A study of the behavior of Fe and Ni on MoS2

A correlation of AES and work function measurements of Fe and Ni on MoS₂ indicated that, near room temperature of MoS₂ and low coverage, Fe and Ni formed islands. With increasing coverage the Fe-islands were developed to 3-D small particles, while Ni-islands needed higher temperature for this development. The average size and density of the particles depended on the substrate temperature. Beyond a certain size the Fe-particles began to act catalytically on an interaction of the subsequently deposited Fe with S atoms of the top layer of MoS₂. The Ni particles remained clean up to 800 K and did not interact with S.     

Formation of copper islands on a native SiO2 surface at elevated temperatures

A combination of in situ X-ray photoelectron spectroscopy analysis and ex situ scanning electron- and atomic force microscopy has been used to study the formation of copper islands upon Cu deposition at elevated temperatures as a basis for the guided growth of copper islands. Two different temperature regions have been found: (I) up to 250 °C only close packed islands are formed due to low diffusion length of copper atoms on the surface. The SiO₂ film acts as a barrier protecting the silicon substrate from diffusion of Cu atoms from oxide surface. (II) The deposition at temperatures above 300 °C leads to the formation of separate islands which are (primarily at higher temperatures) crystalline. At these temperatures, copper atoms diffuse through the SiO₂ layer. However, they are not entirely dissolved in the bulk but a fraction of them forms a Cu rich layer in the vicinity of SiO₂/Si interface. The high copper concentration in this layer lowers the concentration gradient between the surface and the substrate and, consequently, inhibits the diffusion of Cu atoms into the substrate. Hence, the Cu islands remain on the surface even at temperatures as high as 450 °C.     

Chemisorption of atomic oxygen on Pd(1 1 1) studied by STM

Atomic oxygen resulting from the dissociation of O₂ on Pd(1 1 1) at low coverage was studied in a variable temperature scanning tunneling microscope (STM) in the range from 30 to 210 K. Oxygen atoms, which typically appear as 30-40 pm deep depressions on Pd(1 1 1), occupy fcc hollow sites and form ordered p(2 × 2) islands upon annealing above 180 K. The mobility of the atoms diminishes rapidly below 180 K, with an approximate diffusion barrier of 0.4-0.5 eV. Oxygen atom pairs produced by thermal dissociation of O₂ at 160 K occupy both fcc and hcp hollow sites. The atoms travel approximately 0.25 nm after dissociation, and the distribution of pairs is strongly influenced by the presence of subsurface impurities within the Pd sample. At much lower temperatures, the STM tip can dissociate oxygen molecules. Dissociation occurs at sample bias voltages exceeding approximately 0.1 V. Following tip-induced dissociation, the product atoms occupy only fcc hollow sites. Oxygen atoms can be manipulated via short range repulsive interactions with the STM tip.     

Interface behavior of Mn/PbTe(111) studied by scanning tunneling microscopy and X-ray photoemission spectroscopy

Mn overlayers growth on PbTe(111) have been investigated by using scanning tunneling microscopy (STM) and X-ray photoemission spectroscopy (XPS). The strong chemical interactions were found during the formation of Mn/PbTe(111) interface. At the initial deposition of Mn, one part of Mn adatoms substitute Pb atoms on the PbTe(111) surface, forming a (√3 × √3)R30° MnTe phase, and the other part of Mn adatoms, together with the kicked-out Pb atoms, nucleate at the boundaries of the MnTe islands, forming loop islands around the MnTe islands as an intermediate state. Finally, they develop into regular 3D Pb capped Mn islands upon further Mn deposition. For Mn growth on the PbTe surface where Pb atoms are almost completely substituted by Mn, the deposited Mn atoms either cooperate into the 3D Pb capped Mn islands promoting the upright growth of the 3D Pb capped Mn islands, or nucleate and grow on the MnTe superstructure areas. Free Pb layer always floats on the top of surface, indicating that Pb layer has smaller surface energy, and Mn adatoms always exchange the positions with the underneath Pb atoms during the growth.     

