Nanosurface Chemistry on Size-Selected Silicon Clusters

Jarrold, Martin F.

doi:10.1126/science.252.5009.1085

Cited by 358 publications

(178 citation statements)

References 79 publications

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“…Many of the observed properties of silicon clusters have been interpreted as evidence for three dimensional reconstruction, 2,3 even for clusters containing up to 70 atoms ͑ϳ10 Å diameter͒. Since small particles of silicon of 20-30 Å diameter have been observed to have crystalline bulklike lattices, 14,15 obtaining information about the structures of small clusters and the transition to bulklike crystalline or amorphous structure would be extremely important in the study of basic material properties and growth processes.…”

Section: Introductionmentioning

confidence: 99%

“…1 Silicon clusters, in particular, have demonstrated many fascinating properties. [2][3][4] While impressive progress has been made in the understanding of this range of matter between atoms and bulk materials, structural information has been more difficult to obtain. High level calculations [5][6][7] and studies using empirical potentials 8,9 predict that silicon clusters differ significantly from the bulk crystal lattice and surfaces, i.e., they are extensively reconstructed compared to microcrystal fragments.…”

Section: Introductionmentioning

confidence: 99%

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Structures and coalescence behavior of size-selected silicon nanoclusters studied by surface-plasmon-polariton enhanced Raman spectroscopy

Honea

Ogura

Peale³

et al. 1999

The Journal of Chemical Physics

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The structures and coalescence behavior of size-selected, matrix-isolated silicon clusters have been studied using surface-plasmon-polariton ͑SPP͒ enhanced Raman spectroscopy. The cluster ions were produced in a laser vaporization source, mass selected then deposited into a co-condensed matrix of Ar, Kr or N 2 on a liquid He cooled substrate. Raman spectra from monodisperse samples of the smaller clusters studied, Si 4 , Si 6 and Si 7 , show sharp, well-resolved, vibrations which are in good agreement with predictions based on ab initio calculations. From these comparisons we confirm that Si 4 is a planar rhombus, and assign Si 6 as a distorted octahedron and Si 7 as a pentagonal bypyramid. Si 5 depositions down to 5 eV did not reveal a measurable Raman spectrum under our experimental conditions. Evidence for cluster-cluster aggregation ͑or fragmentation͒ was observed under some conditions, even for a ''magic number'' cluster such as Si 6 . The spectra of the aggregated small clusters were identical to those observed for directly deposited larger cluster ''bands,'' such as Si [25][26][27][28][29][30][31][32][33][34][35] . The Raman spectra of the aggregated clusters bear some similarity to those of bulk amorphous silicon. Cluster-deposited thin films were prepared by sublimating the matrix material. Even under these ''soft landing'' conditions, changes in the Raman spectrum are observed with the thin films showing even greater similarity to amorphous silicon.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Structures and coalescence behavior of size-selected silicon nanoclusters studied by surface-plasmon-polariton enhanced Raman spectroscopy

Honea

Ogura

Peale³

et al. 1999

The Journal of Chemical Physics

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“…[2][3][4][5][6][7][8] While pure silicon clusters have been often studied as a test model system for quantum theories, doped silicon clusters have even more potential for applications in numerous fields of materials science. 9 Charged…”

Section: Introductionmentioning

confidence: 99%

Vibrational spectra and structures of neutral Si₆X clusters (X = Be, B, C, N, O)

Trường

Savoca

Harding

et al. 2014

Phys. Chem. Chem. Phys.

