Study on structural properties of epitaxial silicon films on annealed double layer porous silicon

In this paper, epitaxial silicon films were grown on annealed double layer porous silicon by LPCVD. The evolvement of the double layer porous silicon before and after thermal annealing was investigated by scanning electron microscope. X-ray diffraction and Raman spectroscopy were used to investigate the structural properties of the epitaxial silicon thin films grown at different temperature and different pressure. The results show that the surface of the low-porosity layer becomes smooth and there are just few silicon-bridges connecting the porous layer and the substrate wafer. The qualities of the epitaxial silicon thin films become better along with increasing deposition temperature. All of the Raman peaks of silicon films with different deposition pressure are situated at 521 cm⁻¹ under the deposition temperature of 1100 °C, and the Raman intensity of the silicon film deposited at 100 Pa is much closer to that of the monocrystalline silicon wafer. The epitaxial silicon films are all (4 0 0)-oriented and (4 0 0) peak of silicon film deposited at 100 Pa is more symmetric.     

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.     

An investigation of natural oxidation process on stain-etched nanoporous silicon by micro-Raman spectroscopy

Micro-Raman spectra of porous silicon (PS) samples as-formed, from stain etching process using heavily doped silicon wafers, and after 750 days storage in air were analyzed around Si peak (300-600 cm⁻¹) and at photoluminescence (PL) range (300-8000 cm⁻¹). The first-order Raman spectra in the vicinity of Si peak were fitted from phonon confinement model including a term taking into account the amorphous phase. This analysis allowed the determination of the correlation length, which corresponds to the crystallite size, also considering the PS natural oxidation process. The photoluminescence band, generated by Si crystallites located on the outermost part of the PS layer, was also fitted with a Gaussian distribution. In order to investigate the porous silicon nanostructure, the micro-Raman spectra were measured for different sets of porous silicon samples. These spectra showed good reproducibility and the effects of the natural oxidation at different periods. A slight decrease in the crystallite size was observed for all samples sets studied, while the spectral part related to the amorphous phase did not describe significant changes. The central position of PL band, analyzed after the oxidation process, exhibited consistently a shift to higher energies. In addition, top view high resolution scanning electron microscopy (HRSEM) images also confirmed a reasonable reproducibility and homogeneity. The results showed that after storing in air, natural oxidation can modify the Si crystallites size at the surface but not increase the amorphous phase.     

High sensitivity of palladium on porous silicon MSM photodetector

In this work, the nanocrystalline porous silicon (PS) is prepared through the simple electrochemical etching of n-type Si (1 0 0) under the illumination of a 100 W incandescent white light. SEM, AFM, Raman and PL have been used to characterize the morphological and optical properties of the PS. SEM shows uniformed circular pores with estimated sizes, which range between 100 and 500 nm. AFM shows an increase in its surface roughness (about 6 times compared to c-Si). Raman spectra of the PS show a stronger peak with FWHM=4.3 cm⁻¹ and slight blueshift of 0.5 cm⁻¹ compared to Si. The room temperature photoluminescence (PL) peak corresponding to red emission is observed at 639.5 nm, which is due to the nano-scaled size of silicon through the quantum confinement effect. The size of the Si nanostructures is estimated to be around 7.8 nm from a quantized state effective mass theory. Thermally untreated palladium (Pd) finger contact was deposited on the PS to form MSM photodetector. Pd/PS MSM photodetector shows lower dark (two orders of magnitude) and higher photocurrent compared to a conventional Si device. Interestingly, Pd/PS MSM photodetector exhibits 158 times higher gain compared to the conventional Si device at 2.5 V.     

Blue–green and red luminescence from ZnO/porous silicon and ZnO:Cu/porous silicon nanocomposite films

Both ZnO and Cu doped ZnO films with strong c-axis preferred orientation have been successfully prepared on porous silicon substrate, formed by electrochemical anodization, using radio frequency reactive magnetron sputtering method. X-ray diffraction measurements showed that the intensity of (0 0 2) diffraction peak first decreased and then increased with the Cu doping content increasing. Meanwhile new weak (1 0 0), (1 0 1), (1 0 2) and (1 1 0) diffraction peaks appeared after doping. The optical band edge of ZnO:Cu films, deduced from the optical absorption spectra, shifted to a longer wavelength comparing with the undoped sample and we attributed this red shift phenomenon to the decreasing of carrier concentration. The broad light emission from 350 to 800 nm was obtained by combining the blue–green emission from ZnO with red–orange emission from porous silicon. This could be used as a source of white light emitting diode chips underlying the importance of our work. The variation and origin of the emission peaks were discussed through the Gaussian deconvolution, and the Raman scattering spectral revealed the characteristics of porous silicon and multiphonon processes.     

