Graphene based Field E ect Transistor and its

Application

A thesis submitted in partial ful llment of the requirements for the

award of the degree of

M.Tech.

in

CSE (V.L.S.I.)

by

Arvind Tyagi
(2012-VLSI-04)

under the guidance of

Dr. Anurag Srivastava

ATAL BIHARI VAJPAYEE

INDIAN INSTITUTE OF INFORMATION
TECHNOLOGY AND MANAGEMENT
GWALIOR-474015
2014
 Checklist

# Items Declaration
1. Is the thesis/report bound as speci ed? Yes No
2. Is the Cover page in proper format as given in Annexure 1 of Yes No
guidelines
for thesis preparation?
3. Is the Title page (Inner cover page) in proper format? Yes No
I. Is the Certi cate from the Supervisor in proper format? Yes No
4.
II. Has it been signed by the Supervisor?
I. Is the Abstract included in the thesis/report properly written Yes No
5. within
400 to 600 words?
II. Have the technical keywords (not more than six) speci ed
properly?
6. Have you included the List of Abbreviations/Acronyms in the the- Yes No
sis/report?
7. Does the thesis/report contain a summary of the literature Yes No
survey?
Does the Table of Contents include page numbers? Yes No
I. Are the Pages numbered properly? (Chapter 1 should start on
page number 1)
8.
II. Are the Figures numbered properly? (Figure Numbers and
Figure Titles should be only at the bottom of the gures)
III. Are the Tables numbered properly? (Table Numbers and
Table Titles should be only at the top of the tables)
IV. Are the Titles for the Figures and Tables proper and sources
ac- knowledged?
V. Are the Appendices numbered properly? Are their titles
appropriate?
9. Have you incorporated feedback received during various stages of Yes No
evalu-
ation?
10. Is the Conclusion of the thesis/report based on discussion of the Yes No
work?
I. Are References or Bibliography given at the end of the Yes No
11. thesis/report?
II. Have the References been cited properly inside the text of the
the- sis/report?
III. Is the citation of References in proper format?
12. Is the thesis/report format and contents are according to the Yes No
guidelines?

ii
 Candidate Declaration
I hereby certify that I have properly checked and veri ed all the items as
pre- scribed in the checklist and ensure that my thesis is in proper format as
speci ed in the guideline for thesis preparation.
I also declare that the work containing in this report is my own work.
I, understand that plagiarism is de ned as any one or combination of the
following:

1.To steal and pass o (the ideas or words of another) as one's

own 2.To use (another's production) without crediting the

source

3. To commit literary theft

4. To present as new and original an idea or product derived from an

existing source.

I understand that plagiarism involves an intentional act by the

plagiarist of using someone else's work/ideas completely/partially and
claiming author- ship/originality of the work/ideas. Verbatim copy as well as
close resemblance to some else's work constitute plagiarism.
I have given due credit to the original authors/sources for all the words,
ideas, diagrams, graphics, computer programmes, experiments, results,
websites, that are not my original contribution. I have used quotation marks
to identify verbatim sentences and given credit to the original
authors/sources.
I a rm that no portion of my work is plagiarized, and the experiments
and results reported in the report/dissertation/thesis are not manipulated.
In the event of a complaint of plagiarism and the manipulation of the
experiments and results, I shall be fully responsible and answerable. My
faculty supervisor(s) will not be responsible for the same.

Signature:

Name: Arvind Tyagi

iii
Roll No.: 2012-VLSI-04
Date: 12-May-2014

iv
 Thesis Certi cate
I hereby certify that the work, which is being presented in the thesis,
entitled Graphene based Field E ect Transistor and its Application, in
ful lment of the requirement for the award of the degree of Master
of Technology and submitted to the institution is an authentic record of my
own work carried out during the period June-2013 to May-2014 under the
supervision of Dr. Anurag Srivastava. I also cited the reference about the
text(s)/ gure(s)/tables(s) from where they have been taken.

Dated: 12-May-2014 Signature of the Candidate

This is to certify that the above statement made by the candidate is

correct to the best of my knowledge.

Dated: Signature of the Supervisor

v
 Abstract
Over the last few decades, the size of eld e ect transistor have been
continuously decreasing, causing the number of transistors per chip to
increases in accordance with Moore's law. The process has caused all
aspects of the silicon CMOS tran- sistor to scale downward in size,
including not only the devices in length and width but also thickness of
gate dielectric. The use of Si in device manufacturing is reaching its
fundamental limitations including scaling limitation and thereby mobility
issue.
Thus in this era of smaller and smarter devices, the researchers have started
their venture of searching of an alternative for Si in Nano electronics. If not
an alter- native then at least as a prospective material for future Nano
electronics, Here graphene has attracted the attention of many due to its
superior mobility, excel- lent thermal conductivity, availability and low cost.
Graphene being regarded as a "miracle material" has proved itself to be a
probable replacement of Si in Nano- scale device manufacturing as being cut
into Nano-meter size layers; the mobility remains high even at room
temperature. An absence of a proper band gap in graphene making it
impossible to turn the conduction o in graphene device, puts graphene-
based device manufacturing under scrutiny.
The present thesis aims to analyse the graphene based eld e ect transistor de-
vices and possible application. All the analysis is performed using systematic
ab-initio approach that relies on density function theory using GGA
approxima- tion. A computational analysis of GFET with varying metal
electrodes (Al, Ag, Au, w, Pt) and dielectric substrates (SiO2, Hf O2,
Al2O3, Ta 2 O 3 , Y2O3) has been done which presents the comparative study of
GFET using di erent dielectric ma- terials as substrate and metal electrodes
as gate terminal. This transistor consist of two metal electrodes (source and
drain) and a graphene layer which acts as a conduction channel between these
two metal electrodes. A number of metal elec- trodes (i.e. Ag, Au, w, Pt) as
well as dielectric substrate materials are examined to analyse the GFET
behavior in terms of conductance and current. The analy- ses resulted in the
most optimized dielectric and metal electrode combination for GFET.
Next graphene is used as a gas sensing application. For this purpose we
have analysed the electronic and transport properties of graphene in order
vi
to sense the presence of gases in the environment. After that sensing properties
like adsorption

vii
energy, charge transfer between molecule and graphene sheet are calculated. And
nally for improving the sensing performance of the device various dopant
and defect techniques like boron, nitrogen, silicon, cobalt and iron are
used.

Keywords-Graphene ,Moleculer adsorpsion, Gas sensor, doping, radio fre-

quency, contact resistance

viii
 Acknowledgement
I am highly indebted to Dr.Anurag Srivastava and obliged for giving
me the autonomy of functioning and experimenting with ideas. I would like
to take this opportunity to express my profound gratitude to him not only for
his academic guidance but also for his personal interest in my report and
constant support cou- pled with con dence boosting and motivating sessions
which proved very fruitful and were instrumental in infusing self-assurance
and trust within me. The nur- turing and blossoming of the present work is
mainly due to his valuable guidance, suggestions, astute judgement,
constructive criticism and an eye for perfection. My mentor always answered
myriad of my doubts with smiling graciousness and prodigious patience,
never letting me feel that I am novices by always lending an ear to my
views, appreciating and improving them and by giving me a free hand in my
report. It's only because of his overwhelming interest and helpful attitude,
the present work has attained the stage it has.

Finally, I am grateful to our Institution and colleagues whose constant

encour- agement served to renew my spirit, refocus my attention and energy
and helped me in carrying out this work.

