Si nanoclusters coupled to Er ions in a SiO2 matrix for optical amplifiers

In this work we will give an overview of the optical properties of Si nanoclusters coupled to Er³⁺ ions in SiO₂ matrices produced by reactive magnetron co-sputtering. We have divided the work into two separate studies realised on the same samples, which are the result of a thorough optimisation work. The first one have been realised in order to get a clear picture of the interaction mechanism. On the second we will show a quantitative evaluation of the potential performances from a material point of view (determination of the whole optically active Er³⁺ content, excitable by direct or indirect means) and actual performance in a waveguide device (determination of internal gain values).     

Si nanocrystals in SiO2 films analyzed by small angle X-ray scattering

Amorphous SiO/SiO₂ multilayers were studied using grazing-incidence small-angle X-ray scattering (GISAXS). Such SiO/SiO₂ superlattices were prepared by alternately magnetron sputtering of 3 nm thin films of SiO and 3 nm of SiO₂ (10 layers each) on Si (100) substrate. Rotation of the Si substrate during evaporation ensures the homogeneity of the films over the whole substrate. After evaporation the samples were annealed at 1050 °C for 2 h in vacuum or in air. The analysis of the 2D GISAXS pattern has shown that Si nanocrystals are formed in the annealed samples. Using a Guinier approximation, the inter-nanocrystal distance (10.5 nm) and radius of gyration (2.3 nm) have been obtained for the samples annealed in vacuum. Samples annealed in air have shown similar peak values which were however, much wider distributed.     

GISAXS study of Si nanoclusters in SiO/SiO2 layers

We present a study on amorphous SiO/SiO₂ superlattice using grazing-incidence small-angle X-ray scattering (GISAXS). Such nanostructured material might be of great interest for photovoltaic conversion and optoelectronics. Amorphous SiO/SiO₂ superlattices were prepared by magnetron sputtering of thin SiO and SiO₂ films (20 layers each) on Si (1 0 0) substrate. Rotation of the Si substrate during evaporation ensures homogeneity of the films over the whole substrate. After the evaporation, the samples were annealed at 1100 °C for 1 h in vacuum. The analysis of the 2-D GISAXS pattern has shown that Si nanocrystals are formed in the remaining SiO₂ films in the annealed samples. From the 2-D GISAXS pattern, their shape, size and inter-particle distance are determined.     

透氧膜法由SiO2直接制备Si

为改变硅生产工艺高污染、高能耗的现状,研究了在CaCl2熔盐中利用固体透氧膜法(SOM)直接电解SiO2制备单质Si,考察了电解电压、电解时间、熔盐温度等参数对电解效果的影响,采用电子扫描显微镜和X射线衍射分析了电解产物形貌及相组成.结果表明:1100℃熔盐中,3.5 V电压下电解2 h,可制得纯Si,电流效率为89%...     

Simulation of Si and SiO2 etching in CF4 plasma

The reactive ion etching (RIE) of Si and SiO₂ in CF₄ plasma is considered. The dependences of RIE rates of Si and SiO₂ on pressure have maxima due to the presence of single-atom vacancies. The RIE rates approach the maximum values at different pressures but at the same concentration of SiF and SiOF molecules in the adsorbed layer. Using the obtained results Si/SiO₂ etching selectivity is investigated.     

High concentration erbium doping of silicon-rich SiO2 thin films on silicon

In this work, high concentration erbium doping in silicon-rich SiO₂ thin films is demonstrated. Si plus Er dual-implanted thermal SiO₂ thin films on Si substrates have been fabricated by using a new method, the metal vapor vacuum arc ion source implantation with relatively low ion energy, strong flux and very high dose. X-Ray photoelectron spectroscopy measurement shows that very high Er concentrations on the surfaces of the samples, corresponding to 10 at.% or the doping level of 10²¹ atoms cm⁻³, are achieved. This value is much higher than that obtained by using other fabrication methods such as the high-energy ion implantation and molecular beam epitaxy. Reflective high-energy electron diffraction, atomic force microscopy and cross-section high-resolution transmission electron microscopy observations show that the excess Si atoms in SiO₂ matrix accumulate to form Si clusters and then crystallize gradually into Si nanoparticles embedded in SiO₂ films during dual-ion implantation followed by rapid thermal annealing. Er segregation and precipitates are not formed. Photoluminescence at the wavelength of 1.54 μm exhibits very weak temperature dependence due to the introduction of Si nanocrystals into the SiO₂ matrix. The 1.54-μm light emission signals from annealed samples decrease by less than a factor of 2 when the measuring temperature increases from 77 K to room temperature.     

