Molecular electronics

CHAPTER-1

INTRODUCTION
The silicon technology can become obsolete in the future like the value technology, about 50 years ago. Scientists and technologists are working in a new field of electronics known as molecular electronics, which is a relatively new field. Molecular electronics is the branch of nanotechnology which deals with the applications and construction of nano building blocks that are used in electronic circuit manufacturing and desgin. It is sometimes called as moletronics. All the major electronic fabrications are supported by molecular electronics. Molecular electronics emerged as an important area of research only in the 1980s. It was through the efforts of late professor Carter of the U.S.A that the field was born. Conventional electronics technology is much indebted to the integrated circuit (IC) technology. IC technology is one of the important aspects that brought about a revolution in electronics. With the gradual increased scale of integration, electronics age has passed through SSI (small scale integration), MSI (medium scale integration), LSI (large scale integration), and ULSI (ultra large scale integration). These may be respectively classified as integration technology with 1-12 gates, 12-30 gates, 30-300 gates, 300-10000 gates, and beyond 10000 gates on a single chip. The density of IC technology is increasing in pace with Famous Moores law of 1965. Till date Moores law about the doubling of the number of components in an I.C every year holds good. He wrote in his original paper entitled Cramming More Components On to Integrated Circuit , that, the complexity for minimum component costs has increased at the rate of roughly a factor of 2 per year. Beyond ULSI, molecular electronics plays a very important role in the field of electronics. Semiconductor integration beyond ULSI, through conventional electronic technology is facing problems with fundamental physical limitations like quantum effects etc. Molecular based electronics can overcome the fundamental physical and economic issues limiting Silicon Technology. For a scaling technology beyond ULSI, prof. Forest Carter put forward a novel idea. In digital electronics, YES and NO states are usually and respectively implemented and/or defined by ON and OFF conditions of a
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Molecular electronics switching transistor. Prof. Carter postulated that instead using a transistor; a molecule (a single molecule or a small aggregate of molecule) might be used to represent the two states, namely YES & NO of digital electronics.

Fig 1.1 - Million Instructions Per Second (MIPS) as projected by Gordon Moore.

The figure 1.1 shows the projected MIPS graph as given by Gordon Moore that can be implemented in the future. We can use positive spin & negative spin of a molecule to represent respectively YES & NO states of binary logic. As in the new concept a molecule rather than a transistor is proposed to be used, the scaling technology may go to molecular scale. It is therefore defined as MSE (molecular scale electronics). MSE is far beyond the ULSI technology in terms of scaling. In order to augment his postulation Prof. Carter conducted a number of international conferences on the subject. The outcome of these conferences has been to establish the field of molecular electronics. However, as of today, molecular electronics is a broad field. The semiconductor devices are fabricated from the top-down approach that employs a variety of sophisticated lithographic and etch techniques to pattern a substrate. This approach has become increasingly challenging as feature size decreases. In particular, at nanometer scale, the electronic properties of Department of ECE, VIT
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Molecular electronics semiconductor structures fabricated via conventional lithographic processes are increasingly difficult to control. In contrast, in molecular electronics, molecules are synthesized from the bottom-up approach that builds small structures from the atomic, molecular, or single device level. It in principle allows a very precise positioning of collections of atoms or molecules with specific functionalities.

Fig 1.2 Projected number of transistors that can be integrated onto a single chip as given by Gordon Moore.

The figure 1.2 depicts the projected number of transistors that can be integrated onto a single chip as given by Gordon Moore. The field is a result of a search for alternative materials, devices and applications of electronics. The field deals with organic materials. The field is a challenge but not a replacement for inorganic electronics on immediate terms. Molecular electronics is a technological challenge to explore the possible application of organic materials, non-linear optics and biologically important materials in the field of electronics. Therefore hopes run high for realization of plastic electronic systems, all optical computers, and chemical or bio-computers with inbuilt thinking functions and biochips etc.

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Molecular electronics In the field of communication the role of optical soliton, which is a by-product of non-linear optics, will be used in the implementation of a very haul (say 50,000 kilometers) with T bits/sec data rate networks. Economic solar cells are another existing promise of molecular electronics. Molecular electronics, which is a high investment and high-risk field, is at the same time a highly promising one. High investment and risks are involved in the initial phases. Under commercial phases the cost molecular systems shall be cheaper.

Fig 1.3 High-performance computing milestones

The figure 1.3 depicts the high-performance computing milestones achieved through the use of modern technology. The prospects of molecular electronics depend on the successful interaction and coordination of scientists of diverse fields like computer, electronics, physics, chemistry, biology, material science, etc. Molecular electronics represent the ultimate challenge in device miniaturization. Molecular devices can have any number of termini with current-voltage responses that would be expected to be nonlinear due to intermediate barriers Department of ECE, VIT
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Molecular electronics or hetero functionalities in the molecular framework while molecular wires refer to especially tailored molecular nanostructures energetic properties. Molecular-scale devices actually operating today include: FETs, junction transistors, diodes, and, molecular and mechanical switches. Logic gates with voltage gain have been built, and many techniques have been demonstrated to assemble nanometer wide wires into large arrays. Programmable and nonvolatile devices which hold their state in a few molecules or in square nanometers of material have been demonstrated.

