Adsorption/desorption kinetics of Na atoms on reconstructed Si (111)-7 × 7 surface

Self-assembled nanostructures on a periodic template are fundamentally and technologically important as they put forward the possibility to fabricate and pattern micro/nano-electronics for sensors, ultra high-density memories and nanocatalysts. Alkali-metal (AM) nanostructure grown on a semiconductor surface has received considerable attention because of their simple hydrogen like electronic structure. However, little efforts have been made to understand the fundamental aspects of the growth mechanism of self-assembled nanostructures of AM on semiconductor surfaces. In this paper, we report organized investigation of kinetically controlled room-temperature (RT) adsorption/desorption of sodium (Na) metal atoms on clean reconstructed Si (111)-7 × 7 surface, by X-ray photoelectron spectroscopy (XPS). The RT uptake curve shows a layer-by-layer growth (Frank-vander Merve growth) mode of Na on Si (111)-7 × 7 surfaces and a shift is observed in the binding energy position of Na (1s) spectra. The thermal stability of the Na/Si (111) system was inspected by annealing the system to higher substrate temperatures. Within a temperature range from RT to 350 °C, the temperature induced mobility to the excess Na atoms sitting on top of the bilayer, allowing to arrange themselves. Na atoms desorbed over a wide temperature range of 370 °C, before depleting the Si (111) surface at temperature 720 °C. The acquired valence-band (VB) spectra during Na growth revealed the development of new electronic-states near the Fermi level and desorption leads the termination of these. For Na adsorption up to 2 monolayers, decrease in work function (−1.35 eV) was observed, whereas work function of the system monotonically increases with Na desorption from the Si surface as observed by other studies also. This kinetic and thermodynamic study of Na adsorbed Si (111)-7 × 7 system can be utilized in fabrication of sensors used in night vision devices.     

STM observation of Ag adatom interactions on the Si(1 1 1)-(7×7) surface

STM imaging of Ag atoms adsorbed on the Si(1 1 1)-(7×7) surface is studied. Appearance of a single Ag adatom on perfect surface is compared with images of adatoms interacting with surface defects and adsorbates. Importance of real-time observation of surface processes for image interpretation is demonstrated on imaging Ag adatoms at various situations. Influence of tunnelling conditions (voltage between a tip and surface) on imaging surface objects is studied and visibility of single Ag adatoms and clusters is discussed.     

Theoretical investigation of atomic structure and electronic properties of Ca/Si(110)-(2 × 1) reconstruction

We have presented first-principles total-energy calculations for the adsorption of Ca metals onto a Si(110) surface. The density functional method was employed within its local density approximation to study the atomic and electronic properties of the Ca/Si(110) structure. We considered the (1 × 1) and (2 × 1) structural models for Ca coverages of 0.5 monolayer (ML) and 0.25 ML, respectively. Our total-energy calculations indicate that the (1 × 1) phase is not expected to occur. It was found that Ca adatoms are adsorbed on top of the surface and form a bridge with the uppermost Si atoms. The Ca/Si(110)-(2 × 1) produces a semiconducting surface band structure with a direct band gap that is slightly smaller than that of the clean surface. One filled and two empty surface states were observed in the gap; these empty surface states originate from the uppermost Si dangling bond states and the Ca 4 s states. It is found that the Ca-Si bonds have an ionic nature and complete charge being transferred from Ca to the surface Si atoms. Finally, the key structural parameters of the equilibrium geometry are detailed and compared with the available results for metal-adsorbed Si(110) surface, Ca/Si(001), and Ca/Si(111) structures.     

