Advanced numerical characterization of silicon with defect by nanoindentation

Nano silicon is widely used as the essential element of complementary metal–oxide–semiconductor (CMOS) and solar cells. It is recognized that today, large portion of world economy is built on electronics products and related services. Due to the accessible fossil fuel running out quickly, there are increasing numbers of researches on the nano silicon solar cells. The further improvement of higher performance nano silicon components requires characterizing the material properties of nano silicon. Specially, when the manufacturing process scales down to the nano level, the advanced components become more and more sensitive to the various defects induced by the manufacturing process. It is known that defects in mono-crystalline silicon have significant influence on its properties under nanoindentation. However, the cost involved in the practical nanoindentation as well as the complexity of preparing the specimen with controlled defects slow down the further research on mechanical characterization of defected silicon by experiment. Therefore, in current study, the molecular dynamics (MD) simulations are employed to investigate the mono-crystalline silicon properties with different pre-existing defects, especially cavities, under nanoindentation. Parametric studies including specimen size and loading rate, are firstly conducted to optimize computational efficiency. The optimized testing parameters are utilized for all simulation in defects study. Based on the validated model, different pre-existing defects are introduced to the silicon substrate, and then a group of nanoindentation simulations of these defected substrates are carried out. The simulation results are carefully investigated and compared with the perfect Silicon substrate which used as benchmark. It is found that pre-existing cavities in the silicon substrate obviously influence the mechanical properties. Furthermore, pre-existing cavities can absorb part of the strain energy during loading, and then release during unloading, which possibly causes less plastic deformation to the substrate. However, when the pre-existing cavities is close enough to the deformation zone or big enough to exceed the bearable stress of the crystal structure around the spherical cavity, the larger plastic deformation occurs which leads the collapse of the structure. Meanwhile, the influence exerted on the mechanical properties of silicon substrate depends on the location and size of the cavity. Substrate with larger cavity size or closer cavity position to the top surface, usually exhibits larger reduction on Young’s modulus and hardness.

The effect of silicate ions on proliferation, osteogenic differentiation and cell signalling pathways (WNT and SHH) of bone marrow stromal cells

Silicon (Si) is a trace element, which plays an important role in human bone growth. Si has been incorporated into biomaterials for bone regeneration in order to improve their osteogenic potential, both in vitro and in vivo. Little is known, however, as to how Si ions elicit their biological response on bone-forming cells. The aim of this study was to investigate the effect of Si ions on the proliferation, differentiation, bone-related gene expression and cell signalling pathways of bone marrow stromal cells (BMSCs) by comparing the BMSC responses to different concentrations of NaCl and Na2SiO3, while taking into account and excluding the effect of Na ions. Our study showed that Si ions at a concentration of 0.625 mM significantly enhanced the proliferation, mineralization nodule formation, bone-related gene expression (OCN, OPN and ALP) and bone matrix proteins (ALP and OPN) of BMSCs. Furthermore, Si ions at 0.625 mM could counteract the effect of the WNT inhibitor (W.I.) cardamonin on the osteogenic genes expression, (OPN, OCN and ALP), WNT and SHH signalling pathway-related genes in BMSCs. These results suggest that Si ions by themselves play an important role in regulating the proliferation and osteogenic differentiation of BMSCs, with the involvement of WNT and SHH signalling pathways. Our study provides evidence to explain possible molecular mechanisms whereby Si ions released from Si-containing biomaterials can acquire enhanced bioactivity at desired concentration.

Hydrogen gas sensing properties of Pt/Ta2O5 Schottky diodes based on Si and SiC substrates

We developed Pt/tantalum oxide (Ta2O5) Schottky diodes for hydrogen sensing applications. Thin layer (4 nm) of Ta2O5 was deposited on silicon (Si) and silicon carbide (SiC) substrates using the radio frequency sputtering technique. We compared the performance of these sensors at different temperatures of 100 °C and 150 °C. At these operating temperatures, the sensor based on SiC exhibited a larger sensitivity, whilst the sensor based on Si exhibited a faster response toward hydrogen gas. We discussed herein, the experimental results obtained for these Pt/Ta2O5 based Schottky diodes exhibited that they are promising candidates for hydrogen sensing applications.

