Molecular electronics
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{{Nanoelec}}
:''For [[Quantum mechanics|quantum mechanical]] study of the [[electron]] distribution in a molecule, see [[stereoelectronics]].''
'''Molecular electronics''' (sometimes called ''moletronics'') is an interdisciplinary theme that spans physics, chemistry, and materials science. The unifying feature of this area is the use of molecular building blocks for the fabrication of electronic components, both passive (e.g. resistive wires) and active (e.g. transistors). The concept of molecular electronics has aroused much excitement both in science fiction and among scientists due to the prospect of size reduction in electronics offered by molecular-level control of properties. Molecular electronics provides a means to extend [[Moore's Law]] beyond the foreseen limits of small-scale conventional silicon [[integrated circuits]].
Due to the broad use of the term, molecular electronics can be split into two related but separate subdisciplines: ''molecular materials for electronics'' utilizes the properties of the molecules to affect the bulk properties of a material, while ''molecular scale electronics'' focuses on single-molecule applications.<ref>{{cite book |last=Petty |first=M.C. |coauthors=Bryce, M.R. & Bloor, D. |title=Introduction to Molecular Electronics |publisher=Oxford University Press |date=1995 |location=New York |pages=1-25 |isbn=0195211561}}</ref><ref>{{cite journal |last=Tour |first=James M. |authorlink=James Tour |coauthors=''et al.'' |title=Recent advances in molecular scale electronics |journal=Annals of the [[New York Academy of Sciences]] |volume=852 |pages=197–204 |date=1998 |doi=10.1111/j.1749-6632.1998.tb09873.x}}</ref>
==Concept genesis and theory==
Study of charge transfer in molecules was advanced in the 1940s by [[Robert Mulliken]] and [[Albert Szent-Györgyi|Albert Szent-Gyorgi]] in discussion of so-called "donor-acceptor" systems and developed the study of charge transfer and energy transfer in molecules.
Likewise, a 1974 paper from [[Mark Ratner]] and Ari Aviram <sup>1</sup> illustrated a theoretical molecular [[rectifier]]. Later, in 1988, Aviram described in detail a theoretical single-molecule [[field-effect transistor]] . Further concepts were proposed by Forrest Carter of the [[Naval Research Laboratory]], including single-molecule [[logic gate]]s.
Unfortunately, the ''direct'' measurement of the electronic characteristics of individual molecules awaited the development of methods for making molecular-scale electrical contacts. This was no easy task. Thus, the first experiment measuring the conductance of a single molecule was only reported in 1997 by Mark Reed and co-workers. Since then, this branch of the field has progressed rapidly. Likewise, as it has become possible to measure such properties directly, the theoretical predictions of the early workers have been mostly confirmed.
[[Image:Gadget128.JPG|frame|right|Voltage-controlled switch, a molecular electronic device from 1974.]]
However, while mostly operating in the [[quantum realm]] of less than 100 nanometers, "molecular" electronic processes often collectively manifest on a macro scale. Examples include [[quantum tunneling]], [[negative resistance]], [[phonon]]-assisted hopping, [[polaron]]s, and the like. Thus, macro-scale active devices were described decades before molecular-scale ones. E.g., in 1974, [[John McGinness]] and his coworkers described [http://www.drproctor.com/os/amorphous.htm] the putative "first experimental demonstration of an operating molecular electronic device"[http://www.annalsonline.org/cgi/content/abstract/1006/1/1]. This was a voltage-controlled switch. As its active element, this device used DOPA [[melanin]], an oxidized mixed polymer of [[polyacetylene]], [[polypyrrole]], and [[polyaniline]]. The "ON" state of this switch exhibited almost metallic conductivity.
Since the 1970's, scientists have developed an entire panoply of new materials and devices. These findings have opened the door to plastic electronics and optoelectronics, which are beginning to find commercial application.
===Charge transfer complexes===
The first highly-conductive organic compounds were the [[Charge transfer complexes]]. In 1954, researchers at Bell Labs and elsewhere reported [[Charge transfer complexes]] with resistivities as low as 8 ohms-cm <ref>Y. Okamoto and W. Brenner ''Organic Semiconductors'', Rheinhold (1964)</ref> <ref>H. Akamatsu, H.Inokuchi, and Y.Matsunaga, “Electrical Conductivity of the Perylene–Bromine Complex” ''Nature'' volume, 173 (1954) 168</ref>. In the early 1970's, salts of [[tetrathiafulvalene]] were shown to exhibit almost metallic conductivity, while superconductivity was demonstrated in 1980. Broad research on charge transfer salts continues today.
