Research proposal

On
Ab inito study of Optical properties of Zinc Oxide by using
different doping elements

By
Shahzada Muzamil

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Literature Survey
The products of semiconductor industry extend worldwide and intensely penetrate
in to daily life of human being. The innovation of first semiconductor transistor at Bell
lab in 1947 was the initial point of semiconductor industry, and then this industry rising
enormously. Then in the 1970’s the step by step progress aroused in the field of quartz
optical fiber and gallium arsenide (GaAs) lasers and III-V compound semiconductors. At
that time silicon (Si) kept the leading role in the commercial market [1]. It has many
applications. It is used for data storage, electronics and photovoltaic applications. In the
development of information technology the first generation semiconductor is Silicon
carbide (SiC) facilitated the commercial industry frequently. The applications of first
generation semiconductor were approximately more than 95% of the semiconductor
devices and more than 99% of integrated circuits were prepared by silicon carbide
materials. Then the 3rd generation semiconductor material was intensify rapidly in
industry and became the central point in research field [2].
Semi conductor physics and surface science being ahead in development have changed
the world in the last 100 years and escort to many scientific applications which are
essential part of our daily lives. In the scientific community ZnO is considered as a
“future material” [3].
Since the discovery of ZnO a lot of work has been done on this because of its wide
applications in the field of optoelectronics, lasers, integrating sensors, UV light emitters,
varisters, and transparent high power electronics, chemical and gas sensing [4].
The research interest in ZnO is increasing day by day due to its popularity in semi
conductor field. The first interest started by research of the lattice parameter done by
M.L. Fuller in 1929 [5]. In 2007 it became the second popular semiconductor after Si.
The commercial availability up to large extent is due to not only growth of high quality
single crystalline ZnO in both epitaxial layers and bulk crystalline form but also in the
field of nanotechnology. The novel electronics, optical, Mechanical and chemical
properties are also introduced.
Mostly the extraordinary properties of ZnO can be attained by doping. Doping can
be related as a word “magically manipulate” which is basically adding a controlled
amount of impurity in semiconductor. For example, for the fabrication of ZnO LED, to

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structure a pn junction, we need both kinds of ZnO n type and p type. To expand the band
gap of ZnO we use Mg or Be etc. At room temperature ZnO has band gap approximately
3.37ev, which is regarded near the ultra-violet (UV) region. As we want to increase its
band gap up to visible region, we have to do band gap engineering. For the contraction of
band gap of ZnO we used cadmium (Cd) etc.
In 2016 Chieh-Cheng Chen et al. [6] analyzed the electronic structure, optical properties
and geometric structure of Al/Ga codoped ZnO. In this work they used ZnO supercell for
construction of Al- and Ga-monodoped Zinc oxide structures and Al/Ga-codoped Zinc
oxide (AGZO). All types of these structures show n type conductivity. In this work as
compared to pure wurtzite ZnO the optical band gap is large. Transmittance can be
increased by the existence of Al. They also analyzed that Zn–O bonds are larger than Al–
O and Ga–O bonds. They represent characteristics of covalent bonding.
In 2015 Qiang Fan et al. [7] investigate the electronic structure and optical belongings of
Al-doped ZnO by Hybrid Functional Calculations. In this work they analyzed that HSE06
hybrid functional is more standard method than PBE approximation for band structure
calculations. They interpret that with the increasing of concentration in Al doping, the
lattice parameter in aluminum doped zinc oxide change in non linear pattern and also
changes occur in lattice parameter as compared to pure ZnO. It represents that n type
ZnO can be acquired by Al doping. In the mean time the optical band gap is increasing
moderately by the increasing of Al doping concentration. In short, we can conclude that
Al doped ZnO can intensify the visible light absorption and can be used as
optoelectronics device applications.
In 2014, P.I.Sukit et al. [8] worked on Ab Initio Study of Doping in Bulk ZnO with the
elements of Group-V. They found that group V elements which lie in the d block of
periodic table are the best cause of p type doping in ZnO. This p type doping can have
simple and complex form of defects. The study about the extensive range of defects and
complexes of defects which are related with N, P AS, Sb impurities is done by use of ab-
initio calculations. They check out the experimental results and theoretical calculations
for all these kinds of defects.
In 2013, Jongbum Kim et al. [9] depicted the experimental and theoretical results for the
Ga doped ZnO polycrystalline films. These films can be utilizing in low loss plasmonic

