1

Synthesis and Characterization of Mn-Doped ZnO Spintronic Materials:

Polycrystalline Ceramics, Thin Films, and Nanostructures








Phan The Long
H. H. Wills Physics Laboratory
University of Bristol







A thesis submitted to the University of Bristol in accordance with the requirements of the
degree of Doctor of Philosophy in the Faculty of Science.




29 October 2008

Main text word count 35 500
2
Abstract
Recent theoretical calculations have predicted that ZnO doped with Mn exhibits room-
temperature ferromagnetism. This has attracted intensive interest, because of its
prospective applications in spintronic devices. However, experimental studies on Mn-
doped ZnO materials have revealed that their magnetic properties vary from the
ferromagnetic through antiferromagnetic and spin-glass to the paramagnetic. This makes
the question of the origin of ferromagnetism in Mn-ZnO materials become more
complicated. It has been suggested their magnetic properties dependent strongly on
structural characterization, preparation conditions and sample processing. To gain more
insight into these problems, we have investigated systematically the structure, optical and
magnetic properties of Mn-doped ZnO materials (including polycrystalline ceramics, thin
films and nanostructures), using XRD, SEM, TEM, EDS, photoluminescence and Raman
scattering spectroscopy, and vibrating sample magnetometry.
For Mn-doped ZnO ceramics annealed at temperatures T
s
= 400 - 1000
o
C, we
observe the incorporation of Mn into ZnO, even for the as-prepared samples. When the
samples are annealed, Mn in the ZnO host lattice is subject to two simultaneous dynamic
tendencies: (i) diffusion of Mn out of ZnO crystals, and (ii) substitution of Mn
2+
for Zn
2+

in the ZnO lattice. These processes take place rapidly at temperatures T
s
700
o
C. The
samples are ferromagnetic if T
s
< 700
o
C, and become antiferromagnetic or diamagnetic if
T
s
> 700
o
C.
Thin film samples of ZnO, Zn
1-x
Mn
x
O and Zn
1-x
Mn
x
O:P (x = 0.01 and 0.02) were
grown by PLD. Our studies reveal an incorporation of Mn and P into the ZnO lattice. The
ferromagnetic ordering increases when ZnO films are doped with Mn and P.
Concerning ZnO nanostructures, we have grown rods, wires, needles, tetrapods and
combs doped with Mn, using direct and indirect routes. For the direct route, Mn-doped
ZnO nanorods, nanowires and nanoneedles were prepared by CVD. For the indirect route,
we follow two steps: (i) synthesis of pure ZnO nanostructures, and (ii) Mn doping into
these nanostructures. Our investigations prove the presence of Mn in the ZnO
nanostructures.
3
Acknowledgements
Firstly, I would like to express my heartfelt gratitude to the supervision of Dr. Roger
Vincent. He always arranges time to teach me principles of transmission electron
microscopy (TEM) and show experimental skills on TEM. His thoughtful
recommendations and incessant encouragement are highly appreciated.
Thanks to Prof. David Cherns and Prof. Walther Schwarzacher for their scientific
comments and helpful discussion on my research work. Their precious suggestions have
helped me to understand much more about the problem and research direction that I have
been dealing with.
I also wish to acknowledge Prof. Seong-Cho Yu (Applied Physics Lab, Chungbuk
National University, South Korea) and Dr. Nguyen Huy Dan (Vietnam Academy of
Science and Technology, Vietnam) for their goodwill in research collaboration.
Three-years funding support from the Oversea Research Student (ORS) Award and
the University of Bristol Postgraduate Research Scholarship is highly appreciated.
Without these, I can not follow the PhD course at the University of Bristol.
Finally, a special thank goes to my beloved wife Tran Thi Thanh Tra, parents,
brothers, sisters and other members in my great family who have always encouraged me
to do my best.
4
Author's Declaration
This thesis is submitted to the University of Bristol in support of an application for
administration to the degree of Doctor of Philosophy. The work described in this
dissertation is that of the Author, except where indicated otherwise, and carried out
between October 2005 and September 2008, under the supervision of Dr. Roger Vincent.
The author assures that no part of this thesis has been previously submitted to any
universities for the award of a degree.

Phan The Long
29 October 2008

i
Contents
1 Introduction and motivation 1
2 Background of zinc oxide
2.1 Brief introduction to zinc oxide ................................................................
2.2 Structural characterization ........................................................................
2.3 Photoluminescence of ZnO .......................................................................
2.4 Raman scattering in ZnO ..........................................................................
2.4.1 Raman scattering ...........................................................................
2.4.2 Raman scattering spectra in experiment ........................................
2.4.3 Raman scattering in ZnO ...............................................................
5
5
6
7
9
9
10
11
3 Sample preparation methods and measurements
3.1 Sample preparation methods .....................................................................
3.1.1 Solid-state reaction method ...........................................................
3.1.2 Pulsed laser deposition ..................................................................
3.1.3 Chemical vapour deposition ..........................................................
3.1.4 An aqueous solution method .........................................................
3.2 Measurements ............................................................................................
3.2.1 X-ray diffraction ............................................................................
3.2.2 Electron microscopy ......................................................................
3.2.3 Raman scattering and photoluminescence .....................................
3.2.4 Electron spin resonance .................................................................
3.2.5 Some other measurements .............................................................
13
13
13
16
18
22
22
22
23
25
26
27
4 Mn-doped ZnO ceramics
4.1 Review of earlier works ............................................................................
4. 2 Sample selection ......................................................................................
28
28
30
ii
4. 3 Results and discussion ..............................................................................
4.3.1 Structural characterization and microanalyses ..............................
4.3.2 Optical properties of Mn-doped ZnO ceramics .............................
4.3.3 Magnetic properties of Mn-doped ZnO ceramics .........................
4.4 Conclusions ...............................................................................................
31
31
52
62
73
5 PLD-grown Mn-doped ZnO thin films
5.1 Sample preparation and description ...........................................................
5.2 Structural analysis .....................................................................................
5.2.1 XRD study .....................................................................................
5.2.2 TEM study .....................................................................................
5.3 Optical absorption study ...........................................................................
5.4 Magnetic properties ..................................................................................
5.5 Conclusions ...............................................................................................
75
75
76
76
78
83
87
90
6 Mn-doped ZnO nanostructures
6.1 Mn-doped ZnO nanostructures prepared by direct route ..........................
6.2 Mn-doped ZnO nanostructures prepared by indirect route .......................
6.2.1 Aqueous solution-grown ZnO nanorods diffused with Mn ..........
6.2.2 CVD-grown ZnO nanostructures diffused with Mn .....................
6.3 Conclusions ...............................................................................................
93
93
101
101
108
111
7 Conclusions and future research
7.1 Mn-doped ZnO polycrystalline ceramics ..................................................
7.2 Mn-doped ZnO thin films ..........................................................................
7.3 Mn-doped ZnO nanostructures .................................................................
7.4 Future research ..........................................................................................
112
112
113
114
115
Appendix 116
Bibliography 118
iii
List of tables
2.1 Raman active phonon frequencies for ZnO at room temperature ...................... 11
2.2 Some important properties of ZnO at room temperature .................................. 12
4.1 Variation of XRD peaks of Zn
x
Mn
y
O
4-
with the annealing temperature .......... 33
4.2 The diffraction angle (2) of the nanoparticles ................................................. 42
4.3 Room temperature frequencies observed in our sample of pure ZnO ............... 53
4.4 Magnetic properties for some manganese oxides ............................................. 73
5.1 Experimental parameters used during the growth of Mn-doped ....................... 76
5.2 Thickness, lattice parameters and bandgap of Mn-doped ............................... 78
5.3 Magnetic properties of thin films ZnO, Mn-doped and (Mn, P)-codoped ZnO 89
5.4 Magnetic property of Mn-doped ZnO films reported in recent studies ............ 91
6.1 Some experimental parameters used to grow Mn-doped ZnO nanostructures 94
A1 Theoretical values of the moment per transition metal ion ................................ 116
A2 Radius of some ions .......................................................................................... 116
iv
List of figures
2.1 Structure of wurtzite ZnO ................................................................................. 6
2.2 Lattice structure of the wurtzite ZnO along the ] 0001 [ direction .....................
7
2.3 Two emission bands in UV and visible regions of some ZnO materials ......... 8
2.4 Possibilities of visual light scattering: Rayleigh scattering .............................. 9
2.5 Rayleigh, Stokes and anti-Stokes lines in RS spectrum of Mn-doped ZnO ..... 10
3.1 TGA data (in air) of ZnO and MnO
2
powders ................................................. 14
3.2 TGA data of MnO
2
and ZnO + 2% MnO
2
....................................................... 14
3.3 A sketch of the mixing process of ZnO and MnO
2
using a milling machine ... 15
3.4 Main processes in fabricating Mn-doped ZnO ceramics ................................. 15
3.5 A schematic diagram of pulsed laser deposition ......................................... 17
3.6 A photograph of a PLD system using to prepare thin films ............................. 17
3.7 A schematic diagram of a CVD system ........................................................... 18
3.8 A photograph of a CVD system used to prepare Mn-doped ZnO .................... 19
3.9 (a) Diagram and (b) photograph of the material source and substrates ............ 19
3.10 A sketch of the growth procedure for Mn-doped ZnO nanostructures ........... 20
3.11 Diagram of the material source and substrates for the growth of pure ZnO .. 20
3.12 A sketch for the growth of pure ZnO nanostructures by CVD ....................... 21
3.13: Arrangement for thermal diffusion of Mn into ZnO nanostructures .............. 21
3.14 Formation of an SAED pattern, parallel illumination .................................... 24
3.15 Formation of micro-diffraction patterns using CBED .................................... 24
3.16 Photograph of a Renishaw Raman spectrometer ....... ................................... 25
3.17 Photograph of a JEOL-TE300 ESR spectrometer .......................................... 26
4.1 XRD patterns of the first series sintered at different temperatures .................. 32
v
4.2 Lattice parameters a, c and V for the first series of samples versus T
s
............ 34
4.3 Variation of the c/a ratio with sintering temperature ...................................... 34
4.4 The variation of the lattice parameter a with respect to T
s
............................... 35
4.5 XRD patterns of the samples from the second series ....................................... 36
4.6 A micrograph of the mixture of ZnO and MnO
2
before milling or grinding ... 37
4.7 Some micrographs of the as-prepared sample .................................................. 38
4.8 Some representative micrographs of the samples ............................................ 40
4.9 A micrograph of a large crystal with T
s
= 800
o
C . .......................................... 40
4.10 Some representative micrographs and SAED patterns ................................... 41
4.11 Some representative micrographs of the nanoparticles ................................... 43
4.12 CBED patterns recorded from the Zn
x
Mn
y
O
4-
nanoparticles......................... 44
4.13 Zone axis diffraction patterns of cubic Zn
x
Mn
y
O
4-
................ ..................... 44
4.14 CBED pattern from Zn
x
Mn
y
O
4-
nanoparticles sintered at 800
o
C ................. 46
4.15 TEM images of the sample sintered at 500
o
C ............................................... 47
4.16 TEM images of the sample sintered at 800
o
C ............................................... 48
4.17 EDS spectra represent to the regions .......................................... ................... 49
4.18 The Mn/Zn ratio obtained from the crystals as a function of T
s
..................... 50
4.19 (a) The Mn/Zn ratio and (b) Mn concentration in ZnO crystals and .............. 51
4.20 The RS spectrum of pure ZnO for an excitation wavelength of 488 nm ....... 52
4.21 RS spectra of Mn-doped ZnO ceramics .......................................................... 55
4.22 The E
2
(high) peak position as a function of T
s
............................................... 56
4.23 RS spectra of the sample sintered at 1000
o
C and pure ZnO .......................... 56
4.24 PL spectra of (a) pure ZnO and (b-f) Mn-doped ZnO ceramics ..................... 60
4.25 PL spectra of the samples sintered at 700 - 1000
o
C ...................................... 61
4.26 The UV-peak position as a function of T
s
....................................................... 61
4.27 Room-temperature ESR spectra of samples in the first series ....................... 63
vi
4.28 The experimental ESR signal of the T
s
= 900
o
C sample ............................... 65
4.29 The allowed transitions of the Mn
2+
hyperfine lines ..................................... 65
4.30 The measurement-temperature dependence of ESR spectra ......................... 66
4.31 Temperature dependences of (a) magnetization ............................................. 67
4.32 The hysteresis loops, M-H curves, for the as-prepared sample ........ ............. 69
4.33 Hysteresis loops for the samples .................................................................... 70
4.34 Temperature dependences of magnetization for the samples ......................... 70
4.35 Hysteresis loops measured at (a) 10 and (b) 300 K ........................................ 72
5.1 XRD patterns for PLD-grown Zn
1-x
Mn
x
O (x = 0.01 and 0.02) films ............... 77
5.2 XRD patterns for PLD-grown Zn
1-x
Mn
x
O:P (x = 0.01 and 0.02) films ........... 77
5.3 Plan-view images with different magnifications for films ........................