Investigation of structural and optical properties of nanoporous GaN film

The structural and optical characteristics of porous GaN prepared by Pt-assisted electroless etching under different etching durations are reported. The porous GaN samples were investigated by scanning electron microscopy (SEM), high-resolution X-ray diffraction (HR-XRD), photoluminescence (PL) and Raman scattering. SEM images indicated that the density of the pores increased with the etching duration; however, the etching duration has no significant effect on the size and shape of the pores. XRD measurements showed that the (0 0 0 2) diffraction plane peak width of porous samples was slightly broader than the as-grown sample, and it increased with the etching duration. PL measurements revealed that the near band edge peak of all the porous samples were red-shifted; however, the porosity-induced PL intensity enhancement was only observed in the porous samples; apart from that, two additional strain-induced structural defect-related PL peaks observed in as-grown sample were absent in porous samples. Raman spectra showed that the shift of E₂ (high) to lower frequency was only found in samples with high density of pores. On the contrary, the absence of two forbidden TO modes in the as-grown sample was observed in some of porous samples.     

Hybrid nanostructured supports for surface enhanced Raman scattering

Porous silicon solid supports with pore diameter 0.5-1 μm, infiltrated with Ag nanostructures for surface enhanced Raman scattering (SERS) were prepared according to two procedures: spontaneous Ag⁺ reduction on the surface of freshly etched porous silicon immersed in Ag⁺ aqueous solutions, or anchoring colloidal Ag nanoparticles on the surface previously functionalized by aminosilane. Using Rhodamine 6G (RH6G) as analyte the detection limits were of the order of 20 μM and 20 nM with porous silicon metalized by the first and second procedure, respectively. This large increase of sensitivity notwithstanding a reduced surface density of Rhodamine 6G obtained on porous silicon metalized by the second procedure is discussed in terms of better hot spot efficiency and reduced aspecific binding out of the hot regions obtained depositing the colloids on the aminosilane functionalized surface.     

The effects of porous silicon on the crystalline properties of ZnO thin films

In the present work, ZnO was deposited on porous silicon substrates by sol-gel spin coating and rf magnetron sputtering. The porous silicon (PS) substrates were formed by electrochemical anodization on p-type (1 0 0) silicon wafer, and the starting material for ZnO was Zinc acetate dehydrate. Raman spectroscopy revealed the good quality of the porous silicon substrate. XRD analysis showed that highly (0 0 2) oriented ZnO thin films were formed. SEM, AFM and optical microscope have been used to understand the effects of the substrate on crystalline properties of the samples. The results indicated that the porous silicon substrate is beneficial to improve the crystalline quality in lattice mismatch heteroepitaxy due to its sponge-like structure.     

Signatures of epitaxial graphene grown on Si-terminated 6H-SiC (0 0 0 1)

Epitaxial graphene layers thermally grown on Si-terminated 6H-SiC (0 0 0 1) have been probed using Auger electron spectroscopy, Raman microspectroscopy, and scanning tunneling microscopy (STM). The average multilayer graphene thickness is determined by attenuation of the Si (L₂₃VV) and C (KVV) Auger electron signals. Systematic changes in the Raman spectra are observed as the film thickness increases from one to three layers. The most striking observation is a large increase in the intensity of the Raman 2D-band (overtone of the D-band and also known as the G′-band) for samples with a mean thickness of more than ∼1.5 graphene layers. Correlating this information with STM images, we show that the first graphene layer imaged by STM produces very little 2D intensity, but the second imaged layer shows a single-Lorentzian 2D peak near 2750 cm⁻¹, similar to spectra acquired from single-layer micromechanically cleaved graphene (CG). The 4-10 cm⁻¹ higher frequency shift of the G peak relative to CG can be associated with charge exchange with the underlying SiC substrate and the formation of finite size domains of graphene. The much greater (41-50 cm⁻¹) blue shift observed for the 2D-band may be correlated with these domains and compressive strain.     

Effect of N ion implantation on the optical properties of an organometallic complex—Zinc cadmium thiocyanate single crystal

A highly efficient non-linear optical organometallic compound zinc cadmium thiocyanate (ZCTC) single crystal was grown by solvent evaporation method. The as grown single crystals were implanted with 45 keV N⁵⁺ ions having energy at various fluencies of 1 × 10¹⁵, 5 × 10¹⁵, 1 × 10¹⁶ and 5 × 10¹⁶ ions/cm². The surface modification induced by the ion implantation was studied using scanning electron microscopy. The UV spectrum shows an increase in absorbance with the increase in the dosage of the ions implanted. There is a red shift in the cut off wavelength due to implantation which may be attributed to the lattice damage produced during implantation. From the Raman spectra, it is observed that there is no shift in the peak positions or any extra peaks due to implantation confirming that the nitrogen ions are not substituted into the lattice. The FWHM, area and intensity of the Raman peak corresponding to CN stretching vibration were calculated and the influence of ion implantation on these parameters was discussed. The effect of implantation on the PL spectra was analysed and discussed in detail. The change in refractive index of the sample due to implantation was reported.     

