Multipeak fitting analysis of Raman spectra on DLCH film

The hydrogenated diamond‐like carbon (DLCH) film with 1‐µm thickness is deposited by direct hydrocarbon gas ion beam method on silicon wafer and annealed at 400 °C. Detailed Raman spectra feature are fitted from nine sets of different peak fitting functions, including Gaussian, Lorentzian and Breit‐Wigner‐Fano (BWF) functions. These fitting results obtained from a two‐peak combination show some specific variances on the G peak position, FWHM_G and I_D/I_G ratio for as‐deposited and as‐annealed DLCH films. The most popular two‐peak fitting method with full Gaussian function tends to exhibit a higher ratio of the G peak position shift and higher I_D/I_G ratio than others fitting methods, the drastic difference among the most popular G (G) & G (D) and B (G) & L (D) schemes also have brought out in I_D/I_G ratio. However, for a more complex four‐peak Gaussian function fitting Raman spectra, the I_D/I_G ratio is close to that of a two‐peak fitting function with a mixture functions of BWF (G) and L (D). Furthermore, a series of systematic peak fitting procedures and comparisons of Raman spectra have been discussed in this study. Copyright © 2009 John Wiley & Sons, Ltd.     

Solid State Reaction of Ruthenium with 6H-SiC Under Vacuum Annealing and the Impact on the Electrical Performance of its Schottky Contact for High Temperature Operating SiC-Based Diodes

Thin films and Schottky diodes dots of ruthenium (Ru) on bulk-grown n-type-6-hexagonal-silicon carbide (6H-SiC) were annealed isochronally in a vacuum furnace at temperatures ranging from 500–1,000 °C. Rutherford backscattering spectroscopy analysis of the thin films showed formation of ruthenium silicide (Ru₂Si₃) at 800 °C, while diffusion of Ru into 6H-SiC commenced at 800 °C. Raman analysis of the thin films annealed at 1,000 °C showed clear D and G carbon peaks which was evidence of formation of graphite. At this annealing temperature, the Schottky contact was observed to convert to an ohmic contact, as evidenced by the linearity of current–voltage characteristic, thereby, rendering the diode unusable. The transformation from Schottky contact to ohmic contact is attributed to graphite formation at the interface.     

Annealing temperature dependence of Raman scattering in Si/SiO2 superlattice prepared by magnetron sputtering

Si/SiO₂ superlattices were prepared by magnetron sputtering, and the deposition temperature and annealing temperature had a great influence on the superlattice structure. In terms of SEM images, the mean size of Si nanocrystals annealed at 1100 °C is larger than that of nanocrystals annealed at 850 °C. It was found that the films deposited at room temperature are amorphous. With increasing deposition temperature, the amorphous and crystalline phases coexist. With increasing annealing temperature, the Raman intensity of the peak near 470 cm⁻¹ decreases, and the intensity of that at 520 cm⁻¹ increases. Also, on increasing the annealing temperature, the Raman peak near 520 cm⁻¹ shifts and narrows, and asymmetry emerges. A spherical cluster is used to model the nanocrystals in Si/SiO₂ superlattices, and the observed Raman spectra are analyzed by combining the effects of confinement on the phonon frequencies. Raman spectra from a variety of nanocrystalline silicon structures were successfully explained in terms of the phonon confinement effect. The fitted results agreed well with the experimental observations from SEM images.     

Fabrication and Characterization of Si Nanocrystals Synthesized by Electron Beam Evaporation of Si and SiO2 Mixture

Silicon nanocrystals synthesized by electron beam （e-beam） evaporation of Si and SiO2 mixture are studied. Rutherford backscattering spectrometry of the as-deposited Si-rich silicon dioxide or oxide （SRO） thin film shows that after evaporation, the Si and SiO2 concentration is well kept, indicating that the e-beam evaporation is suitable for evaporating mixtures of Si and SiO2. The SRO thin films are annealed at different temperatures for two hours to synthesize silicon nanoerystals. For the sample annealed at 1050℃, silicon nanoerystals with different sizes and the mean diameter of 4.5 nm are evidently observed by high resolution transmission electron microscopy （HRTEM）. Then the Raman scattering and photoluminescence spectra arising from silicon nanocrystals are further confirmed the above results.     

