Giuseppe Nicotra

How far will silicon nanocrystals push the scaling limits of NVMs technologies

For the first time, memory devices with optimized high density (2E12#/cm/sup 2/) LPCVD Si nanocrystals have been reproducibly achieved and studied on an extensive statistical basis (from single cell up to 1 Mb test-array) under different programming conditions. An original experimental and theoretical analysis of the threshold voltage shift distribution shows that Si nanocrystals have serious potential to push the scaling of NOR and NAND flash at least to the 35 nm and 65 nm nodes, respectively.

The role of the surfaces in the photon absorption in Ge nanoclusters embedded in silica.

The usage of semiconductor nanostructures is highly promising for boosting the energy conversion efficiency in photovoltaics technology, but still some of the underlying mechanisms are not well understood at the nanoscale length. Ge quantum dots (QDs) should have a larger absorption and a more efficient quantum confinement effect than Si ones, thus they are good candidate for third-generation solar cells. In this work, Ge QDs embedded in silica matrix have been synthesized through magnetron sputtering deposition and annealing up to 800°C. The thermal evolution of the QD size (2 to 10 nm) has been followed by transmission electron microscopy and X-ray diffraction techniques, evidencing an Ostwald ripening mechanism with a concomitant amorphous-crystalline transition. The optical absorption of Ge nanoclusters has been measured by spectrophotometry analyses, evidencing an optical bandgap of 1.6 eV, unexpectedly independent of the QDs size or of the solid phase (amorphous or crystalline). A simple modeling, based on the Tauc law, shows that the photon absorption has a much larger extent in smaller Ge QDs, being related to the surface extent rather than to the volume. These data are presented and discussed also considering the outcomes for application of Ge nanostructures in photovoltaics.PACS: 81.07.Ta; 78.67.Hc; 68.65.-k

Strain relaxation in high Ge content SiGe layers deposited on Si

We have used Raman spectroscopy, transmission electron microscopy, x-ray diffraction, and x-ray photoemission spectroscopy to investigate strain relaxation mechanism of Si0.22Ge0.78 heteroepitaxial layer deposited on Si substrates in tensile, neutral, and compressive strain conditions. The three regimes have been obtained by interposing between the SiGe layer and the substrate a fully relaxed Ge layer, a partially relaxed Ge layer, or growing directly the alloy on Si. We found that the deposition of a Ge buffer layer prior to the growth of the SiGe is very promising in view of the realization of thin virtual substrates on silicon to be used for the deposition of strain-controlled high Ge content SiGe alloys. We demonstrate that this is mainly due to the strain relaxation mechanism in the Ge layer occurring via insertion of pure edge 90° misfit dislocations (MDs) and to the confinement of threading arms in to the Ge layer due to a second MD network formed at the SiGe/Ge heterointerface.

Microstructural evolution of SiOx films and its effect on the luminescence of Si nanoclusters

In this paper we demonstrate that the structural and optical properties of Si nanoclusters (Si ncs) formed by thermal annealing of SiOx films prepared by plasma enhanced chemical vapor deposition (PECVD) and magnetron sputtering are very different. In fact, at a fixed Si excess and annealing temperature, photoluminescence (PL) spectra of sputtered samples are redshifted with respect to PECVD samples, denoting a larger Si ncs size. In addition, PL intensity reaches a maximum in sputtered films at annealing temperatures much lower than those needed in PECVD films. These data are correlated with structural properties obtained by energy filtered transmission electron microscopy and electron energy loss spectroscopy. It is shown that in PECVD films only around 30% of the Si excess agglomerates in clusters while an almost complete agglomeration occurs in sputtered films. These data are explained on the basis of the different initial structural properties of the as-deposited films that become crucial for the sub...

Delaminated Graphene at Silicon Carbide Facets: Atomic Scale Imaging and Spectroscopy

