Advances in nanoscience and nanotechnology critically depend on the development of nanostructures whose properties are controlled during synthesis. We focus on this critical concept using semiconductor nanowires, which provide the capability through design and rational synthesis to realize unprecedented structural and functional complexity in building blocks as a platform material. First, a brief review of the synthesis of complex modulated nanowires in which rational design and synthesis can be used to precisely control composition, structure, and, most recently, structural topology is discussed. Second, the unique functional characteristics emerging from our exquisite control of nanowire materials are illustrated using several selected examples from nanoelectronics and nano-enabled energy. Finally, the remarkable power of nanowire building blocks is further highlighted through their capability to create unprecedented, active electronic interfaces with biological systems. Recent work pushing the limits of both multiplexed extracellular recording at the single-cell level and the first examples of intracellular recording is described, as well as the prospects for truly blurring the distinction between nonliving nanoelectronic and living biological systems.

Nanotechnology offers the promise of enabling revolutionary advances in diverse areas ranging from electronics, optoelectronics, and energy to healthcare. Underpinning the realization of such advances are the nanoscale ma te rials and corresponding nanodevices central to these application areas. Semiconductor nanowires and nanobelts are emerging as one of the most powerful and diverse classes of functional nanoma terials that are having an impact on science and technology. In this issue of MRS Bulletin, several leaders in this vibrant field of research present brief reviews that highlight key aspects of the underlying materials science of nanowires, basic device functions achievable with these materials, and developing applications in electronics and at the interface with biology. This article introduces the controlled synthesis, patterned and designed self-assembly, and unique applications of nanowires in nanoelectronics, nano-optoelectronics, nanosensors, nanobiotechnology, and energy harvesting.

The interface between nanosystems and biosystems is emerging as one of the broadest and most dynamic areas of science and technology, bringing together biology, chemistry, physics, biotechnology, medicine, and many areas of engineering. The combination of these diverse areas of research promises to yield revolutionary advances in healthcare, medicine, and the life sciences through the creation of new and powerful tools that enable direct, sensitive, and rapid analysis of biological and chemical species. Devices based on nanowires have emerged as one of the most powerful and general platforms for ultrasensitive, direct electrical detection of biological and chemical species and for building functional interfaces to biological systems, including neurons. Here, we discuss representative ex amples of nanowire nanosensors for ultrasensitive detection of proteins and individual virus particles as well as recording, stimulation, and inhibition of neuronal signals in nanowire-neuron hybrid structures.

Label-free, real-time, parallel and complementary electrical detection of proteins is demonstrated by p-type and n-type silicon nanowire field-effect transistors in the same arrays. Composed of hundreds of individually electrically addressable nanowire devices with highly sensitive and reproducible performances, these nanowire arrays can be controllably modified by monoclonal antibodies, and show discrete conductance changes characteristic of highly selective binding and unbinding of target proteins, such as prostate specific antigens (PSA), thus providing a general and powerful platform for high-throughput real-time parallel detection and rapid screening of libraries of biomolecules. Studies show that the PSA proteins can be routinely detected at femtomolar concentrations with high selectivity, and simultaneously incorporation of both p-type and n-type silicon nanowire devices enable discrimination against false positive/negative signals. The integrated complementary nanowire sensor arrays open up substantial opportunities for diagnosis and treatment of complex diseases such as cancer, detection of biological threats, and fundamental proteomic and biophysical studies.

Extended abstract of a paper presented at Microscopy and Microanalysis 2004 in Savannah, Georgia, USA, August 1–5, 2004.

We report direct, real-time electrical detection of single virus particles with high selectivity using nanowire field effect transistors. Measurements made with nanowire arrays modified with antibodies for influenza A showed discrete conductance changes characteristic of binding and unbinding in the presence of influenza A but not paramyxovirus or adenovirus. Moreover, simultaneous electrical and optical measurements using fluorescently-labelled influenza A demonstrate conclusively that the conductance changes correspond to binding/unbinding of single viruses at the surface of nanowire devices. In addition, studies of nanowire devices modified with antibodies specific for either influenza or adenovirus show that multiple viruses can be selectively detected in parallel. The possibility of large scale integration of these nanowire devices suggests potential for simultaneous detection of a large number of distinct viral threats at the single virus level.

