Size dependence of the plasmon peak position in electron stimulated photon emission spectra of Ag clusters supported on amorphous carbon film

The plasmon energy of Ag clusters produced on an amorphous carbon substrate by gas-aggregation technique has been measured. It has been determined from the plasmon peak position in the light emission spectrum obtained during bombardment of Ag clusters by low-energy electrons. For Ag cluster films with maximum of the cluster size distribution at 30, 8 and 2.5 nm, the plasmon energy comprised 3.76, 4.13 and 4.28 eV (the wavelength was 330, 300 and 290 nm), respectively. The blue shift of the plasmon energy is probably related to the effect of confounding of collective and single-particle excitations.     

Ag-Co clusters deposition on Ag(100): an atomic scale study

The slowing down of Co₁₀Ag₁₉₁ and Co₂₈₅Ag₃₀₁ nanoclusters on a Ag (100) surface is studied at the atomic scale by means of classical Molecular Dynamics simulations. The slowing down energy, 0.25 to 1.5 eV/atom, is characteristic of low energy cluster beam deposition and aerosol focused beam techniques. The two clusters differentiate by their size, stoechiometry and structure. While Co forms one or several groups just beneath the cluster surface in Co₁₀Ag₁₉₁, Co₂₈₅Ag₃₀₁ displays a core-shell structure where Ag forms one complete monolayer around the Co core. As a consequence of the impact, the smallest cluster undergoes deep reorganization and becomes fully epitaxial with the substrate. The larger one only undergoes partial accommodation and partially retains the memory of its initial morphology. For both, after impact, the Co forms one group covered by Ag. The substrate damage is significant and depends on the slowing down energy. It results in a Ag step surrounding the cluster which may be more than one atomic layers high and isolated add-atoms or small monolayer islands apart from the step. The latter originate from the cluster and the former from the substrate. Further details in the consequences of the impact are given, concerning the cluster penetration, its deformation and lattice distortions, with emphasis on the cluster size and stoechiometry.Received: 11 June 2004, Published online: 31 August 2004PACS: 35.40.-c - 61.46. + w Nanoscale materials: clusters, nanoparticles, nanotubes, and nanocrystals - 07.05.Tp Computer modeling and simulation     

三萘基膦在Ag(110)面上沉积的紫外光电子能谱研究

利用紫外光电子能谱（UPS）对新型有机半导体三萘基膦（TNP）在金属Ag(110)表面上沉积生长及其电子性质等进行了研究.三萘基膦的价带谱峰分别位于费米能级以下38，63，93和110 eV处，其中，价带顶 (HOS)位于费米能级以下约25 eV处.清洁Ag(110)表面的功函数为43 eV.随着三萘基膦在Ag(110)表面的沉积，功函数减小到38 eV，并达到饱和.根据UPS的测量结果，给出了三萘基膦/Ag(110)界面的能带结构，且三萘基膦与衬底Ag之间呈弱相互作用行为. 关键词： 紫外光电子谱 价电子结构 功函数     

Comparison of electronic structures of mass-selected Ag clusters and thermally grown Ag islands on sputter-damaged graphite surfaces

Ag cluster anions consisting of 3–16 atoms were deposited on sputter-damaged HOPG surfaces using a soft-landing technique (mean deposition energy less than 0.2 eV/atom) at room temperature. For investigations of the structures of deposited clusters, X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM) were used. In addition, the chemical properties of deposited clusters were studied using atomic oxygen and CO. Comparison of the properties of deposited Ag clusters and Ag islands with similar sizes grown by evaporating Ag atoms on the same substrate shows different results, implying that two different preparation methods give either different shapes of Ag clusters and islands, or dissimilar metal–support interactions. PACS 73.22.-f     

Electronic structure of Ag adsorbed on Si(111); experiment and theory

Experimental results (low energy electron loss spectroscopy) and band structure calculations relating to the early stages of Ag growth on a Si(111) surface are presented. Crystallography and thermal desorption kinetics studies of this interface, previously published, gave rise to the following conclusions. At room temperature and below 200°C, two-dimensional (2D) (111) epitaxial layers develop on top of a first ordered layer (√3 × √3), while at higher temperatures three-dimensional (3D) clusters develop over this first layer. Low energy electron loss experiments were performed at various surface coverages θ. They display different evolutions according to the growth modes. For the 2D epitaxial growth, one observes the disappearance of the peaks characteristic of a Si surface and the onset of Ag induced peaks located at 7.1 and 4.6 eV at completion of the √3 layer. These peaks narrow and shift to the bulk Ag excitation energies at 7.5 and 4 eV when a second Ag layer is deposited. In order to explain these results, we present a theoretical calculation of the electronic density of states of the interface using a tight binding approximation. This calculation accounts for the development of the Ag d band from the √3 coverage range to the (111) epitaxial Ag planes. The evolution of the spectra when θ is increased is discussed in view of these results.     