...... 79
5.4 SAED patterns of films ZnO, N
2
and N
4
. All diffraction rings ........................ 80
5.5 (a) A plan-view image, and (b) the ] 0001 [ -zone axis diffraction patterns ......
81
5.6 The comparison of cross-section images for (a) ZnO, (b) N
1
, (c) N
2
, (d) N
3
... 82
5.7 A cross-section image of the ZnO film ........... ................................................ 83
5.8 Optical absorption spectra of (a) Mn-doped and (b) (Mn, P)-codoped ZnO .... 84
5.9 The plot of (h)
2
versus h of Mn-doped and (b) (Mn, P)-codoped ZnO ..... 85
5.10 Dependences of E
g
on Mn-doping concentration (x) and P ........................... 86
5.11 Hysteresis loops of (a) pure ZnO, (b) Mn- and (c) (Mn, P)-doped ZnO films 88
6.1 SEM images of Mn-doped ZnO nanorods with different magnifications ........ 95
6.2 SEM images of Mn-doped ZnO nanowires with different magnifications ...... 96
6.3 SEM images of Mn-doped ZnO nanoneedles with different magnifications ... 97
6.4 A SEM-EDS spectrum of Mn-doped ZnO nanorods ...................................... 98
6.5 A TEM-EDS spectrum taken from a single Mn-doped ZnO nanorod ............ 98
6.6 XRD patterns of samples ZnO nanorods doped with different Mn ................. 99
6.7 RS spectra of ZnO nanorods doped with different Mn concentrations ............ 100
vii
6.8 SEM images of as-prepared ZnO nanorods grown by an aqueous solution .... 102
6.9 TGA data of ZnO nanorods grown by an aqueous solution method ............... 103
6.10 A TEM-EDS spectrum of Mn-diffused ZnO nanorods .................................. 104
6.11 Some SEM images: (a and b) of Mn-diffused ZnO nanorods ........................ 105
6.12 TEM images for Mn-diffused ZnO nanorods (sample ZM4) ........................ 106
6.13 A TEM image shows the surface modification of Mn-diffused ZnO ............ 106
6.14 XRD patterns of Mn-doped ZnO nanorods prepared by thermal diffusion ... 107
6.15 Raman scattering spectra of Mn-doped ZnO nanorods .................................. 108
6.16 SEM images show different morphologies of nanotetrapods ......................... 109
6.17 SEM images of ZnO comb-like nanostructures ............................................. 110
A1 XRD patterns of the 10% MnO
2
-90% ZnO sample ......................................... 116
A2 SEM images of Mn-doped ZnO nanorods ........................................................ 117
A3 SEM images of Mn-doped ZnO nanowires ...................... ............................... 117
1
Chapter 1
Introduction and motivation
Besides their mass and electric charge, electrons have an intrinsic angular momentum
called spin. In a magnetic field, there are only two possible orientations of spins: aligned
and anti-aligned with the field, which correspond to spin-up and spin-down states,
respectively. The spin-up and spin-down states have different energies that are similar to
two logical states "1" and "0" used widely in today's digital technology. While
conventional electronic devices rely on only controlling the flow of charge, recent
attempts in employing the spin degree of freedom of the electron, known as spintronics,
to carry information have attracted intensive interest [1-7]. This offers opportunities for
developing a new generation of devices combining standard microelectronics with spin-
dependent effects. The advantages of these devices are nonvolatility, a very high
integration density, ultra-fast data processing speed and low power consumption
compared with conventional charge-based devices. They play an important role in
applications such as high-density information storage, sensitive magnetic sensors,
quantum computers, quantum communication and so forth [2,5,6]. Basically, to make
spintronic devices, it is necessary to create a spin-polarized current in spintronic
materials, and also create a system that is sensitive to the spin polarization of electrons.
There are three material families applicable to spintronic technology including
magnetic metals, metallic alloys and magnetic semiconductors [7]. Among these,
magnetic semiconductors are considered as the most promising candidates, due to the
possibility of integrating electronic, photonic and magnetic properties into a single host
lattice. This could lead to new multifunctional spin-based devices, such as spin-FET (field
effect transistor), spin-LED (light-emitting diode), spin-RTD (resonant tunnelling device),
optical switches operating at teta-hertz frequency, modulators, encoders, etc. [1,5]. The
success of these devices depends critically on our wide and deep understanding of
fundamental spin interactions as well as the roles of dimensionality, impurities, defects
and semiconductor band structure. At the moment, there are several important questions
to be addressed before we can use magnetic semiconductors for spintronic applications
[8]:
2
(i) Can we make ferromagnetic semiconductors at room temperature?
(ii) What is an effective way to create spin-polarized currents in a semiconductor?
(iii) What happens to spin-polarized currents at boundaries between different
semiconductors?
(iv) How long can a spin-polarized current retain its polarization in a
semiconductor?
Concerning the first question, recent theoretical and experimental studies have
revealed that ferromagnetism could be found in wide-band-gap semiconductors of GaN
and ZnO doped with transition metals (Sr, Ti, V, Cr, Mn, Fe, Co, Ni, and Cu), so-called
dilute magnetic semiconductors (DMSs) [9-12]. These metals have partially filled 3d
states and contain unpaired electrons (or spins), which are responsible for magnetic
behaviour. Basically, when transition metal ions substitute for cations of a semiconductor
host lattice, the resultant electronic structure is influenced by hybridization between the
3d orbitals of magnetic ions and the p orbitals of neighbouring anions. This hybridization
leads to a strong magnetic interaction between the localized 3d electrons and the carriers
in the valence band of the host lattice [11]. The control of concentration of dopants, and
the finding of mechanisms to achieve high-ferromagnetic ordering at room temperature is
currently an issue of interest.
Due to the preeminent properties of ZnO (such as wide bandgap (E
g
3.37 eV),
large exciton binding energy (60 meV), high luminescence efficiency, transparency,
piezoelectricity, simple growth and growth of many novel nanostructures [11,13-16]),
ZnO-based DMSs have attracted much interest, particularly for the two material systems
of Mn- and Co-doped ZnO [17-68]. Having reviewed earlier studies on these two
systems, it is found that magnetic properties reported by research groups are
contradictory: for example, low-temperature ferromagnetism was reported in Refs.
[18,36,39,55,58-60,62,67,69,70], above room-temperature ferromagnetism in Refs.
[9,18,22,26,30,31,36,37,40,41,43-54,56,61,68,70-76], while diamagnetic, paramagnetic
or spin-glass behaviors were also reported in Refs. [19,29,34,35,38,40-42,57,63-66,72,77-
79]. These results make the question of the origin of ferromagnetism in Mn- and Co-
doped ZnO DMSs becomes more complicated.
For Mn-doped ZnO, substitution of Mn
2+
for Zn
2+
in the ZnO host lattice could give
a high-magnetization value when the material is in ferromagnetic state, since spin number
of Mn
2+
(in the haft-filled d-shell) is 5, which can gives a maximum moment value of
5
B
/Mn
2+
(
B
is the Bohr magnetron) [80]; those for other metal ions can be seen in Table
3
A1 (Appendix). However, the ferromagnetism in this material system depends
remarkably on sample types (i.e., bulk single crystal, polycrystalline ceramics, thin films
or nanostructures), fabrication and processing conditions, and Mn concentration. In
general, polycrystalline ceramics processed at temperatures below 700
o
C exhibits room-
temperature ferromagnetic ordering [9,18,40,41,71-73,76,81], at higher annealing
temperatures samples become paramagnetic, antiferromagnetic or spin-glass
[9,29,40,71,72,76,82]. For Mn-doped ZnO thin films prepared by radio-frequency
magnetron sputtering [14,45,46,50,61,62,83] and pulsed laser deposition [14,53,72-
76,80,84-87], most of them show the ferromagnetic feature at room temperature. The
ferromagnetic ordering declines rapidly when thin films are annealed above 700
o
C. For
nanostructured samples (such as nanoparticles, nanowires, nanorods, tetrapods, etc.), their
magnetic properties reported vary from the diamagnetic [25,64] through low-temperature
ferromagnetic (below 100 K) [22,30,37,55,58-60,67] to the high-temperature
ferromagnetic [26,31,56,68]. Clearly, sample types, fabrication method and conditions
influence strongly the magnetic properties of Mn-doped ZnO materials. This implies that
when we assess or explain the magnetic properties of Mn-doped ZnO, it is necessary to
carry out within samples prepared with similar method and conditions in order to avoid
extrinsic factors dependent on different fabrication methods.
To get more insight into these problems, we plan to investigate systematically the
structural, optical and magnetic properties of Mn-doped ZnO materials prepared by
different methods. Experimental samples including polycrystalline ceramics, thin films
and nanostructures were prepared by solid-state reaction, pulsed laser deposition and
chemical vapour deposition, respectively. Here, the study will focus on topical issues,
such as (i) influences of preparation conditions and processing on structural and physical
properties of Mn-doped ZnO; (ii) the role of Mn; and (iii) the origin of ferromagnetism.
The research method is mainly based on experimental investigations, using X-ray
diffraction, scanning/transmission electron microscopy, energy dispersive X-ray
spectroscopy, photoluminescence and Raman scattering spectroscopy, and a physical
property measurement system (PPMS). Our work includes the following procedures:
- Prepare Mn-doped ZnO samples, including polycrystalline ceramics, thin films
and nanostructures.
- Process the samples after fabricated.
- Investigate their structure, and optical and magnetic properties.
- Study the origin of ferromagnetism in these materials.
4
Thesis organization
The thesis includes seven chapters, which are summarized below:
Chapter 1 - Introduction and motivation: this chapter presents briefly the concept
of spintronics, spintronic materials, and dilute magnetic semiconductors. It also gives the
reason why Mn-doped ZnO materials with different formations and structures have been
chosen for our study.
Chapter 2 - Background of zinc oxide: which provides fundamental knowledge
related to the structure, and optical properties (luminescence and Raman scattering) of
ZnO.
Chapter 3 - Sample preparation methods and measurements: this chapter
presents some physical and chemical methods (including conventional solid-state
reaction, pulsed laser deposition, chemical vapour deposition, aqueous solution, and
thermal diffusion) employed to synthesize Mn-doped ZnO materials. Subsequently,
measurements based on X-ray diffraction, electron microscopy, photoluminescence and
Raman scattering spectroscopy are described.
Chapter 4 - Mn-doped ZnO ceramics: description of experimental results
obtained for Mn-doped ZnO ceramics sintered at 400 - 1000
o
C. The influence of sample
preparation conditions and sintering temperature on the structure, optical and magnetic
properties of this material system are described in this chapter. We show that the
ferromagnetism in Mn-doped ZnO ceramics is generated from secondary phases rather
than Zn
1-x
Mn
x
O.
Chapter 5 - PLD-grown Mn-doped ZnO thin films, showing some results related
to studies of the structure, optical and magnetic properties of PLD-grown thin films (ZnO,
Zn
1-x
Mn
x
O and Zn
1-x
Mn
x
O:P, with x = 0.01 and 0.02). It is shown that doped ZnO films
exhibit ferromagnetic behaviour at 300 K, generated from the doping with Mn and P.
Chapter 6 - Mn-doped ZnO nanostructures: introducing the growth of various
undoped and Mn-doped ZnO nanostructures, such as rods, wires, needles, tetrapods and
combs. Some results based on studies of the structure, and optical properties could
provide indirect evidences that Mn is incorporated into the host lattice of ZnO
nanostructures.
Chapter 7 - Conclusions and future research
Appendix
Bibliography

