Hexagonal Boron Nitride (h-BN)

Hexagonal Boron Nitride is a highly promising material. It consists of boron and nitrogen atoms
which orient in an alternating pattern spanning the hexagonal lattice. It has an atomically smooth
surface that is relatively free of dangling bonds and charge traps. h-BN is stable to decomposition
at temperatures up to 1000 °C in air, 1400 °C in vacuum, and 2800 °C in an inert atmosphere. It
shows remarkable chemical and thermal stabilities. It also has a large optical phonon modes and a
large electrical bandgap. Due to their properties hexagonal boron nitride opens up remarkable
application possibilities. The micro plate formed structure of boron nitride gives this material
extraordinary sliding, lubricating and separating capabilities. Boron nitride is similar to graphite,
but has a whitish color. For this reason, it is also known as "white graphite". Boron nitride has very
good thermal conductivity, which, combined with its low density and extremely low thermal
expansion, leads to excellent thermal shock behavior. It also shows remarkable chemical and
thermal stabilities.

Trend of two dimensional material

Ever since its invention in 2004, the extraordinary properties of two dimensional graphene have
inspired aggressive exploration of other 2D materials, initially focusing on transition metal
dichalcogenides,[1-10] but more recently broadening to the larger family of layered
materials.[11-18] Among the unique physical and chemical characteristics of 2D materials,
electrical and optical properties present specific opportunities in electronic and optoelectronic
devices including transistors, photodetectors, light-emitting diodes, and solar cells. Indeed, the
most optimistic projections view atomically thin 2D materials as a post-silicon alternative as
conventional electronics approach the limits of traditional scaling. Although electronic transport
in bulk layered semiconductors have been studied for over four decades,[22-24] the effects of
reduced screening and quantum confinement in the 2D limit are only beginning to be
unraveled.[25-27]. The weak van der Waals (vdW) interactions that enable facile exfoliation of
atomically thin sheets from layered solids also allow the direct assembly of heterojunctions
consisting of distinct 2D materials.[31-36] 2D materials can also be integrated with other
electronic materials including zero-dimensional (0D) quantum dots, one-dimensional (1D)
nanotubes, and bulk semiconductors to achieve mixed-dimensional vdW heterostructures with
unprecedented device behavior.

2D Hexagonal Boron Nitride

Two dimensional hexagonal boron nitride is a two-species analog to graphene composed of

boron and nitrogen atoms [16*]. The boron and nitrogen atoms orient in an alternating pattern
spanning the hexagonal lattice. Unlike graphene, B and N sites in BN sheet are not equivalent.
The ionic bonding due to a significant amount of charge transfer from B to N atom opens a gap
and hence the BN sheet is a wide gap semiconductor with a direct gap of 4.46eV [6], so that the
BN sheet holds high promise for developing nano-transistors, strikingly in contrast to zero-gap
graphene. Its lattice is somewhat 1.8 percent [2*] larger than graphene. Different elemental
properties have given BN some promising advantages over graphene

 Graphene is a very good conductor of electricity. But it has a zero band gap. That means
there is no energy range in graphene in which electron states can exist. Or in other words,
it’s impossible to switch off graphene. And for a transistor [5], that spells serious trouble.
On the other hand, boron nitride has come forward in this regard with a constantly wide
band gap of 5-6 eV [6]. As a result, we can control the level of electricity here for
different purposes. This property of large band gap has attracted researchers around the
world.
 h-BN also possesses several advantageous properties over graphene. It exhibits much
better chemical and thermal stability compared to graphene, enhanced oxidation
resistance [10], good optical properties [6] and excellent mechanical properties [11,12].
 h-BN and Graphene have very little lattice mismatch, thus Graphene supported on a
hesxagonal boron nitride (h-BN) substrate can have better electron mobility than
graphene mounted on the most common semiconductor substrate, silicon dioxide (SiO2)
[7,8,9].
Boron Nitride nanoribbon

Boron nitride nanosheets which are cut into small strips with width less than 50 nm are called
Boron nitride nanoribbon (BNNR). BN nanoribbons (BNNRs), where the charge carriers are
confined in two dimensions and free to move in the third direction, are particularly important due
to their well-defined geometry and possible ease of manipulation. BN nanoribbons posses different
electronic and magnetic properties depending on their size and edge termination.

Recently, the variation in band gaps of BN nanoribbons with their widths and Stark effect due to
applied electric field have been studied.[16,17] Recently the magnetic properties of zigzag BN
nanoribbons (ZBNNRs) have been investigated[18] half metallic properties have been revealed
from these studies which might be important for spintronic applications.

In recent years the electronic properties of hydrogen terminated Zigzag Boron Nitride nanoribbons
have been studied. Yet the electronic properties of ZBNNR with nonmetallic edge termination are
yet to be explored. It has been predicted that ZBNNR may exhibit metallic or half metallic property
when its edge is terminated with non-metallic material.

1.4 Motivation

In Hexagonal Boron Nitride the boron and nitrogen atoms orient in an alternating pattern
spanning the hexagonal lattice. But like graphene, hexagonal boron nitride can be constructed
into boron nitride nanoribbons (BNNRs) with an armchair or zigzag edge in the same manner
[17]. Due to the electronegativity of nitrogen and the electropositivity of boron, zigzag boron
nitride nanoribbons (ZBNNRs) have one edge that’s more negatively charged and one end that is
more positively charged. Armchair boron nitride nanoribbons (ABNNR) do not exhibit edge
structures that are purely positively charged or purely negatively charged since there are a
mixture of boron and nitrogen atoms that define the edges.

A theoretical study has found that ABNNRs always display nonmagnetic semiconducting
features no matter both edges are fully bare or hydrogen(H)-passivated [8]. However, situations
for ZBNNRs are more complicated. In this thesis change in electronic properties due to different
non-metallic passivation of ZBNNRs are examined. Here Zigzag Boron Nitride Nanoribbons
edge has been terminated with Hydrogen, Oxygen, Fluorine and Phosphorus and there
corresponding bandstructure and density of states (DOS) has been generated. The results from
this simulation procedure will be helpful for further studies in this field related to single layer
hexagonal boron nitride.

Objectives:

The main objectives of this research can be listed as follows

 To determine the effect electronic properties of Zigzag Boron Nitride Nanoribbons.

 To determine the bandstructure of Zigzag Boron Nitride Nanoribbons with non-metallic

edge termination.

 To determine the density of states of Zigzag Boron Nitride Nanoribbons with non-
metallic edge termination.

1.5 A preview of this thesis

The dissertation starts with explaining the unique features and versatile application of Hexagonal
Boron Nitride . Then a comparative study between Graphene and h-BN is discussed. The
objective of this research is also discussed here to give the reader a better overview of the entire
thesis work.

The dissertation is comprised of the following chapters:

Chapter 3 provides fundamental and basic knowledge about boron nitride. The different
crystalline forms of boron nitride, their synthesis, various properties and applications have been
discussed here.

Chapter 4 discusses the density functional theory (DFT) and how it is used to determine the
electronic properties. It provides a brief description about how the structures were modeled using
Virtual Nanolab software. It also explains the computational methodology in determining the
electronic properties using Quantum Espresso software.
Chapter 5 is a presentation of results obtained through DFT and Quantum Espresso such as band
structures and DOS.

Chapter 6 summarizes the results of this work and proposes the guidelines for future work.