Laser-induced tuning of graphene field-effect transistors for pH sensing.

Here we demonstrate, using pulsed femtosecond laser-induced two-photon oxidation (2PO), a novel method of locally tuning the sensitivity of solution gated graphene field-effect transistors (GFETs) without sacrificing the integrity of the carbon network of chemical vapor deposition (CVD) grown graphene. The achieved sensitivity with 2PO was (25 ± 2) mV pH-1 in BIS-TRIS propane HCl (BTPH) buffer solution, when the oxidation level corresponded to the Raman peak intensity ratio I(D)/I(G) of 3.58. Sensitivity of non-oxidized, residual PMMA contaminated GFETs was 20-22 mV pH-1. The sensitivity decreased initially by 2PO to (19 ± 2) mV pH-1 (I(D)/I(G) = 0.64), presumably due to PMMA residue removal by laser irradiation. 2PO results in local control of functionalization of the CVD-grown graphene with oxygen-containing chemical groups enhancing the performance of the GFET devices. The GFET devices were made HDMI compatible to enable easy coupling with external devices for enhancing their applicability.

Photodeposition of RuO x Nanostructures on TiO2 Films with a Controllable Morphology.

RuO2/TiO2 catalysts have shown broad use in promoting a variety of photocatalytic phenomena, such as water splitting and the photodecomposition of organic dyes and pollutants. Most current methods of photodepositing ruthenium oxide species (RuO x ) onto titanium dioxide (TiO2) films involve precursors that are either difficult to produce and prone to decomposition, such as RuO4, or require high-temperature oxidations, which can reduce the quality of the resulting catalyst and increase the risks and toxicity of the procedure. The present work demonstrates the photodeposition of RuO x onto TiO2 films, using potassium perruthenate (KRuO4) as a precursor, by improving substantially a procedure known to work on TiO2 nanopowders. In addition to demonstrating the applicability of this method of photodeposition to TiO2 films, this work also explores the importance of the material phase of the TiO2 substrate, outlines viable concentrations and photodeposition times at a given optical intensity, and demonstrates that the morphology of the photodeposited nanostructures changes from cauliflower-like spheroids to a matted, porous sponge-like structure with the addition of methanol to the precursor solution. This morphology change has not been documented previously. By providing an explanation for this difference in the morphology, this work provides both newer insights into the photodeposition process and provides an excellent foundation for future procedures, allowing a more targeted and controlled deposition based on the desired morphology.

Multi-photon patterning of photoactive o-nitrobenzyl ligands bound to gold surfaces.

We quantitatively investigate lithographic patterning of a thiol-anchored self-assembled monolayer (SAM) of photocleavable o-nitrobenzyl ligands on gold through a multi-photon absorption process at 1.7 eV (730 nm wavelength). The photocleaving rate increases faster than the square of the incident light intensity, indicating a process more complex than simple two-photon absorption. We tentatively ascribe this observation to two-photon absorption that triggers the formation of a long-lived intermediate aci-nitro species whose decomposition yield is partially determined either by absorption of additional photons or by a local temperature that is elevated by the incident light. At the highest light intensities, thermal processes compete with photoactivation and lead to damage of the SAM. The threshold is high enough that this destructive process can largely be avoided, even while power densities are kept sufficiently large that complete photoactivation takes place on time scales of tens of seconds to a few minutes. This means that this type of ligand can be activated at visible and near infrared wavelengths where plasmonic resonances can easily be engineered in metal nanostructures, even though their single-photon reactivity at these wavelengths is negligible. This will allow selective functionalization of plasmon hotspots, which in addition to high resolution lithographic applications would be of benefit to applications such as Surface Enhanced Raman Spectroscopy and plasmonic photocatalysis as well as directed bottom-up nanoassembly.

Light-Directed Patchy Particle Fabrication and Assembly from Isotropic Silver Nanoparticles.

We demonstrate the creation of anisotropic patchy silver nanospheroids (AgNSs) using linearly polarized UV light and a photo-uncaging o-nitrobenzyl-based ligand, which anchors to the AgNSs by two gold-sulfur bonds. Exposure to a 1 J/cm2 dose of UV light induces a photo-uncaging reaction in the ligand that reveals a primary amine on the surface. By using linearly polarized UV light, we meter the exposure dose such that only the poles of the nanoparticle receive a full dose, limiting the photo-uncaging reaction primarily to the particle's plasmonic hot spots. We reveal this anisotropy by preferentially adhering negatively charged gold nanospheres (AuNSs) to the AgNSs' poles by using the electrostatic attraction between them and the positively charged primary amines generated by photo-uncaging. When the assembly is performed onto silver particles that are immobilized on a substrate, it results in nanoscale structures with a strong tendency to align with the polarization of the exposing light. This manifests in polarimetric spectroscopy as a linear dichroism aligned with the polarization direction.