Thursday, July 28, 2011

Nanoelectronics, Molecular Scale Electronics, and Molecular Logic Gate

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In 1965 Gordon Moore observed that silicon transistors were undergoing a continual process of scaling downward, an observation which was later codified as Moore's law. Since his observation transistor minimum feature sizes have decreased from 10 micrometers to the 45-65 nm range in 2007; one minimum feature is thus roughly 180 silicon atoms long. The field of nanoelectronics aims to enable the continued realization of this law by using new methods and materials to build electronic devices with feature sizes on the nanoscale.

Nanoelectronics refer to the use of nanotechnology on electronic components, especially transistors. Although the term nanotechnology is generally defined as utilizing technology less than 100 nm in size, nanoelectronics often refer to transistor devices that are so small that inter-atomic interactions and quantum mechanical properties need to be studied extensively. As a result, present transistors do not fall under this category, even though these devices are manufactured with 45 nm, 32 nm, or 22 nm technology.

Nanoelectronics are sometimes considered as disruptive technology because present candidates are significantly different from traditional transistors. Some of these candidates include: hybrid molecular/semiconductor electronics, one dimensional nanotubes/nanowires, or advanced molecular electronics.

The volume of an object decreases as the third power of its linear dimensions, but the surface area only decreases as its second power. This somewhat subtle and unavoidable principle has huge ramifications. For example the power of a drill (or any other machine) is proportional to the volume, while the friction of the drill's bearings and gears is proportional to their surface area. For a normal-sized drill, the power of the device is enough to handily overcome any friction. However, scaling its length down by a factor of 1000, for example, decreases its power by 10003 (a factor of a billion) while reducing the friction by only 10002 (a factor of "only" a million). Proportionally it has 1000 times less power per unit friction than the original drill. If the original friction-to-power ratio was, say, 1%, that implies the smaller drill will have 10 times as much friction as power. The drill is useless.

For this reason, while super-miniature electronic integrated circuits are fully functional, the same technology cannot be used to make working mechanical devices beyond the scales where frictional forces start to exceed the available power. So even though you may see microphotographs of delicately etched silicon gears, such devices are currently little more than curiosities with limited real world applications, for example, in moving mirrors and shutters. Surface tension increases in much the same way, thus magnifying the tendency for very small objects to stick together. This could possibly make any kind of "micro factory" impractical: even if robotic arms and hands could be scaled down, anything they pick up will tend to be impossible to put down. The above being said, molecular evolution has resulted in working cilia, flagella, muscle fibers and rotary motors in aqueous environments, all on the nanoscale. These machines exploit the increased frictional forces found at the micro or nanoscale. Unlike a paddle or a propeller which depends on normal frictional forces (the frictional forces perpendicular to the surface) to achieve propulsion, cilia develop motion from the exaggerated drag or laminar forces (frictional forces parallel to the surface) present at micro and nano dimensions. To build meaningful "machines" at the nanoscale, the relevant forces need to be considered. We are faced with the development and design of intrinsically pertinent machines rather than the simple reproductions of macroscopic ones.
All scaling issues therefore need to be assessed thoroughly when evaluating nanotechnology for practical applications.

Nanofabrication

For example, single electron transistors, which involve transistor operation based on a single electron. Nanoelectromechanical systems also fall under this category. Nanofabrication can be used to construct ultradense parallel arrays of nanowires, as an alternative to synthesizing nanowires individually.

Nano Material Electronics

Besides being small and allowing more transistors to be packed into a single chip, the uniform and symmetrical structure of nanotubes allows a higher electron mobility (faster electron movement in the material), a higher dielectric constant (faster frequency), and a symmetrical electron/hole characteristic.
Also, nanoparticles can be used as quantum dots.

Molecular electronics

Single molecule devices are another possibility. These schemes would make heavy use of molecular self-assembly, designing the device components to construct a larger structure or even a complete system on their own. This can be very useful for reconfigurable computing, and may even completely replace present FPGA technology.
Molecular electronics is a new technology which is still in its infancy, but also brings hope for truly atomic scale electronic systems in the future. One of the more promising applications of molecular electronics was proposed by the IBM researcher Ari Aviram and the theoretical chemist Mark Ratner in their 1974 and 1988 papers Molecules for Memory, Logic and Amplification. This is one of many possible ways in which a molecular level diode / transistor might be synthesized by organic chemistry. A model system was proposed with a spiro carbon structure giving a molecular diode about half a nanometre across which could be connected by polythiophene molecular wires. Theoretical calculations showed the design to be sound in principle and there is still hope that such a system can be made to work.


