David J. Norris

On-chip natural assembly of silicon photonic bandgap crystals

Photonic bandgap crystals can reflect light for any direction of propagation in specific wavelength ranges. This property, which can be used to confine, manipulate and guide photons, should allow the creation of all-optical integrated circuits. To achieve this goal, conventional semiconductor nanofabrication techniques have been adapted to make photonic crystals. A potentially simpler and cheaper approach for creating three-dimensional periodic structures is the natural assembly of colloidal microspheres. However, this approach yields irregular, polycrystalline photonic crystals that are difficult to incorporate into a device. More importantly, it leads to many structural defects that can destroy the photonic bandgap. Here we show that by assembling a thin layer of colloidal spheres on a silicon substrate, we can obtain planar, single-crystalline silicon photonic crystals that have defect densities sufficiently low that the bandgap survives. As expected from theory, we observe unity reflectance in two crystalline directions of our photonic crystals around a wavelength of 1.3 micrometres. We also show that additional fabrication steps, intentional doping and patterning, can be performed, so demonstrating the potential for specific device applications.

Doping semiconductor nanocrystals

Doping—the intentional introduction of impurities into a material—is fundamental to controlling the properties of bulk semiconductors. This has stimulated similar efforts to dope semiconductor nanocrystals. Despite some successes, many of these efforts have failed, for reasons that remain unclear. For example, Mn can be incorporated into nanocrystals of CdS and ZnSe (refs 7–9), but not into CdSe (ref. 12)—despite comparable bulk solubilities of near 50 per cent. These difficulties, which have hindered development of new nanocrystalline materials, are often attributed to ‘self-purification’, an allegedly intrinsic mechanism whereby impurities are expelled. Here we show instead that the underlying mechanism that controls doping is the initial adsorption of impurities on the nanocrystal surface during growth. We find that adsorption—and therefore doping efficiency—is determined by three main factors: surface morphology, nanocrystal shape, and surfactants in the growth solution. Calculated Mn adsorption energies and equilibrium shapes for several nanocrystals lead to specific doping predictions. These are confirmed by measuring how the Mn concentration in ZnSe varies with nanocrystal size and shape. Finally, we use our predictions to incorporate Mn into previously undopable CdSe nanocrystals. This success establishes that earlier difficulties with doping are not intrinsic, and suggests that a variety of doped nanocrystals—for applications from solar cells to spintronics—can be anticipated.

Hot-electron transfer from semiconductor nanocrystals.

Hot on the Trail Solar cells essentially operate by absorbing light, which needs to be above a certain energy threshold. The absorbed light then liberates charges within the solar cell to carry electrical current. Unfortunately, the liberated charges behave the same way whether they are excited right at the threshold (e.g., by visible light) or well above it (by ultraviolet light), which leads to any excess energy being dissipated as waste heat. Tisdale et al. (p. 1543) have documented a potential first step toward resolving this inefficiency. Specifically, electrons excited by light absorption in lead selenide nanocrystals were able to migrate to an adjacent titanium dioxide surface without releasing their excess energy to heat. The next step will be to devise a means of harnessing the stored energy in a circuit. Extraction of highly excited electrons formed in a light-absorbing material may make solar cells more efficient. In typical semiconductor solar cells, photons with energies above the semiconductor bandgap generate hot charge carriers that quickly cool before all of their energy can be captured, a process that limits device efficiency. Although fabricating the semiconductor in a nanocrystalline morphology can slow this cooling, the transfer of hot carriers to electron and hole acceptors has not yet been thoroughly demonstrated. We used time-resolved optical second harmonic generation to observe hot-electron transfer from colloidal lead selenide (PbSe) nanocrystals to a titanium dioxide (TiO2) electron acceptor. With appropriate chemical treatment of the nanocrystal surface, this transfer occurred much faster than expected. Moreover, the electric field resulting from sub–50-femtosecond charge separation across the PbSe-TiO2 interface excited coherent vibrations of the TiO2 surface atoms, whose motions could be followed in real time.

Ultrasmooth patterned metals for plasmonics and metamaterials.