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Molecular electronics

CHAPTER-2

HISTORY OF MOLECULAR ELECTRONICS

Study of charge transfer in molecules was advanced in the 1940s by Robert Mulliken and Albert Szent-Gyorgi in discussion of so-called "donor-acceptor" systems and developed the study of charge transfer and energy transfer in molecules. In the year 1958, the RCA (Radio Corporation of America) proposed the micro-module for the American army. Likewise, a 1974 paper from Mark Ratner and Avi Aviram illustrated a theoretical molecular rectifier. This paper illustrated a theoretical molecular rectifier and generalized molecular conduction in molecular electronics. They discussed theoretically the possibility of constructing a very simple electronic device, a rectifier, based on the use of a single organic molecule. It was turned out in later years that observing true molecular rectification is very difficult. Their proposal formed a brave attempt that would strengthen the foundations of the field with hopes of electronic applications truly at the molecular scale Later, Aviram detailed a singlemolecule field-effect transistor in 1988. Further concepts were proposed by Forrest Carter of the Naval Research Laboratory, including single-molecule logic gates.

Fig 2.1 - Forrest Carter explaining molecular electronics.

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Molecular electronics Apart from the Aviram and Ratner proposal, molecular electronics received an initial boost from the experimental discovery of conducting polymers in the mid-seventies. Before this date, organic molecules (which form crystals or polymers) were considered insulating or at best weakly conducting semi-conductors. In 1974, McGinness, Corry, and Proctor reported the first molecular electronic device in the journal Science. As its active element, this voltage-controlled switch used melanin, an oxidized mixed polymer of polyacetylene, polypyrrole, and polyaniline. The "ON" state of this switch exhibited extremely high conductivity. This device is now in the Smithsonian's collection of historic electronic devices. As Hush notes, their material also showed negative differential resistance, "a hallmark of modern advances in molecular electronics". Melanin is also the first example of a "self-doped" organic semiconductor, though McGinness et al also looked at dopants such as diethyamine.

Fig 2.2-Micro-elements and the fully assembled micro-module as proposed by the RCA. module.

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Molecular electronics A few years later, in 1977, Shirakawa, Heeger and MacDiarmid rediscovered the potential high conductivity of oxidized (doped) polyacetylene, producing a passive highly-conductive form of polyacetylene. For this discovery and its subsequent development, they received the 2000 Nobel prize in physics. Subsequently, chemists greatly improved the conductance of conjugated polymers. These findings opened the door to plastic electronics and optoelectronics, which are beginning to find extensive commercial application.

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Molecular electronics

CHAPTER-3

WORKING OF MOLECULAR ELECTRONICS

Molecular electronics works at the smallest scale involving single molecules, its characteristics and sub properties. It deals with the substance which are considered to be un explorable in the field of electronics. It also implements all the major laws of electronics in the practical ground basis so that original implementation of theoretical frame work can be seen. Many major components in the field of chemistry, physics, biological science and electronics are the gift of molecular electronics. With the help of this wonderful technology the building blocks of structures can be used in intense and complex fabrications of integrated circuits. It can control the molecular scale properties of individual atom of matter according to the use. The direct measurement of material properties is one of the most vital feature of molecular electronics which cannot be found in any other technology. In assembling molecular circuits, instead of building individual components on a chip, we can synthesize molecules with structures possessing desired electronic configurations and attach/interconnect them into an electronic circuit using surface attachment techniques like self assembly.

3.1. Self Assembled Monolayer.

Self assembly is a phenomenon in which atoms, molecules, or groups of molecules arrange themselves spontaneously into regular patterns and even relatively complex systems without outside intervention. Self Assembled Monolayers (SAMs) are ordered molecular structures formed by the adsorption of an active surfactant on a solid surface. A SAM film can be deposited on a substrate surface simply by exposing the surface to an environment containing surface active molecular species for a certain period of time. The molecules will be spontaneously oriented towards the substrate surface and form an energetically favourable ordered layer. During this process, the surface active head group of the molecule chemically reacts with and chemisorbs onto the substrate. Since the self assembling system attempts to reach a thermodynamically stable state driven by the global minimization of free energy, it Department of ECE, VIT
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Molecular electronics tends to eliminate growing foreign or faulty structures of molecules during the assembly process. This simple process with its intrinsic error-correction advantage makes SAMs inherently manufacturable and thus technically attractive and cost effective. In addition SAMs can be designed and engineered to provide extremely high functional density.

Fig 3.1 A general diagram depicting self assembled monolayer. The SAM formed by an organic compound called as alkanethiolate is of importance in the field of molecular electronics. The surface of gold nano particles become highly corrugated by the adsorption of alkanethiolate self-assembled monolayers. Furthermore, as the temperature is increased, the SAMs dissolve into the gold nanoparticle, creating a liquid mixture at temperatures much lower than the melting temperature of the gold nanoparticle. By analyzing the mechanical and chemical properties of gold nanoparticles at temperatures below the melting point of gold, with different SAM chain lengths and surface coverage properties, we can know that the system is metastable. This SAM layer can be highly useful since gold has a very good conductivity. While SAMs are often allowed to form over 12 to 72 hours at room temperature, SAMs of alkanethiolates form within minutes. Department of ECE, VIT
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Molecular electronics

Fig 3.2 Formation of SAM by alkanethiolates on gold surface.

