Martin Moskovits

Highly-ordered carbon nanotube arrays for electronics applications

Highly-ordered arrays of parallel carbon nanotubes were grown by pyrolysis of acetylene on cobalt within a hexagonal close-packed nanochannel alumina template at 650 °C. The nanotubes are characterized by a narrow size distribution, large scale periodicity, and high densities. Using this method ordered nanotubes with diameters from 10 nm to several hundred nm and lengths up to 100 μm can be produced. The high level of ordering and uniformity in these arrays is useful for applications in data storage, field emission displays and sensors, and offers the prospect of deriving computational functions from the collective behavior of symmetrically coupled nanotubes. The fabrication method used is compatible with standard lithographic processes and thus enables future integration of such periodic carbon nanotube arrays with silicon microelectronics.

An autonomous photosynthetic device in which all charge carriers derive from surface plasmons

Solar conversion to electricity or to fuels based on electron-hole pair production in semiconductors is a highly evolved scientific and commercial enterprise. Recently, it has been posited that charge carriers either directly transferred from the plasmonic structure to a neighbouring semiconductor (such as TiO₂) or to a photocatalyst, or induced by energy transfer in a neighbouring medium, could augment photoconversion processes, potentially leading to an entire new paradigm in harvesting photons for practical use. The strong dependence of the wavelength at which the local surface plasmon can be excited on the nanostructure makes it possible, in principle, to design plasmonic devices that can harvest photons over the entire solar spectrum and beyond. So far, however, most such systems show rather small photocatalytic activity in the visible as compared with the ultraviolet. Here, we report an efficient, autonomous solar water-splitting device based on a gold nanorod array in which essentially all charge carriers involved in the oxidation and reduction steps arise from the hot electrons resulting from the excitation of surface plasmons in the nanostructured gold. Each nanorod functions without external wiring, producing 5 × 10(13) H₂ molecules per cm(2) per s under 1 sun illumination (AM 1.5 and 100 mW cm(-2)), with unprecedented long-term operational stability.

Surface roughness and the enhanced intensity of Raman scattering by molecules adsorbed on metals

Greatly enhanced Raman scattering from monolayers of pyridine adsorbed on silver has been reported by several authors. I propose that the anomalous intensity arises from preresonant or resonant excitations of conduction electron resonances in adsorbate covered metal bumps on the surface. The bumps form a two‐dimensional colliodlike layer which displays a collective resonance at a frequency which depends on the bump density. The model can account for the disparate excitation functions reported by two groups in terms of varying degrees of roughness. The apparent lack of enhancement with metals other than Group Ib is also explained.

Surface selection rules

The modification of the absorption, emission, and Raman scattering intensities of molecules near metal surfaces is discussed with emphasis on the last. These modifications are usually referred to as surface selection rules. We show that in Raman scattering, the ‘‘rule,’’ which states that only those modes will be active which belong to the irreducible representation to which α′zz also belongs, is only approximately obeyed. The circumstances under which modes which are represented by nondiagonal derived polarizibility tensors are ‘‘surface‐active’’ are considered, as well as the geometrical strategies which should be followed in studying the Raman spectra of molecules adsorbed on flat, metal surfaces.

Magnetic properties of Fe deposited into anodic aluminum oxide pores as a function of particle size

A combination of magnetic and electron microscopic measurements on iron deposited in chemically widened anodic aluminum oxide films has allowed us to relate the coercivity of these materials to the dimensions of the metal particles. The coercivity is found to be highly anisotropic and to depend on the aspect ratio of the metallic particles. The functional dependence of Hc on the aspect ratio fits the expression reported by Jacobs and Bean [Phys. Rev. 100, 1060 (1955)] for magnetization reversal by symmetric fanning. This is likely due to the fact that in our unannealed samples the metal deposit consists of a cylindrical assembly of fused single‐domain particles. Pore widening by chemical dissolution of the anodic oxide is found to depend quadratically on the time that the sample is soaked in the acid bath.

