Luminescence induced by a scanning-tunneling microscope as a nanophotonic probe

The luminescence of nanostructured systems can be excited highly locally by the tip of a Scanning Tunneling Microscope (STM). We first present briefly the principles of this STM-induced luminescence. Then we present a review of selected results in STM-induced luminescence from the point of view of nano-scale photonics. We illustrate various contrast mechanisms with different examples of nanostructured systems. To cite this article: F. Silly, F. Charra, C. R. Physique 3 (2002) 493–500.     

Electron stimulated desorption induced by the scanning tunneling microscope

The use of the scanning tunneling microscope (STM) as an excitation source and a probe of electron stimulated desorption on the atomic scale is reviewed. The case of H desorption from H-terminated Si(001) is examined in detail. Experimental results on excitation thresholds, desorption cross-sections, isotope effects and site-selectivities are presented. Evidence for mechanisms involving direct electronic and hot ground-state desorption, as well as a novel multiple-vibrational excitation mechanism is discussed. Using the latter mechanism, the ultimate resolution limit of selective single atom desorption is achieved. New results on desorption from Si dihydride, including a proposed mechanism for the STM-induced H/Si(001)-3 × 1 to 2 × 1 conversion, are presented. Possible applications of STM-induced desorption in nanofabrication are considered.     

Triphenylene adsorption on Cu(111) and relevant graphene self-assembly

Investigations on adsorption behavior of triphenylene(TP) and subsequent graphene self-assembly on Cu(111) were carried out mainly by using scanning tunneling microscopy(STM).At monolayer coverage,TP molecules formed a longrange ordered adsorption structure on Cu(111) with an uniform orientation.Graphene self-assembly on the Cu(111) substrate with TP molecules as precursor was achieved by annealing the sample,and a large-scale graphene overlayer was successfully captured after the sample annealing up to 1000 K.Three different Moire patterns generated from relative rotational disorders between the graphene overlayer and the Cu(111) substrate were observed,one with 40 rotation between the graphene overlayer and the Cu(111) substrate with a periodicity of 2.93 nm,another with 70 rotation and 2.15 nm of the size of the Moire supercell,and the third with 100 rotation with a periodicity of 1.35 nm.     

Inelastic spectroscopy identification of STM-induced benzene dehydrogenation

Inelastic electron tunneling spectroscopy (IETS) performed with the scanning tunneling microscope (STM) has been deemed as the ultimate tool for identifying chemicals on the atomic scale. However, IETS-based chemical analysis is error-prone due to the numerous degrees of freedom of chemisorbed molecular systems. First-principles simulations of IETS are presented that, by quantitative comparison with the experimental spectra, permit one to determine the final products of an STM-induced reaction on chemisorbed benzene. Our simulations reveal that IETS possesses an enhanced sensitivity to atomic structure as compared to topographic imaging due to both its energy and space resolution.     

Laser-induced charge transfer and photodesorption of Cs at Cu(111): quantum dynamical model simulations

We present electronic and nuclear quantum model simulations for the direct, laser-induced charge transfer from a Cu(111) surface state to an unoccupied resonance state of an adsorbed Cs atom, and the resulting nuclear dynamics. Based on a modified one-electron model potential adopted from Chulkov et al., we determine energies and lifetimes of electronic states of Cs/Cu(111) at low coverage. In addition, semiempirical nuclear potential energy surfaces of the electronic ground and the antibonding excited states along the Cs-Cu distance are designed and used for nuclear dynamics. For both models, electronic and nuclear, we perform open-system quantum dynamics with the goals (i) to estimate the excitation (charge transfer) and Cs desorption probabilities and (ii) to optimize the charge-transfer process by pulse shaping and the desorption of Cs from the Cu surface by vibrationally exciting the Cs-Cu bond. PACS 79.20.La; 71.10.Li     

Scattering of surface state electrons at large organic molecules

The scattering of surface state electrons at Lander-type molecules on Cu(111) is investigated by means of scanning tunneling microscope (STM) experiments at low temperature and model calculations. Specific information concerning the electronic interaction of the different internal groups of the molecule with the surface is obtained. Remarkably, the central molecular wire of the molecule, although decoupled from the surface by spacer groups and therefore not visible in STM images, is the main one responsible for scattering of surface state electrons.     

