Synthesis and analysis of silicon nanowire below Si-Au eutectic temperatures using very high frequency plasma enhanced chemical vapor deposition

Silicon nanowires (SiNWs) were synthesized from pure silane precursor gas and Au nanoparticles catalyst at below Au-Si eutectic temperature. The SiNWs were grown onto Si (1 1 1) substrates using very high frequency plasma enhanced chemical vapor deposition via a vapor-solid-solid mechanism at temperatures ranging from 363 to 230 °C. The morphology of the synthesized SiNWs was characterized by means of field emission scanning electron microscope equipped with energy dispersive X-ray, high resolution transmission electron microscopy, X-ray diffraction technique and Raman spectroscope. Results demonstrated that the SiNWs can be grown at the temperature as low as 250 °C. In addition, it was revealed that the grown wires were silicon-crystallized.     

Selective formation of silicon nanowires on pre-patterned substrates

In this paper, the selective growth of silicon nanowires (SiNWs) was studied. With the aid of photolithography, the vertically aligned silicon nanowires were selectively formed on the patterned substrates via an electroless metal deposition (EMD) method under normal conditions (room temperature, 1 atm). Low-pressure chemical vapor deposition (LPCVD) silicon nitride was used as the masking layer for SiNWs preparation. The scanning electron microscope was used to examine the etching results. Both the patterned and the unpatterned silicon substrates were used for study. The results indicated that the growth rates of the SiNWs upon the patterned and the unpatterned substrates are different. For the patterned substrates, the growth rate of SiNWs is dependent upon the pattern shape. The influence of length-to-width ratio for the rectangular-shaped patterns was studied. It is concluded that by designing the proper length-to-width ratio, the nanowires with different lengths can be fabricated simultaneously on the same substrate.     

Catalyst formation at various temperatures by hydrogen radical treatment and synthesis of silicon nanowires

Metal nanocrystals as catalyst from a metal oxide film were fabricated at various temperatures after hydrogen radical treatment and great quantities of silicon nanowires (SiNWs) were successfully synthesized using the hydrogen microwave afterglow deposition method. Indium (In) metal nanocrystals with size of about 12 nm were obtained from indium oxide film after hydrogen radical pre-treatment for 5 min at 400 °C and their quantity reached approximately 3 × 10¹⁰ cm⁻². Subsequently, a numerous SiNWs were grown with the crystal diffraction of (1 1 1), (2 2 0) and (3 1 1). The diameters of the SiNWs mainly ranged from 5 to 120 nm and their lengths extended to about 8.5 μm.     

Competition between surface energy and interphase energy in transition region and diameter-dependent orientation of silicon nanowires

A small sandwiched transition region between the Au catalysis droplet and silicon nanowires (SiNWs) is proposed to investigate the diameter-dependent orientation of SiNWs grown by the vapor-liquid-solid (VLS) mechanism. Atomic-scale calculation shows that for a given transition region width, there is always a critical diameter. Below the critical value, surface energy dominates and the 〈1 1 0〉 orientation is preferred, whereas at larger diameters, the interphase energy dominates and SiNWs grow along the 〈1 1 1〉 direction. The variability of the critical diameter is also included in our model by adjusting the transition region width. The theoretical results are in agreement with those from experiments.     

Photoluminescence from Er-doped silicon rich oxide thin films

 Photoluminescence (PL) properties of Er-doped silicon rich oxide thin films deposited on Si substrate by co-evaporation of silicon monoxide and Er under different atmospheres are investigated. The samples exhibit luminescence peak at 1.54 μm which could be assigned to the recombination in intra-4f Er³⁺ transition. PL shows that this transition is highest when ammonia atmosphere is used during deposition followed by an annealing temperature at 850 °C in 95% N₂+5% H₂ gas (forming gas). In fact, we believe that the presence of the N atoms around Er ions increases the intensity of the 1.54 μm luminescence.     

Enhanced field emission and patterned emitter device fabrication of metal-tetracyanoquinodimethane nanowires array

Ag(TCNQ) and Cu(TCNQ) nanowires were synthesized via vapor-transport reaction method at a low temperature of 100 °C. Field emission properties of the as-obtained nanowires on ITO glass substrates were studied. The turn-on electric fields of Ag(TCNQ) and Cu(TCNQ) nanowires were 9.7 and 7.6 V/μm (with emission current of 10 μA/cm²), respectively. The turn-on electric fields of Ag(TCNQ) and Cu(TCNQ) nanowires decreased to 6 and 2.2 V/μm, and the emission current densities increased by two orders at a field of 8 V/μm with a homogeneous-like metal (e.g. Cu for Cu(TCNQ)) buffer layer to the substrate. The improved field emission is due to the better conduct in the nanowires/substrate interface and higher internal conductance of the nanowires. The patterned field emission cathode was then fabricated by localized growing M-TCNQ nanowires onto mask-deposited metal film buffer layer. The emission luminance was measured to be 810 cd/m² at a field of 8.5 V/μm.     

