MOLECULAR ELECTRONICS

By Ganesh Ram 11MNT0034

Molecular Electronics
Molecular electronics or moletronics, involves the study and
application of molecular building blocks for the fabrication of electronic components.

This includes both bulk applications of conductive polymers as well

as single-molecule electronic components.

New and emerging technology.

Use of different states of a molecule for information storage - basis
of molecular electronics.

Why Molecular Electronics?

Size - The size scale of molecules is between 1 and 100 nm, a scale that permits functional nanostructures. Manufacturing - One can exploit specific intermolecular interactions to form structures by nanoscale self-assembly. Dynamic Stereochemistry - Many molecules have multiple stable isomers with distinct optical and electronic properties Synthetic tailorability - The tools of molecular synthesis are highly developed. Flexible. Biodegradable.

Classification
Molecular Materials for Electronics - Utilizes the unique
properties of a molecule to affect the bulk properties of a material.

Examples: Commercial products LCD, OLED & Plastic electronics.

Molecular Scale Electronics - Uses single molecules, or nanoscale

collections of single molecules, as electronic components. Examples: Molecular Switch, DNA electronics.

Molecular Memory Structures-Possibilities

Molecules have many unpaired spins can be aligned parallel or anti-parallel state to preferred spin orientation.
(+) (-) 0 1

Some molecules exist in trans and cis configurations. Reversible configuration change can serve as binary memory.

Trans 0

Cis 1

Molecular Memory Structures-Possibilities

Another possibility is donor - acceptor bridge complex. The donor is in reduced state before transfer and afterwards in oxidized state which can be used for binary representation.

Reduced 0

Oxidized 1

Charge Transport Mechanism

A linear Chain, or alkane: One electrode functions as an electron donor and the other as an electron acceptor and are bridged by alkane. Rate constant for electron transfer KET=Ae-l where, - energy dependent parameter & l - bridge length. When voltage is applied, current through the junction decreases exponentially with increasing chain length, and the alkane serves as a simple energy barrier.

PROCEEDINGS OF THE IEEE, VOL. 87, NO. 4, APRIL 1999

A donor-bridge-acceptor (DBA) molecule: The donor and acceptor sites are part of the molecule and is separated by a bridge that has molecular orbitals of differing energy. Electron-type superexchange - electrons tunnel from the right electrode into the acceptor state when a bias is applied may coherently transfer to the donor state before tunneling to the left electrode. Hole-type superexchange - the tunneling from the molecule into the left electrode might occur first, followed by refilling of the molecular level from the right.

PROCEEDINGS OF THE IEEE, VOL. 87, NO. 4, APRIL 1999

A molecular quantum dot system: Model for investigating molecule - electrode interactions and quantum effects in charge transport through molecular junctions. Molecules contain a principal functional group that bridges two electrodes. Fractured gold wire that forms a pair of electrodes. The transport is dominated by the single metal atom contained in the molecule.

PROCEEDINGS OF THE IEEE, VOL. 87, NO. 4, APRIL 1999

 An organic molecule with several different functional groups bridge the electrode gap. The molecule shown is a rotaxane, which displays a diverse set of localized molecular sites along the extended chain. Red and Green sites provide positions on which the sliding rectangular unit (blue) can stably sit. Another example of a complex molecule bridge - short DNA chain.

PROCEEDINGS OF THE IEEE, VOL. 87, NO. 4, APRIL 1999

Mechanism of Electronic Conduction

Two types of processes required for conduction. Charge transport along the chain - Possible if pseudo particles(particle like excitations of various kinds) like solitons and polarons are formed.

Negative Soliton

Positive Soliton

Negative Polaron

Positive Polaron

Charge transport between the chains - Variable range hopping mechanism.

Conducting Polymers, Wiley & Sons Ltd, USA

Molecular Semiconductors for application in organic electronics

n-Type Semiconductors
Name
7,7,8,8-Tetracyanoquinodimethane (TCNQ), 98%

Structure

2,3,5,6-Tetrafluoro-7,7,8,8tetracyanoquinodimethane 97% Perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA), 97%

N,N-Dipentyl-3,4,9,10-perylenedicarboximide (PTCDI-C5), 98%

Chem. Rev. 2007, 107, 953;

p-Type Semiconductors
Name 2,2:5,2-Terthiophene, 99% Structure

3,3-Dihexyl-2,2:5,2:5,2quaterthiophene, 95%

3,3-Didodecyl2,2:5,2:5,2quaterthiophene, 97%

Dibenzotetrathiafulvalene, 97%

Chem. Rev. 2007, 107, 953;

Molecular Self Assembly

Devices

Organic Field Effect Transistor

OFET is a field effect transistor using an organic semiconductor in its channel. Developed to realize low-cost, large-area electronic products and biodegradable electronics. Device geometry - Bottom gate with top drain and source electrodes. Organic polymers (like PMMA) as dielectric.