Date: 12-May-2014 Arvind Tyagi

ix
Contents

Abstract...............................................................vi
List of Figures.........................................................x
List of Abbreviations................................................xiii
List of Symbols......................................................xiv

1 Introduction1

2 Motivation3

3 Literature Review4
3.1 Related work.......................................................4
3.1.1 Graphene metal contact.................................5
3.1.2 Graphene FET for high frequency application........5
3.1.3 Focus on gate dielectric...................................6
3.2 Graphene as a gas sensor application..........................8

4 Objectives11

5 Methodology12

6 Results and Discussions14

6.1 Analysis with di erent type of metal electrode...................15
6.1.1 Tungsten electrode...........................................16
6.1.2 Gold electrode.................................................17
6.1.3 Silver electrode...............................................18
6.2 Analysis for Ag electrode with edge doped di erent metal
ele- ment(Fe,Co,Ni)
20
6.2.1 By using single edge doped with Co.....................20
6.2.2 By using single edge doped with Fe.....................21
6.2.3 By using single edge doped with Ni.....................22
6.2.4 By using both edge doped with Ni......................24

x
 6.3 Doping of di erent elements at central edge......................26
6.4 Graphene based HCN Sensor: Ab-intio Analysis...........29
6.5 Graphene based ammonia Sensor: Ab-intio Analysis.........33
6.6 Sensing properties of Graphene................................35
6.7 Improving Sensing performance of Graphene by dopant and defect39

7 Conclusion44

References46

xi
List of Figures

1.1 Important milestones of the evolution of graphene electronics[1].1

3.1 Textbook topology of a Si MOSFET.........................4

3.2 Structure of Graphene FET.......................................5

6.1 Structure of BASIC GFET....................................14

6.2 Variation of conductance with temperature for GFET............15
6.3 Structure of GFET with tungsten electrode...................16
6.4 Variation of conductance with temperature for GFET with
tung- sten electrode
16
6.5 Structure of GFET with gold electrode.........................17
6.6 Variation of conductance with temperature for GFET with
gold electrode
17
6.7 Structure of GFET with silver electrode.......................18
6.8 Variation of conductance with temperature for GFET with
silver electrode
18
6.9 variation of conductance with T for GFET with silver electrode,Hf
O2 dielectric.............................................................19
6.10 comparison of conductances of GFET using di erent metal electrodes19
6.11................................................................St
ructure of GFET with silver electrode and one edge doped with
Co
20
6.12................................................................V
ariation of conductance with T for GFET. Ag electrode, one
edge doped with Co
20
6.13 Structure of GFET with silver electrode and one edge doped with Fe21
6.14...............................................................pl
xii
 ot of conductance with T for GFET with Ag electrode,one edge
doped with Fe.....................................................21
6.15 Structure of GFET with silver electrode and one edge doped with Ni22
6.16................................................................V
ariation of conductance with T with Ag electrode, one edge
doped with Ni
22
6.17.................................................................pl
ot conduction with T. Ag electrode, HFO2 dielectric, one edge
doped with Ni
23

xii
i
6.18 Comparison of Conductances using di erent doping at single edge23
6.19................................................................St
ructure of GFET with silver electrode and both edge doped
with Ni
24
6.20................................................................V
ariation of conductance with T. Ag electrode, both edge doped
with Ni
24
6.21.................................................................C
onductance with T. Ag electrode, Hf O2 dielectric, both edge
doped with Ni
25
6.22.................................................................C
omparison of Conductances using doping at di erent number
of edges
25
6.23................................................................St
ructure of GFET with silver electrode and central edge
doped with boron.
26
6.24.................................................................V
ariation of Conductance with temp. for central edge doped
by boron atom.
26
6.25.................................................................St
ructure of GFET with silver electrode and central edge
doped with nitrogen.
27
6.26..................................................................V
ariation of Conductance with temp. for central edge doped
by nitrogen atom.
27
6.27.................................................................St
ructure of GFET with silver electrode and central edge
doped with Phosphorus.
28
6.28 Comparison of Conductances using di erent doping at central edge.28

xiv
6.29.................................................................Schematic of
pristine Graphene sheet..............................................30
6.30.................................................................schematic of
Graphene sheet in HCN environment...............................30
6.31.................................................................Band Structure of
pristine Graphene sheet..............................................31
6.32 Band Structure of Graphene sheet in presence of single HCN molecule31
6.33.................................................................B
and Structure diagram for Graphene sheet presence of
double molecules of HCN
31
6.34 comparision of conductance with di erent number of HCN molecules32
6.35.................................................................I-V characteristics
of pristine graphene sheet...........................................32
6.36.................................................................I-
V characteristics of pristine graphene sheet presence of single
HCN molecule
32
6.37.................................................................I-
V characteristics of pristine graphene sheet presence of single
HCN molecule
32
6.38................................................................Schematic of
Graphene sheet in ammonia environment........................33
6.39.................................................................B
and Structure of Graphene sheet in presence of single ammonia
molecule
33
6.40................................................................B
and Structure of Graphene sheet in presence of two
ammonia molecules
34

xv
6.41 Conductance of Graphene sheet for di erent number of NH 3 molecules34
6.42 Current vs Electrode biasing for di erent number of NH3 molecules34
6.43................................................................St
ructure of Graphene with three di erent adsorption sites, the
center of Hexagon (C), Top of a carbon atom (T), middle of
a C-C bond (B).....................................................35
6.44.................................................................St
ructure of graphene with H2S, S atoms pointing to the the
surface (u)
35
6.45.................................................................St
ructure of graphene with H2S, S atoms pointing away from
the surface (d)
36
6.46.................................................................H2
S on graphene: the adsorption energy (Ea), the distance of
H2S above the graphene surface (d), and the charge transfer
from the molecule to graphene (Q) for six di erent geometries.
36
6.47.................................................................St
ructure of graphene with CO, O atoms pointing away from
the surface (u)
37
6.48.................................................................St
ructure of graphene with CO, O atoms pointing away from
the surface (d)
37
6.49.................................................................C
O on graphene: the adsorption energy (Ea), the distance of
CO above the graphene surface (d), and the charge transfer
from the molecule to graphene (Q) for seven di erent
geometries.
37
6.50.................................................................St
ructure of graphene with NO, O atoms pointing away from
the surface (u)
38
6.51.................................................................St

xvi
 ructure of graphene with NO, O atoms pointing away from
the surface (d)
38
6.52.................................................................N
O on graphene: the adsorption energy (Ea), the distance of
NO above the graphene surface (d), and the charge transfer
from the molecule to graphene (Q) for six di erent geometries.
38
6.53 Schematic of graphene with NH 3 , N atoms pointing to the surface39
6.54 Top view of graphene with NH 3, N atoms pointing to the surface40
6.55.................................................................Schematic of
graphene with NH3 and defect...................................40
6.56.................................................................Schematic of
graphene with NH3 and boron doping...........................41
6.57.................................................................Schematic of
graphene with NH3 and nitrogen doping.........................41
6.58.................................................................Schematic of
graphene with NH3 and silicon doping...........................41
6.59.................................................................Schematic of
graphene with NH3 and cobalt doping...........................42
6.60.................................................................Schematic of
graphene with NH3 and iron doping..............................42
6.61................................................................. N
H 3 on graphene: the adsorption energy (Ea), the distance of
NH 3 above the graphene surface (d), and the charge transfer
from the molecule to graphene (Q) for seven di erent
geometries.
43

xvi
i
List of Abbreviations

MOSFET Metal-oxide-semiconductor eld-e ect

transistor GFET Garphene eld e ect transistor

G Graphene

DG Doped Graphene

SIG Silicon doped Graphene

ALG Aluminium doped

Graphene SS Subthreshold

Slope

HCE Hot carrier e ects

xvi
ii
List of Symbols

Cox Gate oxide capacitance

L Gate length
q charge
µ Mobility
ND Doping concentration
tsi Thickness of the silicon
ID Drain Current
Wsi Width of the device
VT thermal voltage
∈si permittivity of
Si VT H Threshold
Voltage VG Gate
Voltage
VDS Drain Source Voltage
∈ permittivity of oxide
ox
tox Thickness of oxide
gm Transconductance
fT Cuto frequency
Cgs gate-to-source capacitance
Cgd gate-to-drain capacitance
gm/Ids Transconductance-to-drain current ratio
Rc Contact Resistance

xix
Chapter 1

Introduction

Graphene is a two dimensional, one atom thick crystal of carbon ordered

in a hexagonal honeycomb structure. Graphene has been a scienti c thought
experi- ment ever since the 1940. However for decades single layer of
graphene did not exist because it was thermodynamically unstable. This
viewpoint remains till the single layer of graphene was found out in 2004
[1].

