隧道电子激发的辛硫醇条纹相自组装膜上卟啉单分子荧光

利用扫描隧道显微镜诱导发光技术,对单个卟啉分子的电致荧光现象进行了研究. 为了避免金属衬底对单个卟啉分子的荧光淬灭,利用条纹状辛硫醇自组装膜作为脱耦合层,实现了单个中性卟啉分子的电致荧光,并且发现分子荧光的产生呈现双极性特征. 另外,分子瓣上的荧光强度要强于分子中心的荧光强度.     

Novel near-infrared photoluminescence from platinum(II)-porphyrin (PtOEP) aggregates

We investigated photoluminescence of the phosphorescent molecule platinum(II)-2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrin. In neat films prepared by organic molecular beam deposition or precipitation from solution, we observe a near infrared emission feature around 1.65 eV, caused by aggregation effects.     

STM/STS observation of ferrocene derivative adduct to C60 on HOPG

The C₆₀ONCFn cycloadduct (Fn=ferrocene) was prepared in the reaction between C₆₀ and ferrocene oxime, the ferrocene derivative was bound to C₆₀ at the 6–6 bond by a heterocyclic oxygen–nitrogen–carbon ring; the compound was stable in air. The compound dissolved in dichloroethane was deposited on HOPG and observed by UHV STM/STS methods. The molecules of C₆₀ONCFn formed several-microns-long straight chains with clearly visible adducted groups pointing to one side of the chain. The STM/STS observations are discussed within the terms of semiempirical quantum chemical molecular modeling.     

STM images from diamond surfaces: steps towards comparisons of experiment and theory

Stable clean and hydrogenated diamond (100) and (111) surface reconstructions found by density functional molecular dynamics (DFMD) are characterized in their surface electronic properties. For sufficiently large surface slab supercells we have calculated the spatially resolved charge densities of the highest occupied surface states at constant height, which are compared with recently obtained images from scanning tunneling microscopy. The calculated charge-density distributions represent signatures of the considered surfaces which might be used to understand and to classify as-grown diamond surfaces.     

Discrete dihedral-angle modulation in porphyrin wheels adsorbed on Cu(1 0 0) observed by scanning tunneling microscopy

Conformations of two dodecameric porphyrin wheels adsorbed on a Cu(1 0 0) were probed by using scanning tunneling microscopy (STM). Whereas a wheel consisting of six meso-meso linked diporphyrins was detected as uniform ring structure, several different images with three discrete molecular heights were detected for a wheel consisting of six meso-meso, β-β,β-β triply-linked planar diporphyrins. These results indicate that the former has a conformation similar to that in a free space, while the latter has various conformations with respect to orientation of planar diporphyrin units toward the metal surface. Several discrete STM images of the latter have been interpreted in terms of possible eight conformations, which vary as to relative orientation of neighboring diporphyrin units.     

Transport at surface nanostructures measured by four-tip STM

For in situ measurements of local electrical conductivity of well-defined crystal surfaces in ultrahigh vacuum, we have developed two kinds of microscopic four-point probe methods. One is a ‘four-tip STM prober’, in which independently driven four tips of scanning tunneling microscope (STM) are used for four-point probe conductivity measurements. The probe spacing can be changed from 500 nm to 1 mm. The other one is monolithic micro-four-point probes, fabricated on silicon chips, whose probe spacing is fixed around several μm. These probes were installed in scanning-electron-microscopy/electron-diffraction chambers, in which the structures of sample surfaces and probe positions were in situ observed. The probes can be positioned precisely on aimed areas on the sample with aid of piezo-actuators. With these machines, the surface sensitivity in conductivity measurements has been greatly enhanced compared with macroscopic four-point probe method. Then the conduction through the topmost atomic layers (surface-state conductivity) and influence of atomic steps upon conductivity could be directly measured. The STM prober is mainly described here.     