Thermal evolution of the morphology of Ni/Ag/Si(111)-√3 × √3 surface

The temperature-driven changes in morphology of the interface formed by room temperature (RT) deposition of Ni atoms onto an Ag/Si(111)-√3 × √3 surface were investigated by scanning tunneling microscopy. Roughly 70% of Ni deposition diffused into bulk substrate within the temperature range between RT and 573 K. The images as obtained after annealing up to 670 K correspond to the formation of nano-sized islands of nickel silicides. Two types of islands, large triangular islands typical of the whole range of applied coverage, and smaller islands of different shapes, coexist at Ni coverage higher than 1 monolayer. Annealing above 870 K led to the formation of a 7 × 7 phase in coexistence with small 5 × 5 domains at the expense of a complete disappearance of the √3 × √3 phase. Also, formation of Ni,Si alloy was observed at the temperature, along with segregation of bulk-dissolved Ni species onto the surface.     

TOF-SARS study of hydrogen adsorption and desorption kinetics on Si(1 0 0)

The kinetics of atomic hydrogen isothermal adsorption and desorption on a Si(1 0 0) surface was studied using the time-of-flight scattering and recoiling spectrometry technique at temperatures below and above the thermal desorption threshold. A continuous decrease in saturation coverage with temperature under constant atomic hydrogen exposure has been observed in both regions for temperatures in the range 325-820 K. For T_S=500-650 K, the decrease is described by a kinetic model where Eley-Rideal (ER) abstraction is responsible for hydrogen removal from the surface and hydrogen coverage depends on the temperature due to the changing rate of migration from precursor to primary monohydride sites. For T_S=650 K and higher, in addition to the ER abstraction, the thermal desorption from primary monohydride sites leads to a further decrease of the saturation coverage. The first-order desorption rates after source shut-off have been measured and an activation barrier of 1.89 eV has been obtained.     

Adsorption of Ni on Si(1 0 0) surface

The chemisorption of one monolayer Ni atoms on ideal Si(1 0 0) surface is studied by using the self-consistent tight binding linear muffin-tin orbital method. Energies of adsorption systems of Ni atoms on different sites are calculated. It is found that Ni atoms can adsorb at fourfold site above the surface and bridge site below the surface. The adsorption of Ni atoms can readily diffuse and penetrate into the subsurface. A Ni, Si mixed layer might exist at the Ni-Si(1 0 0) interface. The layer projected density states are calculated and compared with that of the clean surface. The charge transfers are also investigated.     

Structure of Pt3Co(1 1 0)c(2×4)-O surface studied by scanning tunneling microscopy

A Pt₃Co(1 1 0)c(2×4)-O surface has been investigated by scanning tunneling microscopy (STM), low-energy electron diffraction, and Auger electron spectroscopy. At a very initial oxidation stage exposed at 500°C, creation of missing and/or added row structures running to the [0 0 1] direction on clean Pt₃Co(1 1 0)2×1 surface was imaged from the steps. The surface is fully covered by a well-ordered c(2×4) structure at 2 L oxygen exposure. Atomic-resolution STM image shows the added row-type anti-phase Co-O zigzag chains along the [0 0 1] direction. Based on the images, the structure model for the c(2×4) surface was suggested as a first oxidized layer, which comes from the chemical reaction forming stoichiometric Co monoxide. Further oxygen exposure above 5 L, Co-O clusters imaged to large dots were formed on the surface with the size of about 5-7 Å.     

Thickness dependent reactivity and coercivity for ultrathin Co/Si(111) films

For Co/Si(111) films thinner than 15 ML, the thickness dependent reactivity and magnetic properties have been systematically studied. As the Co coverage increases, Co adatoms on the Si(111) surface show enhanced chemical reactivity for oxidation due to the change of the chemical state. After the saturation oxygen exposure, oxygen atoms interact with a thick Co layer to form a rougher interface. Complex adsorption kinetics of oxygen in the Co layer is observed. From the depth-profiling measurements for Co layers close to the Co-Si interface, the sputtering rate is enhanced due to that the solid surfaces of Si and Co-Si compounds are resistive against oxidation. The descending of the Kerr intensity by saturation oxygen exposure shows the limited diffusion length of oxygen atoms into the films. The inertness of the Co-Si interface, the reduction of pure cobalt and imperfection introduced by oxygen influence the coercivity of O/Co/Si(111).     

