iv

ACKNOWLEDGEMENT

With thankful heart I express my gratitude to my research supervisor

Dr.C. Muthamizhchelvan Director (Engineering &Technology), for his

positive approach, drive and dedicated guidance that brought me thus far until

the completion of this work.

It is my pleasure and proud privilege to place on record my gratitude to

the management of SRM University for creating a conducive atmosphere for

pursuing research. In particular, I thank our Chancellor, Dr.T.R.Pachamuthu,

President, Prof.P.Sathyanarayanan, for the Pilot Project Scheme, that funded

to procure the simulation tool which aided this work to be possible. I also

thank Vice Chancellor, Dr. M. Ponnavaikko and Pro Vice Chancellor,

Dr.T.P. Ganesan for their motivation and support.

I thank Dr. D. Narayana Rao, Director (Research) and Dr. Kasmir

Raja, Dean (Research), and Dr. P.K.A. Muniswaran, Director (OFD) for

their help and encouragement.

My special thanks to Dr. T. Pradeep, Professor, Department of

Chemistry, IIT Madras and Dr. R. Jayavel, Director, Centre for Nanoscience

and Nanotechnology, Anna University for their directed thoughts and eye

opening suggestions provided for the progress of this work.

My sincere thanks to Dr. S. Balakrishnan and Dr. P. S. Reddy for

their timely help and support.

 v

It is my duty to thank Dr. S. Malarvizhi, Professor and Head,

Department of ECE and all faculty members both teaching and non teaching

for lending a cheerful help whenever required. I wish to thank

Dr. S. Jayashri, the then head of ECE department for her initial efforts and

inspiration towards this work.

I am indebted to thank Dr. D. John Thiruvadigal, Professor and Head,

Department of Physics & Nanotechnology for his wholehearted help

throughout the period of my research and Mrs. C. Preferencial Kala for the

timely help.

Thank you is a too small word to express my gratitude to my family

members, especially to my little children J. Rhema & J. Rishon for their

moral support.

Above all I thank the almighty because every good gift and every

perfect gift comes down from the father of light. Marvelous are His works.

How great is the sum of them!

Place: KATTANKULATHUR Signature of the Scholar

Date: P.ARUNA PRIYA

 vi

ABSTRACT

During the last few decades semiconductor based computational power

doubled every eighteen months as predicted by Intel co-founder G. Moore.

This rapid growth is mainly based on an increase in the number of transistors

per unit area and an increase of clock speed. If this trend in miniaturization

was to be continued, the size of electronic components would reach the

molecular scale within ten years.

If top-down approaches in fabricating electronic devices as used in the

semiconductor industries for last few decades are adopted for further down

scaling, quantum phenomena such as tunneling cannot be avoided and the

control of doping is also problematic in the ultra small nano scale devices.

Even if these problems might be overcome, a strong increase of processing

and fabrication costs appears inevitable.

Hence, it is natural to suggest building up electronic components with a

bottom-up approach. Nowadays many researchers are exploring new device

architectures, to be built by bottom-up techniques and have received great

attention in recent years. Molecular electronics is believed to be one of the

very potential technologies in nano scale regime beyond the limit of silicon

technology.
 vii

There is a hope for the realization of circuit elements, built from such

systems which outclass today’s electronic circuits with respect to both

efficiency and miniaturization. This is still a field of intense fundamental

research, the reason being the impact on the measured conductance properties

due to both the chemical nature of the molecule and its bonding to the lead

surfaces is not consistently understood. Because of this lack of understanding,

intense theoretical studies go along with the experiments. The ultimate aim of

this work is to correlate the molecular electronic structure with the conduction

properties in a predictive manner, which would be a crucial step towards a

directed design of molecular electronic devices.

The first chapter of the thesis deals with the motivation of the research

work. We have listed the limitations of the top down approaches and the need

for bottom up approach. We have discussed the various approaches to

fabricate nano scale devices with elaborate explanation of the molecular

electronics. We have explained how the molecule is sandwitched between two

electrodes and how this configuration can be partitioned to be represented

mathematically. Theoretically this separation is useful to be treated by

quantum chemical method.

In the second chapter the theoretical methods that are adopted for

modeling the system is detailed. We start with the schrodinger equation which

helps to represent the molecule on the Hamiltonian form and how the energy

levels are described. We analyse how the Fermi energy of the molecule is
 viii

determined and the significance of the electro chemical potential (Fermi level)

for a single molecule. When the molecule is attached to the contact it does not

remain neutral but picks up a fractional charge which shifts the Fermi level up

or down. In this chapter we also note the molecular energy levels like HOMO

& LUMO are involved in charge distribution. The theoretical model to

simulate electron flow through the molecular device, developed in this work is

explained in detail.

The third chapter of this thesis is dedicated to show how the

conductance properties of a molecular electronic device are influenced by

change in geometrical alignment of the molecule bridging the electrodes. We

present the modeling results due to variation in the attachment of the leads to

the molecules. The effect of isomers has profound impact on electrical

properties of the device. Significant properties are noted when the charging

parameter is varied the transport challenges faced in the molecular device is

addressed in detail.

The fourth chapter is directed to model the conductance at the interface.

We start the analysis with a simpler case of varying the distance between the

molecule and the gold contacts. The results shows transmission is changed or

reduced as the distance is changed. The molecule is not directly attached to the

electrodes but rather through linkers. We have analysed the influence of

different linkage on transport properties. The result shows that the interface

between the gold electrodes and the linkage also called anchors plays a vital
 ix

role in the electrical characteristics. The results are discussed. This chapter

also deals with asymmetric or non linear characteristics of the molecular

junction. The device which shows a ohmic behavior produced non-linear

characteristics when the coupling at the junction is non symmetrical.

The fifth chapter is devoted to the application of the model to simulate

few simple molecular devices in electronics industries. The goal of molecular

electronics is to fabricate nano device conductors, diodes, rectifiers, memory

devices & switches that are equivalent to semiconductor devices. We have

simulated these devices to prove that the existing semiconductor technology

can be replaced by molecular devices. These theoretical results will contribute

to the design and fabrication of molecular electronics devices in future.

The sixth chapter summarizes the results of the present investigations

and also suggests the possible work that can be continued further. The results

of the above investigation have been published in the international journals

and also presented in various national and international conferences.