Selected Topics in Nanoscience and Nanotechnology

The following sections are included:

• Preface

• CONTENTS

Nanotechnology is vital to the fabrication of integrated circuits, memory devices, display units, biochips and biosensors. Scanning probe microscope (SPM) has emerged to be a unique tool for materials structuring and patterning with atomic and molecular resolution. SPM includes scanning tunneling microscopy (STM) and atomic force microscopy (AFM). In this chapter, we selectively discuss the atomic and molecular manipulation capabilities of STM nanolithography. As for AFM nanolithography, we focus on those nanopatterning techniques involving water and/or air when operated in ambient. The typical methods, mechanisms and applications of selected SPM nanolithographic techniques in nanoscale structuring and fabrication are reviewed.

Nanoscale characterization is a key field in nanoscience and technology as it provides fundamental understanding of the properties and functionalities of materials down to the atomic and molecular scale. In this article, we review the development and application of scanning tunneling microscope (STM) techniques in nanoscale characterization. We will discuss the working principle, experimental setup, operational modes, and tip preparation methods of scanning tunneling microscope. Selected examples are provided to illustrate the application of STM in the nanocharacterization of semiconductors. In addition, new developments in STM techniques including spin-polarized STM (SP-STM) and multiprobe STM (MP-STM) are discussed in comparison with conventional non-magnetic and single tip STM methods.

EUV lithography is the exposure technology in which even 15 nm node which is the limit of Si device can be achieved. Unlike the conventional optical lithography, this technology serves as a reflection type optical system, and a multilayer coated mirror is used. Development of manufacturing equipment is accelerated to aim at the utilization starting from 2011. The critical issues of development are the EUV light source which has the power over 115 W and resist with high sensitivity and low line edge roughness (LER).

X-ray lithography with synchrotron radiation is an important nanolithographic tool which has unique advantages in the production of high aspect ratio nanostructures. The optimum synchrotron radiation spectrum for nanometer scale X-ray lithography is normally in the range of 500 eV to 2 keV. In this paper, we present the main methods, equipment, process parameters and preliminary results of nanofabrication by proximity X-ray lithography within the nanomanufacturing program pursued by Singapore Synchrotron Light Source (SSLS). Nanostructures with feature sizes down to 200 nm and an aspect ratio up to 10 have been successfully achieved by this approach.

In this paper, a summary of some of the recent research efforts in our laboratory on chemical interactions at noble metal nanoparticle surfaces is presented. The article is divided into five sections, detailing with (i) interactions of simple halocarbons with gold and silver nanoparticle surfaces at room temperature by a new chemistry and the exploitation of this chemistry in the extraction of pesticides from drinking water, (ii) interaction of biologically important proteins such as Cyt c, hemoglobin and myoglobin as well as a model system, hemin with gold and silver nanoparticles and nanorods forming nano–bio conjugates and their surface binding chemistry, (iii) formation of polymer–nano composites with tunable optical properties and temperature sensing characteristics by single and multi-step methodologies, (iv) nanomaterials-based flow sensors and (v) composites of noble metal nanoparticles and metallic carbon nanotubes showing visible fluorescence induced by metal–semiconductor transition.

Diamond-like carbon (DLC) is a form of amorphous carbon which has high fraction of sp³ hybridization. Due to its nature of sp³ bonding, diamond-like carbon has been shown to have excellent properties similar to that of diamond. This includes high hardness, excellent wear-resistance, large modulus and chemically inert. Traditional applications include wear resistant coatings and protective film. This article intends to review the synthesis and material properties of diamond-like carbon as well as its potential as a novel material for applications in nano-architecture and nano-mechanical devices. An introduction into metal-dopants in diamond-like carbon film will be briefly mentioned as well as techniques on the design and fabrication of this material.

As an efficient and cost-effective method to synthesize nanomaterials, the hotplate technique has been reviewed in this article. Systematic studies have been carried out on the characterizations of the materials synthesized. In addition to the direct preparation of nanomaterials on metals, this method has been extended to the substrate-friendly and plasma-assisted hotplate synthesis. Apart from chemically pure nanostructures, a few nanohybrids were synthesized, further demonstrating the flexibility of this technique. The investigations on their applications indicate that they are promising material systems with potential applications in field emission devices, gas sensors, Li-ion batteries and ultrafast optical devices.