5
Chapter 2
Background of zinc oxide
2.1 Brief introduction to zinc oxide
Zinc oxide (ZnO) is a transparent wide-band-gap semiconductor (E
g
3.37 eV) with
a direct electronic transition across the band gap. Recently, it has been of interest because
of its prospective applications in blue-ultraviolet light emitters, varistors, transparent
high-power electronics, surface acoustic wave devices, piezoelectric transductors, and
chemical and bio-sensors [13,15,88-90]. Some optoelectronic applications of ZnO overlap
with those of GaN, another wide-band-gap semiconductor with E
g
3.39 eV at 300 K
[91]. However, ZnO has some potential advantages such as the commercial availability of
fairly high-quality bulk single crystals and a large exciton binding energy of 60 meV.
This ensures an intense near-band-edge excitonic emission above room temperature,
because the value 60 meV is 2.4 times higher than the room-temperature thermal energy
(k
B
T = 25 meV). While n-type ZnO crystal-growth technology is extremely simple,
resulting in a potentially lower cost for ZnO-based devices, the fabrication of p-type
material becomes more difficult. The successful growth of p-type ZnO by doping with
nitrogen, phosphorus or arsenic has been described in only a very limited number of
publications [92-95].
Apart from the above properties, ZnO has additional properties which make it
preferable over other wide-band-gap materials. Some experiments have shown that ZnO
is very resistive to high-energy radiation, making it a very suitable candidate for space
applications. Also, ZnO is easily etched in acids and alkalis, and this provides an
opportunity for fabrication of small-size devices. Furthermore, by controlling the doping
level the electrical properties of ZnO can be changed from insulator through n-type
semiconductor to metal while maintaining optical transparency that makes it useful for
transparent electrodes in flat-panel displays and solar cells [13].
Recent studies have shown that ZnO exhibits a variety of novel nanoscale
structures, such as rods, wires, belts, tubes, needles, tetrapods, rings, combs and so forth
[15,96]. This opens up new options for applications in micro-optoelectronic devices,
micro-electromechanical systems (MEMs), and energy nanogenerators [97]. The doping
6
of transition metals into these structures is also an issue of current interest, because of the
possibility of fabricating ZnO-based ferromagnets for spintronic devices operating at
room temperature [11,12], as described in Chapter 1.
2.2 Structural characterization
ZnO is a II-VI semiconductor compound (molar mass and density are 81.4 g/mol
and 5.605 g/cm
3
, respectively) and has the wurtzite-type structure with a hexagonal unit
cell. It belongs to the space group of
4
6v
C or P6
3
mc. At room temperature, the lattice
constants mostly range from 3.2475 to 3.2501 for the a parameter and 5.2042 to 5.2075
for the c parameter. The c/a ratio ranges from 1.593 to 1.604, whereas the ideal
hexagonal structure shows c/a = 3 / 8 1.633 [13,14,89,98]. In the unit cell, interatomic
distances and angles in ZnO are as follows [98]
Zn-Zn = 3.209 - 3.25
Zn-O = 1.973 - 1.992
O-Zn-O = 108.1 - 110.8
o
.
Figure 2.1 shows a schematic diagram of the ZnO wurtzite structure. One can see that
each Zn (or O) atom is tetrahedrally coordinated to four O (or Zn) atoms, where the Zn d-
electrons hybridize with the O p-electrons. Layers occupied by zinc atoms alternate with
layers occupied by oxygen atoms.

Figure 2.1: Structure of wurtzite ZnO, each Zn (or O) atom is tetrahedrally coordinated to
four O (or Zn) atoms.

7

Figure 2.2: Lattice structure of the wurtzite ZnO along the ] 0001 [ direction (the left
figure), and Zn
2+
and O
2-
surfaces (the right figure) [99].

Also, ZnO is a polar semiconductor. The oppositely charged ions produce positively
charged Zn-(0001) and negatively charged O-(0001) surfaces, resulting in a normal dipole
moment and spontaneous polarization along the c = ] 0001 [ axis. For most ZnO materials,
a common growth direction is parallel to the c axis. The determination of whether they
grow in ] 0001 [ and/or ] 1 000 [ direction is also a subject of interest, particularly for
nanostructured ZnO materials. Conventionally, the positive direction ] 0001 [ corresponds
to the direction along the bond from cation to anion, i.e. Zn-O bond, see Fig. 2.2.
Knowledge of the absolute growth direction is a key factor to explain the growth
mechanism of a crystal, as well as the surface chemistry.
2.3 Photoluminescence of ZnO
Luminescence of a material is a non-equilibrium process, which always requires an
excitation source. Depending on types of excitation sources, we have different scientific
terms of luminescence, such as photoluminescence (PL) using optical excitation from
lamps or lasers, electroluminescence (EL) using an electric current, and
cathodoluminescence (CL) using a beam of electrons. Among these experimental
methods, PL is used widely to study optical properties of wide-band-gap semiconductors.
Typically, there are two kinds of PL. The first one is intrinsic luminescence associated
with the recombination of electron-hole pairs (excitons), and the other is extrinsic
luminescence associated with impurities and/or defects [100]. These emissions could be
observed clearly when studying PL spectra of ZnO [14,16,101,102].
8
350 400 450 500 550 600 650 700 750
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
ZnO nanorods
(CVD method)

Wavelength (nm)
Commercial ZnO
Defect-related emission

Band edge
emission
ZnO nanorods
(chemical method)

Figure 2.3: Two emission bands in UV and visible regions of some ZnO materials.
At room temperature, PL spectra of ZnO-based materials usually consists of two
emission bands centred in ultraviolet (UV) and visible regions [13,14,16,17,101-104], see
Fig. 2.3. The UV emission is associated with the near-band-edge exciton recombination.
Its peak position ranges between 375 and 400 nm, which depends strongly on crystal size,
impurity concentration and excitation energy density [14]. The visible emission is a broad
band ranging from green to orange wavelengths (Fig. 2.3), and is assigned to impurities
and/or defects. The crystal quality, morphology, preparation conditions and processing
influence significantly the peak position and intensity of this emission, see Fig. 2.3. This
makes identification of the origin of the visible emission, particularly for green
luminescence become very complicated [16,101,102,104]. For many applications, the
intensity of the visible emission is desired to be as low as possible. The intensity ratio of
UV to visible emissions is considered an important criterion to evaluate the quality of
ZnO. However, this evaluation is sometime problematic, due to the dependence of visible
emission intensity on experimental conditions such as excitation density and wavelength,
and radiation area [103].
In spite of considerable research on the room-temperature PL spectra of ZnO
[14,16,96,101-103,105], there are still two important questions remain unsolved
(i) The origin of emissions in the visible luminescence region.
9
(ii) Under which circumstances is PL intensity of UV higher (or lower) than that of
visible emission?
2.4 Raman scattering in ZnO
2.4.1 Raman scattering
Raman scattering (RS) is an inelastic scattering of a photon by a molecule or a solid.
When an incident photon interacts with a medium, it can be scattered in one of three
following ways: (i) it is elastically scattered and thus retain its incident energy (so-called
Rayleigh scattering), (ii) it is inelastically scattered by quasi-particle excitations of the
medium, thereby either giving energy to the medium (Stokes scattering) or, (iii) removing
energy from the medium (anti-Stokes scattering) [106]. The description of these processes
is shown in Fig. 2.4. In solids, the quasi-particle excitations studied are most commonly
phonons (lattice vibrations), but other excitations can give rise to Raman scattering such
as molecular rotational excitations (rotons), free-carrier excitations (plasmons) or
magnetic excitations (magnons). A coupling between incident photons and quasi-particle
excitations results in photon emission from the medium which is shifted in frequency
from the incident excitation photon.