3.2. Molecular charge transport theory.

The electron transport through molecular devices is slightly different from what is observed from traditional conductors. In a semiconductor or metal wire, charge transport is ohmic: For a given wire diameter, longer wires have proportionately higher resistance. Such a picture is usually wrong for molecules because of the localized nature of most molecular electronic states. In molecular electronics, if we consider one electrode functions as an electron donor and the other as an electron acceptor, then the electrodes will be bridged by a linear chain (an alkane). Current through a junction decreases exponentially with increasing chain length, and the alkane effectively serves as a simple energy barrier separating the two electrodes. The possible mechanisms for electron transport are much richer for the electron Donor-Bridgeelectron Acceptor (DBA) molecular junction. DBA complexes serve as models for understanding how charge transport mechanisms in solution translate into the conductivity of solid-state molecular junctions. In DBA complexes, the donor and acceptor sites are part of the molecule, and the lowest unoccupied sites on the donor and acceptor components are Department of ECE, VIT
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Molecular electronics separated from one another by a bridging component that has molecular orbital of differing energy. In a process called electron-type super exchange; electrons tunnel from the right electrode into the acceptor state when a bias is applied. Then it may coherently transfer to the donor state before tunneling to the left electrode. Alternatively, in hole-type super exchange, the tunneling from the molecule into the left electrode might occur first, followed by refilling of the molecular level from the right. In fact, both processes will occur, and it is their relative rates that determine the nature of coherent conductance through a DBA junction. A third possibility is that an electron from the donor can jump to the acceptor due to either thermal or electrical excitation. The diversity of conduction mechanisms represents an opportunity to manipulate the electrical properties of junctions through synthetic modification. The observed conduction in DBA molecular junctions usually differs radically from that in traditional ohmic wires and can more closely resemble coherent transport in mesoscopic structures. Key factors include a dependence on the rates of intermolecular electron transfer between the donor and acceptor sites. This dependence can be exploited: The donor and acceptor components could be designed to differ energetically from one another, so that even with no applied bias voltage, the energy landscape is asymmetric. Under some conditions, the conductance of a DBA junction can vary with the sign of the applied voltage; such junctions represent a molecular approach toward controlling current rectification. The competition between charge transport mechanisms through a DBA molecule can also be affected by the bridge. Shorter bridges produce larger amounts of wave function overlap between the donor and acceptor molecular orbitals. For a short bridge (510 ), the super exchange mechanism will almost always dominate. For sufficiently long bridges, the hopping mechanism will almost always dominate. The molecular structure of the bridge can be synthetically varied to control the relative importance of the two mechanisms. Certain molecules will isomerismthat is, change shapeupon receiving a charge or being placed in a strong field, and in many cases, such transformations can be tightly controlled. Different molecular isomers are characterized by different energies and possibly by different relative rates for the hopping and super exchange transport mechanisms. Driven molecular isomerization therefore presents opportunities for designing switches and other Department of ECE, VIT
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Molecular electronics active device elements. Molecular quantum dots represent a simpler energy level system than DBA junctions, and have become the model systems for investigating basic phenomena such as moleculeelectrode interactions and quantum effects in charge transport through molecular junctions. The choice of electrodes in molecular electronics is based on molecule-electrode interactions. The chemical interaction between the molecule and the electrode will likely modify the molecules electron density in the vicinity of the contacting atoms and, in turn, modify the molecular energy levels or the barriers within the junction. The clear result is that the molecular and interface functions are inseparable and thus must be considered as a single system.

3.2. Implementation through other compounds.

The approach involves the design and synthesis of dyads, triads and other super molecular species using the techniques of organic chemistry. The newly-prepared molecules are then studied by a variety of physical methods, including time-resolved laser spectroscopy, NMR spectroscopy, and cyclic voltammetry in order to determine how and how well they functioned as molecular electronic elements. The information gained can then be used to design new generations of these molecules. Once functional molecular photovoltaics, logic gates, or other elements have been prepared, ways must be developed for interfacing these with electronic circuits.

Fig 3.3 Individual structure of buckminsterfullerene. Department of ECE, VIT

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Molecular electronics

Fig 3.2 Structure of Buckminsterfullerene used in molecular connection.

The triad shown above is an example of a molecule that may be useful in molecular electronic applications. Buckminsterfullerene (C60) and its relatives have generated considerable excitement in recent years due to their status as new and unusual forms of carbon which are completely unrelated to the many carbon compounds synthesized by living organisms. In spite of their non-biological origin, it turns out that fullerenes are nearly ideal as components of molecules that mimic natural photosynthetic energy and electron transfer. This molecular "triad" consists of a synthetic porphyrin covalently linked to both a fullerene (C60) and a carotenoid polyene. The state obtained using buckminsterfullerene has a relatively long lifetime, and stores a considerable fraction of the light energy as electrochemical potential energy. This conversion of light energy to electrochemical potential is analogous to the way plants carry out solar energy harvesting during photosynthesis. The charge-separated state is formed even at 8 degrees Kelvin in a frozen environment, and ultimately decays by charge recombination to yield the carotenoid triplet excited state, rather than the original ground-state molecule. The generation in the triad of a long-lived charge separated state by photo induced electron transfer, the low-temperature electron transfer behavior, and the formation of a triplet state by charge recombination are phenomena heretofore observed mostly in photosynthetic reaction centers. The triads are molecular-scale photovoltaic cells. Their nanometer size and their ability to generate an electrical response to light may help point the way to the development of molecular-scale optoelectronic devices for communications, data processing, and sensor applications. In fact, the triad shown above
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Molecular electronics functions as a molecular-scale AND logic gate. Two inputs (light and a weak magnetic field) are required to switch on the output of the gate, which may be detected optically or electrically.