A mass spectrometry study of XCO+, X = Si, Ge : Is SiCO+ a main group carbonyl? Comments on the bonding in ground state SiCO and the Si,C,O (+) potential energy surface

The cation\[Si,C,O](+) has been generated by 1) the electron ionisation (EI) of tetramethoxysilane and 2) chemical ionisation (CI) of a mixture of silane and carbon monoxide. Collisional activation (CA) experiments performed for mass-selected \[Si,C,O](+), generated by using both methods, indicate that the structure is not inserted OSiC+; however, a definitive structural assignment as Si+-CO, Si+-OC or some cyclic variant is impossible based on these results alone. Neutralisation-reionisation (+NR+) experiments for EI-generated \[Si,C,O](+) reveal a small peak corresponding to SiC+, but no detectable SiO+ signal, and thus establishes the existence of the Si+-CO isomer. CCSD(T)//B3LYP calculations employing a triple-zeta basis set have been used to explore the doublet and quartet potential-energy surfaces of the cation, as well as some important neutral states The results suggest that both Si+-CO and Si+ - OC isomers are feasible; however, the global minimum is (2)Pi SiCO+. Isomeric (2)Pi SiOC+ is 12.1 kcal mol(-1) less stable than (2)Pi SiCO+, and all quartet isomers are much higher in energy. The corresponding neutrals Si-CO and Si-OC are also feasible, but the lowest energy Si - OC isomer ((3)A") is bound by only 1.5 kcal mol(-1). We attribute most, if nor all, of the recovery signal in the +NR' experiment to SiCO+ survivor ions. The nature of the bonding in the lowest energy isomers of Si+ -(CO,OC) is interpreted with the aid of natural bond order analyses, and the ground stale bonding of SiCO+ is discussed in relation to classical analogues such as metal carbonyls and ketenes.

The effect of microscopic texture on the direct plasma surface passivation of Si solar cells

Textured silicon surfaces are widely used in manufacturing of solar cells due to increasing the light absorption probability and also the antireflection properties. However, these Si surfaces have a high density of surface defects that need to be passivated. In this study, the effect of the microscopic surface texture on the plasma surface passivation of solar cells is investigated. The movement of 105 H+ ions in the texture-modified plasma sheath is studied by Monte Carlo numerical simulation. The hydrogen ions are driven by the combined electric field of the plasma sheath and the textured surface. The ion dynamics is simulated, and the relative ion distribution over the textured substrate is presented. This distribution can be used to interpret the quality of the Si dangling bonds saturation and consequently, the direct plasma surface passivation.

Plasma-enabled, catalyst-free growth of carbon nanotubes on mechanically-written Si features with arbitrary shape