Raman-spectroscopy study of PbTiO3 thin films grown on Si substrates by metalorganic chemical vapor deposition

Raman spectra have been investigated in PbTiO₃ thin films grown on Si by metalorganic chemical vapor deposition. A large grazing-angle scattering technique was taken to measure the temperature dependence of Raman spectra below room temperature. All Raman modes in the thin films are assigned and compared with those in the bulk single crystal, a newA ₁(TO) soft mode at 104 cm^–1 was recorded which satisfies the Curie-Weiss relation ² =A(T _c –T). Intensities of theA ₁(1TO) andE(1TO) modes were anomalously strengthened with increasing temperature. Raman modes for the thin films exhibit remarkable frequency downshift and upshift which is related to the effect of internal stress.     

富硅氮化硅薄膜的制备及其光学带隙研究

采用双极脉冲磁控反应溅射法在不同参数条件下制备了一系列氮化硅薄膜。利用数字式显微镜和紫外-可见光光谱仪研究了沉积薄膜的表面形貌及其光学带隙,利用共焦显微拉曼光谱仪比较了硅衬底、氮化硅薄膜退火前后的拉曼光谱。结果表明,氮气流量对薄膜的光学带隙影响较大,制备的薄膜主要为富硅氮化硅薄膜。原沉积薄膜的拉曼光谱存在明显的非晶硅和单晶硅峰,退火处理后非晶硅峰减弱或消失,表明薄膜出现明显的结晶化;单晶硅峰出现频移现象,表明薄膜中出现硅纳米颗粒,平均尺寸约为6.6 nm。     

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.     

Origin of the Raman mode at 379 cm−1 observed in ZnO thin films grown on sapphire

In this work, we present a detailed Raman scattering study to clarify the origin of the mode at 379 cm⁻¹ which is observed in Raman spectra of the ZnO films grown on c‐sapphire substrates and generally attributed to the A₁‐transverse optical (A₁‐TO) mode of ZnO. The studied ZnO films were deposited by metal‐organic chemical vapor deposition on c‐sapphire and (0001) ZnO substrates. In the z(−,−)z̄ backscattering configuration, the A₁‐TO mode is forbidden, while the 379 cm⁻¹ peak is still observed in the as‐deposited film grown on sapphire substrate. However, this mode is not observed in Raman spectra of the as deposited film grown on ZnO substrate. We suggest that the peak at 379 cm⁻¹ is the E_1g mode of the sapphire substrate which is allowed in z(−,−)z̄ backscattering configuration. The effects of annealing, the substrate and the collection cross‐section on Raman active modes were analyzed. Copyright © 2011 John Wiley & Sons, Ltd.     

The nano-structural properties of hydrogenated a-Si and Si-C thin films alloys by GISAXS and vibrational spectroscopy

Amorphous hydrogenated silicon (a-Si:H) with high hydrogen content (10-40 at.%), and non-stehiometric silicon-carbon (Si_1−xC_x) thin films with a variation of the carbon to silicon ratio up to 0.3, were deposited by using a magnetron sputtering source. The Si_1−xC_x thin films were partially crystallised after deposition by thermal annealing up to 1050 °C.The GISAXS (Grazing Incidence Small Angle X-ray Scattering) spectra of all of the prepared specimens indicate the presence of “particles” in the “bulk” of the films. For the a-Si:H samples, “particles” are most probably voids agglomerates with a variation in size between 3 and 6 nm. The mean value of the size distribution of the “particles” increases while its width slightly decreases with the hydrogen content in the film. This indicates a better structural ordering which is consistent with the results of Raman spectroscopy that show a decrease of the ratio between intensities of transversal acoustic (TA) and transversal optic (TO) phonon peaks, I_TA/I_TO, and a narrowing of the TO peak with increasing hydrogen content. These results are discussed as a consequence of the beneficial influence of hydrogen bombardment during the film growth.For Si_1−xC_x thin films, the “particles” are assumed to be SiC nano-crystals with a size between 2 and 14 nm and they are larger in films with a higher carbon concentration. Inside each of the films, the crystals are larger closer to surface and they grow faster in the direction parallel to the surface than in that which is perpendicular to it.     