LEED and AES study of the interaction of H2S and Mo (100)

Previous studies of the adsorption of H₂S on Mo (100) at low pressures have been extended to higher pressures. Earlier work was repeated on two separate crystals to ensure reproducibility. The initial rate of sulphure adsorption as measured by AES is proportional to the partial pressure of H₂S and not strongly dependent on temperature indicating a non-activated initial process. For pressures up to 10^?2Torr no MoS₂ nuclei were seen over a wide range of temperatures. The first appearance of MoS₂occurred after an exposure of 0.1 Torr H₂S for 30 min with the crystal at 500°C. Diffraction from the MoS₂ was weak indicating that the nuclei were not fully developed. Four-fold symmetrical streaks from the underlying metal could be seen, thus enabling the epitaxy to be deduced by inspection. The basal plane of MoS₂aligns parallel to the original Mo (100) surface with [100]MoS₂∥[010] forming one domain and [100]MoS₂∥[001]Mo forming another. The change from a 2D chemisorbed sulphur layer to a 3D bulk compound produces significant changes in Auger spectra at low energies.     

Intermixing at the interface of the system Nb/Fe(1 1 0) investigated by STM

The growth of niobium on the Fe(1 1 0) surface at a deposition temperature between room temperature (RT) and 680 K was studied using in situ STM and LEED. At RT we observe no indication of intermixing. Although a final roughness of only 1.7 Å is reached, the crystalline quality is low. At elevated growth temperatures the development of a surface alloy was observed, whose formation is ascribed to an exchange mechanism through which Nb adatoms are incorporated into the Fe surface. These Nb atoms arrange themselves in chains along the [0 0 1] direction. The expelled Fe atoms form islands on the Nb/Fe-alloy substrate. At higher coverage additionally a Nb wetting layer and intermixed 3D islands evolve.     

Hydrogen on hybrid MoS2/graphene nanostructures

Transition metal dichalcogenides are rising candidates for the replacement of Pt catalysts in water splitting. In this theoretical study we focus on the hydrogen evolution reaction part of this process and on how hydrogen (H) interacts with MoS₂ nanostructures, free‐standing or positioned on a graphene substrate. Density functional theory calculations confirm the stability of such nanostructures and our results for H on several configurations, from 2D infinite monolayers to quasi‐1D MoS₂ ribbons and quasi‐0D MoS₂ flakes, are presented. We calculate the adsorption energy of H atoms on various sites of the MoS₂ nanostructures, notably at Mo and S active edges. Comparing free‐standing and MoS₂/graphene hybrid systems we find that the effect of the support on the adsorption of H on MoS₂ nanostructures is quite significant when the substrate induces strain. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

In situ oxidation study of MgO(1 0 0) supported Pd nanoparticles

We have investigated the oxidation behavior of Pd nanoparticles grown epitaxially on MgO(1 0 0) single crystal substrates. We find that the interaction of oxygen with octahedral Pd nanoparticles at 500 K can be subdivided in three stages: above 10⁻⁶ mbar O₂ pressure, the particles start to flatten; above 10⁻³ mbar, the particles begin to shrink laterally and to be less truncated at the corners. The formation of epitaxial bulk PdO sets in at oxygen pressures above 0.1 mbar, which is accompanied by a continuous shrinkage of the Pd particles. Our results point to a novel nanoparticle oxidation mechanism: the Pd particles act as dissociation centers for O₂ and serve at the same time as source for Pd atoms resulting in epitaxial PdO growth on MgO(1 0 0).     

Kinetic Monte Carlo simulation of the growth of metal clusters on regular array of defects on insulator

A Kinetic Monte Carlo simulation of the nucleation and growth of Pd clusters on a nanostructured alumina substrate is presented. The new Monte Carlo simulation program allows to derive the 3D shape of the growing clusters without performing a full all atoms simulation. The simulation shows, like in previous pure 2D simulations, that clusters nucleate exclusively on the defects of the nanostructure in a limited range of substrate temperature. Around 300 K, the clusters have a compact faceted shape and they grow, at not too large coverage, layer by layer. These results are in agreement with previous studies of the nucleation and growth of Pd clusters on an ultrathin alumina film on Ni₃Al (1 1 1).     

