Resonant Raman spectroscopy has been employed to explore the first-and higher-order phonon spectra of several kinds of II-VI nanocrystals (NCs), with the aim of better understanding of the nature of phonon modes and forming a unified view onto the vibrational spectrum of semiconductor NCs. Particularly, besides the previously discussed TO, SO, LO, and 2LO modes, the combinational modes of TO+LO and SO+LO can be assumed to account for the lineshape of the spectrum below 2LO band. No trace of 2TO or 2SO band was detected, what can be the result of the dominance of Fröhlich mechanism in electron-phonon coupling in II-VI compounds. The resonant phonon Raman spectrum of NCs smaller than 2 nm is shown to be dominated by a broad feature similar to the SO mode of larger NCs or phonon density of states of a bulk crystal.The understanding of the phonon spectrum of semiconductor nanocrystals (NCs), electron-phonon coupling (EPC), dependence of the phonon spectra on the NC size, surfacebound moieties, and extended environment is of a large fundamental and application significance [1][2][3][4][5][6][7][8][9][10][11] due to the determinant role phonons play in the optical and electrical properties of semiconductor nanostructures [12,13]. Though a number of in-depth studies have addressed the phonon spectra of colloidal [14][15][16][17][18][19][20], glass-embedded [21][22][23] NCs, and epitaxial nanostructures [24][25][26], a significant divergence of the results exists concerning both the nature of the modes and their response to such factors as size, surface conditions, properties of the hosting medium and so forth. In particular, the apparently similar Raman spectra of a wide range of compounds (e.g., II-VI, III-V, and IV) and NC morphologies (dots, rods, tetrapods, wires, and discs) have been assigned differently.Recently, attempts were made to build a general picture of the phonon spectrum of various semiconductor NCs, based on analysis of the experimental Raman data and appropriate models [14,27,28]. This paper further explores the first-and higher-order phonon spectra of several kinds of II-VI NCs, as well as their similarity to other compounds, with the aim of better understanding of the vibrational spectrum of small NCs. High-quality NC samples were selected for this study in order to resolve Raman features, which are usually smeared by size dispersion, structural disorder, or low signal-to-noise ratio.The NC samples studied in this work have been prepared by means of colloidal chemistry according to protocols reported elsewhere [29][30][31][32], and CdSe, CdS, and CdTe NC samples of the same mean diameter (∼4 nm) were selected. Another sort of NCs studied were ultrasmall NCs of about 1.8 nm mean diameter, which revealed distinct Raman spectra. The attempts to measure the size and shape of these NCs directly by electron microscopy were unsuccessful [19], obviously due to ultrasmall NC size and charging of the stabilizing polymer. The broad X-ray features of these ultrasmall NCs [3] indicated their small size or/and n...

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Resonant Raman scattering spectra of ultrasmall (<2 nm) magic‐size nanocrystals (NCs) are reported. The spectra of CdS and CdSx Se1‐x NCs, resonantly excited with 325 nm and 442 nm laser lines, correspondingly, reveal broad features in the range of bulk optical phonons. The relatively large width, ∼50 cm‐1, and downward shift, ∼20 cm‐1, of the Raman bands with respect to the longitudinal optical phonon in bulk crystals and large NCs are discussed based on the breaking of the translational symmetry and bond distortion in these ultrasmall NCs. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

Most of Earth’s diamonds are connected with deep-seated mantle rocks; however, in recent years, μm-sized diamonds have been found in shallower metamorphic rocks, and the process of shallow-seated diamond formation has become a hotly debated topic. Nanodiamonds occur mainly in chondrite meteorites associated with organic matter and water. They can be synthesized in the stability field of graphite from organic compounds under hydrothermal conditions. Similar physicochemical conditions occur in serpentinite-hosted hydrothermal systems. Herein, we report the first finding of nanodiamonds, primarily of 6 and 10 nm, in Hyblean asphaltene-bearing serpentinite xenoliths (Sicily, Italy). The discovery was made by electron microscopy observations coupled with Raman spectroscopy analyses. The finding reveals new aspects of carbon speciation and diamond formation in shallow crustal settings. Nanodiamonds can grow during the hydrothermal alteration of ultramafic rocks, as well as during the lithogenesis of sediments bearing organic matter.

The phonon modes of self-assembled Ge/Si quantum dots grown by molecular-beam epitaxy in an apparatus integrated with a chamber of the scanning tunneling microscope into a single high-vacuum system are investigated using Raman spectroscopy. It is revealed that the Ge-Ge and Si-Ge vibrational modes are considerably enhanced upon excitation of excitons between the valence band Λ 3 and the conduction band Λ 1 (the E 1 and E 1 + ∆ 1 transitions). This makes it possible to observe the Raman spectrum of very small amounts of germanium, such as one layer of quantum dots with a germanium layer thickness of ≈ 10 Å. The enhancement of these modes suggests a strong electron-phonon interaction of the vibrational modes with the E 1 and E 1 + ∆ 1 excitons in the quantum dot. It is demonstrated that the frequency of the Ge-Ge mode decreases by 10 cm -1 with a decrease in the thickness of the Ge layer from 10 to 6 Å due to the spatial-confinement effect. The optimum thickness of the Ge layer for which the size dispersion of quantum dots is minimum is determined.

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