Figure 2.4: Possibilities of visual light scattering: Rayleigh scattering (no Raman effect),
Stokes scattering (a molecule absorbs energy), and anti-Stokes scattering (a molecule
loses energy). In this figure, E
i
(= h
o
) and E
s
are incident and scattering energies,
respectively, and E
v
= h
v
is energy of a quasi-particle excitation with frequency
v
.
10
-600 -400 -200 0 200 400 600
21200 21000 20800 20600 20400 20200 20000 19800

o
=20491.8 cm
-1
(i.e.,
o
=488 nm)
Frequency,
s
(cm
-1
)
Rayleigh Stokes lines anti-Stokes lines
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
Raman shift, (cm
-1
)
(
o
-
v
)
(
o
+
v
)



Figure 2.5: Rayleigh, Stokes and anti-Stokes lines in RS spectrum of Mn-doped ZnO
excited by a wavelength
o
= 488 nm (
o
20491.8 cm
-1
). Also, the spectrum shows the
relation between absolute values of scattering frequency (
s
, the above horizontal axis)
and Raman shift (, the below horizontal axis).
2.4.2 Raman scattering spectra in experiment
Typically, an RS spectrum of a molecule or a solid usually combines three
scattering processes as mentioned (i.e., Rayleigh, Stokes and anti-Stokes scatterings).
Among them, the Rayleigh line is located at the spectral centre (coincident with the
frequency of incident photons
o
), while Stokes (
o
-
v
) and anti-Stokes (
o
+
v
) lines
are symmetrical around the Rayleigh line, for example see in Fig. 2.5 (which shows a RS
spectrum of Mn-doped ZnO). This feature can be used to distinguish the difference
between luminescence and RS spectra. For normal analyses, it is usual to study the Stokes
lines, because their intensity is much higher than that of anti-Stokes lines. In discussion of
RS spectra, frequency shifts from the frequency of incident photons are conventionally
used rather than their absolute values.


11
The frequency difference between the incident and scattered photons () is called
the Raman shift, which is measured in unit of wavenumber (cm
-1
) and defined as
s o


1 1
=
, (2.1)
where
o
and
s
are wavelengths (in cm) of incident and Raman scattered photons,
respectively. As an example is shown in Fig. 2.5, for a RS spectrum of Mn-doped ZnO
excited at 488 nm (
o
20491.8 cm
-1
), which is represented in both absolute values of
Raman scattering frequency (
s
) and the Raman shift (). For the Raman shift, the
frequency (
o
20491.8 cm
-1
) of incident photons is shifted to zero, and thus Stokes and
anti-Stokes shift frequencies are symmetrically on the right and left, respectively, of this
zero point, see Fig. 2.5. Our Raman studies focus mainly on the Raman shift range of 100
- 800 cm
-1
.
2.4.3 Raman scattering in ZnO
Raman spectroscopy is used widely to study structural changes, defects, grain size
and secondary phases present in doped ZnO materials, where the Raman scattering (RS)
signal is dependent on the electron-phonon interaction [20-22,33,107-110]. Theoretically,
wurtzite-type ZnO belongs to the symmetry group
4
6v
C with two formula units in the
primitive cell. At the point of Brillouin zone, group theory predicts the following set of
optical modes:
opt
= A
1
+ 2B
1
+ E
1
+ 2E
2
[111,112]. Among these, B
1
(high) and B
1
(low)
are inactive modes, E
2
(high) and E
2
(low) modes are non-polar Raman active, and the two
infrared-active modes of A
1
and E
1
are polar. These modes can be seen to split into
E
1
(LO) and A
1
(TO) (note: LO - longitudinal optical and TO - transversal optical) for
propagation perpendicular to the c axis, and E
1
(TO) and A
1
(LO) for parallel propagation
[20,106,110-113]. For propagation at an angle other than 0
o
or 90
o
to the c axis, mixed
modes are obtained. Table 2.1 shows some Raman active modes of ZnO determined from
theoretical predictions and experiment.
Table 2.1: Raman active phonon frequencies (in cm
-1
) for ZnO at room temperature,
obtained from theoretical predictions [13] and experiment [111].
Mode E
2
(low) A
1
(TO) E
1
(TO) E
2
(high) A
1
(LO) E
1
(LO)
Theory 98 382 407 433 548 628
Experiment 99 378 410 438 574 590
12
It should be noticed that E
2
(low) is associated with the vibration of the heavy Zn
sublattice, while E
2
(high) involves only the O atoms [13]. They are characteristic of
wurtzite ZnO. The size and quality of ZnO crystals and the presence of impurities and/or
defects affect directly spectral parameters of these modes [19-22,24,39,108,109].
In closing, Table 2.2 provides some information relating to the structural and
physical properties of ZnO at room temperature.
Table 2.2: Some important properties of ZnO at room temperature [13,14,76,89,90].
Property Value
Space group
4
6v
C or P6
3
mc
a () 3.2475 - 3.2501
c () 5.2042 - 5.2075
c/a 1.593 - 1.604 (ideal = 1.633)
Molar mass (g/mol) 81.4
Density (g/cm
3
) 5.605
Stable crystal structure Wurtzite
Band gap (eV) 3.37
Intrinsic carrier concentration (/cm
3
) less than 10
6
(max n-type doping > 10
20
cm
-3

electrons; max p-type doping < 10
17
cm
-3
holes)
Electron effective mass,
o e
m m /
*

0.24 - 0.28
Heavy hole effective mass,
o hh
m m /
*

0.59 - 0.78
Exciton binding energy (meV) 60
Exciton effective mass,
o ex
m /
*

0.20 - 0.31
Refractive index 2.008, 2.029
Crystal field parameter, (eV) 0.041 - 0.048
Electron Hall mobility for low n-type
conductivity, cm
2
/V.s
200
Hole Hall mobility for low p-type
conductivity, cm
2
/V.s
5 - 50
Static dielectric constant 8.656
Melting point

(
o
C) 1975
Debye temperature,
D
(
o
C) 672.5
Thermal conductivity (W.cm
-1
/
o
C) 0.6, 1.0 - 1.2
Linear expansion coefficient, a (/
o
C) 6.5x10
-6

Linear expansion coefficient, c(/
o
C) 3.9x10
-6

Heat capacity, C
p
(cal/mol.K) 9.6
13
Chapter 3
Sample preparation methods and measurements
3.1 Sample preparation methods
This section presents some sample preparation methods employed to synthesize Mn-
doped ZnO materials including polycrystalline ceramics, thin films and nanostructures.
The polycrystalline ceramics and thin films are prepared by conventional solid-state
reaction and pulsed laser deposition (PLD), respectively. Nanorods can be grown by both
aqueous solution and chemical vapour deposition (CVD). The other structures are
fabricated by CVD with control of the growth conditions. The following subsections will
describe these methods applied to prepare experimental samples.
3.1.1 Solid-state reaction method
The solid-state reaction method, or conventional ceramic technique, is a simple
route and usually employed to make porcelain products. The main features of this method
are based on mechanical and thermal processes including milling, mixing, pressing and
sintering [114]. Normally, when we intend to synthesize any ceramic compositions, the
melting point and structural phase transition temperatures of initial materials must be
carefully investigated. This ensures that the sintering temperature is high enough to
promote chemical reactions between initial compounds.
For our study, the initial powders of ZnO and MnO
2
(4N, 99.99 %) were combined
in an appropriate atomic mass ratios of Zn and Mn to make Zn
1-x
Mn
x
O compositions.
Thermal gravimetric analysis (TGA) data for these powders are shown in Fig. 3.1. In the
temperature range investigated, ZnO crystals are quite stable, where the loss of weight at
1000
o
C is just about 0.6 wt.%. However, MnO
2
transforms to oxidation states Mn
2
O
3
and
Mn
3
O
4
at about 565 and 920
o
C, respectively, see Fig. 3.1. The weight loss of MnO
2
at
1000
o
C is about 12 wt.%. Earlier studies [72,73] have indicated that the presence of ZnO
in MnO
2
strongly stimulates decomposition of MnO
2
even at low temperatures, as shown
in Fig. 3.2.
14
0 100 200 300 400 500 600 700 800 900 1000 1100
0.88
0.90
0.92
0.94
0.96
0.98
1.00
920
o
C
565
o
C
Temperature (
o
C)
Mn
3
O
4
Mn
2
O
3
N
o
r
m
a
l
i
z
e
d

w
e
i
g
h
t

(
a
.

u
.
)
MnO
2
ZnO

Figure 3.1: TGA data (in air) of ZnO and MnO
2
powders in the temperature range 20 -
1000
o
C, measured with Shimadzu TGA-50H.

Figure 3.2: TGA data of MnO
2
and ZnO + 2% MnO
2
[72]; the presence of ZnO around
MnO
2
particles promoted decomposition of MnO
2
even at very low temperatures.
15
In the present work, we synthesized two series of samples to investigate the
dependence of structural and physical properties on sample preparation conditions as
follows:
For the first series, the stoichiometric mixture was wet mixed overnight in a plastic
jar by a mixing machine, using zirconia milling balls and high-purity water. A diagram of
the mixing process taking place in the jar is shown in Fig. 3.3. After mixing, the
suspension mixture is filtered from the milling balls, and dried at 120
o
C. The dried
mixture then was ground well and calcined at 400
o
C for 8 hrs. Finally, the mixture was
pressed into pellets and sintered in air at different temperatures ranging between 400 and
1000
o
C for 12 hrs. The pellets sintered at high temperatures were cooled slowly to room
temperature. A diagram showing the main processes in synthesizing ceramic samples is
sketched in Fig. 3.4.

Figure 3.3: A sketch of the mixing process of ZnO and MnO
2
using a milling machine;
ZnO and MnO
2
powders, zirconia milling balls and high-purity water were put in the
plastic jar.

