On the preparation and electronic properties of clean W(1 1 0) surfaces

We have studied the influence of oxygen pressure during the cyclic annealing used for the cleaning of W(1 1 0) surfaces. For this purpose the surface morphology and electronic properties are measured by means of scanning tunneling microscopy (STM) and spectroscopy (STS), respectively. It is found that the surfaces with impurity atom densities as low as 2 × 10⁻³ can be obtained by gradually reducing the oxygen pressure between subsequent annealing cycles down to about 2 × 10⁻⁸ mbar in the final cycle. Only on the clean surface a bias-dependent spatial modulation of the local density of states (LDOS) is observed at step edges and around impurity sites by STS. In addition, we find a pronounced peak in the occupied states. In combination with density functional theory calculations these features can be traced back to a dispersive p_z-d_xz-type surface resonance band and the lower band edge of a surface state, respectively.     

STM analysis of triosmium carbonyl cluster adsorption at HOPG

The study of metallic carbonyl clusters as precursors in tailoring the heterogeneous metal catalysts has been of great importance. The catalytic nature of the adsorbed clusters in thin film form depends on the chemical properties of the substrate used. The metal-support interaction will determine various properties such as the surface morphology, adsorption features and the structural orientations. We report a scanning tunneling microscopy (STM) study of an osmium carbonyl cluster (Os₃(CO)₁₁(NCCH₃)) adsorbed on highly oriented pyrolytic graphite (HOPG). STM measurements showed that the osmium carbonyl cluster interacts with HOPG in such a way that it adsorbs on the basal plane showing regular lattice structure, whereas the axial planes of the HOPG surface shows no ordered structure. The regular cluster lattice structure of the carbonyl cluster on the basal plane of the graphite has lattice parameters of a=1.4 nm and b=1.5 nm. We believe that the regular orientation of the cluster indicates a monolayer adsorption of the cluster on the graphite basal planes. Scanning tunneling spectroscopy (STS) measurements also indicated an insulating behavior for the cluster molecules on HOPG, with a significant energy gap value of ca. 300 mV. The cluster interaction at the active sites, i.e. axial planes of the graphite, was also observed by in situ STM measurements.     

A comparative STM study of Ru nanoparticles deposited on HOPG by mass-selected gas aggregation versus thermal evaporation

Scanning tunneling microscopy was used to compare the morphologies of Ru nanoparticles deposited onto highly-oriented graphite surfaces using two different physical vapour deposition methods; (1) pre-formed mass-selected Ru nanoparticles with diameters between 2 nm and 15 nm were soft-landed onto HOPG surfaces using a gas-aggregation source and (2) nanoparticles were formed by e-beam evaporation of Ru films onto HOPG. The particles generated by the gas-aggregation source are round in shape with evidence of facets resolved on the larger particles. Annealing these nanoparticles when they are supported on unsputtered HOPG resulted in the sintering of smaller nanoparticles, while larger particles remained immobile. Nanoparticles deposited onto sputtered HOPG surfaces were found to be stable against sintering when annealed. The size and shape of nanoparticles deposited by e-beam evaporation depend to a large extent on the state of the graphite support and the temperature. Ru deposition onto unsputtered HOPG is characterised by bimodal growth with large flat particles formed on the substrate terraces and smaller diameter particles aligned along the substrate steps. Evaporation onto sputtered HOPG results in the formation of 2 nm round particles with a narrow size distribution. Finally, thermal deposition onto both sputtered and unsputtered HOPG at 660 °C results in larger particles showing a flat Ru(0 0 0 1) top facet.     

