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Wednesday, June 30, 2010

Science and engineering on the nanoscale

SI prefixes
PrefixSymbol1000m10nDecimalShort scaleLong scaleSince[1]
yottaY1000810241000000000000000000000000SeptillionQuadrillion1991
zettaZ1000710211000000000000000000000SextillionTrilliard1991
exaE1000610181000000000000000000QuintillionTrillion1975
petaP1000510151000000000000000QuadrillionBilliard1975
teraT1000410121000000000000TrillionBillion1960
gigaG100031091000000000BillionMilliard1960
megaM100021061000000Million1960
kilok100011031000Thousand1795
hectoh100023102100Hundred1795
decada10001310110Ten1795
100001001One
decid10001310−10.1Tenth1795
centic10002310−20.01Hundredth1795
millim1000−110−30.001Thousandth1795
microμ1000−210−60.000001Millionth1960[2]
nanon1000−310−90.000000001BillionthMilliardth1960
picop1000−410−120.000000000001TrillionthBillionth1960
femtof1000−510−150.000000000000001QuadrillionthBilliardth1964
attoa1000−610−180.000000000000000001QuintillionthTrillionth1964
zeptoz1000−710−210.000000000000000000001SextillionthTrilliardth1991
yoctoy1000−810−240.000000000000000000000001SeptillionthQuadrillionth1991
  1. The metric system was introduced in 1795 with six prefixes. The other dates relate to recognition by a resolution of the CGPM.
  2. The 1948 recognition of the micron by the CGPM was abrogated in 1967.

Nanotechnology, shortened to "nanotech", is the study of the controlling of matter on an atomic and molecular scale. Generally nanotechnology deals with structures sized between 1 to 100 nanometer in at least one dimension, and involves developing materials or devices within that size.

Nanotechnology is very diverse, ranging from extensions of conventional device physics to completely new approaches based upon molecular self-assembly, from developing new materials with dimensions on the nanoscale to investigating whether we can directly control matter on the atomic scale.

There has been much debate on the future implications of nanotechnology. Nanotechnology has the potential to create many new materials and devices with a vast range of applications, such as in medicine, electronics, biomaterials and energy production. On the other hand, nanotechnology raises many of the same issues as with any introduction of new technology, including concerns about the toxicity and environmental impact of nanomaterials,[1] and their potential effects on global economics, as well as speculation about various doomsday scenarios. These concerns have led to a debate among advocacy groups and governments on whether special regulation of nanotechnology is warranted.




Origins

Buckminsterfullerene C60, also known as the buckyball, is a representative member of thecarbon structures known asfullerenes. Members of the fullerene family are a major subject of research falling under the nanotechnology umbrella.

The first use of the concepts found in 'nano-technology' (but pre-dating use of that name) was in "There's Plenty of Room at the Bottom," a talk given by physicistRichard Feynman at an American Physical Society meeting at Caltech on December 29, 1959. Feynman described a process by which the ability to manipulate individual atoms and molecules might be developed, using one set of precise tools to build and operate another proportionally smaller set, and so on down to the needed scale. In the course of this, he noted, scaling issues would arise from the changing magnitude of various physical phenomena: gravity would become less important, surface tension and van der Waals attraction would become increasingly more significant, etc. This basic idea appeared plausible, and exponential assembly enhances it with parallelism to produce a useful quantity of end products. The term "nanotechnology" was defined by Tokyo Science University ProfessorNorio Taniguchi in a 1974 paper[2] as follows: "'Nano-technology' mainly consists of the processing of, separation, consolidation, and deformation of materials by one atom or by one molecule." In the 1980s the basic idea of this definition was explored in much more depth by Dr. K. Eric Drexler, who promoted the technological significance of nano-scale phenomena and devices through speeches and the books Engines of Creation: The Coming Era of Nanotechnology (1986) andNanosystems: Molecular Machinery, Manufacturing, and Computation,[3] and so the term acquired its current sense. Engines of Creation: The Coming Era of Nanotechnology is considered the first book on the topic of nanotechnology. Nanotechnology and nanoscience got started in the early 1980s with two major developments; the birth of cluster science and the invention of the scanning tunneling microscope (STM). This development led to the discovery of fullerenes in 1985 and carbon nanotubes a few years later. In another development, the synthesis and properties of semiconductor nanocrystals was studied; this led to a fast increasing number of metal and metal oxide nanoparticles and quantum dots. The atomic force microscope (AFM or SFM) was invented six years after the STM was invented. In 2000, the United States National Nanotechnology Initiative was founded to coordinate Federal nanotechnology research and development and is evaluated by the President's Council of Advisors on Science and Technology.



