Here we show the first direct extinction spectra of single one-dimensional (1D) semiconductor nanostructures obtained at room temperature utilizing a spatial modulation approach. (1) For these materials, ensemble averaging in conventional extinction spectroscopy has limited our understanding of the interplay between carrier confinement and their electrostatic interactions. (2-4) By probing individual CdSe nanowires (NWs), we have identified and assigned size-dependent exciton transitions occurring across the visible. In turn, we have revealed the existence of room temperature 1D excitons in the narrowest NWs.

We demonstrate the solution-phase synthesis of CdS/CdSe, CdSe/CdS, and CdSe/ZnTe core/shell nanowires (NWs). On the basis of bulk band offsets, type-I and type-II heterostructures are made, contributing to the further development of low-dimensional heteroassemblies using solution-phase chemistry. Core/shell wires are prepared by slowly introducing shell precursors into a solution of premade core NWs dispersed in a noncoordinating solvent at moderate temperatures (215-250 degrees C). Resulting heterostructures are characterized through low- and high-resolution transmission electron microscopy, selected area electron diffraction, and energy dispersive X-ray analysis. From these experiments, initial shell growth appears to occur through either Stranski-Krastanov or Volmer-Weber island growth. However, beyond a critical shell thickness, nucleation of randomly oriented nanocrystals results in a polycrystalline coat. In cases where overcoating has been achieved, corresponding elemental analyses show spatially varying compositions along the NW radial direction in agreement with expected element ratios. Electronic interactions between the core and shell were subsequently probed through optical studies involving UV-vis extinction spectroscopy, photoluminescence experiments, and transient differential absorption spectroscopy. In particular, transient differential absorption studies reveal unexpected shell-induced changes in core NW Auger kinetics at high carrier densities. Previously seen three-carrier Auger kinetics in CdS (bimolecular in CdSe) NWs were suppressed by the presence of a CdSe (CdS) shell. These observations suggest the ability to influence NW optical/electrical properties by coating them with a surrounding shell, a method which could be important for future NW optical studies as well as for NW-based applications.

There has recently been much work on using nanowires for various applications. Examples include photodetectors and photovoltaics. One of the main reasons for this stems from the nanowire’s asymmetric shape, which, in principle, facilitates the ready band transport of carriers. As a consequence, effective mobilities should be larger than those of comparable quantum dot devices. At the same time, a less recognized advantage of nanowires over nanocrystals is their sizable absorption cross sections. Namely, circularly polarized nanowire cross sections in the visible are routinely on the order of 10−12 cm2 μm−1 to 10−10 cm2 μm−1 whereas those of dots range from 10−15 cm2 to 10−18 cm2. When scaled for volume differences, best case nanowire cross sections are still larger than those of nanocrystals by roughly an order of magnitude. This could, in turn, offer additional benefits for nanowire-based devices.

Optical molecular imaging employs relatively harmless, low-energy light and technically straightforward instrumentation. Self-illuminating, chemiluminescent systems are especially attractive since they have inherently high signal contrast due to the lack of background emission. Currently, chemiluminescence imaging involves short-lived molecular species that are not stored but instead generated in situ, and they typically emit visible light, which does not penetrate far through heterogeneous biological media. Here, we describe a new paradigm for optical molecular imaging using squaraine rotaxane endoperoxides (SREPs), interlocked fluorescent and chemiluminescent dye molecules that have a squaraine chromophore encapsulated inside a macrocycle endoperoxide. SREPs can be stored indefinitely at temperatures below −20 °C, but upon warming to body temperature they undergo a unimolecular chemical reaction and emit near infrared light that can pass through a living mouse. Dye-stained microparticles are easily prepared for in vivo near-infrared optical imaging using commercial imaging stations.