Figure 1.1: Important milestones of the evolution of graphene electronics[1]

charge carrier mobility of graphene is very high in the order of

1,000cm2/Vs even at room temperatures. Where charge carrier mobility of
doped Si is only 1,000cm2/Vs [7]. From analysis of electronic properties of

1
graphene it was found

2
that the valance and conductance bands touches eachother at the Dirac
cone, which shows its ambipolar conduction capabilities (i.e. the ability to
conduct both holes and electrons). graphene is considered to exhibit one of
the highest charge carrier mobility of all materials. Its intrinsically high
mobility makes it a promising material for ultrafast electronics operating in
THz frequencies. How- ever, as of today, using graphene for logic devices
is still a problem [4,7].
As state above, the valance and conductance bands of graphene meet at the
Dirac point, which means that single layer graphene is a semimetal with no
band gap. Modulating the source drain current using the gate voltage in
graphene eld e ect transistor simply shifts the Fermi energy from allowing
hole conduction to allow- ing electron conduction and vice versa, with no
band gap in between. Graphene transistor thus has very low on/o current
ratio.in e ect the transistor is unable to turn o . Attempts to create a band
gap in graphene are still being investigated [5].
Graphene has a zero-bandgap it means switched from on state to o state is
not possible. The de ciency of a band gap is major problem, if graphene is
utilized in logic circuits application in the same way as now a days silicon is
utilized as the material in complementary metal oxide semiconductor logic
circuits. Nonetheless, the zero band gap of large area graphene is not an
issue in all applications. One such example is radio frequency (RF)
applications, where having no energy gap is not an issue. Not only the
Transistors eld but also graphene can be utilized in other elds like sensor
applications, graphene is used as a sensing material very accurately by using
some dopant and defect techniques.Graphene can be used as thin lm
electrodes, as photodetector to name a few. The most studied graphene
transistor today is the graphene eld-e ect transistor (GFET). The
operation principle of a GFET is based on the ambipolar electric eld e
ect in one and few- layer graphene . The ambipolar eld e ect is due to a
small overlap in the valence and conductance bands. The structure of a GFET
resembles that of silicon FETs. Electric eld is utilized to control the electric
current through the device [1,5,6].

3
Chapter 2

Motivation

Over the past ve decades, the size of eld e ect transistor have been
getting exponentially smaller, causing the number of transistor's per chip to
increase in accordance with Moore's law, the process has ca used all aspects
of the silicon CMOS transistor to scale downward in size, including not only
the devices length and width but also the thickness of the gate dielectric. As
the gate dielectric falls below about 1.3nm in thickness, direct electron
tunneling creates intolerable large leakage currents, essentially turning the
insulator transparent to electrons. The leakage current per transistor,
multiplied by the many millions of transistor's per chip.
In order to reduce transistor leakage current, researchers in both academic
and industry have looked beyond silicon altogether in search for ever
improved tran- sistor's in terms of size, speed and application. Organic
and polymer eld e ect transistors have uses in exible circuits and display
technologies. Yet its useful- ness in logic is limited since the highest
reported charge carrier mobility's have been well below 10cm2/Vs and
switching frequencies have been limited to about 1KHz. Carbon nanotubes,
which have charge carrier mobility's on the order of 10,000 cm2/Vs, have
been successfully used in eld e ect transistor as well but controlling all
the relevant nanotube characteristics, such as radius, chirality and doping
has thus remained an unsolved problem. When a carbon nanotube is "un-
rolled" it becomes graphene. Graphene retains many of the bene ts of
carbon nanotubes, including high charge carrier mobility's. thus, many
researchers are now focusing on graphene for high mobility eld e ect
transistor.

4
Chapter 3

Literature Review

The basis topology of any eld e ect transistor consists of a semiconductor,

source, drain, gate and gate dielectric. Graphene eld e ect transistors are
simply FETs with graphene as the conduction channel. The graphene rests on
some sort of insulator, such as SiC (if graphene is made by SiC
submilation) or SiO2 on top of a Si wafer. Unlike the textbook Si MOSFET,
where the source/drain contacts are doped into a bulk piece of Si. The
source/drain contacts for a graphene eld e ect transistor are usually thin
metal lms deposited directly onto the graphene itself [1]. A comparison of
the traditional Si eld e ect transistor topology and the graphene eld e
ect transistor topology shown in gure 2

Figure 3.1: Textbook topology of a Si MOSFET

3.1 Related work

Some works done in the selection of suitable metal electrode so that the
contact resistance between graphene metal interfaces is minimum hence we
get a higher conductance and large drive current for this various types of

5
metal electrode are taken into account and analyzing them we get silver
electrode gives higher value

6
 Figure 3.2: Structure of Graphene FET

of conductance [8,9,10].
Further study the choice of higher value of dielectric greatly improves the
transcon- ductance of the device. We use the di erent combination of metal
electrode and dielectric material so that the overall performance of the
device increases. we
ndout that Hf O2 gives better conductance result [3].

3.1.1 Graphene metal contact

Contact resistance of graphene can be measure by the several

methodologies in- cluding the transfer length, four-probe/two-probe, and
residual resistance meth- ods.we are using last two methods to measure the
contact resistance value.In contact resistance value share of graphene sheet
shoud be very low in order to better device performance [8, 9]. Adhesive
capability of Silver is excellent on SiO2 substrate or other insulators. Hence it
is used as metal electrodes in carbon- based devices [10].
Total resistance between two contacts is add up of semiconductor resistance,
con- tact resistance, and the metal resistance, where resistance of metal is
very low so it can be neglectedcan be neglected. Now if we deducting the
graphene resistance from the total resistance, than we get the total
contact resistance[8, 10].

3.1.2 Graphene FET for high frequency application

Due to the high vale of charge carrier mobility and saturation velocity
Graphene is very useful in high speed electronics application.But the on/o
current ratio of GFET (graphene eld e ect transistor)is very low because
7
graphene has zero bandgap thus it can not be used in logic device
application [5]. There is de ciency

8
of techniques that can be open a sizable gap without degrading the electronic
prop- erties of graphene. But still graphene is very useful material in some
appliction like radio frequency (r.f.) electronic applications because in r.f.
application there is not need of large on/o ratio[4,7].
For high-performance r.f. applications, FETs should answer rapidly to the
gate voltage (Vg), which needs short gates. Scaling of gate length (Lgate) of
graphene FETs has been experimentally determined, it is noted that the
intrinsic cut-o frequency (fT ) of graphene is reciprocal of gate length.
Wich means when the gate length is decreases than intrinsic cut-o
frequency (fT ) is increases.And also if the intrinsic cut-o frequency (fT ) is
increases than the speed of the device increases[16].

