Self-organization of bimetallic PdAu nanoparticles on SiO<Subscript>2</Subscript> surface

Bimetallic PdAu nanoparticles on SiO₂ substrate were produced by a sequential room-temperature sputtering deposition method. By the atomic force microscopy technique we studied the nanoparticles self-organization mechanisms in various conditions. First, Pd nucleation and growth proceeds at the substrate defects and the Pd nanoparticles density increase rapidly. During the second sputtering deposition, Au atoms adsorb on the SiO₂ and diffuse toward Pd nanoparticles without forming new nuclei. The Au atoms are trapped by the preformed Pd nanoparticles, forming PdAu bimetallic nanoparticles which size increases. Furthermore, fixing the amount of deposited Pd and increasing the amount of deposited Au, we analyzed the evolution of the PdAu film surface morphology: we observe that the PdAu grows initially as three-dimensional islands; then the PdAu film morphology evolves from compact three-dimensional islands to partially coalesced worm-like structures, followed by a percolation morphology and finally to a continuous and rough film. The application of the interrupted coalescence model allowed us to evaluate the critical mean island diameter R _c ≈ 2.8 nm for the partial coalescence process. The application of the dynamic scaling theory of growing interfaces allowed us to evaluate the dynamic growth exponent β = 0.21 ± 0.01 from the evolution of the film surface roughness. Finally, fixing the amount of deposited Pd and Au we studied the self-organization mechanism of the PdAu nanoparticles induced by thermal processes performed in the 973–1173 K temperature range. The observed kinetic growth mechanism is consistent with a surface diffusion-limited ripening of the nanoparticles with a temperature-dependent growth exponent. The dependence of the growth exponent on the temperature is supposed to be linked to the variation with the temperature of the characteristics of the PdAu alloy. The activation energy for the surface diffusion process was evaluated in 0.54 ± 0.03 eV.     

New approach to the growth of SiOx nanowire bunch using Au catalyst and SiNx film on Si substrate

SiO_x nanowire bunches were fabricated on a SiN_x film with Au catalytic metal in the presence of an Ar flow of 50 sccm at 1150 °C. The resulting samples were characterized by field-emission scanning electron microscopy, transmission electron microscopy and energy dispersive X-ray spectroscopy. A SiN_x film serves as a barrier to the diffusion of Si atoms from the Si substrate to the catalytic Au metal, where a substrate is a Si source material for SiO_x nanowire (NW) growth. Using this process, we could temporally control the initial growth step of SiO_x NWs and easily grow the NW bunch.     

Synthesis and photoluminescence of aligned SiO<Subscript>x</Subscript> nanowire arrays

Aligned SiO_x nanowire arrays standing on a Si substrate were successfully synthesized using a simple method by heating a single-crystalline Si slice covered with SiO₂ nanoparticles at 1000 °C in a flowing Ar atmosphere. The SiO_x nanowire arrays were characterized by scanning electron microscopy and transmission electron microscopy. The SiO_x nanowires become progressively thinner from bottom to top. The formation process of the SiO_x nanowire arrays is closely related to a vapor–solid mechanism. Room-temperature photoluminescence measurements under excitation at 260 nm showed that the SiO_x nanowire arrays had a strong blue–green emission at 500 nm (about 2.5 eV), which may be related to oxygen defects. Received: 29 April 2002 / Accepted: 30 April 2002 / Published online: 10 September 2002 RID="*" ID="*"Corresponding author. Fax: +86-551-559-1434, E-mail: gwmeng@mail.issp.ac.cn     

Investigation of the electronic properties of Au nanoclusters in SiO<Subscript>2</Subscript> by combined scanning tunneling/atomic force microscopy

The tunneling of electrons through Au nanoc lusters formed by pulsed laser deposition in a SiO₂ thin film on a Si substrate has been investigated by combined scanning/atomic force microscopy (STM/AFM). Conducting Pt-coated Si cantilevers were used. The feedback was maintained via the AFM channel, and the current-voltage (I-V) characteristics of the tunnel contact between the AFM probe and the n ⁺-Si substrate through a =4-nm-thick SiO₂ film with Au nanoclusters =2 nm in diameter were measured simultaneously. The current image of the structure contained areas of increased current (tunnel-current channels) 2–15 nm in size, related to tunneling of electrons through Au nanoclusters in SiO₂. The I-V characteristics recorded in the tunnel-current channels exhibit specific features related to the Coulomb blockade of electron tunneling through Au nanoclusters.     