Electronic structure of Co islands grown on the √3 × √3-Ag/Ge(111) surface

By means of room temperature scanning tunneling spectroscopy (RT STS), we have studied the electronic structure of two different Ag/Ge(111) phases as well as Co islands grown on the √3 × √3-Ag/Ge (111) forming either √13 × √13 or 2 × 2 patterns. The spectrum obtained from 4 × 4-Ag/Ge(111) structure shows the existence of a shoulder at 0.7 V which is also present in the electronic structure of the Ge(111)-c2 × 8 and indicates donation of Ge electrons to electronic states of the Ag-driven phase. However, this fact is not supported by the electronic spectrum taken from the √3 × √3-Ag/Ge (111). The complexity of the Co-√13 × √13 islands bonding with the substrate is mirrored by a large number of peaks in their electronic spectra. The spectra obtained from the Co-2 × 2 islands which had grown on the step differ from those taken from Co-2 × 2 islands located along the edge of the terrace by a number of peaks at negative sample bias. This discrepancy is elucidated in terms of dissimilarities of Co-substrate interaction accompanying Co islands growth on different areas of the stepped surface.     

DFT study of the coverage effects for Al adsorption on Si(1 1 1) surfaces

Density functional theory (DFT) calculations have been carried out to investigate the interactions between the Si(1 1 1) surface and the Al adatoms. Different adsorption sites and coverage effects have been considered. For low Al coverage, the threefold-filled adsorption site is the most energy favored site. With the increase of Al coverage, adatom-adatom interactions become increasingly important and Al atomic chains or clusters are formed. With the clean Si(1 1 1) surface of metallic feature, we found that 1/3 ML Al adsorption leads to a semiconducting surface. The results for the electronic behavior suggest the formation of the polarized covalent bonding between the Al adatom and the Si(1 1 1) surface.     

Motion and conversion energies of adatom and adatom clusters on gold (0 0 1) surface

Beginning of epitaxial growth of vapor deposition on (0 0 1) surface has been studied by use of molecular dynamics. The activation energies of motion and conversion can be calculated using an embedded atom potential at any temperatures. The activation energy of the motion of a gold adatom on (0 0 1) surface of gold is calculated to be 0.41 eV. The activation energies of dissociation in the direction of a di-adatom is 0.72 eV from the nearest neighbor to the next nearest neighbor, and 0.27 eV from the next nearest neighbor to the third neighbor. Butterfly motion of a di-adatom is 0.42+0.12 eV=0.54 eV. Tri-adatoms are classified by the angle between the two bonds in the adatoms and the lengths of the two bonds. The conversion energies of tri-adatoms have also been calculated. The activation energy for the motion of an adatom on (0 0 1) surface is much higher than those corresponding the motion on (1 1 1) surfaces.     

Ordered mixed surface structures formed by coadsorption of dissimilar metal atoms on Cu(0 0 1)

We have found that various ordered mixed surface structures are formed by coadsorption of two dissimilar metal atoms on Cu(0 0 1) at room tepmerature, using low-energy electron diffraction (LEED) I-V analysis. As coadsorbates, we employed Mg, Bi, Li and K, and surface structures formed by the coadsorption systems of (Mg, Li), (Mg, K) and (Mg, Bi) are presented. A tensor LEED analysis provided detailed geometries of the coadsorbates and the substrate surface. It was found that the surface structures in the above three coadsorption sytems exhibit the restructuring of the Cu(0 0 1) surface. The phase separation into individual adsorbates does not take place, implying that some additional stabilization arises. We demonstrate two origins for the stabilization of the ordered mixed surface structures on Cu(0 0 1). Structures and features formed by the individual adsorption of Mg, Bi, Li and K atoms on Cu(0 0 1) are described first, then those of (2√2×√2)R45°-Mg,Li, (√5×√5)R26.7°-Mg,K, c(2×2)-Mg,Bi, and c(6×4)-Mg,Bi structures formed by the coadsorption are presented. We consider on the basis of the determined structural parameters the question why ordered mixed surface structures are formed instead of the phase separation.     