Device Preparation
Thermally oxidized silicon - substrate for OFETs where the silicon dioxide serves as the gate insulator. The active FET layer is deposited onto this substrate using either (i) thermal evaporation, (ii) coating from organic solution, or (iii) electrostatic lamination. The first two techniques result in polycrystalline active layers easier to produce, but poor transistor performance. Electrostatic lamination - Manual peeling of a thin layer off a single organic crystal, results in a superior single-crystalline active layer. The thickness of the gate oxide and the active layer is below one micrometer.

Journal of Sci. Technol. Adv. Mater.,2009, 10 (2): 024314.

Merits of OFETs
OFETs, has high carrier mobility. The operation of the device depends on the ratio of layer thickness
and depletion length, which is smaller in the organics than in Si due to the smaller dielectric constant.

Mechanical flexibility > Si based FET

Scalable to smaller sizes Cost effective

Organic Light Emitting Diode

An OLED is a light-emitting diode (LED) in which the emissive electroluminescent layer is a film of organic compound. Layer of organic semiconductor material is between two electrodes. One of these electrodes is transparent. OLEDs are used to create digital displays in devices such as television screens, computer monitors & gaming consoles. There are two main families of OLEDs: those based on small molecules and those employing polymers. OLED display works without a back light.

Device Geometry
OLED is composed of a layer of organic materials situated between two electrodes, the anode and cathode, deposited on a substrate. However multilayer OLEDs can be fabricated with two or more layers in order to improve device efficiency. Many modern OLEDs incorporate a simple bilayer structure, consisting of a conductive layer and an emissive layer. Commonly used device architectures: Graded Heterojunction, Stacked OLED, Inverted OLED Graded Heterojunction improves quantum efficiency.

Applied Physics Letters 97: 083308.

Advantages
Less expensive to produce Light weight and flexible plastic substrates Wider viewing angle Improved brightness Better power efficiency

Future of Electronics
Timeframe
Now

Product
Flat screen displays

Comments
Phones and digital cameras
Low speed applications Biological Computers & general devices Solar Cells Requires significant advances in processing

1-5 years

Disposable soft Circuitry (TFTs) Sensors Soft-solid memory Soft-solid photovoltaics

5-10 Years

>10 Years

Nanoelectronics Spintronics

Challenges: The fundamental challenges of realizing a true molecular electronics technology are daunting. Controlled fabrication to within specified tolerancesand its experimental verificationis a particular problem. Robust modelling methods required to understand the performance of solid-state molecular devices. Challenges involve finding fabrication approaches that can couple the densities achievable through lithography with those achievable through molecular self assembly. Controlling the properties of moleculeelectrode interfaces and constructing molecular electronic devices that can exhibit signal gain are also problems
Physics Today 2003; 43-49

Future of Molecular Electronics

Future of Molecular Electronics

Rapid progress is being made to address these challenges. Voltage-gated, single-molecule devices may emerge as the highresolution spectroscopy tool that will eventually link experiment and theory. Nanowire field-effect transistors have demonstrated gain and so the challenge may be one of integration of multiple device types rather than discovery of new devices.

Physics Today 2003; 43-49

References
1. 2. 3. 4.

5.

James Heath and Mark Ratner. Molecular electronics. Physics Today, 2003; 43-49. Mark Reed. Molecular Scale electronics. Proceedings of the IEEE, Vol. 87, No. 4, April 1999. Shirota, Y; Kageyama, H. Chem. Rev. 2007, 107, 953; Tatsuo Hasegawa and Jun Takeya. "Organic field-effect transistors using single crystals". Sci. Technol. Adv. Mater. 10 ,2009 Holmes, Russell; Erickson, N. Highly efficient, single-layer organic light-emitting devices based on a graded-composition emissive layer. Applied Physics Letters 97: 08330

Thank You