CO dynamics induced by tunneling electrons: differences on Cu(110) and Ag(110)

The electronic current originating in a scanning tunneling microscope (STM) can be used to induce motion and desorption of adsorbates on surfaces. The manipulation of CO molecules on noble metal surfaces is an academic case that has received little theoretical attention. Here, we do thorough density functional theory calculations that explore the chemisorption of CO on Cu(110) and Ag(110) surface and its vibrational properties. The STM induced dynamics are explored after excitation of the highest lying mode, the C–O stretch. In order to give a complete account of this dynamics, the lifetime of the different CO modes is evaluated (by only including the mode decay into electronic excitations of the host surface) as well as the intermode coupling. Hence, after excitation of the stretch mode, the lower-energy modes are populated via intermode coupling and depopulated by electron-hole excitations. This study reveals the intrinsic features of the STM induced motion of CO on Cu(110) and Ag(110).     

Open-system density matrix description of an STM-driven atomic switch: H on Si(100)

Previous experiments indicate that an STM (scanning tunnelling microscope) can be used to switch a hydrogen atom at a partially hydrogen-covered Si(100)-2×1 surface, from one Si atom of a Si dimer to a neighbouring, empty Si site [U.J. Quaade et al., Surf. Sci. 415, L1037, 1998]. It has been suggested that the switching occurs via a transient positive ion resonance state. In an earlier paper, we have examined the switching process for the “above threshold” regime when the bias is large enough to directly populate the positive ion resonance. In the present paper we study the “below threshold” regime instead, where the switching is more appropriately modelled as a ladder climbing over the barrier, in the ground electronic state. For this purpose we solve the Liouville–von Neumann equation in Lindblad form, describing a switching H atom on a Si dimer. STM-induced transition rates between vibrational levels are estimated from cluster calculations, assuming contributions both from a dipole and a resonance scattering mechanism. Vibrational relaxation is also included, as well as finite temperature and field effects. The switching rate in a current regime of about 1 to 10 nA scales highly non-linearly with current, and it is found to be governed by vibrational “ladder climbing” and subsequent tunnelling through the top of the ground state barrier. Multi-phonon processes also play a role. As a result of tunnelling, pronounced isotope effects are observed when replacing H with D. It is further argued that resonance-mediated inelastic scattering dominates over dipole excitation, and that the STM switch is stable also at room temperature.     

Spiral evolution in a confined geometry

Supported nanoscale lead crystallites with a step emerging from a noncentered screw dislocation on the circular top facet were prepared by rapid cooling from just above the melting temperature. STM observations of the top facet show a nonuniform rotation rate and shape of the spiral step as the crystallite relaxes. These features can be accurately modeled using curvature driven dynamics, as in classical models of spiral growth, with boundary conditions fixing the dislocation core and regions of the step lying along the outer facet edge.     

Reconstruction behaviour of fcc(110) transition metal surfaces and their vicinals

The fcc(110) surfaces are well known for their strong tendency to missing-row (MR) type reconstructions either in the clean state (Au, Pt) or driven by adsorbates (Ni, Cu, Pd, Ag). The present knowledge on the different reconstruction behaviour of flat (110) surfaces is reviewed. The survey focuses on recent scanning tunneling microscopy (STM) studies, which for the first time also elucidate the dynamics of the reconstruction process for the various systems. An overview of our recent STM and low energy electron diffraction studies on vicinal Au(110) and Ni(110) surfaces is given, aiming for a deeper understanding of the influence of steps on reconstruction behaviour of fcc(110) surfaces on the one hand, and on the stability of reconstructing vicinal surfaces on the other. Finally, we report on the reconstruction behaviour of Ir(110), which stabilizes in the clean state by formation of mesoscopic (331) facets and dereconstructs to the (1×1) phase upon oxygen adsorption at 700–900 K.     

