James M. Kikkawa

Lateral drag of spin coherence in gallium arsenide

The importance of spin-transport phenomena in condensed-matter physics has increased over the past decade with the advent of metallic giant-magnetoresistive systems and spin-valve transistors. An extension of such phenomena to semiconductors should create possibilities for seamless integration of ‘spin electronics’ with existing solid-state devices, and may someday enable quantum computing schemes using electronic spins as non-local mediators of coherent nuclear spin interactions. But to realize such goals, spin transport must be effected without destroying the relevant spin information. Here we report time-resolved optical studies of non-local Faraday rotation in n-type bulk gallium arsenide, which show macroscopic lateral transport of coherently precessing electronic spins over distances exceeding 100 micrometres. The ability to drag these spin packets by their negative charge, without a substantial increase in spin decoherence, is a consequence of the rather weak entanglement of spin coherence with orbital motion in this system.

Binary nanocrystal superlattice membranes self-assembled at the liquid-air interface

The spontaneous organization of multicomponent micrometre-sized colloids or nanocrystals into superlattices is of scientific importance for understanding the assembly process on the nanometre scale and is of great interest for bottom-up fabrication of functional devices. In particular, co-assembly of two types of nanocrystal into binary nanocrystal superlattices (BNSLs) has recently attracted significant attention, as this provides a low-cost, programmable way to design metamaterials with precisely controlled properties that arise from the organization and interactions of the constituent nanocrystal components. Although challenging, the ability to grow and manipulate large-scale BNSLs is critical for extensive exploration of this new class of material. Here we report a general method of growing centimetre-scale, uniform membranes of BNSLs that can readily be transferred to arbitrary substrates. Our method is based on the liquid–air interfacial assembly of multicomponent nanocrystals and circumvents the limitations associated with the current assembly strategies, allowing integration of BNSLs on any substrate for the fabrication of nanocrystal-based devices. We demonstrate the construction of magnetoresistive devices by incorporating large-area (1.5 mm × 2.5 mm) BNSL membranes; their magnetotransport measurements clearly show that device magnetoresistance is dependent on the structure (stoichiometry) of the BNSLs. The ability to transfer BNSLs also allows the construction of free-standing membranes and other complex architectures that have not been accessible previously.

A Generalized Ligand-Exchange Strategy Enabling Sequential Surface Functionalization of Colloidal Nanocrystals

The ability to engineer surface properties of nanocrystals (NCs) is important for various applications, as many of the physical and chemical properties of nanoscale materials are strongly affected by the surface chemistry. Here, we report a facile ligand-exchange approach, which enables sequential surface functionalization and phase transfer of colloidal NCs while preserving the NC size and shape. Nitrosonium tetrafluoroborate (NOBF4) is used to replace the original organic ligands attached to the NC surface, stabilizing the NCs in various polar, hydrophilic media such as N,N-dimethylformamide for years, with no observed aggregation or precipitation. This approach is applicable to various NCs (metal oxides, metals, semiconductors, and dielectrics) of different sizes and shapes. The hydrophilic NCs obtained can subsequently be further functionalized using a variety of capping molecules, imparting different surface functionalization to NCs depending on the molecules employed. Our work provides a versatile ligand-exchange strategy for NC surface functionalization and represents an important step toward controllably engineering the surface properties of NCs.

Photoluminescence and band gap modulation in graphene oxide

We report broadband visible photoluminescence from solid graphene oxide, and modifications of the emission spectrum by progressive chemical reduction. The data suggest a gapping of the two-dimensional electronic system by removal of π-electrons. We discuss possible gapping mechanisms, and propose that a Kekule pattern of bond distortions may account for the observed behavior.

Electron Spin and Optical Coherence in Semiconductors

Semiconductors are ubiquitous in device electronics because their charge distributions are easily shaped and controlled to make logic gates. Since gate switching and intercommunication rates limit device speed, efforts to improve computational power have led the semiconductor industry to push devices to ever‐shrinking sizes. Yet, as advances in this area have improved the function of todays chip architectures, miniaturization may soon bring additional complications in the form of quantum mechanical effects. Because quantum systems tend to behave statistically, these effects will introduce unpredictable fluctuations in essential; design parameters, such as charge distribution, that will affect performance as device sizes shrink.

Thermal conductivity and interfacial resistance in single-wall carbon nanotube epoxy composites

We report thermal conductivity measurements of purified single-wall carbon nanotube (SWNT) epoxy composites prepared using suspensions of SWNTs in N-N-Dimethylformamide (DMF) and surfactant stabilized aqueous SWNT suspensions. Thermal conductivity enhancement is observed in both types of composites. DMF-processed composites show an advantage at SWNT volume fractions between ϕ∼0.001 to 0.005. Surfactant processed samples, however, permit greater SWNT loading and exhibit larger overall enhancement (64±9)% at ϕ∼0.1. The enhancement differences are attributed to a ten-fold larger SWNT/solid-composite interfacial thermal resistance in the surfactant-processed composites compared to DMF-processed composites. The interfacial resistance is extracted from the volume fraction dependence of the thermal conductivity data using effective medium theory. [C. W. Nan, G. Liu, Y. Lin, and M. Li, Appl. Phys. Lett. 85, 3549 (2004)].