===Conducting polymers===
The linear-backbone "polymer blacks" (polyacetylene, polypyrrole, and polyaniline) and their copolymers are the main class of conductive polymers. Historically, these are known as [[Melanins]].
In 1963 Australians DE Weiss and coworkers reported [http://www.drproctor.com/os/weiss.htm] iodine-doped oxidized [[polypyrrole]] blacks with resistivities as low as 1 ohm/cm. Subsequent papers [http://www.publish.csiro.au/nid/51/paper/CH9650477.htm][http://www.publish.csiro.au/nid/51/paper/CH9650487.htm] reported resistances as low as 0.03 Ohm/cm. With the notable exception of [[Charge transfer complex]]es (some of which are even [[superconductor]]s), organic molecules had previously been considered insulators or at best weakly conducting [[semiconductors]].
Over a decade later in 1977, Shirakawa, Heeger, and MacDiarmid reported equivalent high conductivity in rather similarly oxidized and iodine-doped [[polyacetylene]]. They later received the 2000 [[Nobel prize]] in chemistry for " The discovery and development of conductive polymers " [http://nobelprize.org/nobel_prizes/chemistry/laureates/2000/index.html]. The Nobel citation made no reference to Weiss ''et al's'' similar earlier work. Also see [[Nobel Prize controversies]].
==C<sub>60</sub> and carbon nanotubes==
===From graphite to C<sub>60</sub>===
In [[polymers]], classical organic molecules are composed of both carbon and hydrogen (and sometimes additional compounds such as nitrogen, chlorine or sulphur). They are obtained from petrol and can often be synthethized in large amounts. Most of these molecules are insulating when their length exceeds a few nanometers. However, naturally occurring carbon is conducting. In particular, graphite (recovered from coal or encountered naturally) is conducting. From a theoretical point of view, [[graphite]] is a [[semi-metal]], a category in between metals and semi-conductors. It has a layered structure, each sheet being one atom thick. Between each sheet, the interactions are weak enough to allow an easy manual cleavage.
Tailoring the [[graphite]] sheet to obtain well defined nanometer-sized objects remains a challenge. However, by the close of the twentieth century, chemists were exploring methods to fabricate extremely small graphitic objects that could be considered single molecules. After studying the interstellar conditions under which carbon is known to form clusters, [[Richard Smalley|Richard Smalley's]] group (Rice university, Texas) set up an experiment in which graphite was vaporized using laser irradiation. Mass spectrometry revealed that clusters containing specific "magic numbers" of atoms were stable, in particular those clusters of 60 atoms. [[Harry Kroto]], an English chemist who assisted in the experiment, suggested a possible geometry for these clusters - atoms covalently bound with the exact symmetry of a soccer ball. Coined buckminsterfullerenes, buckyballs or [[Fullerene|C<sub>60</sub>]], the clusters retained some properties of graphite, such as conductivity. These objects were rapidly envisioned as possible building blocks for molecular electronics.
===Carbon nanotubes===
:''See [[Carbon nanotubes]] and [[fullerenes]]''
==Theory of Molecular Electronics==
The theory of single molecule devices is particularly interesting since the system under consideration is an open quantum system in [[nonequilibrium]] (driven by voltage). In the low bias voltage regime, the nonequilibrium nature of the molecular junction can be ignored, and the current-voltage characteristics of the device can be calculated using the equilibrium electronic structure of the system. However, in stronger bias regimes a more sophisticated treatment is required, as there is no longer a [[variational principle]]. In the elastic tunneling case (where the passing electron does not exchange energy with the system), the formalism of [[Rolf Landauer]] can be used to calculate the transmission through the system as a function of bias voltage, and hence the current. In inelastic tunneling, an elegant formalism based on the non-equilibrium [[Green's functions]] of [[Leo Kadanoff]] and [[Gordon Baym]], and independently by [[Leonid Keldysh]] was put forth by [[Ned Wingreen]] and [[Yigal Meir]]. This Meir-Wingreen formulation has been used to great success in the molecular electronics community to examine the more difficult and interesting cases where the transient electron exchanges energy with the molecular system (for example through electron-phonon coupling or electronic excitations).
==Recent Progress ==
Recent progress in [[nanotechnology]] and nanoscience has facilitated both experimental and theoretical study of molecular electronics. In particular, the development of the [[scanning tunneling microscope]] (STM) and later the [[atomic force microscope]] (AFM) have facilitated manipulation of single-molecule electronics.
The first widely reported result was using a mechanical break junction approach to connect two gold electrodes to a sulfur-terminated [[molecular wire]] by [[Mark Reed]] and [[James Tour]].
A collaboration of researchers at [[Hewlett-Packard|HP]] and [[UCLA]], led by James Heath, Fraser Stoddart, R. Stanley Williams, and Philip Kuekes, has developed molecular electronics based on [[rotaxane]]s and [[catenane]]s.
