Effects of gas pressure on the synthesis and photoluminescence properties of Si nanowires in VHF-PECVD method

Silicon nanowires (SiNWs) were grown on an Au-coated Si(111) substrate at various gas pressures by very high frequency plasma enhanced chemical vapor deposition via the vapor–liquid–solid mechanism. The synthesized SiNWs were characterized by field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, high-resolution transmission electron microscopy, Raman spectroscopy and photoluminescence (PL). The SiNWs were sharp needle-shaped and possessed highly crystalline core and oxide amorphous shell. As the gas pressure increases from 70 mtorr to 85 mtorr, the average diameter of the SiNWs decreases from 250 nm to 70 nm. Furthermore, the density of the nanowires increases with the gas pressure. The PL spectra revealed a peak at about 400 nm and a broadband emission at about 700 nm.     

Structural investigations of silicon nanostructures grown by self-organized island formation for photovoltaic applications

The self-organized growth of crystalline silicon nanodots and their structural characteristics are investigated. For the nanodot synthesis, thin amorphous silicon (a-Si) layers with different thicknesses have been deposited onto the ultrathin (2 nm) oxidized (111) surface of Si wafers by electron beam evaporation under ultrahigh vacuum conditions. The solid phase crystallization of the initial layer is induced by a subsequent in situ annealing step at 700 °C, which leads to the dewetting of the initial a-Si layer. This process results in the self-organized formation of highly crystalline Si nanodot islands. Scanning electron microscopy confirms that size, shape, and planar distribution of the nanodots depend on the thickness of the initial a-Si layer. Cross-sectional investigations reveal a single-crystalline structure of the nanodots. This characteristic is observed as long as the thickness of the initial a-Si layer remains under a certain threshold triggering coalescence. The underlying ultra-thin oxide is not structurally affected by the dewetting process. Furthermore, a method for the fabrication of close-packed stacks of nanodots is presented, in which each nanodot is covered by a 2 nm thick SiO₂ shell. The chemical composition of these ensembles exhibits an abrupt Si/SiO₂ interface with a low amount of suboxides. A minority charge carrier lifetime of 18 µs inside of the nanodots is determined.     

Evolution and defect analysis of vertical graphene nanosheets

We report catalyst‐free direct synthesis of vertical graphene nanosheets (VGNs) on SiO₂/Si and quartz substrates using microwave electron cyclotron resonance – plasma enhanced chemical vapor deposition. The evolution of VGNs is studied systematically at different growth stages. Raman analysis as a function of growth time reveals that two different disorder‐induced competing mechanisms contributing to the defect band intensity. The VGNs grown on SiO₂/Si substrates predominantly consists of both vacancy‐like and hopping defects. On the other hand, the VGNs grown on quartz substrates contain mainly boundary‐like defects. X‐ray photoemission spectroscopy studies also corroborate Raman analysis in terms of defect density and vacancy‐like defects for the VGNs grown on SiO₂/Si substrates. Moreover, the grown VGNs exhibit a high optical transmittance from 95% to 78% at 550 nm and the sheet resistance varies from 30 to 2.17 kΩ/sq. depending on growth time. Copyright © 2014 John Wiley & Sons, Ltd.     

Synchrotron radiation interference in front of the silicon absorption edge for silicon-on-insulator structures

The synchrotron radiation (SR) interference phenomenon has been for the first time observed in a strained silicon nanolayer deposited on a dielectric SiO₂ layer (∼150 nm) on Si (100) single crystalline substrates (silicon-on-insulator (SOI) structures). Strong oscillations of spectra intensity depending on photon energy have been detected in the energy range preceding the elementary silicon Si L _2,3 absorption edge (≤100 eV) at grazing angles of SR smaller than 21° in the X-ray photoeffect quantum yield structure. The phase of the spectra oscillation structure is reversed for small variations of grazing angle in the 4°–21° range. The silicon nanolayer thickness (∼180 nm) has been estimated in the three-layer, Si nanolayer-SiO₂-Si substrate structure with the use of neighbor maxima positions of ultrasoft X-ray radiation interference in XANES (X-ray absorption near edge structure) spectra. A decrease in the crystal lattice parameter of a strained silicon layer along the normal to substrate has been determined by X-ray diffraction. An increase in the Si-Si interatomic distances in the strained silicon nanolayer lattice of SOI structure has been found using ultrasoft X-ray emission spectroscopy data.     