Absorption cross sections ((sigma)abs) of single branched CdSe nanowires (NWs) have been measured by photothermal heterodyne imaging (PHI). Specifically, PHI signals from isolated gold nanoparticles (NPs) with known cross sections were compared to those of individual CdSe NWs excited at 532 nm. This allowed us to determine average NW absorption cross sections at 532 nm of (sigma)abs = (3.17 +/- 0.44) x 10(-11) cm2/microm (standard error reported). This agrees well with a theoretical value obtained using a classical electromagnetic analysis ((sigma)abs = 5.00 x 10(-11) cm2/microm) and also with prior ensemble estimates. Furthermore, NWs exhibit significant absorption polarization sensitivities consistent with prior NW excitation polarization anisotropy measurements. This has enabled additional estimates of the absorption cross section parallel ((sigma)abs) and perpendicular ((sigma)abs(perpendicular) to the NW growth axis, as well as the corresponding NW absorption anisotropy ((rho)abs). Resulting values of (sigma)abs = (5.6 +/- 1.1) x 10(-11) cm2/microm, (sigma)abs(perpendicular) = (1.26 +/- 0.21) x 10(-11) cm2/microm, and (rho)abs = 0.63+/- 0.04 (standard errors reported) are again in good agreement with theoretical predictions. These measurements all indicate sizable NW absorption cross sections and ultimately suggest the possibility of future direct single NW absorption studies.

We investigate the excitation polarization anisotropy of individual semiconductor nanowires (NWs) by monitoring their band edge emission above 680 nm in order to clarify the origin of their strong polarization response. Samples studied include both CdSe and CdSe/CdS core/shell nanowires grown using solution chemistry as well as analogous wires made via chemical-vapor-deposition (CVD). In the limit of optically thick wires, with radii above ∼25 nm, we find NW optical responses consistent with the interaction between strong dielectric contrast influences and the onset of bulk-like behavior. Namely, a sizable wavelength dependence of the excitation polarization anisotropy (ρ(exc)) exists when NW diameters become comparable to the wavelength of light inside the wire. As a consequence, pronounced ρ(exc) rolloffs occur at short wavelengths. By contrast, thinner wires do not exhibit such wavelength dependencies, in agreement with earlier studies. We quantitatively explain observed wavelength sensitivities by modeling the NW as an absorbing dielectric cylinder under plane wave excitation. A comparison of predicted ρ(exc)-values to experimental numbers shows good agreement and confirms the existence of wavelength-dependent ρ(exc)-values in optically thick wires. Additional results of the model include generalized expressions for NW linear absorption cross-sections under parallel, perpendicular, and circularly polarized excitation. This study therefore adds to a growing body of knowledge about NW polarization anisotropies, specifically, their response in a size regime where dielectric contrast effects compete with the onset of bulk-like behavior.

Excitation/emission polarization anisotropies (ρexc∕emm) of single CdSe nanowires (NWs) were studied for their size, frequency, and dielectric environment dependencies. Single NW optical experiments show strong ρexc dielectric environment dependencies for both thick and thin NWs in agreement with classical dielectric contrast models. Furthermore, no excitation frequency sensitivities were seen for both thick and thin wires, in air and under poly(methyl methacrylate) (PMMA). Moderate radial dependencies were also found for NWs embedded in PMMA. Complementary emission anisotropy measurements yielded significant radial and dielectric environment sensitivities with statistically smaller ρemm values than ρexc. A moderate ρemm frequency dependence was observed for thin NWs in PMMA.

This paper describes an experimental technique for measuring the extinction cross-section of anisotropic nanomaterials. The experiments are performed by focusing a laser beam to a diffraction-limited spot under an optical microscope, and using a photoelastic modulator (PEM) to rotate the polarization of the light beam. Monitoring the transmitted beam with a lock-in amplifier referenced to twice the resonant frequency of the PEM yields the difference in extinction for light polarized parallel and perpendicular to the optical axis of the nanostructure. These experiments are the single particle analog of polarization modulation microscopy (PMM). Experimental results for gold nanorods and CdSe nanowires are presented that demonstrate the sensitivity and properties of this technique. In particular, we show that by collecting images at two laser polarizations separated by 45°it is possible to construct an extinction cross-section image. The advantages and disadvantages of the PMM technique compared to existing ways of measuring the extinction of nanoparticles (photothermal heterodyne imaging and spatial modulation spectroscopy) are discussed. Results from experiments where we collected simultaneous absorption and emission images are also presented for different shaped CdSe nanowires. These measurements provide insight into how the structure of the nanowire affects its photophysics. † Part of the special issue "Protected Metallic Clusters, Quantum Wells, and Metallic Nanocrystal Molecules".