Nanoelectronic devices



Radios

Nanoradios have been developed structured around carbon nanotubes.

Computers

Simulation result for formation of inversion channel (electron density) and attainment of threshold voltage (IV) in a nanowire MOSFET. Note that the threshold voltage for this device lies around 0.45V.

Nanoelectronics holds the promise of making computer processors more powerful than are possible with conventional semiconductor fabrication techniques. A number of approaches are currently being researched, including new forms of nanolithography, as well as the use of nanomaterials such as nanowires or small molecules in place of traditional CMOS components. Field effect transistors have been made using both semiconducting carbon nanotubes[9] and with heterostructured semiconductor nanowires.

Energy production
Research is ongoing to use nanowires and other nanostructured materials with the hope to create cheaper and more efficient solar cells than are possible with conventional planar silicon solar cells. It is believed that the invention of more efficient solar energy would have a great effect on satisfying global energy needs.

There is also research into energy production for devices that would operate in vivo, called bio-nano generators. A bio-nano generator is a nanoscale electrochemical device, like a fuel cell or galvanic cell, but drawing power from blood glucose in a living body, much the same as how the body generates energy from food. To achieve the effect, an enzyme is used that is capable of stripping glucose of its electrons, freeing them for use in electrical devices. The average person's body could, theoretically, generate 100 watts of electricity (about 2000 food calories per day) using a bio-nano generator. However, this estimate is only true if all food was converted to electricity, and the human body needs some energy consistently, so possible power generated is likely much lower. The electricity generated by such a device could power devices embedded in the body (such as pacemakers), or sugar-fed nanorobots. Much of the research done on bio-nano generators is still experimental, with Panasonic's Nanotechnology Research Laboratory among those at the forefront.


Molecular logic gate
A molecular logic gate is a molecule that performs a logical operation on one or more logic inputs and produces a single logic output. Much academic research is dedicated to the development of these systems and several prototypes now exist. Because of their potential utility in simple arithmetic these molecular machines are also called moleculators.

Molecular logic gates work with input signals based on chemical processes and with output signals based on spectroscopy. One of the earlier water solution-based systems exploits the chemical behavior of compounds A and B in scheme 1.

Scheme 1. Molecular logic gates de Silva 2000


Compound A is a push-pull olefin with the top receptor containing four carboxylic acid anion groups (and non-disclosed counter cations) capable of binding to calcium. The bottom part is a quinoline molecule which is a receptor for hydrogen ions. The logic gate operates as follows.

Without any chemical input of Ca2+ or H+, the chromophore shows a maximum absorbance in UV/VIS spectroscopy at 390 nm. When calcium is introduced a blue shift takes place and the absorbance at 390 nm decreases. Likewise addition of protons causes a red shift and when both cations are in the water the net result is absorption at the original 390 nm. This system represents a XNOR logic gate in absorption and a XOR logic gate in transmittance.

In compound B the bottom section now contains a tertiary amino group also capable of binding to protons. In this system fluorescence only takes place when both cations are present and therefore the system represents an AND logic gate.

With both systems run in parallel and with monitoring of transmittance for system A and fluorescence for system B the result is a half-adder capable of reproducing the equation 1+1=2.

In a modification of system B not two but three chemical inputs are simultaneously processed in an AND logic gate. An enhanced fluorescence signal from the compound depicted below is obtained only in the presence of hydrogen, zinc and sodium ions through interaction with respectively the amine, carboxylate and crown ether receptors and this system can be potentially applied in disease screening (lab-on-a-molecule) because these ions are all physiologically relevant.

Scheme 2. Lab On A Molecule


In another XOR logic gate system the chemistry is based on the pseudorotaxane depicted in scheme 3. In organic solution the electron deficient diazapyrenium salt (rod) and the electron rich 2,3-dioxynaphthalene units of the crown ether (ring) self-assemble by formation of a charge transfer complex.

