Role of buffer layer in electronic structures of iron phthalocyanine molecules on Au(111)

We investigate the electronic structures of one and two monolayer iron phthalocyanine (FePc) molecules on Au(111) surfaces. The first monolayer FePc is lying flat on the Au(111) substrate, and the second monolayer FePc is tilted at～15° relative to the substrate plane along the nearest neighbour [101ˉ] direction with a lobe downward to the central hole of the unit cell in the first layer. The structural information obtained by first-principles calculations is in agreement with the experiment results. Furthermore, it is demonstrated that the electronic structures of FePc molecules in one-monolayer FePc/Au(111) system are perturbed significantly, while the electronic structures of FePc molecules in the second monolayer in two-monolayer FePc/Au(111) system remain almost unchanged due to the screening of the buffer layer on Au(111).     

金衬底调控单层二硫化钼电子性能的第一性原理研究

基于密度泛函的第一性原理研究了金衬底对单层二硫化钼电子性能的调控作用. 从结合能、能带结构、电子态密度和差分电荷密度四个方面进行了深入研究. 结合能计算确定了硫原子层在界面的排布方式, 并指出这种吸附结构并不稳定. 能带结构分析证实了金衬底与单层二硫化钼形成肖特基接触, 并出现钉扎效应. 电子态密度分析表明金衬底并没有影响硫原子和钼原子之间的共价键, 而是通过调控单层二硫化钼的电子态密度增加其导电率. 差分电荷密度分析表明单层二硫化钼的导电通道可能在界面处产生. 研究结果可对单层二硫化钼晶体管的建模和实验制备提供指导.     

Ultrahigh resolution electron microscopy of the surface structure of (110) Ag2O

An ultrahigh resolution transmission electron microscope and diffraction investigation of the residual oxidized silver on the surface of (111) Au films has shown that it is possible to resolve a monolayer coverage of silver atoms and the atomic structure of crystalline Ag₂O surfaces. Localized patches often under 100 Å in lateral extent show a reoriented (110) oxide which often exhibits a (2 × 1) surface superstructure. The structure of various different layer coverages has been analyzed from the high resolution micrographs via digital image processing and model building to interpret surface morphology.     

Electronic structure of the Au-intercalated graphene/Ni(111) surface

We report the electronic structure of the Au-intercalated graphene/Ni(111) surface using angle-resolved photoemission spectroscopy and low energy electron diffraction. The graphene/Ni(111) shows no Dirac cone near the Fermi level and a relatively broad C 1s core level spectrum probably due to the broken sublattice symmetry in the graphene on the Ni(111) substrate. When Au atoms are intercalated between them, the characteristic Dirac cone is completely recovered near the Fermi level and the C 1s spectrum becomes sharper with the appearance of a 10?×?10 superstructure. The fully Au-intercalated graphene/Ni(111) surface shows a p-type character with a hole pocket of ～0.034?Å^?1 diameter at the Fermi level. When the surface is doped with Na and K, a clear energy gap of ～0.4?eV is visible irrespective of alkali metal.     

Adsorption configurations of carbon monoxide on gold monolayer supported by graphene or monolayer hexagonal boron nitride: a first-principles study

Using density functional theory with a semiempirical van der Waals approach proposed by Grimme, the adsorption behavior of carbon monoxide on a gold monolayer supported by graphene or monolayer hexagonal boron nitride has been investigated. Based on the changes in the Dirac cone of graphene and a Bader charge analysis, we observe that the Au(111) monolayer gains a small charge from graphene and monolayer h-BN. The adsorbed CO molecule adopts similar adsorption configurations on Au(111)/graphene and Au(111)/h-BN with Au-C distance 2.17?2.50 Å and Au-C-O angle of 123.9°–139.6°. Moreover, we found that for low CO coverages, bonding to the gold surface is surprisingly energy-favorable. Yet the CO adsorption binding energy diminishes at high coverage due to the repulsive van der Waals interactions between CO molecules.     

Formation of Two-Dimensional AgTe Monolayer Atomic Crystal on Ag(111) Substrate

We report on the formation of two-dimensional monolayer AgTe crystal on Ag(111) substrates. The samples are prepared in ultrahigh vacuum by deposition of Te on Ag(111) followed by annealing. Using a scanning tunneling microscope(STM) and low electron energy diffraction(LEED), we investigate the atomic structure of the samples.The STM images and the LEED pattern show that monolayer AgTe crystal is formed on Ag(111). Four kinds of atomic structures of AgTe and Ag(111) are observed:(i) flat honeycomb structure,(ii) bulked honeycomb,(iii)stripe structure,(iv) hexagonal structure. The structural analysis indicates that the formation of the different atomic structures is due to the lattice mismatch and relief of the intrinsic strain in the AgTe layer. Our results provide a simple and convenient method to produce monolayer AgTe atomic crystal on Ag(111) and a template for study of novel physical properties and for future quantum devices.     