Fundamental concepts

One nanometer (nm) is one billionth, or 10−9, of a meter. By comparison, typical carbon-carbon bond lengths, or the spacing between these atoms in a molecule, are in the range 0.12–0.15 nm, and aDNA double-helix has a diameter around 2 nm. On the other hand, the smallest cellular life-forms, the bacteria of the genus Mycoplasma, are around 200 nm in length.

To put that scale in another context, the comparative size of a nanometer to a meter is the same as that of a marble to the size of the earth.[4] Or another way of putting it: a nanometer is the amount an average man's beard grows in the time it takes him to raise the razor to his face.[4]

Two main approaches are used in nanotechnology. In the "bottom-up" approach, materials and devices are built from molecular components which assemble themselves chemically by principles ofmolecular recognition. In the "top-down" approach, nano-objects are constructed from larger entities without atomic-level control.[5]

Areas of physics such as nanoelectronics, nanomechanics and nanophotonics have evolved during the last few decades to provide a basic scientific foundation of nanotechnology




Larger to smaller: a materials perspective

Image of reconstruction on a cleanGold(100) surface, as visualized usingscanning tunneling microscopy. The positions of the individual atoms composing the surface are visible.

A number of physical phenomena become pronounced as the size of the system decreases. These include statistical mechanical effects, as well as quantum mechanical effects, for example the “quantum size effect” where the electronic properties of solids are altered with great reductions in particle size. This effect does not come into play by going from macro to micro dimensions. However, quantum effects become dominant when the nanometer size range is reached, typically at distances of 100 nanometers or less, the so called quantum realm. Additionally, a number of physical (mechanical, electrical, optical, etc.) properties change when compared to macroscopic systems. One example is the increase in surface area to volume ratio altering mechanical, thermal and catalytic properties of materials. Diffusion and reactions at nanoscale, nanostructures materials and nanodevices with fast ion transport are generally referred to nanoionics. Mechanical properties of nanosystems are of interest in the nanomechanics research. The catalytic activity of nanomaterials also opens potential risks in their interaction with biomaterials.

Materials reduced to the nanoscale can show different properties compared to what they exhibit on a macroscale, enabling unique applications. For instance, opaque substances become transparent (copper); stable materials turn combustible (aluminum); insoluble materials become soluble (gold). A material such as gold, which is chemically inert at normal scales, can serve as a potent chemical catalyst at nanoscales. Much of the fascination with nanotechnology stems from these quantum and surface phenomena that matter exhibits at the nanoscale.


Simple to complex: a molecular perspective

Modern synthetic chemistry has reached the point where it is possible to prepare small molecules to almost any structure. These methods are used today to manufacture a wide variety of useful chemicals such as pharmaceuticals or commercial polymers. This ability raises the question of extending this kind of control to the next-larger level, seeking methods to assemble these single molecules into supramolecular assemblies consisting of many molecules arranged in a well defined manner.

These approaches utilize the concepts of molecular self-assembly and/or supramolecular chemistry to automatically arrange themselves into some useful conformation through a bottom-up approach. The concept of molecular recognition is especially important: molecules can be designed so that a specific configuration or arrangement is favored due to non-covalent intermolecular forces. The Watson–Crick basepairing rules are a direct result of this, as is the specificity of an enzyme being targeted to a single substrate, or the specific folding of the protein itself. Thus, two or more components can be designed to be complementary and mutually attractive so that they make a more complex and useful whole.