An added tertiary amine like tributylamine forms a 1:2 adduct with the diazapyrene and the complex gets dethreaded. This process is accompanied by an increase in emission intensity at 343 nm resulting from freed crown ether. Added trifluoromethanesulfonic acid reacts with the amine and the process is reverted. Excess acid locks the crown ether by protonation and again the complex is dethreaded.

Scheme 3. Pseudorotaxane logic gate


A full adder system based on fluorescein is able to compute 1+1+1=3.


Molecular Scale Electronics
Conventional electronics have traditionally been made from bulk materials. Ever since its invention in 1958 the performance and complexity of integrated circuits has been growing exponentially (a trend also known as Moore’s law) and has forced the feature sizes of the embedded components to shrink accordingly. As the structures become smaller the sensitivity for deviations increases and in a few generations, when the minimum feature sizes reaches 13 nm, the composition of the devices will have to be controlled to a precision of a few atoms in order for the devices to work. With the bulk approach having inherent limitations in addition to becoming increasingly demanding and expensive, the idea was born that the components could instead be built up atom for atom in a chemistry lab (bottom up) as opposed to carving them out of bulk material (top down). This idea is the reasoning behind molecular electronics with the ultimate miniaturization being components contained in single molecules.

In single molecule electronics, the bulk material is replaced by single molecules. That is, instead of creating structures by removing or applying material after a pattern scaffold, the atoms are put together in a chemistry lab. This way billions of billions of copies are made simultaneously (typically more than 10 20 molecules are made at once) while the composition of molecules are controlled down to the last atom. The molecules utilized have properties that resemble traditional electronic components such as a wire, transistor or rectifier.

Single molecule electronics is an emerging field, and entire electronic circuits consisting exclusively of molecular sized compounds are still very far from being realized. However, the continuous demand for more computing power together with the inherent limitations of the present day lithographic methods make the transition seem unavoidable. Currently, the focus is on discovering molecules with interesting properties and on finding ways to obtaining reliable and reproducible contacts between the molecular components and the bulk material of the electrodes.

Molecular electronics operates in the quantum realm of distances less than 100 nanometers. The miniaturization down to single molecules brings the scale down to a regime where quantum effects are important. As opposed to the case in conventional electronic components, where electrons can be filled in or drawn out more or less like a continuous flow of charge, the transfer of a single electron alters the system significantly. This means that when an electron has been transferred from the source electrode to the molecule, the molecule gets charged up and makes it much harder for the next one to transfer (see also Coulomb blockade). The significant amount of energy due to charging has to be taken into account when making calculations about the electronic properties of the setup and is highly sensitive to distances to conducting surfaces nearby.

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).
Further, connecting single molecules reliably to a larger scale circuit has proven to be a great challenge and constitute a significant hindrance to commercialization.

Common for molecules utilized in molecular electronics is that the structures contain a lot of alternating double and single bonds (see also Conjugated system). The reason for this is that such a pattern delocalizes the molecular orbitals making it possible for electrons to move freely over the conjugated area.

Wires



The sole purpose of molecular wires is to electrically connect different parts of a molecular electrical circuit. As the assembly of these and their connection to a macroscopic circuit is still to be mastered, the focus of research in single molecule electronics is primarily on the functionalized molecules: molecular wires are characterized by containing no functional groups and are hence composed of plain repetitions of a conjugated building block. Among these are the carbon nanotubes that are quite large compared to the other suggestions but have shown very promising electrical properties.
The main problem with the molecular wires is to obtain good electrical contact with the electrodes so that the electrons can move freely in and out of the wire.

Transistors

Single molecule transistors are fundamentally different than the ones known from bulk electronics. The gate in a conventional (field-emission) transistor determines the conductance between the source and drain electrode by controlling the density of charge carriers between them, whereas the gate in a single molecule transistor controls the feasibility of a single electron to jump on and off the molecule by modifying the energy of the molecular orbitals. One of the effects of this difference is that the single molecule transistor is almost binary: it is either ON or OFF. This opposes its bulk counterparts which have quadratic responses to gate voltage.