Field emission properties of carbon nanotubes grown on silicon nanowire arrays

Carbon nanotubes are synthesized on the silicon nanowire arrays which are fabricated on silicon substrate by chemical vapor depositing SiCl₄ and H₂ gases in the presence of Au catalysts. The silicon nanowires are single-crystal with lengths up to 100 μm and diameters ranging from 50 to 500 nm. The tangled carbon nanotubes are grown directly from the surface of Si nanowires. The field emission properties of the carbon nanotubes are investigated at the gap of 200 μm. The low turn on and threshold fields are obtained. The stabilization of the emission currents is also presented.     

Nanospherical Surface‐Supported Seeded Growth of Au Nanowires: Investigation on a New Growth Mechanism and High‐Performance Hydrogen Peroxide Sensors

In this paper, a novel strategy with a new growth mechanism for fast and large‐scale growth of Au long nanowires on high‐curvature SiO₂ nanospherical surfaces has been developed. The synthesis includes three steps, i.e., amino modification of SiO₂ nanospheres, Au seed loading on aminated SiO₂ nanospheres and subsequently, Au seed‐mediated nanowire growth on SiO₂ nanospheres. The prepared Au nanowires (Au NWs) (exhibit long length, high aspect ratio, and good flexibility, and can naturally form the dense nanowire film, which is promising as a stable conductive electrode. In addition, the effect of synthetic conditions such as reactant feeding order, Au seeds and SiO₂@Au seeds on the morphology of Au nanostructures (nanowires, nanoteeth, and nanoflowers) has been investigated. It is found that Au seeds and high‐curvature SiO₂ nanospherical surfaces are necessary conditions for the successful preparation of Au NWs and nanowire films. The different growth mechanisms for Au NWs and nanoteeth have been proposed and discussed. Moreover, the novel nonenzymatic H₂O₂ sensor based on Au NWs exhibits much enhanced performance such as higher sensitivity, stability, and selectivity, wider linear range and lower detection limit, compared with that of Au nanoparticles‐based H₂O₂ sensor.     

A high efficient antireflective down-conversion Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Bi<Superscript>3+</Superscript>, Yb<Superscript>3+</Superscript> thin films

The high efficient antireflective down-conversion Y₂O₃:Bi, Yb films have been prepared successfully on Si(100) substrates by pulsed laser deposition (PLD) method, Upon excitation of ultraviolet photon varying from 300 to 400 nm, near-infrared emission of Yb³⁺ was observed for the film, can be efficiently absorbed by silicon (Si) solar cell. Most interestingly, there is a very low average reflectivity 1.46% for the incident light from 300 to 1100 nm. To the best of our knowledge, this is the lowest reflectance for the down-conversion thin films prepared by cost efficient method. The surface topography of the high efficient antireflective films can be controllably tuned through the substrate template regulation by optimizing process parameters. Besides, the results showed that there is a close relationship between luminescent property and morphology of the film. With the change of the surface morphology, the intensity of Bi³⁺ and Yb³⁺ emission peaks increase first and then decrease. The obtained results demonstrate that this film can enhance the Si solar cell efficiency through light trapping and spectrum shifting.     

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.     

Nanoparticle-Coated Silicon Nanowires

The synthesis of silicon nanowires that are densely coated with silicon nanoparticles is reported. These structures were produced in a two-step process, using a method known as hypersonic plasma particle deposition. In the first step, a Ti–Si nanoparticle film was deposited. In the second step the Ti-source was switched off, and nanoparticle-coated nanowires grew under the simultaneous action of Si vapor deposition and bombardment by Si nanoparticles. Total process time, including both steps, equaled 5 min, and resulted in formation of a dense network of randomly oriented nanowires covering1.5 cm² of substrate area. The nanowires are composed of single-crystal Si. The diameters of the nanowires vary over the range 100–800 nm. Each nanowire has a crystalline TiSi₂ catalyst particle, believed to have been solid during nanowire growth, at its tip.     

Pd-Si薄膜固相反应的透射电子显微镜研究

本工作利用透射电子显微术研究了Pd-Si薄膜固相反应的初始生成相及生成相Pd₂Si与(111)取向Si衬底的取向关系随Pd膜厚度、退火温度等因素的变化规律。实验结果表明:在衬底保持室温的条件下,Pd沉积到Si(111)上时也能够生成一层外延的Pd₂Si,其厚度足以在常规的选区电子衍射中产生明显的信号。在170℃退火时,Pd-Si反应即可持续到生成200nm厚的外延的Pd₂Si。在Pd膜厚度为400nm的条件下,Pd₂Si与Si(111)衬底的取向关系为[0001]_(Pd2Si)轴织构。 关键词：     