Controlling the Self-Assembly Structure of Magnetic Nanoparticles and Amphiphilic Block-Copolymers: From Micelles to Vesicles

We report how to control the self-assembly of magnetic nanoparticles and a prototypical amphiphilic block-copolymer composed of poly(acrylic acid) and polystyrene (PAA-b-PS). Three distinct structures were obtained by controlling the solvent-nanoparticle and polymer-nanoparticle interactions: (1) polymersomes densely packed with nanoparticles (magneto-polymersomes), (2) core-shell type polymer assemblies where nanoparticles are radially arranged at the interface between the polymer core and the shell (magneto-core shell), and (3) polymer micelles where nanoparticles are homogeneously incorporated (magneto-micelles). Importantly, we show that the incorporation of nanoparticles drastically affects the self-assembly structure of block-copolymers by modifying the relative volume ratio between the hydrophobic block and the hydrophilic block. As a consequence, the self-assembly of micelle-forming block-copolymers typically produces magneto-polymersomes instead of magneto-micelles. On the other hand, vesicle-forming polymers tend to form magneto-micelles due to the solubilization of nanoparticles in polymer assemblies. The nanoparticle-polymer interaction also controls the nanoparticle arrangement in the polymer matrix. In N,N-dimethylformamide (DMF) where PS is not well-solvated, nanoparticles segregate from PS and form unique radial assemblies. In tetrahydrofuran (THF), which is a good solvent for both nanoparticles and PS, nanoparticles are homogeneously distributed in the polymer matrix. Furthermore, we demonstrated that the morphology of nanoparticle-encapsulating polymer assemblies significantly affects their magnetic relaxation properties, emphasizing the importance of the self-assembly structure and nanoparticle arrangement as well as the size of the assemblies.

Computational Design of Virus-like Protein Assemblies on Carbon Nanotube Surfaces

Proteins are designed to bind to specific surfaces while also presenting a programmed surface superstructure. There is a general need for the engineering of protein-like molecules that organize into geometrically specific superstructures on molecular surfaces, directing further functionalization to create richly textured, multilayered assemblies. Here we describe a computational approach whereby the surface properties and symmetry of a targeted surface define the sequence and superstructure of surface-organizing peptides. Computational design proceeds in a series of steps that encode both surface recognition and favorable intersubunit packing interactions. This procedure is exemplified in the design of peptides that assemble into a tubular structure surrounding single-walled carbon nanotubes (SWNTs). The geometrically defined, virus-like coating created by these peptides converts the smooth surfaces of SWNTs into highly textured assemblies with long-scale order, capable of directing the assembly of gold nanoparticles into helical arrays along the SWNT axis.

Optical Manipulation of Nuclear Spin by a Two-Dimensional Electron Gas

Conduction electrons are used to optically polarize, detect, and manipulate nuclear spin in a (110) GaAs quantum well. Using optical Larmor magnetometry, we find that nuclear spin can be polarized along or against the applied magnetic field, depending on field polarity and tilting of the sample with respect to the optical pump beam. Periodic optical excitation of the quantum-confined electron spin reveals a complete spectrum of optically induced and quadrupolar-split nuclear resonances, as well as evidence for Deltam = 2 transitions.

Tailoring hot-exciton emission and lifetimes in semiconducting nanowires via whispering-gallery nanocavity plasmons

The manipulation of radiative properties of light emitters coupled with surface plasmons is important for engineering new nanoscale optoelectronic devices, including lasers, detectors and single photon emitters. However, so far the radiative rates of excited states in semiconductors and molecular systems have been enhanced only moderately, typically by a factor of 10-50, producing emission mostly from thermalized excitons. Here, we show the generation of dominant hot-exciton emission, that is, luminescence from non-thermalized excitons that are enhanced by the highly concentrated electromagnetic fields supported by the resonant whispering-gallery plasmonic nanocavities of CdS-SiO(2)-Ag core-shell nanowire devices. By tuning the plasmonic cavity size to match the whispering-gallery resonances, an almost complete transition from thermalized exciton to hot-exciton emission can be achieved, which reflects exceptionally high radiative rate enhancement of >10(3) and sub-picosecond lifetimes. Core-shell plasmonic nanowires are an ideal test bed for studying and controlling strong plasmon-exciton interaction at the nanoscale and opens new avenues for applications in ultrafast nanophotonic devices.