Imaging nano-objects by linear and nonlinear optical absorption microscopies.

Absorption based microscopy measurements are emerging as important tools for studying nanomaterials. This review discusses the three most common techniques for performing these experiments: transient absorption microscopy, photothermal heterodyne imaging, and spatial modulation spectroscopy. The focus is on the application of these techniques to imaging and detection, using examples taken from the authors' laboratory. The advantages and disadvantages of the three methods are discussed, with an emphasis on the unique information that can be obtained from these experiments, in comparison to conventional emission or scattering based microscopy experiments.

Near-infrared croconaine rotaxanes and doped nanoparticles for enhanced aqueous photothermal heating.

The photothermal effect is the generation of heat by molecules or particles upon high-energy laser irradiation, and near-infrared absorbers such as gold nanoparticles and organic dyes have a range of potential photothermal applications. The favourable photothermal properties of thiophene-functionalised croconaine dyes were recently discovered. The synthesis and properties of novel croconaine rotaxane and pseudorotaxane architectures capable of efficient photothermal performance in both organic and aqueous environments are reported. The versatility of this dye-encapsulation strategy was demonstrated by the preparation of two organic croconaine rotaxanes using different synthetic methods: the formation of an aqueous pseudorotaxane association complex, and the synthesis of water-soluble, croconaine-doped silicated micelle nanoparticles. All of these near-infrared-absorbing systems exhibit excellent photothermal behaviour, with pseudorotaxane and rotaxane formation vital for effective aqueous heat generation. Dye encapsulation provides steric protection to enhance the stability of a water-sensitive croconaine dye, while rotaxane-doped nanoparticles avoid detrimental band broadening caused by chromophore coupling.

Spatial modulation spectroscopy of graphene sheets.

Two different samples of graphene, multi-layer flakes on Si/SiO2 substrates and single layer graphene on glass, have been examined by reflectivity contrast and spatial modulation spectroscopy measurements. For the multi-layer graphene flakes, the reflectivity contrast and spatial modulation spectroscopy measurements are in good agreement, validating the application of spatial modulation spectroscopy to two-dimensional samples. The measurements for single layer graphene on glass show features that correspond to increases and decreases in reflectivity. The features with increased reflectivity are assigned to small regions of multilayer graphene or polymer, and the features with decreased reflectivity are assigned to holes in the graphene film. Using a model for thin film reflectivity we calculate the size dependent spatial modulation signal for the holes, and find that a significant number of holes have a larger than expected signal. This could arise from the presence of multi-layers of graphene in the sample, or because of optical resonance effects for the holes.

Time-Resolved Studies of the Acoustic Vibrational Modes of Metal and Semiconductor Nano-objects.

Over the past decade, there have been a number of transient absorption studies of the acoustic vibrational modes of metal and semiconductor nanoparticles. This Perspective provides an overview of this work. The way that the frequencies of the observed modes depend on the size and shape of the particles is described, along with their damping. Future research directions are also discussed, especially how these measurements provide information about the way nano-objects interact with their environment.

Detection of single gold nanoparticles using spatial modulation spectroscopy implemented with a galvo-scanning mirror system.

The optical extinction of single nanoparticles can be sensitively detected by spatial modulation spectroscopy (SMS), where the particle is moved in and out of a tightly focused laser beam with a piezo-device. Here we show that high sensitivity can be obtained by modulating the beam with a galvo-mirror system, rather than by moving the sample. This work demonstrates an inexpensive method for making a SMS microscope, and shows how an existing laser scanning microscope can be adapted for SMS measurements. The galvo-mirror technique also allows SMS measurements to be performed in a liquid, which is difficult to do with piezo-modulation.

Imaging the extent of plasmon excitation in Au nanowires using pump-probe microscopy.

Knowledge of how energy and charge carriers move in nanoscale systems is essential for engineering efficient devices. In this Letter, we demonstrate a technique to directly image dynamics in nanostructures based on laser scanning transient absorption microscopy, which provides near diffraction-limited spatial resolution and ultrafast time resolution. The capabilities of the technique are demonstrated by experiments on propagating surface plasmon polariton modes of Au nanowires, although these measurements can be used to study a variety of fluorescent and nonfluorescent systems.