Structure,the lattice dynamic,and the dielectric characteristics of Sr<Subscript>0.5</Subscript>Ba<Subscript>0.5</Subscript>Nb<Subscript>2</Subscript>O<Subscript>6</Subscript> films

Solid solution Sr_0.5Ba_0.5Nb₂O₆ films have been synthesized on a (111)Pt/(001)Si substrate by rf deposition in an oxygen atmosphere. The depolarized Raman spectra, the structure, and the dielectric characteristics of the films have been studied over a wide temperature range. It is found that the films were singlephase, had the tetragonal tungsten bronze structure, and had a pronounced axial texture with axis 001 directed perpendicular to the substrate surface. It is shown that the film material undergoes a diffuse phase transition to the state of a relaxor ferroelectric in the temperature range 300–425 K. Possible reasons of the regularities observed are discussed.     

Influence of the Si/SiO<Subscript>2</Subscript> interface on the charge carrier density of Si nanowires

The electrical properties of Si nanowires covered by a SiO₂ shell are influenced by the properties of the Si/SiO₂ interface. This interface can be characterized by the fixed oxide charge density Q_f and the interface trap level density D_it. We derive expressions for the effective charge carrier density in silicon nanowires as a function of Q_f, D_it, the nanowire radius, and the dopant density. It is found that a nanowire is fully depleted when its radius is smaller than a critical radius a_crit. An analytic expression for a_crit is derived. PACS 68.65.-k; 61.46.+w; 81.10.Bk     

Analysis of the oscillation intensity of RHEED specular reflection during the MBE growth of CaF<Subscript>2</Subscript>/Si/CaF<Subscript>2</Subscript> structures

The results of analysis of the oscillation intensity of RHEED specular reflection during the MBE growth of CaF₂/Si(111) structures in a wide temperature range from 100 to 600°С are presented. It is shown that the preliminary formation of a 2D Si buffer layer provides the two-dimensional growth of CaF₂ layers. Possible reasons which for the disruption of 2D growth at high substrate temperatures are discussed.     

Study of the features of BaF<Subscript>2</Subscript> heteroepitaxy on CaF<Subscript>2</Subscript>/Si(100) layers obtained in the high-temperature growth mode

The surface morphology of BaF₂ epitaxial films grown by MBE (molecular beam epitaxy) in various modes on the surface of CaF₂/Si(100) is investigated by AFM. The CaF₂ layers on Si(100) are obtained in the high-temperature growth mode (Т _S = 750°C). It is shown that the epitaxy of BaF2 at a temperature of 600°C at the initial stage of growth leads to the formation of defects such as perforations in the epitaxial film, while epitaxy at a temperature of 750°C provides a defect-free film with a surface morphology suitable for the subsequent growth of semiconductors of IV–VI type and solid solutions based on them.     

X-ray spectral analysis of the interface of a thin Al<Subscript>2</Subscript>O<Subscript>3</Subscript> film prepared on silicon by atomic layer deposition

The extent and phase chemical composition of the interface forming under atomic layer deposition (ALD) of a 6-nm-thick Al₂O₃ film on the surface of crystalline silicon (c-Si) has been studied by depthresolved, ultrasoft x-ray emission spectroscopy. ALD is shown to produce a layer of mixed Al₂O₃ and SiO₂ oxides about 6–8 nm thick, in which silicon dioxide is present even on the sample surface and its concentration increases as one approaches the interface with the substrate. It is assumed that such a complex structure of the layer is the result of interdiffusion of oxygen into the layer and of silicon from the substrate to the surface over grain boundaries of polycrystalline Al₂O₃, followed by silicon oxidation. Neither the formation of clusters of metallic aluminum near the boundary with c-Si nor aluminum diffusion into the substrate was revealed. It was established that ALD-deposited Al₂O₃ layers with a thickness up to 60 nm have similar structure.     

An investigation into ultra-thin pseudobinary oxide (TiO<Subscript>2</Subscript>)<Subscript>x</Subscript>(Al<Subscript>2</Subscript>O<Subscript>3</Subscript>)<Subscript>1-x</Subscript> films as high-<Emphasis Type="Italic">k</Emphasis> gate dielectrics

