CERTIFICATE
Certified that the dissertation report entitled “Synthesis and Study of room
temperature ferromagnetism in Ni doped ZnO nanocrystals” which is being
submitted by Vidhi Goyal (Roll No.: 2534/06) in partial fulfillment for the award of the
degree of Master of Technology in Nanotechnology of National Institute of Technology,
Kurukshetra is a record of bonafide work carried by her from dated 23 th January 2008
to 18th July 2008 under our supervision and guidance.
.
Dr. B. K. Kaushik Dr. Sujeet Chaudhary
Professor Associate Professor
Department of Physics Department of Physics
NIT, Kurukshetra IIT, Delhi
(Internal Guide) (External Guide)
i
DECLARATION
I hereby declare that the Project entitled “Synthesis and Study of room
temperature ferromagnetism in Ni doped ZnO nanocrystals ” is an authentic work
carried out by me at Indian Institute of Technology, Delhi under the kind supervision of
Dr. B. K. Kaushik, Professor, Department of Physics, National Institute Technology
Kurukshetra and Dr. Sujeet Chaudhary, Associate Professor, Indian Institute of
Technology, Delhi for the fulfillment of award of degree of M.Tech in Nanotechnology.
Dated: Vidhi Goyal
(Roll No:-2534/06)
ii
ACKNOWLEDGEMENTS
On submission of my thesis, I would like to express my esteemed sense of gratitude
to Dr. B. K. Kuashik, Professor, Department of Physics, National Institute of Technology
Kurukshetra and Dr. Sujeet Chaudhary, Associate Professor, Department of Physics,
Indian Institute of Technology, Delhi for their guidance. Both of them very helpful and I
have grown to respect them immensely. Their constant encouragement, positive criticism
and concern will be remembered always.
I would also like to extend my gratitude to Dr. S. K. Chakarvarti (Chairman, Physics
Department) and all my professors here in NIT who has helped me during my degree.
My warmest thanks to Prof. S. C. Kashyap (Program-Coordinator , M.Tech, IIT Delhi)
for his proper guidance and encourangement during my project work.
I express my sincere thanks to Ms. Kanwal Preet Bhatti for her support and assistance
during my project work. It is a great pleasure to working with her.
I am also thankful to all Thin film laboratory members for their moral support during my
stay in IIT Delhi.
I would like to express my deep gratefulness to my parents and family who, in many
ways encouraged me and provided moral support.
Last, but not the least, I wish to express my gratitude to the almighty for giving me
direction, patience and strength for completing my research work
Vidhi Goyal
(Roll No:-2534/06)
iii
ABSTRACT
Dilute Magnetic semiconductors (DMSs) are promising for applications in the emerging
field of spintroncs. For realizing practical devices, a key requirement is that the host
material be ferromagnetic at or above room temperature. It has been reported that the
wide band gap semiconductor ZnO exhibits ferromagnetism with a Curie temperature
above room temperature when the oxide is doped with a few atomic percent of transition
element. Therefore I have prepared the Ni doped ZnO bulk nanocrystalline samples and
investigate their structural and magnetic properties to find out the origin of
ferromagnetism in the DMS.
ZnO:Ni nanocrystalline samples were prepared by chemical route. The Zn1-xNixO
samples exibit room temperature ferromagnetism. The x-ray diffraction analysis confirms
that the secondary phase of NiO is also present in addition to the expected Zn1-xNixO
phase. Further, with the increase in Ni concentration, a decrease in lattice parameter ‘a’
and ‘c’ is observed, which indicates the substitution of Zn2+ by Ni2+. The resistivity of
these samples is found to be very high, which suggest that the observed room temperature
ferromagnetic behavior could be explained on the basis of bound magnetic polaron
theory.
iv
CONTENTS
Page No.
CERTIFICATE
i
DECLARATION
ii
ACKNOWLEDGEMENTS
iii
ABSTRACT iv
CONTENTS
V
LIST OF FIGURES
VIII
LIST OF TABLES
X
Chapter 1: Introduction
1.1 What is Spintronics?
1
1.2 Advantages of Spin 2
1.3 Branches of spintronics
2
1.3.1 Metal based spintronics
2
v
1.3.2 Semiconductor spintronics
3
1.4 Datta Das spin Effect
4
1.5 Dilute Magnetic Semiconductors
5
1.6 Why ZnO is used?
6
1.7 Key requirement of spintronics
7
1.8 Present Status on Transition Metal Doped ZnO
7
1.9 Sulubility limits of TMs in Zinc oxide
8
1.10 Mechanisms of ferromagnetism 11
1.10.1 Direct exchange 11
1.10.2 Carrier mediated exchange 12
1.10.3 Super exchange 15
1.10.4 Double Exchange
16
1.11 Objective of the project
16
vi
Chapter 2
Experimental and Characterization Techniques
2.1 Experimental : Synthesis of sample 17
2.1.1 chemical method 17
2.2 Sample Characterization 19
2.2.1 X-Ray Diffraction (XRD) 19
2.2.2 Vibrating sample magnetometer (VSM) 22
Chapter 3
Result and Discussion
3.1. Sructural and Phase Analysis
25
3.1.1. Effect of Ni concentration
25
3.1.2 Effect of Sintering at Different Temperatures
27
3.2. Room Temperature Magnetic Behaviour of Ni doped ZnO
31
3.2.1. Effect of Ni Concentration 31
3.2.2 Effect of Sintering at Different Temperatures
32
3.3 Possible origin of FM in Ni:ZnO system 40
vii
Chapter 4
Conclusions and Scope of further Work
4.1 Conclusions 41
4.2. Scope of further Work 42
References
LIST OF FIGURES
viii
CHAPTER 1 Page No.