苯并咪唑苝与金属Ag的界面电子结构研究

利用同步辐射光电子能谱实验技术考察了苯并咪唑苝(BZP)和Ag的界面形成过程与电子结构.单层覆盖度以下时，BZP分子与Ag有弱相互作用，在有机分子禁带中出现明显界面反应态，结合能位于0.9eV.单层铺满后，BZP分子呈现三维岛式生长，且与Ag的相互作用逐渐减弱，同时最高占据分子轨道由于终态效应逐渐向高结合能方向位移至体相结合能位置(2.3eV). Ag衬底上BZP分子的生长导致样品表面功函数减小，表明形成了表面偶极势(Δ=0.3eV)，且电子从有机分子向金属Ag偏移.最后，考察了BZP/Ag 关键词： 有机-金属界面 电子结构 光电子能谱 同步辐射     

Structures and stability of Ag clusters on Ag(1 1 1) and Ni(1 1 1) surfaces

The structures of the lowest total energy for small Ag_N clusters with N = 2-20, which are grown on Ag(1 1 1) and Ni(1 1 1) surfaces, have been determined using a combination of the embedded-atom method and the basin-hopping algorithm. It is found that the particularly stable Ag clusters with N<18 have similar geometries on both surfaces when comparing clusters of the same size. On the other hand, the geometries of the less stable Ag clusters in the same size range differ for the two surfaces. From N?18, the sizes of the particularly stable structures are different for the two different substrates. Due to the large size mismatch of the two types of atoms it is energetically unfavorable for Ag to form a pseudomorphic monolayer structures on Ni(1 1 1) and there is considerable strain produced at the interface. The effect of this strain and the increased adatom-substrate interactions lead to irregular and elongated structures of the adsorbed Ag clusters.     

Deposition of Ni<Subscript> 13</Subscript> and Cu<Subscript> 13</Subscript> clusters on Ni(111) and Cu(111) surfaces

The soft deposition of Ni₁₃ and Cu₁₃ clusters on Ni(111) and Cu(111) surfaces is studied by means of constant-energy molecular-dynamics simulations. The atomic interactions are described by the Embedded Atom Method. It is shown that the shape of the nickel clusters deposited on Cu(111) surfaces remains rather intact, while the copper clusters impacting on Ni(111) surfaces collapse forming double and triple layered products. Furthermore, it is found that for an impact energy of 0.5 eV/atom the structures of all investigated clusters show the lowest similarity to the original structures, except for the case of nickel clusters deposited on a Cu(111) surface. Finally, it is demonstrated that when cluster and substrate are of different materials, it is possible to control whether the deposition results in largely intact clusters on the substrate or in a spreading of the clusters. This separation into hard and soft clusters can be related to the relative cohesive energy of the crystalline materials.     

低能Pt原子团簇沉积过程的分子动力学模拟

利用分子动力学模拟系统研究了低能Pt38,Pt141和Pt266原子团簇与Pt(001)表面的相互作用过程,详细分析了初始原子平均动能为0.1,1.0和10eV的原子团簇的沉积演化过程及其对基体表面形貌的影响.研究表明,初始原子平均动能是描述低能原子团簇的重要参量.当团簇的平均原子动能较低时,团簇对基体表层原子点阵损伤较小,基本属于沉积团簇;随着入射团簇的原子平均动能的增加,团簇对表层原子点阵结构的破坏能力增强,当团簇的原子平均动能增加到10eV时,团簇已经显现出注入特征.低能原子团簇对基体表面形貌的影响 关键词： 分子动力学模拟 低能原子团簇 载能沉积     

Light emission from Ag cluster films excited by conduction current

The light emission spectra obtained for a silver cluster film, excited by the passage of electrical current through it, were measured by the charge‐coupled device (CCD) combined with a monochromator in the spectral range 200 ≑ 1050 nm (6.2 ≑ 1.18 eV). This film is a two‐dimensional ensemble of Ag clusters linked by tunneling on a dielectric substrate. It was shown that the light emission spectra had a number of features, and the shape of spectrum depends on a voltage applied to the film. With increasing the voltage the spectrum starts to extend to high energies. The light emission in the visible spectral region was observed already at 1 V applied to the film, i.e., the photon energy can exceed the excitation energy. It means that this phenomenon is not trivial. In order to explain these results, an assumption about the electron gas heating in metal clusters may be used.     

