brillouin zone at photon energies of 17 and 21.2 eV. Three surface related states were observed in the direction. In the direction, at least two surface states were seen. The calculated band structure using the single-domain HCC model for Li/Ge(1 1 1)–3 × 1 was in good agreement with experiment, allowing for the determination of the origin of the experimentally observed surface states. In the Ge core-level spectra, two surface related components were identified, both at lower binding energy with respect to the Ge bulk peak. Our DFT calculations of the surface core-level shifts were found to be in fair agreement with the experimental results. Finally, in contrast to the Li/Si(1 1 1)–3 × 1 case, no double bond between Ge atoms in the top layer was found
Thin manganese silicide films of different thicknesses on Si(111) have been studied in detail by low-energy electron diffraction (LEED), scanning tunneling microscopy, and scanning tunneling spectroscopy (STM/STS). Up to a Mn coverage of 3–4 monolayers (ML), island formation is favored. For higher Mn coverages up to 12 ML uniform film growth is found. The silicide film morphology at low coverages supports a layered Mn-Si film structure. The silicide surfaces displayed a √3×√3 LEED pattern. STM images recorded from the √3×√3 surfaces mostly show a hexagonal pattern but a honeycomb pattern has also been observed. A surface atomic structure based on chained Mn triangles is proposed. Our STM results are in good agreement with a recent theoretical model. The high-quality STS spectra recorded from the different surfaces show a clear metallic character at 1.5 ML and higher coverages. The filled-state features in the STS spectra at surfaces with 3–4 ML Mn coverages are similar to earlier published angle-resolved photoelectron spectroscopy data.
Thin manganese germanide films with different thicknesses on Ge(111) have been studied in detail by low-energy electron diffraction (LEED), scanning tunneling microscopy, and core-level spectroscopy (CLS). Annealing of the deposited Mn on Ge(111)c(2×8) between 330-450 C resulted in well-ordered Mn5Ge3 surfaces as seen by intense 3×3 LEED spots. Up to a coverage of 24 monolayers (ML), island formation is favored. At a coverage of 32 ML a well ordered Mn5Ge3 film was found to fully cover the surface. High-resolution Ge 3d CLS spectra were recorded with photon energies between 50 and 110 eV at normal and 60 emission angles. In contrast to earlier results, three components have been used in the line-shape analysis to achieve a consistent fit over the energy and angular range. In addition, three components have been identified for the Mn 2p CLS spectra. The two major components fit well with a layered Mn germanide structure suggested in the literature.
The atomic and electronic structure of the Mn5Ge3(001) surface grown on Ge(111) c(2×8) has been studied in detail by angle-resolved photoelectron spectroscopy (ARPES), scanning tunneling microscopy (STM), and scanning tunneling spectroscopy. ARPES spectra recorded from the Γ̅ -K̅ -M̅ and Γ̅ -M̅ -Γ̅ directions of the surface Brillouin zone show six surface-related features. The STM images recorded at biases higher/lower than ±0.4 V always show a honeycomb pattern with two bright protrusions in each unit cell. At lower biases, a hexagonal, intermediate transition, and a honeycomb pattern are observed. These can be explained as arising from Mn and Ge atoms in the sublayer arranged in triangular structures and Mn atoms in the top layer arranged in a honeycomb structure, respectively. The photoemission and STM data from the germanide surface are discussed and compared to earlier published theoretical, photoelectron spectroscopy, and scanning tunneling microscopy studies.
The Mn/Si(111)-√3×√3 surface has been studied in detail by low energy electron diffraction (LEED), angle-resolved photoelectron spectroscopy (ARPES), and core-level photoelectron spectroscopy (CLS). Annealing of the deposited manganese resulted in a well-ordered surface as seen by intense √3×√3 LEED spots. ARPES spectra recorded in the Γ̅ -K̅ -M̅ direction of the √3×√3 surface Brillouin zone show five surface related features in the band gap while in the Γ̅ -M̅ -Γ̅ direction four surface features are observed. The high-resolution Si 2p CLS data were recorded at photon energies between 108–140 eV both at normal and 60° emission angle. The bulk component was identified from the bulk sensitive spectrum recorded at a photon energy of 108 eV. To achieve a consistent core-level fitting over the whole energy and angular range, five components were introduced in the line-shape analysis. The photoemission data from the √3×√3 surface have been discussed and compared with a recent theoretical model. The findings here support a layered Mn silicide film structure.