Influence of substrate temperature and ion-beam energy on the syntheses of aluminium nitride thin films by nitrogen-ion-assisted pulsed-laser deposition

Aluminium nitride (AlN) thin films have been grown on Si(100), Si(111) and Sapphire Al₂O₃(001) substrates by pulsed KrF excimer laser (wavelength 248 nm, duration 30 ns) ablation of an AlN target with the assistance of nitrogen-ion-beam bombardment. The influence of process parameters such as substrate temperature and ion-beam energy has been investigated in order to obtain high-quality AlN films. The AlN films deposited by pulsed-laser deposition (PLD) have been characterized by X-ray diffraction (XRD) to determine the crystalline quality, grain size and growth orientation with respect to the substrate. The XRD spectra of AlN films on Si(100), Si(111) and Sapphire substrates yield full-width-half-maximum (FWHM) values of approximately 1.6. The bonding characteristics in the films have been evaluated by Raman spectroscopy. The chemical composition of the films has been characterized by X-ray photoelectron spectroscopy (XPS). The surface morphology of the films has been measured by atomic force microscopy (AFM). At a substrate temperature of at least 600 °C, polycrystalline AlN films with orientations of AlN(100) and AlN(101) have been synthesized. PACS 68.55.-a; 81.15.Fg; 77.84.Bw     

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.     

Synthesis of Graphene Nanoparticles and Their Application in Surface Raman Enhancement

Multilayer graphene-enclosed nickel nanoparticles have been prepared on the SiO₂/Si substrate using chemical vapor deposition. Rhodamine 6 G was used as a molecule probe to detect if the multilayer graphene-enclosed nickel nanoparticles can be applied in surface-enhanced Raman spectroscopy. The experimental results indicated that the Raman signals of C-C stretching within the benzene ring of rhodamine 6 G can be observed only on the multilayer graphene-enclosed nickel nanoparticle substrate rather than on reference substrates such as SiO₂/Si and Ni/SiO₂/Si. This suggests that the mechanism of Raman enhancement for rhodamine 6 G molecules on graphene is through the π–π bond coupling between them.     

Surface chemical states of barium zirconate titanate thin films prepared by chemical solution deposition

Ba(Zr_0.05Ti_0.95)O₃ (BZT) thin films grown on Pt/Ti/SiO₂/Si(1 0 0) substrates were prepared by chemical solution deposition. The structural and surface morphology of BZT thin films has been studied by X-ray diffraction (XRD) and scanning electron microscope (SEM). The results showed that the random oriented BZT thin film grown on Pt/Ti/SiO₂/Si(1 0 0) substrate with a perovskite phase. The SEM surface image showed that the BZT thin film was crack-free. And the average grain size and thickness of the BZT film are 35 and 400 nm, respectively. Furthermore, the chemical states and chemical composition of the films were determined by X-ray photoelectron spectroscopy (XPS) near the surface. The XPS results show that Ba, Ti, and Zr exist mainly in the forms of BZT perovskite structure.     

Evolution of phase purity and texture on annealing of BiFeO3 thin film prepared by sol-gel technique

We report preparation of phase pure BiFeO₃ thin films on glass, ITO and Si(100) substrates through chemical route using spin coating technique. Sol-gel process was adopted to prepare the films using bismuth nitrate and iron nitrate as precursors. X-Ray diffraction and Raman spectroscopy studies revealed amorphous nature of the as deposited films. Rhombohedral crystalline phase of BiFeO₃ evolved on annealing the films at 500°C, but with Bi₂Fe₄O₉ and Bi₂₄Fe₂O₃₉ as impurity phases. Increasing the annealing temperature to 550°C caused a drastic reduction of the impurity phases and at 600°C, the films were phase-pure BiFeO₃. Micro Raman spectra showed features consistent with the reported characteristic peaks of BiFeO₃ crystalline phase for films annealed at 500 and 550°C. Crystallite size obtained from X-ray diffraction line width analysis are within 30 to 40 nm. Atomic force microscopy (AFM) however showed grain size of ∼192 nm, indicating polycrystalline nature of the grains.      

非晶Si/SiO2超晶格的制备及其光谱研究

用磁控溅射方法在玻璃基底上制备了非晶Si/SiO₂超晶格.利用透射电子显微镜 (TEM) 和X射线衍射技术对其结构进行了分析,结果表明,超晶格中Si层大部分区域为非晶相,局域微区呈现有序结构,其厚度由1.8—3.2nm变化,SiO₂层厚度为4.0nm.并采用多种光谱测量技术,如吸收光谱、光致发光光谱和Raman光谱技术,对该结构的光学性质进行了系统研究.结果表明,随纳米Si层厚度的减小,光学吸收边以及光致荧光峰发生明显蓝移,Raman峰发生展宽,即观测到明显的量 关键词：     

Preferred orientations in nano-gold/silica/silicon interfaces

Gold in contact with silicon substrates Si(1 0 0), Si(1 1 1), and SiO₂ is studied by thermal evaporation and annealing in N₂ using the modified sphere-plate technique. The final orientation distribution of crystalline Au films grown on Si substrate systems that incorporate a native amorphous oxide layer of silica and Au on amorphous silica (SiO₂ glass) substrates is influenced by preferred orientations and twinning. Experimental evidence suggests that the orientation of Au{1 1 1} close packed planes (multiply twinned) was found to be of low-energy as the annealing temperature was increased to 530 °C and 920 °C. Additional orientations were observed for Au{1 0 0} on Si(1 0 0) substrates and Au{1 0 0}, {1 1 0}, and {3 1 1} on SiO₂ substrates. After annealing at 920 °C the size distribution of the gold particles was determined to be within the range of 20-800 nm while the morphology of gold surface appears spherical to faceted in character. These results show similarities to recent findings for smaller nano-size 1D particles, islands and thin Au films on silicon annealed over lower temperature ranges.     