Photoluminescence activity of Yang and Secco etched multicrystalline silicon material

Ultraviolet and blue-green photoluminescence (PL) was investigated on multicrystalline silicon (mc-Si) samples chemically etched by Secco and Yang solutions. The samples were characterized by dislocation density (10⁵-10⁶ cm⁻²). The form of etched pits is triangular with Yang etch and like a honeycomb with Secco etch as observed with a scanning electron microscope (SEM). These textures of mc-Si wafers give a PL activity similar to that obtained with nanostructures of porous silicon (PS) as reported in the literature. The ultraviolet PL spectra observed with Yang etch shift to the blue-green spectrum range when applying Secco etch. In our experiments we have observed 3-5 μm diameter macro pores separated by a high density of nanowalls. These observations suggest that the origin of the PL activity are quantum dots resulting from the silicon nanocrystallites obtained after few minutes of chemical etching.     

空间限制与应变对发光多孔硅喇曼光谱的影响

发光多孔硅的喇曼光谱在５２０ｃｍ^－１附近呈现一锐峰，峰位的红移随多孔度的增大而增大采用微晶模型拟合喇曼谱的线形，发现除了光学声子的空间限制效应，硅单晶的应变对峰位的移动也有显著贡献。通过谱形的拟合估算了硅微粒的应变，与已报道的Ｘ射线衍射结果相一致。在多孔硅的喇曼光诸中没有观察到起源于非晶硅的光散射信号。 关键词：     

Raman scattering and optical absorption studies of an orbital ordered Ca2RuO4

We have reported the Raman scattering and infrared absorption results on a t_2g orbital ordered Ca₂RuO₄. At 10 K, a strong and clear peak was observed in Raman scattering near 1360 cm⁻¹ with x′x′ geometry. In contrast to optic phonon modes, the peak does not show any frequency shift but rapidly decreases with increasing temperature. In addition, the peak is not observed in infrared absorption measurement. By comparing the previous Raman scattering results for several transition metal oxides, we have discussed the possible origins and ambiguities of the intriguing peak in Ca₂RuO₄.     

Strong ultraviolet emission from zinc oxide thin films prepared by electrophoretic deposition

In this paper, we report a simple and efficient method to prepare high-quality nanocrystalline ZnO films by electrophoretic deposition. Absorption spectrum and transmission electron microscope image indicated that the average size of ZnO nanoparticles is about 9.5 nm. A strong ultraviolet emission peak at 384 nm is observed and the deep-level emission band is barely observed at room temperature. X-ray diffraction pattern revealed that the ZnO film has a polycrystalline hexagonal wurtzite structure. The Raman spectrum showed a typical resonant multi-phonon process within the ZnO film. The frequency shift of 1 LO phonon was about 583 cm⁻¹.     

Silicon donor and Stokes terahertz lasers

Two types of lasers based on hydrogen-like impurity-related transitions in bulk silicon operate at frequencies between 1 and 7 THz (wavelength range of 50-230 μm). These lasers operate under mid-infrared optical pumping of n-doped silicon crystals at low temperatures (<30 K). Dipole-allowed optical transitions between particular excited states of group-V substitutional donors are utilized in the first type of terahertz silicon lasers. These lasers have a gain ∼1-3 cm⁻¹ above the laser thresholds (>1 kW cm⁻²) and provide 10 ps-1 μs pulses with a few mW output power on discrete lines. Raman-type Stokes stimulated emission in the range 4.6-5.8 THz has been observed from silicon crystals doped by antimony and phosphorus donors when optically excited by radiation from a tunable infrared free electron laser. The scattering occurs on the 1s(E)→1s(A₁) donor electronic transition accompanied by an emission of the intervalley transverse acoustic g-phonon. The Stokes lasing has a peak power of a few tenths of a mW and a pulse width of a few ns. The Raman optical gain is about 7.4 cm GW⁻¹ and the optical threshold intensity is ∼100 kW cm⁻².     

Effect of Cr implantation on structural and optical properties of AlN thin films

Molecular beam epitaxy (MBE) grown AlN thin layer on sapphire substrates have been implanted with Cr⁺ ions for various dose from 10¹³ to 10¹⁵ cm⁻². The analyses were carried out by an X-ray diffractometer (XRD), Raman spectroscopy, a spectrophotometer and spectroscopic ellipsometry (SE) for structural and optical analyses. E₂(high) and A₁(LO) Raman modes of AlN layer have been observed and analyzed. The behavior of Raman shift and the variation in intensity and in peak width of Raman modes as a function of ions flux are explained on the basis of chromium substituting aluminum atom and implantation-induced lattice damage. Both Raman and X-ray analyses reveal that the incorporation of chromium atoms increases in the host lattice with the increasing of Cr ions fluence. The band gap energy was determined by using transmission spectra. It was found that the band gap energy decreases as the ion dose increases. The band gap of the unimplanted AlN is 6.02 eV and it decreases down to 5.92 eV for the Cr⁺-implanted AlN with a ion dose of 1×10¹⁵ cm⁻². Optical properties such as optical constants of the samples were examined by using a spectroscopic ellipsometer. It was observed that the refractive index (n) decreases with the increasing of ion dose.     