STM/STS characterization of platinum silicide nanostructures grown on a Pt(1 1 1) surface

Formation of the platinum silicides nanostructures and their electronic properties have been studied using scanning tunneling microscopy and scanning tunneling spectroscopy. The investigated structures have been grown by solid state epitaxy upon deposition of the Si atoms (coverage about 0.2 ML) and sequential annealing at temperature range 600-1170 K. The formation of the Pt₂Si and PtSi islands was investigated until the Si atoms embedded into the Pt substrate at the 1170 K. The images of the silicides structures and Pt substrates with atomic resolution have been recorded. The evolution of the spectroscopic curves both for substrates and nanostructures, corresponding to the structural and sizes changes, have been shown.     

在扫描隧穿显微镜实验中开展研究性学习的教学与实践

介绍了在扫描隧穿显微镜实验中开展研究性学习的教学与实践．举例介绍了具体做法及取得的教学效果。     

Current-distance-voltage characteristics of electron tunneling through an electrochemical STM junction

We have studied the electron tunneling process through an electrochemical scanning tunneling microscopic (STM) junction formed by a gold tip and a gold electrode immersed in an inert NaClO₄ solution. Current-distance-voltage characteristics of the tunneling process are examined by simultaneous measurement of tunneling current, voltage, and distance. The results indicate that the tunneling voltage across the junction changes with tunneling distance; however, tunneling conductance is an inverse exponential function of distance over the entire investigated range of tunneling current, voltage, and distance. The results provide clear evidence for the validity of a one-dimensional tunneling model for the aqueous tunneling process. Implications of the observation are mentioned with regard to the distance-dependent STM imaging and the origin of a low tunneling barrier height.     

The effect of intermolecular interactions on photoluminescence of a porphyrin side-chain polymer

Photoluminescence properties and exciton decay dynamics in a porphyrin side-chain polymer, poly[porphyrin acrylate- acrylonitrile (abbreviated p[(por)A-AN]), have been investigated by femtosecond time-resolved photoluminescence spectroscopy. All the luminescences of p[(por)A-AN] films are due to the emissive decay of the photoexcited singlet excitons in the porphyrins. The luminescence efficiencies and lifetimes are increased for samples from pure films to dilute blend films. However, they are increased as the intrachain concentration of the porphyrin sidechain groups is decreased. The intrachain rotation motions of porphyrin sidechain groups result in the initial ultrafast luminescence decays, which are much faster than those due to the interchain interactions. All the samples show no significant red-shift and broadening of the transient luminescence spectra. The interchain and intrachain nonradiative exciton relaxation processes may play an important role in the luminescence dynamics in the p[(por)A-AN] films. The possible origin of different intrachain and interchain dynamic behaviours in p[(por)A-AN] films is discussed.     

Insight into STM image contrast of n-tetradecane and n-hexadecane molecules on highly oriented pyrolytic graphite

Two-dimensional ordered patterns of n-tetradecane (n-C₁₄H₃₀) and n-hexadecane (n-C₁₆H₃₄) molecules at liquid/graphite interface have been directly imaged using scanning tunneling microscope (STM) under ambient conditions. STM images reveal that the two different kinds of molecules self-organize into ordered lamellar structures in which alkane chains of the molecules extend along one of three equivalent lattice axes of highly oriented pyrolytic graphite (HOPG) basal plane. For n-C₁₄H₃₀ molecules, the molecular axes are observed to tilt by 60° with respect to inter-lamellar trough lines and the carbon backbones of the alkane chains are perpendicular to the HOPG basal plane in an all-trans conformation. However, for n-C₁₆H₃₄ molecules, the molecular axes are perpendicular to lamellar borders (90°) and the planes of the all-trans carbon skeletons are parallel to the graphite basal plane. The results clearly indicate that outmost hydrogen atoms of the alkane chains dominate atom-scaled features of the STM images. That is, in the case of long-chain alkane molecules, topographic effects dominantly determine STM image contrast of the methylene regions of the alkane chains that are adsorbed on HOPG.     

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.     

