Raman spectroscopic studies of ZnSe/GaAs interfaces

ZnSe/semi‐insulating GaAs interfaces were studied by observing photogenerated plasmon–LO (PPL) coupled modes by nonresonant micro‐Raman spectroscopy. The effect of the carriers generated by the focused laser beam was investigated for a series of different thicknesses of ZnSe epitaxial layers. The PPL mode in GaAs was observed in the micro‐Raman spectra for all samples, but with different magnitude. The plasma is believed to be an electron gas as a result of the negative nature of the interfacial region that contains predominantly hole traps. The free carrier concentration is estimated to be > 10¹⁸ cm⁻³ and their lifetime ∼0.1 ns. This relatively long lifetime suggests that the ZnSe/GaAs interface has to be of high structural quality leading to a low recombination velocity. ZnSe/GaAs heterostructures of less crystalline quality (as determined by resonant Raman measurements) shows the effect of photogenerated carriers only to lesser extent. Copyright © 2007 John Wiley & Sons, Ltd.     

Time‐resolved free carrier lifetime microscopy in bulk GaN

A novel setup for lifetime microscopy measurements was designed and applied for carrier lifetime mapping in a bulk GaN. Photoexcitation by a picosecond UV pump and detection of time‐resolved free carrier absorption (FCA) images on a CCD camera enabled the mapping of carrier lifetime distribution with a spatial resolution of 5 μm. The spatial variation of lifetime in the bulk HVPE‐grown GaN revealed the presence of different‐size crystalline grains, with lifetime peaking up to 70 ns in the centers of the largest grains (～20 μm in diameter) and dropping to 10 ns in the small ones, while the spatially averaged lifetime was 40 ns. The inhomogeneity was ascribed to the interplay of nonradiative diffusion‐limited recombination at grain boundaries and a bulk lifetime in the crystallite centers. The numerical solution of spatially‐resolved carrier decay rate in the crystallite centers at high injection levels and comparison with experimental data provided a bulk nonradiative recombination time of ～70 ns. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Thermal activation and deactivation of grown‐in defects limiting the lifetime of float‐zone silicon

By studying the minority carrier lifetime in recently manufactured commercially available n‐ and p‐type float‐zone (FZ) silicon from five leading suppliers, we observe a very large reduction in the bulk lifetime when FZ silicon is heat‐treated in the range 450–700 °C. Photoluminescence imaging of these samples at the wafer scale revealed concentric circular patterns, with higher recombination occurring in the centre, and far less around the periphery. Deep level transient spectroscopy measurements indicate the presence of recombination active defects, including a dominant center with an energy level at ～E_v + 0.5 eV. Upon annealing FZ silicon at temperatures >1000 °C in oxygen, the lifetime is completely recovered, whereby the defects vanish and do not reappear upon subsequent annealing at 500 °C. We conclude that the heat‐treatments at >1000 °C result in total annihilation of the recombination active defects. Without such high temperature treatments, the minority carrier lifetime in FZ silicon is unstable and will affect the development of high efficiency (>24%) solar cells and surface passivation studies.     

Interfacial electronic properties of Au?GaAs interfaces studied by photomodulation Raman spectroscopy (pump–probe technique)

Photomodulation Raman spectroscopy (PM‐RS) was employed to investigate the interfacial properties of Au: n‐type GaAs interfaces, using the forbidden longitudinal optical (LO) phonon scattering as a probe. In PM‐RS, the photomodulating pump beam (PB) is incident on the sample while the Raman measurements are in progress; hence, PM‐RS can be viewed as a pump–probe technique. The photogenerated carriers partly neutralize the surface charges, which decreases the interfacial field and consequently the intensity of forbidden LO scattering. Two molecular beam epitaxy (MBE) junctions of 80 Å Au on n‐type GaAs (001) substrate with two different doping densities were used. The total surface charge density and change in the band bending were obtained as a function of the PB intensity considering a constant depletion electric field for the lower doped sample. Furthermore, the interfacial minority carrier trap lifetime was determined through dynamical measurements of the PM‐RS intensity. Copyright © 2010 John Wiley & Sons, Ltd.     