Fig. 1.1 Datta Das Spin FET 4
Fig. 1.2. Plots of xlimit of Zn1-xTMxO at different Tg. The asymmetric
9
error bar of -50 °C is associated with each data point
Fig.1.3 Phase diagrams showing the relation between growth
parameters 10
(Tg and x) and single/multiple phases of Zn1-xTMxO
Fig. 1.4 Antiparallel alignment for small interatomic distances 12
Fig. 1.5 Parallel alignment for large interatomic distances 12
Fig. 1.6 ferromagnetism arising from the interaction between the free carriers 13
Fig 1.7 Bound magnetic polaron 14
Fig. 1.8 Double Excahnge Interaction 16
CHAPTER 2
Fig. 2.1 The basic principle of X- ray diffraction
20
Fig. 2.2 Schematic diagram of Brentano Geometry employed
21
for x-ray diffraction for powder specimen
Fig.2.3 Simplified block diagram of the model 155 magnetometer
24
CHAPTER 3
Fig. 3.1 XRD plot of various as calcined (500o C, 1h) ZnO:Co samples
26
containing 1, 2, 5, 7 and 10 at % of Ni.
Fig. 3.2 XRD plot of ZN1 series sample sequentially sintered at different 28
ix
temperatures
Fig. 3.3 XRD plot of ZN2 series sample sequentially sintered at different 28
temperatures.
Fig. 3.4 XRD plot of ZN5 series sample sequentially sintered at different 29
temperatures.
Fig. 3.5 XRD plot of ZN5 series sample upto 800, 12 hours in a slow 29
scan region exhibiting the development of NiO peaks
Fig. 3.6 XRD plot of ZN7 series sample sequentially sintered at different 30
Temperatures
Fig. 3.7 XRD plot of ZN10 series sample sequentially sintered at different 30
Temperatures
Fig. 3.8 The M-H curve of all the as calcined samples recorded at 300K. 32
Fig. 3.9 The M-H curve of the ZN1 series samples recorded at 300K. 34
Fig. 3.10 The Ferromagnetic component (FM) extracted from the as observed 34
M-H plots of the ZN1 series samples recorded at 300K.
Fig. 3.11 The M-H curve of the ZN2 series samples recorded at 300K 35
Fig. 3.12 The Ferromagnetic component (FM) extracted from the as observed 35
M-H plots of the ZN2 series samples recorded at 300K
Fig. 3.13 The M-H curve of the ZN5 series samples recorded at 300K 36
Fig 3.14 The Ferromagnetic component (FM) extracted from the as observed 37
M-H Plots of the ZN5 series samples recorded at 300K
Fig 3.15 The M-H curve of the ZN7 series samples recorded at 300K 38
Fig. 3.16 The Ferromagnetic component (FM) extracted from the as observed 38
M- H plots of the ZN7 series samples recorded at 300K
Fig. 3.17 The M-H curve of the ZN10 series samples recorded at 300K 39
Fig. 3.18 The Ferromagnetic component (FM) extracted from the as observed 39
M-H plots of the ZN10 series samples recorded at 300K
x
LIST OF TABLES
CHAPTER 3
Table 3.1 The Rietveld refined lattice parameters ‘a’, ‘c’ and the crystallite 27
size of all the as calcined samples
Table 3.2 Particle size of all the samples sintered at different temperatures. 31
xi
Fig. 1.2 Schematic showing some potential atomic configurations that can be
present when a transition metal is doped into a semiconductor lattice 9
Fig. 1.3 Representation of magnetic polarons. Cation sites are represented by
small circles. Oxygen is not shown; the unoccupied sites are represented
by squares 12
Fig. 1.4 Qualitative electron energy-level diagrams for transition metal oxides 15
Fig. 1.5 Crystal diagrams for the two most stable polymorphs of TiO2. (a) Anatase
(b) Rutile 16
Fig. 1.6 Unit cell of polymorphs of TiO2 16
CHAPTER 2
Fig. 2.1 Principle Sputtering 23
Fig. 2.2 Placement of magnets inside the source Magnetron 24
Fig. 2.3 Sputtering Unit 24
Fig. 2.4 Schematic of a reactive RF Magnetron Co–Sputtering system 26
CHAPTER 3
Fig. 3.1 The basic principle of X- ray diffraction 29
Fig. 3.2 Schematic diagram of the glancing angle X-ray diffraction 30
Fig. 3.3 Simplified block diagram of the Model 155 Magnetometer 32
Fig. 3.4 Schematic Diagram of UV-VIS-NIR Spectrophotometer 33
CHAPTER 4
Fig. 4.1 Vacuum deposition system before installing the 2˝magnetron
(with Diffusion Pump) 37
Fig. 4.2 (a) Reactive RF magnetron sputtering system (with TMP)
(b) Magnetron (2˝ Dia) 37
xii
xiii