Perfectly Flat? Plasmonic devices, which exploit the interactions of light with surface electrons, show great promise for applications in sensing, communications, and energy conversion. A key hindrance is the deposition of patterned metals used for plasmonics, because, as deposited, the terminal surfaces are rough and not amenable to patterning by directional dry-etching techniques. Nagpal et al. (p. 594) use patterned silicon substrates on which they add gold, silver, or copper and then apply an epoxy layer to the deposited metal. When pulled apart, the metal separates from the silicon, where the adhesion is poorer, leaving an ultra-smooth surface. The resulting surface plasmon propagation lengths approach the theoretical values for perfectly flat films. Films with enhanced surface-plasmon propagation may find use in sensing and communications devices. Surface plasmons are electromagnetic waves that can exist at metal interfaces because of coupling between light and free electrons. Restricted to travel along the interface, these waves can be channeled, concentrated, or otherwise manipulated by surface patterning. However, because surface roughness and other inhomogeneities have so far limited surface-plasmon propagation in real plasmonic devices, simple high-throughput methods are needed to fabricate high-quality patterned metals. We combined template stripping with precisely patterned silicon substrates to obtain ultrasmooth pure metal films with grooves, bumps, pyramids, ridges, and holes. Measured surface-plasmon–propagation lengths on the resulting surfaces approach theoretical values for perfectly flat films. With the use of our method, we demonstrated structures that exhibit Raman scattering enhancements above 107 for sensing applications and multilayer films for optical metamaterials.

Engineering metallic nanostructures for plasmonics and nanophotonics

Metallic nanostructures now play an important role in many applications. In particular, for the emerging fields of plasmonics and nanophotonics, the ability to engineer metals on nanometric scales allows the development of new devices and the study of exciting physics. This review focuses on top-down nanofabrication techniques for engineering metallic nanostructures, along with computational and experimental characterization techniques. A variety of current and emerging applications are also covered.

Three-Dimensional Imaging of Single Molecules Solvated in Pores of Poly(acrylamide) Gels

Individual fluorescent molecules and individual singly labeled proteins were observed in the water-filled pores of poly(acrylamide) gels by far-field microscopy. Brownian motion was markedly reduced by the gel framework, thus enabling extended study of single fluorophores in aqueous environments. A highly axially dependent laser field was used both to excite the fluorophores and to image the molecules in three dimensions. Single molecules were followed as they moved within and through the porous gel structure. In contrast to dry polymeric hosts, these water-based gels may form a useful medium for single-molecule studies of biological systems in vitro.

Solar Cells Based on Junctions between Colloidal PbSe Nanocrystals and Thin ZnO Films

We report a new type of excitonic solar cell based on planar heterojunctions between PbSe semiconductor nanocrystals and thin ZnO films. These solar cells generate large photocurrents and higher photovoltages compared to Schottky cells assembled with similar nanocrystal films. When illuminated with 100 mW/cm(2) simulated AM1.5 spectrum, these solar cells exhibit short-circuit currents between 12 and 15 mA/cm(2), open-circuit voltages up to 0.45 V, and a power conversion efficiency of 1.6%. The photovoltage depends on the size of the nanocrystals, increasing linearly with their effective band gap energy.

Plasmonic Films Can Easily Be Better: Rules and Recipes

High-quality materials are critical for advances in plasmonics, especially as researchers now investigate quantum effects at the limit of single surface plasmons or exploit ultraviolet- or CMOS-compatible metals such as aluminum or copper. Unfortunately, due to inexperience with deposition methods, many plasmonics researchers deposit metals under the wrong conditions, severely limiting performance unnecessarily. This is then compounded as others follow their published procedures. In this perspective, we describe simple rules collected from the surface-science literature that allow high-quality plasmonic films of aluminum, copper, gold, and silver to be easily deposited with commonly available equipment (a thermal evaporator). Recipes are also provided so that films with optimal optical properties can be routinely obtained.

Electronic Impurity Doping in CdSe Nanocrystals

We dope CdSe nanocrystals with Ag impurities and investigate their optical and electrical properties. Doping leads not only to dramatic changes but surprising complexity. The addition of just a few Ag atoms per nanocrystal causes a large enhancement in the fluorescence, reaching efficiencies comparable to core-shell nanocrystals. While Ag was expected to be a substitutional acceptor, nonmonotonic trends in the fluorescence and Fermi level suggest that Ag changes from an interstitial (n-type) to a substitutional (p-type) impurity with increased doping.

Size control and quantum confinement in Cu2ZnSnS4 nanocrystals.

Starting with metal dithiocarbamate complexes, we synthesize colloidal Cu(2)ZnSnS(4) (CZTS) nanocrystals with diameters ranging from 2 to 7 nm. Structural and Raman scattering data confirm that CZTS is obtained rather than other possible material phases. The optical absorption spectra of nanocrystals with diameters less than 3 nm show a shift to higher energy due to quantum confinement.