Protecting TERS probes from degradation: extending mechanical and chemical stability

The detailed surface chemistry of aluminum oxide protected silver films for use specifically in surface enhanced Raman spectroscopy and tip enhanced Raman spectroscopy (TERS) was investigated. We have demonstrated that increased storage and scanning use lifetimes for silver plasmonic structures are directly connected with the elimination of chemical degradation at the plasmonic structure surface. X‐ray photoelectron spectroscopy of the metal films confirmed that a 2–3 nm thick coating of aluminum oxide prevented chemical attack of the underlying silver film for three months of storage in a desiccator, significantly increasing the storage lifetime of current probes. The scanning lifetime of a TERS probe when used to image a hard patterned silicon substrate was doubled with the addition of this protective coating. These measurements were performed without laser illumination in order to separate laser‐induced heating degradation from pure mechanical degradation of the metallized probe currently encountered during TERS data collection. Copyright © 2013 John Wiley & Sons, Ltd.     

Extremely low surface recombination in 1 Ω cm n‐type monocrystalline silicon

A key requirement in the recent development of highly efficient silicon solar cells is the outstanding passivation of their surfaces. In this work, plasma enhanced chemical vapour deposition of a triple layer dielectric consisting of amorphous silicon, silicon oxide and silicon nitride, charged extrinsically using corona, has been used to demonstrate extremely low surface recombination. Assuming Richter's parametrisation for bulk lifetime, an effective surface recombination velocity S_eff = 0.1 cm/s at Δn = 10¹⁵ cm^–3 has been obtained for planar, float zone, n ‐type, 1 Ω cm silicon. This equates to a saturation current density J_0s = 0.3 fA/cm², and a 1‐sun implied open‐circuit voltage of 738 mV. These surface recombination parameters are among the lowest reported for 1 Ω cm c‐Si. A combination of impedance spectroscopy and corona‐lifetime measurements shows that the outstanding chemical passivation is due to the small hole capture cross section for states at the interface between the Si and a‐Si layer which are hydrogenated during nitride deposition. (© 2016 The Authors. Phys. Status Solidi RRL published by WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Thermal deactivation of lifetime‐ limiting grown‐in point defects in n‐type Czochralski silicon wafers

In this study, we uncover a recombination‐active grown‐in defect reducing the minority carrier lifetime of Czochralski grown n‐type silicon from 5 ms to below 2 ms. We also demonstrate that the defect can be de‐activated by annealing between 300 °C and 360 °C. Our experimental findings suggest that vacancy‐related pairs incorporated during ingot growth may be responsible for the decreased minority carrier lifetime. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Deactivation of the boron–oxygen recombination center in silicon by illumination at elevated temperature

The boron–oxygen‐related recombination center responsible for the light‐induced degradation of solar cells made on boron‐doped oxygen‐contaminated silicon is deactivated by simultaneously annealing the silicon wafer in the temperature range 135–210 °C and illuminating it with white light. The recombination lifetime after deactivation is found to be stable under illumination at room temperature. The deactivation process is shown to be thermally activated with an activation energy of 0.7 eV. Based on the experimental findings, a defect reaction model is proposed explaining the deactivation of the boron–oxygen center. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Coherent molecular vibrational dynamics of CH2 stretching modes in polyethylene studied by femtosecond‐CARS

We have studied the coherent molecular vibrational dynamics of CH₂ stretching modes in polyethylene by time‐resolved femtosecond coherent anti‐Stokes Raman spectroscopy. We observed that the coherent vibrational relaxation of symmetric CH₂ stretching modes in polyethylene at room temperature is much faster than that previously measured in polyvinyl alcohol. In addition, it was detected that, at low temperature, the coherent vibrational relaxation of the symmetric stretching modes evidently becomes slower compared with that at room temperature. These temperature‐dependent measurements enable us to discriminate the contribution of pure dephasing mechanism, due to phonons and two‐level systems in polymer, from the contribution of lifetime of the vibrational excited state to the coherent vibrational relaxation of CH₂ stretching modes. We conclude that the coherent vibrational relaxation of symmetric CH₂ stretching modes at room temperature consists of the contribution of lifetime and approximately 1.5 times larger contribution of pure dephasing. Copyright © 2015 John Wiley & Sons, Ltd.     

Stilbazolium merocyanine dye determination in different solutions,concentrations and colloids using SERS

Surface‐enhanced Raman scattering (SERS) measurements were carried out on stilbazolium merocyanine dye in methanol and pyridine solvents. Both solutions were measured in a series of concentrations covering a range of 5 × 10⁻⁵ M to 5 × 10⁻⁸ M . In these measurements, Ag and Au colloids were used, and the results have shown that Ag colloids yield better enhancement in the Raman spectra of this dye. Moreover, the effect of adding NaCl solution to the SERS samples was also studied. All measurements were carried out using the state‐of‐the‐art ChiralRaman instrument, which utilizes a 532 nm laser source. We report here on the success of using SERS to obtain Raman spectra of merocyanine dye at very low concentrations in an attempt to find a new approach that can be used for further investigations of the dye. The SERS spectra are reported here, and the results from different solutions, colloids, concentrations and pH values are compared. Copyright © 2006 John Wiley & Sons, Ltd.     