Point defects along metallic atomic wires on vicinal Si surfaces: Si(5 5 7)–Au and Si(5 5 3)–Au

Point defects on the metallic atomic wires induced by Au adsorbates on vicinal Si surfaces were investigated using scanning tunneling microscopy and spectroscopy (STM and STS). High-resolution STM images revealed that there exist several different types of defects on the Si(5 5 7)–Au surface, which are categorized by their apparent bias-dependent images and compared to the previous report on Si(5 5 3)–Au [Phys. Rev. B (2007) 205325]. The chemical characteristics of these defects were investigated by monitoring them upon the variation of the Au coverage and the adsorption of water molecules. The chemical origins and the tentative atomic structures of the defects are suggested as Si adatoms (and dimers) in different registries, the Au deficiency on terraces, and water molecules adsorbed dissociatively on step edges, respectively. STS measurements disclosed the electronic property of the majority kinds of defects on both Si(5 5 7)–Au and Si(5 5 3)–Au surfaces. In particular, the dominating water-induced defects on both surfaces induce a substantial band gap of about 0.5 eV in clear contrast to Si adatom-type defects. The conduction channels along the metallic step-edge chains thus must be very susceptible to the contamination through the electronic termination by the water adsorption.     

Influence of Tb incorporation on the structural and the optical properties of ZnO nanoparticles

Structural and optical properties of the Tb doped ZnO nanoparticles are systematically studied as a function of the Tb mole-fraction. Our study suggests that the Tb incorporates mostly on the surface and affects the optical properties of the ZnO nanoparticles by influencing the attachment of certain adsorbed groups, which are found to be responsible for the appearance of a broad green luminescence (GL) band in the photoluminescence spectra recorded for these nanoparticles. It has been found that the accumulation of Tb on the surface of the nanoparticles not only enhances the band edge to green luminescence intensity ratio under the vacuum condition but also increases the band gap energy by introducing a hydrostatic compressive strain in individual nanoparticles, which provides a unique opportunity to study the pressure dependence of the optical properties of nanoparticles without applying any external pressure. The hydrostatic compressive strain is explained in terms of the increase of the surface strain energy as a result of the Tb accumulation on the surface of the nanoparticles. The average value of the surface energy density for the particles has been estimated as a function of Tb mole-fraction. The pressure coefficient of the band gap which is obtained from the variation of the band gap energy with the hydrostatic strain has been found to decrease significantly with the particle size for the ZnO nanoparticles.     

Cross-sectional scanning tunneling microscopy and spectroscopy of strain in buried heterostructure lasers

Cross-sectional scanning tunneling microscopy and spectroscopy have been used to probe the unreconstructed (1 1 0) surface of a commercially available buried heterostructure laser in ultra high vacuum. Complex re-growth above the non-linear blocking layers is shown to induce tensile strain in the device. Spectroscopic measurements show an increase in both the density of filled valence band states and empty conduction band states as a result of the strain, with a particularly large increase at −3.1 V. Current imaging tunneling spectroscopy measurements show an increase in the tunneling current in to and out of the strained regions at both gap voltage polarities, consistent with the spectroscopy. Moving towards tensile strain, InP is known to maintain much the same bandgap, with the split-off level and lower lying states being drawn up towards the valence band edge, consistent with the data.     

纳米NiO的制备及其谱学特性研究

以醋酸镍、氢氧化钠为原料,吐温80为分散剂,通过固相反应制备了纳米级NiO。 用X射线衍射仪、透射电子显微镜、傅里叶红外光谱、紫外-可见分光光度等方法对材料的粒径、晶格畸变率、形貌以及红外、紫外-可见光的吸收性能进行了表征。结果表明：制得的纳米NiO产物为球形、属立方晶系,粒径大小在9～30 nm左右;晶格畸变率随粒径的增大而减小;纳米NiO红外吸收峰出现在437 cm-1处,与普通粒径的NiO光谱纯(484 cm-1)相比,其吸收峰红移了47 cm-1,体现了纳米NiO的表面效应;不同粒径大小的NiO对紫外-可见光的吸收特性不同。普通粒径的NiO光谱纯在紫外-可见光区域没有吸收,颗粒尺寸越小吸收波长越短,10 nm NiO的紫外-可见光吸收峰位于309 nm处,直接跃迁的光学能带隙约为4.2 eV,比体相材料(3.65 eV)增加0.55 eV,表现出明显的量子尺寸效应。对纳米NiO的谱学特性研究表明该材料在光电领域具有潜在的应用价值。     

