The role of interfacial charge transfer-type interactions in the decay of plasmon excitations in metal nanoparticles.

This perspective describes the influence of interfacial charge transfer-type interactions on the optical spectra and hot electron cooling processes in plasmonic nanoparticles (NPs), and ongoing work to optimize these interactions for charge extraction from the plasmon or hot electron state. The manuscript focuses on interfaces of metal NPs with organic molecules and with semiconductors. Charge extraction from multi-electron excited states has applications in photodetection, sensing, and conversion of solar energy to electricity and fuels.

Identification of parameters through which surface chemistry determines the lifetimes of hot electrons in small Au nanoparticles.

This paper describes measurements of the dynamics of hot electron cooling in photoexcited gold nanoparticles (Au NPs) with diameters of ∼3.5 nm, and passivated with either a hexadecylamine or hexadecanethiolate adlayer, using ultrafast transient absorption spectroscopy. Fits of these dynamics with temperature-dependent Mie theory reveal that both the electronic heat capacity and the electron-phonon coupling constant are larger for the thiolated NPs than for the aminated NPs, by 40% and 30%, respectively. Density functional theory calculations on ligand-functionalized Au slabs show that the increase in these quantities is due to an increased electronic density of states near the Fermi level upon ligand exchange from amines to thiolates. The lifetime of hot electrons, which have thermalized from the initial plasmon excitation, increases with increasing electronic heat capacity, but decreases with increasing electron-phonon coupling, so the effects of changing surface chemistry on these two quantities partially cancel to yield a hot electron lifetime of thiolated NPs that is only 20% longer than that of aminated NPs. This analysis also reveals that incorporation of a temperature-dependent electron-phonon coupling constant is necessary to adequately fit the dynamics of electron cooling.

Multi-scale Plasmonic Nanoparticles and the Inverse Problem.

This Perspective describes how multi-scale plasmonic structures with two or more length scales (fine, medium, coarse) provide an experimental route for addressing the inverse problem. Specific near-field and far-field optical properties can be targeted and compiled into a plasmon resonance library by taking advantage of length scales spanning three orders of magnitude, from 1 nm to greater than 1000 nm, in a single particle. Examples of multi-scale 1D, 2D, and 3D gold structures created by nanofabrication tools and templates are discussed, and unexpected optical properties compared to those from their smaller counterparts are emphasized. One application of multi-scale particle dimers for surface-enhanced Raman spectroscopy is also described.

Ligand-controlled rates of photoinduced electron transfer in hybrid CdSe nanocrystal/poly(viologen) films.

This paper describes a study of the rates of photoinduced electron transfer (PET) from CdSe quantum dots (QDs) to poly(viologen) within thin films, as a function of the length of the ligands passivating the QDs. Ultrafast (<10 ps), quantitative PET occurs from CdSe QDs coated with HS-(CH(2))(n)-COOH for n = 1, 2, 5, and 7 to viologen units. The observed decrease in the magnitude of the PET rate constant with n is weaker than that expected from the decay of the electron tunneling probability across extended all-trans mercaptocarboxylic acids but well-described by electron tunneling across a collapsed ligand shell. The PET rate constants for films with n = 10 and 15 are much slower than those expected based on the trend for n = 1-7; this deviation is ascribed to the formation of bundles of ligands on the surface of the QD that make the tunneling process prohibitively slow by limiting access of the viologen units to the surfaces of the QDs. This study highlights the importance of molecular-level morphology of donor and acceptor materials in determining the rate and yield of interfacial photoinduced electron transfer in thin films.

A Three-Channel Spectrometer for Wide-Field Imaging of Anisotropic Plasmonic Nanoparticles.

A three-channel spectrometer (3CS) based on a commercial digital camera was developed to distinguish among tens of large (>100 nm), anisotropic plasmonic particles with various shapes, orientations, and compositions on a surface simultaneously. Using band pass filters and polarizers, the contrast of 3CS images could be enhanced to identify specific orientation and composition characteristics of gold and gold-silver nanopyramids and as well as the direction of the longest arm of gold nanostars.

Optical properties of anisotropic core-shell pyramidal particles.

This paper describes an approach to fabricate anisotropic core-shell particles by assembling dielectric beads within fabricated noble metal pyramidal structures. Particles with gold (Au) shells and different dielectric cores were generated, and their optical properties were characterized by single particle spectroscopy. Because of their unique geometry, these particles exhibit multiple plasmon resonances from visible to near-IR wavelengths.