Self-organization of bimetallic PdAu nanoparticles on SiO<Subscript>2</Subscript> surface

Bimetallic PdAu nanoparticles on SiO₂ substrate were produced by a sequential room-temperature sputtering deposition method. By the atomic force microscopy technique we studied the nanoparticles self-organization mechanisms in various conditions. First, Pd nucleation and growth proceeds at the substrate defects and the Pd nanoparticles density increase rapidly. During the second sputtering deposition, Au atoms adsorb on the SiO₂ and diffuse toward Pd nanoparticles without forming new nuclei. The Au atoms are trapped by the preformed Pd nanoparticles, forming PdAu bimetallic nanoparticles which size increases. Furthermore, fixing the amount of deposited Pd and increasing the amount of deposited Au, we analyzed the evolution of the PdAu film surface morphology: we observe that the PdAu grows initially as three-dimensional islands; then the PdAu film morphology evolves from compact three-dimensional islands to partially coalesced worm-like structures, followed by a percolation morphology and finally to a continuous and rough film. The application of the interrupted coalescence model allowed us to evaluate the critical mean island diameter R _c ≈ 2.8 nm for the partial coalescence process. The application of the dynamic scaling theory of growing interfaces allowed us to evaluate the dynamic growth exponent β = 0.21 ± 0.01 from the evolution of the film surface roughness. Finally, fixing the amount of deposited Pd and Au we studied the self-organization mechanism of the PdAu nanoparticles induced by thermal processes performed in the 973–1173 K temperature range. The observed kinetic growth mechanism is consistent with a surface diffusion-limited ripening of the nanoparticles with a temperature-dependent growth exponent. The dependence of the growth exponent on the temperature is supposed to be linked to the variation with the temperature of the characteristics of the PdAu alloy. The activation energy for the surface diffusion process was evaluated in 0.54 ± 0.03 eV.     

Effect of precursor on growth and morphology of MoS2 monolayer and multilayer

The rise of two-dimensional (2D) material is one of the results of successful efforts of researchers which laid the path to the new era of electronics. One of the most exciting materials is MoS₂. Synthesis has been always a major issue as electronic devices need reproducibility along with similar properties for mass productions. Chemical vapor deposition (CVD) is one of the successful methods for 2D materials including graphene. Furthermore, the choice of starting materials for Mo and S source is crucial. The different source has different effects on the layers and morphology of MoS₂ films. In this work, we have extensively studied the CVD technique to grow few layers of MoS₂ with two precursors MoO₃ and MoCl₅, show remarkable changes. The MoO₃ source gives a triangular shaped MoS₂ monolayer while that of MoCl₅ can achieve uniform MoS₂ without triangle. The absence of geometric shapes with MoCl₅ is poorly understood. We tried to explain with MoCl₅ precursor, the formation of continuous monolayer of MoS₂ without any triangle on the basis of chemical reaction formalism mostly due to one step reaction process and formation of MoS₂ from gas phase to the solid phase. The film synthesized by MoCl₅ is more continuous and it would be a good choice for device applications.     

The effect of bias voltage and working pressure on S/Mo ratio at MoS2-Ti composite films

S/Mo ratio has a crucial effect on the tribological properties of MoS₂-Ti composite films. The deposition parameters as such bias voltage and working pressure play a dominant role on the change of this ratio value. To determine the effect of working pressure and bias voltage on S/Mo ratio, MoS₂-Ti composite films were deposited on glass wafers by pulsed-dc magnetron sputtering (PMS). The deposition process was performed for nine different test conditions at various levels of target current, working pressure, and substrate voltage using the Taguchi L₉(3⁴) experimental method. It was observed that the chemical composition of MoS₂-Ti composite films was significantly affected by sputtering parameters. It was also observed that S/Mo ratio decreased as the bias voltage increased at a constant working pressure and S/Mo ratio increased with increasing working pressure at a constant bias voltage.     