3.1.3 Focus on gate dielectric

For reliable high performance devices, the interface between the conduction
chan- nel and the gate dielectric must have minimal interface trap densities (i.e.
dangling bonds) and minimal carrier scattering (to maximize mobility).
Eventually, it was found that thermally grown SiO2 provided the best gate
dielectric semiconductor interface due to the fact that thermal SiO2 is
produced when O2 incorporates into, rather than onto, a Si wafer. It was
partially because of SiO2 that the electronic device industry adopted Si
[2].
Thus, the choice of gate dielectric will greatly impact the behavior of
graphene based FETs. Unlike traditional FETs with a Si conduction
channel, FETs with a graphene conduction channel will not have the option
of growing a gate dielectric such as SiO2,necessitating the deposition of a
dielectric onto graphene. Experi- ence from Si technology development show
that deposited dielectrics usually have problematic interface layers. Charge
trapping a ects carrier mobility and often shifts transistor threshold
voltages [1].
The choice of dielectric material and deposition technique can potentially greatly
a ect the performance of graphene based FETs. There are three types of
solid state electronic materials: conductors, semiconductors, and insulators.
In a con- ductor, electrons can move freely from one atom or molecule to

9
another, thereby allowing charge carriers to conduct current. In contrast, a
dielectric is an elec-

1
trical insulator in which the opposite is true. Electrons in a dielectric can
only move within, rather than between, atoms and molecules (unless the charge
carrier traverses a large band gap). This forces the electrons to stretch and
rotate to form dipole moments, causing the dielectric material to become
polarized under an applied electric eld. The extent to which a material
becomes polarized is a physical property of the material and is
quantitatively captured by its dielectric constant [7].
Dielectrics are commonly used as the sandwich layer between the plates of a
par- allel plate capacitor. An external eld E causes the dielectric material to
polarize, creating a polarization eld P in the opposite direction of E,
thus e ectively decreasing the E eld in the dielectric. This in turn causes
an increase in the system's capacitance: for an air lled capacitor, C =
K∈0A/t, where ∈0 is the permittivity of free space. For a dielectric lled
capacitor, C = K∈0A/t, where K is the dielectric constant. In the MISFET
(metal-insulator-semiconductor FET) topology, a dielectricisusedasa sandwich
layer between the metal gate electrode and the semiconductor. This metal-
insulator-semiconductor capacitor is called the MIS capacitor for short. The
most common MISFETs are MOSFETs, where the insulator is SiO2.Hence the
name metal-oxide-semiconductor FET[6,7]. In the ideal situation, the
amount of charge that is induced to ow depends only on the capacitance of
the MIS-capacitor. Ignoring the e ects of the inversion capac- itance, the
inversion charge is represented by the basic capacitor equation Q = CV ,
with K ∈0 A/t. An increase in C will result in a larger Q and ultimately
result in a larger source-drain current even though other parameters are
held con- stant. However, in the physical MIS capacitor system, several non-
idealities exist. Accumulation of xed charge can shift the threshold gate
voltage, sometimes hys- terically. Film defects, charge traps at the dielectric
semiconductor interface, and various types of scattering mechanisms can
drastically reduce charge carrier mo- bility, causing the source-drain
current to drop [3].
For the past few decades, the scaling of Si technology has increased C by
de- creasing t. However, as t cannot be decreased without exposing the
system to further quantum tunneling, researchers are looking to increase C

1
by increasing K. Hence, the future of transistor technology will most likely
incorporate high-K di-

1
electric materials. It has been mentioned above that the use of a high-K
dielectric material for Si technology will aid in device performance by
increasing the FET current while holding other parameters (voltage, capacitor
area, dielectric thick- ness) constant. If instead a low-K material is used, then
either A would increase or t would have to decrease even more, neither of
which would be feasible for small, low-power circuits. However, it is
important to note that high-K materials have their drawbacks[3].
First, dielectric materials with larger atoms (such as Hf and Ti compared
to Si) generally tend to have larger higher dielectric constants, but the
tradeo is that these materials also have smaller band gaps. Smaller band
gaps would increase the probability of charge carrier tunneling, and this
problem will o set some of the high-K gains in increased physical thickness.
Second, it is now understood that the physical properties responsible for the
high K are likely to degrade carrier mobility, at least for Si MOSFETs .This
consequence is one major disadvantage of a high-K dielectric when
compared to SiO2 for silicon CMOS [3,6] circuitry.

3.2 Graphene as a gas sensor application

Graphene is an ideal material for use as the channel material in eld e
ect tran- sistors because of its atness, high mobility charge carriers and
ballistic transport at the micron level. The absence of a band gap in its
electronic structure makes it impossible to turn of the FET which is a
shortcoming that needs to be overcome if one wants to use graphene FET's
for the usual applications in electronics. But for other applications of
graphene-based eld e ect devices (FED), such as gas sensors, this is a
less important issue [18].
To fully feat the hypothesis of graphene sensors, it is very crucial to realize
the interaction among a graphene surface and adsorbing molecules. The
adsorption process on graphene is examined for the di erent molecules that were
investigated in the experiment. The adsorption of single NH3, CO, NO and
NO2 molecules on a pure graphene substrate is studied within the DFT
formalism. The optimum adsorption positions and orientations of the
molecules on the graphene surface are examined and the adsorption
1
energies are calculated. Molecular doping, i.e. charge transfer between the
molecules and the graphene surface, is analyzed in

1
light of the molecular orbital theory [18, 19].
The use of graphene as very sensitive gas sensors has stimulated a lot of
theoret- ical work on this subject [18, 19, and 20]
Graphene can be well described as one-atom thick layer of graphite in which
all the carbon atoms are sp2-bonded that are densely packed in a
honeycomb crystal lattice. Due to its 2-D structure, its entire volume is
exposed to external environ- ment for the detection of adsorbed molecules.
Intrinsically graphene is insensitive due to lack of dangling bonds on its
surface. But it can be made sensitive by pas- sivizing with hydrogen atoms or
functionalizing it with thin lm of polymer. This thin layer helps in absorbing
gaseous molecules. Recently carbon based chemical sensors are regarded as
one of the most useful application because of their high- sensitivity to
many gas molecules like NH3, CO and NO2 etc. [21].
Graphene materials have been proved for the fabrication of gas sensors
because of their high electron mobility, excellent strength and low weight
[22].The mechanical cleavage method has been utilized for fabricating
graphene based carbon dioxide (CO2) gas sensor whose advantages are high
sensitivity, fast response time, short recovery time, and low power
consumption [23]. The sensing performance of a graphene gas sensor using
ozone treatment has been reported with nitrogen diox- ide (NO2) gas which
remarkably enhances the sensing performances in terms of percentage
response, detection limit and response time [24]. Doped graphenes with
silicon and aluminium atoms(SiG and AlG) have also been analysed to sense
toxic HCN which shows that electronic properties of AlG are more sensitive
to- ward adsorption of HCN molecules[25].
The interaction between hydrogen sulphite (H2S) and graphene has been
inves- tigated by density functional theory calculations which con rms the
that Ca, Co and Fe doped and defective graphene nanosheets show much
higher a nities to H2S molecule in comparison to pristine graphene [26]. The
adsorption of various gas molecules (H2, O2, H2O, NH3, NO, NO2, and CO)
on monolayer MoS2 has been investigated using ab-initio calculations in
which the most stable adsorption con guration, adsorption energy, and
charge transfer are obtained and it is shown that all the molecules are

1
weakly adsorbed on the monolayer MoS2 surface and act as charge
acceptors for the monolayer, except NH3 which is found to be a

1
charge donor [27]. On the other hand, the adsorption/desorption of
ammonia molecules on a graphene surface has also been investigated by
studying the Fermi level shift [28]. Not only pristine graphene sheet,
graphene based FET is also a promising nano-device as far as the sensing
application is concerned. Graphene can also be extensively used in bio-
sensors like glucose, Cyt-c, NADH, Hb, choles- terol etc.[29].
Our group has recently reported the work on electronic properties of
graphene nano ribbons and sheets having di erent widths [30]. Hydrogen
cyanide is a lin- ear molecule where the carbon atom is associated with
nitrogen through a strong triple bond and hydrogen. Plucking o the hydrogen
atom leaves the strongly re- active and negatively charged cyanide ion [31].
It is known to form strong bonds with metal and this property is utilized in
purifying gold from its ore. Another fact about hydrogen cyanide is that in
air it is extremely harmful for human body as about 3200 mg/m3 of
Hydrogen cyanide concentration in air will kill a human in just 60 seconds.
When cyanide ions present in the human body, it halts the cellular
respiration by acting as a monopolistic inhibitor for an enzyme in mito-
chondria called cytochrome c oxidase, which a ects the cellular nervous
system and causes death [32, 33].

