Fano resonance in heavily doped porous silicon

Unexpectedly, the Fano resonance caused by the interference of continuum electron excitations with the longitudinal optical (LO) phonons was observed in random porous Si by Raman scattering. The analysis of the experimental data shows that the electron states trapped at the Si SiO₂ interface dominate in the observed Raman scattering. The gap energy associated with the interface states was determined. Copyright © 2011 John Wiley & Sons, Ltd.     

Submicron resolution carrier lifetime analysis in silicon with Fano resonances

Defect rich regions in multicrystalline silicon are investigated by Raman spectroscopy at high and low injection levels. By analyzing the Fano type asymmetry and the spectral position of the first order Raman peak crucial properties such as recombination lifetime, doping density and stress can be extracted simultaneously. Due to the small wavelength of the excitation laser the spatial resolution of these measurements is significantly below 1 µm, which gives new insight into the impact of defects on the carrier recombination lifetime. The results are evaluated by comparing them to micro‐photoluminescence and synchrotron X‐ray fluorescence measurements. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Raman spectroscopy for study of interplay between phonon confinement and Fano effect in silicon nanowires

A combined effect of doping (type and species) and size on Raman scattering from silicon (Si) nanowires (NWs) has been presented here to study interplay between quantum confinement and Fano effects. The SiNWs prepared from low doping Si wafers show only confinement effect, as evident from the asymmetry in the Raman line‐shape, irrespective of the doping type. On the other hand SiNWs prepared from wafer with high doping shows the presence of electron–phonon interaction in addition to the phonon confinement effect as revealed from the presence of asymmetry and antiresonence in the corresponding Raman spectra. This combined effect induces an extra asymmetry in the lower energy side of Raman peak for n‐type SiNWs whereas the asymmetry flips from lower energy side to the higher energy side of the Raman peak in p‐type SiNWs. Such an interplay can be represented by considering a general Fano‐Raman line‐shape equation to take care of the combined effect in SiNWs. Copyright © 2015 John Wiley & Sons, Ltd.     

Simple and inexpensive instrument for deep‐UV Raman spectroscopy

Deep‐UV Raman spectroscopy is a powerful way to collect chemically specific information about complex samples. The availability of inexpensive and reliable light sources in the spectral region below 250 nm has been always considered a major bottleneck problem on the way of a widespread of this powerful spectroscopic technique. We report on the efficient fourth‐harmonic generation of a low‐power microchip Nd:YAG laser operating at 946 nm. High‐quality deep‐UV Raman spectra were collected using a newly developed laser source. Copyright © 2013 John Wiley & Sons, Ltd.     

Temperature‐depending Raman line‐shift of silicon carbide

Silicon carbide (SiC) is often used for electronic devices operating at elevated temperatures. Spectroscopic temperature measurements are of high interest for device monitoring because confocal Raman microscopy provides a very high spatial resolution. To this end, calibration data are needed that relate Raman line‐shift and temperature. The shift of the phonon wavenumbers of single crystal SiC was investigated by Raman spectroscopy in the temperature range from 3 to 112°C. Spectra were obtained in undoped 6H SiC as well as in undoped and nitrogen‐doped 4H SiC. All spectra were acquired with the incident laser beam oriented parallel as well as perpendicular to the c‐axis to account for the anisotropy of the phonon dispersion. Nearly all individual peak centers were shifting linearly towards smaller wavenumbers with increasing temperature. Only the peak of the longitudinal optical phonon A₁(LO) in nitrogen‐doped 4H SiC was shifting to larger wavenumbers. For all phonons, a linear dependence of the Raman peaks on both parameters, temperature and phonon frequency, was found in the given temperature range. The linearity of the temperature shift allows for precise spectroscopic temperature measurements. Temperature correction of Raman line‐shifts also provides the ability to separate thermal shifts from mechanically induced ones. Copyright © 2009 John Wiley & Sons, Ltd.     