Nucleation of small metal particles on ultrathin SiO2 films on Si

Metal particles of Pt, Ni, Au and Ag, typically less than 50 Å in diameter, were deposited by vacuum evaporation onto substrates of ultrathin (～25 Å) SiO₂ on Si. The particle size and charge were determined by transmission electron microscopy and MOS type capacitance-voltage measurements, respectively. It was observed that the Pt and Ni particles were smaller and more closely spaced than Au and Ag particles under comparable deposition conditions. The particle charge for Pt and Ni appeared to exceed that for Au and Ag for the same substrate coverage, suggesting possible charge contributions to heterogeneous nucleation. Since Pt and Ni particles were observed to carry a positive charge, they are presumably stabilized at negative substrate sites; the opposite appears to be true for Au and Ag.     

Structural and optical properties of the SiO2-P2O5 films obtained by sol-gel method

A comparative study of the sol-gel films prepared in the SiO₂-P₂O₅ system starting with triethylphosphate, triethylphosphite and phosphoric acid as P precursors was performed. The work addresses basic aspects of physics, chemistry, and engineering of oxide films for applications in microelectronics, sensing, nano-photonics, and optoelectronics by establishing the influence of different precursors on the composition, structure and optical properties of the obtained films. The influence of the type of substrate (glass and indium tin oxide coated glass) and of the thermal treatment (200 and 500 °C) on their structure and properties was studied. By spectroscopic ellipsometry, X-Ray photoemission spectroscopy and atomic force microscopy measurements the high vaporization of the phosphorous during the densification of the films by thermal treatment was noticed when P-alkoxides were used. The phosphoric acid that forms chemical bond with silica network during the sol-gel process leads to better incorporation of P in the silica network as compared to the P-alkoxides.     

The large modification of phase transition characteristics of VO2 films on SiO2/Si substrates

The vanadium oxide (VO₂) films have been prepared on SiO₂/Si substrates by using a modified Ion Beam Enhanced Deposition (IBED) method. During the film deposition, high doses of Ar⁺ and H⁺ ions have been implanted into the deposited films from the implanted beam. The resistance change of the VO₂ films with temperature has been measured and the phase transition process has been observed by using the X-ray Diffraction technique. The phase transition of the IBED VO₂ films starts at a low temperature of 48 °C and ends at a high temperature of 78 °C. It is found that the phase transition characteristics can be adjusted by changing the annealing temperature or the time and the phase transition characteristics of the IBED VO₂ films depend on the quantity and location of argon atoms in the film matrix.     

Si nanocrystals formation in SiO2 by ion implantation: The effects of RTA and UV irradiation on photoluminescence

Si ion implantation was widely used to synthesize specimens of SiO₂ containing supersaturated Si and subsequent high temperature annealing induces the formation of embedded luminescent Si nanocrystals. In this work, the potentialities of excimer UV-light (172 nm, 7.2 eV) irradiation and rapid thermal annealing (RTA) to enhance the photoluminescence and to achieve low temperature formation of Si nanocrystals have been investigated. The Si ions were introduced at acceleration energy of 180 keV to fluence of 7.5 × 10¹⁶ ions/cm². The implanted samples were subsequently irradiated with an excimer-UV lamp. After the process, the samples were rapidly thermal annealed before furnace annealing (FA). Photoluminescence spectra were measured at various stages at the process. We found that the luminescence intensity is strongly enhanced with excimer-UV irradiation and RTA. Moreover, effective visible photoluminescence is found to be observed even after FA at 900 °C, only for specimens treated with excimer-UV lamp and RTA. Based on our experimental results, we discuss the effects of excimer-UV lamp irradiation and RTA process on Si nanocrystals related photoluminescence.     

Liquid petroleum gas sensor based on SnO2/Pd composite films deposited on Si/SiO2 substrates

SnO₂/Pd composite films were synthesized by d.c. sputtering of a SnO₂ target followed by thermal evaporation of a thin layer of Pd on top of it. This structure, deposited on Si wafer with 300 μm SiO₂ on the top, was subjected to rapid thermal annealing at 573 K for 5 min for the incorporation of Pd in SnO₂. The films were characterized by microstructural, optical, FTIR and Raman studies. Liquid petroleum gas (LPG) sensing measurements were carried out on these films. Sensitivity of 72% was obtained at an operating temperature of ∼573 K. The response time for these sensors was found to be ∼27 s. Sensitivity was found to increase with grain growth at higher sensing temperatures. It could be observed that the selectivity for LPG is extremely good as compared to that of methane, hydrogen, CO₂ and C₂H₅OH.     