CW measurements of resonance Raman profiles,line‐widths,and cross‐sections of fluorescent dyes: application to Nile Blue A in water and ethanol

The aim of this work is to illustrate the power of recently developed methods for measuring resonance Raman scattering (RRS) spectra of efficient fluorophores (using a standard continuous wave excitation and a charge‐coupled device (CCD)‐based Raman spectrometer), by applying them to a detailed study of a specific fluorophore: Nile Blue A. A combination of methods are used to measure the RRS properties of Nile Blue A in water (quantum yield (QY) of 4%) and ethanol (QY of 22%) at excitation wavelengths between 514 and 647 nm, thus covering both pre‐resonance and RRS conditions. Standard Raman measurements are used in situations where the fluorescence background is small enough to clearly observe the Raman peaks, while the recently introduced polarization‐difference RRS and continuously shifted Raman scattering are used closer to (or at) resonance. We show that these relatively straightforward methods allow us to determine the Raman cross‐sections of the most intense Raman peaks and provide an accurate measurement of their line‐width; even for broadenings as low as ∼ 4 cm ^{− 1}. Moreover, the obtained Raman excitation profiles agree well with those derived from the optical absorption by a simple optical transform model. This study demonstrates the possibility of routine RRS measurements using standard Raman spectrometers, as opposed to more complicated time‐resolved techniques. Copyright © 2013 John Wiley & Sons, Ltd.     

Photoconductance‐calibrated photoluminescence lifetime imaging of crystalline silicon

We use photoluminescence (PL) measurements by a silicon charge‐coupled device camera to generate high‐resolution lifetime images of multicrystalline silicon wafers. Absolute values of the excess carrier density are determined by calibrating the PL image by means of contactless photoconductance measurements. The photoconductance setup is integrated in the camera‐based PL setup and therefore identical measurement conditions are realised. We demonstrate the validity of this method by comparison with microwave‐detected photoconductance decay measurements. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Temporary Surface Passivation for Characterisation of Bulk Defects in Silicon: A Review

Accurate measurements of the bulk minority carrier lifetime in high‐quality silicon materials is challenging due to the influence of surface recombination. Conventional surface passivation processes such as thermal oxidation or dielectric deposition often modify the bulk lifetime significantly before measurement. Temporary surface passivation processes at room or very low temperatures enable a more accurate measurement of the true bulk lifetime, as they limit thermal reconfiguration of bulk defects and minimize bulk hydrogenation. In this article we review the state‐of‐the‐art for temporary passivation schemes, including liquid immersion passivation based upon acids, halogen‐alcohols and benzyl‐alcohols, and thin film passivation usually based on organic substances. We highlight how exceptional surface passivation (surface recombination velocity below 1 cm s^?1) can be achieved by some types of temporary passivation. From an extensive review of available data in the literature, we find p‐type silicon can be best passivated by hydrofluoric acid containing solutions, with superacid‐based thin films showing a slight superiority in the n‐type case. We review the practical considerations associated with temporary passivation, including sample cleaning, passivation activation, and stability. We highlight examples of how temporary passivation can assist in the development of improved silicon materials for photovoltaic applications, and provide an outlook for the future of the field.

     

Exploring the possible interlinked structures in single‐wall carbon nanotubes under pressure by Raman spectroscopy

High‐pressure Raman measurements on single‐wall carbon nanotubes (SWNTs) have been carried out in a diamond anvil cell by using two wavelength lasers: 830 and 514.5 nm. Irrespective of using a pressure transmitting medium (PTM) or not, we found that nanotubes undergo similar transformations under pressure. The pressure‐induced changes in Raman signals at around 2 and 5 GPa are attributed to the nanotube cross‐section transitions from circle to ellipse and then to a flattened shape, respectively. Especially with pressure increasing up to 15–17 GPa, we observed that the third transition takes place in both the Raman wavenumber and the linewidth of G‐band. We propose explanations that the interlinked configuration with sp³ bonds forms in the bundles of SWNTs under pressure, which was the cause for the occurrence of those Raman anomalies, similar to the structural‐phase transition of graphite above 14 GPa. Our TEM observations and Raman measurements on the decompressed samples support this transition picture. Copyright © 2012 John Wiley & Sons, Ltd.     

