Excited-state dynamics in diketopyrrolopyrrole-based copolymer for organic photovoltaics investigated by transient optical spectroscopy

We investigate the photoexcited state dynamics in a donor-acceptor copolymer, poly{3,6-dithiophene-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]- pyrrole-1,4-dione-alt-naphthalene} (pDPP-TNT), by picosecond fluorescence and femtosecond transient absorption spectroscopies. Timeresolved fluorescence lifetime measurements of pDPP-TNT thin films reveal that the lifetime of the singlet excited state is 185 ± 5 ps and that singlet-singlet annihilation occurs at excitation photon densities above 6 × 1017 photons/cm3. From the results of singlet-singlet annihilation analysis, we estimate that the single-singlet annihilation rate constant is (6.0 ± 0.2) × 109cm3 s-1 and the singlet diffusion length is -7 nm. From the comparison of femtosecond transient absorption measurements and picosecond fluorescence measurements, it is found that the time profile of the photobleaching signal in the charge-transfer (CT) absorption band coincides with that of the fluorescence intensity and there is no indication of long-lived species, which clearly suggests that charged species, such as polaron pairs and triplet excitons, are not effectively photogenerated in the neat pDPP-TNT polymer.

Towards improved precision in the quantification of surface-enhanced Raman scattering (SERS) enhancement factors: A renewed approach

This paper demonstrates a renewed procedure for the quantification of surface-enhanced Raman scattering (SERS) enhancement factors with improved precision. The principle of this method relies on deducting the resonance Raman scattering (RRS) contribution from surface-enhanced resonance Raman scattering (SERRS) to end up with the surface enhancement (SERS) effect alone. We employed 1,8,15,22-tetraaminophthalocyanato-cobalt(II) (4α-CoIITAPc), a resonance Raman- and electrochemically redox-active chromophore, as a probe molecule for RRS and SERRS experiments. The number of 4α-CoIITAPc molecules contributing to RRS and SERRS phenomena on plasmon inactive glassy carbon (GC) and plasmon active GC/Au surfaces, respectively, has been precisely estimated by cyclic voltammetry experiments. Furthermore, the SERS substrate enhancement factor (SSEF) quantified by our approach is compared with the traditionally employed methods. We also demonstrate that the present approach of SSEF quantification can be applied for any kind of different SERS substrates by choosing an appropriate laser line and probe molecule.

A homogeneous surface-enhanced Raman scattering platform for ultra-trace detection of trinitrotoluene in the environment

A facile and sensitive surface-enhanced Raman scattering substrate was prepared by controlled potentiostatic deposition of a closely packed single layer of gold nanostructures (AuNS) over a flat gold (pAu) platform. The nanometer scale inter-particle distance between the particles resulted in high population of ‘hot spots’ which enormously enhanced the scattered Raman photons. A renewed methodology was followed to precisely quantify the SERS substrate enhancement factor (SSEF) and it was estimated to be (2.2 ± 0.17) × 105. The reproducibility of the SERS signal acquired by the developed substrate was tested by establishing the relative standard deviation (RSD) of 150 repeated measurements from various locations on the substrate surface. A low RSD of 4.37 confirmed the homogeneity of the developed substrate. The sensitivity of pAu/AuNS was proven by determining 100 fM 2,4,6-trinitrotoluene (TNT) comfortably. As a proof of concept on the potential of the new pAu/AuNS substrate in field analysis, TNT in soil and water matrices was selectively detected after forming a Meisenheimer complex with cysteamine.

Raman spectroscopy techniques for detection of energetic materials at high and low concentration

This thesis presents the development of a rapid, sensitive and reproducible spectroscopic method for the detection of TNT in forensic and environmental applications. Simple nano sensors prepared by cost effective methods were utilized as sensitive platforms for the detection of TNT by surface enhanced Raman spectroscopy. The optimization of the substrate and the careful selection of a suitable recognition molecule contributed to the significant improvements of sensitive and selective targeting over current detection methods. The work presented in this thesis paves the way for effective detection and monitoring of explosives residues in law enforcement and environmental health applications.

Rapid isolation and detection of erythropoietin in blood plasma by magnetic core gold nanoparticles and portable Raman spectroscopy

Isolating, purifying, and identifying proteins in complex biological matrices is often difficult, time consuming, and unreliable. Herein we describe a rapid screening technique for proteins in biological matrices that combines selective protein isolation with direct surface enhanced Raman spectroscopy (SERS) detection. Magnetic core gold nanoparticles were synthesised, characterised, and subsequently functionalized with recombinant human erythropoietin (rHuEPO)-specific antibody. The functionalized nanoparticles were used to capture rHuEPO from horse blood plasma within 15 minutes. The selective binding between the protein and the functionalized nanoparticles was monitored by SERS. The purified protein was then released from the nanoparticles’ surface and directly spectroscopically identified on a commercial nanopillar SERS substrate. ELISA independently confirmed the SERS identification and quantified the released rHuEPO. Finally, the direct SERS detection of the extracted protein was successfully demonstrated for in-field screening by a handheld Raman spectrometer within 1 minute sample measurement time.

