Photoluminescence properties of size-selected Si nanocluster films prepared by laser ablation

Size-dispersed Si nanocluster films have been synthesized by a method of crossing an Ar gas beam perpendicularly to a silicon cluster beam that is produced by a laser ablation technique. Flight directions of the nanoclusters are changed due to Ar gas collisions, and smaller nanoclusters are deflected further from the axis of the primary cluster beam. The size-dispersed nanocluster films exhibit strong red photoluminescence (PL) after exposure to the air. The PL peak energy changes between 1.42 and 1.72 eV depending on the sample position. The average diameter of the oxidized nanoclusters characterized by transmission electron microscopy is 10 nm at the position of the primary cluster beam axis and becomes smaller as deviated from the axis. The relation between the PL peak energy and the size of the oxidized Si nanoclusters is discussed. Received: 4 May 2000 / Accepted: 9 May 2000 / Published online: 13 July 2000     

Photoluminescence dynamics of organic molecule-passivated Si nanoclusters

The size-selected phenyl-passivated Si nanoclusters with the mean diameters of 1.5 and 1.3 nm have been prepared in the solution route. The intense PL observed in Si nanoclusters, in which the band gap energies increase up to approximately 4 eV, originates from electron-hole pair recombination. From time-resolved PL, two kinds of exponential PL decay components with fast and slow lifetime were observed. The identical decays with slow lifetime will be derived from the surface states of Si nanoclusters passivated by phenyl molecules. The size-dependent zero-phonon assisted optical transitions by quantum size effects occur at a high rate of sub-nanosecond timescale.     

Atomic force microscopy of Au deposition from aqueous HF onto Si(111)

Non-contact atomic force microscopy (AFM) was employed following emersion to examine Au nanoclusters deposited from aqueous mixtures of HF and 10⁻⁴ M KAu(CN)₂ onto Si(111). As the HF concentration is increased, the growth rates both parallel and perpendicular to the substrate of the approximately oblate Au hemispheroids increase. AFM images were obtained for times at which previously reported in situ second harmonic generation signals from the interface reach a maximum. At the time when the second harmonic enhancement is maximized during deposition from 0.500 (5.00) M HF, the Au nanoclusters have an average diameter of 94 (109) nm and an average height of 3.6 (9.5) nm. These cluster diameters can be understood qualitatively by the shift of the plasmon resonance due to depolarization as the cluster size increases, causing the resonant second harmonic enhancement at 532 nm to pass through a maximum at cluster diameters in the range 90–110 nm.     

Photoelectric properties of the GeSi/Si heterostructures with self-assembled nanoclusters grown by sublimation molecular beam epitaxy in a GeH4 medium

The photosensitivity (PS) spectra of the GeSi/Si(001) heterostructures with self-assembled nanoclusters grown by sublimation molecular beam epitaxy in a GeH₄ medium have been studied by photo-emf spectroscopy at the semiconductor/electrolyte junction (PSE) and by photo-emf and photocurrent spectroscopy of Schottky barriers including the temperature dependence of the PS spectra in the temperature range of 10–300 K. The bands related to the phonon assisted and phonon-less interband of spatially indirect optical transitions in the GeSi nanoclusters have been observed in the PS spectra even at 300 K. The scatter effect of the GeSi nanoclusters in size and/or in composition on the PS spectrum’s edge shape has been theoretically considered. The emission theory of the photoexcited carriers from the quantum wells of the GeSi/Si nanoclusters built-in to a Schottky barrier (p-tn junction, semiconductor/electrolyte junction) has been developed.     

Bistable coupling states measured on single Co nanoclusters deposited on CoO(111)

We describe novel features of the induced magnetic anisotropy in Co nanoclusters coupled with a CoO(111) layer. Individual cluster magnetism was studied using new microbridge superconducting quantum interference devices. Intrinsically, the Co clusters are single domains with an effective anisotropy constant K(F)≈1.5×10(6) erg·cm(-3). A bistable state of the ferromagnetic-antiferromagnetic coupling is revealed, with a maximum bias systematically observed along CoO[10 ?1] and an interfacial coupling energy of 0.9 erg·cm(-2). The small bias observed in cluster assembly results from an averaging over the two opposite stable states.     