The calculation of transition probabilities for atomic oxygen

In this contribution we present scanning tunnelling microscopy (STM) and spectroscopy (STS) investigations on isolated cobalt clusters in contact with Ge(001). Mass-filtered nanoparticles with diameters ranging from 3 to 11 nm are generated using an arc cluster ion source (ACIS) and deposited under soft landing conditions (E_kin/atom < 0.5 eV). Since the tip radius is of the same order as the nanoparticle diameters the recorded STM images are significantly affected by tip folding. By means of the “blind reconstruction method" it is possible to approximate the tip shape. After a respective deconvolution of the image structural features of the particle facets become observable. According to the equilibrium shape of the clusters being a truncated octahedron in the size range under investigation, hexagonal and rectangular features appear in the images. STS is sensitive to occupied and unoccupied states near the Fermi level and reveals the existence of distinct states in the tunnelling conductivity of the substrate as well as on the clusters. The richly structured density of states of the germanium surface serves here as tip condition test. First measurements of the tunnelling conductivity of the Co_N/Ge(001) are presented and discussed.     

光照法在玻璃基底上原位生长金纳米结构及其光谱性质

 以硅烷化后吸附粒径小于10 nm的金种子的玻璃片为基底,聚乙烯吡咯烷酮为还原剂,在荧光灯照射条件下还原氯金酸,制备出表面具有金纳米粒子聚集结构的基底。用原子力显微镜、扫描电镜、X射线衍射、吸收和荧光光谱研究了基底的性质。结果表明：随着光照时间增加至20 h,金种子长大为平均粒径140 nm的不规则状多晶粒子,且出现双层粒子堆叠。基底的吸收光谱上出现了由金粒子的表面等离子体激元偶极子耦合引发的强烈吸收峰,随着粒子粒径增大,耦合峰在600~800 nm波段内连续红移升高,表明耦合程度不断增强。在223 nm紫外光的激发下,基底的荧光光谱上在405 nm处出现发射峰,是由金粒子表面激发电子和空穴的复合辐射造成的,发光强度随着基底上粒子平均尺度增加而减弱。     

钯金属吸附对半导体性碳纳米管电输运的影响

利用物理蒸发技术,在半导体性的碳纳米管上沉积钯金属,利用导电原子力显微镜检测钯吸附对碳纳米管电输运的影响.结果表明:沉积的钯在碳纳米管上形成纳米颗粒,随着钯颗粒密度的增加,半导体性碳纳米管逐渐向金属性转变.利用第一性原理计算了吸附有钯原子的半导体性单壁碳纳米管的能带结构.研究发现,钯的覆盖率越高,其禁带宽度越窄,直至为零,定性说明了实验结果的合理性. 关键词： 单壁碳纳米管 钯纳米颗粒 导电原子力显微镜 第一性原理计算     

Size-dependent single electron tunneling effect in Au nanoparticles

We investigated single electron tunneling (SET) behavior of dodecanethiol-coated Au nanoparticles of two different sizes (average sizes are 5 nm and 2 nm) using nanogap electrodes, which have a well-defined gap size, at various temperatures. The Coulomb staircases and the Coulomb gap near-zero bias voltage caused by the suppression of the tunneling electrons due to the Coulomb blockade effect were observed in the current-voltage (I-V) curves of both sizes of nanoparticles at a low temperature (10 K). At room temperature, the Coulomb gap was observed only in the I-V curve of the smaller nanoparticles. This result indicates that the charging energy of the smaller nanoparticles is enough to overcome the thermal energy at room temperature. This suggests that it is possible to operate the SET devices at room temperature using the smaller nanoparticles as a Coulomb island.     

