JOURNAL OF

Materials

Feature Article

Science and technology of nanomaterials: current status and future prospects
C. N. R. Rao*a,b and A. K. Cheethama Materials Research Laboratory, University of California, Santa Barbara, CA 93106, USA. E-mail: cnrrao@jncasr.ac.in b Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur, Bangalore, 560 064, India Received 8th June 2001, Accepted 7th August 2001 First published as an Advance Article on the web 10th October 2001
a

CHEMISTRY

The science and technology of nanomaterials has created great excitement and expectations in the last few years. By its very nature, the subject is of immense academic interest, having to do with very tiny objects in the nanometer regime. There has already been much progress in the synthesis, assembly and fabrication of nanomaterials, and, equally importantly, in the potential applications of these materials in a wide variety of technologies. The next decade is likely to witness major strides in the preparation, characterization and exploitation of nanoparticles, nanotubes and other nanounits, and their assemblies. In addition, there will be progress in the discovery and commercialization of nanotechnologies and devices. These new technologies are bound to have an impact on the chemical, energy, electronics and space industries. They will also have applications in medicine and health care, drug and gene delivery being important areas. This article examines the important facets of nanomaterials research, highlighting the current trends and future directions. Since synthesis, structure, properties and simulation are important ingredients of nanoscience, materials chemists have a major role to play.

Introduction
Nanotechnology is the term used to describe the creation and exploitation of materials with structural features in between those of atoms and bulk materials, with at least one dimension
Table 1 Typical nanomaterials Size (approx.) (a) Nanocrystals and clusters (quantum dots) Other nanoparticles (b) Nanowires Nanotubes (c) 2-Dimensional arrays (of nano particles) Surfaces and thin films (d) 3-Dimensional structures (superlattices)

in the nanometer range (1 nm ~ 1029 m). Table 1 lists typical nanomaterials of different dimensionalities. The properties of materials with nanometric dimensions are significantly different from those of atoms or bulk materials. Suitable control of the properties of nanometer-scale structures can lead to new science as well as new products, devices and technologies. The underlying theme of nanotechnology is miniaturization, the importance of which was pointed out by Feynman1 as early as 1959 in his often-cited lecture entitled ‘‘There is plenty of room at the bottom’’. The challenge is to beat Moore’s law2 and accommodate 1000 CDs in a wristwatch.3 There has been explosive growth of nanoscience and technology in the last decade, primarily because of the availability of new methods of synthesizing nanomaterials, as well as tools for characterization and manipulation (Table 2). Several innovative methods for the synthesis of nanoparticles and nanotubes, and their assemblies, are now available. There is a better understanding of the size-dependent electrical, optical and magnetic properties of individual nanostructures of semiconductors, metals and other materials. Besides the established techniques of electron microscopy, crystallography and spectroscopy, scanning probe microscopies have provided powerful tools for the study of nanostructures. Novel methods of fabricating patterned nanostructures, as well as new device and fabrication concepts, are constantly being discovered. Nanostructures have also been ideal for computer simulation and modelling, their size being sufficiently small to accommodate considerable rigour in treatment. In computations on ˚ nanomaterials,4 one deals with a spatial scaling from 1 A to

Materials Metals, semiconductors, magnetic materials Ceramic oxides Metals, semiconductors, oxides, sulfides, nitrides Carbon, layered metal chalcogenides Metals, semiconductors, magnetic materials Various materials Metals, semiconductors, magnetic materials

diameter 1–10 nm diameter 1–100 nm diameter 1–100 nm diameter 1–100 nm several nm2–mm2 thickness 1–1000 nm Several nm in all three dimensions

Table 2 Different methods of synthesis and investigation of nanomaterials Scale (approx.) 0.1–10 nm Synthetic methods Covalent synthesis Structural tools Vibrational spectroscopy NMR Diffraction methods Scanning probe microscopies (SPM) SEM, TEM, SPM SEM, TEM Theory and simulation Electronic structure

v1–100 nm 100 nm–1 mm

Self-assembly techniques Processing, modifications

Molecular dynamics and mechanics Coarse-grained models, hopping etc.