Doping of magic nanoclusters in the submonolayer In/Si(100) system

Si(100)4 x 3-In reconstruction is essentially a superlattice of magic (identical-size) Si7In6 nanoclusters. Using scanning tunneling microscopy (STM) observations, we have found that under appropriate growth conditions up to 35% of these clusters can be modified; namely, two Si atoms in the cluster can be replaced by two In atoms, thus forming a Si5In8 cluster. This modification can be considered as a doping of the magic cluster, as it changes the electronic properties of the cluster from semiconducting towards metallic. The doped cluster is less rigid than the ordinary one and swings in the electrical field of the STM tip. The atomic structure and stability of the doped magic cluster have been examined using first-principles total-energy calculations.     

The microstructure and magnetic behavior of Co nanostructured film prepared by energetic cluster beam deposition

Cobalt nanostructured films were successfully prepared by depositing Co clusters onto a Si(100) substrate in our home-made cluster beam deposition apparatus. During preparation, the energy of the cluster beam was accelerated by applying an external electric field. The effect of the cluster beam energy on the microstructure, phase transformation and magnetic behavior was investigated for the cluster-assembled film in the case of both low energy cluster deposition and energetic cluster deposition. The scanning electron microscopy observation confirms that the films are assembled by the regular spherical nanoclusters. Compared with the low-energy Co cluster-assembled film, the magnetization of the energetic Co cluster-assembled film was improved significantly. The present work describes an effective way to prepare the magnetic nanostructured films.     

Low energy alkali ion scattering investigation of Au nanoclusters grown on silicon oxide surfaces

The atomic and electronic structures of Au nanostructures grown by deposition onto various silicon oxide surfaces were probed with low energy alkali ion scattering. Charge state-resolved time-of-flight spectra of scattered 2 keV ³⁹K⁺ ions were collected from Au deposited onto an untreated Si wafer with a native oxide, a thermally grown oxide surface, and atomically-clean Si(111). It is shown that nanoclusters form on both oxides, but not on the clean Si. A quantitative analysis of the ion scattering spectra indicates that the nanoclusters are initially flat, two-dimensional structures that start to develop a second layer at about 0.5 Å of deposited Au and then form three-dimensional islands. The neutral fraction of scattered 2 keV ³⁹K⁺ ions decreases with deposition indicating changes in the quantum state occupancy with cluster size. The shapes of the clusters differ on the native and thermal oxides, leading to shape-dependent neutralization.     

Optical band gap of Si nanoclusters

We discuss the nature of the optical transitions in porous silicon and in Si nanoclusters in the light of recent theoretical calculations. The accuracy of the different techniques used to calculate the band gap of Si nanoclusters is analyzed. We calculate the electronic structure of crystallites in the Si-III (BC8) crystalline phase which is known to have a direct gap and we examine the effect of quantum confinement on clusters of SiGe alloy and amorphous silicon. The comparison with the experiments for all the systems suggests the possibility of different channels for the radiative recombination.     

Excess Si concentration dependence of the photoluminescence of Si nanoclusters in SiO2 fabricated by ion implantation

A method for the fabrication of luminescent Si nanoclusters in an amorphous SiO₂ matrix by ion implantation and annealing, and the detailed mechanisms for the photoluminescence are reported. We have measured the implanted ion dose, annealing time and excitation energy dependence of the photoluminescence from implanted layers. The samples were fabricated by Si ion implantation into SiO₂ and subsequent high-temperature annealing. After annealing, a photoluminescence band below 1.7 eV has been observed. The peak energy of the photoluminescence is found to be independent of annealing time and excitation energy, while the intensity of the luminescence increases as the annealing time and excitation energy increase. Moreover, we found that the peak energy of the luminescence is strongly affected by the dose of implanted Si ions especially in the high dose range. These results indicate that the photons are absorbed by Si nanoclusters, for which the band-gap energy is modified by the quantum confinement effects, and the emission is not simply due to direct electron–hole recombination inside Si nanoclusters, but is related to defects probably at the interface between Si nanoclusters and SiO₂, for which the energy state is affected by Si cluster–cluster interactions. It seems that Si nanoclusters react via a thin oxide interface and the local concentrations of Si nanoclusters play an important role in the peak energy of the photoluminescence.     