Such bottom-up approaches should be capable of producing devices in parallel and be much cheaper than top-down methods, but could potentially be overwhelmed as the size and complexity of the desired assembly increases. Most useful structures require complex and thermodynamically unlikely arrangements of atoms. Nevertheless, there are many examples of self-assembly based on molecular recognition in biology, most notably Watson–Crick basepairing and enzyme-substrate interactions. The challenge for nanotechnology is whether these principles can be used to engineer new constructs in addition to natural ones.


Molecular nanotechnology: a long-term view

Molecular nanotechnology, sometimes called molecular manufacturing, describes engineered nanosystems (nanoscale machines) operating on the molecular scale. Molecular nanotechnology is especially associated with the molecular assembler, a machine that can produce a desired structure or device atom-by-atom using the principles of mechanosynthesis. Manufacturing in the context ofproductive nanosystems is not related to, and should be clearly distinguished from, the conventional technologies used to manufacture nanomaterials such as carbon nanotubes and nanoparticles.

When the term "nanotechnology" was independently coined and popularized by Eric Drexler (who at the time was unaware of an earlier usage by Norio Taniguchi) it referred to a future manufacturing technology based on molecular machine systems. The premise was that molecular scale biological analogies of traditional machine components demonstrated molecular machines were possible: by the countless examples found in biology, it is known that sophisticated, stochastically optimised biological machines can be produced.

It is hoped that developments in nanotechnology will make possible their construction by some other means, perhaps using biomimetic principles. However, Drexler and other researchers[8] have proposed that advanced nanotechnology, although perhaps initially implemented by biomimetic means, ultimately could be based on mechanical engineering principles, namely, a manufacturing technology based on the mechanical functionality of these components (such as gears, bearings, motors, and structural members) that would enable programmable, positional assembly to atomic specification.[9] The physics and engineering performance of exemplar designs were analyzed in Drexler's book Nanosystems.

In general it is very difficult to assemble devices on the atomic scale, as all one has to position atoms on other atoms of comparable size and stickiness. Another view, put forth by Carlo Montemagno,[10] is that future nanosystems will be hybrids of silicon technology and biological molecular machines. Yet another view, put forward by the late Richard Smalley, is that mechanosynthesis is impossible due to the difficulties in mechanically manipulating individual molecules.

This led to an exchange of letters in the ACS publication Chemical & Engineering News in 2003.[11] Though biology clearly demonstrates that molecular machine systems are possible, non-biological molecular machines are today only in their infancy. Leaders in research on non-biological molecular machines are Dr. Alex Zettl and his colleagues at Lawrence Berkeley Laboratories and UC Berkeley. They have constructed at least three distinct molecular devices whose motion is controlled from the desktop with changing voltage: a nanotube nanomotor, a molecular actuator,[12] and a nanoelectromechanical relaxation oscillator.[13]

An experiment indicating that positional molecular assembly is possible was performed by Ho and Lee at Cornell University in 1999. They used a scanning tunneling microscope to move an individual carbon monoxide molecule (CO) to an individual iron atom (Fe) sitting on a flat silver crystal, and chemically bound the CO to the Fe by applying a voltage.


Current research

Graphical representation of a rotaxane, useful as a molecular switch.

Sarfus image of a DNA biochip elaborated by bottom-up approach.

This device transfers energy from nano-thin layers of quantum wells to nanocrystalsabove them, causing the nanocrystals to emit visible light.[14]


Nanomaterials

This includes subfields which develop or study materials having unique properties arising from their nanoscale dimensions.[15]















Bottom-up approaches

These seek to arrange smaller components into more complex assemblies.


Top-down approaches

These seek to create smaller devices by using larger ones to direct their assembly.