The effect of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) adsorption on the physical properties of the two-dimensional (2D) atomic layer superconductor (ALSC) In/Si(111)-(7×3) has been studied by angle-resolved photoelectron spectroscopy, transport measurements, and scanning tunneling microscopy. Hole doping from the adsorbed molecules has been reported to increase the superconducting transition temperature Tc of this ALSC, and the molecular spin tends to decrease it. Owing to its large electron affinity and its nonexistent spin state, the adsorption of PTCDA was expected to increase Tc. However, the PTCDA adsorption dopes only a small number of holes in the In layers and causes a suppression of Tc with a sharp increase in the normal-state sheet resistance followed by an insulating transition. Taking the disordering of the arrangement of PTCDA into account, we conclude that the increase in resistance is due to the localization effect originating from the random potential that is induced by the disordered PTCDA molecules. The present result also indicates the importance of the crystallinity of a 2D molecular film adsorbed on ALSCs.
The surface electronic structure of Ge(111)c(2x8) was studied by experimental techniques [low-energy electron diffraction, scanning tunneling microscopy (STM), and angle-resolved photoelectron spectroscopy (ARPES)] and theoretical band-structure calculations. Bias-dependent STM images exhibit two different types of adatoms (A(T),A(R)) and rest atoms (R-T,R-R) confirming the presence of asymmetries within the c(2x8) cell. The ARPES study resulted in a more detailed picture of the surface electronic structure of the Ge(111)c(2x8) surface compared to earlier studies. The energy dispersion curves showed the presence of seven surface bands labeled A1, A2, A2', A3, A4, A4', and A5. The experimental surface bands were compared to the calculated band structure of the full c(2x8) unit cell. The most important results are (i) we have identified a split surface-state band in the photoemission data that matches a split between R-T and R-R derived rest atom bands in the calculated surface band structure. This allows us to identify the upper A2 band with the R-R and the lower A2' band with the R-T rest atoms. (ii) The uppermost highly dispersive band (A1) originates from states below the adatom and rest atom layers and should not be confused with rest atom bands A2 and A2'. (iii) The bias-dependent changes in the adatom/rest atom contrast in the experimental STM images were closely reproduced by simulated STM images generated from the calculated electronic structure. (iv) A split was observed in the back-bond derived surface band at higher emission angles (A4 and A4')
The electronic structure of H/Ge(111)1×1 was investigated using angle-resolved photoelectron spectroscopy. Spectra were measured along the high-symmetry lines of the 1×1 surface Brillouin zone. In the G-K-M direction, two surface states, labeled a and a1, were found in the lower and upper band-gap pockets. The a and a1 surface states are associated with the Ge-H bonds and the Ge-Ge backbonds, respectively. In the G-M direction, only the Ge-H surface state, a, can be identified. It is found in the band-gap pocket around the M point. The two hydrogen-induced surface states on H/Ge(111)1×1 show strong similarities with the corresponding surface states on H/Si(111)1×1. Results from H/Ge(111)1×1 and H/Si(111)1×1 are compared in this Brief Report
Silver thin films have been formed by room temperature deposition of Ag on In/Si(111)-√3 × √3. The Ag films have been investigated using both angle-resolved photoelectron spectroscopy (ARPES) and scanning tunnelingmicroscopy and spectroscopy (STM/STS). This creates a powerful link between the electronic structures and the film morphology. The valence band spectra show a clear evidence of quantum well state (QWS) formation already for a 2 monolayer (ML) film. This QWS moves towards the Fermi level for the 3 ML film, which also reveals a second QWS. The QWSs’ dispersions have been plotted along the ΓM and ΓK symmetry lines of the 1×1 surface Brillouin zone (SBZ), where the ΓM direction shows the umklapp-mediated QWSs. The valence band spectra for the 3 ML Ag film also show a strong Ag sp band close to the edge of the Ag(111) 1×1 SBZ. In the STS spectrum from 2 ML, two peaks are visible below the Shockley surface state. These peaks are compared with the ARPES data and attributed to different features of the QWS
Silver thin films have been formed on the Sn/Si(111)-(√3 ×√3)-R30 degrees surface at room temperature. The film morphologies, growth and electronic structures have been studied by scanning tunneling microscopy/spectroscopy (STM/STS), low-energy electron diffraction (LEED) and angle-resolved photoelectron spectroscopy (ARPES). The first layer of Ag forms an interface which consists of atomic rows with three-fold symmetry oriented along the Si(111)-1 x 1 directions. On top of the interface, Ag grows as an uniform thin film, following a layer-by-layer mode. The electronic structures of the films have been studied by STS for coverages between 1-5 monolayers (MLs). The STS spectra show peaks in the occupied electronic states which move towards the Fermi level with increased film thicknesses. These peaks have been attributed to quantum well states. ARPES measurements have been performed for 1 and 2 ML Ag coverage on Sn/Si(111)-(√3 ×√3)-R30 degrees, where the resulting thicknesses were confirmed by STM. The spectra reveal that quantum well states appear first for the 2 ML film.