Ti掺杂ZnTe体材料的优化光致发光光谱

针对光致发光光谱法研究ZnTe:Ti的困难,对包括激发能量、激发功率与激发光斑大小、水汽干扰和测量温度等实验条件进行了细致的优化.发现: (1)低于ZnTe禁带宽度的激发能量能给出相对强的光致发光光谱; (2) 水汽干扰既影响谱线的相对强度又增大谱线能量的测定误差; (3)相对强的激光聚焦有利于获得较好的光致发光光谱.可靠地观察到位于3903.5和3905.9cm^-1能量位置处的零声子光致发光谱线. 根据两谱线的能量间距和相对强度随 温度的变化关系,并借助于晶体场理论对四面体晶体场中 关键词： Ti掺杂 ZnTe 光致发光     

STM imaging of electrically floating islands

Appearances and disappearances of Gd islands grown on top of a W(1 1 0) substrate were observed in time scales of hours after exposing the surface to a few Langmuirs of hydrogen. The phenomenon is presented and explained in terms of (temporary) creation of electrically floating islands, due to electrical decoupling of the island and substrate by the hydrogen that diffuses into the island/substrate interface. The disappearance of such an island is explained by forming a double barrier junction consisting of two tunneling barriers in series, causing, by charging, the potential of the island to become equal to that of the tip. The island then becomes “invisible” and the tip follows the corrugation of the surface under the substrate. The reappearance follows hydrogen mobility that retains the electrical conductivity of the island-substrate interface.     

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.     

Development of a miniature STM holder for study of electronic conductance of metal nanowires in UHV-TEM

A new miniature scanning tunneling microscope (STM) holder was developed in order to simultaneously investigate electronic conductance and structure of nanowires in an ultra high-vacuum electron microscope (UHV-TEM). A thin gold wire held between the STM tip and substrate stage of the specimen holder was stretched to form a suspended gold nanowire. The new TEM-STM system allowed us to measure electronic conductance at intervals of 20 ms, and to record high-resolution TEM images on videotape at 30 fps. Suspended gold nanowires formed from [1 1 0] oriented electrodes were well-elongated. In contrast, [1 0 0] and [1 1 1] electrodes produced nanowires with short necks. Electronic conductance was found to change as nanowire structure changed, with conductance quantization in units of 2e²/h, where e is the electron charge and h is Planck’s constant, only being exhibited for well-elongated nanowires.     

Visible photoluminescence and its mechanisms from a-SiOx : H films with different stoichiometry

The photoluminescence (PL) properties of H-rich amorphous silicon oxide thin films prepared by dual-plasma chemical vapor deposition have been studied. The three commonly reported PL bands centered around 1.7, 2.1 and 2.9 eV have been detected from the same type of a-SiO_x : H material, only by varying the oxygen content (x≈1.35, 1.65, 2). In order to characterize the PL bands, the samples in as-prepared and annealed states up to 900°C have been analyzed by XPS, FT-IR, gas effusion, ESR and ellipsometry. Temperature quenching experiments are crucial to distinguish the 1.7 eV band, fully consistent with a bandtail-to-bandtail transition, from radiative defect luminescence mechanisms attributed either to defects related to Si–OH groups (2.9 eV) or to oxygen vacancy defects (2.1 eV).     

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.     

Effect of multiple tips on light emission induced by STM from gold nanostructures

Light emission induced by scanning tunneling microscope on gold islands grown on MoS₂ surfaces has been investigated. Surface geometry and roughness show that different apexes of the same tip can modify the energy of photons emitted in the tunneling junction. Comparisons of topography and photon map are used to locate islands imaged twice and to represent approximately the tip shape used. Light emission spectroscopy on the same island with two apexes of the multiple tip reveals variations of emission properties according to the apex used, showing the importance of tip geometry in the emission process induced by tip induced plasmon modes.     

Visible photoluminescence from Ge quantum dots

Spectroscopic analyses on stacked Ge quantum dots (QDs) on Si (1 0 0) substrates are presented. Strong and visible photoluminescence around 620 nm from stacked Ge QDs is observed. The luminescence is intense and clearly visible to the naked eye at both room temperature and low temperature. We have investigated the temperature dependence of the luminescence, as well as the composition of Ge dots via transmission electron microscopy and the Raman spectroscopy. Possible causes of the visible luminescence are also speculated in this report.