Simulations of Si and SiO2 etching in SF6 + O2 plasma

Chemical etching of Si and SiO₂ in SF₆ + O₂ plasma is considered. The concentrations of plasma components are calculated using values extrapolated from experimental data. Resulting calculations of plasma components are used for the calculation of Si and SiO₂ etching rates. It is found that the reaction constants for reactions of F atoms with Si atoms and SiO₂ molecules are equal to (3.5 ± 0.1) × 10⁻² and (3.0 ± 0.1) × 10⁻⁴, respectively. The influence of O₂ addition to SF₆ plasma on the etching rate of Si is quantified.     

Adsorption of single Ag and Cu atoms on regular and defective MgO(0 0 1) substrates: an ab initio study

The DFT slab calculations were performed for Ag and Cu atoms adsorbed on both regular and defective MgO(0 0 1) substrates. Both metal atoms and surface O vacancies (F_s centers) were distributed uniformly with a concentration of one Ag, Cu or F_s per 2×2 surface supercell. Surface O²⁻ ions are energetically more preferable for metal-atom adsorption on a regular substrate as compared to Mg²⁺ ions. The nature of the interaction between Ag or Cu adatoms and a defectless MgO substrate is physisorption (despite the difference in the adsorption energies: 0.62 vs. 0.39 eV per Cu and Ag adatom, respectively). Above the F_s centers, metal atoms are bounded much stronger when compared with regular O²⁻ sites (2.4  vs. 2.1 eV per Cu and Ag adatoms, respectively). This is accompanied by a substantial charge transfer towards each adatom (Δq_Cu=0.41e and Δq_Ag=0.32e) as well as a formation of partly covalent Me-F_s bonds across the interface (Mulliken bond populations p_Cu-Fs=0.25e and p_Ag-Fs=0.33e).     

A study on phase relations and texture of Co1 − xPtx (0.09 < x < 0.86) nanowire arrays

Based on Rietveld refinement of X-ray diffraction patterns, the phase structure and microstructural parameters of Co_1 − xPt_x nanowires are determined for a range of Pt content. The phase structure of the as-deposited Co_1 − xPt_x(0.09 < x < 0.86) nanowire arrays changes progressively from hcp ε-Co to a mixture of the hcp ε-Co and fcc α-Co,Pt solid solution and finally to pure fcc Co,Pt solid solution with Pt content increasing . Moreover, the texture parameter P₍₁₁₁₎ has a maximum value with Pt content of 50% confirmed by the (111) pole figure measurement. It is suggested that this contributes to enhance magnetocrystalline anisotropy, resulting in a relatively high squareness and coercivity for the nanowires.     

Behavior of N atoms after thermal nitridation of Si1 − xGex surface

Behavior of N atoms after thermal nitridation of Si_1 − xGe_x (100) surface in NH₃ atmosphere at 400 °C was investigated. X-ray photoelectron spectroscopy (XPS) results show that N atomic amount after nitridation tends to increase with increasing Ge fraction, and amount of N atoms bonded with Ge atoms decreases by heat treatment in H₂ at 400 °C. For nitrided Si_0.3Ge_0.7(100), the bonding between N and Si atoms forms Si₃N₄ structure whose amount is larger than that for nitrided Si(100). Angle-resolved XPS measurements show that there are N atoms not only at the outermost surface but also beneath surface especially in a deeper region around a few atomic layers for the nitrided Si(100), Si_0.3Ge_0.7(100) and Ge(100). From these results, it is suggested that penetration of N atoms through around a few atomic layers for Si, Si_0.3Ge_0.7 and Ge occurs during nitridation, and the N atoms for the nitrided Si_0.3Ge_0.7(100) dominantly form a Si₃N₄ structure which stably remains even during heat treatment in H₂ at 400 °C.     