[edit]Functional approaches

These seek to develop components of a desired functionality without regard to how they might be assembled.

[edit]Biomimetic approaches

  • Bionics or biomimicry seeks to apply biological methods and systems found in nature, to the study and design of engineering systems and modern technology. Biomineralization is one example of the systems studied.

[edit]Speculative

These subfields seek to anticipate what inventions nanotechnology might yield, or attempt to propose an agenda along which inquiry might progress. These often take a big-picture view of nanotechnology, with more emphasis on its societal implications than the details of how such inventions could actually be created.

  • Molecular nanotechnology is a proposed approach which involves manipulating single molecules in finely controlled, deterministic ways. This is more theoretical than the other subfields and is beyond current capabilities.
  • Nanorobotics centers on self-sufficient machines of some functionality operating at the nanoscale. There are hopes for applying nanorobots in medicine,[20][21][22] but it may not be easy to do such a thing because of several drawbacks of such devices.[23] Nevertheless, progress on innovative materials and methodologies has been demonstrated with some patents granted about new nanomanufacturing devices for future commercial applications, which also progressively helps in the development towards nanorobots with the use of embedded nanobioelectronics concepts.[24][25]
  • Programmable matter based on artificial atoms seeks to design materials whose properties can be easily, reversibly and externally controlled.
  • Due to the popularity and media exposure of the term nanotechnology, the words picotechnology and femtotechnology have been coined in analogy to it, although these are only used rarely and informally.

[edit]Tools and techniques

Typical AFM setup. A microfabricated cantilever with a sharp tip is deflected by features on a sample surface, much like in a phonograph but on a much smaller scale. Alaser beam reflects off the backside of the cantilever into a set of photodetectors, allowing the deflection to be measured and assembled into an image of the surface.

There are several important modern developments. The atomic force microscope (AFM) and the Scanning Tunneling Microscope (STM) are two early versions of scanning probes that launched nanotechnology. There are other types of scanning probe microscopy, all flowing from the ideas of the scanning confocal microscope developed by Marvin Minsky in 1961 and the scanning acoustic microscope (SAM) developed by Calvin Quate and coworkers in the 1970s, that made it possible to see structures at the nanoscale. The tip of a scanning probe can also be used to manipulate nanostructures (a process called positional assembly). Feature-oriented scanning-positioning methodology suggested by Rostislav Lapshin appears to be a promising way to implement these nanomanipulations in automatic mode. However, this is still a slow process because of low scanning velocity of the microscope. Various techniques of nanolithography such as optical lithography, X-ray lithography dip pen nanolithography, electron beam lithography or nanoimprint lithography were also developed. Lithography is a top-down fabrication technique where a bulk material is reduced in size to nanoscale pattern.

Another group of nanotechnological techniques include those used for fabrication of nanowires, those used in semiconductor fabrication such as deep ultraviolet lithography, electron beam lithography, focused ion beam machining, nanoimprint lithography, atomic layer deposition, and molecular vapor deposition, and further including molecular self-assembly techniques such as those employing di-block copolymers. However, all of these techniques preceded the nanotech era, and are extensions in the development of scientific advancements rather than techniques which were devised with the sole purpose of creating nanotechnology and which were results of nanotechnology research.

The top-down approach anticipates nanodevices that must be built piece by piece in stages, much as manufactured items are made. Scanning probe microscopy is an important technique both for characterization and synthesis of nanomaterials. Atomic force microscopes and scanning tunneling microscopes can be used to look at surfaces and to move atoms around. By designing different tips for these microscopes, they can be used for carving out structures on surfaces and to help guide self-assembling structures. By using, for example, feature-oriented scanning-positioning approach, atoms can be moved around on a surface with scanning probe microscopy techniques. At present, it is expensive and time-consuming for mass production but very suitable for laboratory experimentation.