The following article is an edited transcript based on the MRS Medalist presentation given by Charles M. Lieber of Harvard University on December 4, 2002, at the Materials Research Society Fall Meeting in Boston. Lieber received the Medal “for controlled synthesis of nanowire and nanotube materials.” This presentation begins with an introduction to the bottom-up paradigm of nanoscience and nanotechnology. The key concepts of this paradigm are explored through studies outlining progress toward meeting the challenge of nanocomputing through the assembly of functional nanowire elements. The richness of the bottom-up paradigm and nanowire building blocks is then illustrated with the development of chemical and biological nanosensors. Finally, the uniqueness of nanowires is exemplified through discussion of the assembly of nanophotonic devices, including the demonstration of multicolor and addressable nanoscale light-emitting diodes, nanowire injection lasers, and assembled arrays of these nanophotonic sources. Challenges and goals for realizing nanotechnologies in the future are discussed in the conclusion.

Scanning tunneling microscopy and spectroscopy have been used to characterize the atomic structure and tunneling density of states of individual single wall carbon nanotubes (SWNT's) and ropes containing many SWNT's. Analysis of atomically resolved SWNT images shows that the nanotubes consist of a wide range of diameters and helicities with no one structure clearly dominant. Tunneling spectroscopy measurements made simultaneously on atomically resolved SWNT's exhibit semiconducting and metallic behavior that depend predictably on helicity and diameter. In addition the band gaps of the semiconducting tubes were also found to depend inversely on diameter. These results are compared to theoretical predictions, and the implications of these studies as well as important future directions are discussed.

A chemical approach to the formation of columnar defects involving the growth and incorporation of MgO nanorods into high temperature superconductors (HTS's) has been developed. MgO nanorods were incorporated into Bi2Sr2CaCu2Oz, Bi2Sr2Ca2Cu3Oz, and Tl2Ba2Ca2Cu3Oz superconductors at areal densities up to 2 × 1010/cm2. Microstructural analyses of the composites demonstrate that the MgO nanorods create a columnar defect structure in the HTS matrices, form a compositionally sharp interface with the matrix, and self-organize into orientations perpendicular and parallel to the copper oxide planes. Measurements of the critical current density demonstrate significant enhancements in the MgO nanorod/HTS composites at elevated temperatures and magnetic fields compared with reference samples.

Chemical force microscopy (CFM) has been used to measure adhesion and friction forces between probe tips and substrates covalently modified with self-assembled monolayers (SAMs) that terminate in distinct functional groups. Probe tips have been modified with SAMs using a procedure that involves coating commercial Si3N4 cantilever/tip assemblies with a thin layer of polycrystalline Au followed by immersion in a solution of a functionalized thiol. This methodology provides a reproducible means for endowing the probe with different chemical functional groups.

A force microscope has been used to characterize the adhesive interactions between probe tips and substrates that have been modified with SAMs which terminate with COOH and CH3 functional groups in ethanol water solvent. Force versus distance curves recorded under ethanol show that the interaction between COOH/COOH > CH3/CH3 > COOH/CH3. The measured adhesive forces were found to agree well with predictions of the Johnson, Kendall, and Roberts (JKR) theory of adhesive contact, and thus show that the observed adhesion forces correlate with the surface free energy

The composition and properties of the sp2-bonded carbon nitride precursor paracyanogen (pCN) has been studied at high pressures and temperatures. Paracyanogen decomposes to carbon and molecular nitrogen with the decomposition temperature increasing with pressure over the range of 3 to 19 GPa. Prior to decomposition, pCN can be transformed to an atmospheric-pressure quenchable phase that is more than 25% higher in density and over an order of magnitude harder than the starting material. Structural analysis of this quenchable phase shows, however, that it consists of a sp2-bonded network. In addition, the decomposition kinetics of paracyanogen have been studied in detail. Rapid, self-propagating decomposition occurs above a threshold temperature. Below this, decomposition rates exhibit an Arrhenius behavior with activation energy and volume of 2.7 eV and 3.9 Å3, respectively The decomposition rates depend on the nitrogen density and decrease significantly with lower nitrogen concentration. Kinetic effects favoring a graphite-like, sp2-bonded structure may preclude the high-pressure synthesis of superhard, sp3-bonded carbon nitride solids below their thermodynamic stability limit, unless an optimally designed precursor is employed.