Electroluminescence with micro-watt output from ultra-small sized Si quantum dots/amorphous SiO2 multilayers prepared by laser crystallization method

We report the fabrication of Si quantum dots (QDs)/SiO₂ multilayers by using KrF excimer laser (248 nm) crystallization of amorphous Si/SiO₂ multilayered structures on ITO coated glass substrates. Raman spectra and transmission electron microscopy demonstrate the formation of Si QDs and the size can be controlled as small as 1.8 nm. After laser crystallization, Al electrode is evaporated to obtain light emitting devices and the room temperature electroluminescence (EL) can be detected with applying the DC voltage above 8 V on the top gate electrode. The luminescent intensity increases with increasing the applied voltage and the micro-watt light output is achieved. The EL behaviors for samples with different Si dot sizes are studied and it is found that the corresponding external quantum efficiency is significantly enhanced in sample with ultra-small sized Si QDs.     

Substrate-induced stress in silicon nanocrystal/SiO2 multilayer structure

A Raman frequency upshift of nc-Si phonon mode is observed at room temperature, which is attributed to a strong compressive stress in Si nanocrystals. The 10-period amorphous-Si(3 nm)/amorphous-SiO₂ (3 nm) layers are deposited by high vacuum radio-frequency magnetron sputtering on quartz and sapphire substrates at different temperatures. The samples are then annealed in N₂ atmosphere at 1100 ℃ for 1 h for Si crystallization. It is demonstrated that the presence of a supporting substrate at the high grown temperature can induce different types of stresses in the Si nanocrystal layers. The strain is attributed to the difference in thermal expansion coefficient between the substrate and the Si/SiO₂ SL film. Such a substrate-induced stress indicates a new method to tune the optical and the electronic properties of Si nanocrystals for strained engineering.     

Poly(vinylpyrrolidone)‐stabilized silver nanoparticles for strained‐silicon surface enhanced Raman spectroscopy

Poly(vinylpyrrolidone)‐stabilized silver nanoparticles deposited onto strained‐silicon layers grown on graded Si_1−xGe_x virtual substrates are utilized for selective amplification of the Si–Si vibration mode of strained silicon via surface‐enhanced Raman scattering spectroscopy. This solution‐based technique allows rapid, highly sensitive and accurate characterization of strained silicon whose Raman signal would usually be overshadowed by the underlying bulk SiGe Raman spectra. The analysis was performed on strained silicon samples of thickness 9, 17.5 and 42 nm using a 488 nm Ar⁺ micro‐Raman excitation source. The quantitative determination of strained‐silicon enhancement factors was also made. Copyright © 2011 John Wiley & Sons, Ltd.     

Formation of silicon oxide nanowires directly from Au/Si and Pd–Au/Si substrates

Amorphous silicon oxide (SiO_x) nanowires were directly grown by thermal processing of Si substrates. Au and Pd–Au thin films with thicknesses of 3 nm deposited on Si (0 0 1) substrates were used as catalysts for the growth of nanowires. High-yield synthesis of SiO_x nanowires was achieved by a simple heating process (1000–1150 °C) in an Ar ambient atmosphere without introducing any additional Si source materials. The as-synthesized products were characterized by field-emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, and transmission electron microscopy measurements. The SiO_x nanowires with lengths of a few and tens of micrometers had an amorphous crystal structure. The solid–liquid–solid model of nanowire formation was shown to be valid.     

Growth of single-walled carbon nanotubes on silicon nanowires

Single-walled carbon nanotubes (SWNTs) have been grown on silicon nanowires (SiNWs) by ethanol chemical vapor deposition (CVD) with Co catalysts. We have found that a surface SiO_x layer of SiNWs is necessary for the formation of active Co catalysts. In fact, the yield of the SWNT/SiNW heterojunctions gradually decreases as the thickness of the surface SiO_x layer decreases. Since thin SiNWs are transparent to an electron beam, the Co nanoparticles on SiNWs can be easily observed as well as SWNTs by TEM. Therefore, the relationship between the diameters of each SWNT and its catalyst nanoparticle has been investigated. The diameters of SWNTs are equal to or slightly smaller than those of the catalyst nanoparticles.     