Atomic-resolution structural and spectroscopic characterization techniques (scanning transmission electron microscopy and electron energy loss spectroscopy) are combined with nanoscale electrical measurements (conductive atomic force microscopy) to study at the atomic scale the properties of graphene grown epitaxially through the controlled graphitization of a hexagonal SiC(0001) substrate by high temperature annealing. This growth technique is known to result in a pronounced electron-doping (∼10(13) cm(-2)) of graphene, which is thought to originate from an interface carbon buffer layer strongly bound to the substrate. The scanning transmission electron microscopy analysis, carried out at an energy below the knock-on threshold for carbon to ensure no damage is imparted to the film by the electron beam, demonstrates that the buffer layer present on the planar SiC(0001) face delaminates from it on the (112n) facets of SiC surface steps. In addition, electron energy loss spectroscopy reveals that the delaminated layer has a similar electronic configuration to purely sp2-hybridized graphene. These observations are used to explain the local increase of the graphene sheet resistance measured around the surface steps by conductive atomic force microscopy, which we suggest is due to significantly lower substrate-induced doping and a resonant scattering mechanism at the step regions. A first-principles-calibrated theoretical model is proposed to explain the structural instability of the buffer layer on the SiC facets and the resulting delamination.

Nanocrystal metal-oxide-semiconductor memories obtained by chemical vapor deposition of Si nanocrystals

We have realized nanocrystal memories by using silicon quantum dots embedded in silicon dioxide. The Si dots with the size of few nanometers have been obtained by chemical vapor deposition on very thin tunnel oxides and subsequently coated with a deposited SiO2 control dielectric. A range of temperatures in which we can adequately control a nucleation process, that gives rise to nanocrystal densities of ∼3×1011 cm−2 with good uniformity on the wafer, has been defined. The memory effects are observed in metal-oxide-semiconductor capacitors or field effect transistors by significant and reversible flat band or threshold voltage shifts between written and erased states that can be achieved by applying gate voltages as low as 5 V. The program-erase window does not exhibit any change after 105 cycles on large area cells showing that the endurance of such a memory device which uses a thinner tunnel oxide is potentially much higher than that of standard nonvolatile memories. Moreover, good retention results are ...

First and second-order Raman scattering in Si nanostructures within silicon nitride

First and second-order Raman analysis on annealed silicon nitride films is reported. Possible formation of amorphous Si nanoparticles after an intermediate treatment is deduced from the occurrence of a resonant spectrum. After nucleation of Si nanocrystals, with a model description of the first-order spectra it is possible to access information regarding mean radius, size dispersion, and crystalline phase fraction consistent with the fundamental data derived from microscopy. Substantial increase in second to first order intensity ratio is also observed: Enhanced electron–phonon coupling in both amorphous and crystalline Si nanoparticles is suggested.

Nucleation kinetics of Si quantum dots on SiO2

The formation of Si quantum dots on SiO2 by chemical vapor deposition of SiH4 has been investigated in the range from the submonolayer to the complete coverage with Si. In order to investigate the very early stages of the nucleation process of Si on SiO2, the energy filtered transmission electron microscopy has been chosen as the main characterization technique, because of the high spatial resolution typical of the transmission electron microscopy analysis, coupled to the compositional information obtained by the electron energy loss spectroscopy. The plan view configuration has been used to measure the dot size distributions down to dimensions of about 1 nm, and in cross section to evaluate the dot wetting angle. For all the several experimental conditions, a wetting angle distribution has been obtained and has shown to be centered at about 90°. Data on the dot size distributions are shown and discussed in the framework of a continuous nucleation model, which has been implemented to take into account the...

Matrix role in Ge nanoclusters embedded in Si3N4 or SiO2

Ge nanoclusters (NCs), synthesized by ion implantation and annealing up to 900 °C, result small (∼2 nm) and amorphous in Si3N4, crystalline and much larger in SiO2. The NCs ripening and crystallization kinetics in Si3N4 is retarded by larger interfacial energy and lower diffusivity of Ge in comparison to SiO2. Ge NCs absorb light more efficiently when embedded in Si3N4 than in SiO2. A significant effect of the barrier height on absorption was evidenced, in agreement with effective mass theory predictions. The smaller bandgap of Ge NCs embedded in Si3N4 and their closeness is promising features for light harvesting applications.

Quantitative determination of the clustered silicon concentration in substoichiometric silicon oxide layer

We present an analytical methodology, based on electron energy loss spectroscopy (EELS) and energy-filtered transmission electron microscopy, which allows us to quantify the clustered silicon concentration in annealed substoichiometric silicon oxide layers, deposited by plasma-enhanced chemical vapor deposition. The clustered Si volume fraction was deduced from a fit to the experimental EELS spectrum using a theoretical description proposed to calculate the dielectric function of a system of spherical particles of equal radii, located at random in a host material. The methodology allowed us to demonstrate that the clustered Si concentration is only one half of the excess Si concentration dissolved in the layer.