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aNeutral silicon clusters doped with first row elements (Si 6 X) have been generated (X = B, C, N, O) and characterized by infrared-ultraviolet (IR-UV) two-photon resonance-enhanced ionization spectroscopy (X = C, O) and quantum chemical calculations (X = Be, B, C, N, O, Si). In the near threshold UV photoionization, the ion signal of specific cluster sizes can be significantly enhanced by resonant excitation with tunable IR light prior to UV irradiation, allowing for the measurement of the IR spectra of Si 7 , Si 6 C, and Si 6 O clusters.Structural assignments are achieved with the help of a global optimization procedure using density functional theory (DFT). The most stable calculated structures show the best agreement between predicted and measured spectra. The dopant atoms in the Si 6 X clusters have a negative net charge and the Si atoms act as electron donors within the clusters. Moreover, the overall structures of the Si 6 X clusters depend strongly on the nature of the dopant atom, i.e., its size and valency. While in some of the Si 6 X clusters one Si atom in Si 7 is simply substituted by the dopant atom (X = Be, B, C), other cases exhibit a completely different geometry (X = N, O). As a general trend, doping of the Si 7 cluster with first-row dopants is predicted to shift the optically allowed electronic transitions into the visible or even near-IR spectral range due to symmetry reduction or the radical character of the doped cluster.

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“…Over the past two decades or so, small silicon clusters have been extensively studied both experimentally [1][2][3][4][5][6][7][8] and theoretically. A central issue concerning the small clusters Si n is their lowest-energy geometric structures, namely, their global minima as a function of the cluster size n. For nр7, the global minima are firmly established by both ab initio calculations and Raman or infrared spectroscopy measurements, whereas for nр13 the global minima are also well established by ab initio calculations.…”

Section: Introductionmentioning

confidence: 99%

Global geometry optimization of silicon clusters described by three empirical potentials

Yoo

Zeng

2003

The Journal of Chemical Physics

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The ''basic-hopping'' global optimization technique developed by Wales and Doye is employed to study the global minima of silicon clusters Si n (3рnр30) with three empirical potentials: the Stillinger-Weber ͑SW͒, the modified Stillinger-Weber ͑MSW͒, and the Gong potentials. For the small-sized SW and Gong clusters (3рnр15), it is found that the global minima obtained based on the basin-hopping method are identical to those reported by using the genetic algorithm ͓Iwamatsu, J. Chem. Phys. 112, 10976 ͑2000͔͒, as well as with those by using molecular dynamics and the steepest-descent quench ͑SDQ͒ method ͓Feuston, Kalia, and Vashishta, Phys. Rev. B 37, 6297 ͑1988͔͒. However, for the mid-sized SW clusters (16рnр20), the global minima obtained differ from those based on the SDQ method, e.g., the appearance of the endohedral atom with fivefold coordination starting at nϭ17, as opposed to nϭ19. For larger SW clusters (20рn р30), it is found that the ''bulklike'' endohedral atom with tetrahedral coordination starts at n ϭ20. In particular, the overall structural features of SW Si 21 , Si 23 , Si 25 , and Si 28 are nearly identical to the MSW counterparts. With the SW Si 21 as the starting structure, a geometric optimization at the B3LYP/6-31G͑d͒ level of density-functional theory yields an isomer similar to the ground-stateisomer of Si 21 reported by Pederson et al. ͓Phys. Rev. B 54, 2863 ͑1996͔͒.

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Nanosurface Chemistry on Size-Selected Silicon Clusters

Cited by 358 publications

References 79 publications

Structures and coalescence behavior of size-selected silicon nanoclusters studied by surface-plasmon-polariton enhanced Raman spectroscopy

Structures and coalescence behavior of size-selected silicon nanoclusters studied by surface-plasmon-polariton enhanced Raman spectroscopy

Vibrational spectra and structures of neutral Si₆X clusters (X = Be, B, C, N, O)

Global geometry optimization of silicon clusters described by three empirical potentials

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Nanosurface Chemistry on Size-Selected Silicon Clusters

Cited by 358 publications

References 79 publications

Structures and coalescence behavior of size-selected silicon nanoclusters studied by surface-plasmon-polariton enhanced Raman spectroscopy

Structures and coalescence behavior of size-selected silicon nanoclusters studied by surface-plasmon-polariton enhanced Raman spectroscopy

Vibrational spectra and structures of neutral Si6X clusters (X = Be, B, C, N, O)

Global geometry optimization of silicon clusters described by three empirical potentials

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Vibrational spectra and structures of neutral Si₆X clusters (X = Be, B, C, N, O)