Non‐invasive depth profiling by space and time‐resolved Raman spectroscopy

Time‐resolved Raman spectroscopy, spatially offset Raman spectroscopy and time‐resolved spatially offset Raman spectroscopy (TR‐SORS) have proven their capability for the non‐invasive profiling of deep layers of a sample. Recent studies have indicated that TR‐SORS exhibits an enhanced selectivity toward the deep layers of a sample. However, the enhanced depth profiling efficiency of TR‐SORS, in comparison with time‐resolved Raman spectroscopy and spatially offset Raman spectroscopy, is yet to be assessed and explained in accordance to the synergistic effects of spatial and temporal resolutions. This study provides a critical investigation of the depth profiling efficiency of the three deep Raman techniques. The study compares the efficiency of the various deep Raman spectroscopy techniques for the stand‐off detection of explosive precursors hidden in highly fluorescing packaging. The study explains for the first time the synergistic effects of spatial and temporal resolutions in the deep Raman techniques and their impact on the acquired spectral data. Copyright © 2013 John Wiley & Sons, Ltd.     

Micro‐Raman depth profiling of silicon amorphization induced by high‐energy ion channeling implantation

In this work, we study the silicon amorphization dependence on the crystal depth induced by 6‐MeV Al²⁺ ions implanted in the <110> and randomly oriented silicon crystal channels, which was not directly experimentally accessible in the previous similar high‐energy ion–crystal implantation cases. Accordingly, the micro‐Raman spectroscopy scanning measurements along the crystal transversal cross section of the ion implanted region were performed. The ion fluence was 10¹⁷ particles/cm². The scanning steps were 0.2 and 0.3 µm, for the channeling and random ion implantations, respectively. The obtained results are compared with the corresponding Rutherford backscattering spectra of 1.2‐MeV protons in the random and channeling orientations measured during the channeling implantation. Additionally, scanning electron microscope picture was taken on the transversal cross section of the implanted region in the channeling implantation case. We show here that the obtained silicon amorphization maxima are in excellent agreement with the corresponding estimated maxima of the aluminum concentration in silicon. This clearly indicates that the used specific micro‐Raman spectroscopy scanning technique can be successfully applied for the depth profiling of the crystal amorphization induced by high‐energy ion implantation. Copyright © 2013 John Wiley & Sons, Ltd.     

Enhanced Raman scattering in multilayer structures of porous silicon

Multiple enhancement of the Raman scattering efficiency is observed in porous‐silicon‐based one‐dimensional photonic bandgap (PBG) structures with tunable reflection and dispersion under excitation at 1.06 µm. The experimental results are explained as being due to the resonant increase in the effective Raman susceptibility at light wavelengths close to the PBG edges. This effect is discussed in view of possible applications in the Raman spectroscopy of molecules embedded in porous media as well as in the Raman laser based on silicon. Copyright © 2011 John Wiley & Sons, Ltd.     

Micro‐Raman investigation of transition‐metal‐doped ZnO nanoparticles

We measured the Raman spectra of ZnO nanoparticles (ZnO‐NPs), as well as transition‐metal‐doped (5% Mn(II), Fe(II) or Co(II)) ZnO nanoparticles, with an average size of 9 nm. A typical Raman peak at 436 cm⁻¹ is observed in the ZnO‐NPs, whereas Zn_1−xMn_xO, Zn_1−xFe_xO and Zn_1−xCo_xO presented characteristic peaks at 661, 665 and 675 cm⁻¹, respectively. These peaks can be related to the formation of Mn₃O₄, Fe₃O₄ and Co₃O₄ species in the doped ZnO‐NPs. Moreover, these samples were analyzed at various laser powers. Here, we observed new vibrational modes (512, 571 and 528 cm⁻¹), which are specific to Mn, Fe and Co dopants, respectively, and ZnO‐NPs did not reveal any additional modes. The new peaks were interpreted either as disorder activated phonon modes or as local vibrations of Mn‐, Fe‐ and Co‐related complexes in ZnO. Copyright © 2007 John Wiley & Sons, Ltd.     

Micro‐Raman scattering spectroscopy study of Li‐doped and undoped ZnO needle crystals

ZnO nanostructures have attracted great attention for possible applications in optoelectronic and spintronic devices. The electrical resistivity because of carriers can be improved by the introduction of Li ions, as Li is a possible dopant for achieving p‐type ZnO. We have carried out a comprehensive micro‐Raman scattering study of the phonons in 1% Li‐ and undoped ZnO needle crystals grown and annealed at 1073 K for 1 and 2 h under oxygen environment. Phonon mode of doped and undoped ZnO does not show any measurable shift for the doping concentration of 1%. As line width is related to point defect density, we find for both Li‐ and undoped ZnO crystals the crystallinity is improving towards the tip of the needle crystals. Copyright © 2008 John Wiley & Sons, Ltd.     