Work is also being done on the use of single-wall carbon nanotubes as field-effect transistors. Most of this work is being done by [[International Business Machines|IBM]].
The Aviram-Ratner model for a molecular rectifier, which until recently was entirely theoretical, has been confirmed experimentally and unambiguously in a number of experiments by a group led by Geoffrey J. Ashwell at [[Cranfield University]], UK.[http://www.rsc.org/ej/JM/2003/b304465n.pdf],[http://www.rsc.org/ej/JM/2004/b403942d.pdf],[http://www.rsc.org/ej/JM/2004/b411343h.pdf] Many rectifying molecules have so far been identified, and the number and efficiency of these systems is expanding rapidly.
[[Supramolecular electronics]] is a new field that tackles electronics at a [[supramolecular chemistry|supramolecular]] level.
An important issue in molecular electronics is the determination of the resistance of a single molecule (both theoretical and experimental). For example, Bumm, et al[http://www.sciencemag.org/cgi/content/abstract/271/5256/1705] used STM to analyze a single molecular switch in a [[self-assembled monolayer]] to determine how conductive such a molecule can be. Another problem faced by this field is the difficulty to perform direct characterization since imaging at the molecular scale is often difficult in many experimental devices.
==See also==
* [[Single-molecule magnet]]
* [[Stereoelectronics]]
* [[Organic Semiconductors]]
* [[Conductive polymers]]
* [[Molecular conductance]]
* [[Software for molecular mechanics modeling | Software for molecular modeling]]
==Further reading==
*For the history of the field, see the following references:
**Kwok, K.; Ellenbogen, J. C. [http://www.mitre.org/work/tech_papers/tech_papers_02/02_0239/index.html “Moletronics: future electronics”] Materials Today 2002, volume 5, pages 28-37.
**Cassoux, P. “Molecular Metals: Staying Neutral for a Change” Science Science 2001 volume 291, pages 263-264. [DOI: 10.1126/science.291.5502.263.
**"An Overview of the First Half-Century of Molecular Electronics" by Noel S. Hush, ''Ann. N.Y. Acad. Sci. 1006:'' 1–20 (2003) and
**Bendikov, M; Wudl, F; Perepichka, D. F. “Tetrathiafulvalenes, Oligoacenenes, and Their Buckminsterfullerene Derivatives: The Brick and Mortar of Organic Electronics” Chemical Reviews 2004, volume 104, 4891-4945.
==References==
{{reflist}}
# [http://dx.doi.org/10.1016/0009-2614(74)85031-1 Aviram, A. & Ratner, M.A. Molecular Rectifiers. Chem. Phys. Lett. 29, 277 (1974).]
# BA Bolto, R McNeill and DE Weiss, Electronic Conduction in Polymers. III. Electronic Properties of Polypyrrole, Australian Journal of Chemistry 16(6) 1090 - 1103 (1963) [http://www.drproctor.com/os/weisspaper.pdf]
# [[John McGinness]], Corry, P, Proctor, P.H. Amorphous Semiconductor Switching in Melanins,''Science, vol 183'', 853-855 (1974) [http://www.drproctor.com/os/amorphous.htm]
# S. J. Tans, M. H. Devoret, H. Dai, A. Thess, R. E. Smalley, L. J. Geerligs, & C. Dekker, Nature, vol 386, 474 (1997).
# [http://www.nature.com/nature/journal/v318/n6042/abs/318162a0.html H. W. Kroto, J. R. Heath, S. C. O'Brien, R. F. Curl & R. E. Smalley, Nature, vol 318, 162 (1985)]
# [http://www.nature.com/nature/journal/v329/n6139/abs/329529a0.html H. W. Kroto, Nature, vol 329, 529 (1987)]
# T. Oberlin, M. Endo, & T. Koyama, Journ. of Crystal Growth, 32, 335 (1976).
# [http://www.rsc.org/CFmuscat/intermediate_abstract.cfm?FURL=/ej/JM/2002/b110591b/b110591b.PDF&TYP=003 Geoffrey J. Ashwell and Daniel S. Gandolfo, J. Mater. Chem. 12]
# M.A. Reed, C. Zhou, C.J. Muller, T.P. Burgin, and J.M. Tour, “Conductance of a molecular junction”, Science 278, 252 (1997).
[[Category:Molecular electronics|*]]
[[Category:Nanoelectronics]]
[[Category:Organic polymers]]
[[Category:Organic semiconductors]]
[[Category:Conductive polymers]]
[[cs:Molekulární elektronika]]
[[es:Electrónica molecular]]
[[fr:Électronique moléculaire]]