甘氨酸在Cu(111)表面吸附的扫描隧道显微镜研究

用超高真空扫描隧道显微镜(UHV-STM)研究了室温下甘氨酸在Cu(111)表面的吸附行为.实验发现,在低覆盖度下甘氨酸分子在表面表现为二维气体.当覆盖度足够高时,甘氨酸分子最终会形成二维固相结构,为(4×8)超结构.针对这种结构提出了两种可能的结构模型,模型能够很好地解释STM图.当覆盖度介于气相和固相之间时,根据蒸镀条件和退火条件的不同,表面可能出现两种不同的中间相,一种为条纹结构,另一种为六角结构,对于中间相有待于进一步的研究 关键词： 表面吸附 甘氨酸 铜 扫描隧道显微术     

铜箔上生长的六角氮化硼薄膜的扫描隧道显微镜研究

利用扫描隧道显微镜研究了采用化学气相沉积法在铜箔表面生长出的高质量的六角氮化硼薄膜. 大范围的扫描隧道显微镜图像显示出该薄膜具有原子级平整的表面, 而扫描隧道谱则显示, 扫描隧道显微镜图像反映出的是该薄膜样品的隧穿势垒空间分布. 极低偏压的扫描隧道显微镜图像呈现了氮化硼薄膜表面的六角蜂窝周期性原子排列, 而高偏压的扫描隧道显微镜图像则呈现出无序和有序排列区域共存的电子调制图案. 该调制图案并非源于氮化硼薄膜和铜箔衬底的面内晶格失配, 而极有可能来源于两者界面处的氢、硼和/或氮原子在铜箔表面的吸附所导致的隧穿势垒的局域空间分布.     

Impurity states and interlayer tunneling in high temperature superconductors

We argue that the scanning tunneling microscope (STM) images of resonant states generated by doping Zn or Ni impurities into Cu-O planes of BSCCO are the result of quantum interference of the impurity signal coming from several distinct paths. The impurity image seen on the surface is greatly affected by interlayer tunneling matrix elements. We find that the optimal tunneling path between the STM tip and the metal (Cu, Zn, or Ni) d(x(2)-y(2)) orbitals in the Cu-O plane involves intermediate excited states. This tunneling path leads to the fourfold nonlocal filter of the impurity state in Cu-O plane that explains the experimental impurity spectra. Applications of the tunneling filter to the Cu vacancy defects and "direct" tunneling into Cu-O planes are also discussed.     

Structural properties of Cu clusters on Si(1 1 1):Cu2Si magic family

Basing on the results of the scanning tunneling microscopy (STM) observations and density functional theory (DFT) calculations, the structural model for the Cu magic clusters formed on Si(1 1 1)7 × 7 surface has been proposed. Using STM, composition of the Cu magic clusters has been evaluated from the quantitative analysis of the Cu and Si mass transport occurring during magic cluster converting into the Si(1 1 1)‘5.5 × 5.5’-Cu reconstruction upon annealing. Evaluation yields that Cu magic cluster accommodates 20 Cu atoms with 20 Si atoms being expelled from the corresponding 7 × 7 half unit cell (HUC). In order to fit these values, it has been suggested that the Cu magic clusters resemble fragments of the Cu₂Si-silicide monolayer incorporated into the rest-atom layer of the Si(1 1 1)7 × 7 HUCs. Using DFT calculations, stability of the nineteen models has been tested of which five models appeared to have formation energies lower than that of the original Si(1 1 1)7 × 7 surface. The three of five models having the lowest formation energies have been concluded to be the most plausible ones. They resemble well the evaluated composition and their counterparts are found in the experimental STM images.     