Figure 3.4: Main processes in fabricating Mn-doped ZnO ceramics using the solid-state
reaction method.
16
For the second series, the stoichiometric mixture was mixed and ground by hand
without high-purity water, using a mortar and pestle. This process was repeated several
times after pre-annealing at 400
o
C for 8 hrs. After that, the next steps were carried out as
described above.
It was expected that ZnO and MnO
2
masses would combine stoichiometrically to
form compositions Zn
1-x
Mn
x
O basing on the following chemical reaction:
(1-x)ZnO + xMnO
2
= Zn
1-x
Mn
x
O +
2
x
O
2
. (3.1)
However, such nominal compositions are very difficult to achieve, because MnO
2
reduces
to oxidation states such as Mn
2
O
3
and Mn
3
O
4
(see Fig. 3.3) that can form Zn-related
manganese oxides (i.e., Mn
2-x
Zn
x
O
3
and/or Mn
3-x
Zn
x
O
4
) at higher sintering temperatures.
3.1.2 Pulsed laser deposition
Pulsed laser deposition (PLD) is a physical vapour deposition process, carried out in
a vacuum system, that shares some characteristics in common with molecular beam
epitaxy and sputtering deposition [115]. The description of this operation is shown in Fig.
3.5(a). A pulsed laser is focused onto a target of the material to be deposited. During
PLD, the target rotates around the target-holder axis while the laser beam vibrates slowly
from the center to edge of the target. This ensures that the laser beam scans every point on
the target surface. At sufficiently high laser energy density, the laser beam vaporizes or
ablates a small amount of the material and creates a plasma plume, as can be seen in Fig.
3.5(b). The ablated material is ejected from the target in a highly forward-directed plume.
The ablation plume provides the material flux, which deposits on a substrate put in front
of the plasma plume. The quality of films depends on optimizing many experimental
parameters such as laser energy density, pulse repetition rate, substrate temperature,
working pressure and deposition duration. A photograph of a PLD system is shown in
Fig. 3.6.
In our work, we have grown Mn-doped and (Mn, P)-codoped ZnO thin films using
PLD. Firstly, the targets ZnO, Zn
1-x
Mn
x
O and Zn
1-x
Mn
x
O:1 mol% Zn
3
P
2
(x = 0.01 and
0.02) were made by means of a conventional solid-state reaction, as described above. For
Zn
1-x
Mn
x
O and Zn
1-x
Mn
x
O:1 mol% Zn
3
P
2
(x = 0.01 and 0.02), initial powders of ZnO,
MnO
2
and/or Zn
3
P
2
were combined in appropriate ratios of atomic masses of Zn and Mn,
and then wet mixed overnight with zirconia-milling balls and high-purity water.
Afterwards, the suspension mixtures were filtered from the milling balls, and dried at 120
o
C. The dried mixtures were re-ground into powder and calcined at 400
o
C for 8 hrs. After
17
this step, pure ZnO and the mixtures were pressed into the targets with 2.54 cm diameter
and 1.5 cm thickness. They were re-annealed in air at 400
o
C for 12 hrs. The final
products obtained include five targets ZnO, Zn
0.99
Mn
0.01
O, Zn
0.98
Mn
0.02
O, Zn
0.99
Mn
0.01
O:1
mol% Zn
3
P
2
and Zn
0.98
Mn
0.02
O:1 mol% Zn
3
P
2
. It should be noticed that the P doping from
Zn
3
P
2
is to introduce a higher concentration of holes in Mn-doped ZnO films, which
could happen when P
3-
substitutes for O
2-
in the ZnO host lattice.

Figure 3.5: (a) A schematic diagram of pulsed laser deposition; and (b) a photograph of
the plasma plume ejected from a target.

Figure 3.6: A photograph of the PLD system using to prepare thin films.
18
The deposition of the films was carried out in a vacuum chamber with a working
pressure of about 10
-3
Torr. The distance between the target and substrates was about 8.0
cm. Before the deposition process, air in the chamber was removed by backfilling Ar gas
and then pumping out until the pressure in the chamber was reduced to about 3x10
-7
Torr.
An excimer laser Lambda-Physik Compex 102 (KrF) supplied by a voltage of 30 kV
operating at 248 nm was used to bombard the targets. The maximum repetition frequency
and pulse energy of the laser are 20 Hz and 300 mJ, respectively.
For growth on SiO
2
(0.2m)/Si(001) substrates, after checking X-ray diffraction
from many films, we found optimal conditions (which are the substrate temperature and
working pressure) in order to obtain films with their crystals oriented along the c axis
perpendicular to the substrate. Such crystals were expected to be defect free. Here, films
were prepared from five targets, including ZnO, Zn
1-x
Mn
x
O and Zn
1-x
Mn
x
O:1 mol%
Zn
3
P
2
(x = 0.01 and 0.02). The experimental parameters chosen for growing these films
will be described in detail in Chapter 5.
3.1.3 Chemical vapour deposition
Chemical vapour deposition (CVD) is a generic name for a group of processes that
involve depositing a solid material from its gaseous phase. It is considered as one of the
most effective methods for growing nanostructured ZnO-based materials [13,15,116]. A
CVD system usually consists of some basic components such as a reactor chamber,
temperature controller, gas delivery system and vacuum pumps, as depicted in Fig. 3.7.

Figure 3.7: A schematic diagram of a CVD system.
19
Figure 3.8 is a photograph of our CVD system that has been employed to synthesize
Mn-doped ZnO nanostructures. We have found that pure ZnO materials prepared by CVD
show many novel nanoscale structures including rods, wires, needles, combs, tetrapods
and so forth. These structures are very sensitive to change growth conditions, such as
temperature, pressure, gas flow, substrate, and deposition time. The fabrication of the
above structures doped with Mn is really difficult if starting from precursors containing
Zn and Mn elements. Thus, we have used both direct and indirect routes to synthesize
these Mn-doped nanostructures.

Figure 3.8: A photograph of a CVD system used to prepare Mn-doped ZnO
nanostructures.

Figure 3.9: (a) Diagram and (b) photograph of the material source and substrates used to
grow Mn-doped ZnO nanostructures.
20

Figure 3.10: A sketch of the growth procedure for Mn-doped ZnO nanostructures by
CVD.
For direct growth, we have used Zn and MnCl
2
.4H
2
O powders as precursors to
prepare Mn-doped ZnO nanowires, nanorods and nanoneedles; the melting points of Zn
and MnCl
2
.4H
2
O are about 420 and 58
o
C (boiling point: 198
o
C) , respectively. The
weight ratio of Zn to MnCl
2
.4H
2
O is changed to synthesize ZnO materials doped with
different Mn concentrations. The mixture of Zn + MnCl
2
.4H
2
O was loaded in a ceramic
boat and put in the center of a horizontal quartz tube, which acts as the vapour source.
Si(001) substrates coated with Au nanoparticles were arranged on the top of this material
source, as shown in Fig. 3.9. Before deposition, air in the tube was removed by
backfilling with Ar gas and then pumping out until the pressure in the chamber was
reduced to ~10
-3
Torr. Ar gas was used as a carrier gas at a flow rate of about 150 sccm
(standard cubic centimeters per minute). The growing process was carried out at
temperatures between 420 and 550
o
C for 60 - 120 minutes, under a working pressure of
about 150 Torr (~0.2 bar). The detailed description of the growth of Mn-doped ZnO
nanostructures is shown in Fig. 3.10.

Figure 3.11: Diagram of the material source and substrates for the growth of pure ZnO
nanostructures by CVD.
21

Figure 3.12: A sketch for the growth of pure ZnO nanostructures by CVD.

Figure 3.13: Arrangement for thermal diffusion of Mn into ZnO nanostructures.
For the indirect route, we have grown pure ZnO nanostructures (including rods,
tetrapods and combs), and then doped Mn into these structures using thermal diffusion.
Concerning the first step, the vapour source was about 1.0 g Zn powder, which was
loaded in a ceramic boat and placed in the centre of the quartz tube furnace, as described
above. The Si substrates coated with Au nanoparticles were arranged upstream on an
alumina plate, which was near the vapour source, see Fig. 3.11. The growth was carried
out under atmospheric pressure at temperatures between 630 - 700
o
C, using Ar at a flow
rate of about 300 sccm (standard cubic centimeter per minute) as a carrier gas. After 6-10
hrs growth, the system was cooled down to room temperature, and we obtained ZnO
nanostructures. The diagram describing the growth of pure ZnO nanostructures is shown
in Fig. 3.12. It should be noted that the residual oxygen in the reactor tube and/or in the
Ar gas was exploited as an oxygen source. In the case of no Au particles, it was too hard
to obtain ZnO nanostructures grown directly from the Si substrates, particularly nanorods
and nanowires. For other nanostructures (i.e., tetrapods and combs), we found that they
floated on the surface of a thin-film layer, which was considered as a buffer layer. In this
case, the nanostructures could develop from Zn droplets.
To diffuse Mn into these ZnO nanostructures, we have used Mn metal fragments.
ZnO on the Si substrate was covered with the smooth surface of a Mn fragment. The
distance between them was maintained at about 1 mm (see Fig. 3.13) to avoid direct
22
thermal reaction [71,72]. The combination was then placed in the quartz tube at the centre
of the CVD system. The thermal diffusion process was carried out in vacuum at ~10
-3