1
Chapter 4

Objectives

The objective of this dissertation is to study the characteristics of the

graphene Field e ect transistor and present the application based on it. For
this purpose, Initially atomistix tool kit 11.2.2 is used for ab initio analysis of
graphene devices. After that a graphene FET will be designed and extract
the parameters in order to obtain the optimized graphene eld e ect
transistor devices.

1
Chapter 5

Methodology

Designing of graphene based eld e ect transistor.The source/drain contacts

for a graphene eld e ect transistor are usually thin metal lms deposited
directly onto the graphene itself. Then analysis the conductance and drive
current. Conduc- tance value is very low so for improving conductance
various techniques is used. First we are using di erent combination of metal
electrode and high-k dielectric material so we get improve value of
conductance results in next part we are use di erent types of doping such as
edge doping for further improve the conductance of device.

1. Structural and electrical analysis of graphene and its applications.

Tools required: Atomistix Tool kit
13.8.1 Analysis:-

(a) Band structure calculations

(b) Conductance and its dependence on temperature and
bias (c)Current analysis
(d)Applications

2. Designing of graphene Based Field e ect transistors.

Tools required: - Atomistic Tool kit
13.8.1 Analysis: -

(a) Driving Current Capability

(b)Dielectric Optimization
(c)Conductance Analysis

1
 (d)Source-Drain optimization

3. Designing of graphene based Field e ect transistor with edge doping of

dif- ferent metal element.
Tools required: - Atomistix Tool kit
13.8.1 Analysis:-

(a) Conductance and its dependence on temperature and

Bias (b)Current Analysis

4. Analysis the sensing properties of

Graphene Tools required: Atomistix
Tool kit 13.8.1 Analysis: -

(a) Adsorption energy (Ea)

calculations (b)Charge transfer
calculation

5. Analysis the dopant and defect e et on sensing performance of

Graphene Tools required: Atomistix Tool kit 13.8.1
Analysis: -

(a) Adsorption energy (Ea)

calculations (b)Charge transfer
calculation

2
Chapter 6

Results and Discussions

Figure 6.1: Structure of BASIC GFET

Computational Details

• The length of both the electrodes has been taken as 7.38 Angstroms.

• The length of the central region has been taken as 19.694 Angstroms.

• The dielectric thickness is 3.07 Angstroms while dilectric constant has

been taken di erently for di erent cases. (for this case,3.9εis used)

• the C-C bond distance is 1.42 Angstroms while C-H bond distance is
1.101 Angstroms.

These parameters are considered for almost all the analyses.

2
 Figure 6.2: Variation of conductance with temperature for GFET

Fig. 6.1 shows the Basic structure of graphene eld e ect transistor. In
GFET graphene is a semiconductor it acts as a conduction channel between
source and drain. SiO2 is taken as dielectric material. Fig. 6.2 shows the
variation of con- ductance with temperature it is noted value of
conductance is around 1.0e-06 S and maximum value of conductance is
1.30e-06 S. value of conductance is very low so for improving conductance
we are using some techniques.

6.1 Analysis with di erent type of metal electrode

In this section, the di erent electrodes have been analysed in order to
choose best electrode for the source and drain metal electrodes. We are
using di erent kind of metal electrode whose contact resistance with graphene
interface is minimum. Hence if contact resistance between graphene metal
contact is decreases than conductance is increases.

2
6.1.1 Tungsten electrode

Figure 6.3: Structure of GFET with tungsten electrode

Figure 6.4: Variation of conductance with temperature for GFET with

tungsten electrode

Fig. 6.3 we are using tungsten electrodes. Fig. 6.4 shows the variation of
conduc- tance with temperature. It is noted conductance value is not
improve in presence of tungsten electrode. Now we are using some other
metal electrode.

2
6.1.2 Gold electrode

Figure 6.5: Structure of GFET with gold electrode

Figure 6.6: Variation of conductance with temperature for GFET with gold
elec- trode

Fig. 6.5 shows the structure of GFET with gold electrodes. Fig. 6.6
Shows the variation of conductance with temperature. Conductance is
decreases with temperature because mobility of metal is decrease with
temperature. It is noted that conductance value is improved in presence
of gold electrode.

2
6.1.3 Silver electrode

Figure 6.7: Structure of GFET with silver electrode

Figure 6.8: Variation of conductance with temperature for GFET with

silver electrode

g. 6.7 shows the structure of GFET with silver electrodes. Fig. 6.8
shows the variation of conductance with temperature. It is noted silver
electrode gives the high value of conductance with variation of temperature
. Because contact resistance between silver graphene interface is
minimum.
In g. 6.9 We are using high-k dielectric material Hf O2, by using Hf O2 with
silver electrode conductance value is further improved. g. 6.10 shows the
comparison of conductance for di erent meatal electrode from comparison
plot it is clear silver gives maximum conductance.
2
Figure 6.9: variation of conductance with T for GFET with silver electrode,Hf
O2 dielectric

Figure 6.10: comparison of conductances of GFET using di erent metal electrodes

2
6.2 Analysis for Ag electrode with edge doped dif-
ferent metal element(Fe,Co,Ni)
In this analysis for further improve device conductance and drive current we
are using some doping techniques like one edge doping and both edge doping
and we are seen by using these doping techniques performance of device is
greatly improved.

6.2.1 By using single edge doped with Co

Figure 6.11: Structure of GFET with silver electrode and one edge doped
with Co

Figure 6.12: Variation of conductance with T for GFET. Ag electrode, one

edge doped with Co

Fig. 6.11 shows the structure of GFET with silver electrodes and one edge
doped with Co. Fig. 6.12 shows the variation of conductance with
temperature. It is noted by edge doping with Co conductance is not much
improve if we compare without edge doping.

2
6.2.2 By using single edge doped with Fe

Figure 6.13: Structure of GFET with silver electrode and one edge doped with Fe

Figure 6.14: plot of conductance with T for GFET with Ag electrode,one

edge doped with Fe

Fig. 6.13 shows the structure of GFET with silver electrodes and one edge
doped with Fe. Fig. 6.14 shows the variation of conductance with
temperature. It is noted by edge doping with Fe conductance value is
improve as compare to Co doping.

2
6.2.3 By using single edge doped with Ni

Figure 6.15: Structure of GFET with silver electrode and one edge doped with Ni

Figure 6.16: Variation of conductance with T with Ag electrode, one edge

doped with Ni

Fig. 6.15 shows the structure of GFET with silver electrodes and one edge
doped with Ni. Fig. 6.16 shows the variation of conductance with
temperature. It is observed by edge doping with Ni gives the best
conductanc result.So In furthur analysis we are using edge doping with Ni.