低能Cu13团簇沉积薄膜的分子动力学模拟研究

利用分子动力学模拟方法对Cu₁₃团簇在Fe（001）表面上沉积薄膜进行了研究,分析了不同沉积条件对薄膜生长模式的影响,对比分析了不同沉积条件下表面粗糙度、缺陷分布和外延度等薄膜性质的差异。Cu₁₃团簇的初始沉积能量范围为0.1~10.0 eV/atom,沉积率为1.0 clusters/ps,衬底温度分别为300,700和1 000 K。模拟结果表明:团簇初始沉积能量主要影响薄膜生长模式,当初始沉积能量为7.5 eV/atom的Cu₁₃团簇沉积到温度为300 K的Fe（001）表面时,可形成表面光滑、内部缺陷少和较好外延度的高质量Cu薄膜。     

Assembly and interaction of Au/C core-shell nanoparticles

The formation of Au/C core-shell structures from C-supported Au nanoparticles, and their thermally and electron beam induced interactions are studied by real-time TEM. At temperatures below 400 °C no C-shell is assembled, and closely spaced Au nanoparticles interact by coalescence. At high temperatures (400-800 °C) the Au particles are transformed into Au/C core-shell structures via encapsulation into curved, fullerene-like C shells. The shells initially passivate the Au cores and inhibit their coalescence. But under electron irradiation, the Au cores can break free from their shells, and hence can coalesce. Surprisingly, at this stage the assembled C-sheets may actually enhance the coalescence process by driving the directed motion of Au/C particles and causing the efficient contraction of widely spaced particle ensembles.     

Magic polyicosahedral core-shell clusters

A new family of magic cluster structures is found by genetic global optimization, whose results are confirmed by density functional calculations. These clusters are Ag-Ni and Ag-Cu nanoparticles with an inner Ni or Cu core and an Ag external shell, as experimentally observed for Ag-Ni, and present a polyicosahedral character. The interplay of the core-shell chemical ordering with the polyicosahedral structural arrangement gives high-symmetry clusters of remarkable structural, thermodynamic, and electronic stability, which can have high melting points (they melt higher than pure clusters of the same size), large energy gaps, and (in the case of Ag-Ni) nonzero magnetic moments.     

Shell-driven magnetic stability in core-shell nanoparticles

The magnetic properties of ferromagnetic-antiferromagnetic Co-CoO core-shell nanoparticles are investigated as a function of the in-plane coverage density from 3.5% to 15%. The superparamagnetic blocking temperature, the coercivity, and the bias field radically increase with increasing coverage. This behavior cannot be attributed to the overall interactions between cores. Rather, it can be semiquantitatively understood by assuming that the shells of isolated core-shell nanoparticles have strongly degraded magnetic properties, which are rapidly recovered as nanoparticles come into contact.     

Excited-state relaxation of Ag8 clusters embedded in helium droplets

Neutral silver clusters Ag(N) are grown in ultracold helium nanodroplets. By exploiting a strong absorption resonance recently found for Ag8, first photoelectron spectra of this neutral species are recorded. Variation of the laser photon energy reveals that direct vertical two-photon ionization is hindered by rapid relaxation into the lower edge of a long-living excited state manifold. The analysis of the dynamics gives a precise value of (6.89+/-0.09) eV for the vertical ionization potential of Ag8. The influence of the helium matrix on photoemission is discussed.     

The Fate of a Cluster Colliding onto a Substrate Dissipation of Translational Kinetic Energy

The fate of clusters emitted onto a substrate falls into several categories including repulsion, soft landing, migration, and explosion, depending on the interaction between the cluster and the substrate. This dynamic behavior of the clusters controls thin-film formation processes from clusters such as cluster ion beam deposition and chemical vapor deposition. Here we describe the collision processes of both Al and Au clusters with a kinetic energy of 0.56 eV/atom onto an amorphous SiO₂ substrate studied by molecular dynamics simulation, focusing on the dissipation of translational kinetic energy during the collision process. The simulation elucidated that the activation of thermal vibrational energy of the substrate promoted the sticking of the colliding clusters on the substrate. This result suggests that the dissipation of the translational kinetic energy of the colliding cluster is one of the factors that determine the structure formed on a substrate from vapor phase.     