Nonlithographic nano-wire arrays: fabrication, physics, and device applications

A novel system of nanostructures is described consisting of nonlithographically produced arrays of nano-wires directly electrodeposited into porous anodic aluminum oxide templates. Using this method regular and uniform arrays of metal or semiconductor nano-wires or nano-dots can be created with diameters ranging from /spl sim/5 nm to several hundred nanometers and with areal pore densities in the /spl sim/10/sup 9/-10/sup 11/ cm/sup -2/ range. We report on the present state of their fabrication, properties, and prospective device applications. Results of X-ray diffraction, Raman and magnetic measurements on metal (Ni, Fe) and semiconductor (CdS, CdSe, CdS/sub x/Se/sub 1-x/, Cd/sub x/Zn/sub 1-x/S and GaAs) wires are presented. The I-V characteristics of two terminal devices made from the nano-arrays are found to exhibit room temperature periodic conductance oscillations and Coulomb-blockade like current staircases. These observations are likely associated with the ultra-small tunnel junctions that are formed naturally in the arrays. Single-electron tunneling (SET) In the presence of interwire coupling in these arrays is shown to lead to the spontaneous electrostatic polarization of the wires. Possible device applications such as magnetic memory or sensors, electroluminescent flat-panel displays, and nanoelectronic and single-electronic devices are also discussed.

Mesoporous Multifunctional Upconversion Luminescent and Magnetic "Nanorattle" Materials for Targeted Chemotherapy

Nanorattles consisting of hydrophilic, rare-earth-doped NaYF(4) shells each containing a loose magnetic nanoparticle were fabricated through an ion-exchange process. The inner magnetic Fe(3)O(4) nanoparticles are coated with a SiO(2) layer to avoid iron leaching in acidic biological environments. This multifunctional mesoporous nanostructure with both upconversion luminescent and magnetic properties has excellent water dispersibility and a high drug-loading capacity. The material emits visible luminescence upon NIR excitation and can be directed by an external magnetic field to a specific target, making it an attractive system for a variety of biological applications. Measurements on cells incubated with the nanorattles show them to have low cytotoxicity and excellent cell imaging properties. In vivo experiments yield highly encouraging tumor shrinkage with the antitumor drug doxorubicin (DOX) and significantly enhanced tumor targeting in the presence of an applied magnetic field.

Plasmonic Photoanodes for Solar Water Splitting with Visible Light

We report a plasmonic water splitting cell in which 95% of the effective charge carriers derive from surface plasmon decay to hot electrons, as evidenced by fuel production efficiencies up to 20-fold higher at visible, as compared to UV, wavelengths. The cell functions by illuminating a dense array of aligned gold nanorods capped with TiO(2), forming a Schottky metal/semiconductor interface which collects and conducts the hot electrons to an unilluminated platinum counter-electrode where hydrogen gas evolves. The resultant positive charges in the Au nanorods function as holes and are extracted by an oxidation catalyst which electrocatalytically oxidizes water to oxygen gas.

Plasmonic Photosensitization of a Wide Band Gap Semiconductor: Converting Plasmons to Charge Carriers

A fruitful paradigm in the development of low-cost and efficient photovoltaics is to dope or otherwise photosensitize wide band gap semiconductors in order to improve their light harvesting ability for light with sub-band-gap photon energies.(1-8) Here, we report significant photosensitization of TiO2 due to the direct injection by quantum tunneling of hot electrons produced in the decay of localized surface-plasmon polaritons excited in gold nanoparticles (AuNPs) embedded in the semiconductor (TiO2). Surface plasmon decay produces electron-hole pairs in the gold.(9-15) We propose that a significant fraction of these electrons tunnel into the semiconductors conduction band resulting in a significant electron current in the TiO2 even when the device is illuminated with light with photon energies well below the semiconductors band gap. Devices fabricated with (nonpercolating) multilayers of AuNPs in a TiO2 film produced over 1000-fold increase in photoconductance when illuminated at 600 nm over what TiO2 films devoid of AuNPs produced. The overall current resulting from illumination with visible light is ∼50% of the device current measured with UV (ℏω>Eg band gap) illumination. The above observations suggest that plasmonic nanostructures (which can be fabricated with absorption properties that cover the full solar spectrum) can function as a viable alternative to organic photosensitizers for photovoltaic and photodetection applications.

Nanowires formed in anodic oxide nanotemplates

A simple electrochemical method is described for producing metal or semiconductor nanowires with diameters in the continuous range 10 to 200 nm. The technique involves a three-step process that begins with the electrochemical generation of an aluminum oxide template with uniform nanometer-sized pores, followed by the deposition of metal or semiconductor in them. The nanowires are then exposed for study or device fabrication by etching back the oxide matrix. Examples of cadmium nanowires fabricated by this technique are shown.