Simple method for coating Si (1 0 0) surfaces with ferritin monolayers—Iron oxide quantum dots

With the goal to develop iron oxide quantum dots we developed a simple method to spread horse spleen ferritin monolayers on a Si (1 0 0) surface. Application of atomic force microscopy and spectroscopic ellipsometry showed the existence of regions with dense ferritin monolayers. Application of transmission electron microscopy identified the core of the spread ferritin as FeO nanocrystals.     

Effects of stress on the interfacial reactions of metal thin films on (0 0 1)Si

The influences of stress on the interfacial reactions of Ti and Ni metal thin films on (0 0 1)Si have been investigated. Compressive stress present in the silicon substrate was found to retard significantly the growth of Ti and Ni silicide thin films. On the other hand, the tensile stress present in the silicon substrate was found to enhance the formation of Ti and Ni silicides. For Ti and Ni on stressed (0 0 1)Si substrates after rapid thermal annealing, the thicknesses of TiSi₂ and NiSi films were found to decrease and increase with the compressive and tensile stress level, respectively. The results clearly indicated that the compressive stress hinders the interdiffusion of atoms through the metal/Si interface, so that the formation of metal silicide films was retarded. In contrast, tensile stress facilitates the interdiffusion of atoms. As a result, the growth of Ti and Ni silicide is promoted.     

Composition dependent thermoelectric properties of sintered Mg2Si1−xGex (x = 0 to 1) initiated from a melt-grown polycrystalline source

Fabrication of Mg₂Si_1−xGe_x (x = 0-1.0) was carried out using a spark plasma sintering technique initiated from melt-grown polycrystalline Mg₂Si_1−xGe_x powder. The thermoelectric properties were evaluated from RT to 873 K. The power factor of Mg₂Si_1−xGe_x with higher Ge content (x = 0.6-1.0) tends to decrease at higher temperatures, and the maximum value of about 2.2 × 10^− 5 Wcm^− 1K^− 2 was observed at 420 K for Mg₂Si and Mg₂Si_0.6Ge_0.4. The coexistence of Si and Ge gave rise to a decrease in the thermal conductivity in the Mg₂Si_1−xGe_x. The values close to 0.02 Wcm^− 1K^− 1 were obtained for Mg₂Si_1−xGe_x (x = 0.4-0.6) over the temperature range from 573 to 773 K, with the minimum value being about 0.018 Wcm^− 1K^− 1 at 773 K for Mg₂Si_0.4Ge_0.6. The maximum dimensionless figure of merit was estimated to be 0.67 at 750 K for samples of Mg₂Si_0.6Ge_0.4.     

Site dependent metal adsorption on (3 × 3) h-BN monolayer: Stability, magnetic and optical properties

Cu, Pd and Au metal adatom adsorption on different adsorption sites of graphene analog h-BN monolayer is presented. The results demonstrate that the atop N (A_N) being the most favorable site for Cu while atop B (A_B) for Pd/Au; as well as occurrence of chemisorption is also found in these sites. A general model has been proposed which essentially indicate electronegativity (χ) to be the governing reason regarding the choice of adsorption sites on h-BN sheet in a way such that the adatoms with χ < 2.04 are the most stable on A_N site while adatoms with χ lying in the range 2.04-3.04 are the most stable on A_B site. A detail study regarding magnetic properties reveal 100% spin polarization at Fermi level i.e. half metallic characteristics and 1μ_B/supercell magnetic moment in case of Cu and Au adatom adsorption at the most favorable sites. For Cu adsorbed h-BN system, the half metallic characteristics and strong chemical bonds arise from good hybridization at 0 eV between the outermost 2p orbital of nitrogen and the outermost 4s orbital of copper and at −1.49 eV between Cu 3d and 4s orbital with N 2p orbital. A thorough optical study on the above mentioned systems exhibits evolution/disappearance of different hump/shoulder peaks in the calculated absorption coefficient vs. energy plot which may be useful for experimental identification of the adsorbed systems.