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Khatana Gurjar
Khatana Gurjar
CHAPTER 1
INTRODUCTION
Molecular electronics, also called moletronics, is an interdisciplinary subject that spans chemistry, physics and materials science. The unifying feature of molecular electronics is the use of molecular building blocks to fabricate electronic components, both active and passive. The concept of molecular electronics has aroused great excitement, both in science fiction and among scientists. This is because of the prospect of size reduction in electronics which is offered by molecular-level control of properties. Molecular electronics provides means to extend Moores Law beyond the foreseen limits of small-scale conventional silicon integrated circuits. Molecular Electronics is recognized as a key candidate to succeed the silicon based technology once we have arrived at the end of the semiconductor roadmap. The use of organic molecules in nano scale nonlinear circuits offers many opportunities for new types of devices, which will differ in fabrication, functionality, and architecture Molecular electronics involves the study and application of molecular building blocks for the fabrication of electronic components.[1]. The concept of molecular electronics is not new in the field of technology and science. its core concepts were originated with the concept of nano electronics. In 1997 the first ever theory for the moelcular electronics was given by by Mark Reed and co-workers. Its one of the important discpline that provides us way for dealing with all the electronic characteristics of conductors ,insulators and semi conductors .molecular electronics has two sub disciplines[1] molecular materials for electronics molecular scale electronics
Both of them collectively give high tech and ultra intelligent devices to be used in various kind of applications.This field is progressing rapidly and supporting nano electronics in order to develop excellent applications. Molecular electronics is a poorly defined term. Some authors refer to it as any molecular-based system, such as a film or a liquid crystalline array. Other authors, including Tour J. M., prefer to reserve the term molecular electronics for single-molecule tasks, such as single molecule-based devices or even single molecular wires. Due to the broad use of this term, molecular electronics are split into two related but separate subdi sciplines by Petty M. C.molecular materials for electronic utilizes the properties of the molecules to affect the bulk properties of a material, while molecular scale electronics focuses on single-molecule applications.[1] Molecular electronics represent the ultimate challenge in device miniaturization. Molecular devices can have any no of termini with current-voltage responses that would be expected to be nonlinear due to intermediate barriers 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
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techniques have been demonstrated to assemble nanometer wide wires into large arrays. Programmable and non-volatile devices which hold their state in a few molecules or in square nanometers of material have been demonstrated[1]. This idea was tested by a 1974 paper entitled Molecular Rectifiers by Mark Ratner and Ari Aviram.7 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 has 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, in 1988, Aviram described in detail a theoretical single-molecule field-effect transistor.8 Further concepts were proposed by Forrest Carter5 of the Naval Research Laboratory, including single-molecule logic gates. These were all theoretical constructs and not concrete devices. The direct measurement of the electronic characteristics of individual molecules has to wait for the development of new techniques which are capable of making reliable electrical contacts at the molecular scale. This was not an easy task. The first experiment measuring the conductance of a single molecule was only reported in 1997 by Mark Reed and co-workers. Since then, the development of nano-scale measuring techniques has progressed rapidly and the theoretical predictions of the early workers have mostly been confirmed. Rapid progress in molecular electronics has been made in the last three decades owing to advent of new characterization techniques[1]. Molecular electronics is a branch of applied physics which aims at using molecules as passive or active electronic component. These molecules will perform the functions currently performed by semiconductors In the natural word moleculse are used for many purpose.Using molecule based materials for electronics sensing and optoelectronics is a new endeavor called molecular electronics and the subject both of riveting new research and substantial popular press interest[1].