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Molecular electronics

CHAPTER-4

ORGANIC DEVICES
Organic electronics, plastic electronics or polymer electronics, is a branch of electronics dealing with conductive polymers and conductive small molecules. It is called 'organic electronics because the polymers and small molecules are carbon-based. This contrasts with traditional electronics, which relies on inorganic conductors and semiconductors, such as copper and silicon, respectively. Molecular Electronics, as on date, can be divided into broad areas: Molecular materials of electronics (MME), and Molecular scale electronics (MSE). MME deals with the use of macroscopic or bulk properties of molecules or macromolecules or organic materials in electronic devices. MSE deals with microscopic properties, say spin or dipole moment, etc of a single molecule or a small aggregate of molecules for application in electronics. The main categories of MME are organic semiconductors or molecular semiconductors and metals. Liquid crystalline materials, piezo- and pyroelectric materials, photo and electro-chromic materials, non-linear optical materials and biologically important materials for electronics. The use of molecular organic materials as active elements in electronic devices was actually augmented with the discovery of conducting polymers in mid 1970s. Traditionally polymers are flexible, versatile and easy to process. These properties, along with the electrical property of conducting polymers that behave like a conventional inorganic semiconductor (silicon or gallium arsenide, etc.), make the polymer a material of hot current research. But the requirement is that the molecular organic material should behave like a real semiconductor. If any molecular material is to be considered as a semi conductor, it has to posses reasonable charge carrier mobility and demonstrate the existence of controllable band gap of the order of 0.75 to 2 e V. There are very few molecular materials that will fulfill these requirements.

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Molecular electronics The solid state error of electronics owes much to the discovery of p-n junction, which is based on the flow of electricity through silicon. The flow of electricity can be controlled by adding impurities to silicon.

Fig 4.1 Typical resistivity of differ materials.

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Molecular electronics Mobilities are seen to be low in molecular organic materials. Polymers have a leading high mobility charge carriers. But while some of these are insulators and cannot be doped, others are too impure and too inhomogeneous to access experimental high mobilities. Despite this, the conjugated or conducting polymers exhibited high carrier mobilities when doped. Several experiments confirm that synthesized conducting polymers could be employed as either metallic or semi conducting component of a metal-semiconductor junction device such as Schottky and p-n junction diode, with rectification ratios in excess of thousands. There are reports of polymer based MISFET (metal insulator semiconductor field effect transistor) devices with mobilities as high as 0.1 cm sq / volt sec, total organic (polymer) transistor and LED with quantum efficiencies in the region of 1% photons per electrons. Organics, which are intrinsically p-type in semi conducting behavior, have been widely experimented with conjugated polymers. There are n-type organic semiconductors. Their behavior is found when TNCQ (tetracyanoquinodimethane) is used as the active semi conducting materials in MISFETs. The maximum field mobility has been observed as 3x10-5 cm sq / volt sec. An active polymer transistor was first reported by Burroughes et al in 1988. The device had some important features such as no chemical doping or side reactions and insensitivity to disorder. But the operating frequency was low due to low carrier mobility. However Prof. Francis Garnier and co-workers achieved a dramatic lead in 1990. They reported a total organic transistor known as organic FET. The transistor is a metal insulator semiconductor structure comprising an oxidized silicon substrate and a semiconductor polymer layer. It has great flexibility and can even function when it is bent. The operating speed is still poor. There are also reports of organic FET from Dr.Friend and co-workers Cavendish Laboratory of Cambridge. All FETs reported so far show a poor current and a power handling capability in comparison with inorganic FETs, in addition to low operating frequency. These problem need to be address before organic FETs can be used in place of inorganic FETs. Pure semi conducting polymers can be used in display devices. These conjugated with improved impurity have shown very strong photoluminescence. Conjugated polymers can be used to manufacture LEDs out of plastic. This has immense application in computer and TV screens.

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Fig 4.2 Organic LEDs.

Fig 4.3 Organics based flexible display.

To provide pixelled large area flat screen displays, two stumbling blocks, which are to be overcome, are efficiency and lifetime. LEDs should have at least 10% efficiency before they can be used in commercial areas. On the other hand, where as a minimum of 10000 hrs lifetimes is required for flat screen or panel displays. Vast amount of research is being carried out in the field of organic materials. Two of the molecules that have been used to demonstrate current carrying molecular scale structures are poly phenylene-based chains and carbon nanotubes.

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CHAPTER-5

POLYPHENYLENE BASED CHAINS

Poly-phenylene vinylene (PPV) is a conducting polymer of the rigid-rod polymer host family. Polyphenylene based molecular wires and switches use chains of organic aromatic benzene rings. Recently, it has been shown by several research groups that molecules of this type conduct electrical currents. In addition, polyphenylenes as well as similar organic molecules have been shown to be capable of switching small currents. An individual benzene ring less one of its hydrogens, giving the phenyl group C6H5, can be bonded as a group to other molecular components. By removing two hydrogens, giving the group C6H4, we can have two binding sites in the ring. Polyphenylenes are obtained by binding phenylenes to each other on both sides and ending the chain-like structures with phenyl groups obtain Polyphenylenes. These can be made in different shapes and lengths. Other types of molecular groups (e.g., singly-bonded aliphatic groups, doubly-bonded ethanol groups, and triple bonded ethanol or acetylene groups) may be inserted into a Polyphenylene chain to make Polyphenylene-based aromatic molecules with useful structures and properties. Sensitive experiments by various investigators have shown that Polyphenylene based molecules conduct electricity. In one experiment, an electrical current was passed through a monolayer of approximately 1,000 Polyphenylenebased molecular wires that were arranged in a nanometer-scale pore and adsorbed to metal contacts on either end. The system was prepared so that all the molecules of the nanopore were identical three benzene-ring polyphenylene-based chain molecules. The measured current that passed through the molecular-wires was 30 m A, or about 30 n A per molecule. This works out to about 200 billion electrons per second being transmitted across the short polyphenylene-based molecular wire.