Tuning of the periodicity of stable self-organized metallic templates

The atomic and electronic structures of Pb bilayer/Pt(111) are investigated with two theoretical calculations.We find that the stable (2 × 2)/(3 × 3) Pb/Pt(111) structure is a promising candidate for being used as a template with self-organized ordered Pb semi-cluster array on the first Pb monolayer.This stable structure can realize the ordered Au single-atom array around the Pb semi-clusters that can cause selective adsorption of noble atoms.The size of Pb magic number semi-cluster plays a more important role in determining the periodicity of the template than the lattice constant misfit between the substrate and the overlayer.This leads to quite a different periodicity between the two stable templates,which are (2 × 2)/(3 × 3) Pb/Pt(111) and Pb/Cu(111).Therefore,by considering the size of the stable semi-clusters and carefully selecting different substrate materials,we can tune the density of Pb semi-clusters as the nucleation points and then tune the periodicity of the stable template.     

Fabrication and characterization of a Cu seed layer on a 60-nm trench-patterned SiO2 substrate by a self-assembled-monolayer (SAM) process

Continuous electroless deposition of a 10-nm thick layer of Cu was successfully performed on a SiO₂/Si substrate coated with a 3-nm Au catalytic layer. The Au catalytic layer was formed by a self-assembled monolayer (SAM) process terminated with NH₂ headgroups, upon which negatively charged Au particles were deposited via electrostatic interaction with the positively charged NH₂-SAM. The Au and NH₂-SAM layers were analyzed by X-ray photoelectron spectroscopy (XPS) and contact angle analysis. Atomic force microscopy, field emission scanning electron microscopy, and XPS revealed that the Cu layer formed by this electroless processes had good step-coverage, small grain size, and excellent adhesion to the substrate. The proposed process is a very promising method for fabrication of a conductive Cu seed layer in a 60-nm trench-pattern.     

Formation of nanoislands in the course of copper deposition on a Cu(111)-(9 × 9)-Ag surface

The process of copper deposition on a structured Cu(111)-(9 × 9)-Ag surface, which represents a (9 × 9) loop dislocation network, is studied by scanning tunneling microscopy. It is found that, when the substrate temperature is 100 K and the copper coverage is 0.1–0.4 of a monolayer, islands of a size no greater than 50 Å are formed at the Ag/Cu(111) interface. The islands remain stable as the sample is heated to room temperature. The shape and boundaries of the nanoislands follow the initial surface superstructure and are determined by the nonuniformity of the interaction of the upper silver layer with the copper substrate. The mechanism of island formation and the origin of their stability are explained in terms of the atom exchange between the adsorbate and substrate.     

Admetal-induced substrate surface restructuring during metal-on-metal electrochemical deposition studied by in situ scanning tunneling microscopy

Based on time-dependent in situ scanning tunneling microscopy (STM) studies, we demonstrate that for Ni on Ag(111) and Ru on Au(111), electrochemical metal-on-metal deposition can result in pronounced substrate surface restructuring. For Ni/Ag(111), we observe that at low deposition flux and low coverage, Ni submonolayer islands at steps are partly embedded in the Ag terraces, whereas at higher deposition flux and higher coverage, substrate restructuring results in the formation of monolayer bays in the Ag terraces. We suggest that this restructuring process proceeds predominantly via step edge diffusion of Ag atoms. For Ru/Au(111), the formation of fjords and monolayer holes in the Au terraces is observed at low and high Ru coverage, respectively. The importance of the Au surface mobility for the restructuring process is demonstrated by comparing experiments in H₂SO₄ and HCl solutions, in which Au exhibits strongly different surface mobilities. For this system, restructuring involves Au diffusion along Au steps, Au atom detachment from the Au steps, and upward exchange diffusion. According to these observations and their comparison with similar findings for vacuum deposition, we conclude that this restructuring requires (i) a high substrate surface mobility and (ii) a stronger bonding of substrate atoms to deposit islands than to the substrate.     

Potential-induced strain relaxation in au mono- and bilayer films on Pt(111) electrode surfaces

In situ scanning tunneling microscopy observations of 1-2 monolayer thick Au films on Pt(111) electrodes are presented, which show a complex, potential-dependent structural phase behavior of the Au film. Starting from a pseudomorphic structure at <0.35 V(Ag/AgCl), a sequence of transitions into dislocation network structures occurs with increasing potential: (1x1)--> "striped phase" --> "hex phase" in the Au bilayer, (1x1)--> striped phase in the Au monolayer. This is explained by a reduction of the in-plane stress in the Au surface layer(s) due to anion adsorption and a strain energy minimization as described by the Frenkel-Kontorova model.     