2
Figure 6.17: plot conduction with T. Ag electrode, HFO2 dielectric, one edge
doped with Ni

Figure 6.18: Comparison of Conductances using di erent doping at single edge

3
6.2.4 By using both edge doped with Ni

Figure 6.19: Structure of GFET with silver electrode and both edge doped
with Ni

Figure 6.20: Variation of conductance with T. Ag electrode, both edge doped

with Ni

Fig. 6.19 shows the structure of GFET with silver electrodes and both edge
doped with Ni. Fig. 6.20 shows the variation of conductance with
temperature. It is noted both edges doping with Ni signi cantly improved
the conductance value as compare to one edge doping.
Figure 6.22 shows the comparison of conductances of Graphene eld e ect
tran- sistor using silver electrodes and HfO2 as dielectric. With the analysis,
we can conclude that, proposed con guration with doping of Nickel at single
edge is less conductive than doping at both edge.

3
Figure 6.21: Conductance with T. Ag electrode, Hf O2 dielectric, both edge
doped with Ni

Figure 6.22: Comparison of Conductances using doping at di erent

number of edges

3
6.3 Doping of di erent elements at central edge.
By using Boron Edge

Figure 6.23: Structure of GFET with silver electrode and central edge doped
with boron.

Figure 6.24: Variation of Conductance with temp. for central edge doped
by boron atom.

Fig 6.23 shows the structure of GFET with silver electrodes and central edge
doped with boron. Fig. 6.24 shows the variation of conductance with
temperature. By using boron doping, number of holes in the valance band
increases, hence conductance increases.

3
By using Nitrogen Edge

Figure 6.25: Structure of GFET with silver electrode and central edge doped
with nitrogen.

Figure 6.26: Variation of Conductance with temp. for central edge doped
by nitrogen atom.

Fig 6.25 shows the structure of GFET with silver electrodes and central edge
doped with nitrogen. Fig. 6.26 shows the variation of conductance with
temperature. By using nitrogen doping, number of electrons in the
conduction band increases, hence conductance increases.

3
By using Phosphorus Edge
Fig 6.27 shows the structure of GFET with silver electrodes and central edge

Figure 6.27: Structure of GFET with silver electrode and central edge doped
with Phosphorus.

doped with phosphorus. Fig.6.28 shows the comparison of conductances of

GFET using silver electrode and central edge doped with boron, nitrogen and
phosphorus. It is clearly shown that doping with nitrogen atom gives the
highest conductance result due to higher mobility of electrons than holes.

Figure 6.28: Comparison of Conductances using di erent doping at central edge.

3
6.4 Graphene based HCN Sensor: Ab-intio Anal-
ysis
Graphene based gas sensor that shows remarkably di erent properties as a
result of gaseous environment near to Graphene surface. The electronic and
transport properties have been analysed in HCN environment. All the
analysis is performed using systematic ab-initio approach that relies on
density function theory using GGA approximation. Conductance analysis as a
function of temperature con rms that the conductivity of pristine graphene
sheet is much higher and it falls consid- erably even when a single molecule
of HCN comes in contact with the graphene surface. Experimental results
clearly show a considerable deviation in electronic properties of graphene
with changing gas environment. This validates the sensing capacity of
graphene sheet to act as a gas sensor for HCN presence in environ-
ment.
Computational Details

Present analysis has been performed on atomistic toolkit 13.8.1 (ATK-VNL).

ATK supports ab-initio study based on non-equilibrium greens function
(NEGF) and density function theory. The prime objective of this work is to
analyse the sens- ing ability of graphene sheet in gaseous environment.
Graphene sheet acts as conduction channel between two electrodes. The
schematic of device shown in g- ure (6.29) Using this device we obtained its
total energy, transmission spectrum, current-voltage characteristics,
conductance and its dependence on temperature.in next step, HCN molecules
has been attached at the graphene surface (shown in
gure(6.30)) and analysed the same electronic properties.
Result and Discussions

The conduction band and the valance band are overlapping each other in
case of pristine graphene sheet. Hence, shows the metallic behaviour of
graphene at room temperature.It can be observed from these plots that the
pristine graphene sheet is having an approximate zero band gap ( gure
6.31). Hence, it con rms the metallic behaviour of graphene sheet at room
temperature where as in the presence of single HCN molecule at the surface
of graphene sheet, the metallicity of the system decreases to the great
3
extent, shown in gure (6.32). Further on increasing the number of HCN
molecules, the metallic behaviour of graphene re-

3
duces completely. Like when the two HCN molecules comes closure to the
surface of graphene sheet, the metallic behaviour of graphene changes
completely in to the semiconducting, having an indirect band gap of
0.098 eV ( gure 6.33).

Figure 6.29: Schematic of pristine Graphene sheet

Figure 6.30: schematic of Graphene sheet in HCN environment

3
 Figure 6.31: Band Structure of pristine Graphene sheet

Figure 6.32: Band Structure of Graphene sheet in presence of single HCN molecule

Figure 6.33: Band Structure diagram for Graphene sheet presence of

double molecules of HCN

Hence HCN is one of the most poisonous gases, and the high sensitivity of
graphene sheet towards HCN plays an important role in its detection and
hence plays a vital role as far as the environment safety is concerned.

3
 Figure 6.34: comparision of conductance with di erent number of HCN
molecules

Figure 6.35: I-V characteristics of pristine graphene sheet

Figure 6.36: I-V characteristics of pristine graphene sheet presence of single

HCN molecule

Figure 6.37: I-V characteristics of pristine graphene sheet presence of single

HCN molecule

4
6.5 Graphene based ammonia Sensor: Ab-intio Anal-
ysis
For analysis the Graphene based ammonia sensor molecules of ammonia has
been attached at the graphene surface (shown in gure (6.38)) and analysed
the same electronic properties that are analysed for HCN sensor. A nite
bandgap exists between conduction band and the valance band in case of
graphene present in ammonia environment. This shows the decrease in
conductivity of the system at room temperature. From the band structure
and conductance we can conclude that in presence of ammonia gas molecule,
the forbidden energy gap increases and the metallic behaviour of graphene
sheet decrease

Figure 6.38: Schematic of Graphene sheet in ammonia environment

Figure 6.39: Band Structure of Graphene sheet in presence of single ammonia

molecule

As the number of molecule at the graphene surface increases, the metallic

be- haviour of the proposed device decreases and it changes in to
semiconductor From the current vs. electrode biasing
plot shown in gure (6.42), it can be analysed that graphene alone conducts

4
more current (i.e. 0 to 135 micro A) with the applied biasing voltage
(i.e. from 0 V to 1 V) at its electrodes. The

4
Figure 6.40: Band Structure of Graphene sheet in presence of two
ammonia molecules

Figure 6.41: Conductance of Graphene sheet for di erent number of NH3

molecules

Figure 6.42: Current vs Electrode biasing for di erent number of NH3 molecules

high current is attributed to its high conductance and zero band gap at
room temperature. In case of nanotube with single ammonia molecule
environment, the current limits to a comparatively narrow range (i.e.
from 0 to 75.7 micro
A) for the same biasing voltage (i.e. 0 V to 1 V). As the number of
ammonia molecules at the surface of graphene increases, the conductance
decreases, in turn current also decreases. The same behaviour follows for two
ammonia molecule at the nanotube surface (i.e. 0 to 62.7 micro A) too.
4
6.6 Sensing properties of Graphene

For each molecule there are three di erent positions are considered, First is
top of a carbon atom (T), the second is center of a carbon hexagon (C)
and the third is center of a carbon-carbon Bond (B) (see Fig.6.43). For
these places, di erent orientations of the molecules are determined. Then
for all the cases charge transfer between molecules (by using mullicun
population) and adsorption energy is computed. The adsorption energy (Ea) is
de ned here as the energy of the isolated graphene sheet and isolated
molecule minus the energy of the fully relaxed graphene sheet with The
molecule adsorbed to it.First examined the non- magnetic molecules CO and
H2S, than after examine the paramagnetic ones, NO and NO2.