Low‐temperature photoluminescence of oxide‐covered single‐layer MoS2

We present a photoluminescence study of single‐layer MoS₂ flakes on SiO₂ surfaces. We demonstrate that the luminescence peak position of flakes prepared from natural MoS₂, which varies by up to 25 meV between individual flakes, can be homogenized by annealing in vacuum. We use HfO₂ and Al₂O₃ layers prepared by atomic layer deposition to cover some of our flakes. In these flakes, we observe a suppression of the low‐energy luminescence peak which appears in asprepared flakes at low temperatures. We infer that this peak originates from excitons bound to surface adsorbates. We also observe different temperature‐induced shifts of the luminescence peaks for the oxide‐covered flakes. This effect stems from the different thermal expansion coefficients of the oxide layers and the MoS₂ flakes. It indicates that the single‐layer MoS₂ flakes strongly adhere to the oxide layers and are therefore strained. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The interaction of CO and O2 with thin islands of Pd

The adsorption and coadsorption of CO and O₂ on islands of Pd about 7 monolayers thin was investigated by TPD and AES. It was found that CO decomposes much less on the Pd islands grown on W(110)-c(14 × 7)-0 than on small particles of Pd on bulk oxide substrates (mica, sapphire). Also, oxygen interacts unusually strong with the island surfaces at temperatures as low as about 600 K. These new results are attributed mainly to SMSI (strong metal/support interaction). Detailed studies of Pd island growth on W(110)-c(14 × 7)-O show that the island thickness can be varied systematically from ～ 3 to ～ 8 monolayers.     

Development of a new molecular dynamics method for tribochemical reaction and its application to formation dynamics of MoS2 tribofilm

Recently we have developed a novel molecular dynamics program NEW-RYUDO-CR, which can deal with chemical reactions. The developed method has been applied to the study of tribochemical reaction dynamics of MoS₂ tribofilm on iron surface. The initially amorphous MoS₂ layer self-organized its structure as result of the tribochemical reactions and formed layered MoS₂ tribofilm. The friction coefficient significantly decreased as the MoS₂ tribofilm was formed. Besides, sliding was observed between sulfur layers of MoS₂ tribofilms which occurred due to repulsive Coulombic interaction forces between sulfur atoms. This indicates that the formation of the layered MoS₂ tribofilm is important to achieve better lubrication properties.     

Electronic structure of the PLD grown mixed phase MoS2/GaN interface and its thermal annealing effect

We report the electronic structure of Molybdenum disulfide (MoS₂) ultrathin 2D films grown by pulsed laser deposition (PLD) on top of GaN/c-Al₂O₃ (0001) substrates annealed up to 550 °C in an ultrahigh vacuum. Our X-ray photoemission spectroscopy (XPS) study shows that the grown films are mixed phase character with semiconducting 2H and metallic 1T phases. After ultrahigh vacuum (UHV) annealing, the 1T/2H phase ratio is significantly modified and film-substrate bonding becomes the leading factor influencing variation of mixed phase compositions. The semiconducting phase is partially transformed to metallic phase by thermal annealing; suggesting that the metallic phase observed here may indeed have more stability compared to the semiconducting phase. The notable enhancement of the 1T/2H ratio induces significant changes in Ga 3d core level spectra taken from bare GaN and MoS₂/GaN sample. The impact of S and/or Mo atoms on the Ga core level spectra is further pronounced with the thermal annealing of grown films. The analysis shows that an enhancement of 1T metallic phase with thermal annealing in MoS₂ layers is manifested by the occurrence of new spectral component in the Ga 3d core level spectra with the formation of Ga-S adlayer interaction through the Ga bonding in defect assisted GaN structure.     