For comparison, a larger molecule, the carbon nanotube (bucky tube) has been measured transmitting currents in the range 20 to 500 n A, or 120 billion to 3 trillion electrons per

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Molecular electronics second. The polyphenylene-based molecular-wires do not carry as much current as the bucky tubes however, because of their very small cross-sectional areas; their current densities are the same as those of the carbon nanotubes. These current densities are quite high - about a half a million times greater than that of a copper wire. Polyphenylene-based molecules also have the advantage of a well-defined chemistry, synthetic flexibility, and more than a century of experience studying and manipulating them. J.M. Tour who has made mole quantities of these molecules has refined the synthetic techniques for conductive polyphenylene-based chains. These Polyphenylene-based chains have come to be known as Tour wires". The way energy is transferred or channeled from one end of a molecule to the other is via p-type orbital lying above and below the plane of the molecule. These p-type orbital can extend over the length of the molecule thus connecting with the neighboring molecule creating a polyphenylene-based chain. Polyphenylenes will conduct current as long as conjunction among p-bonded components is maintained. Polyphenylene-based molecules bonded with multiply bonded groups (such as ethenyl, HC=CH-, or ethynyl, -C=C-) are also conductive.

Fig 5.1 Phenylene group.

Fig 5.2 Structure of polyphenylene. Due to this, triply bonded ethynyl or acetylenic linkages can be inserted as spacers between phenyl rings in a Tour wire. Spacers are needed to eliminate steric interference between hydrogen atoms bonded to adjacent rings. Steric interference can affect the extent of p-orbital overlap between adjacent rings thereby reducing conduciveness.

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Molecular electronics

CHAPTER-6

CARBON NANOTUBES
A second type of molecule that can be used for a molecular electronic backbone is the carbon nanotube or bucky tube. Carbon nanotubes (CNTs) are allotropes of carbon with a cylindrical nanostructure. Nanotubes have been constructed with length-to-diameter ratio of up to 132,000,000:1, significantly larger than for any other material. Nanotubes are members of the fullerene structural family. Their name is derived from their long, hollow structure with the walls formed by one-atom-thick sheets of carbon, called graphene. These sheets are rolled at specific and discrete chiral angles, and the combination of the rolling angle and radius decides the nanotube properties; for example, whether the individual nanotube shell is a metal or semiconductor. Nanotubes are categorized as single-walled nanotubes (SWNTs) and multi-walled nanotubes (MWNTs). Individual nanotubes naturally align themselves into "ropes" held together by van der Waals forces, more specifically, pi-stacking. The chemical bonding of nanotubes is composed entirely of sp2 bonds, similar to those of graphite. These bonds, which are stronger than the sp3 bonds found in alkanes and diamond, provide nanotubes with their unique strength. These cylindrical carbon molecules have unusual properties, which are valuable for nanotechnology, electronics, optics and other fields of materials science and technology. In particular, owing to their extraordinary thermal conductivity and mechanical and electrical properties, carbon nanotubes find applications as additives to various structural materials. When used on micropattened semiconductor surfaces, these carbon nanotube structures make a very conductive wire. They differ in diameters and chiralities and come in a range of conductive properties ranging from excellent conduction to pretty good insulation. Bucky tubes are fairly new to the world of chemistry having only been discovered and characterized in the last two decades. Once made, carbon nanotubes are stable but they are made only under extreme conditions. Their synthesis is neither selective nor precise. During synthesis many molecules form in a range of structures. To get the precision required to function in electronic circuits, the use of physical inspection and manipulation of the molecules, one at a time, is needed. Currently, researches have been under taken to exploit the functionalities of carbon nanotubes. The need Department of ECE, VIT
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Molecular electronics for this research is fuelled by the fact that the polyphenylene backbone is not the most conductive and the most conductive carbon nanotube, is not chemically flexible.

Fig 6.1 Structure of a carbon nanotube.

6.1. Potential uses of carbon nanotubes.

Nanotube-based transistors, also known as carbon nanotube field-effect transistors (CNTFETs), have been made that operate at room temperature and that are capable of digital switching using a single electron. However, one major obstacle to realization of nanotubes has been the lack of technology for mass production. In 2001 IBM researchers demonstrated how metallic nanotubes can be destroyed, leaving semiconducting ones behind for use as transistors. Their process is called "constructive destruction," which includes the automatic destruction of defective nanotubes on the wafer. This process, however, only gives control over the electrical properties on a statistical scale. The first nanotube integrated memory circuit
was made in 2004. One of the main challenges has been regulating the conductivity of nanotubes.

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Depending on subtle surface features a nanotube may act as a plain conductor or as a semiconductor. A fully automated method has however been developed to remove non-semiconductor tubes.