Electronic properties of monolayer copper selenide with one-dimensional moiré patterns

Strain engineering is a vital way to manipulate the electronic properties of two-dimensional (2D) materials. As a typical representative of transition metal mono-chalcogenides (TMMs), a honeycomb CuSe monolayer features with one-dimensional (1D) moiré patterns owing to the uniaxial strain along one of three equivalent orientations of Cu(111) substrates. Here, by combining low-temperature scanning tunneling microscopy/spectroscopy (STM/S) experiments and density functional theory (DFT) calculations, we systematically investigate the electronic properties of the strained CuSe monolayer on the Cu(111) substrate. Our results show the semiconducting feature of CuSe monolayer with a band gap of 1.28 eV and the 1D periodical modulation of electronic properties by the 1D moiré patterns. Except for the uniaxially strained CuSe monolayer, we observed domain boundary and line defects in the CuSe monolayer, where the biaxial-strain and strain-free conditions can be investigated respectively. STS measurements for the three different strain regions show that the first peak in conduction band will move downward with the increasing strain. DFT calculations based on the three CuSe atomic models with different strain inside reproduced the peak movement. The present findings not only enrich the fundamental comprehension toward the influence of strain on electronic properties at 2D limit, but also offer the benchmark for the development of 2D semiconductor materials.     

Observation of Si(111) and gold-deposited Si(111) surfaces using micro-probe reflection high-energy electron diffraction

Observations of clean Si(111) and gold-deposited Si(111) surfaces have been performed using micro-probe reflection high-energy electron diffraction. It was found that many atomic steps on a Si(111) surface run in nearly the same direction, about 9° off the [1&#x0304;1&#x0304;2] direction. When gold was deposited on this surface at a substrate temperature of about 800°C, 5 × 1, diffuse √3 × √3R30°, sharp √3 × √3 R30° structures and Au clusters appeared on the surface with continuation of the deposition. During the deposition process, it was found that one kind of Si(111) 5 × 1 Au domain grew selectively along these atomic steps and nearly covered the entire surface. A phenomenon of gold clusters moving during the deposition was also observed. These clusters all moved in nearly the same direction so as to climb the atomic steps.     

Formation, electronic structure, and stability of film nanophases of transition metals on silicon

This paper is devoted to the study of the morphology, growth, electronic structure, and stability of ultrathin (0.03–3 nm) Co and Fe films on the Si(111) and Si(100) surfaces using Auger-electron spectroscopy, electron-energy loss spectrometry, low-energy electron diffraction, and atomic-force microscopy. It is shown that layer-by-layer growth of the metal with the formation of the film nanophase and the segregation of a submonolayer amount of Si on the film’s nanophase surface occurs during the process of layer-by layer growth of Co and Fe on Si(111)-7 × 7 and Si(100)-2 × 1 at room temperature after the growth of two-dimensional metal phases (the surface phase, the monolayer, and two metal monolayers). After these stages, the formation and growth of the bulk’s metal phase with the dissolution of silicon segregated before occur. It is shown that the upper layers of Si adjoining the surface phase, the monolayer, and two Co and Fe monolayers have respectively three different densities of the electron plasma that are higher than the density of the electron plasma in the volume of the silicon substrate. The nonmonotonous character of the morphological and chemical stability of Fe films with quantum-size thicknesses on Si(100) is discovered. After annealing, the film is first smooth, then it is nonuniform across its thickness; afterwards it is again smooth and then nonuniform across its thickness. In this case, the metal phase, different Fe silicides, and the bulk’s metal phase form successively in Fe films on Si(100) after annealing.     

Interfacial structure of Co porphyrins on Au(111) electrode: Interaction of porphyrin molecules with substrate

Interfacial structures of cobalt(II) porphine (CoP) and [2,3,7,8,12,13,17,18‐octaethyl‐21H,23-H-porphine]cobalt(II) (CoOEP) have been studied on Au(111) electrode using electrochemical scanning tunneling microscopy (EC-STM), in-situ X-ray diffraction, and density functional theory (DFT) calculations. The adsorption of porphyrins affects the reconstruction of Au(111) surface. The adsorption of CoP causes a lifting of the reconstruction to a complete 1 × 1 structure of Au(111). On CoOEP modified Au(111), the unit cell periodicity of the reconstructed substrate structure expands compared with the √3 × 23 structure of bare Au(111). The same expanded substrate structure was observed on Au(111) modified with OEP without the coordinated Co ion; the coordinated metal ion of the adsorbed porphyrin molecule does not affect the substrate structure. This result indicates that the interaction of conjugated π electrons of porphyrin with the substrate is stronger than that of the coordinated Co ion. In-situ X-ray diffraction and DFT calculation support non-covalent interaction of porphyrins with the Au(111) surface.     