Surface-enhanced Raman scattering of molecules adsorbed on nanocrystalline Au and Ag films formed at the organic-aqueous interface

Surface-enhanced Raman scattering (SERS) of pyridine adsorbed on ultrathin nanocrystalline Au and Ag films generated at the liquid-liquid interface has been investigated. The shifts and intensification of bands formed with these films comprising metal nanoparticles are comparable to those found with other types of Au and Ag substrates. SERS of rhodamine 6G adsorbed on Ag films has also been studied. The results demonstrate that nanocrystalline metal films prepared by the simple method involving the organic-aqueous interface can be used effectively for SERS investigations.

Ion irradiation as a tool for modifying the surface and optical properties of plasma polymerised thin films

Radio frequency (R.F.) glow discharge polyterpenol thin films were prepared on silicon wafers and irradiated with I10+ ions to fluences of 1 × 1010 and 1 × 1012 ions/cm2. Post-irradiation characterisation of these films indicated the development of well-defined nano-scale ion entry tracks, highlighting prospective applications for ion irradiated polyterpenol thin films in a variety of membrane and nanotube-fabrication functions. Optical characterisation showed the films to be optically transparent within the visible spectrum and revealed an ability to selectively control the thin film refractive index as a function of fluence. This indicates that ion irradiation processing may be employed to produce plasma-polymer waveguides to accommodate a variety of wavelengths. XRR probing of the substrate-thin film interface revealed interfacial roughness values comparable to those obtained for the uncoated substrate's surface (i.e., both on the order of 5 Å), indicating minimal substrate etching during the plasma deposition process.

The study of oxidation state of manganese in lead oxyhalide glasses by optical spectroscopy

Abstaract is not available.

Spectrally broadened excitonic absorption and enhanced optical nonlinearities in Dy3+-doped ZnO nanoparticles

We have synthesized Dy3+-doped ZnO nanoparticles at room temperature through the sol-gel method. X-ray diffraction and Scanning electron microscopic studies confirm the crystalline nature of the particles. Excitonic absorption of ZnO shows three different bands, and we observe that incorporation of Dy3+ results in the shifting and broadening of the n=1 absorption band of ZnO. Photoluminescence studies done at the excitation wavelength of 335 nm show broad emission containing five different bands. Open-aperture z-scan studies done at 532 nm using 5 ns laser pulses show an optical limiting behavior, which numerically fits to a three-photon type absorption process. The nonlinearity is essentially resonant, as it is found to increase consistently with Dy3+ concentration. This feature makes Dy3+-doped ZnO a flexible optical limiter for potential device applications.

Acoustic and optical phonon dynamics from femtosecond time-resolved optical spectroscopy of the superconducting iron pnictide Ca(Fe0.944Co0.056)(2)As-2

We report the temperature evolution of coherently excited acoustic and optical phonon dynamics in the superconducting iron pnictide single crystal Ca(Fe0.944Co0.056)(2)As-2 across the spin density wave transition at T-SDW similar to 85 K and the superconducting transition at T-SC similar to 20 K. The strain pulse propagation model applied to the generation of the acoustic phonons yields the temperature dependence of the optical constants, and longitudinal and transverse sound velocities in the temperature range from 3.1 K to 300 K. The frequency and dephasing times of the phonons show anomalous temperature dependence below T-SC indicating a coupling of these low-energy excitations with the Cooper-pair quasiparticles. A maximum in the amplitude of the acoustic modes at T similar to 170 is seen, attributed to spin fluctuations and strong spin-lattice coupling before T-SDW. Copyright (c) EPLA, 2012

Impact of chemical treatment on the surface, structure, optical and electrical properties of SnS thin films

The impact of chemical treatment on the surface morphology and other physical properties of tin monosulphide (SnS) thin films have been investigated. The SnS films treated with selected organic solvents exhibited strong improvement in their crystalline-quality and considerable decrease in electrical resistivity. Particularly, the films treated with chloroform showed very low electrical resistivity of similar to 5 Omega cm and a low optical band gap of 1.81 eV as compared to untreated and treated SnS films with other chemicals. From these studies we realized that the chemical treatment of SnS films has strong impact on their surface morphology and also on other physical properties. (C) 2012 Elsevier B.V. All rights reserved.

Surface morphology, optical properties and conductivity changes of poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) by using additives

The optical properties and electrical conductivity of highly conducting poly(3,4-ethylenedioxythiophene) (PEDOT) doped with poly(styrenesulfonate) (PSS) are reported as a function of the processing additive conditions. The addition of dimethyl sulfoxide (DMSO) increases the conductivity and modifies the dielectric response as observed from the ellipsometric studies. Also the surface roughness and morphology change with the composition of PEDOT: PSS: DMSO and film deposition conditions. The real part of the dielectric function becomes negative in highly conducting samples, indicating the presence of delocalized charge carriers. The real and imaginary parts of the refractive index were determined as a function of wavelength. The results are consistent with the increase in conductivity upon the addition of DMSO.

Interconnected, ultrafine osmium nanoclusters: preparation and surface enhanced Raman scattering activity

Interconnected Os nanochains consisting of ultrafine particles prepared using a simple procedure yield a coupled surface plasmon peak in the visible region and can be used as substrates for surface enhanced Raman scattering of various analytes.

Spontaneous assembly of iridium nanochain-like structures: surface enhanced Raman scattering activity using visible light

A facile, environmentally friendly approach to synthesize branched Ir nanochain-like structures under mild conditions, using polyfunctional capping molecules in an aqueous medium is reported; the nanostructures exhibit a surface plasmon resonance peak (SPR) in the visible region and serve as an active substrate for surface enhanced Raman scattering studies.