Torr. Mn concentration in ZnO nanostructures could be controlled by changing
temperature or diffusion time.
3.1.4 An aqueous solution method
Another simple effective method which allows us to obtain a large amount of ZnO
nanorods is aqueous chemical reaction. We also used this method to grow pure ZnO
nanorods, and then used thermal diffusion (as described above) to dope Mn in these
nanorods. Firstly, a mixture of 1.19 g zinc nitrate hexahydrate (Zn(NO
3
)
2
6H
2
O, 98 %)
and 0.56 g hexa-methyltetramine (C
6
H
12
N
4
, 99 %) with a 1:1 mole ratio was dissolved in
200 ml of high-purity water with a concentration 0.02 M. The substrates were cleaned in
an ultrasonic bath with acetone (15 minutes) and methanol (10 minutes), and were then
placed in the bottom of a glass cup containing the solution. The deposition process was
carried out at 95
o
C for 2 - 3 hrs in an oven. The products obtained on the substrates were
rinsed with high-purity water and then dried at 100
o
C. During the growth process, the
following chemical reactions could happen in the solution [88,117]
C
6
H
12
N
4
+ 6H
2
O 6HCHO + 4NH
3
(3.2)
NH
3
+ H
2
O + NO
3
-
NH
4
NO
3
+ OH
-
(3.3)
2OH
-
+ Zn
2+
ZnO(seed) + H
2
O (3.4)
ZnO(seed) ZnO(crystal). (3.5)
3.2 Measurements
After fabrication, the samples of Mn-doped ZnO ceramics, thin films and
nanostructures were studied to investigate the structural, optical and magnetic properties,
using X-ray diffraction (XRD), electron microscopy, spectroscopy and magnetometry. In
this part, we introduce briefly the apparatus and measurements performed on our samples.
3.2.1 X-ray diffraction
To check the structure, including any Mn-related secondary phases present in the
samples, we have used X-ray diffraction (XRD) by means of an X'Pert Philips
diffractometer. Measurements were carried out in the 2 range from 27 to 65
o
, with a
scanning step of 0.02 . The X-ray radiation source was CuK
1
( =1.5406 ), at applied
23
voltage and current 40 kV and 30 mA, respectively. Commercial ZnO powder was used
as a reference sample to calibrate XRD data acquired from the experimental samples.
3.2.2 Electron microscopy
The morphology of nanostructured samples was imaged by using field-emission
scanning electron microscopy (FE-SEM, JEOL-JSM 6330F) working at 10 kV, with a
current of 12 - 12.5 A. The distance between the probe and the samples was about 10 -
15 mm. For microstructure analyses, all the samples including polycrystalline ceramics,
thin films and nanostructures were examined by transmission electron microscopy (TEM,
EM 430 or JEOL 2010 TEM) working at 250 kV for Philips EM 430 and at 200 kV for
JEOL 2010 TEM. The Mn concentration in the sample was obtained by means of energy
dispersive X-ray spectroscopy (EDS) linked with FE-SEM or JEOL 2010 TEM. For
TEM-EDS measurements, we mixed a small amount of pure ZnO commercial powders
with the Mn-doped ZnO samples. Before recording TEM-EDS spectra, we looked for
appropriate regions of the samples where the weight percentages of Zn and O in pure ZnO
particles are about 80.3 and 19.7 at.%. After that, the EDS spectra in the range 0-20 keV
were recorded for Mn-doped crystals located around these pure ZnO particles. For a
probe size of about 20 nm, the EDS spectra were taken several times from a sample area
of each crystal, with an estimated error of about 2 %.
Before performing TEM investigations, a very small amount of Mn-doped ZnO
polycrystalline ceramics and nanostructures were arranged on a copper mesh. For thin
films, however, they were cut and glued on a copper grid, and then polished using
diamond lapping films and precision ion polishing system (PIPS, Model 691) [118]. Both
plan-view and cross-section samples were prepared in our work, which allowed us to
investigate the orientation of crystals. Detailed descriptions of how to prepare plan-view
and cross-section samples can found elsewhere in Refs. [118-120].
The specimens were mounted into a double-tilt goniometer, and then loaded into the
microscope, illuminated, and the beam aligned. A certain element of luck was required
when selecting a suitable crystal to study. It was important that the crystal lays in a
horizontal plane, perpendicular to the electron beam. The specimen height could be
adjusted so that the crystal was eucentric [121]. Subsequently, the crystal was tilted to
observe and record clear TEM images and diffraction patterns. These procedures often
required a number of iterations and also re-adjustment of the specimen height to account
for large tilt angles or for any loss of eucentricity around the major tilt axis. For
conventional selected area electron diffraction (SAED), a selected-area aperture defined
24
the area from which the pattern could be recorded. In this case, a parallel electron beam
illuminated the specimen, see Fig. 3.14.

Figure 3.14: Formation of an SAED pattern, parallel illumination.

Figure 3.15: Formation of micro-diffraction patterns using CBED, array of discs in
diffraction plane corresponding to spots in SAED.
25
For tiny crystals with dimensions of several tens of nanometers (nanoparticles),
where SAED is not applicable since the limit of area selection (aperture size) is about 0.5
m, we used convergent beam electron diffraction (CBED) [79,122], see Fig. 3.15. In this
case, C
1
lens was at position 5 and the size of the electron beam probe focused on
nanoparticles was about 20-30 nm. Micro-diffraction patterns were recorded for major
zone axes.
3.2.3 Raman scattering and photoluminescence
Raman scattering (RS) spectra in backscattering configuration were acquired from
Renishaw spectrometers. Excitation wavelengths were from a water-cooled Spectra-
Physics Series 2000 argon-ion laser operated at 488 nm (2.54 eV) and from an air-cooled
Kimmon helium-cadmium (He-Cd) laser operated at 325 nm (3.84 eV). Figure 3.16
shows a photograph of a Renishaw Raman spectrometer, which uses a Leica DMLM
microscope attached to the main spectrometer body. The x40 and x15 objectives were
used to change the excitation density over a volume of the sample. Before carrying out a
Raman measurement, the spectrometers were calibrated carefully [106] based on
characteristic frequency shifts for diamond and silicon at about 1332 and 520 cm
-1
,
respectively.
Photoluminescence (PL) spectra of the samples were also acquired from one of
these spectrometers using an excitation wavelength of 325 nm. The excitation power
could be changed by either control of the laser output or using neutral-density filters in
the laser beam path. All of RS and PL spectra were recorded at room temperature.

Figure 3.16: Photograph of a Renishaw Raman spectrometer [106].
26
3.2.4 Electron spin resonance
Electron spin resonance (ESR) is a sensitive probe for determining electronic
structure and the spatial distribution of ferromagnetic and paramagnetic species in a
material. It is directly sensitive to unpaired electrons, and is therefore the method of
choice for studying metal ions and defect centers present in semiconductors.
We used this technique to investigate the spin dynamics of Mn dopants in Mn-
doped ZnO samples. Particularly, isolated Mn
2+
ions in the ZnO crystal field exhibit the
characteristic hyperfine lines caused by electron-nuclear interactions, which are easy to
detect at room temperature. Here, ESR measurements were performed at Chungbuk
National University (South Korea) using a Jeol JES-TE300 ESR Spectrometer (see Fig.
3.17), in the temperature range between 77 and ~500 K. The microwave frequency was
maintained at 9.2 GHz (X-band) while the applied magnetic field was scanned from 0 to
10 kOe. For polycrystalline ceramics, small amounts (20 mg) of each powdered sample
were loaded into quartz tube holders, whilst the thin-film and nanostructured samples on
Si substrates were mounted on quartz rods. They were then inserted into the microwave
cavity.

Figure 3.17: Photograph of a JEOL-TE300 ESR spectrometer [123].
27
3.2.5 Some other measurements
Apart from the above measurements, we have studied room-temperature optical
absorption of Mn-doped ZnO thin films using UV-3600 UV-VIS-NIR Spectrophotometer
(Shimadzu), in Laboratoire de Spectroscopie Ultrarapide (Ecole Polytechnique Fdrale
de Lausanne, Switzerland). To carry out this work, the films were deposited on quartz
substrates by pulse laser deposition under fabrication conditions similar to those deposited
on the Si substrates.
To investigate magnetic properties of the samples, we used a physical property
measurement system (PPMS-6000) at Institute of Materials Science (Vietnam Academy
of Science and Technology), where magnetic field could be changed from -50 to 50 kOe.
Hysteresis loops were recorded at two temperatures of 5 and 300 K. Temperature
dependences of magnetization were measured in the range from 4.5 to 300 K. In the case
of the thin films, the film plane and magnetic field were parallel.
28
Chapter 4
Mn-doped ZnO ceramics
This chapter presents experimental results obtained for polycrystalline Mn-doped ZnO
ceramics sintered at temperatures between 400 and 1000
o
C. The aim is to study
systematically the influences of sample preparation conditions and sintering temperature
on the structure, optical and magnetic properties of this material system. The possibility
of Mn substitution into Zn sites in the ZnO host matrix is also considered. X-ray
diffraction (XRD) and TEM equipped with EDS are employed to analyze structure and
distribution of Mn in crystals. Based on the results obtained, the origin of magnetism in
the samples is discussed.
4.1 Review of earlier works
Following the theoretical prediction of Dietl et al. [12] in 2000, the first
experimental evidence showing room-temperature ferromagnetic ordering was reported
by Sharma et al. [9,76] for polycrystalline Mn-doped ZnO compounds prepared by
conventional solid-state reaction in air. This phenomenon appeared only when Mn-doped
ZnO ceramics were sintered at temperatures below 700
o
C. The increase of sintering
temperature (T
s
) above 700
o
C suppressed ferromagnetic ordering, and samples became
paramagnetic. By measuring the T
s
dependence of element distribution maps (performed
on JSM-840 SEM), Sharma et al. [9] observed Mn clustering in the samples sintered at
temperatures T
s
> 600
o
C. It was inferred from these observations that the collapse of the
room-temperature ferromagnetic ordering was due to the presence of Mn clusters which
promoted development of an antiferromagnetic or paramagnetic phase. The
ferromagnetism observed in samples processed at low temperatures was attributed to a
uniform solution of Mn in the ZnO host lattice.
One year later, Kundaliya et al. [73] repeated Sharma's study [9,76] to investigate
the origin of room-temperature ferromagnetism in the Zn-Mn-O system processed at low
temperatures. By analyzing chemical reaction kinetics between the precursors ZnO and
MnO
2
, and by investigating the inter-diffusion of thin-film bilayers based on these two
oxides, they concluded that the ferromagnetism in Mn-doped ZnO is associated with a
29
metastable oxide phase rather than carrier-induced interaction between separated Mn
atoms in the ZnO host matrix. Their study implied that the uniform solution of Mn in
ZnO, as mentioned by Sharma et al. [9], could not occur for low-temperature processing.
It was proposed that Zn diffused into Mn oxides to form metastable compounds of
Zn
x
Mn
2-x
O
3-
, which were considered as the origin of room-temperature ferromagnetism.
In another work performed on bulk 2 at.% Mn-doped ZnO sintered at temperatures
300 - 1000
o
C, Blythe et al. [71] also found similar results as reported by Sharma et al.
[9,76], where the room-temperature ferromagnetic phase is destroyed by increasing T
s