In contrast, bottom-up techniques build or grow larger structures atom by atom or molecule by molecule. These techniques include chemical synthesis, self-assembly and positional assembly. Dual polarisation interferometry is one tool suitible for characterisation of self assembled thin films. Another variation of the bottom-up approach is molecular beam epitaxy or MBE. Researchers at Bell Telephone Laboratories like John R. Arthur. Alfred Y. Cho, and Art C. Gossard developed and implemented MBE as a research tool in the late 1960s and 1970s. Samples made by MBE were key to the discovery of the fractional quantum Hall effect for which the 1998 Nobel Prize in Physics was awarded. MBE allows scientists to lay down atomically precise layers of atoms and, in the process, build up complex structures. Important for research on semiconductors, MBE is also widely used to make samples and devices for the newly emerging field of spintronics.

However, new therapeutic products, based on responsive nanomaterials, such as the ultradeformable, stress-sensitive Transfersome vesicles, are under development and already approved for human use in some countries.[citation needed]

[edit]Applications

As of August 21, 2008, the Project on Emerging Nanotechnologies estimates that over 800 manufacturer-identified nanotech products are publicly available, with new ones hitting the market at a pace of 3–4 per week.[26] The project lists all of the products in a publicly accessible online.[27] Most applications are limited to the use of "first generation" passive nanomaterials which includes titanium dioxide in sunscreen, cosmetics and some food products; Carbon allotropes used to produce gecko tape; silver in food packaging, clothing, disinfectants and household appliances; zinc oxide in sunscreens and cosmetics, surface coatings, paints and outdoor furniture varnishes; and cerium oxide as a fuel catalyst.[28]

One of the major application of nanotechnology is in the area of nanoelectronics with MOSFET's being made of small nanowires ~10 nm in length. Here is a simulation of such a nanowire

The National Science Foundation (a major distributor for nanotechnology research in the United States) funded researcher David Berube to study the field of nanotechnology. His findings are published in the monograph Nano-Hype: The Truth Behind the Nanotechnology Buzz.[29] This study concludes that much of what is sold as “nanotechnology” is in fact a recasting of straightforward materials science, which is leading to a “nanotech industry built solely on selling nanotubes, nanowires, and the like” which will “end up with a few suppliers selling low margin products in huge volumes." Further applications which require actual manipulation or arrangement of nanoscale components await further research. Though technologies branded with the term 'nano' are sometimes little related to and fall far short of the most ambitious and transformative technological goals of the sort in molecular manufacturing proposals, the term still connotes such ideas. According to Berube, there may be a danger that a "nano bubble" will form, or is forming already, from the use of the term by scientists and entrepreneurs to garner funding, regardless of interest in the transformative possibilities of more ambitious and far-sighted work.[30]

[edit]Implications

Because of the far-ranging claims that have been made about potential applications of nanotechnology, a number of serious concerns have been raised about what effects these will have on our society if realized, and what action if any is appropriate to mitigate these risks.

There are possible dangers that arise with the development of nanotechnology. The Center for Responsible Nanotechnology suggests that new developments could result, among other things, in untraceable weapons of mass destruction, networked cameras for use by the government, and weapons developments fast enough to destabilize arms races ("Nanotechnology Basics").

One area of concern is the effect that industrial-scale manufacturing and use of nanomaterials would have on human health and the environment, as suggested by nanotoxicology research. Groups such as the Center for Responsible Nanotechnology have advocated that nanotechnology should be specially regulated by governments for these reasons. Others counter that overregulation would stifle scientific research and the development of innovations which could greatly benefit mankind.