Figure 6.43: Structure of Graphene with three di erent adsorption sites, the
center of Hexagon (C), Top of a carbon atom (T), middle of a C-C bond
(B)

H2S on graphene

Figure 6.44: Structure of graphene with H2S, S atoms pointing to the the
surface (u)

Two positions of the H2S molecule are examined, The rst is S atoms
pointing to the the surface (u) and the second is S atoms pointing away from

4
the surface (d).

4
Figure 6.45: Structure of graphene with H2S, S atoms pointing away from
the surface (d)

Figure 6.46: H2S on graphene: the adsorption energy (Ea), the distance of
H2S above the graphene surface (d), and the charge transfer from the
molecule to graphene (Q) for six di erent geometries.

CO on graphene
Three di erent positions were used for the CO molecule. In which Two
positions molecule perpendicular to the surface, like the C atoms below the
O atom (u) and C atoms above the O atoms (d), and in one position atoms
are parallel to the surface (n).
From table, it can be seen that the CO molecule always acts as a donor.
Charge transfer between molecule and graphene sheet is not much a ected
by the chang- ing of position of atoms it is only depends on the orientation
of the molecule. The charge transfer is highest in u orientation,smallest in d
orientation and interme- diate in n orientation.

4
Figure 6.47: Structure of graphene with CO, O atoms pointing away from
the surface (u)

Figure 6.48: Structure of graphene with CO, O atoms pointing away from
the surface (d)

Figure 6.49: CO on graphene: the adsorption energy (Ea), the distance

of CO above the graphene surface (d), and the charge transfer from the
molecule to graphene (Q) for seven di erent geometries.

4
NO on graphene
Three di erent positions are examined for the NO molecule. Two with the
molecule perpendicular to the surface, like the N atom below the O atom
(u) and N atom above the O atom (d),and in one position atoms are parallel
to the surface (n).

Figure 6.50: Structure of graphene with NO, O atoms pointing away from
the surface (u)

Figure 6.51: Structure of graphene with NO, O atoms pointing away from
the surface (d)

Figure 6.52: NO on graphene: the adsorption energy (Ea), the distance

of NO above the graphene surface (d), and the charge transfer from the
molecule to graphene (Q) for six di erent geometries.

4
6.7 Improving Sensing performance of Graphene
by dopant and defect

The interaction among ammonia NH 3 and graphene was determined using

den- sity functional theory method and nonequilibrium Greens function
method. The electronic properties of NH 3 graphene systems were analyze by
tuning up the ge- ometries of NH 3 molecule toward 2D nanosheets of pristine
( gure 6.53), defective ( gure 6.55) and doped graphene ( gure 6.56 to
gure 6.60). It was observed that Co and Fe doped and defective graphene
nanosheets show higher interaction to NH 3 molecule in comparison to pristine
graphene. The strong interactions among NH 3 and graphene nanosheets can
extend to dramatic alters the electronic and magnetic characterstics of
graphene. The electronic transport characterstics of Fe doped graphene
nanosheets show that the chemical sensors manufactured by ma- terials
could show more prominent sensibility for observing NH 3 gas, in compare
with the devices made with pristine graphene. It is possible to design NH3
chem- ical sensors with highly amended performances, using graphene
nanosheets as sensing materials with appropriate metal dopants or defects.
Each structure was fully relaxed, and the calculated adsorption energy, charge
transfer, and distance between the adsorbed molecule and the graphene
nanosheets are summarized in Table.

Figure 6.53: Schematic of graphene with NH3, N atoms pointing to the surface

In case of pristine graphene charge transfer between graphene and NH 3

which is zero. which veri es their weak interaction. The results expose that
the pristine graphene is una ected to NH 3 molecule.

4
 Figure 6.54: Top view of graphene with NH3, N atoms pointing to the surface

Figure 6.55: Schematic of graphene with NH3 and defect

For the graphene with defects, the adsorption energy of NH3 on the
defective graphene can reach -0.57 eV, which is more than four times
higher than that of the pristine graphene. The strong interaction should be
attributed to the presence of dangling bonds in the defective graphene caused
by the missed carbon atom. The con gurations for graphene doped with B
and N interacting with NH 3 were also studied. The adsorption energies for
the B−graphene and N−graphene are
-0.10 Ev and +0.11 eV, respectively, and these results further con rm that
they exhibit weaker bindings in comparison with the interaction between
NH 3 and pristine graphene of -0.14 eV. In contrast, the geometry of
graphene doped with Si the Ead of NH 3 on Si−graphene is found to be -
0.55 eV, which con rms that the Si graphene is more favourable for NH 3
adsorption than the pristine graphene.

In order to enhance the sensing performances of NH3 sensors NH3

molecule on the surface of graphene substituted with transition metal
atoms including Co and Fe. It was found that the two metal-doped
graphene can bind NH 3 molecule with adsorption energies of−1.42 and

5
−1.98 eV, respectively, which (Co and Fe) are more than one order of
magnitude higher than that of the pristine

5
 Figure 6.56: Schematic of graphene with NH3 and boron doping

Figure 6.57: Schematic of graphene with NH3 and nitrogen doping

Figure 6.58: Schematic of graphene with NH3 and silicon doping

5
Figure 6.59: Schematic of graphene with NH3 and cobalt doping

Figure 6.60: Schematic of graphene with NH3 and iron doping

5
graphene, and are also much higher than that of Si−graphene. The hybrids of

Figure 6.61: NH3 on graphene: the adsorption energy (Ea), the distance
of NH 3 above the graphene surface (d), and the charge transfer from the
molecule to graphene (Q) for seven di erent geometries.

transition metal-doped graphene are thus expected to exhibit highly

enhanced sensing ability for detecting NH 3 molecule, compared to pristine,
B−graphene, N−graphene and Si−graphene. Because absorption energy of
NH 3 molecule on the surface of Fe–graphene is the highest among the
metal/graphene, the NH3
/ Fe−graphene was thus compared to pristine, defect−and Si−graphene
systems for further understanding the electric and magnetic properties of doped
graphene. Though the above calculation suggests that the Si−graphene or
metal−graphene exhibit improved sensing properties than the pristine
graphene.

5
Chapter 7

Conclusion

Initially,several metal electrodes have been examined to minimize the contact

resis- tance between graphene metal interface. For this purpose,the metal
electrodes like tungsten (w), gold (Au), silver (Ag) etc. are used and from the
conductance plot, it can be concluded that silver is the most optimized
electrode for Graphene Filed E ect Transistor.So, for further analysis, the
silver electrode has been selected as permanent electrode for Graphene
Field E ect Transistor. After that,di erent dielectric materials have been
examined and it can be concluded from the electri- cal analysis that HFO 2 is
the best optimized dielectric for Graphene Field E ect Transistor in terms
of conductance. After these analyses, A device has been pro- posed with
using silver electrode and HFO 2 dielectric. This proposed device signi
cantly improves the conductance and driving current of the GFET device. For
further improving the performance,several doping techniques have been in-
vestigated like single edge and double edge doping with Iron (Fe), Cobalt
(CO), Nickel (Ni). In application part graphene is used as a gas sensing
application. An ab-initio study was performed on graphene in its pristine
state as well in HCN and ammonia gas environment. It was observed that
the graphene sheet shows metallic behaviour in terms of its energy band
gap. As the system enters in HCN and ammonia environment, the band gap
increases and system starts showing semiconducting behaviour. After that
sensing properties like adsorption energy, charge transfer between molecule
and graphene sheet are calculated. From sens- ing properties of graphene it
was observed that charge transfer is mainly in uence when the orientation of
molecules are changed. Charge transfer is not much af- fected by changing

5
the position of molecules. than nally improving the sensing

5
performance of the device for this purpose various dopant and defect
techniques are used like boron, nitrogen, silicon, cobal and iron dopant
techniques and than it is observe that graphene modi ed with Fe and defect
exhibit highly enhanced H2S sensing behaviors compare to pristine graphene
and other dopant techniques.