Damping of the acoustic vibrations of a suspended gold nanowire in air and water environments.

The lifetimes of the acoustic vibrations of metal nanostructures depend sensitively on the properties of the environment, such as the acoustic impedance and viscosity. In order to accurately study these effects, they have to be separated from the damping processes that are inherent to the nanostructure. Here we show that this can be done experimentally by investigating individual gold nanowires suspended over a trench in air and liquid environments. The experiments were done by ultrafast pump-probe microscopy, recording transient absorption traces at the same point on the nanowire in both environments. These first experiments were performed with water, and the measured vibrational quality factors due to the presence of water were compared to continuum mechanics calculations for a cylinder in a homogeneous environment. Good agreement was found between the experimental quality factors and the calculated values. The continuum mechanics analysis shows that damping is dominated by the acoustic impedance of the solvent rather than by its viscosity for the nanowires in the present experiments. This experimental technique opens up the possibility of studying the effect of viscosity on the high frequency vibrational motions of nanostructures for a variety of liquids.

Picosecond kinetics of strongly coupled excitons and surface plasmon polaritons.

Coupling between excitons of CdSe nanocrystal quantum dots (NQDs) and surface plasmon polaritons (SPPs) of an Ag film attached to a prism have been studied by steady-state and transient reflectivity measurements in the Kretschmann geometry. In these experiments, the angle of incidence of the probe beam selects hybrid exciton/SPP states with different wavevectors and exciton/SPP compositions. The dynamics measured in the transient reflectivity experiments are sensitive to the composition of the hybrid states. Specifically, fast dynamics are observed at probe wavevectors where the lower hybrid state has predominant SPP character. In contrast, at probe wavevectors where the lower hybrid state is predominantly excitonic, the dynamics are similar to that measured for CdSe NQDs on glass.

Optical detection of single nano-objects by transient absorption microscopy.

In recent years there has been considerable effort in developing ultra-sensitive imaging techniques based on absorption. This mini-review describes recent results from our laboratory on detecting single nano-objects using transient absorption microscopy. This technique is extremely flexible, allowing the detection of single semiconductor and metal nanostructures with high sensitivity. The goal of this review is to illustrate key points in implementing transient absorption microscopy for ultra-sensitive detection, as well as to discuss the advantages and disadvantages of this technique compared to other optical absorption based methods.

Charge carrier trapping and acoustic phonon modes in single CdTe nanowires.

Semiconductor nanostructures produced by wet chemical synthesis are extremely heterogeneous, which makes single particle techniques a useful way to interrogate their properties. In this paper the ultrafast dynamics of single CdTe nanowires are studied by transient absorption microscopy. The wires have lengths of several micrometers and lateral dimensions on the order of 30 nm. The transient absorption traces show very fast decays, which are assigned to charge carrier trapping into surface defects. The time constants vary for different wires due to differences in the energetics and/or density of surface trap sites. Measurements performed at the band edge compared to the near-IR give slightly different time constants, implying that the dynamics for electron and hole trapping are different. The rate of charge carrier trapping was observed to slow down at high carrier densities, which was attributed to trap-state filling. Modulations due to the fundamental and first overtone of the acoustic breathing mode were also observed in the transient absorption traces. The quality factors for these modes were similar to those measured for metal nanostructures, and indicate a complex interaction with the environment.

Ultrafast Spatial Imaging of Charge Dynamics in Heterogeneous Polymer Blends.

Proof-of-concept transient absorption microscopy (TAM) with simultaneously high spatial and temporal resolution was demonstrated to image charge generation and recombination in model systems of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) blends upon extended thermal annealing. Significant spatial heterogeneity in charge generation and recombination dynamics was revealed on the length scale of hundreds of nanometers near the micrometer-sized PCBM crystallites, suggesting that information obtained in ensemble measurements by integrating over microscopically inhomogeneous areas could be misleading. In contrast to previous studies, high sensitivity of our instrumentation allows us to employ low excitation intensities to minimize higher-order recombination processes. TAM provides a unique noncontact tool to probe local functionality in microscopically heterogeneous energy harvesting systems.