Determination of nonradiative decay rate in electron-hole drops in Ge at 1.6°K

We show that microwave photoconductivity measurements of optically excited carriers in Ge at 1.6°K can be used to determine the importance of nonradiative recombination within electron-hole liquid drops. Our results show that the nonradiative lifetime is 80 μsec from which we calculate a radiative efficiency of 0.5 ± 0.1 for the condensed phase.     

Monitoring of the growth of microcrystalline silicon by plasma‐enhanced chemical vapor deposition using in‐situ Raman spectroscopy

Raman spectra of microcrystalline silicon layers have been recorded in‐situ during growth. The spectra have been collected under realistic conditions for solar cell deposition. To enable these measurements an electrode with an optical feed through has been developed. By using a metallic grid to shield the feed through it is possible to achieve homogeneous deposition of µc‐Si:H at a sufficient optical transmission. In‐situ Raman measurements were carried out during the deposition of a layer with an intentionally introduced gradient in crystallinity that was seen in‐situ as well in reference measurements performed on the same layer ex‐situ. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Polarization‐dependent Raman spectroscopy of LiBH4 single crystals and Mg(BH4)2 powders

The phonons and the crystal structure of the complex hydride LiBH₄ are studied on single crystals using micro‐Raman spectroscopy. The symmetry of the modes is determined by polarization‐dependent measurements at liquid helium temperature, allowing a better comparison and a more reliable assignment to the computed phonon wavenumbers. This has led to the revision of some former assignments made from Raman measurements on polycrystalline samples. In addition, a higher integration time allowed the detection of very weak lines, so that 35 out of 36 predicted Raman lines have been identified. We have also performed explorative Raman measurements on Mg(BH₄)₂ powders. In contrast to LiBH₄, the very poor crystallinity of this material inhibits the exploitation of the full potential of Raman spectroscopy. Only broad lines are observed, which we compare to phonon wavenumbers calculated for various possible structures using density functional theory. Copyright © 2011 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.     

Raman spectral probe on increased local vibrational modes and phonon lifetimes in Ho3+‐doped Bi2O3 micro‐rods

We report the appearance and enhancement in intensity of impurity related local vibrational modes in Bi₂O₃ : Ho micro‐rods along with normal modes. Pure and Ho‐doped Bi₂O₃ micro‐rods were synthesized by conventional co‐precipitation method at 60 °C. The structural and morphological studies were carried out using powder X‐ray diffraction technique and scanning electron microscopy, respectively. Raman spectroscopic studies reveal the existence of local phonon vibrational modes (LVM) due to the incorporation of Ho³⁺. Harmonic approximation method was employed to find the dopant‐related peak in the Raman spectra. Variation in full width at half maximum for LVM with increase in Ho³⁺ was also investigated. This increase in FWHM indicates the decrease in crystallinity of the doped samples. The phonon lifetime calculation carried out for each samples and the decrease in phonon lifetime with doping concentration make this material a potential candidate for optical and electronic applications. Copyright © 2016 John Wiley & Sons, Ltd.     

An original approach for Raman spectroscopy analysis of radioactive materials and its application to americium‐containing samples

An approach for Raman measurements of highly radioactive samples is presented here. The innovative part of this approach lies in the fact that no single part of the Raman equipment is in direct contact with the radioactive sample, as the sample is sealed in an alpha‐tight capsule. Raman analysis is effectively performed through the optical‐grade quartz window closing the capsule. This allows performing micro‐Raman measurements on radioactive samples with no limitations on the laser source wavelength, polarisation mode, spectrometer mode and microscope mode (provided the focal length of the microscope objective is greater than the thickness of the quartz window and with sub mg samples). Some example results are shown and discussed. In particular, some spectral features of americium‐containing oxide nuclear fuel specimens are presented. Raman spectra clearly reveal in these specimens the presence of abundant oxygen defects induced in the fcc fluorite lattice by trivalent americium. In order to complete the analysis the Raman spectrum of pure americium dioxide was also measured with a lower energy excitation source compared with previous research. The current results seem to be consistent with the possible occurrence of a photolysis process induced by the Raman laser, resulting in the formation of hyperstoichiometric americium sesquioxide Am₂O_{3 + z}. Such a photolytic process is deemed to be unavoidable when visible lasers are used as excitation sources for the Raman analysis of americium dioxide. © 2015 The Authors Journal of Raman Spectroscopy Published by John Wiley & Sons, Ltd.