Electron and lattice structure of ultra thin Ag films on Si(1 1 1) and Si(0 0 1)

We studied the low temperature (T ? 130 K) growth of Ag on Si(0 0 1) and Si(1 1 1) flat surfaces prepared by Si homo epitaxy with the aim to achieve thin metallic films. The band structure and morphology of the Ag overlayers have been investigated by means of XPS, UPS, LEED, STM and STS. Surprisingly a (√3 × √3)R30° LEED structure for Ag films has been observed after deposition of 2-6 ML Ag onto a Si(1 1 1)(√3 × √3)R30°Ag surface at low temperatures. XPS investigations showed that these films are solid, and UPS measurements indicate that they are metallic. However, after closer STM studies we found that these films consists of sharp Ag islands and (√3 × √3)R30°Ag flat terraces in between. On Si(0 0 1) the low-temperature deposition yields an epitaxial growth of Ag on clean Si(0 0 1)-2 × 1 with a twinned Ag(1 1 1) structure at coverage’s as low as 10 ML. Furthermore the conductivity of few monolayer Ag films on Si(1 0 0) surfaces has been studied as a function of temperature (40-300 K).     

Transformation of the short-range order upon melting of Cu<Emphasis Type="Italic">Hal</Emphasis> nanocrystals in glasses

The reduced density of states at the edge of interband transitions in CuCl and CuBr nanocrystals is described by a step at T → 0. As the temperature increases, the step is smeared toward the band gap and the long-wavelength absorption tail agrees with the Urbach rule. A change in the phase state of CuCl or CuBr nanoparticles (the crystal-melt transition) is accompanied by an insignificant change in the band gap, and the long-wavelength absorption tail for the interband transitions considerably extends deeper into the band gap as compared to that for crystals at the same temperature. The change observed in the band gap upon melting is explained by the transformation of short-range order in CuCl and CuBr melts. An increase in thermal smearing of the long-wavelength absorption tail for nanomelts is associated with the severalfold increase in the amplitude of thermal fluctuations of the band gap, possibly, due to the disappearance of the long-range order in the melts. A lower melting temperature of large (>30 nm) CuCl and CuBr particles as compared to the melting temperature of bulk samples indicates the presence of the second component NaCl or NaBr. Consequently, the CuCl-NaCl and CuBr-NaBr eutectic nanosystems undergo melting and crystallization. A small shift in the band gap observed in this case upon melting confirms the conclusion drawn by Zalkin that eutectic melts have a microheterogeneous structure.     

Transition from zero-dimensional to one-dimensional behavior in InAs and CdSe nanorods

Tunneling and optical spectroscopy performed on InAs nanorods 7–25 nm long, reveal a clear dependence of the band gap on length. This (zero-dimension like) behavior is different from that of CdSe rods, where the band gap is nearly independent of length, a signature of quasi-one-dimensionality. The transition between these two regimes is governed by the ratio between the Bohr radius and the nanorods length. The gaps measured by tunneling spectroscopy are larger than the optical gaps by a factor that depends on the tunneling configuration. This is attributed to a combination of the Coulomb interaction and the voltage division between the two tunnel junctions in the STM experiment. However, the tunneling gaps were found to reduce in dense aggregates of rods.     

Measuring the Au(1 1 1) surface state at the solid–liquid interface

We present the first direct observation of an occupied noble metal surface state at the metal/liquid interface. The Au(1 1 1) Shockley-like surface state was measured by scanning tunneling spectroscopy (STS) at the Au(1 1 1)/n-tetradecane interface. These results show that the surface state of gold survives in a liquid environment, and can be probed by STS. More generally it indicates that STS can be used to study electronic properties of surfaces at the solid/liquid interface, and that spectra can be directly compared to measurements and calculations of a surface’s electronic structure in ultra-high vacuum.     