The crystal structures and electronic and magnetic properties of conducting molecular magnets developed by our group are reviewed from the viewpoints of our two current strategies for increasing the efficiency of the π–d interaction. (EDTDM)₂FeBr₄ is composed of quasi-one-dimensional donor sheets sandwiched between magnetic anion sheets. The ground state of the donor layer changes from the insulator state to the metallic state by the application of pressure. When it is near to the insulator-metal phase boundary pressure, the magnetic order of the anion spins considerably affects the transport properties of the donor layer. The crystal structure of (EDO–TTFBr₂)₂FeX₄ (X = Cl, Br) is characterized by strong intermolecular halogen-halogen contacts between the organic donor and FeX₄ anion molecules. The presence of the magnetic order of the Fe³⁺ spins and relatively high magnetic order transition temperature proves the role of the halogen-halogen contacts as exchange interaction paths.

The porphyrin macrocycle is one of the most frequently investigated functional molecular entities and can be incorporated into advanced functional nanomaterials upon formation of organized nanostructures. Thus, study of the science and technology of porphyrin assemblies has attracted many organic, biological and supramolecular chemists. A wide variety of nanostructures can be obtained by supramolecular self-assembly because the porphyrin moiety is amenable to chemical modifications through thoughtful synthetic design and moderate preparative effort. Some recent developments in porphyrin assembly, obtained through various supramolecular approaches, are briefly summarized. Topics described in this review are classified into four categories: (i) non-specific assemblies; (ii) specific assemblies; (iii) assemblies in organized films; (iv) molecular-level arrangement. We present examples in the order of structural precision of assemblies.

The present article reviews the self-assembly of oligopeptides to form nanostructures, both in solution and in solid state. The solution structures of the peptides were examined using circular dichroism and dynamic light scattering. The solid state assembly was examined by adsorbing the peptides onto a mica surface and analyzing it using atomic force microscopy. The role of pH and salt concentration on the peptide self-assembly was also examined. Nanostructures within a size range of 3–10 nm were obtained under different conditions.

Tissues, cells and biomolecules can experience changes in their structural and mechanical properties during the occurrence of certain diseases. Recent advances in the fields of nanotechnology, biomechanics and cell and molecular biology have led to the development of state-of-the-art and novel biophysical and nanotechnological tools to probe the mechanical properties of individual living cells and biomolecules. Here we will review the basic principles and application of some of these nanotechnological tools used to relate changes in the elastic and viscoelastic properties of cells to alterations in the cellular and molecular structures induced by diseases such as malaria and cancer. Knowing the ways and the extent to which mechanical properties of living cells are altered with the onset of disease progression will be crucial for us to gain vital insights into the pathogenesis and pathophysiology of malaria and cancer, and potentially offers the opportunity to develop new and better methods of detection, diagnosis and treatment.

Nanomedicine is to apply and further develop nanotechnology to solve problems in medicine, i.e. to diagnose, treat and prevent diseases at the cellular and molecular level. This article demonstrates through a full spectrum of proof-of-concept research, from nanoparticle preparation and characterization, in vitro drug release and cytotoxicity, to in vivo pharmacokinetics and xenograft model, how nanoparticles of biodegradable polymers could provide an ideal solution for the problems encountered in the current regimen of chemotherapy. A system of vitamin E TPGS coated poly(lactic-co-glycolic acid) (PLGA) nanoparticles is used as an example for paclitaxel formulation as a model drug. In vitro HT-29 cancer cell viability experiment demonstrated that the paclitaxel formulated in the nanoparticles could be 5.64 times more effective than Taxol^® after 24 hr of treatment. In vivo pharmacokinetics showed that the drug formulated in the nanoparticles could achieve 3.9 times higher therapeutic effects judged by area-under-the curve (AUC). One shot can realize sustainable chemotherapy of 168 hr compared with 22 hr for Taxol^® at a single 10mg/kg dose. Xenograft tumor model further confirmed the advantages of the nanoparticle formulation versus Taxol^®.