Simple, rapid, catalyst-free synthesis of complex patterns of long, vertically aligned multiwalled carbon nanotubes, strictly confined within mechanically-written features on a Si(1 0 0) surface is reported. It is shown that dense arrays of the nanotubes can nucleate and fully fill the features when the low-temperature microwave plasma is in a direct contact with the surface. This eliminates additional nanofabrication steps and inevitable contact losses in applications associated with carbon nanotube patterns. Using metal catalyst has long been considered essential for the nucleation and growth of surface-supported carbon nanotubes (CNTs) [1] and [2]. Only very recently, the possibility of CNT growth using non-metallic (e.g., oxide [3] and SiC [4]) catalysts or artificially created carbon-enriched surface layers [5] has been demonstrated. However, successful integration of carbon nanostructures into Si-based nanodevice platforms requires catalyst-free growth, as the catalyst nanoparticles introduce contact losses, and their catalytic activity is very difficult to control during the growth [6]. Furthermore, in many applications in microfluidics, biological and molecular filters, electronic, sensor, and energy conversion nanodevices, the CNTs need to be arranged in specific complex patterns [7] and [8]. These patterns need to contain the basic features (e.g., lines and dots) written using simple procedures and fully filled with dense arrays of high-quality, straight, yet separated nanotubes. In this paper, we report on a completely metal or oxide catalyst-free plasma-based approach for the direct and rapid growth of dense arrays of long vertically-aligned multi-walled carbon nanotubes arranged into complex patterns made of various combinations of basic features on a Si(1 0 0) surface written using simple mechanical techniques. The process was conducted in a plasma environment [9] and [10] produced by a microwave discharge which typically generates the low-temperature plasmas at the discharge power below 1 kW [11]. Our process starts from mechanical writing (scribing) a pattern of arbitrary features on pre-treated Si(1 0 0) wafers. Before and after the mechanical feature writing, the Si(1 0 0) substrates were cleaned in an aqueous solution of hydrofluoric acid for 2 min to remove any possible contaminations (such as oil traces which could decompose to free carbon at elevated temperatures) from the substrate surface. A piece of another silicon wafer cleaned in the same way as the substrate, or a diamond scriber were used to produce the growth patterns by a simple arbitrary mechanical writing, i.e., by making linear scratches or dot punctures on the Si wafer surface. The results were the same in both cases, i.e., when scratching the surface by Si or a diamond scriber. The procedure for preparation of the substrates did not involve any possibility of external metallic contaminations on the substrate surface. After the preparation, the substrates were loaded into an ASTeX model 5200 chemical vapour deposition (CVD) reactor, which was very carefully conditioned to remove any residue contamination. The samples were heated to at least 800 °C to remove any oxide that could have formed during the sample loading [12]. After loading the substrates into the reactor chamber, N2 gas was supplied into the chamber at the pressure of 7 Torr to ignite and sustain the discharge at the total power of 200 W. Then, a mixture of CH4 and 60% of N2 gases were supplied at 20 Torr, and the discharge power was increased to 700 W (power density of approximately 1.49 W/cm3). During the process, the microwave plasma was in a direct contact with the substrate. During the plasma exposure, no external heating source was used, and the substrate temperature (∼850 °C) was maintained merely due to the plasma heating. The features were exposed to a microwave plasma for 3–5 min. A photograph of the reactor and the plasma discharge is shown in Fig. 1a and b.

Plasma enables edge-to-center-oriented graphene nanoarrays on Si nanograss

The formation of clearly separated vertical graphenenanosheets on silicon nanograss support is demonstrated. The plasma-enabled, two-stage mask-free process produced self-organized vertical graphenes of a few carbon layers (as confirmed by advanced microanalysis), prominently oriented in the substrate center–substrate edge direction. It is shown that the width of the alignment zone depends on the substrate conductivity, and thus the electric field in the vicinity of the growth surface is responsible for the graphene alignment. This finding is confirmed by the Monte Carlo simulations of the ion flux distribution in the silicon nanograss pattern.

Plasma-enabled growth of single-crystalline SiC/AlSiC Core–Shell nanowires on porous alumina templates

We report the catalyst-free synthesis of the arrays of core–shell, ultrathin, size-uniform SiC/AlSiC nanowires on the top of a periodic anodic aluminum oxide template. The nanowires were grown using an environmentally friendly, silane-free process by exposing the silicon supported porous alumina template to CH4 + H2 plasmas. High-resolution scanning and transmission electron microscopy studies revealed that the nanowires have a single-crystalline core with a diameter of about 10 nm and a thin (1–2 nm) amorphous AlSiC shell. Because of their remarkable length, high aspect ratio, and very high surface area-to-volume ratio, these unique structures are promising for nanoelectronic and nanophotonic applications that require efficient electron emission, light scattering, etc. A mechanism for nanowire growth is proposed based upon the reduction of the alumina template to nanosized metallic aluminum droplets forming between nanopores. The subsequent incorporation of silicon and carbon atoms from the plasma leads to nucleation and growth from the top of the alumina template.

Highly efficient silicon nanoarray solar cells by a single-step plasma-based process

Highly efficient solar cells (conversion efficiency 11.9%, fill factor 70%) based on the vertically aligned single-crystalline nanostructures are fabricated without any pre-fabricated p-n junctions in a very simple, single-step process of Si nanoarray formation by etching p-type Si(100) wafers in low-temperature environment-friendly plasmas of argon and hydrogen mixtures.

Plasma-made silicon nanograss and related nanostructures

Plasma-made nanostructures show outstanding potential for applications in nanotechnology. This paper provides a concise overview on the progress of plasma-based synthesis and applications of silicon nanograss and related nanostructures. The materials described here include black silicon, Si nanotips produced using a self-masking technique as well as self-organized silicon nanocones and nanograss. The distinctive features of the Si nanograss, two-tier hierarchical and tilted nanograss structures are discussed. Specific applications based on the unique features of the silicon nanograss are also presented.