纳米团簇熔化过程的分子动力学模拟

本文采用分子动力学结合嵌入原子多体势,模拟了不同半径的Ni纳米团簇的升温熔化过程,研究团簇尺寸对熔点和表面能的影响.模拟结果表明:团簇的熔点显著低于体材料的熔点.团簇熔化的过程首先是在团簇的表面出现预熔,然后向团簇内部扩展,直到整个团簇完全熔为液态.在模拟的纳米尺度范围内,团簇的熔点与团簇尺寸基本成线性关系.团簇的表面能随着团簇尺寸的增大而减小,而且表面能均高于体材料的表面能.     

Study of the tunnel conductance and electronic screening in nanoclusters of d metals on graphite surface

The evolution of the electronic structure of pulsed-laser-deposited nanoclusters of noble and transition metals (Au, Cu, Ni, Co, Cr) on a graphite surface with a decrease in their size from 10 to 1 nm has been investigated by scanning tunnel spectroscopy, X-ray photoelectron spectroscopy, and Auger electron spectroscopy. The data obtained suggest that the properties of nanoclusters differ from metallic when the lateral cluster size reaches ～2–3 nm and the height reaches ～1 nm and that the shape of clusters (transition from three-dimensional to two-dimensional ones) significantly affects their transition to the nonmetallic state.     

Magnetic enhancement in cobalt-manganese alloy clusters

Magnetic moments of Co(N)Mn(M) and Co(N)V(M) clusters (N < or = 60; M < or = N/3) are measured in molecular beams using the Stern-Gerlach deflection method. Surprisingly, the per atom average moments of Co(N)Mn(M) clusters are found to increase with Mn concentration, in contrast to bulk CoMn. The enhancement with Mn doping is found to be independent of cluster size and composition in the size range studied. Meanwhile, Co(N)V(M) clusters show reduction of average moments with increasing V doping, consistent with what is expected in bulk CoV. The results are discussed within the virtual bound states model.     

Ion beam induced formation and interrogation of Au nanoclusters

Low-energy ion bombardment of a Au thin film by 0.5 keV Ar+ forms self-organized nanoclusters that display quantum size effects. The reduction of Au coverage with sputtering time is quantified with x-ray photoemission spectroscopy, and a decrease of both the rms roughness and correlation length is measured by STM. Neutralization of scattered 3 keV Na+ and K+ alkali-metal ions is used to probe the electronic states of the sputter-induced nanoclusters. The neutral fractions gradually increase as the cluster dimensions decrease, indicating that the electronic structure is similar to that of clusters grown by deposition.     

Structure and magnetic properties of Co nanoclusters fabricated by ion beam synthesis in SiO2 films

Co nanoparticles fabricated by ion beam synthesis in SiO₂ films were investigated with transmission electron microscopy and superconducting quantum interference device technique. Variation of the thermal treatment enables the formation of Co nanoclusters of different sizes ranging from 2 to 40 nm. Small nanoclusters of about 2–3 nm are amorphous, whereas clusters above 7 nm show the configuration of cubic Co nanocrystals. Measurements of magnetisation at temperatures between 2 K and 360 K reveal superparamagnetic behaviour for the small nanoclusters up to 3 nm and ferromagnetism for clusters above 7 nm. Received: 12 February 2001 / Accepted: 3 May 2001 / Published online: 27 June 2001     

Iron/iron oxide core-shell nanoclusters for biomedical applications

Biocompatible magnetic nanoparticles have been found promising in several biomedical applications for tagging, imaging, sensing and separation in recent years. Most magnetic particles or beads currently used in biomedical applications are based on ferromagnetic iron oxides with very low specific magnetic moments of about 20–30 emu/g. Here we report a new approach to synthesize monodispersed core-shell nanostructured clusters with high specific magnetic moments above 200 emu/g. Iron nanoclusters with monodispersive size of diameters from 2 nm to 100 nm are produced by our newly developed nanocluster source and go to a deposition chamber, where a chemical reaction starts, and the nanoclusters are coated with iron oxides. HRTEM Images show the coatings are very uniform and stable. The core-shell nanoclusters are superparamagnetic at room temperature for sizes less than 15 nm, and then become ferromagnetic when the cluster size increases. The specific magnetic moment of core-shell nanoclusters is size dependent, and increases rapidly from about 80 emu/g at the cluster size of around 3 nm to over 200 emu/g up to the size of 100 nm. The use of high magnetic moment nanoclusters for biomedical applications could dramatically enhance the contrast for MRI, reduce the concentration of magnetic particle needs for cell separation, or make drug delivery possible with much lower magnetic field gradients     