Sulfide-assisted growth of silicon nano-wires by thermal evaporation of sulfur powders

Silicon nanowires (SiNWs) with a diameter of 20 nm were synthesized by the thermal evaporation of sulfur powders on silicon wafers. The source of the SiNWs came from the silicon substrates. It is considered that the generated SiS compound assisted the formation of SiNWs. Finally, the Raman shift of SiNWs was discussed.     

Fluorescence sensor for Cu(II) based on R6G derivatives modified silicon nanowires

A fluorescence sensor for selective detection of Cu(II) is realized by covalently immobilizing derivatives of rhodamine6G (R6G) on the surface of silicon nanowires (SiNWs). It features the release of R6G from the SiNWs in the presence of Cu(II), which causes a significant enhancement of the fluorescence over other metal ions. The present Cu(II) sensor has good selectivity and sensitivity, and exhibits a linear response in the range of 0.0-7.0 μM Cu(II). Different from conventional Cu(II) sensor with fluorescence quenching, the present sensor based on fluorescence enhancement facilitates the practical application. Especially, the release of the R6G from SiNWs could be utilized as fluorescent labeling for Cu(II) in microenvironment.     

Raman spectroscopy and field electron emission properties of aligned silicon nanowire arrays

Arrays of aligned silicon nanowire (SiNW) were synthesized on a silicon (1 0 0) substrate by self-assembling electroless nanoelectrochemistry. Compared with that of bulk crystal silicon, the first-order Raman peak of the silver cap-removed SiNW arrays shows a downshift and asymmetric broadening due to the phonon quantum confinement effects, and intensity enhancement. Field electron emission from the SiNWs was also investigated. The turn-on field was found to be about 12 V/μm at a current density of 0.01 mA/cm². These highly densified and ordered SiNW arrays can be expected to have favorable applications in vacuum electronic or optoelectronic devices.     

Study of porous carbon thin films produced by pulsed laser deposition

Amorphous carbon is an interesting material and its properties can be varied by tuning its diamond-like (sp³) fractions. The diamond-like fractions in an amorphous carbon films depends on the kinetic energy of the deposited carbon ions. Porous amorphous carbon thin films were deposited onto silicon substrates at room temperature in a vacuum chamber by Glancing Angle Pulsed Laser Deposition (GAPLD). Krypton fluoride (248 nm) laser pulses with duration of 15 ns and intensities of 1-20 GW/cm² were used. In GAPLD, the angles between the substrate normal and the trajectory of the incident deposition flux are set to be almost 90°. Porous thin films consisting of carbon nanowires with diameters less than 100 nm were formed due to a self-shadowing effect. The kinetic energies of the deposited ions, the deposition rate of the films and the size of the nanowires were investigated. The sp³ fraction of the porous carbon films produced at intensity around 20 GW/cm² were estimated from their Raman spectra.     

The optoelectronic properties of silicon films deposited by inductively coupled plasma CVD

Hydrogenated amorphous and microcrystalline silicon films were deposited by inductively coupled plasma chemical vapor deposition (ICP-CVD) at low substrate temperatures using H₂-diluted SiH₄ as a source gas. High-density plasma generated by inductively coupled excitation facilitates the crystallization of silicon films at low temperatures, and microcrystalline silicon films were obtained at the substrate temperature as low as 180 °C. The columnar structure of the films becomes more and more compact with an increase of their crystallinity. The reduction of hydrogen content in the films causes a narrowing of the optical bandgap and an enhancement of the absorption with increasing the substrate temperature. The microcrystalline silicon films show two electronic transport mechanisms: one is related to the density of state distribution in the temperature region near room temperature and the other is the variable range hopping between localized electronic states close to the Fermi level below 170 K. A reasonable explanation is presented for the dependence of the optoelectronic properties on the microstructure of the silicon films. The films prepared at a substrate temperature of 300 °C have highly crystalline and compact columnar structure, high optical absorption coefficient and electrical conductivity, and a low hydrogen content of 3.8%.     