Influence of temperature-pressure treatment on heavily hydrogenated silicon surface

Microstructure and related properties of hydrogenated silicon samples, Si:H, treated at high-temperature (HT) up to 1270 K under hydrostatic argon pressure (HP) up to 1.1 GPa are investigated. To prepare Si:H, Czochralski grown 0 0 1 oriented single crystalline Si wafer with 50 nm thick surface SiO₂ layer was heavily implanted with hydrogen using the immersion plasma source of hydrogen ions with energy 24 keV.The surface of HT-HP treated Si:H was characterised by scanning electron microscopy. Reflectivity pattern measurements in the wavelength range of 350-2000 nm have been performed to analyse their surface and bulk properties. The volume averaging method for a model of layer-like structure has been used to simulate the HT-HP treated Si:H. The analysis of Si:H samples suggests the multi-layer structure composed of Si, Si:H, SiO, SiO₂, and of porous Si layers in the sub-surface region. The porous Si:H samples model is in good consistency with experimental data from reflectance measurements.     

Pulsed plasma ion source to create Si nanocrystals in SiO2 substrates

A pulsed KrF excimer laser of irradiance of about 10⁸ W/cm² was utilized to synthesize Si nanocrystals on SiO₂/Si substrates. The results were compared with that ones obtained by applying low bias voltage to Si(1 0 0) target in order to control the kinetic energy of plasma ions. Glancing incidence X-ray diffraction spectra indicate the presence of silicon crystalline phases, i.e. (1 1 1) and (2 2 0), on SiO₂/Si substrates. The average Si nanocrystal size was estimated to be about 45 nm by using the Debye-Scherrer formula. Scanning electron microscopy and atomic force microscopy images showed the presence of nanoparticles of different size and shape. Their distribution exhibits a maximum concentration at 49 nm and a fraction of 14% at 15 nm.     

Correlation of size and oxygen bonding at the interface of Si nanocrystal in Si–SiO2 nanocomposite: A Raman mapping study

Raman spectroscopy/mapping is used to investigate the variation of Si phonon wavenumbers, i.e., lower wavenumber (LW ~ 495–510 cm⁻¹) and higher wavenumber (HW ~ 515–519 cm⁻¹) phonons, observed in Si–SiO₂ multilayer nanocomposite (NCp) grown using pulsed laser deposition. Sensitivity of Raman spectroscopy as a local probe to surface/interface is effectively used to show that LW and HW phonons originate at surface (Si–SiO₂ interface) and core of Si nanocrystals, respectively. The consistent picture of this understanding is developed using Raman spectroscopy monitored laser heating/annealing and cooling experiment at the site of the desired wavenumber, chosen with the help of Raman mapping. Raman spectra calculations for Si₄₁ cluster with oxygen and hydrogen termination show strong mode at 512 cm⁻¹ for oxygen terminated cluster corresponding to the vibration of surface Si atoms. This supports our attribution of LW phonons to be originating at the Si–SiO₂ surface/interface. These results along with XPS show that nature of interface (oxygen bonding) in turn depends on the size of nanocrystals and LW phonons originate at the surface of smaller Si nanocrystals. The understanding developed can conclude the ongoing debate on large variation in Si phonon wavenumbers of Si–SiO₂ NCps in the literature. Copyright © 2015 John Wiley & Sons, Ltd.     

Effect of Gold Nanoparticles and Unwanted Residues on Raman Spectra of Graphene Sheets

We report the effect of gold nanoparticles (AuNPs) and unwanted sodium citrate residues (UnR) left after deposition of AuNPs by drop-casting method on the Raman spectra of graphene sheets (GS). The AuNPs solution was deposited on three different substrates: 5.0 wt% Yb³⁺-doped (Q5) phosphate glass, silica glass (S1), and Si/SiO₂-300 nm (S2) substrates. For Q5 substrate, a slight increase in intensity of the G peak was observed, mostly for thinner layers, which can be attributed to a weak SERS effect shielded by UnR. The combination of the following aspects: a blue shift of the G band position, a slight increase in the FWHM (Full Width at Half Maximum), and a slight increase of the Raman intensities of both G and 2D bands in other GS without UnR supports the argument of shielded SERS effect. On the other hand, the effects of UnR on the S1 and S2 substrates produce a decrease on the Raman intensities of G and 2D bands, opposite to the effect produced by the AuNPs; this result was found more intense for the S2 substrate in relation to S1. This is possibly caused by the greater amount of UnR accumulated on the Si/SiO₂ substrate, due to its higher hydrophilicity in relation to other samples. Additional Raman measurements reveal that the Raman intensity of GS in all substrates is unaffected by the presence of a possible humidity on GS, revealing the effect of UnR. Hence, it is vital to understand how residues influence the salient features of GS/AuNPs.