above 700
o
C. Interestingly, for a non-sintered mixture of powders, they found that the
ferromagnetism depended on the grinding time. The saturation magnetization increased
with increasing the grinding time up to 15 hrs. The authors suggested that the
ferromagnetism in the non-sintered mixture of powders was due to a phase Zn
1-x
Mn
x
O
generated by the grinding, resembling mechanical alloying [71], where high local
temperatures and interparticle pressures are generated at the points-of-contact between
powder grains. This phase would be located on the surface of MnO
2
and ZnO particles.
The results of these studies have generated considerable interest. Several research
groups [18,36,39-41,72] attempted to synthesize high-quality Mn-doped ZnO samples,
and investigated the influence of preparation conditions on their magnetic properties.
Many suppositions have been proposed to clarify the nature of room-temperature
magnetism in this material system. Chen et al. [39] studied 2 at.% Mn-doped ZnO
sintered at 600
o
C in air and Ar gas. The room-temperature ferromagnetic phase was
observed only in the sample annealed in Ar gas, whereas the samples annealed in air
seemed anti-ferromagnetic. In Refs. [18,40,41], Bhatti and Zhang et al. investigated
samples with Mn concentrations varied over a wider range. They also described results
similar to those reported by Sharma et al. [9,76]. The authors suggested that the room-
temperature ferromagnetic ordering in low-temperature processed samples was caused by
a randomly distributed impurity phase produced by local dissolution of ZnO and MnO
2
,
definitely from neither Zn
1-x
Mn
x
O nor a uniform solution of Mn in ZnO. Having used
TEM equipped with EDS, Costa-Kramer et al. [36] indicated that the reaction between
ZnO and MnO
2
led to the appearance of a new phase, probably related to the diffusion of
Zn into MnO
2
nanoparticles. This phase was considered to be responsible for the
ferromagnetic ordering. No diffusion of Mn cations into ZnO particles was observed in
this work.
30
Clearly, the origin of ferromagnetism in the low-temperature processed Zn-Mn-O
system, based on experimental results, is in confusion and contradiction with each other.
This is certainly due to differences in the sample-preparation routes which may lead to the
appearance of Mn- and Zn-related secondary phases which are not well known. However,
most authors agree that the ferromagnetism is associated with a metastable phase formed
by the diffusion of Zn into manganese oxides.
To gain more insight into this problem, Garcia and Lopez-Ponce et al. [72,75]
deposited ZnO/MnO
2
multilayers and then studied thermal diffusion across the interface.
They observed the diffusion of Zn into MnO
2
to form a spinel-like phase of Zn
z
Mn
3-z
O
4
,
even at low temperatures. Consequently, both Mn
3+
and Mn
4+
cations coexisted at the
interface of ZnO/MnO
2
bilayers. The magnetic interaction between them was
ferromagnetic, and could be explained within the framework of the double-exchange
mechanism. In the absence of sufficient sensitivity to detect low levels of Mn, they
assumed that there was no diffusion of Mn into ZnO crystals.
Based upon the research on polycrystalline Zn-Mn-O samples reviewed above, there
are several problems which require further study:
(i) Influence of sample-preparation conditions on secondary phases,
(ii) The possibility of Mn diffusion into ZnO crystals,
(iii) The nature of magnetism in this material system with respect to the sintering
temperature.
To address these issues, we have prepared polycrystalline Mn-doped ZnO
compounds and analyzed in detail their structure using XRD, TEM equipped with EDS.
Their magnetic properties were assessed by a physical property measurement system
(PPMS) and electron spin resonance. Also, we used Raman scattering and
photoluminescence spectroscopy as additional tools to study processes taking place when
our samples are sintered at different temperatures.
4.2 Sample selection
If the Mn atoms do not diffuse into ZnO crystals, the distribution of Mn in the Zn-
Mn-O system is not homogeneous, and the presence of ZnO around MnO
2
promotes the
development of phases related to the manganese oxides, considered to be the origin of the
room-temperature ferromagnetism. It follows that the room-temperature ferromagnetism
in Mn-doped ZnO ceramics is not associated with Mn
2+
ions located at the Zn sites in
ZnO crystals, but due to manganese oxides. To get more insight into these problems, in
31
the present work we have selected a composition of ZnO doped with 8 at.% Mn (i.e., x =
0.08 in Eq. 3.1). With this concentration, we believe that manganese-related secondary
phases would be observed more easily than in samples doped with low Mn concentrations
of 1 - 2 %. Here, our samples are divided into two series as follows:
The first series includes seven samples sintered at temperatures between 400 and
1000
o
C, with an increment T = 100
o
C. For this series, the precursors were wet mixed
over night by a milling machine using zirconia balls and high-purity water.
The second series has two samples sintered at 500 and 800
o
C, where their
precursors were mixed and ground by hand without high-purity water.
Detailed descriptions on the preparation of these samples are given in Chapter 3.
Some reference compounds of manganese oxides such as Mn
2
O
3
, Mn
3
O
4
and ZnMn
2
O
4

were also prepared.
4. 3 Results and discussion
4.3.1 Structural characterization and microanalyses
4.3.1.1 X-ray diffraction study
Figure 4.1 shows X-ray diffraction (XRD) patterns of the first series sintered at
temperatures T
s
= 400 - 1000
o
C. Comparing to XRD profiles of ZnO and manganese
oxides, we have identified the origin of diffraction peaks generated from two structural
phases. The first one is from the ZnO-wurtzite structure while the other is from a
manganese oxide composition of ZnMnO
3
with the spinel-type structure, which was
reported in a pioneering work by Toussaint [124]. After Toussaint [124], other authors
also observed the presence of this phase in Zn-Mn-O compositions [29,70,125,126]
without giving any comment or further study concerned the unreason in its chemical
formula when it was considered it as a spinel-type composition. Basically, the spinel has a
general formula AB
2
O
4
(or [A]
tet
[B]
oct
O
4
, where A and B can be divalent, trivalent, or
quadrivalent cations, including magnesium, zinc, iron, manganese, aluminium, chromium,
titanium and so forth) with A in tetrahedral 8a sites and B in octahedral 16d sites. Having
compared the chemical formula ZnMnO
3
described by Toussaint [124] with the spinel
formula AB
2
O
4
, we can see a significant difference in their chemical formulae. Our
following work proves that the composition ZnMnO
3
must be re-defined as Zn
2
MnO
4
, the
so-called inverse spinel structure (i.e. B
2
AO
4
or [B]
tet
[A,B]
oct
O
4
, where A is in octahedral
sites and B could be in both tetrahedral and octahedral sites). Detailed descriptions about
these spinel structures could be found anywhere in Refs. [127-129]. In our case, because
32
the Mn/Zn ratio in composition Zn
2
MnO
4
varies to sintering temperature T
s
, we write it in
a general form of Zn
x
Mn
y
O
4-
., with x 2 and y 1 when changing T
s
(which is being
discussed later). The indices of reflections from these two phases of wurtzite ZnO and
inverse spinel Zn
x
Mn
y
O
4-
(ZMO) are labelled in Fig. 4.1.
30 35 40 45 50 55 60 65
(
2
2
2
)
Z
M
O
(
4
0
0
)
Z
M
O
(
3
1
1
)
Z
M
O
(
2
2
0
)
Z
M
O
(
1
0
3
)
Z
n
O
(
1
1
0
)
Z
n
O
(
1
0
2
)
Z
n
O (
1
0
1
)
Z
n
O
(
0
0
2
)
Z
n
O
(
1
0
0
)
Z
n
O

(
5
1
1
)
Z
M
O
(
4
4
0
)
Z
M
O
(
4
2
2
)
Z
M
O
As-prep.
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
T
an
(
0
C)
1000
900
800
700
600
500
400
2 (Degree)
ZnO

Figure 4.1: XRD patterns of the first series sintered at different temperatures compared to
those of ZnO and the as-prepared sample. Two phases of the ZnO wurtzite and
Zn
x
Mn
y
O
4-
(ZMO) with indexes are shown.
For the first phase with the ZnO wurtzite structure, its XRD-peak positions {i.e.,
indices (100), (002), (101), (102), (110) and (103)} change with T
s
, exhibiting a change in
lattice parameters a, c and V. We have calculated these parameters basing on XRD data,
and the results are shown in Fig. 4.2. One can see that a, c and V for all the samples (even
the as-prepared sample) are higher than those of ZnO. They are unchanged in the range T
s
= 400 - 700
o
C, but decrease for T
s
> 700
o
C. Here, the volume of the cell decreases but
the shape of the cell remains the same (see Fig. 4.3, which shows the dependence of the
c/a ratio on T
s
), revealing a uniform variation of the ZnO lattice in both the a- and c-
33
directions, consistent with the presence of Mn in the ZnO host lattice. Comparing with
pure ZnO, the change in the lattice parameters of the Mn-doped ZnO samples is about 0.2
- 0.5 % while the change in the c/a ratio is below 0.1 %.
Table 4.1: Variation of XRD peaks (2) of Zn
x
Mn
y
O
4-
with the annealing temperature
(T
s
). The identification of these indices is referred to Ref. [124].
Sintering temperature T
s
(
o
C) Peak
index
As-
prep
400 500 600 700 800 900 1000
(220) 29.76 29.91 29.99 29.92 29.98 30.03 29.96 29.96
(311) 35.35 35.34 35.39 35.34 35.31 35.39 35.46 --
(222) -- -- -- 36.94 36.91 37.02 37.05 37.04
(400) 42.78 43.11 43.07 43.01 42.98 43.10 43.24 43.66
(422) 53.36 53.39 53.48 53.45 53.39 53.46 53.56 53.76
(511) -- -- -- 56.88 56.91 56.95 57.03 57.73
(440) -- -- -- -- -- -- 62.15 62.13

Regarding to the secondary phase of Zn
x
Mn
y
O
4-
, the increase in sintering
temperature leads to an increase in its XRD intensity, which reaches a maximum value at
800
o
C. At higher sintering temperatures (T
s
> 800
o
C), the XRD intensity of this phase
decreases. Similar behavior has been observed in Zn
1-x
Mn
x
O samples prepared by the co-
precipitation method described by Pieteado et al. [125]. Table 4.1 shows the variation of
XRD peaks of this phase versus T
s
. One can see that the peaks shift slightly towards
higher diffraction angles as increasing T
s
. Among them, the strong peaks centered at
about 30 and 35
o
corresponding to indices (220) and (311), respectively, appear soon
after milling and mixing the precursors ZnO and MnO
2
, see XRD of the as-prepared
sample in Fig. 4.1. Since Zn
x
Mn
y
O
4-
is known as the cubic spinel structure [124], by
means of the relation between the Miller indices and lattice parameters for a cubic cell
[122,130]
2
2 2 2
2
1
a
l k h
d
hkl
+ +
= , (4.1)
34
5.21
5.22
5.23
5.24
3.25
3.26
3.27
0 200 400 600 800 1000
47.7
48.0
48.3
48.6
(b)
(a)
c

(

)
a

(

)

ZnO
(c)
ZnO

o
o
o
V

(
A
3
)
T
s
(
o
C)
ZnO


Figure 4.2: Lattice parameters a, c and V (with 0.1 % error bars) for the first series of
samples as a function of T
s
; the solid lines are to guide the eye.
0 200 400 600 800 1000
1.598
1.599
1.600
1.601
1.602
1.603
1.604
1.605
ZnO
Zn-Mn-O ceramics
c
/
a

r
a
t
i
o
T
s
(
o
C)


