Raul D. Rodriguez

Investigation of second- and third-harmonic generation in few-layer gallium selenide by multiphoton microscopy

Gallium selenide (GaSe) is a layered semiconductor and a well-known nonlinear optical crystal. The discovery of graphene has created a new vast research field focusing on two-dimensional materials. We report on the nonlinear optical properties of few-layer GaSe using multiphoton microscopy. Both second- and third-harmonic generation from few-layer GaSe flakes were observed. Unexpectedly, even the peak at the wavelength of 390 nm, corresponding to the fourth-harmonic generation or the sum frequency generation from third-harmonic generation and pump light, was detected during the spectral measurements in thin GaSe flakes.

Tunable Graphene–GaSe Dual Heterojunction Device

A field-effect device based on dual graphene-GaSe heterojunctions is demonstrated. Monolayer graphene is used as electrodes on a GaSe channel to form two opposing Schottky diodes controllable by local top gates. The device exhibits strong rectification with tunable threshold voltage. Detailed theoretical modeling is used to explain the device operation and to distinguish the differences compared to a single diode.

Chemical post-treatment and thermoelectric properties of poly(3,4-ethylenedioxylthiophene):poly(styrenesulfonate) thin films

We report on the modification of the thermoelectric properties of poly(3,4-ethylenedioxylthiophene):poly(styrenesulfonate) (PEDOT:PSS) thin films by means of a simple post treatment of the solid thin films realized by drop-coating. We show that the organic polar solvents, dimethyl sulfoxide and ethylene glycol as secondary dopants for PEDOT:PSS, only affect the film morphology for which a high electrical conductivity is observed. In contrast, ethanolamine (MEA) and ammonia solutions are reduction agents that improve the density of PEDOT chains in the reduced forms (polaron and neutral states), resulting in the trade-off between Seebeck coefficient and electrical conductivity. Furthermore, we show that the nature of amines determines the reduction degree: the nitrogen lone pair electrons in MEA are easier to be donated than those in ammonia solution and will therefore neutralize the PEDOT chains.

Compact metal probes: a solution for atomic force microscopy based tip-enhanced Raman spectroscopy.

There are many challenges in accomplishing tip-enhanced Raman spectroscopy (TERS) and obtaining a proper tip is probably the greatest one. Since tip size, composition, and geometry are the ultimate parameters that determine enhancement of intensity and lateral resolution, the tip becomes the most critical component in a TERS experiment. However, since the discovery of TERS the cantilevers used in atomic force microscopy (AFM) have remained basically the same: commercial silicon (or silicon nitride) tips covered by a metallic coating. The main issues of using metal-coated silicon cantilevers, such as wearing off of the metal layer or increased tip radius, can be completely overcome by using all-metal cantilevers. Until now in TERS experiments such probes have only been used in a scanning tunneling microscope or in a tuning fork-based shear force microscope but not in AFM. In this work for the first time, we show the use of compact silver cantilevers that are fully compatible with contact and tapping modes in AFM demonstrating their superb performance in TERS experiments.

The substrate matters in the Raman spectroscopy analysis of cells

Raman spectroscopy is a powerful analytical method that allows deposited and/or immobilized cells to be evaluated without complex sample preparation or labeling. However, a main limitation of Raman spectroscopy in cell analysis is the extremely weak Raman intensity that results in low signal to noise ratios. Therefore, it is important to seize any opportunity that increases the intensity of the Raman signal and to understand whether and how the signal enhancement changes with respect to the substrate used. Our experimental results show clear differences in the spectroscopic response from cells on different surfaces. This result is partly due to the difference in spatial distribution of electric field at the substrate/cell interface as shown by numerical simulations. We found that the substrate also changes the spatial location of maximum field enhancement around the cells. Moreover, beyond conventional flat surfaces, we introduce an efficient nanostructured silver substrate that largely enhances the Raman signal intensity from a single yeast cell. This work contributes to the field of vibrational spectroscopy analysis by providing a fresh look at the significance of the substrate for Raman investigations in cell research.

Low-Cost Al2O3 Coating Layer As a Preformed SEI on Natural Graphite Powder To Improve Coulombic Efficiency and High-Rate Cycling Stability of Lithium-Ion Batteries.

Coulombic efficiency especially in the first cycle, cycling stability, and high-rate performance are crucial factors for commercial Li-ion batteries (LIBs). To improve them, in this work, Al2O3-coated natural graphite powder was obtained through a low-cost and facile sol-gel method. Based on a comparison of various coated amounts, 0.5 mol % Al(NO3)3 (vs mole of graphite) could bring about a smooth Al2O3 coating layer with proper thickness, which could act as a preformed solid electrolyte interface (SEI) to reduce the regeneration of SEI and lithium-ions consumption during subsequent cycling. Furthermore, we examined the advantages of Al2O3 coating by relating energy levels in LIBs using density functional theory calculations. Owing to its proper bandgap and lithium-ion conduction ability, the coating layer performs the same function as a SEI does, preventing an electron from getting to the outer electrode surface and allowing lithium-ion transport. Therefore, as a preformed SEI, the Al2O3 coating layer reduces extra cathode consumption observed in commercial LIBs.