银团簇纳米颗粒的制备及其光吸收谱性质

 采用自悬浮定向流技术制备银团簇纳米颗粒，理论分析了银团簇的成核机理与影响因素，实验研究了制备条件和工艺。结果表明：惰性气体的冷却效率、气体流速和压强、金属熔球的温度和大小是控制颗粒尺寸大小及分布的关键条件，制备粒径小于10 nm的团簇颗粒须采用氦气为载流气体；团簇颗粒流速越大，颗粒粒径越小，尺寸分布越窄，但颗粒生成数量越少。性能表征说明：制备的颗粒呈较规则的球形，为面心立方结构，分散均匀，表面纯净无氧化，粒径分布窄。理论与实验研究了银团簇纳米颗粒的光学吸收谱性质，证明表面等离子共振吸收峰与颗粒的尺寸有很强的相关性，随着颗粒尺寸的减小，由于量子尺寸效应，吸收峰将发生宽化和蓝移。     

Synthesis of hydrophobic gold nanoclusters: growth mechanism study,luminescence property and catalytic application

One-pot synthesis of well dispersed, size-controlled gold nanoparticles with the average size of 10–15 nm and luminescent gold nanoclusters with average size of 1.7–2.0 nm were successfully achieved by thermal decomposition of gold organometallic precursor CH₃AuPPh₃ in the presence of thiol surfactants in o-xylene. Only difference between the preparations of two types of Au nanoparticles is the amount of thiol surfactant employed. The mechanistic study of formation of gold nanoparticles was carried out by analyzing the samples at different reaction time intervals and revealed that two-staged growth process was involved. The nanoclusters showed strong red emission with the maximum intensity at about 600 nm. The maximum room temperature photoluminescence quantum yield was measured as 1.2%. The catalytic ability of the Au nanoclusters to promote Suzuki–Miyaura coupling involving the C–C bond formation was also investigated.     

表面氧钝化碳化硅纳米团簇电子结构和光学性质的第一性原理研究

基于密度泛函理论(DFT)和广义梯度近似(GGA),对氧钝化条件下4H-SiC纳米团簇的电子结构和光学性质进行了研究。计算了不同直径的4H-SiC纳米球氧钝化后的能带结构、电子态密度和光学性质。团簇的尺度在0.4~0.9 nm之间,构建表面仅存在硅氧双键和表面仅存在碳氧双键的两种模型。研究表明硅氧双键和碳氧双键所引起的缺陷态位于原4H-SiC的价带和导带之间,并且缺陷态与价带顶的能量差随纳米团簇颗粒直径的增大而减小;缺陷态主要是由Si原子外层电子和氧原子外层电子轨道杂化引起的。同时,由于氧的存在,对碳化硅的结构产生一定的影响,这也是缺陷态形成的一个原因。另外,碳氧双键和硅氧双键钝化对4H-SiC纳米团簇的光学性质有着不同的影响。在表面仅存在C=O的情况下,4H-SiC纳米团簇表现出各向同性的性质。在表面仅存在Si=O的情况下,4H-SiC纳米团簇表现出各向异性的性质。     

Exclusion zone surrounding silicon nanoclusters formed by rapid thermal chemical vapour deposition on SiO2

We present results of an experimental investigation on the nearest-neighbour distance of silicon nanoclusters obtained by chemical vapour deposition of silane on silicon oxide substrates. Structural characterization has been performed by means of energy filtered transmission electron microscopy, which allowed us to observe dot sizes down to 0.5 nm in radius. We have found that silicon nanodots after deposition are separated by a minimum distance of about 4 nm. This effect has also been observed on samples deposited in the same conditions on substrates which have been subjected to different chemical treatments. The phenomenon is attributed to the existence of a capture zone, within which new deposited Si monomers preferentially contribute to the growth of a previously nucleated seed rather than aggregate to form a new nucleus. As a confirmation of this hypothesis, the average dot radius has been observed to be proportional to the capture region size, thus indicating a scaling behaviour for this process. Moreover when the inter-dot distance distribution is scaled to its average value, it collapses into a universal curve.