STM study of acetylene reaction with Si(1 1 1): observation of a carbon-induced Si(1 1 1)√3×√3R30° reconstruction

The first stages of acetylene reaction with the Si(1 1 1)7 × 7 reconstructed surface kept at 600 °C are studied by recording scanning tunneling microscopy (STM) images during substrate exposure at a C₂H₂ pressure of 2 × 10⁻⁴ Pa (2 × 10⁻² mbar). We observed the progressive substitution of the 7 × 7 reconstruction with a carbon induced Si(1 1 1)√3×√3R30° reconstruction characterized by an atomic distance of 0.75 ± 0.02 nm, very close to that of the silicon 7 × 7 adatoms. This means that a carbon enrichment of the silicon outermost layers occurs giving rise to the formation of a Si-C phase different from the √3×√3R30° reconstruction typical of Si terminated hexagonal SiC(0 0 0 1) surface with an atomic distance of 0.53 nm. To explain STM images, we propose a reconstruction model which involves carbon atoms in T₄ and/or S₅ sites, as occurring for B doped Si(1 1 1) surface. Step edges and areas around the silicon surface defects are the first regions involved in the reaction process, which spreads from the upper part of the step edges throughout the terraces. Step edges therefore, progressively flakes and this mechanism leads, for the highest exposures, to the formation of large inlets which makes completely irregular the straight edge typical of the Si(1 1 1)7 × 7 terraces. These observations indicate that there occurs an atomic diffusion like that driving the meandering effect. Finally, the formation of a few crystallites is shown also at the lowest acetylene exposures. This is the first STM experiment showing the possibility to have carbon incorporation in a Si(1 1 1) matrix for higher amounts than expected, at least up to 1/6 of silicon atomic layer.     

Evidence of formation of tetravacancies in uniformly oxygen irradiated n-type silicon

High purity n-type silicon single crystal with resistivity in the order of 4000 Ω cm has been irradiated with high-energy oxygen ions at room temperature up to a fluence of 5E15 ions/cm². The energy of the beam was varied from 3 to 140 MeV using a rotating degrader to achieve a depthwise near-uniform implantation profile. Radiation induced defects and their dynamics have been studied using positron annihilation spectroscopy along with isochronal annealing up to 700 °C in steps of 50 °C for 30 min. After annealing the sample at 200 °C for 30 min, formation of silicon tetravacancies has been noticed. The formation of the tetravacancies was found to be due to agglomeration of divacancies present in the irradiated sample. An experimentally obtained positron lifetime value of 338±10 ps has been reported for silicon tetravacancies, which has a very close agreement with the value obtained from recent theoretical calculations. The tetravacancies were found to dissociate into trivacancy clusters upon further annealing. The trivacancies thus obtained were observed to agglomerate beyond 400 °C to form larger defect clusters. Finally, all the defects were found to anneal out after annealing the sample at 650 °C.     

Effects of post-thermal annealing temperature on the optical and structural properties of gold particles on silicon suboxide films

In this work, silicon suboxide (SiO_x) thin films were deposited using a RF magnetron sputtering system. A thin layer of gold (Au) with a thickness of about 10 nm was sputtered onto the surface of the deposited SiO_x films prior to the thermal annealing process at 400 °C, 600 °C, 800 °C and 1000 °C. The optical and structural properties of the samples were studied using scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR) and optical transmission and reflection spectroscopy. SEM analyses demonstrated that the samples annealed at different temperatures produced different Au particle sizes and shapes. SiO_x nanowires were found in the sample annealed at 1000 °C. Au particles induce the crystallinity of SiO_x thin films in the post-thermal annealing process at different temperatures. These annealed samples produced silicon nanocrystallites with sizes of less than 4 nm, and the Au nanocrystallite sizes were in the range of 7-23 nm. With increased annealing temperature, the bond angle of the Si-O bond increased and the optical energy gap of the thin films decreased. The appearance of broad surface plasmon resonance absorption peaks in the region of 590-740 nm was observed due to the inclusion of Au particles in the samples. The results show that the position and intensity of the surface plasmon resonance peaks can be greatly influenced by the size, shape and distribution of Au particles.     

Annealing ambient on the evolution of He-induced voids in silicon

The effects of annealing ambient on the He-induced voids in silicon were investigated using the combination of the Doppler broadening spectroscopy using a variable-energy positron beam and cross-section transmission electron microscopy (XTEM). A 〈1 0 0〉-oriented silicon wafer was implanted with He ions at an energy of 15 keV to a dose of 2 × 10¹⁶ cm⁻² at room temperature. Post-implantation, the samples were annealed at a temperature of 1000 °C in the ambient of vacuum, argon, nitrogen, air and oxygen. Positron annihilation spectroscopy (PAS) spectra varied with the annealing ambient. XTEM micrographs demonstrated that the density of He-induced voids could be influenced by the annealing ambient.     