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HISTORY OF MOLETRONICS
1950s- INVENTION OF TRANSISTOR 1956- ARTHUR VON GAVE IDEA ABOUT MOLECULAR ENGINEERING 1960s & 1970s- EXPERIMENTS ALL AROUND THE WORLD 1981-STM INVENTED (FIRST TOOL TO PROVIDE ABILITY TO SEE AT A[1]
The microelectronics and computer revolution arguably is one of the most important technological advancement of our times, one that has drastically changed the way we work and live. The success of the microelectronics industry is attributed in large parts to our ability to shrink the transistor size in complementary metal-oxide semiconductor (CMOS) integrated circuits down to an ever smaller dimension (currently at 60 nm). This increasing miniaturization has allowed an exponential growth in computing power as the number of transistors in integrated circuits doubles every 18 months. This is the famous Moores law However, as the size of the transistor[2]
Figure 1.2: Schematic diagram of a Field Effect Transistor (N-type shown here)
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CHAPTER 2
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: Compared to CMOS, the use of molecules in Molecular electronics offers a number of advantages. Organic molecules are extremely diverse and their behaviors can be tailored by chemical synthesis. There is also a great potential for a bottom-up approach to manufacture integrated circuits using self-assembly. While it is becoming prohibitively expensive to fabricate Si of increasingly smaller dimensions due to stringent environmental conditions, self-assembly and chemical synthesis are relatively cheaper to perform. More importantly, because of their small size, very dense circuits could be built. As all molecules of one type are identical, they should also have identical characteristics, thus avoiding the present problem of variability in components.[3]
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. Molecular Electronics is a way to extend Moores Law past the limits of standard semiconductor Circuits.[3]
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.[3]
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 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
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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[3].
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CHAPTER3
MOLECULAR ELECTRONIC SYSTEMS
In order to perform as an electronic material, molecules need a set of overlapping electronic states. These states should connect two or more distant functional points or groups in the molecule. A conjugated orbital system is required for a typical candidate of molecular electronics. This conjugated system needs to extend on an -framework with terminal functional groups. Molecules for electronic applications generally have 1-, 2-, or 3-dimensional shapes as depicted which provides stable connection of the material to the metallic electrodes or inorganic substrates, is the caudal functional group of the organic electronic material. It is important to note that each part of an organic molecule used as the active component in nano scale electronic device has their own contribution. In general, by measuring the conductivity of a series of systematically modified molecules, the contribution of each component can be determined. For example, by varying the molecular alligator clip.[4]
surface metal clusters. The number of reported surface active organ sulfur compounds and their derivatives that form monolayers on gold include, di-n-alkyl sulfide, di-n-alkyl disulfides, thiophenols, thiophenes, mercaptopyridines, mercaptoanilines, xanthates, cysteines,thiocarbamates, thiocarbaminates, thioureas, mercaptoimidazoles, ditellurides and alkaneselenols. SAMs of alkanethiolates on Au surfaces are the most studied and well understood[4] .
Figure 3.1 Representative alligator clips for forming SAMs. 1,2-dioctyldisulfane (a); bis(4,4biphenyl)ditelluride (b); benzenethiol (c); benzene-1,4-dithiol (d); S-phenylethanethioate (e); S,S-1,4-phenylene diethanethioate (f); 4,4-biphenyl selenoacetate (g); phenyl isocyanide (h);1,4-phenylene diisocyanide (i); 2-nitro-1,4-bis(phenylethynyl)benzene diazonium tetrafluoroboride (j)
as a low resistance bridge between the two contacts. Instead of flowing through the molecule, electrical current tends to pass through the low-resistance bridge. More recently,proposed a metal-free system in which the two sides of a molecular monolayer attached to single-crystal silicon and a mat of single-walled carbon nanotubes, respectively Figure .Such a design eliminated the metal nanofilaments effect and switching property was observed under an applied field.[5]
(a)
(b)
Figure 3.2 (a) Metal-molecule-metal junction with metal nanofilaments effect. (b) Carbon nanotube-molecule-silicon junction. Therefore it is critical to understand the correlation of the interface energy levels which demands both theoretical and experimental study. A relevant consideration involves how the chemical nature of the molecule-electrode interface affects the rest of the molecule. The zero-bias coherent conductance of a molecular junction may be described as a product of functions that describe the molecules electronic structure and the molecule-electrode interfaces. However, it is likely that the chemical interaction between the molecule and the electrode will 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. There is little doubt that the molecular and interface functions must be considered in tandem in theoretical studies.[5]
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backbone, the polyphenylene backbone, is not the most conductive and the most conductive, the carbon nanotube, is not the most flexible chemically[7].