STM-induced molecular fluorescence from porphyrin molecules on metal substrates

Molecular fluorescence from ultrathin layers of H₂TBP porphyrin on Au(100) and ZnTBP porphyrin on Cu(100) has been generated by the electrical excitation using an ultrahigh-vacuum scanning tunneling microscope. The molecular origin of luminescence is justified by the good agreement of STM-induced emission spectra with conventional photoluminescence data excited from bulk molecules. The electronic states of top-layer molecules are effectively decoupled from the metal surface by controlling the thickness of molecular layers in a nanoscale regime. The porphyrin molecules are excited by the injection of hot electrons and then decay radioactively in a similar way to the photoluminescence process. These results provide a feasibility for the development of nanoscale molecular light source and spectroscopy. PACS  73.21.Ac; 68.37.Ef; 33.50.-j; 73.20.Mf     

Acetylene on Cu(111): imaging a molecular surface arrangement with a constantly rearranging tip

Acetylene on Cu(111) is investigated by scanning tunnelling microscopy (STM); a surface pattern previously derived from diffraction measurements can be validated, if the variation of the STM image transfer function through absorption of an acetylene molecule onto the tip apex is taken into account. Density functional theory simulations point to a balance between short-range repulsive interactions of acetylene/Cu(111) associated with surface stress and longer range attractive interactions as the origin of the ordering.     

Time and energy dependent dynamics of the STM tip — graphene system

Probability current and probability density of wave packets was calculated by solving the three dimensional time-dependent Schrödinger equation for a local potential model of the scanning tunneling microscope (STM) tip — graphene system. Geometrical and electronic structure effects of the three dimensional tunneling process are identified by studying three models of increasing complexity: a jellium half space, a narrow jellium sheet, and a local one electron pseudopotential. It was found that some of the key characteristics of the STM tip — graphene tunneling process are already present at the simple jellium models. In the STM tip — jellium half space system the direction of the momentum does not change during the tunneling event, hence this setup is characterised by introducing an effective distance. For the STM tip — narrow jellium sheet system the direction of the momentum is changed from vertical to horizontal during the tunneling event. The wave packet preferentially tunnels into the bound state of the jellium sheet. For the atomistic model of the graphene sheet an anisotropic spreading of the wave packet was found for hot electrons. This may open new opportunities to build carbon based nanoelectronic devices.     

Monolayered adatom aggregation induced by metallofullerene molecules on Cu(100)

The adsorption and self-assembly of Gd@C₈₂ molecules on Cu(100) surface have been investigated using scanning tunneling microscopy (STM). The metallofullerene molecules in the assemblies showed two characteristic apparent heights in the STM images. STM manipulation and spectroscopy was performed and revealed the formation of Cu adatom islands underneath the Gd@C₈₂ molecules. The monolayered Cu aggregates were resulted from the adatom–molecule complexation, which is supported by density functional theory (DFT) calculations that show charge transfer and electrostatic interactions between Gd@C₈₂ and adatoms. In addition, sub-molecularly resolved STM images demonstrated the structural and orientational ordering of Gd@C₈₂ assemblies upon thermal annealing. DFT calculations demonstrated that Gd atom located at the lower part of the carbon cage is a favored adsorption configuration for Gd@C₈₂ molecules adsorbed on Cu(100).     

Local spectroscopy of image-potential-derived states: from single molecules to monolayers of benzene on Cu(111)

Stark-shifted image-potential states were measured with an STM tip for benzene adsorbed on a Cu(111) surface. A single benzene molecule locally shifts the position of the first image state toward the Fermi level by 0.2 eV relative to its position on the clean surface. The energetic position of this molecule-modified state shifts to lower energy with increasing coverage of benzene on the surface. This is attributed to local surface potential changes that are correlated with the lowering of the crystal work function due to adsorption of benzene.