UV‐resonance Raman micro‐spectroscopy to assess residual chromophores in cellulosic pulps

Ultraviolet‐resonance Raman (UV‐RR) micro‐spectroscopy is an appropriate and sensitive tool to assess the chromophore structures in bleached cellulosic pulps used for papermaking. The particular selectivity in detection and identification of chromophores in pulps is achieved by acquiring the UV‐RR spectra in the solid state with laser excitation at 325 nm. This wavelength corresponds to absorption of poly‐unsaturated chromophore structures in partially bleached/fully bleached pulps, and linearly correlated with the signal at ca 1600 cm⁻¹ in the UV‐RR spectra. The characteristic vibrations from particular pulp chromophore structures have been assigned from experiments with model compounds, thus allowing the establishment of a UV‐RR database. Among the components of bleached pulp, the xylan–lignin complex was suggested to be an important source of chromophores. The monitoring of pulp bleaching by UV‐RR allowed us to suggest that it is the formation of new polysaccharide‐derived chromophores upon bleaching that hinders development of further brightness and is co‐responsible for the brightness reversion of fully bleached pulps. Copyright © 2010 John Wiley & Sons, Ltd.     

Acceleration and mitigation of carrier‐induced degradation in p‐type multi‐crystalline silicon

Recently, a new carrier‐induced defect has been reported in multi‐crystalline silicon (mc‐Si), and has been shown to be particularly detrimental to the performance of passivated emitter and rear contact (PERC) cells. Under normal conditions, this defect can take years to fully form. This Letter reports on the accelerated formation and subsequent passivation of this carrier‐induced defect through the use of high illumination intensity and elevated temperatures resulting in passivation within minutes. The process was tested on industrial mc‐Si PERC solar cells, where degradation after a 100 hour stability test was suppressed to only 0.1% absolute compared to 2.1% for non‐treated cells. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Light‐induced degradation in indium‐doped silicon

Light‐induced degradation of charge carrier lifetime was observed in indium‐doped silicon. After defect formation, an annealing step at 200 °C for 10 min deactivates the defect and the initial charge carrier lifetime is fully recovered. The observed time range of the defect kinetics is similar to the well known defect kinetics of the light‐induced degradation in boron‐doped samples. Differences between defect formation in boron‐ and indium‐doped silicon are detected and discussed. A new model based on an acceptor self‐interstitial A_Si–Si_i defect is proposed and established with experimental findings and existing ab‐initio simulations.

     

Abnormal Raman spectra in Er‐doped BaTiO3 ceramics

Greatly enhanced and abnormal Raman spectra were discovered in the nominal (Ba_{1 − x}Er_x)Ti_{1 − x/4}O₃ (x = 0.01) (BET) ceramic for the first time and investigated in relation to the site occupations of Er³⁺ ions. BaTiO₃ doped with Ti‐site Er³⁺ mainly exhibited the common Raman phonon modes of the tetragonal BaTiO₃. Er³⁺ ions substituted for Ba sites are responsible for the abnormal Raman spectra, but the formation of defect complexes will decrease spectral intensity. A large increase in intensity showed a hundredfold selectivity for Ba‐site Er³⁺ ions over Ti‐site Er³⁺ ions. A strong EPR signal at g = 1.974 associated with ionized Ba vacancy defects appeared in BET, and the defect chemistry study indicated that the real formula of BET is expressed by (Ba_{1 − x}Er_3x/4)(Ti_{1 − x/4}Er_x/4)O₃. These abnormal Raman signals were verified to originate from a fluorescent effect corresponding to ⁴S_3/2→⁴I_15/2 transition of Ba‐site Er³⁺ ions. The fluorescent signals were so intense that they overwhelmed the traditional Raman spectra of BaTiO₃. The significance is that the abnormal Raman spectra may act as a probe for the Ba‐site Er³⁺ occupation in BaTiO₃ co‐doped with Er³⁺ and other dopants. A new broad EPR signal at g = 2.23 was discovered, which originated from Er³⁺ Kramers ions. Copyright © 2014 John Wiley & Sons, Ltd.     