DOI: 10.1039/b105058n

J. Mater. Chem., 2001, 11, 2887–2894 This journal is # The Royal Society of Chemistry 2001

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Fig. and their potential applications. Nature. Fig. Quantum computing6 has made a good start and appropriate quantum algorithms have been developed. There are many examples which demonstrate the current achievements and paradigm shifts in this area. to explore and establish nanodevice concepts and systems architecture.7–10 Nearly monodisperse nanocrystals of materials with narrow size distributions have been prepared by several workers. Mater. Manna. Wickham. MoS2. organic and biological systems. thereby affording new heterostructures and metastable phases. size-dependent Coulomb blockade and the associated scaling laws. Copyright Nature 2000. W. 4 shows an electron microscopy image of aligned multiwalled nanotubes. the nonmetallic gap in metal nanocrystals. organize and tailor-make materials at the nanoscale is. 5). Yang. Ber. we will present the important highlights in the field of nanomaterials related to their synthesis and assembly. (b) low-resolution images of quantum rods of different aspect ratios. in nanoelectronics and computer technology.. 2 Size-dependence of the wavelength of the absorption threshold in semiconductors. 2000.3 nm radius being familiar ones. The availability of such nanocrystals has enabled better studies of sizedependent properties such as size-controlled light emission properties of semiconductor nanocrystals. of very recent origin.14 Fig. Assembling the nanostructures into ordered arrays is often necessary to render them functional and operational. including biologically-inspired systems. These wide-ranging applications may indeed usher in a new direction in manufacturing and in the electronics. 903. shape and structure. 1. semiconductors and magnetic materials by employing colloid chemical methods. as well as in medicine and health care. unlike ordinary nanotubes which can be metallic or insulating. Alivisatos. Bunsen-Ges. space. In addition. It is by a combination of novel nanobuilding units and strategies for assembling them that nanostructured materials and devices with new capabilities can be generated. Especially noteworthy is the recent synthesis of Y-junction carbon nanotubes (Fig.g. with control of the shape in some instances. Size-dependent 2888 J. (Reproduced by permission from ref. and to improve known investigative methods while discovering better tools for the characterization of nanostructures. (c) 3-dimensional orientation. to connect nanoscience to molecular electronics and biology. Chem. 404. 10. P. 1 TEM images of CdSe quantum rods: (a). 2 and 3 illustrate some typical size-dependent properties of materials. Peng. Phys. In the last decade. J. Nanotubes of other inorganic materials. (Reproduced by permission from A. Copyright VCH 1995. Fig. E. it is now possible to carry out atomic layer-by-layer deposition of films. 2001. For example. the limit of accuracy going beyond 1 kcal mol21. 11. 59. A. 1995. Scher.13 much has been achieved in the synthesis of multiwalled and single-walled nanotubes and bundles of aligned nanotubes. X. Nanostructured polymers formed by the ordered self-assembly of triblock copolymers and nanostructured high-strength materials (e. 2887–2894 properties have been exploited for biological tagging. all with control of size. Not everything in nanoscience is new. however. representative references to help describe the present status of the subject. Chem. many existing technologies employ nanoscale processes. transmission electron microscopy (TEM) images of CdSe nanorods are shown in Fig.) Synthesis and assembly The synthesis of nanomaterials spans inorganic. Ordered arrays or superlattices of nanocrystals of metals and semiconductors have been prepared by several workers. STM images of quantum dots (e. which can act as vital components in nanoelectronics15 since. there has also been considerable progress in the preparation of nanocrystals of metals. catalysis and photography being well-known examples..11 There is a qualitative change in some facets of synthesis.1 mm and temporal scaling from 1 fs to 1 s. Henglein. Carbon nanotubes have been doped with nitrogen and boron. nanoparticles (powders) of ceramic materials have been produced on a large scale by employing both physical and chemical methods.) . 99.4. and have cited key. We have endeavoured to make the article concise and illustrative rather than encyclopedic.g. Prototype circuits involving nanoparticles and nanotubes for nanoelectronic devices have been fabricated. In this article. Kadavanich and A. Cu/Cr nanolayers) are other examples... L. chemical and energy industries.g.5 Some of the potential applications of nanotechnology which will have the greatest societal and economic impact are in the production of novel materials and devices. experimental tools for their investigation. To illustrate this aspect. Our capability to synthesize. a germanium pyramid on a silicon surface) and of the quantum corral of 48 Fe atoms placed in a circle of 7. modelling and simulation. the preparation of thin films being one such. kinks or bends will act as metal– insulator junctions. The immediate goals of the science and technology of nanomaterials must be to fully master the synthesis of isolated nanostructures (building blocks) and their ensembles and assemblies with the desired properties. for example using semiconductor nanocrystals as fluorescent biological labels.12 Since the discovery of carbon nanotubes. in particular those of layered metal chalcogenides (e. to generate new classes of high-performance materials.

A variety of inorganic. of semiconductors) provides the means to introduce functionality into the substrate that is coupled to that on the surface. and nanomanipulators are being used with scanning and transmission electron microscopes. There has been a constant quest for crystalline solids with giant pores and several have been synthesized recently. U. the engineering of new polymeric structures by using dendrimers and block copolymers deserves special mention19 (see Fig.29 Equally interesting are the macroporous solids (pore diameters 100–1000 nm) prepared by templating crystalline arrays of silica or polymer spheres. scanning tunnelling spectroscopy provides important information on electronic structure and properties.28 Mesoporous fibers and spheres of silica and other materials have also been prepared. 2887–2894 2889 WS2. 9) have been formed by self-assembly. for example). Copyright Elsevier 1998. Phys.21 Fig. N. Experimental tools As mentioned earlier. combined with high-resolution electron microscopy. 7 shows a TEM image of Pd nanocrystals containing 1415 atoms. Vinod. Thus.32 Newer versions of nanomanipulators will have to be developed by using technologies such as nanoelectromechanical systems (NEMS). sulfides and other materials have been prepared by various methods.and three-dimensional arrays of nanocrystals of semiconductors.) is noteworthy that self-assembly of objects of varying sizes (nm to mm) occurs through weak interactions. Kulkarni and C. has enabled direct images of structures to be obtained and aided the study of properties. G. Similarly. 2000. By varying the spacer length (or crystal size). U. Preparation of nanoparticles of therapeutic drugs would directly help in drug targeting.24 Single crystals of single-walled carbon nanotubes (Fig.. G. 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