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materials. The optical properties of films can be remarkably influenced by alloying
effects. Even at comparatively low gallium concentrations of approximately 1 wt%, the
alloying outcomes have significant effect. Therefore GZO films can be used in low less
plasmonic materials. This research gives insight view for the understanding of
mechanism of doping for heavily doped ZnO and also for different materials as
transparent conducting oxides.
In 2012, Zuo Chunying [10] et al., investigated the electronic structure and optical
belongings of C–F–Be doped in wurtzite Zinc oxide. In this work they used density
functional theory to calculate the supercells of doped and undoped zinc oxide. The
Perdew–Burke–Ernzerhof exchange-correlation functional form of (GGA) generalized
gradient approximation is used. On the crystal structure the impact of C doping, C-F
codoping, and C-F-Be cluster doping can be evaluated by calculated data. Similarly the
electronic structure, formation energy, optical properties and the connection between
band gap and strain can be analyzed. We can see that p type ZnO can be achieved by
incorporation of Carbon. In the optical properties the dielectric functions have imaginary
part, and it represents that in the energy region strong absorption occurs as compared to
ZnO. This research work is very important for the future developing ZnO because it
explains p type conductive attribute and exhibit interesting performance in low energy
region.
In 2012 Hsuan-Chung Wu et al. [11] analyzed the optical properties, electronic properties
and formation energies of pure and Si-doped ZnO by using density functional theory and
Hubbard U(DFT + Ud + Up) method. They found the lattice constants differences
between theoretical and experimental research. According to them the difference in lattice
constants values is within 1% and band gap of pure ZnO is almost same as experimental
results. The three kinds of defects models shows n type conductivity attribute. They
conclude that for the electric and optical properties of ZnO the existence of interstitial Si
atoms was inferior idea [11].

In 2010 Zuo Chun-Ying et al. [12], investigated the N-Ag co-doping effect for the
electronic properties in p type ZnO. In this work the investigation of band structure,
geometry structure and density of states for doped and undoped ZnO has been done by

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using first principle calculations. The solubility of solid ZnO which is doped in double
acceptors can be enhanced by two impurities which can activate each other. As if we
compare calculated values in model V and model 1V, the total energy is less in model IV
that’s why it is more stable. The results shows that the concentration of carriers is
increased in ZnO crystal which co doped by Ag and N. Also this co doped structure is
very stable and helpful for the construction of p-type ZnO.

Justification
The aim of this work is to check and enhanced the optical properties of ZnO by using
different doping elements. For this purpose we will use density functional theory and
Hubbard U(DFT + Ud + Up) method. The calculations in my work will be performed
based on the DFT within the projector augmented wave (PAW) method as execute in the
Vienna ab-initio Simulation Package (VASP) code or Wien2K code.
If we dope Al the optical band gap and electrical conductivity moderately increase with
the increasing of concentration of Al doping [15]. By comparing the optical properties of
ZnO crystals, using different kinds of optical techniques, it is concluded that the room
temperature band gap is 3.3 eV [16]. At 3.15 eV due to fact of valence band donor
transition many researches reports the band gap approximately 3.1 eV and 3.2 eV [17].
This can give influence on the absorption spectrum. Similarly Bulk ZnO has commonly
been considered as multifunctional materials for energy and optoelectronics applications.
It will be more useful toward the future research. The proposed easy approach for the
optical properties of ZnO will provide guidance for the experimentation at large scale.
The engineering of Band-gap of ZnO can be attained by alloying with MgO or CdO etc.
The Addition of Mg increases the band gap of ZnO, whereas cadmium Cd decreases the
band gap, analogous to the belongings of Al and In in GaN [18].
Literature survey indicates that no or very little work has been reported on the optical
properties of ZnO by doping different elements by using density functional theory. It is
therefore, aimed to develop rapid, efficient and cost effective procedure for the
development of optical properties of ZnO.