Determination of the disorder profile in an ion‐implanted silicon carbide single crystal by Raman spectroscopy

Silicon carbide is an interesting material for GEN IV fission reactor projects because of its excellent properties. However, these properties will be altered under extreme conditions such as irradiation because of accumulation of damage. Mechanisms playing a role in defect formation require further studies in the case of high energy heavy ion irradiations. In this work a silicon carbide single crystal slice has been implanted with 20 MeV Au ions and probed by using Raman spectrometry. The resulting Raman spectra recorded as a function of depth clearly show a damaged zone, in which the width is in agreement with the projected range of the incident ions (R_p) calculated by using SRIM code. In this area, three damaged zones have been brought to light because of the high spatial resolution of the Raman spectrometry technique. The existence of these zones is discussed with regard to the different energy loss regimes of the implanted ions such as the electronic and nuclear ones. Copyright © 2012 John Wiley & Sons, Ltd.     

In situ monitoring of solid‐state transition of p‐aminobenzoic acid polymorphs using Raman spectroscopy

The purpose of this study is to investigate the mechanism of solid‐state polymorphic transition of p‐aminobenzoic acid (PABA) using in situ Raman spectroscopy measurement. The polymorphic transition experiments were conducted on a micro quartz vessel mounted on a microscope, hot and cold stage, under isothermal conditions. The temperature was precisely controlled by a standalone temperature controller equipped with liquid nitrogen cooling system. The Raman spectroscopy probe was positioned on the surface of the solid sample in the micro vessel. The polymorphic transition progression was in situ monitored and recorded by Raman spectroscopy. Based on the polymorphic transition rate resulted from the quantitative analysis of Raman spectra, the mechanism of solid‐state polymorphic transition of PABA was examined by various empirical kinetic models. An Arrhenius analysis was also performed to calculate activation energies from 134.7 kJ mol⁻¹ to 137.7 kJ mol⁻¹ for the transition. The results demonstrated that in situ Raman spectroscopy is a valuable and accurate technique to probe polymorphic transition process. Copyright © 2009 John Wiley & Sons, Ltd.     

Micro‐Raman study of orbiton–phonon coupling in YbVO3

First‐order and multiphonon Raman active excitations are studied in YbVO₃ as a function of temperature in the orthorhombic and monoclinic phases. Below T ≃ 170 K, a G‐type orbital ordering with a concomitant monoclinic transition occurs. They enhance the phonon polarizabilities, allowing the resolution of room‐temperature bands, and activate new excitations around 700 cm⁻¹. Below T ∼ 65 K, the 700 cm⁻¹ excitations disappear, indicating a C‐type orbital ordering and a return to the orthorhombic structure. The observed phonon combinations around 1400 cm⁻¹ with a dominant Jahn‐Teller vibration at ∼690 cm⁻¹ reflect a possible orbiton‐phonon coupling. Copyright © 2011 John Wiley & Sons, Ltd.     

Temperature‐dependent Raman spectroscopy of BaTiO3 nanorods synthesized by using a template‐assisted sol–gel procedure

In the present work, multiphase polycrystalline BTO nanorods were synthesized using template‐assisted sol–gel deposition and their structural evolution was studied using thermo Raman spectroscopy, X‐ray diffractometry and high‐resolution transmission electron microscopy (HRTEM). In the BTO nanorods, the tetragonal phase was the dominant one, while both Raman and HRTEM indicated a coexistence with the high‐temperature hexagonal polymorph. This phase was stable across the whole of the investigated temperature range (from −95 °C to 200 °C). The investigated nanorods underwent a diffuse phase transition from tetragonal to cubic with respect to the temperature, whereas the final phase‐transition temperature was shifted to higher values compared to that expected for BTO. The low‐temperature orthorhombic‐to‐rhombohedral phase transition was also shifted to higher temperatures. These differences could be explained by the strain induced by the presence of hexagonal nanolamellas intergrown within the tetragonal nanocrystals. This result indicates that the temperature of the ferroelectric phase transition in polycrystalline BTO nanorods can be manipulated by introducing a stable hexagonal phase. Copyright © 2012 John Wiley & Sons, Ltd.