Size effects on the magnetic and optical properties of CuO nanoparticles

Optical and magnetic studies on CuO nanoparticles prepared by a chemical route are reported and the effect of size variation on these properties is discussed. SEM images show that the nanoparticles are interlinked into microspheres with the cages containing visible nanoscale holes. Diffuse reflectance spectroscopy indicates a consistent red shift in the fundamental band gap (indirect band gap) from 1.23 to 1 eV as the size decreases from 29 to 11 nm. This observed red shift is attributed to the presence of defect states within the band gap. A clear blue shift is observed in the direct band gap of these nanoparticles presumably due to the quantum confinement effects. Air-annealed samples show a paramagnetic response whereas particles annealed in a reducing atmosphere show additionally a weak ferromagnetic component at room temperature. For both types of particles, the paramagnetic and ferromagnetic moments, respectively, increase with decreasing size. The role of oxygen vacancies is understood to relate to the generation of free carriers mediating ferromagnetism between Cu spins. AC susceptibility measurements show both the antiferromagnetic transitions of CuO including the one at 231 K which is associated with the onset of the spiral antiferromagnetic phase transition.     

Hopping motion of chlorine atoms on Si(1 0 0)-(2 × 1) surfaces induced by carrier injection from scanning tunneling microscope tips

Injection of tunneling electrons and holes from the probe tips of a scanning tunneling microscope was found to enhance the hopping motion of Cl atoms between neighboring dangling-bond sites of Si dimers on Si(1 0 0)-(2 × 1) surfaces, featured by the rate of hopping linearly dependent on the injection current. The hopping rate formed peaks at sample biases of V_S∼+1.25 and −0.85 V, which agree with the peaks in the local density of states spectrum measured by scanning tunneling spectroscopy. The Cl hopping was enhanced at Cl-adsorbed sites even remote from the injection point. The Cl hopping by hole injection was more efficiently enhanced by sweeping the tip along the Si dimer row than by tip-sweeping along the perpendicular direction. Such anisotropy, on the other hand, was insignificant in the electron injection case. All of these findings can be interpreted by the model that the holes injected primarily into a surface band originated from the dangling bonds of Si dimers propagate quite anisotropically along the surface, and become localized at Cl sites somehow to destabilize the Si-Cl bonds causing hopping of the Cl atoms. The electrons injected into a bulk band propagate in an isotropic manner and then get resonantly trapped at Si-Cl antibonding orbitals, resulting in bond destabilization and hopping of the Cl atoms.     

Exact calculation of the current in a one-dimension model of a scanning tunneling microscope

Electric current as a function of applied voltage have been calculated between two one-dimensional semi-infinite atomic chains. A tight-binding two band model and the modified tight-binding equations technique have been used. The current derivatives are compared with the surface local density of states. The comparison shows that the current derivatives reproduce the local density of states with a significant distortion. It occurs due to wave vector dependence of the transmission coefficient of electronic waves falling on the interface between the chains.     

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.     

Optical properties of silicon nanoparticles synthesized via electrical spark discharge in water

In this paper, we report a simple and low-cost technique for fabrication of silicon nanoparticles via electrical spark discharge between two plane silicon electrodes immersed in deionized water (DI). The pulsed spark discharge with the peak current of 60 A and a duration of a single discharge pulse of 60 μs was used in our experiment. The structure, morphology, and average size of the resulting nanoparticles were characterized by means of X-Ray Diffraction (XRD), Raman spectroscopy and transmission electron microscopy (TEM). TEM images illustrated nearly spherical and isolated Si nanoparticles with diameters in the 3–8 nm range. The Raman peaks of the samples were shifted to the lower wave numbers in comparison to this of bulk crystalline silicon indicating the existence of tiny particles. The optical absorption spectrum of the nanoparticles was measured in the violet–visible (UV–Vis) spectral region. By measuring of the band gap we could estimate the average size of the prepared particles. The silicon nanoparticles synthesized exhibited a photoluminescence (PL) band in the violet-blue region with a double peak at around 417 and 439 nm. It can be attributed to oxide-related defects on the surface of silicon nanoparticles, which can act as the radiative centers for the electron-hole pair recombination.