Fig 6.2 Different configurations of a carbon nanotube. Another way to make carbon nanotube transistors has been to use random networks of them. By doing so one averages all of their electrical differences and one can produce devices in large scale at the wafer level. This approach was first patented by Nanomix Inc. It was first published in the academic literature by the United States Naval Research Laboratory in 2003 through independent research work. This approach also enabled Nanomix to make the first transistor on a flexible and transparent substrate. Large structures of carbon nanotubes can be used for thermal management of electronic circuits. An approximately 1 mmthick carbon nanotube layer was used as a special material to fabricate coolers, this material has very low density, ~20 times lower weight than a similar copper structure, while the cooling properties are similar for the two materials. Overall, incorporating carbon nanotubes as transistors into logic-gate circuits with densities comparable to modern CMOS technology has not yet been demonstrated. Carbon nanotubes can also be used in paper batteries, solar cells and for developing ultracapacitors.

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CHAPTER-7

MOLECULAR ELECTRONIC COMPONENTS

Development has been undertaken by several researchers on a variety of molecular electronic components for use in molecular circuits. Here, two particular components, aliphatic molecular insulators and diode switches, that in concept can be used with Tour wires to build the computational devices are focused on.

7.1. Aliphatic molecular insulators.

Aliphatic organic molecules have nodes in their electron densities above the atomic nuclei. For this reason, they cannot transport unimpeded electrical current when placed under a voltage bias. This enables aliphatic molecules or groups to act like resistors.

7.2. Diode switches.

A diode is a two terminal device in which current may pass in one direction through the device, but not the in the other direction, and in which the conduction of current may be switched on or off. Two important types of molecular-scale diode switches have been demonstrated: rectifying diodes and resonant tunneling diodes. Both are modeled after familiar solid-state analogies.

7.2.1. Rectifying diodes.

Rectifying diodes, also called molecular rectifiers, use structures that make it more difficult for an electric current to go through them in one direction, usually termed reverse direction from terminal B to A, than it is to go the opposite forward direction from A to B. Rectifying diodes have been elements of analog and digital circuits since the beginning of the electronic revolution. They have also had a role in the forming and testing of strategies for molecular scale electronics. In fact, the first theoretical paper on molecular electronics was a paper entitled Molecular Rectifiers by A. Aviram and M.A. Ratner that appeared in the journal Chemical Physics Letters in November 1974. But it was only in 1997 that, building on earlier experiments; two separate groups demonstrated practical molecular Department of ECE, VIT
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Molecular electronics rectifiers. R.M. Metzger at the University of Alabama led one group and the other led by M.A. Reed at Yale University.

Fig 7.1 Rectifying diodes.

7.2.2. Resonant Tunneling Diodes (RTDs).

Unlike the rectifying diode, current can pass easily in both directions through an RTD. The RTD uses electron energy quantization to permit the amount of voltage bias across the source and drain to control the diode so as to switch current on and off, and so as to keep electrical current going from the source to the drain. An experimental RTD of a working electronic device has been synthesized by Tour and demonstrated by Reed. The device is a molecular analog of a larger solid-state RTD that has commonly been fabricated in III-V semiconductors and used in solid state, quantum-effect circuitry.

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7.3. Advantages of polyphenylene-based structures.

With Polyphenylene-based molecules, it is relatively easy to propose complex molecular structures that are needed for digital logic and to know ahead of time that the needed structures can be synthesized. For their size, polyphenylene-based molecular devices conduct an impressive current of electrons. Tour-wire-based molecular digital logic has another advantage. Since polyphenylene-based molecules are so much smaller than carbon nanotubes, when electronic logic structures are finally synthesized and operated, they will represent the ultimate in digital electronic logic miniaturization. Any other structure will likely be as large or larger. It is unlikely that any working structure will be smaller.

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CHAPTER-8

REALIZATION OF BASIC CIRCUITS

8.1. Molecular AND and OR gates using diode-diode logic.

The circuits for the AND and OR digital logic gates which use diode-diode logic structures have been known for decades. Molecular logic gates constructed from the selected diode molecule would measure about 3 nm x 4 nm. That area is about one million times smaller than would be the area of a corresponding semiconductor logic element.

Fig 8.1 Symbol of AND gate.

Fig 8.2 Symbol of OR gate.

8.2. Molecular XOR gates using molecular RTDs and molecular rectifying diodes.
To make a NOT gate with diodes, we need to use resonant tunneling diodes. Using a ReedTour molecular RTD and two polyphenylene-based rectifying diodes, an XOR gate measuring about 5 nm x 5 nm can be built. The three switching devices used are built with polyphenylene-based Tour wire backbones.

Fig 8.3 Symbol of XOR gate.

8.3. Molecular electronic half adder.

With a complete set of molecular logic gates, larger structures can be made that implement higher binary digital functions. An electronic half adder can be built using Tour wires and Department of ECE, VIT
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Molecular electronics molecular AND and XOR gates and measuring only 10 nm x 10 nm. When currents and voltages representing two addends are passed through the molecular half adder, they will be added electronically. The half adder will have two inputs that split the current introduced so that the current passes through both of the logic gates regardless of which input receives the current. Results from the AND and XOR gates are delivered to separate outputs.

Fig 8.4 Half adder circuit.

By using an out-of-plane connector structure, an in-plane molecular wire can be passed over making it possible to connect the gates. Even though the input to each molecular lead is split, signal loss should not be a problem because the signal is recombined on the output side of the structure. A three-methylene aliphatic chain resistor can be embedded in the output lead to help minimize signal loss.

8.4. Molecular electronic full adder.

By combining two half adders plus an OR gate, you can make a molecular electronic full adder measuring about 25 nm x 25 nm.