Growth mechanism and structure of ultrathin palladium films formed by deposition on Mo(100)

The growth mechanism, structure and thermal stability of monolayer and ultrathin Pd films formed by vapor deposition on Mo(100) were studied using AES, LEED, and TPD. Pd film growth at 150 K is described well by a Frank-van der Merwe (FM) or layer-by-layer growth mechanism with a small amount of layer disorder and/or non-ideal layering. The Pd monolayer is pseudomorphic with the Mo(100) substrate lattice as shown by LEED. Pd films deposited on Mo(100) at 450 and 600 K grow by forming three-dimensional (3D) islands on top of an initially formed Pd monolayer, i.e., a Stranski-Krastanov growth mode. Alloying could also explain the AES curves at these temperatures. Thermal desorption of Pd from multilayer films begins at 1250 K with an activation energy of 100 kcal/mol. This is 7 kcal/mol higher than the bulk sublimation energy of palladium due to interaction with the molybdenum substrate and was observed for films as thick as 20 layers. Pd desorption is kinetically limited by decomposition of a Pd-Mo alloy and/or diffusion of Pd from the subsurface layers of Mo to the surface. Annealing studies show that the Pd monolayer is stable to 1200 K, but that agglomeration of Pd into 3D islands and possibly alloy formation occurs upon heating thicker films above 400 K.     

Structural evolution of sulfur overlayers on Pd(1 1 1)

Low energy ion scattering spectroscopy (LEISS) has been used to characterize the evolution of ordered structures of S on the Pd(1 1 1) surface during annealing. During exposure of the Pd(1 1 1) surface to 0.7 L H₂S at 300 K—conditions that produce the S(√3 × √3)R30 overlayer—the intensity of the Pd LEIS signal decreases and a feature assigned to adsorbed S appears as the adsorbed layer forms. When the surface is held at 300 K after exposure to H₂S is stopped, the LEIS Pd intensity partially recovers and the S signal weakens, presumably as surface S atoms assume their equilibrium positions in the S(√3 × √3)R30 overlayer. Subsequent annealing of the S(√3 × √3)R30 structure at 700 K causes it to convert into a S(√7 × √7)R19 overlayer, whose LEIS spectrum is identical to that of clean Pd(1 1 1). The absence of LEIS evidence for S atoms at the exposed surface of the S(√7 × √7)R19 overlayer is at odds with published models of a mixed Pd-S top layer. Despite the similarity of the LEIS spectra of Pd(1 1 1) and Pd(1 1 1)-S(√7 × √7)R19, their activities for dissociative hydrogen adsorption are very different—the former readily adsorbs hydrogen at 100 K, while the latter does not—suggesting that S exerts its influence on surface chemistry from subsurface locations.     

Growth mechanism of the Pd(100)-p(2×2)-p4g-Al surface alloy

We have studied the growth mechanism of a Pd(100)-p(2×2)-p4g-Al surface alloy by scanning tunneling microscopy (STM). The surface alloy has a bilayer structure and is formed by annealing at 450–700 K (depending on the initial aluminum coverage) after the deposition of aluminum on Pd(100) at room temperature. The ratio of the surface-alloy coverage to the initial aluminum coverage is found to be constant (0.44) irrespective of the initial aluminum coverage from 0.5 monolayers (ML) up to 2 ML. The growth mechanism of the surface alloy is proposed on the basis of the STM measurements at various annealing temperatures. Upon annealing at 450 K, some of the surface aluminum atoms migrate into the bulk and, instead, palladium atoms come out to the surface. These palladium atoms react with aluminum atoms remaining on the surface to form a surface alloy. When the initial aluminum coverage is less than 1 ML, bilayer-high islands of the surface alloy with an average area of 100 nm² are formed at 450–500 K, which diffuse on the terrace at 500–700 K and coalesce to form larger islands. A possible role of the percolation transition of aluminum islands in the formation of the surface alloy is discussed.     

RHEED and Auger study of the MoO3(010) surface interaction with H2S/H2 mixture and pure H2S

Pure single crystals of MoO₃ were carefully grown by physical vapor transport. The initial stages of the interaction of H₂S with a MoO₃ (010) surface were studied by RHEED and AES at low pressure p <133 Pa and at T < 700 K. Three main stages were found: (a) The formation of either a completely disordered sulphur adiayer (with pure H₂S) or a superstructure MoO₃(010)-[2 × 1]S (with H₂S/H₂). (b) A reduction of MoO₃ producing oriented three-dimensional MoO₂ islands, (c) An epitaxial overgrowth of MoS₂ from the MoO₂ three-dimensional crystallites.