Joshua T. Stecher

Exploiting Plasmon-Induced Hot Electrons in Molecular Electronic Devices

Plasmonic nanostructures can induce a number of interesting responses in devices. Here we show that hot electrons can be extracted from plasmonic particles and directed into a molecular electronic device, which represents a new mechanism of transfer from light to electronic transport. To isolate this phenomenon from alternative and sometimes simultaneous mechanisms of plasmon-exciton interactions, we designed a family of hybrid nanostructure devices consisting of Au nanoparticles and optoelectronically functional porphyin molecules that enable precise control of electronic and optical properties. Temperature- and wavelength-dependent transport measurements are analyzed in the context of optical absorption spectra of the molecules, the Au particle arrays, and the devices. Enhanced photocurrent associated with exciton generation in the molecule is distinguished from enhancements due to plasmon interactions. Mechanisms of plasmon-induced current are examined, and it is found that hot electron generation can be distinguished from other possibilities.

One-Pot Solvothermal Synthesis of Highly Emissive, Sodium-Codoped, LaF3 and BaLaF5 Core-Shell Upconverting Nanocrystals

We report a one-pot solvothermal synthesis of sub-10 nm, dominant ultraviolet (UV) emissive upconverting nanocrystals (UCNCs), based on sodium-codoped LaF3 and BaLaF5 (0.5%Tm; 20%Yb) and their corresponding core@shell derivatives. Elemental analysis shows a Na-codopant in these crystal systems of ~20% the total cation content; X-ray diffraction (XRD) data indicate a shift in unit cell dimensions consistent with these small codopant ions. Similarly, X-ray photoelectron spectroscopic (XPS) analysis reveals primarily substitution of Na+ for La3+ ions (97% of total Na+ codopant) in the crystal system, and interstitial Na+ (3% of detected Na+) and La3+ (3% of detected La3+) present in (Na)LaF3 and only direct substitution of Na+ for Ba2+ in Ba(Na)LaF5. In each case, XPS analysis of La 3d lines show a decrease in binding energy (0.08–0.25 eV) indicating a reduction in local crystal field symmetry surrounding rare earth (R.E.3+) ions, permitting otherwise disallowed R.E. UC transitions to be enhanced. Studies that examine the impact of laser excitation power upon luminescence intensity were conducted over 2.5–100 W/cm2 range to elucidate UC mechanisms that populate dominant UV emitting states. Low power saturation of Tm3+ 3F3 and 3H4 states was observed and noted as a key initial condition for effective population of the 1D2 and 1I6 UV emitting states, via Tm-Tm cross-relaxation.

Synthesis and Characterization of Ultrathin Silver Sulfide Nanoplatelets

We report the synthesis of ultrathin silver sulfide (Ag2S) nanoplatelets (NPLs) synthesized via a one-pot method in ethylene glycol with 3-mercaptopropionic acid serving as both the sulfur precursor and the platelet ligand. The colloidally synthesized nanoplatelets are exceptionally thin, with a thickness of only 3.5 ± 0.2 Å and a 1S exciton Bohr diameter to confinement ratio of ∼12.6. The NPL growth is shown to be quantized by layer thickness using absorption and photoluminescence (PL) spectroscopy. Transmission electron microscopy, atomic force microscopy, and X-ray diffraction analyses of the NPLs show that they correspond to the (202) plane of the β-Ag2S structure. The PL quantum yield of these NPLs is ∼30%, suggesting their potential use in biomedical imaging. Optoelectronic properties were evaluated via sensitized photocurrent spectroscopy with the resulting spectra closely matching the distinctive absorption spectral shape of the Ag2S NPLs.