银/二氧化钛核壳纳米颗粒对碲化镉纳米晶的荧光增强研究

利用新合成的复合纳米结构银/二氧化钛核壳纳米颗粒,研究了金属银纳米颗粒对碲化镉纳米晶层荧光的增强情况.结果表明,这种新型复合金属纳米结构能极大地增强发光纳米晶层的荧光强度.银/二氧化钛核壳纳米颗粒是以水合肼、硝酸银和四异丙氧基钛为原材料,利用胶体化学法在水溶液中合成.透射电子显微镜图片表明这种新合成的银/二氧化钛纳米材料基本上呈球形,有较为明显的核壳结构,中间黑色的核是银纳米颗粒,外层颜色较浅部分是二氧化钛壳层.另外,包裹二氧化钛壳层后,银纳米颗粒的表面等离子吸收带从409 nm红移至430 nm,也证实了这种新型核壳纳米材料的形成.将此合成方法得到的银/二氧化钛纳米颗粒和碲化镉纳米晶用旋转涂覆方法进行直接组合后,得到了银纳米颗粒对碲化镉纳米晶荧光的明显增强,并对其增强的物理过程进行了讨论.这种能够增强荧光团发光的新型复合银纳米结构将在发光器件、荧光成像、生物探测等方面具有一定的应用价值.     

Quantum size effect in electron transmission through Cu and Ag films on W(110)

The transmission coefficient of very low energy electrons ( ? 10 eV) normally incident on (111) epitaxial films of Cu and Ag on W(110) is modulated by interference between scattering from the vacuum/metal and metal/metal interfaces. Comparison with calculations of free-electron scattering from a one-dimensional potential model, in which grading of the metal/metal interface is represented by a smoothing of the potential step, indicates that this interface is abrupt within approximately one layer spacing. We obtain a value of 11.0 (8.0) ± 1.0 eV for the inner potential of Cu (Ag) and mean free path lengths of $\text{39 ± 8}\text{A}\text{?}$ at an energy of 7.0 eV relative to the Fermi energy and $\text{29 ± 11}\text{A}\text{?}$ at 9.0 eV for Cu, and $\text{25 ± 10}\text{A}\text{?}$ at 7.5 eV for Ag. Work function values are obtained by the field emission retarding potential technique. We investigate the effects of the surface potential barrier, inelastic scattering and surface roughness, and evaluate the validity of the one-dimensional model presented.     

High stability of the goldalloy fullerenes:A density functional theory investigation of M₁₂@Au₂₀（M=Na,Al,Ag,Sc,Y,La,Lu,and Au） clusters

Discovering highly stable metal fullerenes such as the celebrated C 60 is interesting in cluster science as they have potential applications as building blocks in new nanostructures.We here investigated the structural and electronic properties of the fullerenes M 12 @Au 20(M=Na,Al,Ag,Sc,Y,La,Lu,and Au),using a first-principles investigation with the density functional theory.It is found that these compound clusters possess a similar cage structure to the icosahedral Au 32 fullerene.La 12 @Au 20 is found to be particularly stable among these clusters.The binding energy of La 12 @Au 20 is 3.43 eV per atom,1.05 eV larger than that in Au 32.The highest occupied molecular orbital-lowest unoccupied molecular orbital(HOMO-LUMO) gap of La 12 @Au 20 is only 0.31 eV,suggesting that it should be relatively chemically reactive.     

Ag(110)表面吸附酞菁铜分子的紫外光电子谱研究

用紫外光电子能谱(UPS)研究了酞菁铜分子在Ag(110)单晶表面上的吸附,随着酞菁铜分子覆盖度增加,衬底Ag的3d电子信号逐渐减弱,在此能带区域出现两个新的谱峰,这两个与吸附有机分子轨道有关的谱峰的束缚能分别为4.45 和6.36 eV.随着覆盖度的增加,在结合能为1.51和9.20 eV处又出现了两个谱峰,它们同样来自吸附有机分子的轨道.随着覆盖度的继续增加,上述四个谱峰的强度逐渐增加,其能量位置均发生了明显的偏移.根据角分辨光电子能谱的实验结果,酞菁铜分子的分子平面基本与衬底表面平行.密度泛函理论计 关键词： 酞菁铜 紫外光电子谱 吸附电子态 密度泛函理论