Other experts, including director of the Woodrow Wilson Center's Project on Emerging Nanotechnologies David Rejeski, have testified[31] that successful commercialization depends on adequate oversight, risk research strategy, and public engagement. Berkeley, California is currently the only city in the United States to regulate nanotechnology;[32] Cambridge, Massachusetts in 2008 considered enacting a similar law,[33] but ultimately rejected this.[34]

[edit]Health and environmental concerns

Some of the recently developed nanoparticle products may have unintended consequences. Researchers have discovered that silver nanoparticles used in socks only to reduce foot odor are being released in the wash with possible negative consequences.[35] Silver nanoparticles, which are bacteriostatic, may then destroy beneficial bacteria which are important for breaking down organic matter in waste treatment plants or farms.[36]

A study at the University of Rochester found that when rats breathed in nanoparticles, the particles settled in the brain and lungs, which led to significant increases in biomarkers for inflammation and stress response.[37] A study in China indicated that nanoparticles induce skin aging through oxidative stress in hairless mice.[38][39]

A two-year study at UCLA's School of Public Health found lab mice consuming nano-titanium dioxide showed DNA and chromosome damage to a degree "linked to all the big killers of man, namely cancer, heart disease, neurological disease and aging".[40]

A major study published more recently in Nature Nanotechnology suggests some forms of carbon nanotubes – a poster child for the “nanotechnology revolution” – could be as harmful as asbestos if inhaled in sufficient quantities. Anthony Seaton of the Institute of Occupational Medicine in Edinburgh, Scotland, who contributed to the article on carbon nanotubes said "We know that some of them probably have the potential to cause mesothelioma. So those sorts of materials need to be handled very carefully.".[41] In the absence of specific nano-regulation forthcoming from governments, Paull and Lyons (2008) have called for an exclusion of engineered nanoparticles from organic food.[42] A newspaper article reports that workers in a paint factory developed serious lung disease and nanoparticles were found in their lungs.[43]

[edit]Regulation

Calls for tighter regulation of nanotechnology have occurred alongside a growing debate related to the human health and safety risks associated with nanotechnology. Furthermore, there is significant debate about who is responsible for the regulation of nanotechnology. While some non-nanotechnology specific regulatory agencies currently cover some products and processes (to varying degrees) – by “bolting on” nanotechnology to existing regulations – there are clear gaps in these regimes.[44] In "Nanotechnology Oversight: An Agenda for the Next Administration,"[45] former EPA deputy administrator J. Clarence (Terry) Davies lays out a clear regulatory roadmap for the next presidential administration and describes the immediate and longer term steps necessary to deal with the current shortcomings of nanotechnology oversight.

Stakeholders concerned by the lack of a regulatory framework to assess and control risks associated with the release of nanoparticles and nanotubes have drawn parallels with bovine spongiform encephalopathy (‘mad cow’s disease), thalidomide, genetically modified food,[46] nuclear energy, reproductive technologies, biotechnology, and asbestosis. Dr. Andrew Maynard, chief science advisor to the Woodrow Wilson Center’s Project on Emerging Nanotechnologies, concludes (among others) that there is insufficient funding for human health and safety research, and as a result there is currently limited understanding of the human health and safety risks associated with nanotechnology.[47] As a result, some academics have called for stricter application of the precautionary principle, with delayed marketing approval, enhanced labelling and additional safety data development requirements in relation to certain forms of nanotechnology.[48]

The Royal Society report[49] identified a risk of nanoparticles or nanotubes being released during disposal, destruction and recycling, and recommended that “manufacturers of products that fall under extended producer responsibility regimes such as end-of-life regulations publish procedures outlining how these materials will be managed to minimize possible human and environmental exposure” (p.xiii). Reflecting the challenges for ensuring responsible life cycle regulation, the Institute for Food and Agricultural Standards has proposed standards for nanotechnology research and development should be integrated across consumer, worker and environmental standards. They also propose that NGOs and other citizen groups play a meaningful role in the development of these standards.

In October 2008, the Department of Toxic Substances Control (DTSC), within the California Environmental Protection Agency, announced its intent to request information regarding analytical test methods, fate and transport in the environment, and other relevant information from manufacturers of carbon nanotubes.[50] The purpose of this information request will be to identify information gaps and to develop information about carbon nanotubes, an important emerging nanomaterial

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