Wafer-scale synthesis of defined polymer brushes under ambient conditions

A method is presented that allows for the first time the preparation of highly defined polymer brush coatings on the wafer-scale under ambient conditions (room temperature, exposure to air) from a broad variety of monomers. The discovered high oxygen-tolerance of the surface-initiated Cu(0)-mediated controlled radical polymerization (SI-CuCRP) yields entire wafers homogeneously covered by a polymer brush of linear, high molar mass polymers with narrow dispersities (Đ = 1.1) at extremely high grafting densities (≈1 chain per nm2). The low-tech and air tolerant method requires only ≲4 mL reaction solution containing a monomer and a ligand between two facing substrates. Thus, the SI-CuCRP is scalable to any surface area with minimal costs and minimal equipment. Despite the simplicity of the method, the high endgroup fidelity of SI-CuCRP is demonstrated by the preparation of a tetrablock copolymer brush which is the first example of a higher order block copolymer brush prepared by any surface-initiated polymerization. Finally, we present a new facile lithographic technique, the copper plate proximity printing (CP3), which relies on the proximity of the bulk copper surface to the initiator-bearing substrate. The CP3 is resist- and development-free and transfers the copper plate profile (of a copper coin) directly into an image composed of a 3D polymer brush.

Self-Assembly of Hydrophobin Protein Rodlets Studied with Atomic Force Spectroscopy in Dynamic Mode

We have investigated the self-assembling properties of the class I hydrophobin Vmh2 isolated from the fungus Pleurotus ostreatus. Five different hydrophobin self assembled samples including monolayers, bilayers, and rodlets have been prepared by Langmuir technique and studied at the nanoscale. Local wettability and visco-elasticity of the different hydrophobins samples were obtained from atomic force spectroscopy experiments in dynamic mode performed at different, controlled relative humidity (RH) values. It was found that hydrophobins assembled either in rodlets or in bilayer films, display similar hydropathicity and viscoelasticity in contrast to the case of monolayers, whose hydropathicity and viscoelasticity depend on the adopted preparation method (Langmuir-Blodgett or Langmuir-Schaeffer). The comparison with monolayers properties evidences a rearrangement of the bilayers adsorbed onto solid substrates. It is shown that this rearrangement leads to the formation of a stable hydrophobic film, and that the rodlets structure consists in fragments of restructured proteins bilayers. Our results support the hypothesis that the observed variations in the viscoelastic properties could be ascribed to the localization of the large flexible loop, typical of Class I hydrophobins which appears free at the air interface for LB monolayers but not for the other samples. These findings should now serve future developments and applications of hydrophobin films beyond the archetypal monolayer.

Chemical stability of plasmon-active silver tips for tip-enhanced Raman spectroscopy

Abstract Silver nanostructures are used in tip- and surface-enhanced Raman spectroscopy due to their high electric field enhancement over almost the entire visible spectral range. However, the low chemical stability of silver, compared to other noble metals, promotes silver sulfide and sulfate formation which decreases its plasmonic activity. This is why silver tips are usually prepared on the same day of the experiments or are disregarded in favour of gold that is chemically more stable. Since silver degradation cannot be avoided, we hypothesized that a protection layer may be able to minimize or control degradation. In this contribution, we report the successful preparation of 4-biphenylthiol and 4’-nitro-4-biphenylthiol self-assembled monolayers on silver tips in order to protect them against tarnishing and to investigate the effect on the life-time of the plasmonic activity. The electrochemically etched wire surface was probed via Raman spectroscopy and scanning electron microscopy. The best long term stability and resistance against corrosion was shown by a monolayer of 4-biphenylthiol formed from dimethylformamide which did not display any degradation of the metallic tip during the observed period. Here, we demonstrate an easy and straightforward approach towards increasing the chemical stability of silver TERS-active probes.

Enhanced field emission from cerium hexaboride coated multiwalled carbon nanotube composite films: A potential material for next generation electron sources

Intensified field emission (FE) current from temporally stable cerium hexaboride (CeB6) coated carbon nanotubes (CNTs) on Si substrate is reported aiming to propose the new composite material as a potential candidate for future generation electron sources. The film was synthesized by a combination of chemical and physical deposition processes. A remarkable increase in maximum current density, field enhancement factor, and a reduction in turn-on field and threshold field with comparable temporal current stability are observed in CeB6-coated CNT film when compared to pristine CeB6 film. The elemental composition and surface morphology of the films, as examined by scanning electron microscopy, transmission electron microscopy, and energy dispersive X-ray measurements, show decoration of CeB6 nanoparticles on top and walls of CNTs. Chemical functionalization of CNTs by the incorporation of CeB6 nanoparticles is evident by a remarkable increase in intensity of the 2D band in Raman spectrum of coated films as c...