As potential gate dielectric materials, pseudobinary oxide (TiO₂)_x(Al₂O₃)_1-x (0.1≤x≤0.6) films (TAO) were deposited on Si (100) substrates by pulsed-laser deposition method and studied systematically via various measurements. By a special deposition process, including two separate steps, the TAO films were deposited in the form of two layers. The first layer was deposited at room temperature and the second layer was completed at the substrate temperature of 400 °C. Detailed data show that the properties of the TAO films are closely related to the ratio between TiO₂ and Al₂O₃. The existence of the first layer deposited at room temperature can effectively restrain the formation of the interfacial layer. And according to the results of X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy performed on the films, no other information belonging to the silicon oxide could be observed. For the (TiO₂)_0.4(Al₂O₃)_0.6 film, the best result has been achieved among all samples and its dielectric constant is evaluated to be about 38. It is valuable for the amorphous TAO film as one of the promising dielectric materials for high-k gate dielectric applications. PACS 77.55.+f; 73.40.Qv; 81.15.Fg     

Electron-assisted chemical etching of oxidized chromium

Electron-assisted chemical etching of oxidized chromium, CrO_x, has been studied by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and atomic force microscopy (AFM). Two model substrates were used—10 nm CrO_x deposited on Si(1 0 0) that was covered with either native oxide or a 20 nm Au/Pd alloy film. Using chlorine and/or oxygen as etching gases, the experiments were conducted in a customized high vacuum system, equipped with a high density electron source and a low pressure reaction cell. On both substrates, electron-assisted chemical etching of CiO_x was detected by SEM, EDS and AFM. Making the method questionable for etching applications, there is substantial substrate damage associated with the etching. The SEM images indicate strongly inhomogeneous material removal, apparently initiated and propagated from specific but unidentified sites. In the experiments involving the Au/Pd film, there was phase separation of Au and Pd, and dewetting to form metallic islands. AFM data show that the etched holes were as deep as 200 nm, confirming relatively rapid etching of the Si substrate after the top layer of Cr oxide was removed.     

Electrodeposition and magnetic properties of Ni nanowire arrays on anodic aluminum oxide/Ti/Si substrate

Ni nanowire arrays with different diameters have now been extended to directly fabricate in porous anodic alumina oxide (AAO) templates on Ti/Si substrate by direct current (DC) electrodeposition. An aluminum film is firstly sputter-deposited on a silicon substrate coated with a 300 nm Ti film. AAO/Ti/Si substrate is synthesized by a two-step electrochemical anodization of the aluminum film on the Ti/Si substrate and then used as template to grow Ni nanowire arrays with different diameters. The coercivity and the squareness in parallel direction of Ni nanowires with about 10 nm diameters are 664 Oe and 0.90, respectively. The Ni nanowire arrays fabricated on AAO/Ti/Si substrates should lead to practical applications in ultrahigh-density magnetic storage devices because of the excellent properties.     

Ferroelectric and dielectric properties of SrBi<Subscript>4</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript> thin films grown on Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> film layer

Ferroelectric and dielectric properties of bilayered ferroelectric thin films, SrBi₄Ti₄O₁₅ grown on Bi₄Ti₃O₁₂, were investigated. The thin films were annealed at 700°C under oxygen atmosphere. The bilayered thin films were prepared on a Pt(111)/Ti/SiO₂/Si substrate by a chemical solution deposition method. The dielectric constant and dielectric loss of the bilayered thin films were 645 and 0.09, respectively, at 100 kHz. The value of remnant polarization (2P _r) measured from the ferroelectric thin film capacitors was 60.5 μC/cm² at electric field of 200 kV/cm. The remnant polarization was reduced by 22% of the initial value after 10¹⁰ switching cycles. The results showed that the ferroelectric and dielectric properties of the SrBi₄Ti₄O₁₅ on Bi₄Ti₃O₁₂ ferroelectric thin films were better than those of the SrBi₄Ti₄O₁₅ grown on a Pt-coated Si substrate suggesting that the improved properties may be due to the different nucleation and growth kinetics of SrBi₄Ti₄O₁₅ on the c-axis-oriented Bi₄Ti₃O₁₂ layer or on the Pt-coated Si substrate.     

The Influence of B<Subscript>2</Subscript>H<Subscript>6</Subscript> on the Growth of Silicon Nanowire

The un-doped and boron-doped silicon nanowires (SiNWs) were grown via vapor–liquid–solid (VLS) mechanism by low pressure chemical deposition (LPCVD). The diameters of un-doped and boron-doped SiNWs varied from 18.5 to 75.3 nm and 26.6 to 66.1 nm, respectively. The critical growth temperature of boron-doped SiNWs is 10°C lower than that of un-doped ones and the diameters of the boron-doped SiNWs is always larger than that of the un-doped ones under different growth temperatures. This is because that the introduction of diborane enhanced the dissociation of SiH₄ which determines the growth process of SiNW. A growth process of silicon nanowire is proposed to describe the influence of B₂H₆.