Quantitative analysis of hydrogen in amorphous silicon using Raman scattering spectroscopy

Hydrogenated amorphous silicon (a‐Si:H) films were studied using infrared and Raman spectroscopy. We have experimentally found that ratios of Raman scattering cross‐sections for Si–H to Si–Si bonds and for Si–H₂ to Si–Si bonds are equal to 0.65 ± 0.07 and 0.25 ± 0.03, respectively. It allows to measure the concentration of hydrogen in a‐Si:H films. The developed approach can be applied for in situ control of hydrogen in a‐Si:H films and also suitable for thin a‐Si:H films on substrates that are opaque in infrared spectral region. Copyright © 2013 John Wiley & Sons, Ltd.     

X-ray photoelectron spectroscopy investigations of Si in non-stoichiometric SiNx LPCVD multilayered coatings

Si nanocrystals were formed in the non-stoichiometric Si-enriched SiN_x low-pressure chemical vapor deposited (LPCVD) coatings on Si wafers treated by various modes. The coating structure as a function of technological conditions was investigated by ellipsometry and X-ray photoelectron spectroscopy (XPS) depth profiling. It was found that nanocomposites on base of SiN_x films enriched by Si have a complex multilayered structure varying in dependence of deposition and annealing parameters. Analysis of the XPS spectra and Si 2s peaks shows the existence and quantity of four chemical structures corresponding to the Si–O, Si–N states, nanocrystalline and amorphous Si. The XPS results show evolution of the chemical structure of silicon nitride and formation of Si nanocrystals. It was found:

• The LPCVD technology of nanocrystals formation allows to get enough high concentration of Si nanocrystals on different depths from the sample surface.

• The volume fraction of nanocrystalline and amorphous Si is changed with depth; this relation depends from SiN_x composition and annealing parameters.

• XPS detects these two phase compositions of Si nanoparticles in SiN_x and SiO₂ layers. The ellipsometry, HR-TEM, and XPS results are in good agreement.

Effects of magnesium film thickness and annealing temperature on formation of Mg2Si films on silicon (1 1 1) substrate deposited by magnetron sputtering

Magnesium films of various thicknesses were first deposited on silicon (1 1 1) substrates by magnetron sputtering method and then annealed in annealing furnace filled with argon gas. The effects of the magnesium film thickness and the annealing temperature on the formation of Mg₂Si films were investigated by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM). The Mg₂Si thin films thus obtained were found to be polycrystalline and the Mg₂Si (2 2 0) orientation is preferred regardless of the magnesium film thickness and annealing temperature. XRD results indicate that high quality magnesium silicide films are produced if the magnesium/silicon samples are annealed at 400 °C for 5 h. Otherwise, the synthesized films annealed at annealing temperatures lower than 350 °C or higher than 450 °C contain magnesium crystallites or magnesium oxide. SEM images have revealed that microstructure grains in the polycrystalline films are about 1-5 μm in dimensions, and the texture of the Mg₂Si films becomes denser and more homogeneous as the thickness of the magnesium film increases.     