Scanning tunneling microscopy (STM) is a powerful tool for nanoscale research since it can both create and probe the properties of nanostructures. We have used STM to create T-phase TaSe2 nanocrystals embedded in H-phase TaSe2 through a tip-induced solid-solid phase transition at liquid He temperature. Atomic-resolution images have been used to develop a structural model to understand this solid-solid phase transformation. Furthermore, STM studies of the charge density wave (CDW) state in the T-TaSe2 nanocrystals have been used to address CDW physics in finite dimensions.

Thin films of diamond-like carbon have been grown by pulsed laser deposition using a Nd:YAG laser at 532 nm. Time-of-flight mass spectroscopy was used to investigate the effects of laser power density and background gas pressure on the plume characteristics including the species in the plume and the kinetic energy distribution of each species. We found that with increasing laser power density (1) the relative amount of C+ ions increases, (2) the kinetic energy distributions of C+ get broader and can be deconvoluted into fast and slow components, and (3) the kinetic energy of the fast component of C+ ions increases from several to 40 eV. The resistivity and the local carbon bonding in films grown under these same conditions were also characterized. It was found that there is direct correlation between the characteristics of fast part of C+ ions in the plume and the diamond-like properties of the thin films. Under optimal growth conditions diamond-like carbon films with a large fraction of sp3 bonding can be prepared, although the maximum fraction appears to saturate at 70%. The implications of these results are discussed.

Recent research on the growth and structure of carbide nanorods is reviewed. Carbide nanorods have been prepared by reacting carbon nanotubes with volatile transition metal and main group oxides and halides. Using this approach it has been possible to obtain solid carbide nanorods of TiC, SiC, NbC, Fe3C, and BCx having diameters between 2 and 30 nm and lengths up to 20 µm. Structural studies of single crystal TiC nanorods obtained through reactions of TiO with carbon nanotubes show that the nanorods grow along both [110] and [111] directions, and that the rods can exhibit either smooth or saw-tooth morphologies. Crystalline SiC nanorods have been produced from reactions of carbon nanotubes with SiO and Si-iodine reactants. The preferred growth direction of these nanorods is [111], although at low reaction temperatures rods with [100] growth axes are also observed. The growth mechanisms leading to these novel nanomaterials have also been addressed. Temperature dependent growth studies of TiC nanorods produced using a Ti-iodine reactant have provided definitive proof for a template or topotactic growth mechanism, and furthermore, have yielded new TiC nanotube materials. Investigations of the growth of SiC nanorods show that in some cases a catalytic mechanism may also be operable. Future research directions and applications of these new carbide nanorod materials are discussed.

Recent research on carbon nitride thin films grown using pulsed laser deposition combined with atomic beam techniques is reviewed. the composition, growth mechanism and phases of these films have been systematically investigated. the nitrogen composition was found to increase to a limiting value of 50% as the fluence was decreased for laser ablation at both 532 nm and 248 nm wavelengths. Time of flight mass spectroscopy investigations of the ablation products have shown that the fluence variations affect primarily the yield of the carbon reactant. these experiments demonstrate that the overall film growth rate determines the average nitrogen composition, and furthermore, suggest that a key step in the growth mechanism involves a surface reaction between carbon and nitrogen. INfrared spectroscopy has been used to assess the phases present in the carbon nitride thin films as a function of the overall nitrogen content. these measurements have shown that a cyanogen-like impurity occurs in films with nitrogen compositions greater than 30%. Studies of thermal annealing have shown, however, that this impurity phase can be eliminated to yield a single phase C2N material. IN addition, systematic studies of the electrical resistivity and thermal conductivity of the carbon nitride films are discussed.