Spatially offset Raman microspectroscopy of highly scattering tissue: theory and experiment

Spatially Offset Raman Spectroscopy (SORS) has seen considerable interest in recent years as a tool for noninvasively acquiring Raman spectra from beneath the surface of a sample. One of the major limitations of the SORS technique is that accurate knowledge of the optical properties of the medium is required to translate an offset into a sample depth. We report on the benefits of preforming SORS using micron offset distances as opposed to the more typical millimeter offsets used. Monte Carlo simulations are used to demonstrate that at these small offsets, the results depend less on the scattering coefficient of the material. These results provide new insights into the SORS technique and will improve the practical application of SORS in the future.     

Active layer materials coated with Teflon AF nano-films deposited from solutions in supercritical CO2 for fuel cell applications

In the present work we suggest a new approach to the thin-film design of active layers for electrodes of fuel cells with phosphoric acid electrolyte in a polymer matrix. A fluoropolymer binder is introduced into common Pt@C active layer materials using supercritical (SC) CO₂ as a solvent. Unique wetting properties of this non-hazardous and environmentally friendly solvent allow one to deposit highly uniform thin fluoropolymer films on dispersed carbon supports. As a result, well-percolated gas-permeable fluoropolymer phases are produced in active layers already at comparatively small polymer loadings. Teflon AF 2400 was chosen as a stable high-molecular-weight fluoropolymer soluble in SC CO₂ with high oxygen permeability and high T_g value. Fluoropolymer-containing active layer materials prepared via the SC CO₂ deposition routes were studied by means of cyclic voltammetry and were tested in operating fuel cells using steady state voltammetry and electrochemical impedance spectroscopy. Polarization curves of operating fuel cells indicate that the optimal content of deposited from SC CO₂ fluoropolymer in active layer is about 3–5%. Results of impedance spectra fitting yield information used to explain the detected values of optimal loading.     

Weak mismatch epitaxy and structural Feedback in graphene growth on copper foil

Graphene growth by low-pressure chemical vapor deposition on low cost copper foils shows great promise for large scale applications. It is known that the local crystallography of the foil influences the graphene growth rate. Here we find an epitaxial relationship between graphene and copper foil. Interfacial restructuring between graphene and copper drives the formation of (n10) facets on what is otherwise a mostly Cu(100) surface, and the facets in turn influence the graphene orientations from the onset of growth. Angle resolved photoemission shows that the electronic structure of the graphene is decoupled from the copper indicating a weak interaction between them. Despite this, two preferred orientations of graphene are found, ±8° from the Cu[010] direction, creating a non-uniform distribution of graphene grain boundary misorientation angles. Comparison with the model system of graphene growth on single crystal Cu(110) indicates that this orientational alignment is due to mismatch epitaxy. Despite the differences in symmetry the orientation of the graphene is defined by that of the copper. We expect these observations to not only have importance for controlling and understanding the growth process for graphene on copper, but also to have wider implications for the growth of two-dimensional materials on low cost metal substrates.      

Radiative transfer codes for atmospheric correction and aerosol retrieval: intercomparison study

Results are summarized for a scientific project devoted to the comparison of four atmospheric radiative transfer codes incorporated into different satellite data processing algorithms, namely, 6SV1.1 (second simulation of a satellite signal in the solar spectrum, vector, version 1.1), RT3 (radiative transfer), MODTRAN (moderate resolution atmospheric transmittance and radiance code), and SHARM (spherical harmonics). The performance of the codes is tested against well-known benchmarks, such as Coulson's tabulated values and a Monte Carlo code. The influence of revealed differences on aerosol optical thickness and surface reflectance retrieval is estimated theoretically by using a simple mathematical approach. All information about the project can be found at http://rtcodes.ltdri.org.     

Theory of inversion with two-dimensional regularization: profiles of microphysical particle properties derived from multiwavelength lidar measurements

We present the theory of inversion with two-dimensional regularization. We use this novel method to retrieve profiles of microphysical properties of atmospheric particles from profiles of optical properties acquired with multiwavelength Raman lidar. This technique is the first attempt to the best of our knowledge, toward an operational inversion algorithm, which is strongly needed in view of multiwavelength Raman lidar networks. The new algorithm has several advantages over the inversion with so-called classical one-dimensional regularization. Extensive data postprocessing procedures, which are needed to obtain a sensible physical solution space with the classical approach, are reduced. Data analysis, which strongly depends on the experience of the operator, is put on a more objective basis. Thus, we strongly increase unsupervised data analysis. First results from simulation studies show that the new methodology in many cases outperforms our old methodology regarding accuracy of retrieved particle effective radius, and number, surface-area, and volume concentration. The real and the imaginary parts of the complex refractive index can be estimated with at least as equal accuracy as with our old method of inversion with one-dimensional regularization. However, our results on retrieval accuracy still have to be verified in a much larger simulation study.     

Coercivity and domain structure of nanograined Fe–C alloys after high-pressure torsion

The microstructure and magnetic properties of binary hypo- and hyper-eutectoid Fe–C alloys were studied. The investigations have been carried out on the samples in the as-cast state, after a long annealing at 725 °C and on the specimens after the high-pressure torsion (HPT). The deformation was carried out at the ambient temperature and the pressure of 5 GPa. The grain size after HPT is in the nanometer range. Long annealing leads to a drastic decrease of the coercivity in comparison with the as-cast alloys. In all alloys the coercivity H _c increases with increasing carbon content. The distance L between pinning points for domain walls decreases with increasing carbon content. Increase of the coercivity and decrease of L are more pronounced below the eutectoid concentration. The coercivity of the nanostructured samples is higher than that of the as-cast alloys. Due to the pinning of domain walls by the cementite particles, the hysteresis loop in the coarse-grained alloys both in as-cast and annealed states has a narrowing near the zero magnetization.     