Kinetics of the initial stage of silicon surface oxidation : Deal–Grove or surface nucleation?

The nucleation-initiated oxidation of a Si surface at very low temperatures in plasmas is demonstrated experimentally, in contrast to the Deal-Grove mechanism, which predicts Si oxidation at a Si/SiO interface and cannot adequately describe the formation of SiO nanodots and oxidation rates at very low (several nanometers) oxide thickness. Based on the experimental results, an alternative oxidation scenario is proposed and supported by multiscale numerical simulations suggesting that saturation of micro- and nanohillocks with oxygen is a trigger mechanism for initiation of Si surface oxidation. This approach is generic and can be applied to describe the kinetics of low-temperature oxidation of other materials. © 2009 American Institute of Physics.

Self-organized vertically aligned single-crystal silicon nanostructures with controlled shape and aspect ratio by reactive plasma etching

The formation of vertically aligned single-crystalline silicon nanostructures via "self-organized" maskless etching in Ar+ H 2 plasmas is studied. The shape and aspect ratio can be effectively controlled by the reactive plasma composition. In the optimum parameter space, single-crystalline pyramid-like nanostructures are produced; otherwise, nanocones and nanodots are formed. This generic nanostructure formation approach does not involve any external material deposition. It is based on a concurrent sputtering, etching, hydrogen termination, and atom/radical redeposition and can be applied to other nanomaterials.

Controlled-bandgap silicon nitride nanomaterials : deterministic nitrogenation in high-density plasmas

To overcome major problems associated with insufficient incorporation of nitrogen in hydrogenated amorphous silicon nitride (a-SiNx:H) nanomaterials, which in turn impedes the development of controlled-bandgap nanodevices, here we demonstrate the possibility to achieve effective bandgap control in a broad range by using high-density inductively coupled plasmas. This achievement is related to the outstanding dissociation ability of such plasmas. It is shown that the compositional, structural, optical, and morphological properties of the synthesized a-SiNx:H nanomaterials can be effectively tailored through the manipulation of the flow rate ratio of the silane to nitrogen gases X. In particular, a wide bandgap of 5.21 eV can be uniquely achieved at a low flow rate ratio of the nitrogen to silane gas of 1.0, whereas typically used values often exceed 20.0. These results are highly-relevant to the development of the next-generation nanodevices that rely on the effective control of the functional nano-layer bandgap energies.

Effect of elemental composition and size on electron confinement in self-assembled SiC quantum dots : a combinatorial approach

A high level of control over quantum dot (QD) properties such as size and composition during fabrication is required to precisely tune the eventual electronic properties of the QD. Nanoscale synthesis efforts and theoretical studies of electronic properties are traditionally treated quite separately. In this paper, a combinatorial approach has been taken to relate the process synthesis parameters and the electron confinement properties of the QDs. First, hybrid numerical calculations with different influx parameters for Si1-x Cx QDs were carried out to simulate the changes in carbon content x and size. Second, the ionization energy theory was applied to understand the electronic properties of Si1-x Cx QDs. Third, stoichiometric (x=0.5) silicon carbide QDs were grown by means of inductively coupled plasma-assisted rf magnetron sputtering. Finally, the effect of QD size and elemental composition were then incorporated in the ionization energy theory to explain the evolution of the Si1-x Cx photoluminescence spectra. These results are important for the development of deterministic synthesis approaches of self-assembled nanoscale quantum confinement structures.

Surface plasmon enhancement of optical absorption in thin-film silicon solar cells

Strong electromagnetic field enhancement that occurs under conditions of the surface plasmon excitation in metallic nanoparticles deposited on a semiconductor surface is a very efficient and promising tool for increasing the optical absorption within semiconductor solar cells and, hence, their photocurrent response. The enhancement of the optical absorption in thin-film silicon solar cells via the excitation of localized surface plasmons in spherical silver nanoparticles is investigated. Using the effective medium model, the effect of the nanoparticle size and the surface coverage on that enhancement is analyzed. The optimum configuration and the nanoparticle parameters leading to the maximum enhancement in the optical absorption and the photocurrent response in a single p-n junction silicon cell are obtained. The effect of coupling between the silicon layer and the surface plasmon fields on the efficiency of the above enhancement is quantified as well.