5
Bibliography

[1]A. K. Geim, "Graphene: Status and prospects," Science, vol. 324, no.
5934, pp. 1530-1534, Jun. 2009.

[2]P. Avouris, Z. H. Chen, and V. Perebeinos, "Carbon-based electronics,"

Na- ture Nanotechnology 2, 605-615, Apr. 2007.

[3]A. Javey, H. Kim, M. Brink, Q. Wang, A. Ural, J. Guo, P.

McIntyre, P. McEuen, M. Lundstrom, and H. Dai, "High-k dielectrics for
advanced carbon nanotube transistors and logic gates," Nat Mater, vol.
1, pp. 241-246, Jan. 2002.

[4]I. Meric, M. Y. Han, A. F. Young, B. Oezyilmaz, P. Kim, and K.

Shepard, "Current saturation in zero-bandgap, top-gated graphene eld-
e ect transis- tors," Nature Nanotechnology, March. 2008.

[5]I. Meric, N. Baklitskaya, P. Kim, and K. Shepard, "RF performance of

top- gated, zero- bandgap graphene eld-e ect transistors," in
IEEEInternational Electron Devices Meeting, Oct. 2008.

[6] Lemme, M.C., Echtermeyer, T.J. Baus, M.; Kurz, H. A, " graphene
eld- e ect device, " IEEE Electron. Dev. Lett. 2007, 28, 282-284.

[7] Castro Neto, A.H.; Guinea, F.; Peres, N.M.R.; Novoselov, K.S.; Geim,
A.K. The electronic properties of graphene. The electronic properties of
graphene.
Rev. Mod. Phys. 2009, 81, 109-162

[8] Nagashio, K.; Nishimura, T.; Kita, K.; Toriumi, A. Metal/Graphene

Con- tact as a Performance Killer of Ultra-high Mobility
Graphene—Analysis of Intrinsic Mobility and Contact Resistance.

5
Presented at the International Electron Devices Meeting, Washington
DC, USA, 7-9 December 2009.

5
 [9] Nagashio, K.; Nishimura, T.; Kita, K.; Toriumi, A. Contact resistivity
and current ow path at metal/graphene contact. Appl. Phys. Lett.
2010, 97, 143514:1-143514:3.

[10] Watanabe, E.; Conwill, A.; Tsuya, D.; Koide, Y.,"Low contact
resistance metals for graphene based devices.," Diam. Relat. Mater.
2012, 24, 171-174.

[11]R. Chau, S. Datta, M. Doczy, B. Doyle, B. Jin, J. Kavalieros, A. Majumdar,

M. Metz, and M. Radosavljevic, "Benchmarking nanotechnology for high-
performance and low-power logic transistor applications," IEEE Trans.
Nan- otechnol., vol. 4, no. 2, pp. 153-158, Mar. 2005.

[12]Y. M. Lin, K. A. Jenkins, A. Valdes-Garcia, J. P. Small, D. B. Farmer,

and P. Avouris, "Operation of graphene transistors at gigahertz
frequencies," Nano Lett., vol. 9, no. 1, pp. 422-426, Jan. 2009.

[13]P. A. Khomyakov, G. Giovannetti, P. C. Rusu, G. Brocks, J. van den

Brink, and P. J. Kelly, "First-principles study of the interaction and
charge transfer between graphene and metals," Phys. Rev. B, Condens.
Matter, vol. 79, no. 19, p. 195 425, May 2009.

[14]S. Koswatta, A. Valdes-Garcia, M. Steiner, Y.-M. Lin, and P. Avouris,

"Ulti- mate RF Performance potential of carbon electronics," IEEE Trans.
Microw. Theory Tech., vol. 59, no. 10, pp. 2739-2750, Oct. 2011.

[15]J. Chauhan, L. Liu, Y. Lu, and J. Guo, "A computational study of

high- frequency behavior of graphene eld-e ect transistors," J. Appl.
Phys., vol. 111, May 2012 094313.

[16]Y. Wu, K. A. Jenkins, A. Valdes-Garcia, D. B. Farmer, Y. Zhu, A. A. Bol,

C. Dimitrakopoulos, W. Zhu, F. Xia, P. Avouris, and Y.-M. Lin, "State-
of- the-art graphene high- frequency electronics," Nano Lett., vol. 12,
no. 6, pp. 3062-3067, Jun. 2012

[17]I. Meric, C. Dean, A. Young, J. Hone, P. Kim, and K. Shepard, "Graphene

eld-e ect transistors based on boron nitride gate dielectrics," in Proc.

6
IEEE Int. Electron Devices Meeting,2010, pp. 23.2.1-23.2.4.

6
[18]Zou Y, Li F, Zhu ZH, Zhao MW, Xu XG, et al, "An ab initio study
on gas sensing properties of graphene and Si-doped graphene, " Eur
Phys J B 81: 475- 479.20, March. 2011

[19]O. Leenaerts, B. Partoens, and F. M. Peeters, "Adsorption of H2O,

NH3, CO, NO2, and NO on graphene: A rst-principles study, "
Physical Review B 77, 125416 (2008) (SCI IF: 3.322).

[20]O. Leenaerts, B. Partoens, and F. M. Peeters, "Adsorption of small

molecules on graphene, " Microelectronics Journal 40, 860 (2009)
(SCI IF: 0.859).

[21]Y. Shao, J. Wang, H. Wu, J. Liu, I. A. Aksay and Y. Lin.

Electroanalysis 22, 10 (2010).

[22]W. Yuan and G. Shi. Journal of Materials Chemistry A 1, 35 (2013).

[23]M. G. Chung, D. H. Kim, H. M. Lee, T. Kim, J. H. Choi, D. k. Seo, J.-B. Yoo,

S.-H. Hong, T. J. Kang and Y. H. Kim. Sensors and Actuators B:
Chemical 166–167, 0 (2012).

[24]S. F. Rastegar, A. A. Peyghan and N. L. Hadipour. Applied Surface

Science 265, 0 (2013)

[25]H. J. Yoon, D. H. Jun, J. H. Yang, Z. Zhou, S. S. Yang and M. M.-C. Cheng.

Sensors and Actuators B: Chemical 157, 1 (2011)

[26]Q. Yue, Z. Shao, S. Chang and J. Li. Nanoscale research letters 8, 1

(2013) [27]Y.-H. Zhang, L.-F. Han, Y.-H. Xiao, D.-Z. Jia, Z.-H. Guo and

F. Li. Com-
putational Materials Science 69, 0 (2013)

[28]S.Chen, W. Cai, D. Chen, Y. Ren, X. Li, Y. Zhu, J. Kang and R.S Ruo .
New J. Physics 12, (2010)

[29]T. Kuila, S. Bose, P. Khanra, A. K. Mishra, N. H. Kim and J. H. Lee.

Biosensors and Bioelectronics 26, 12 (2011)

6
[30]A. Srivastava, A. Jain, R. Kurchania and N. Tyagi. Journal of
Computational and Theoretical Nanoscience 9, 7 (2012)

6
[31]P. Patnaik, Handbook of Inorganic Chemicals: McGraw-HILL; 2002.

[32]B. Ballantyne. Developments in toxicology and environmental science

11, (1983)

[33]D. Aitken, D. West, F. Smith, W. Poznanski, J. Cowan, J. Hurtig, et

al., Cyanide toxicity following nitroprusside induced hypotension,
Canadian Anaesthetists' Society journal, 24(1977) 651-60.