THEORETICAL STUDIES ON THE RELATIONSHIP OF CRYSTAL STRUCTURE AND BAND GAPS OF MgO NANOSTRUCTURES

Name: Dzulkhairi Tajuddin Bin Mustaffa

Supervisor: Prof. Dr. Norlida Kamarulzaman Co-supervisor: Dr. Abdel.Baset Mohamed

Contents

Background of the problem/ Study Problem Statement / Problem Identification Research Objective / Research Questions Scope and limitation of the study Conceptual Framework Research Methodology / Research Design / Sampling / Data Collection Plan for Data Analysis Significance of study

Background of the Study

Nanotechnology Nanotechnology can change and modify materials characteristic to the desired properties for applications in specific applications with respect to the materials structure as well as functionalities. The size of nanomaterials is <100nm in at least one dimensional. Equally important is trying to understand the nanomaterials characteristic at the fundamental theoretical level. Material Studio Materials Studio is a collection of different modules of theoretical procedures for trying to understand the characteristic of a material from the theoretical perspective. The aim of the project is to use the software capability and the application to simulate nanostructures and determine their physical properties.

Problem Statement

From literature review, no studies on band gaps of nanostructured Magnesium Oxide (MgO) has been done. There are several experimental work on the band gaps of MgO nanostructures but no theoretical explanation was given. This is because theoretical explanations of nanostructures has a basis in many-body quantum theory which is not easy to handle for ab-initio work. The reason is that equations involve 2nd order differential equations involving many parameters and iterations, therefore making calculation by normal calculation methods virtually impossible. Furthermore, there is correlation with the structure of the materials needed as part of the calculations that makes mathematical software such as Math Lab is not suitable.

Solutions to the Problem

The use of softwares such as Material Studio enables the analysis of problems especially many body problems associated with crystal structure to be analyzed in a suitable and sophisticated computing platform. Generation of crystal structures can be done and parameters varied to explore possible answers to problems. The computing environments in Materials Studio eases complicated calculations needed for solids.

Research Objective

To simulate the nanostructured MgO crystal structure using Material Studio module, Crystal Builder and using structural parameters obtained experimentally. To optimize the size of supercell needed to generate the crystal structure. To optimize the various function parameters such as size of brillouin zone, the plane wave basis set energy cut-off, etc. and obtain band gaps of MgO nanostructures close to experimental data.

Scope and limitation of the study

Generation of the crystal structure unit cell using experimental data from nanocrystalline MgO. Simulation of superstructure and optimizing a suitable superstructure dimension. Obtaining band gap values from the simulation of the structure with optimized parameters.

Research Methodology
Flow Diagram
Crystal Builder CASTEP analysis

Simulate MgO nanostructures Crystal Structure using structural data from experimental data

Acquire Band Gap Energies

Run CASTEP using the structure model

Comparison between theoretical and experimental values

Crystal Builder
Crystal builder The structure of bulk MgO is obtained from data bases. _ Crystal system Cubic, FM3M symmetry. For the value of the lattice parameters and other crystallographic information will be obtained from experimental results and use to simulate the structure. Based on the appropriate supercell, suitable functions will be use to evaluate the band gaps of Mgo nanostructures.

MgO Conventional Cell

MgO Primitive Cell

Samples
MgO Samples Annealing Time ( Annealing o Temperature: 600 C )

MgO 1
MgO 2 MgO 3

1 Hour
2 Hours 3 Hours

MgO 4
MgO 5 MgO 6 MgO 7 MgO 8

5 Hours
10 Hours 24 Hours 48 Hours 72 Hours

CASTEP

The CASTEP programme is a first principles quantum mechanical code for performing electronic structure calculations. The generalized gradient approximation (GGA) with Perdew-Burke-Ernzerhof (PBE) functional will be used as the exchange-correlation effects.

