The physical properties of black silicon (b-Si) formed on Si wafers by reactive ion etching in chlorine plasma are reported in an attempt to clarify the formation mechanism and the origin of the observed optical and electrical phenomena, which are promising for a variety of applications. The b-Si consisting of high density and high aspect ratio sub-micron length whiskers or pillars with tip diameters of well under 3 nm exhibits strong photoluminescence (PL) both in the visible and the infrared, which is interpreted in conjunction with defects, confinement effects and near band-edge emission. Structural analysis indicates that the whiskers are all crystalline and encapsulated by a thin Si oxide layer. The infrared vibrational spectrum of Si-O-Si bondings in terms of transverse-optic (TO) and longitudinal-optic (LO) phonons indicates that disorder induced LO-TO optical mode coupling can be an effective tool in assessing the structural quality of the b-Si. The same phonons are likely coupled to electrons in visible region PL transitions. Field emission properties of these nanoscopic features are demonstrated indicating the influence of the tip shape on the emission. Overall properties are discussed in terms of the surface morphology of the nanowhiskers.

A convenient method has been developed to thin electron beam fabricated silicon nanopillars under controlled surface manipulation by transforming the surface of the pillars to an oxide shell layer followed by the growth of sacrificial ammonium silicon fluoride coating. The results show the formation of an oxide shell and a silicon core without significantly changing the original length and shape of the pillars. The oxide shell layer thickness can be controlled from a few nanometers up to a few hundred nanometers. While downsizing in diameter, smooth Si pillar surfaces of less than 10 nm roughness within 2 microm were produced after exposure to vapors of HF and HNO3 mixture as evidenced by transmission electron microscopy (TEM) analysis. The attempt to expose for long durations leads to the growth of a thick oxide whose strain effect on pillars can be assessed by coupled LO-TO vibrational modes of Si-O bonds. Photoluminescence (PL) of the pillar structures which have been downsized exhibits visible and infrared emissions, which are attributable to microscopic pillars and to the confinement of excited carriers in the Si core, respectively. The formation of smooth core-shell structures while reducing the diameter of the Si pillars has a potential in fabricating nanoscale electronic devices and functional components.

No abstract

Silicon (Si) nanoparticles (NPs) were synthesized by transforming a Si wafer surface to ammonium silicon hexafluoride (ASH) or (NH(4))(2)SiF(6) under acid vapor treatment. Si-NPs which were found to be embedded within the polycrystalline (ASH) layer exhibit a strong green-orange photoluminescence (PL). Differential PL measurements revealed a major double component spectrum consisting of a broad band associated with the ASH-Si wafer interfacial porous oxide layer and a high energy band attributable to Si-NPs embedded in the ASH. The origin of the latter emission can be explained in terms of quantum/spatial confinement effects probably mediated by oxygen related defects in or around Si-NPs. Although Si-NPs are derived from the interface they are much smaller in size than those embedded within the interfacial porous oxide layer (SiO(x), x > 1.5). Transmission electron microscopy (TEM) combined with Raman scattering and Fourier transformed infrared (FTIR) analysis confirmed the presence of Si-NP and Si-O bondings pointing to the role of oxygen related defects in a porous/amorphous structure. The presence of oxygen of up to 4.5 at.% in the (NH(4))(2)SiF(6) layer was confirmed by energy dispersive spectroscopy (EDS) analysis.

The surface of a single crystal Germanium wafer was transformed to crystals of germanium fluorides and oxides upon exposure to a vapor of HF and HNO3 chemical mixture. Structure analysis indicate that the transformation results in a germanate polycrystalline layer consisting of germanium oxide and ammonium fluogermanate with a preferential crystal growth orientation in <101> direction. Local vibrational mode analysis confirms the presence of N-H and Ge-F vibrational modes in addition to Ge-O stretching modes. Energy dispersive studies reveal the presence of hexagonal {\alpha}-phase GeO2 crystal clusters and ammonium fluogermanates around these clusters in addition to a surface oxide layer. Electronic band structure as probed by ellipsometry has been associated with the germanium oxide crystals and disorder induced band tailing effects at the interface of the germanate layer and the bulk Ge wafer. The acid vapor exposure causes Ge surface to emit a yellow photoluminescence at room temperature