This is an agenda-setting and high-profile book that presents an authoritative and cutting-edge analysis of nanoscience and technology. The Oxford Handbook of Nanoscience and Technology provides a comprehensive and accessible overview of the major achievements in different aspects of this field. The Handbook comprises 3 volumes, structured thematically, with 25 chapters each. Volume I presents fundamental issues of basic physics, chemistry, biochemistry, tribology etc. of nanomaterials. Volume II focuses on the progress made with host of nanomaterials including DNA and protein based nanostructures. Volume III highlights engineering and related developments, with a focus on frontal application areas. All chapters are written by noted international experts in the field. The book should be useful for final year undergraduates specializing in the field. It should prove indispensable to graduate students, and serious researchers from academic and industrial sectors working in the field of Nanoscience and Technology from different disciplines including Physics, Chemistry, Biochemistry, Biotechnology, Medicine, Materials Science, Metallurgy, Ceramics, Information Technology as well as Electrical, Electronic and Computational Engineering.

In organic-based electronics, interfacial properties have a profound impact on device performance. The lineup of energy levels is usually dependent on interface dipoles, which may arise from charge transfer reactions. In many applications, metal-organic junctions are prepared under ambient conditions, where direct overlap of the organic system from the metal bands is prevented due to presence of oxides and/or hydrocarbons. We present direct experimental and theoretical evidence showing that the interface energetic for such systems is governed by exchange of an integer amount of electrons.

DFT calculations on tetrakis(dimethylamino)ethylene (TDAE) interacting with a gold surface have been performed. A monolayer of TDAE deposited on a gold surface creates an interface dipole, which decreases the barrier for electron injection from a gold contact into an (organic) electroactive material. This was studied by simulating the complex in two different ways, using a slab model and using a gold cluster surface. These approaches are shown to be complementary: the cluster results apply to the situation of isolated molecules and the slab results describe the case of interacting TDAE molecules on the gold surface. We found that there is a transfer of around one electronic charge per TDAE to the gold in the limit of non-interacting TDAE molecules. This charge transfer results in the formation of an interface dipole and a corresponding lowering of the work function of the surface. The lowering of the work function increases with increasing coverage and is as large as 2.4 eV for a monolayer of TDAE on gold. Due to depolarization effects, the charge transfer in this state is reduced to 0.56 times the electronic charge.

Localization lengths of the electronic states in a disordered two-dimensional system, resembling highly anisotropic molecular crystals such as pentacene, have been calculated numerically using the transfer matrix method. The disorder is based on a model with small random fluctuations of induced molecular dipole moments which give rise to long-range correlated disorder in the on-site energies as well as a coupling between the on-site energies and the intermolecular interactions. Our calculations show that molecular crystals such as pentacene can exhibit states with very long localization lengths with a possibility to reach a truly metallic state. © 2006 The American Physical Society.

This thesis deals with theoretical studies of the electronic structure of molecules used in the context of molecular electronics. Both studies with model Hamiltonians and first principle calculations have been performed. The materials studied include molecular crystals of pentacene and DNA, which are used as active material in field-effect transistors and as tentative molecular wires, respectively. The molecular magnet compound TCNE and surface modification by means of chemisorption of TDAE on gold are also studied.

Molecular crystals of pentacene are reported to have the highest field-effect mobility values for organic thin film field-effect transistors. The conduction process in field-effect transistors applications occurs in a single layer of the molecular crystal. Hence, in studies of transport properties molecular crystals of pentacene can be considered as a two dimensional system. An open question of these system is if the charge transport is bandlike or if as a result of disorder is a hopping process. We address this question in two of the included papers, paper I and paper II.