高速沉积微晶硅薄膜光发射谱的研究

采用PR650光谱光度计对高速沉积微晶硅薄膜的生长过程进行了在线监测研究,并对所对应的材料进行了Raman谱和红外吸收谱(FTIR)的测试.结果表明：能反映材料晶化程度的I_［SiH^*］/I_［Hβ^*］比值在沉积时间为100 s之内有下降的趋势,且反应气体总流量T_fl越小下降趋势越明显,这与拉曼散射光谱对材料的结构测试结果一致;沉积5 min时I 关键词： 高速沉积 微晶硅薄膜 电子温度     

Structure analysis of thin iron-silicide film from φ-scan RHEED Patterson function

The atomic structure of thin iron silicide film, grown epitaxially on the Si(111) surface, has been analyzed by means of the three-dimensional RHEED Patterson function analysis. The iron-silicide-terminated surface with (2 × 2) periodicity has been prepared by a solid-phase epitaxy method. 2 ML of Fe were deposited on the Si(111)-(7 × 7) surface and annealed at 500°C. Three-dimensional Patterson function was calculated from series of φ-scanned RHEED intensity distributions converted to the k-space. The resulting model of γ-FeSi₂ structure consists of two silicide layers faulted to each other with three relaxed Si adatoms above the H₃ site.     

Optical Analysis of Nanocrystalline ZnO Films Coated on Porous Silicon by Radio Frequency (RF) Magnetron Sputtering

Zinc oxide thin films have been deposited onto porous silicon (PSi) substrates at high growth rates by radio frequency (RF) sputtering using a ZnO target. The advantages of the porous Si template are economical and it provides a rigid structural material. Porous silicon is applied as an intermediate layer between silicon and ZnO films and it contributed a large area composed of an array of voids. The nanoporous silicon samples were adapted by photo electrochemical (PEC) etching technique on n-type silicon wafer with (111) and (100) orientation. Micro-Raman and photoluminescence (PL) spectroscopy are powerful and non-destructive optical tools to study vibrational and optical properties of ZnO nanostructures. Both the Raman and PL measurements were also operated at room temperature. Micro-Raman results showed that the A₁(LO) of hexagonal ZnO/Si(111) and ZnO/Si(100) have been observed at around 522 and 530 cm^–1, re- spectively. PL spectra peaks are distinctly apparent at 366 and 368 cm^–1 for ZnO film grown on porous Si(111) and Si(100) substrates, respectively. The peak luminescence energy in nanocrystalline ZnO on porous silicon is blue-shifted with regard to that in bulk ZnO (381 nm). The Raman and PL spectra pointed to oxygen vacancies or Zn interstitials which are responsible for the green emission in the nanocrystalline ZnO.     

Silicon rich silicon oxide films deposited by radio frequency plasma enhanced chemical vapor deposition method: Optical and structural properties

Silicon rich silicon oxide films have been deposited by plasma enhanced chemical vapour deposition using a gas mixture of silane, carbon-di-oxide and hydrogen. Silicon nanocrystals formations in the as deposited silicon rich silicon oxide films have been detected by high resolution transmission electron microscopy, scanning electron microscopy, Raman scattering and X-ray diffraction studies. Structural changes under different deposition condition have been studied by Fourier transform infrared spectroscopy. The oxygen and hydrogen bonding configurations have been obtained from Fourier transform infrared spectroscopy. Room temperature photoluminescence spectra have been observed for the as deposited films. The structural properties together with photoluminescence spectra allowed us to gain insight about the Si nanocrystal formation.     

Si–Si optical phonon behavior in localized Si clusters of Si<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ge<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript> alloy nanocrystals

Raman spectra acquired from Si _x Ge_1−x -nanocrystal-embedded SiO₂ films show dependence of the Si–Si optical phonon frequency on Si content. The frequency upshifts, and peak intensity increases as the silicon concentration increases. For a given Si content, the frequency remains unchanged with annealing temperature. Spectral analysis and density functional theory calculation reveal that the optical Si–Si phonon is related to the formation of localized Si clusters surrounded by Si/Ge atomic layers in the Si _x Ge_1−x nanocrystals and the intensity enhancement arises from the larger cluster size. The synergetic effect of surface tensile stress and phonon confinement determines the Si–Si optical phonon behavior.     