Objective

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 1. To investigate the best computational conditions for the optical properties of ZnO
by doping of different elements includes Magnesium (Mg), Manganese (Mn),
Carbon (C), Beryllium (Be), Boron (B), Aluminum (Al) etc.
2. Correlation between the main technological parameters and material properties.
3. Study of doping mechanisms and enhancement of properties through doping by
different elements, for metals and semiconductor system.
4. To investigate the electronic structure of ZnO and the defects in it, the properties
of point defects are obtained from simulation and modeling.
5. Defects are introduced here to underestimate the band gap.
Methodology
1. All calculations in my work will be performed by DFT within the projector
augmented wave (PAW) method as implemented in the Vienna ab-initio Simulation
Package (VASP) code.
2. The structure optimization will be performed by using the Generalized Gradient
Approximation (GGA) of DFT, employing Perdew–Burke–Ernzerhof (PBE) functional
form.
3: The electronic structures and optical properties will be calculated on the optimized
structures using the hybrid density functional HSE06, which replaces the slowly decaying
long-ranged part of the Fock exchange, by the corresponding density functional
counterpart.
4: To investigate the ab initio calculations which is used in the designing of new valence
electron methods and new spin control methods for semiconductors and comparing the
predictions with experimental results.

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References:

[1] Y. Isseroff and E.A. Carter, “Electronic Structure of Pure and Doped Cuprous
Oxide with Copper Vacancies: Suppression of Trap States”, Chem.
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[2] D.P. Norton, M. Ivill, Y.W. Kwon, “Charge carrier and spin doping in ZnO thin
films Thin Solid Films”, thin solid films, 496, (2006) p. 160 – 168.

[3] Ma. Singh, M. Singh, “Thermal Expansion in Zinc Oxide Nanomaterials”,

Nanoscience and Nanotechnology, 1, (2013), p. 27-29.

[4] P. Judith, P Espitia, N. Fátima Ferreira Soares, “Zinc Oxide Nanoparticles:

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[5] V. A. Coleman, J. E. Bradby, C. Jagadish, “Basic Properties and Applications of
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[6] C.-Cheng Chen, Hsuan-Chung Wu, “Electronic Structure and Optical Property
Analysis of Al/Ga-Codoped ZnO through First-Principles Calculations”
Materials”, 9,(2016) p. 164.
[7] Q. Fana, J. Yang , Y. Yub, J. Zhanga, J. Caoaa, “Electronic Structure and Optical
Properties of Al-doped ZnO from Hybrid Functional Calculations”
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[8] P.I.Sukit Limpijumnong, “Theoretical Study of Defect Signatures in III-Vand II-

VI Semiconductors”, 22, (2006), p. 1-18.
[9] K.Jongbum, Gururaj V. Naik, Alexander V. Gavrilenko, Vladimir “Optical
Properties of Gallium-Doped Zinc Oxide- A Low-Loss Plasmonic Material: First-
Principles Theory and Experiment”PHYSICAL REVIEW X 3, (2013) p. 041037.

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[10] Zuo Chun-Ying, Wen Jing, and Bai Yue-Lei“First-principles investigation of N
Ag co-doping effect on electronic properties in p-type ZnO” Chin. Phys. B19(4),
(2010) 047101.
[11] H.Chung Wu, Y.Chun Peng and T.Ping Shen, “Electronic and Optical Properties of
Substitutional and Interstitial Si-Doped ZnO”materials5 (2012) p1996-1944.
[12] Zuo Chun-Ying, Wen Jing, and Bai Yue-Lei“First-principles investigation of N Ag
co-doping effect on electronic properties in p-type ZnO” Chin. Phys. B19(4),
(2010) 047101.
[13] Z . Ming, Zhang Chuan-Hui, Shen Jiang, “First-principles calculation of
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Electronic Band Structure and Optical Properties of Cr-Doped ZnO”,J. Phys.
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[15] V. Srikant and D. R. Clarke, “On the optical band gap of zinc oxide” journal of
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[16] Y. Ma, G.T. Du, T.P. Yang, D.L. Qiu, Yang, D.L. Liu, “Improving the
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