The effect of etching time of porous silicon on solar cell performance

Porous silicon (PS) layers based on crystalline silicon (c-Si) n-type wafers with (1 0 0) orientation were prepared using electrochemical etching process at different etching times. The optimal etching time for fabricating the PS layers is 20 min. Nanopores were produced on the PS layer with an average diameter of 5.7 nm. These increased the porosity to 91%. The reduction in the average crystallite size was confirmed by an increase in the broadening of the FWHM as estimated from XRD measurements. The photoluminescence (PL) peaks intensities increased with increasing porosity and showed a greater blue shift in luminescence. Stronger Raman spectral intensity was observed, which shifted and broadened to a lower wave numbers of 514.5 cm⁻¹ as a function of etching time. The lowest effective reflectance of the PS layers was obtained at 20 min etching time. The PS exhibited excellent light-trapping at wavelengths ranging from 400 to 1000 nm. The fabrication of the solar cells based on the PS anti-reflection coating (ARC) layers achieved its highest efficiency at 15.50% at 20 min etching time. The I-V characteristics were studied under 100 mW/cm² illumination conditions.     

SERS-active substrates based on n-type porous silicon

Porous silicon (PS) prepared from n-type Si crystal is proposed as a new material for the fabrication of sensitive substrates for surface-enhanced Raman scattering (SERS). The formation procedure for nanostructured silver films on the surface of PS was optimized. Maximum of SERS enhancement for rhodamine 6G probing molecule is observed for samples obtained by the immersion plating from the water solution of AgNO₃ with the 10 mM concentration during 5 min. The dependence of morphological parameters of PS and corresponding silvered surfaces on the anodization current density has been studied. It is shown that the most SERS activities possess substrates produced from PS with lower porosity. The optimum of the PS layer thickness for high Raman signal is about 5 μm. The detection limit for rhodamine 6G adsorbed on Ag-coated PS from the 100 pM solution is established to be comparable with that for p-type PS-based substrates. Thus, the n-type porous silicon is suitable material for the preparation of sensitive SERS-active substrates.     

Structure and hardness of a-C:H films prepared by middle frequency plasma chemical vapor deposition

a-C:H films were prepared by middle frequency plasma chemical vapor deposition (MF-PCVD) on silicon substrates from two hydrocarbon source gases, CH₄ and a mixture of C₂H₂ + H₂, at varying bias voltage amplitudes. Raman spectroscopy shows that the structure of the a-C:H films deposited from these two precursors is different. For the films deposited from CH₄, the G peak position around 1520 cm⁻¹ and the small intensity ratio of D peak to G peak (I(D)/I(G)) indicate that the C-C sp³ fraction in this film is about 20 at.%. These films are diamond-like a-C:H films. For the films deposited from C₂H₂ + H₂, the Raman results indicate that their structure is close to graphite-like amorphous carbon. The hardness and elastic modulus of the films deposited from CH₄ increase with increasing bias voltage, while a decrease of hardness and elastic modulus of the films deposited from a mixture of C₂H₂ + H₂ with increasing bias voltage is observed.     

Near infrared to UV dielectric functions of Al doped ZnO films deposited on c-plane sapphire substrate using pulsed laser deposition

Transparent conducting polycrystalline Al-doped ZnO (AZO) films were deposited on sapphire substrates at substrate temperatures ranging from 200 to 300 °C by pulsed laser deposition (PLD). X-ray diffraction measurement shows that the crystalline quality of AZO films was improved with increased substrate temperature. The electrical and optical properties of the AZO films have been systematically studied via various experimental tools. The room-temperature micro-photoluminescence (µ-PL) spectra show a strong ultraviolet (UV) excitonic emission and weak deep-level emission, which indicate low structural defects in the films. A Raman shift of about 11 cm⁻¹ is observed for the first-order longitudinal-optical (LO) phonon peak for AZO films when compared to the LO phonon peak of bulk ZnO. The Raman spectra obtained with UV resonant excitation at room temperature show multi-phonon LO modes up to third order. Optical response due to free electrons of the AZO films was characterized in the photon energy range from 0.6 to 6.5 eV by spectroscopic ellipsometry (SE). The free electron response was expressed by a simple Drude model combined with the Cauchy model are reported.