Structural and photoluminescence properties of Si nanoclusters obtained by ion implantation into Si3N4 films

In the present paper we report structural and photoluminescence (PL) results from samples obtained by Si implantation into stoichiometric silicon nitride (Si₃N₄) films. The Si excess was introduced in the matrix by 170 keV Si implantation performed at different temperatures with a fluence of Φ=1×10¹⁷ Si/cm². The annealing temperature was varied between 350 and 900 °C in order to form the Si precipitates. PL measurements, with a 488 nm Ar laser as an excitation source, show two superimposed broad PL bands centered around 760 and 900 nm. The maximum PL yield is achieved for the samples annealed at 475 °C. Transmission electron microscopy (TEM) measurements show the formation of amorphous nanoclusters and their evolution with the annealing temperature.     

Effect of substrate temperature on gold-catalyzed silicon nanostructures growth by hot-wire chemical vapor deposition (HWCVD)

The effect of substrate temperature on the structural property of the silicon nanostructures deposited on gold-coated crystal silicon substrate by hot-wire chemical vapor deposition (HWCVD) was studied. The uniformity and size of the as-grown silicon nanostructures is highly influenced by the substrate temperature. XRD, Raman and HRTEM measurements show the silicon nanostructures consist of small crystallites embedded within amorphous matrix. The crystallite size of the as-grown silicon nanostructures decreases with increases in substrate temperature. FTIR shows that these silicon nanostructures are highly disordered for sample prepared at substrate temperature above 250 °C. The correlation of crystallinity and structure disorder of the silicon nanostructures growth at different substrate temperature was discussed.     

Partial crystallization of silicon by high intensity laser irradiation

Commercial single crystal silicon wafers and amorphous silicon films piled on single crystal silicon wafers were irradiated with a femtosecond pulsed laser and a nanosecond pulsed laser at irradiation intensities between 10¹⁷ W/cm² and 10⁹ W/cm². In the single crystal silicon substrate, the irradiated area was changed to polycrystalline silicon and the piled silicon around the irradiated area has spindly column structures constructed of polycrystalline and amorphous silicon. In particular, in the case of the higher irradiation intensity of 10¹⁶ W/cm², the irradiated area was oriented to the same crystal direction as the substrate. In the case of the lower irradiation intensity of 10⁸ W/cm², only amorphous silicon was observed around the irradiated area, even when the target was single crystal silicon. In contrast, only amorphous silicon particles were found to be piled on the amorphous silicon film, irrespective of the intensity and pulse duration.Three-dimensional thermal diffusion equation for the piled particles on the substrate was solved by using the finite difference methods. The results of our heat-flow simulation of the piled particles almost agree with the experimental results.     

Auger and photoluminescence analysis of ZnO nanowires grown on AlN thin film

ZnO nanowires were grown on AlN thin film deposited on the glass substrates using a physical vapor deposition method in a conventional tube furnace without introducing any catalysts. The temperature of the substrates was maintained between 500 and 600 °C during the growth process. The typical average diameters of the obtained nanowires on substrate at 600 and 500 °C were about 57 and 22 nm respectively with several micrometers in length. X-ray diffraction and Auger spectroscopy results showed Al diffused from AlN thin film into the ZnO nanowires for the sample grown at 600 °C. Photoluminescence of the nanowires exhibits appearance of two emission bands, one related to ultraviolet emission with a strong peak at 380-382 nm, and the other related to deep level emission with a weak peak at 503-505 nm. The ultraviolet peak of the nanowires grown at 500 °C was blue shifted by 2 nm compared to those grown at 600 °C. This shift could be attributed to surface effect.     

Silicon nano-wires fabricated by a novel thermal evaporation of zinc sulfide

Silicon nano-wires (SiNWs) with diameter of 30 nm and length of tens of micrometers on silicon wafers were synthesized by a novel thermal evaporation of zinc sulfide. After thermal evaporation at 1080°C for 1 h, crystalline SiNWs were produced. It was found that the tip of SiNWs contained sulfur, while the other places of SiNWs did not. It is considered that the decomposition of SiS resulted in the formation of SiNWs. On the basis of the facts, a sulfide-assisted growth model of SiNWs was suggested.