Comparing the growth of a molecular semiconductor on amorphous and semi-crystalline polycarbonate substrates

Polymeric substrates are of importance in plastic electronics. However, polymeric surfaces can exhibit different morphologies depending on whether they are amorphous or semi-crystalline. This work focuses on the impact of the surface structure of bisphenol A polycarbonate substrates on the nucleation and growth of a p-type semi-conductor, namely zinc phthalocyanine (ZnPc). ZnPc films were deposited under high vacuum at different substrate temperatures on oriented semi-crystalline as well as amorphous substrates of PC. The oriented substrates of PC were prepared by a method combining mechanical rubbing and solvent induced crystallization: the substrates show a periodic and regular alternation of oriented crystalline lamellae. Grazing incidence X-ray diffraction shows that the crystalline lamellae of PC have a preferential (a, c) contact plane. Moreover, the substrates show a bilayer structure made of a 60 nm-thick semi-crystalline overlayer atop an amorphous underlayer. UV–vis spectroscopy shows that the polymorphism of the ZnPc films is not modified by the surface structure of the PC substrate (amorphous versus semi-crystalline). However, the statistical analysis of domain size and density versus substrate temperature T_s evidences different apparent activation energies of the growth mechanism. High Resolution Transmission Electron Microscopy suggests that twinning along a (2 ?1 0) plane accounts for the bifurcations of the in-plane b-axis direction of the ZnPc nanocrystals. On oriented substrates of PC, such bifurcations are partly suppressed by the nanocorrugation of the surface, resulting in larger apparent domain sizes and unidirectional in-plane orientation.     

Efficiency enhancement in organic solar cells with ferroelectric polymers

The recombination of electrons and holes in semiconducting polymer-fullerene blends has been identified as a main cause of energy loss in organic photovoltaic devices. Generally, an external bias voltage is required to efficiently separate the electrons and holes and thus prevent their recombination. Here we show that a large, permanent, internal electric field can be ensured by incorporating a ferroelectric polymer layer into the device, which eliminates the need for an external bias. The electric field, of the order of 50 V μm(-1), potentially induced by the ferroelectric layer is tens of times larger than that achievable by the use of electrodes with different work functions. We show that ferroelectric polymer layers enhanced the efficiency of several types of organic photovoltaic device from 1-2% without layers to 4-5% with layers. These enhanced efficiencies are 10-20% higher than those achieved by other methods, such as morphology and electrode work-function optimization. The devices show the unique characteristics of ferroelectric photovoltaic devices with switchable diode polarity and tunable efficiency.     

Polarisation stabilisation of vertical cavity surface emitting lasers by minimally invasive focused electron beam triggered chemistry

Local electron triggered reactions of functional surface adsorbates were used as a maskless, dry, and minimally invasive nanolithography concept to stabilize the polarisation of individual vertical cavity surface emitting lasers (VCSELs) on a wafer in a post-processing step. Using a 30 keV focused electron beam of a scanning electron microscope and injecting volatile organo-metallic (CH(3))(2)Au(tfa) molecules, polarisation gratings were directly written on VCSELs by dissociating the surface adsorbed molecules. The electron triggered adsorbate dissociation resulted in electrically conductive Au-C nano-composite material, with gold nanocrystals embedded in a carbonaceous matrix. A resistivity of 2500 μ?cm was measured at a typical composition of 30 at.% Au. This material proved successful in suppressing polarisation switching when deposited as line gratings with a width of 200 nm, a thickness of 50 nm, and a pitch of 500 nm and 1 μm. Refractive index measurements suggest that the optical attenuation by the deposited Au-C material is much lower than by pure Au thus giving a low emission power penalty while keeping the polarisation stable.     

Characterization of protein immobilization on nanoporous gold using atomic force microscopy and scanning electron microscopy

Nanoporous gold (NPG), made by dealloying low carat gold alloys, is a relatively new nanomaterial finding application in catalysis, sensing, and as a support for biomolecules. NPG has attracted considerable interest due to its open bicontinuous structure, high surface-to-volume ratio, tunable porosity, chemical stability and biocompatibility. NPG also has the attractive feature of being able to be modified by self-assembled monolayers. Here we use scanning electron microscopy (SEM) and atomic force microscopy (AFM) to characterize a highly efficient approach for protein immobilization on NPG using N-hydroxysuccinimide (NHS) ester functionalized self-assembled monolayers on NPG with pore sizes in the range of tens of nanometres. Comparison of coupling under static versus flow conditions suggests that BSA (Bovine Serum Albumin) and IgG (Immunoglobulin G) can only be immobilized onto the interior surfaces of free standing NPG monoliths with good coverage under flow conditions. AFM is used to examine protein coverage on both the exterior and interior of protein modified NPG. Access to the interior surface of NPG for AFM imaging is achieved using a special procedure for cleaving NPG. AFM is also used to examine BSA immobilized on rough gold surfaces as a comparative study. In principle, the general approach described should be applicable to many enzymes, proteins and protein complexes since both pore sizes and functional groups present on the NPG surfaces are controllable.