Self-assembled hybrid films of phosphotungstic acid and aminoalkoxysilanes on SiO2/Si surfaces

The present paper describes the influence of the chemical structure of two aminoalkoxysilanes: 3-aminopropyltriethoxysilane (APTS) and N-(3-(trimethoxysilyl)-propyl)-ethylenediamine (TSPEN) on the morphology of thin layer hybrid films with phosphotungstic acid (HPW), a Keggin heteropolyanion. X-ray photoelectron spectroscopy analyses indicated that both silane films showed protonated amine species interacting with the heteropolyanion by electrostatic forces as well as the presence of secondary carbamate anions. The hybrid films have different surface morphology according to atomic force microscopy analyses. The hybrid film with TSPEN forms flatter surfaces than the hybrid film with APTS. This effect is ascribed to higher flexibility and chelating ability of the TSPEN on adsorbed molecules. Ultrasonication effect on surface morphology of the hybrid film with APTS plays a fundamental role on surface roughness delivering enough energy to promote surface diffusion of the HPW heteropolyanions. This diffusion results in agglomerate formation, which corroborates with the assumption of electrostatic bonding between the HPW heteropolyanions and the protonated amine surface. These hybrid films could be used for electrochemical sensor design or to build photochromic and electrochromic multilayers.     

Growth and luminescent properties of Lu2SiO5 and Lu2SiO5:Ce single crystalline films

Single crystalline films (SCF) of Lu₂SiO₅ (LSO) and Lu₂SiO₅:Ce (LSO:Ce) silicates with thickness of 2.5-15 μm were crystallized by liquid phase epitaxy method onto undoped LSO substrates from melt-solution based on PbO-B₂O₃ flux. The scintillation and luminescence properties of LSO:Ce SCF were compared with the properties of LSO:Ce single crystal. The peculiarities of luminescence properties of LSO:Ce SCF in comparison with crystal analog can be due to different distribution of Ce³⁺ over the Lu1 and Lu2 positions of LSO host and are further influenced by Pb²⁺ flux-originated contamination.     

Optical properties of single-wall carbon nanotube films deposited on Si/SiO2 wafers

The paper describes a set of simple experiments performed to develop an optical model to describe Si/SiO₂ substrates coated with two transparent films of carbon nanotubes. The final goal is to use such optical model to investigate the interaction of proteins with carbon nanotubes. Experiments were performed to assess light reflection as a function of the wavelength or angle of incidence using two substrates (same material, different amounts) composed of oxidized carbon nanotubes. The experimental results indicate that the selected carbon nanotubes layers are anisotropic and significantly different from each other. Experiments performed by spectroscopic ellipsometry (as a function of the wavelength and incident angle) enabled the development of an effective medium approximation model consisting in a two-fraction phase (arc-evaporated carbon and void space). Furthermore, the model enabled calculating the amount of protein adsorbed on the surface of the carbon nanotube film.     

Natural and persistent superhydrophilicity of SiO2/TiO2 and TiO2/SiO2 bi-layer films

Sol-gel SiO₂/TiO₂ and TiO₂/SiO₂ bi-layer films have been deposited from a polymeric SiO₂ solution and either a polymeric TiO₂ mother solution (MS) or a derived TiO₂ crystalline suspension (CS). The chemical and structural properties of MS and CS bi-layer films heat-treated at 500 °C have been investigated by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscospy. Water contact angle measurements show that MS SiO₂/TiO₂ and CS TiO₂/SiO₂ bi-layer films exhibit a natural superhydrophilicity, but cannot maintain a zero contact angle for a long time over film aging. In contrast, CS SiO₂/TiO₂ bi-layer films exhibit a natural, persistent, and regenerable superhydrophilicity without the need of UV light. Superhydrophilic properties of bi-layer films are discussed with respect to the nature of the TiO₂ single-layer component and arrangement of the bi-layer structure, i.e. TiO₂ underlayer or overlayer.     