It is the quantization of charge into electrons that is responsible for the markedly different behavior compared to bulk electronics. Because of the size of a single molecule, the charging due to a single electron is significant and provides a mean to turn the transistor ON or OFF. For this to work, the electronic orbitals on the transistor molecule cannot be too well integrated with the orbitals on the electrodes. If they are, an electron cannot be said to be located on the molecule or the electrodes and the molecule will function as a wire.

A popular group of molecules, that can work as the semiconducting channel material in a molecular transistor, is the oligopolyphenylenevinylenes (OPVs) that works by the Coulomb blockade mechanism when placed between the source and drain electrode in an appropriate way. Fullerenes work by the same mechanism and have also been commonly utilized.
Semiconducting carbon nanotubes have also been demonstrated to work as channel material but although molecular, these molecules are sufficiently large to behave almost as bulk semiconductors.

The size of the molecules and the low temperature the measurements are being conducted at makes the quantum mechanical states well defined. It is therefore being researched if the quantum mechanical properties can be used for more advanced purposes than simple transistors (e.g. spintronics).

Physicists at the University of Arizona, in collaboration with chemists from the University of Madrid, have designed a single molecule transistor using a ring-shaped molecule similar to benzene. Physicists at Canada's National Institute for Nanotechnology have designed a single-molecule transistor using styrene. Both groups expect (their designs have yet to be experimentally verified) their respective devices to function at room temperature, and to be controlled by a single electron.

Rectifiers (diodes)

Molecular rectifiers are mimics of their bulk counterparts and have an asymmetric construction so that the molecule can accept electrons in one end but not the other. The molecules have an electron donor (D) in one end and an electron acceptor (A) in the other. This way, the unstable state D+ - A- will be more readily made than D- - A+. The result is that an electric current can be drawn through the molecule if the electrons are added through the acceptor end, but not so easily if the reverse is attempted. An example of a molecular rectifier was made by Geoffrey J. Ashwell's Ph.D. students.

Fullerene nanoelectronics


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 synthesized 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'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 C60, the clusters retained some properties of graphite, such as conductivity. These objects were rapidly envisioned as possible building blocks for molecular electronics.

Artifacts

When trying to measure electronic characteristics of molecules, artificial phenomena can occur that can be hard to distinguish from truly molecular behavior. Before they were discovered these artifacts have mistakenly been published as being features pertaining to the molecules in question.
Applying a voltage drop in the order of volts across a nanometer sized junction results in a very strong electrical field. The field can cause metal atoms to migrate and eventually close the gap by a thin filament which can be broken again when carrying a current. The two levels of conductance imitate molecular switching between a conductive and an isolating state of a molecule.
Another encountered artifact is when the electrodes undergo chemical reactions due to the high field strength in the gap. When the bias is reversed the reaction will cause hysteresis in the measurements that can be interpreted as being of molecular origin.
A metallic grain between the electrodes can act as a single electron transistor by the mechanism described above thus resembling the characteristics of a molecular transistor. This artifact is especially common with nanogaps produced by the electromigration technique.
One of the biggest problems with measuring on single molecules is to establish reproducible electrical contact with only one molecule and doing so without shortcutting the electrodes. Because the current photolithographic technology is unable to produce electrode gaps small enough to contact both ends of the molecules tested (in the order of nanometers) alternative strategies are put into use.

One way to produce electrodes with a molecular sized gap between them is break junctions, in which a thin electrode is stretched until it breaks. Another is electromigration. Here a current is lead through a thin wire until it melts and the atoms migrate to produce the gap. Further, the reach of conventional photolithography can be enhanced by chemically etching or depositing metal on the electrodes.
Probably the easiest way to conduct measurements on several molecules is to use the tip of a scanning tunneling microscope (STM) to contact molecules adhered at the other end to a metal substrate.

A popular way to anchor molecules to the electrodes is to make use of sulfurs’ high affinity to gold. In these setups, the molecules are synthesized so that sulfur atoms are placed strategically to function as crocodile clips connecting the molecules to the gold electrodes. Though useful, the anchoring is non-specific and thus anchors the molecules randomly to all gold surfaces. Further, the contact resistance is highly dependent on the precise atomic geometry around the site of anchoring and thereby inherently compromises the reproducibility of the connection.
To circumvent the latter issue, experiments has shown that fullerenes could be a good candidate for use instead of sulfur because of the large conjugated π-system that can electrically contact many more atoms at once than a single atom of sulfur.

