Electromodulation spectroscopy of confined systems

The convolution formalism of Aspnes and Rowe for the dielectric function in the presence of an electric field is applied to electromodulation spectroscopy of confined systems. It is shown that for isolated confined systems where excitonic effects are not important, electromodulation spectroscopy leads to first derivative like optical features of two dimensional critical points. For superlattices in weak fields (neglecting excitonic interactions), the familiar third derivative forms of Aspnes and Rowe are applicable. In contrast, when moderate and high electric fields are applied to superlattices, electromodulation spectroscopy will exhibit optical features characteristic of first derivative line shapes. This phenomenon arises because the electric field causes the envelope functions of the electron and hole states to become spatially localized. The importance of excitons and their inhomogeneous broadening to the experimentally observed line shapes are considered.     

Rare-earth chloride seeded growth of GaN nano- and micro-crystals

A novel rare-earth chloride seed was employed as a catalyst for growth of GaN nano- and micro-crystals on c-, a- and r-plane sapphire. The ErCl₃ seed on the substrate surface enhanced the growth rate and density of the GaN crystals. Distinctive green photoluminescence was measured, confirming that Er³⁺ ions were active in the GaN matrix. This technique can be adapted to selectively grow GaN crystals with emission tailored to the particular optical transitions of the rare-earth seed.     

NIR-FT-SERS of 4″-trimethylsilylethylsulfanyl-4,4′-di(phenyleneethynylene)benzenethiol on Au nanospheres

Oligo(phenyleneethynylene) (OPE) compounds have been identified as promising molecular electronic bridges. Self-assembled monolayers of 4″-trimethylsilylethylsulfanyl-4,4′-phenyleneethynylenebenzene thiol (OPE′) on Au were characterized by surface-enhanced Raman scattering (SERS). The FT-Raman spectrum of OPE′ shows three C–S bands at 834, 1086, and 1131 cm⁻¹. From the FT-Raman to the SERS spectra, the 1086 cm⁻¹ band exhibits a 9 cm⁻¹ red shift. Chemisorption of OPE′ to the gold surface occurs via oxidative cleavage of the disulfide bond and the formation of the Au–S bond. The Au–S vibration is visible in the SERS spectra at 257 cm⁻¹. Peaks due to the S–S and S–H stretch are observed at 544 and 2519 cm⁻¹, respectively, in the FT spectrum, but are unobserved in the surface-enhanced spectra. The C–H stretching region (2700–3350 cm⁻¹) in the spectrum of neat OPE′ shows three distinct bands, whereas the SERS spectra show a single broad band. Assignments of vibrational bands were based on DFT calculations performed at the B3LYP level with good agreement between theoretical and experimental values. An average percent difference of 2.52 was obtained for the non-CH stretching frequencies.     

Investigation of chemically modified barium titanate beads as surface-enhanced Raman scattering (SERS) active substrates for the detection of benzene thiol, 1,2-benzene dithiol, and rhodamine 6G

SERS active surfaces were prepared by depositing silver films using Tollen's reaction on to barium titanate beads. The SERS activity of the resulting surfaces was probed using two thiols (benzene thiol and 1,2-benzene dithiol) and rhodamine 6G. The intensity of the SERS signal for the three analytes was investigated as a function of silver deposition time. The results indicate that the SERS intensity increased with increasing thickness of the silver film until a maximum signal intensity was achieved; additional silver deposition resulted in a decrease in the SERS intensity for all of the studied molecules. SEM measurement of the Ag coated barium titanate beads, as a function of silver deposition time, indicate that maximum SERS intensity corresponded with the formation of atomic scale islands of silver nanoparticles. Complete silver coverage of the beads resulted in a decreased SERS signal and the most intense SERS signals were observed at deposition times of 30 min for the thiols and 20 min for rhodamine 6G.     

Surface-enhanced Raman scattering of a Ag/oligo(phenyleneethynylene)/Ag sandwich

α,ω-Dithiols are a useful class of compounds in molecular electronics because of their ability to easily adsorb to two metal surfaces, producing a molecular junction. We have prepared Ag nanosphere/oligo(phenyleneethynylene)/Ag sol (AgNS/OPE/Ag sol) and Ag nanowire/oligo(phenyleneethynylene)/Ag sol (AgNW/OPE/Ag sol) sandwiches to simulate the architecture of a molecular electronic device. This was achieved by self-assembly of OPE on the silver nanosurface, deprotection of the terminal sulfur, and deposition of Ag sol atop the monolayer. These sandwiches were then characterized by surface-enhanced Raman scattering (SERS) spectroscopy. The resulting spectra were compared to the bulk spectrum of the dimer and to the Ag nanosurface/OPE SERS spectra. The intensities of the SERS spectra in both systems exhibit a strong dependence on Ag deposition time and the results are also suggestive of intense interparticle coupling of the electromagnetic fields in both the AgNW/OPE/Ag and the AgNS/OPE/Ag systems. Three previously unobserved bands (1219, 1234, 2037 cm(-1)) arose in the SER spectra of the sandwiches and their presence is attributed to the strong enhancement of the electromagnetic field which is predicted from the COSMOL computational package. The 544 cm(-1) disulfide bond which is observed in the spectrum of solid OPE but is absent in the AgNS/OPE/Ag and AgNW/OPE/Ag spectra is indicative of chemisorption of OPE to the nanoparticles through oxidative dissociation of the disulfide bond.     

Hole intersubband transitions in GaAs/AlGaAs multiple quantum wells… A new method for determining the Luttinger parameters

Resonant electronic Raman scattering from photoexcited holes has been observed for multiple quantum wells (MQW's) grown in the [111]b and [100] directions. The measurements indicate that the heavy hole mass in the [111] direction is 0.75mo. This value is 2.2 times larger than the value characteristics of the [100] direction. The measurements also quantify the degree of anisotropy for the light holes. We propose a new set of Luttinger parameters that describe the anisotropy of the valence band in GaAs and are consistent with the interband and intersubband transitions observed in [100] and [111]b MQW's.