The conducting properties of DNA are of interest for a broad scientific community. Biologist for understanding of oxidatively damaged DNA and physicist and the electronics community for use as a molecular wire. Some reports on the subject classifies DNA as a conductor while other report insulating behavior. The outcome of the investigations are heavily dependent on the type of DNA being studied, clearly there is a big difference between the natural and more or less random sequence in, e.g., λ-DNA and the highly ordered syntethic poly(G)-poly(C) DNA. It has been suggested that long-range correlation would yield delocalized states, i.e., bandlike transport, in natural DNA, especially in the human chromosome 22. In paper III we show that this is not the case. In general our results show that DNA containing an approximately equal amount of the four basis is an insulator in a static picture.

An emerging research field is spintronics. In spintronic devices the spin of the charge carrier is as important as the charge. One can envision a device where spin alone is the carrier of information. In realizing spintronic devices, materials that are both magnetic and semiconducting are needed. Systems that exhibit both these properties are organic-based magnets. In paper IV the electronic structure of the molecular magnet compound TCNE is studied, both experimentally and theoretically.

The injection of carriers from metal contacts to organic semiconductors is central to the performance of organic based devices. The interface between the metal contact and the organic material has been pointed out to be one of the device parameters that most significantly influences the device performance. This relates to the process of injection of charge carriers in to the organic material. In some contact and organic material combinations the energy barrier for charge injection can be very high. The barrier can be reduced by modify the interface dipole, this is achieved by a monolayer of adsorbed molecules at the interface. The molecule TDAE chemisorbed on gold is studied in paper V.

The electronic structure of tetracyanoethylene (TCNE) has been studied both in its pristine state and upon stepwise rubidium intercalation, by UV and x-ray photoelectron spectroscopy as well as with theoretical calculations. The intercalated system may serve as a model for TCNE-based organometallic magnets, of which the electronic structure remains largely unknown. Rubidium is found to n-dope the TCNE molecules forming Rb⁺TCNE^- with almost complete charge transfer. Calculations show a spin splitting of the former highest occupied molecular orbital level upon Rb doping. We see no evidence for the formation of doubly charged TCNE molecules. A gap opens up at the Fermi energy for Rb⁺TCNE^- due to on-site Coulomb interactions. We estimate the on-site Coulomb interaction of amorphous TCNE doped with Rb to be ∼2 eV.

In the context of molecular based electronics, different molecular systems have been studied. In molecular crystals of pentacene, the conduction process has been reported to occur in a single layer in field-effect transistor applications. The electron localization length and its sensitivity to disorder of such two-dimensional disordered systems have been calculated. The electron localization in DNA has also been investigated. Our results show that DNA containing an approximately equal amount of the four basis is insulating. For instance, the human chromosome 22 is an insulator even though it has long-range correlation, which elsewhere has been suggested to give delocalized states.

The on-site Coulomb interaction has been calculated for rubidium-doped tetracyanoethylene (TCNE). If the electronic state is localized to a small region, e.g., a single molecule, the on-site Coulomb interaction becomes important. The interaction is a measure of the work needed to add an extra electron to the system. When the electronic state is localized to a single molecule/site it becomes large. The result has been used to interpret the outcome of ultraviolet photoelectron spectroscopy (UPS) measurements.

Using the transfer matrix method we have calculated the localization length in a 2D (two dimension) rectangular lattice with both on-site and off-diagonal disorder. Using finite size scaling we show that systems with off-diagonal disorder are much more sensitive to disorder than the system with on-site disorder, e.g. at the same amount of disorder (W=w=2) the localization length for on-site disorder is 10⁴ times longer than for off-diagonal disorder. We consider both isotropic and anisotropic systems, where the latter can be considered as a model for an organic crystal. In the anisotropic case the maximum localization length is at the band center, the isotropic system has a maximum away from the band center.

Electron localization lengths in different DNA sequences have been calculated numerically using the transfer matrix method. It is shown that electronic states associated with guanine can reach fairly long localization lengths in disordered guanine-cytosine double strands if both intra- and interstrand π−π interactions are considered. For DNA sequences containing all four bases, the electronic states become localized to very few base pairs. In particular, the human chromosome 22 and λ-DNA, both with approximately equal concentrations of the four bases, show insulating behavior.