Room temperature photoluminescence mechanism of SiOx film after annealing at different temperatures

SiO_x films were deposited on Si(1 0 0) substrates by evaporation of SiO powder. The samples were annealed from room-temperature (RT) to 1100 °C. After the samples were cooled down to RT, photoluminescence (PL) spectra from these samples were measured. It was found that when the annealing temperature Ta is not higher than 1000 °C, there is a PL centered at 620 nm, and with Ta increasing the intensity increases at first and then decreases when Ta is higher than 500 °C. When Ta is no less than 1000 °C another PL peak located at 720 nm appears. Combined with Raman and XRD spectra, we confirm that the latter PL is from Si nanocrystals that start to form when Ta is higher than 1000 °C. PL spectra for Ta<900 °C were discussed in detail and was attributed to defects in the matrix rather than from Si clusters.     

Porous Silicon as an Intermediate Buffer Layer for Zinc Oxide Nanorods

Zinc thin films were deposited onto porous silicon (PSi) substrates by dc sputtering using a Zn target. These films were then annealed under flowing (6 l/min) oxygen gas environment in the furnace at 600°C for 2 h. Porous silicon is used as an intermediate layer between silicon and ZnO films and it provides a large area composed of an array of voids. The PSi samples were prepared using photoelectrochemical method on n-type silicon wafer with (111) and (100) orientation. To prepare porous structures, the samples were dipped into a mixture of HF:ethanol (1:1) for 5 min with current densities of 50 mA/cm², and subjected to external illumination with a 500 W UV lamp. The surface morphology and the nanorod structure of the ZnO films were characterized by scanning electron microscope (SEM) and X-ray diffraction (XRD). We synthesized the ZnO nanorods with diameter of 80–100 nm without any catalysts or templates. The XRD pattern confirmed that the ZnO nanorods were of polycrystalline structure. The surface-related optical properties have been investigated by photoluminescence (PL) and Raman measurements at room temperature. Micro-Raman results showed that A₁(LO) of hexagonal ZnO/Si(111) and ZnO/Si(100) have been observed at 522 cm^–1 and 530 cm^–1, respectively. PL spectra peaks are clearly visible at 366 cm^–1 and 368 cm^–1 for ZnO film grown on porous Si(111) and Si(100) substrates, respectively. The PL spectral peak position in ZnO nanorods on porous silicon is blue-shifted with respect to that in unstrained ZnO (381 nm).     

Investigation on preparation and physical properties of nanocrystalline Si/SiO2 superlattices for Si-based light-emitting devices

Structures containing silicon nanocrystals (nc-Si) are very promising for Si-based light-emitting devices. Using a technology compatible with that of silicon, a broader wavelength range of the emitted photoluminescence (PL) was obtained with nc-Si/SiO₂ multilayer structures. The main characteristic of these structures is that both layers are light emitters. In this study we report results on a series of nc-Si/SiO₂ multilayer periods deposited on 200 nm thermal oxide SiO₂/Si substrate. Each period contains around 10 nm silicon thin films obtained by low-pressure chemical vapour deposition at T=625°C and 100 nmSiO₂ obtained by atmospheric pressure chemical vapour deposition T=400°C. Optical and microstructural properties of the multilayer structures have been studied by spectroscopic ellipsometry (using the Bruggemann effective medium approximation model for multilayer and multicomponent films), FTIR and UV–visible reflectance spectroscopy. IR spectroscopy revealed the presence of SiO_x structural entities in each nc-Si/SiO₂ interface. Investigation of the PL spectra (using continuous wave-CW 325 nm and pulsed 266 nm laser excitation) has shown several peaks at 1.7, 2, 2.3, 2.7, 3.2 and 3.7 eV, associated with the PL centres in SiO₂, nc-Si and Si–SiO₂ interface. Their contribution to the PL spectra depends on the number of layers in the stack.