Fig 8.5 Full adder circuit. Department of ECE, VIT

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Molecular electronics

8.5. Combining individual devices.

By bonding together existing functional devices, it is thought that devices of higher functions can be made. But when put together, these individual molecular devices will not behave as they do by themselves. The characteristic properties of each device will in general be altered by the quantum wave interference from the electrons in the devices. It is expected that Fermi levels will be affected as well. Software is being developed to deal with quantum mechanical issues so that complete molecular electronic circuits may be understood and built.

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Molecular electronics

CHAPTER-9

APPLICATIONS OF MOLECULAR ELECTRONICS

Molecular electronics has wide range of applications in the work areas of chemistry, Physics, electronics and nano electronics, technology, artificial intelligence and medical equipments. Molecular electronics seeks to be the next technology in the electronics industry where molecules assemble themselves into devices using environmentally friendly and low cost fabrication techniques. It goes beyond the limitations of rigid silicon-based solutions. It implements one or a few molecules to function as connections, switches, and other logic devices in future computational devices. Molecular electronics can be used in emerging technologies ranging from novel optical discs based on bistable biomolecules to conceptual design of the computers based on molecular switches and wires. Almost all the fabricated chips in the intelligent machinery that is used on large scale has molecular electronics involved in its construction. For example resistors and transistors that are used in producing electricity, capacitors in space crafts, automation circuits of robots, strategic plant temperature handlers and CT scan for displaying the infected areas of body. STM and AFM both have molecular electronics involved in their construction. In the field of chemistry it is used to see the chemical reactions in stimulated models of nuclear reactors, and also for measuring the acidic and reactive properties of individual element.

9.1. In CPU design.

The processing speed of existing computers is limited by the time it takes for an electron to travel between devices. Molecular electronics-based computation addresses the ultimate requirements in a dimensionally scaled system: ultra dense, ultra fast and molecular-scale. By the use of molecular scale electronic interconnects, the transmittance times could be minimized. This could result in novel computational systems operating at far greater speeds than conventional inorganic electronics. The design of a molecular CPU can bring great technical renovation in computer science. Department of ECE, VIT
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Molecular electronics

Table 1 shows the main differences between the present bulk electronic devices and the proposed molecular electronic devices.

Table 1 Main characteristics of bulk and molecular CPU circuits. Novel molecular electronics would approach the density of ~1013 logic gates/cm2. It offers a 105 decrease in the size dimensions compared to the present feature of a silicon-based microchip. In addition, the present fastest devices can only operate in nanosecond while the response times of molecular-sized systems can reach the range of femtoseconds. Thus, the speed may be attained to a 106 increase. On the basis of these estimates, a 1011 fold increase in the performance can be expected with molecular electronics, which offers an exciting impetus for intense research and development though numerous obstacles remain.

9.2. Switch using moltronics.

Benzene ring of six carbon atoms along with a few hydrogen atoms thrown in as well is held together in part by a pi bond-a sort of smeared bond in which some of the electrons are loosely shared by all the atoms in a kind of cloud that circles above and below the carbon ring. Its not a broken bond. Instead, its a sort of bond within which electrons are somewhat more able to move. By changing the structure of the molecule, the researchers found that they were able to alter its behavior. They hung molecular fragmentsan NH2 group and an NO2 groupfrom the middle benzene ring. This distorted the electron cloud, making the molecule more susceptible to twisting. By applying a voltage to the molecule, for example, they could cause a - change, a bend or a twist in the molecule. This disrupted the flow of electrons. And, this Department of ECE, VIT
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Molecular electronics twist was reversible. When the voltage was removed, the molecule returned to its original shape, allowing current to pass through once again. In other words, this molecule can act as a switch. It turns electricity on and offa basic characteristic that a computer needs to process information in bits of 1 and 0.

9.3. Memory chip.

Data storage is done by multiporphyrin nanostructures into electronic memory. The application of a voltage causes the molecules to oxidize, or give up electrons. The molecules then retain their positive charge after the electric field is removed, producing a memory effect.

Fig 9.1 Architecture for a proposed molecular memory.

9.4. Memory hold time.

Silicon memory devices retain charged bits for only a millisecond before the charge leaks away. That means that each piece of information must be restored ten to a hundred times a second, which requires substantial amounts of power.

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Molecular electronics Moletronics device retains its electrons for about nearly fifteen minutes. It has the ability to get the information in and out of the systems and using significantly less power.

Fig 9.2 Circuits with 64 bit molecular memory observed at increased magnification.

Voltage pulse yields high conductivity state data bit stored.

Bit is read as high in low voltage region.

Fig 9.2 Molecular random access memory cell.

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CHAPTER-10

NATURE OF MOLECULAR ELECTRONICS

10.1. Advantages of molecular electronics.
Molecular structures are very important in determining the properties of bulk materials, especially for application as electronic devices. The intrinsic properties of existing inorganic electronic materials may not be capable of forming a new generation of electronic devices envisioned, in terms of feature sizes, operation speeds and architectures. However, electronics based on organic molecules could offer the following advantages:

Size - Molecules are in the nanometer scale between 1 and 100 nm. This scale permits small devices with more efficient heat dissipation and less overall production cost to be made.

Power - One of the reasons that transistors are not stacked into 3D volumes today is that the silicon would melt. The inefficiency of the modern transistor is staggering. It is much less efficient at its task than the internal combustion engine. The brain provides an existence proof of what is possible; it is 100 million times more efficient in power/calculation than our best processors. Sure it is slow (under a kHz) but it is massively interconnected (with 100 trillion synapses between 60 billion neurons), and it is folded into a 3D volume. Power per calculation will dominate clock speed as the metric of merit for the future of computation.