Silver has been deposited on the Sn/Ge(111)-(√3×√3)-R30° surface at room temperature. The Ag growth and resulting surface morphology have been investigated using scanning tunneling microscopy. The first layer of silver forms an interface with domains of two different phases. One structure consists of short atomic rows with three-fold symmetry, oriented in the directions of the √3×√3 surface. These rows are separated by a distance equal to and are found to fit a 2√3×√3 unit cell. The other phase is a 3×3 honeycomb structure, oriented in the Ge(111) 1 × 1 directions. Atomic structural models for the two interface phases are proposed, based on two different spin arrangements of the Sn/Ge(111)-√3×√3 surface. The results highlight the topological coupling of the two interface faces. Both interface structures are preserved with additional silver deposition. The second layer of Ag grows with a bulk-like lattice thickness on top of both interfaces. Low-energy electron diffraction on a mostly two layer Ag film reveals that it consists of domains where Ag grows in different orientations. These domains are rotated 30° with respect to each other, and thus mirror the symmetry directions of the two interfacial phases.
Silver thin films have been formed by room temperature deposition of Ag on a Ga/Si(111) (√3 × √3)R30° surface. Scanning tunneling microscopy and spectroscopy (STM/STS) have been used to study both the clean Ga/Si(111) (√3 × √3)R30° surface and Ag films with different coverages. For the film formation, Ag first grows into 2D islands on Ga/Si(111) (√3 × √3)R30°. The first layer of the islands forms atomic lines with three-fold symmetry in the 1 × 1 direction of the underlying Si(111) substrate. From a 2 ML coverage, the growth becomes layer-by-layer mode. STS measurements have been performed on Ag films with different coverages inorder to investigate their electronic structures. Between 2–4 ML, the STS spectra reveal 2 and 3 peaks below the Fermi level. These peaks move towards the Fermi level with increased film thicknesses and thus share the same behavior as those of quantum well states (QWSs). The energy positions of the peaks have been compared with valence band photoelectron spectra in order to assign them to various parts of the QWSs. In addition, the photoemission results also confirm the existence of QWSs for a 2 ML Ag film on Ga/Si(111) (√3 × √3)R30°.
Silver thin films have been created by room temperature deposition on a Ga/Si(111)-√3 x √3 surface and their valence band structures and core levels have been measured by angle-resolved photoelectron spectroscopy (ARPES). Discrete quantum-well states (QWSs) quantized from the Ag sp valence band are observed already at 3 monolayers (ML). The characteristics of the QWSs have been examined in the phase accumulation model for thicknesses between 3 and 12 ML. The phase shift and QWSs binding energies dependence with Ag film thicknesses have all been consistently derived. In-plane energy dispersion follows a parabolic curve, and the effective mass of the QWSs shows an increasing trend with binding energies as well as with reduced film thicknesses. Furthermore, the ARPES measurements reveal umldapp mediated QWSs around the (M)over-bar points of the Si(111) 1 x 1 surface Brillouin zone. The study confirms that the Ga/Si(111)-√3 x √3 surface is a good substrate for growing uniform ultrathin Ag films in room temperature conditions.