Molecular electronics operates in the quantum realm of distances less than 100 nanometers. The miniaturization down to single molecules brings the scale down to a regime where quantum effects are important. As opposed to the case in conventional electronic components, where electrons can be filled in or drawn out more or less like a continuous flow of charge, the transfer of a single electron alters the system significantly. This means that when an electron has been transferred from the source electrode to the molecule, the molecule gets charged up and makes it much harder for the next one to transfer (see also Coulomb blockade). The significant amount of energy due to charging has to be taken into account when making calculations about the electronic properties of the setup and is highly sensitive to distances to conducting surfaces nearby.

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).
Further, connecting single molecules reliably to a larger scale circuit has proven to be a great challenge and constitute a significant hindrance to commercialization.

In their 1940's discussion of so-called "donor-acceptor" complexes, Robert Mulliken and Albert Szent-Gyorgi advanced the concept of charge transfer in molecules. They subsequently further refined the study of both charge transfer and energy transfer in molecules. Likewise, a 1974 paper from Mark Ratner and Ari Aviram 1 illustrated a theoretical molecular rectifier. In 1988, Aviram described in detail a theoretical single-molecule field-effect transistor. Further concepts were p roposed by Forrest Carter of the Naval Research Laboratory, including single-molecule logic gates. A wide range of ideas were presented, under his aegis, at a conference entitled Molecular Electronic Devices in 1988. These were all theoretical constructs and not concrete devices. 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 directly-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 substantially confirmed.


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. In addition, theoretical advances in molecular electronics have facilitated further understanding of non-adibatic charge transfer events at electrode-electrolyte interfaces.

The concept of molecular electronics was first published in 1974 when Aviram and Ratner suggested an organic molecule that could work as a rectifier. Having both huge commercial and fundamental interest much effort was put into proving its feasibility and 16 years later in 1990 the first demonstration of an intrinsic molecular rectifier was realized by Ashwell and coworkers for a thin film of molecules.

The first measurement of the conductance of a single molecule was realised in 1994 by C. Joachim and J. K. Gimzewski and published in 1995 (see the corresponding Phys. Rev. Lett. paper). This was the conclusion of 10 years of research started at IBM TJ Watson, using the scanning tunnelling microscope tip apex to switch a single molecule as already explored by A. Aviram, C. Joachim and M. Pomerantz at the end of the 80's (see their seminal Chem. Phys. Lett. paper during this period). The trick was to use an UHV Scanning Tunneling microscope to allow the tip apex to gently touch the top of a single C60 molecule adsorbed on a Au(110) surface. A resistance of 55 MOhms was recorded together with a low voltage linear I-V. The contact was certified by recording the I-z current distance characteristic, which allows the measurement of the deformation of the C60 cage under contact. This first experiment was followed by the reported result using a mechanical break junction approach to connect two gold electrodes to a sulfur-terminated molecular wire by Mark Reed and James Tour in 1997.

A single-molecule amplifier was implemented by C. Joachim and J.K. Gimzewski in IBM Zurich. This experiment involving a single C60 molecule demonstrated that a single C60 molecule can provide gain in a circuit just by playing with through C60 intramolecular quantum interference effects.
A collaboration of researchers at HP and UCLA, led by James Heath, Fraser Stoddart, R. Stanley Williams, and Philip Kuekes, has developed molecular electronics based on rotaxanes and catenanes.
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 IBM.
Some specific reports of a field-effect transistor based on molecular self-assembled monolayers were shown to be fraudulent in 2002 as part of the Schön scandal.

Until recently entirely theoretical, the Aviram-Ratner model for a unimolecular rectifier has been unambiguously-confirmed in experiments by a group led by Geoffrey J. Ashwell at Bangor University, UK. 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 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. used STM to analyze a single molecular switch in a self-assembled monolayer to determine how conductive such a molecule can be.[18] Another problem faced by this field is the difficulty of performing direct characterization since imaging at the molecular scale is often difficult in many experimental devices.

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