Physics Fundamentals

This theoretical work is based on the Kohn-Sham density functional theory (DFT) widely used in solid state physics and suitable for solid state molecular studies. In molecular solids, there is a collections of atoms whereby the ground state energy can be calculated by the solution of the Schrdinger equation in the time independent non-relativistic consideration on the ground state atoms. The equation used is the Born-Oppenheimer approximation,
^ H (r1, r2, ..., rN) = E (r1, r2, ..., rN)...(1)

Where H Hamiltonian and - Schrdinger wave equation.

The Hamiltonian consist of three terms namely, the kinetic energy, the external potential and the electron-electron interaction. Born-Oppenheimer equation can be deduced to the DFT equation.

Generalized Gradient Approximation (GGA)

There are several functionals that can be used in DFT. We will be using the GGA GGAs for the exchange-correlation energy improve upon the local spin density (LSD) description of atoms, molecules, and solids. GGAs equation:
GGA EXC [n,n] = d 3r f (n,n, n,n)(1)

where,

n and n - electron spin densities f - analytical function

GGA with Perdew-BurkeErnzerhof (PBE)

With reference in [1], Perdew et al have improved the GGA that includes better linear response of the uniform gas, behavior under uniform scalling and smoother potential. The generalized gradient approximation (GGA) with Perdew-Burke-Ernzerhof (PBE) functional is given by,
GGA 3 unif

EXC [n,n] = d r n X (n) FXC ( rs, , s)(2) Where, XC - exchange correlation density rs - local Seitz radius (Wigner Seitz) - relative spin polarization s - dimensionless density gradient

Plan for Data Analysis

Simulation of the crystal structure using Crystal Builder of the MgO nano materials from values obtained experimentally. The software extract structural parameters from the simulated crystal structure to plug into the GGA equations. CASTEP iterates and calculates the equations following the parameters used. The theoretical values will be compared with the experimental values.

Significance of study

In science ,especially physics, a theoretical explanation of phenomenon must have a theoretical basis. Therefore, this work is very important to explain the band gap widening of nano MgO which is a phenomenon observed in nanostructured metal oxides. This research will give information about the functions and parameters used in the equations to give band gaps energies of MgO nanostructures. It is significant to see that variations in the parameters will produce the experimental values and will help materials scientist understand the changes and modification occurring in nanomaterials.

References
[1] J. P. Perdew, K. Burke and M. Ernzerhof Physical Review Letters Vol. 77 (1996) [2] Stewart J. Clark, Matthew D. Segall, Chris J. Pickard, Phil J. Hasnip, Matt I. J. Probert, Keith Refson and Mike C. Payne, Z. Kristallogr. 220 (2005) 567570. [3] L.B. Shi, C.Y.Xu and H.K.Yuan, A CASTEP study on magnetic properties of C-doped ZnO crystal, Physica B 406 (2011) 31873191 [4] John P. Perdew, Kieron Burke and Yue Wang, Generalized gradient approximation for the exchange-correlation hole of a many-electron system, Physical Review B, 54 (1996) [5] Nathan Argaman and Guy Makov, Density Functional Theory an introduction, arXiv:physics/9806013v2 (1999). [6] N. F. Chayed, N. Badar, R. Rusdi, A. Azahidi, N. Kamarulzaman, Journal of Crystal Growth 362 (2013)268270. [7] K. Venkateswara Rao, C.S. Sunandana, Structure and microstructure of combustion synthesized MgO nano particles and nano crystalline MgO thin films synthesized by solution growth route, Journal of Materials Science 43(2008) 146154. [8] X. Fu, Z. Song, G. Wu, J. Huang, X. Duo, C. Lin, Preparation and characterization of MgO thin films by a novel solgel method, Journal of Sol-Gel Science and Technology 16(1999)277281. [9] A. M. E. Raj, L. C. Nehru, M. Jayachandran, C. Sanjeeviraja, Spray pyrolysis deposition and characterization of highly (100) oriented magnesium oxide thin films, Crystal Research and Technology 42(2007)867875. [10] Z. Yuna, Z. Guocai, Synthesis of MgO micro spheres with nano sheets in a mechanical force reactor and its optical property, Materials Science and Engineering B142(2007)9397.
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