Growth mechanism of epitaxial CoSi2 on Si and reactive deposition epitaxy of double heteroepitaxial Si/CoSi2/Si

The growth mechanism of epitaxial CoSi₂ was studied using Co/Ti/Si multilayer solid phase reaction. Results showed that phase formation was controlled by diffusion of Co through the growing CoSi_x, although at the early stage of CoSi₂ growth the diffusion of Co could be controlled by a Ti layer. A reactive deposition technique was also evaluated by using a conventional magnetron sputtering system. Results showed that an epitaxial CoSi₂ layer was formed by controlling the Co sputtering rate not to exceed the Co diffusion rate through CoSi_x. However, the surface of CoSi₂ became rough when the deposition rate was much slower than the Co diffusion rate through CoSi_x. The roughness was caused by the formation of CoSi₂ (111) facets at the interface between CoSi₂ and the Si substrate. Si/CoSi₂/Si double heteroepitaxial structures were fabricated when Si and Co were sequentially sputter-deposited on a Si (100) substrate.     

Sol-gel preparation of near-infrared broadband emitting Er-doped SiO2-Ta2O5 nanocomposite films

This article reports a study on the preparation, densification process, and structural and optical properties of SiO₂-Ta₂O₅ nanocomposite films obtained by the sol-gel process. The films were doped with Er³⁺, and the Si:Ta molar ratio was 90:10. Values of refractive index, thickness and vibrational modes in terms of the number of layers and thermal annealing time are described for the films. The densification process is accompanied by OH group elimination, increase in the refractive index, and changes in film thickness. Full densification of the film is acquired after 90 min of annealing at 900 °C. The onset of crystallization and devitrification, with the growth of Ta₂O₅ nanocrystals occurs with film densification, evidenced by high-resolution transmission electron microscopy. The Er³⁺-doped nanocomposite annealed at 900 °C consists of Ta₂O₅ nanoparticles, with sizes around 2 nm, dispersed in the SiO₂ amorphous phase. The main emission peak of the film is detected at around 1532 nm, which can be assigned to the ⁴I_13/2 → ⁴I_15/2 transition of the Er³⁺ ions present in the nanocomposites. This band has a full width at half medium of 64 nm, and the lifetime measured for the ⁴I_13/2 levels is 5.4 ms, which is broader compared to those of other silicate systems. In conclusion, the films obtained in this work are excellent candidates for use as active planar waveguide.     

Fabrication of luminescent SrWO4 thin films by a novel electrochemical method

Highly crystallized SrWO₄ thin films with single scheelite structure were prepared within 60 min by a cell electrochemical method. X-ray diffraction analysis shows that SrWO₄ thin films have a tetragonal structure. Scanning electron microscopy examinations reveal that SrWO₄ grains grow well in tetragonal tapers and grains like flowers or bunches, which can usually form by using the electrolysis electrochemical method, have disappeared under cell electrochemical conditions. X-ray photoelectron spectra and energy dispersive X-ray microanalysis examinations demonstrate that the composition of the film is consistent with its stoichiometry. These SrWO₄ films show a single blue emission peak (located at 460 nm) using an excitation wave of 230 nm. The speed of cell electrochemical method can be controlled by changing temperature. The optimum treatment temperature is about 50-60 °C.     

Enhanced photoluminescence of CaTiO3:Pr phosphor films deposited on SiO2 buffered Si substrates

CaTiO₃:Pr³⁺ films have been prepared by pulsed-laser deposition method on SiO₂-buffered Si substrates, and their microstructure and photoluminescence properties have been compared with those of the films deposited directly on bare Si substrates. The SiO₂ buffer layers were prepared using thermal oxidization and HF-etching. Photoluminescence intensities of CaTiO₃:Pr³⁺ films on the SiO₂-buffered Si substrates are significantly higher (up to 800%) than those of the films on bare Si substrates, which is attributed to the low refractive index and low light absorption of the SiO₂ buffer layer. This study reveals that the presence of the buffer layer is effective in improving the red emission brightness of CaTiO₃:Pr³⁺ films without sacrificing the surface roughness.     

热蒸发多孔Si/SiO2薄膜的光致发光特性研究

本工作采用热蒸发法制备了多孔Si/SiO_2薄膜,利用拉曼、红外、XRD研究了薄膜的结构,SEM研究了表面形貌,使用光致发光(PL)谱对其发光特性进行了研究。结果表明,激发波长为325nm(2.88eV)时,样品的峰位分别在430nm(2.88eV)、441nm(2.81eV)、523nm(2.47eV)、554nm(2.24eV),激发波长为488nm时,峰位在570nm(2.18eV),采用施主态Si悬挂键≡Si 0位于2.81eV,受主态Si悬挂键≡Si-位于3.00eV处,引入SiOx(x小于2)和Si-O-Si缺陷态能级,能级分别为5.05eV和0.63eV,建立了Si/SiO_2薄膜的能隙态(EGS)模型,并讨论了其发光机制。