Figure 4.1: Carbon nanotube field effect transistor (a) bottom gate (b) top gate Source
4.2 Nanowires
Nanowires are wires of thickness in the range of nanometers. Semiconductor nanowires (GaP, GaN, Si, InP) have been produced for use in electronics. The common technique for the synthesis of nanowires is Vapour-Liquid-Solid growth Just like solid-state Si, semiconductor nanowires can be doped chemically to give p- and n-nanowires. Employing the same principles as the Unlike carbon nanotubes which can be semiconducting or metallic, inorganic nanowires are always semiconducting. Another advantage is the relative ease at which Si-nanowires can be integrated into the current silicon industry process and fabrication. Moreover, nanowire FETs have been found to respond faster than conventional MOSFET One disadvantage is the high cost of large-scale production of nanowires FETs.[8]
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Figure 5.1: Various techniques to measure electronic properties of molecules. (A) Hg drop junction. (B) Mechanically controlled break junctions. (C) Nanopore. (D) Nanowire. (E) Nanoparticle bridge. (F) Crossed wires.(G) STM. (H) Contact CP-AFM. (I) Nanoparticle coupled CP-AFM.
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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 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.[11]
Figure 6.1 A perposed molecular switch based on molecular stereochemistry rather than a external gate
6.2.1 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. Moletronic 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 [11].
Figure 6.3 Circuits contacting 64 bit molecular observed at increasing magnification power. Compared to, say, current equipment, which only runs for a few hours before the batteries wear out, Reed says, machines using molecular memory could run for a week. Theres an energy structure that explains how long a device either silicon, or molecular will hold electrons. They leak out at a certain rate and when you go to a molecular structure, the energies become much bigger. So the leak-out rate is slower.[11]
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While these currents are small in absolute magnitude, their densities are enormous. As many as one trillion electrons per second pass through a single square nanometer each second in these monomolecular semiconductors. Using appropriate nanoscale units, the current density through[12]
Figure 7.1 Programmable/erasable polyphenylene-based switch used by Yale-Rice-PS Moletronics team in molecular RAM cell(a) porphyrin multi-bit memory cell by UCRiversideNCSU Moletronics team(b) ruthenium-based dimer being used in efforts
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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.[14]
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Here it can be pertinent to mention the functioning of p-n junction. 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 Mobilities are seen to be low in molecular organic materials. Polymers took 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 pn junction diode, with rectification ratios in excess of thousands[15] 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[15]. There are recent reports of n-type organic semiconductors. This behavior is found when T N C Q (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.[15] Recently, pure semi conducting polymers have channeled into display devices. These conjugated with improved impurity have shown very strong photoluminescence. The most exciting news is the possibility that conjugated polymers would be used to manufacture LEDs out of plastic. This has immense application computer and TV screens.To provide pixelled large area flat screen displays, two stumbling blocks, which are yet 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 till date, the maximum life of polymer LEDs is reported to be only 1000 hrs.Organic materials have not being able to compete with silicon or inorganic materials to form active electronic devices. Moreover, the materials to be studied, if at all, are yet to be finalized. But there is a worldwide trend towards organics, at least in research areas.
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CHAPTER 10 CONCLUSION
Molecular electronics is an exciting emergent field of study. The reward of research in this area is enormous as the birth of molecular computer implies unprecedented processing power that may enable breakthroughs in artificial intelligence. This paper has given a glimpse at how such an endeavor might be accomplished by introducing the basic ideas in molecular device implementation and electrical characterization methods. The path towards a full working system is still a long one, yet the prospects are bright and great strides have been taken. Even a lot of approach has been proposed in moletronic computer. But there still exists critical problem: most of the technologies are valid only in laboratory condition, and cannot be produced massively
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REFERENCES
1 http://www.ctcase.org/bulletin/16_4/moletronics.html 2 http://seminarprojects.net/t-molecular-electronics-full-report 3 http://seminarprojects.com/s/advantages-of-moletronics 4 http://en.wikipedia.org/wiki/Molecular_scale_electronics 5 http://www.alcatel-lucent.com/bstj/vol05-1926/articles/bstj5-4-555.pdf 6 en.wikipedia.org/wiki/Molecular_electronics 7 www.personal.reading.ac.uk/~scsharip/tubes.htm 8 www.personal.reading.ac.uk/~scsharip/tubes.htm 9 ieeexplore.ieee.org ... Applied Physics Letters 10 www.ruf.rice.edu/~natelson/theses/ward_thesis.pdf 11 http://www.wifinotes.com/nanotechnology/what-is-molecular-electronics.html 12 www.lorentzcenter.nl/lc/web/2012/.../info.php3?. 13 seminarprojects.net/q/advantages-and-disadvantages-of-moletronics 14 mitre.org/work/best_papers/00/ellenbogen_arch/99W0207.pdf 15 www.sigmaaldrich.com/content/dam/.../material_matters_v4n3.pdf
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