Catalytic action of gold atoms on the oxidation of Si(111) surfaces

Auger spectroscopy, electron energy loss spectroscopy and ion depth profiling techniques, under ultra high vacuum conditions, have been used in a comparative study of the oxidation of clean and gold precovered silicon (111) surfaces. Exposure of a Si surface covered by a few Au monolayers to an oxygen partial pressure induces the formation of SiO₄ tetrahedra even at room temperature. In contrast, oxidation under the same conditions of a clean Si(111) surface leads to the well known formation of a chemisorbed oxygen monolayer. In the case of the Au covered surfaces, the enhancement of the oxide growth is attributed to the presence of an AuSi alloy where the hybridization state of silicon atoms is modified as compared to bulk silicon. This Au catalytic action has been investigated with various parameters as the substrate temperature, oxygen partial pressure and Au coverage. The conclusions are two fold. At low temperature (T < 400°C), gold atoms enhance considerably the oxidation process. SiO₄ tetrahedra are readily formed even at room temperature. Nevertheless, the SiO₂ thickness saturates at about one monolayer, this effect being attributed to the lack of Si atoms alloyed with gold in the reaction area. By increasing the temperature (from 20°C to ～400°C), silicon diffusion towards the surface is promoted and a thicker SiO₂ layer can be grown on top of the substrate. In the case of the oxidation performed at temperature higher than 400°C, the results are similar to the one obtained on a clean surface. At these temperatures, the metallic film agglomerates into tridimensional crystallites on top of a very thin AuSi alloyed layer. The fact that the latter has no influence on the oxidation is attributed to the different local arrangement of atoms at the sample surface.     

Monolayer pattern evolution via substrate strain-mediated spinodal decomposition

Investigations of octylsilane (C8H17SiH3) monolayer pattern formation on Au(111) are reported. Scanning tunneling microscopy data display the evolution of a approximately 6 nm scale pattern of interwoven features concomitant with ejection of surface Au atoms and relaxation of the Au(111) 23xsqrt[3] surface reconstruction. Numerical simulations suggest the surface dynamics are governed by a substrate strain-mediated spinodal decomposition mechanism, novel to organic monolayer formation. Collectively, the experimental and theoretical data indicate strain-inducing Si-Au bond interactions drive the pattern formation and the alkyl chains play a negligible role.     

Two commensurate hydrogen-bonded monolayer structures of melamine on Ag(111)

Melamine (1,3,5-triazine-2,4,6-triamine) was deposited on the Ag(111) surface under ultrahigh vacuum conditions. It forms two different monolayer structures, which were investigated by low energy electron diffraction and scanning tunneling microscopy. The α-phase is a honeycomb structure containing two molecules per unit-cell. The molecular orientation within the unit-cell is determined by six hydrogen bonds. The α-phase is kinetically preferred upon deposition at room-temperature and can be transferred to the thermodynamically more stable β-phase by annealing at 333 K. The β-phase has an oblique unit-cell containing four molecules and shows a higher surface density with additional hydrogen bonds between adjacent amino groups. Both structures are commensurate. While the structural motif of the α-phase has been observed before on Au(111) and Ag–Si(111) surfaces, the structure of the β-phase has been so far only theoretically predicted.     

The surface structures growth’s features caused by Ge adsorption on the Au(111) surface

The initial stage of the adsorption of Ge on an Au(111) surface was investigated. The growth and stability of the structures formed at the surface were studied by ultrahigh-vacuum low-temperature scanning tunneling microscopy and analyzed using density functional theory. It was established that the adsorption of single Ge atoms at the Au(111) surface at room temperature leads to the substitution of Au atoms by Ge atoms in the first surface layer. An increasing of surface coverage up to 0.2–0.4 monolayers results in the growth of an amorphous binary layer composed of intermixed Au and Ge atoms. It was shown that the annealing of the binary layer at a temperature of T _s ? 500 K, as well as the adsorption of Ge on the Au(111) surface heated to T _s ? 500 K for coverages up to 1 monolayer lead to a structural transition and the formation of an Au–Ge alloy at least in the first two surface layers. Based on experimental and theoretical data, it was shown that the formation of single-layer germanene on the Au(111) surface for coverages ≤1 monolayer in the temperature range of T _s = 297–500 K is impossible.     

Electronic and magnetic properties of quasifreestanding graphene on Ni

For the purpose of recovering the intriguing electronic properties of freestanding graphene at a solid surface, graphene self-organized on a Au monolayer on Ni(111) is prepared and characterized by scanning tunneling microscopy. Angle-resolved photoemission reveals a gapless linear pi-band dispersion near K[over] as a fingerprint of strictly monolayer graphene and a Dirac crossing energy equal to the Fermi energy (EF) within 25 meV meaning charge neutrality. Spin resolution shows a Rashba effect on the pi states with a large (approximately 13 meV) spin-orbit splitting up to EF which is independent of k.