Assembly - One can exploit different intermolecular interactions to form a variety of structures by the array of self-assembly techniques which are reported in the literature. The scope of application of the self-assembly technique is only limited by the researchers ability to explore.

Manufacturing cost - Many of the molecular electronics designs use simple spin coating or molecular self-assembly of organic compounds. The process complexity is embodied in the Department of ECE, VIT
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Molecular electronics synthesized molecular structures, and so they can literally be splashed on to a prepared silicon wafer. The complexity is not in the deposition or the manufacturing process or the systems engineering. Much of the conceptual difference of nanotech products derives from a biological metaphor: complexity builds from the bottom up and pivots about conformational changes, weak bonds, and surfaces. It is not engineered from the top with precise manipulation and static placement.

Low temperature manufacturing - Biology does not tend to assemble complexity at 1000 degrees in a high vacuum. It tends to be room temperature or body temperature. In a manufacturing domain, this opens the possibility of cheap plastic substrates instead of expensive silicon ingots.

Stereochemistry - A large number of molecules can be made with indistinguishable chemical structures and properties. On the other hand, many molecules can exist as distinct stable geometric structures or isomers. Such geometric isomers exhibit unique electronic properties. Moreover, electronic properties of conformers can be affected by pressure and temperature. We can therefore make use of stereochemistry to tune properties.

Synthetic flexibility - Organic synthesis is extremely versatile. It provides the means to tailor make molecules with the desired physical, chemical, optical and transport properties. The multitude of electronic energy levels in molecules can be fine-tuned by simple variations in molecular structure, e.g., by changing substituents on aromatic rings in conjugated compounds. Moreover, derivation of a molecule can lead to improving the processibility of the material without changing the device properties. This allows an entirely new dimension in engineering flexibility that does not exist with the typical inorganic electronic materials.

10.2. Disadvantages of molecular electronics.

Cost - Molecular electronics is not at all cost effective. Complete fabricated components developed by it are quite expensive and their maintenance cost is also high.
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Molecular electronics Complex operation - This technology is not easily understandable. For proper knowledge, the basic concepts of nanotechnology and nano electronics must be studied first. Difficult error recovery - Difficult error recovery because of high integration at smallest scale, it is hard to detect the physical error in the device. Lack of availability Since the components have high manufacturing cost, its components are not readily available. Need of experts - Specialized engineers and scientists are required to handle and control the risks factors of molecular electronics.

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CHAPTER-11

FUTURE OF MOLECULAR ELECTRONICS

The drive toward yet further miniaturization of silicon-based electronics has led to a revival of efforts to build devices with molecular-scale organic components. However, the fundamental challenges of realizing a true molecular electronics technology are daunting. Controlled fabrication within specified tolerances and its experimental verification are major issues. Self-assembly schemes based on molecular recognition will be crucial for that task. Ability to measure electrical properties of organic molecules more accurately and reliably is paramount in future developments. Fully reproducible measurements of junction conductance are just beginning to be realized in labs at Purdue, Harvard, Yale, Cornell, Delft, and Karlsruhe Universities and at the Naval Research Laboratory and other centers. Working molecular electronic devices exist today. Research progress is steady and strong, giving us cause to believe that molecular electronic systems may be practical in five to ten years. If lithography reaches fundamental physical or economic limits, molecular electronics may allow us to continue observing Moores Law. Regardless, molecular bottom-up fabrication could give us a much better alternative, whose price would depend mainly on design and test cost, instead of billion-dollar factories. Challenges to making this reality are plentiful at every level, some naturally in physics and chemistry, but many in ICCAD. These include fabricating and integrating devices, managing their power and timing, finding faulttolerant and defect-tolerant circuits and architectures and the test algorithms needed to use them, developing latency-tolerant circuits and systems, doing defect-aware placement and routing, and designing, verifying and compiling billion-gate designs and the tools to handle them. Any one of these could block practical molecular electronics if unsolved. Many of these are challenges that will be faced regardless of the underlying technology. Molecular electronics provides a pure and extreme example, and strengthens the case for solving them sooner rather than later.

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Molecular electronics Robust modeling methods are also necessary in order to bridge the gap between the synthesis and understanding of molecules in solution and the performance of solid-state molecular devices. In addition, the searching of fabrication approaches which can couple the densities achievable through lithography with those achievable through molecular assembly is also a great challenge. Controlling the properties of molecule-electrode interfaces and constructing molecular-electronic devices that can exhibit signal gain are also crucial to the development of the field.

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CHAPTER-12

CONCLUSION
Molecular electronics clearly has the advantage of size. It is the future of electronic devices. The components of these circuits are molecules, so the circuit size would inherently range between 1 to 100 NM. Molecular systems, or systems based on small organic molecules, possess interesting and useful electronic properties. The rapidly developing area of organic or plastic electronics is based on these materials. The Investigations of molecular systems that have been performed in the past is influencing the growth of molecular electronics. This in turn is paving the way for fresher discoveries and innovations. Molecular electronics is now being seen as an indispensible tool for producing miniature electronic circuits. This has led to the development of a variety of physical and chemical innovations. The potential application of molecular electronics has already attracted the interest of system developers. Hence, the transition towards molecular electronics has already started. Molecular electronics can revolutionize the technological world as we know it today. Once the technology of molecular electronics becomes fully implemented, we can expect innovations in every field of electronics.

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