Figure 4.3: Variation of the c/a ratio with sintering temperature for 8 at.% Mn-doped
ZnO ceramics (the first series).
35
where a = b = c, we determined a from the indices listed in Table 4.1. Its average value
determined for all the samples is about 8.41 0.02, close to those reported by Toussaint
(8.35 ) [124] and Blasco et al. (8.36 ) [70]. The detail of the T
s
dependence of a can be
also seen in Fig. 4.4. It shows that a gradually decreases with increasing T
s
, particularly
for the samples with T
s
> 600
o
C. This could be related to changes in the particle size and
chemical composition of Zn
x
Mn
y
O
4-
crystals, which are investigated later.
200 400 600 800 1000
8.32
8.36
8.40
8.44
8.48
O

a

(
A
)
T
s
(
o
C)

Figure 4.4: The variation of the lattice parameter a (obtained from XRD peaks) with
respect to T
s
for the secondary phase of cubic Zn
x
Mn
y
O
4-
spinels; the solid line is to
guide the eye only. Error bars of 0.2% are shown.
In point of fact, there are three structure types including hexagonal, tetragonal and
cubic structures for Zn
x
Mn
y
O
4-
that could be formed by reaction between ZnO and
MnO
2
. Among these, the hexagonal (i.e., ZnMnO
3
, as presented in Ref. [131], with x, y
and 1) is formed only at a very high pressure in the presence of KClO
3
, whereas the
tetragonal phase is easily formed by preparation under normal conditions and its chemical
formula is usually ZnMn
2
O
4
(i.e., x 1 and y 2, assigned to normal spinel-type
structures). To form cubic Zn
x
Mn
y
O
4-
spinels (with x 2 and y 1), the synthesis is
usually carried out at high temperatures (above 1100
o
C) [132], in oxygen ambient
[29,70] or by high-energy ball milling [133]. Surprisingly, in our case this phase nucleates
at very low temperature (similar to Ref. [133]), soon after the mixing and milling. We
36
think that the milling and mixing of the precursors generates local heating at the points-
of-contact between grains [71], which promote surface reactions between ZnO crystals
and MnO
2
particles. Concurrently, oxygen is also released due to the decomposition
MnO
2
Mn
2
O
3
, see thermogravimetry analysis (TGA) in Figs. 3.1 and 3.2 for more
details. All of these processes take place in a sealed plastic box, which is a good condition
to form cubic Zn
x
Mn
y
O
4-
spinels. As can be seen in Fig. 4.1, this phase does not change
into other phases for increasing T
s
up to 1000
o
C. Our microanalyses afterwards confirm
that the x and y values in Zn
x
Mn
y
O
4-
of Mn-doped ZnO samples changes with T
s
.
30 35 40 45 50 55 60 65
*

(110)
#
#
o
o
o
o
o o
#
800 (
o
C)

(100)

(103)
(102)
(101)
(002)
o
*


Mn
2
O
3
500 (
o
C)
MnO
2

ZnMn
2
O
4
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)

2 (Degree)


Figure 4.5: XRD patterns of the samples from the second series sintered at 500 and 800
o
C, compared with patterns for the manganese oxides. The symbols o, # and correspond
to XRD peaks from ZnMn
2
O
4
, Mn
2
O
3
and MnO
2
, respectively.
Concerning the second series ground by hand and sintered at 500 and 800
o
C, their
XRD patterns are shown in Fig. 4.5. One can see that besides the indexed peaks coming
from the ZnO wurtzite structure, there are additional peaks coming from manganese
oxides. In this case, the lattice parameters of Mn-doped ZnO are higher than those of pure
ZnO (a = 3.27 and c = 5.23 for the T
s
= 500
o
C sample, and a = 3.27 and c = 5.24
for the T
s
= 800
o
C sample), and are similar to the lattice parameters measured for the
first series, consistent with the incorporation of Mn atoms into ZnO crystals. By
37
comparison with the XRD patterns of manganese oxides, we have confirmed that the
secondary phases appearing in the sample annealed at 500
o
C are MnO
2
(Space group:
P4
2
/mnm [134]) and Mn
2
O
3
(Space group: Ia3 [135]), as shown in Fig. 4.5. At a higher
sintering temperature of T
s
= 800
o
C, only the tetragonal ZnMn
2
O
4
phase (Space group:
I4
1
/amd [136]) is observed. XRD peaks from the manganese oxide phases could not
detected by XRD. These results are consistent with earlier reports [36,70,72,75]. In fact,
careful study of the XRD patterns published by Garcia [72] and Lopez-Ponce et al. [75]
(Appendix, Fig. A1), shows both the cubic Zn
x
Mn
y
O
4-
and tetragonal ZnMn
2
O
4
phases
(i.e., Zn
z
Mn
3-z
O
4
or (Mn
1-z
Zn
z
)Mn
2
O
4
) coexist in their samples. However, the authors
have not discussed this situation. Instead, they mention tetragonal (Mn
1-z
Zn
z
)Mn
2
O
4
only
to explain the magnetic data observed. This could lead to some misunderstanding of the
nature of the magnetism in Mn-doped ZnO ceramics.

Figure 4.6: A micrograph of the mixture of ZnO and MnO
2
before milling or grinding.
The results presented here confirm that sample preparation conditions influence
strongly the structural character of Mn-doped ZnO ceramics. For the first series, their
XRD patterns show that both the ZnO wurtzite and cubic Zn
x
Mn
y
O
4-
phases coexist in
sintered samples. Increasing T
s
does not promote other secondary phases. However, the
XRD patterns of the second series reveal that at a low sintering temperature (T
s
= 500
o
C)
besides ZnO wurtzite there are the phases Mn
2
O
3
and MnO
2
are present. The increase of
T
s
to 800
o
C (the T
s
= 800
o
C sample) promotes formation of the tetragonal ZnMn
2
O
4

structure.
38
4.3.1.2 Transmission electron microscopy study
In this section, we analyze in detail the change in microstructure of the samples with
respect to the sintering by means of transmission electron microscopy (TEM). To carry
out this experiment, powders were distributed onto a copper mesh grid which was then
mounted on a double-tilt sample holder. The electron beam voltage was 250 kV, and the
exposure time for recording TEM images was from 2 to 20 seconds. Figure 4.6 shows a
micrograph of the mixture of the commercial powders (ZnO and MnO
2
) before mixing
and grinding. Their particle size is about 100 - 200 nm. This mixture then was processed
as described in Chapter 3. The following presents TEM analyses for these sample
systems.

Figure 4.7: Some micrographs of the as-prepared sample, which were obtained after wet
mixing ZnO and MnO
2
powders with zirconia milling balls at room temperature.
TEM study of the first series
Having taken into account microstructure of the first series, which was wet mixed
using zirconia milling balls, we find that after 24 hrs mixing (referred to the as-prepared
sample) the morphology of grains was modified very much (see Fig. 4.7) when compared
with the particles shown in Fig. 4.6. There are two characteristic regions corresponding to
different particle sizes. The first one is large crystals with the particle size of about 200
nm, see Fig. 4.7(a), and the other is small particles with the size of 10-30 nm covering on
39
the surface of the large particles, see Fig. 4.7(b,c). These features reveal that the wet
milling of the precursors in a plastic box caused a strong reaction between ZnO and MnO
2

grains. This situation was not considered carefully in previous studies [9,36,39-
41,72,73,76,125], where research was focussed on samples sintered at temperatures above
400
o
C.
To study the change in the size of these crystals with respect to T
s
, we have recorded
the micrographs of all the samples with T
s
= 400 - 1000
o
C. The results obtained are
shown representatively in Fig. 4.8. For the samples sintered at 400 - 700
o
C the sizes of
the large and small particles are almost unchanged compared with the as-prepared sample,
see Figs 4.8(a,b). However, for T
s
= 800 - 1000
o
C the sizes of the large crystals increase
to the range of 0.2 1.0 m, and the small particles become bigger in the range of 50-80
nm, and become bonded to the surface of the large crystals, see Figs 4.8(c,d). Notably, the
nanoparticles corresponding to the T
s
= 400 - 700
o
C samples are damaged easily by
focusing the electron beam on a small area, revealing that they have poor thermal contact
with the larger crystals. For the samples sintered at higher temperatures (T
s
= 800 - 1000
o
C), this situation does not happen, and all crystals have good quality which allowed us to
perform further investigations.
An important problem that needs to be clarified is the structure of the particles (i.e.,
large and small crystals) observed in TEM images. In an attempt to deal with this aspect,
we have employed the TEM techniques of selected area electron diffraction (SAED) and
convergent beam electron diffraction (CBED) [122]. For the large crystals, their structure
was determined by SAED, since their particle size is relatively large and they have good
quality. We have examined many crystals and have found that these crystals always have
the ZnO wurtzite structure. Their electron diffraction patterns for two representative zone
axes ] 0 2 11 [ and ] 0001 [ are shown in Fig. 4.9.
Regarding the small particles (referred to nanoparticles), there are two sintering
temperature regions (T
s
< 800
o
C and T
s
800
o
C) where the quality and average size of
the nanoparticles are different. For the T
s
< 800
o
C samples, the nanoparticles with the
size of about 10-30 nm gather in clusters, which cover the surface of ZnO crystals. When
the electron beam is focused on a small area of these particles, they can often re-
crystallize into a particle with a larger size. This instability may be attributable to a
combination of beam heating, poor thermal contact with the ZnO crystals and perhaps an
unstable crystal structure. We have performed TEM investigations on the clusters instead
of individual particles. Fig. 4.10 shows micrographs and SAED images of the as-prepared
40

Figure 4.8: Some representative micrographs of the samples belonging to the first series
sintered at (a) 600, (b) 700, (c) 800 and (d) 1000
o
C.

Figure 4.9: A micrograph of a large crystal with T
s
= 800
o
C, and indexed diffraction
patterns for two selected electron beam directions ] 0 2 11 [ and ] 0001 [ . The dotted circle is
the area where the SAED patterns were recorded.
41

Figure 4.10: Some representative micrographs and SAED patterns of the nanoparticles
sintered at temperatures T
s
< 800
o
C: (a) the as-prepared, (b) T
s
= 400
o
C and (c) T
s
= 700
o
C samples. The dotted circles on the micrographs are areas where the diffraction images
were recorded.
42
Table 4.2: The diffraction angle (2) of the nanoparticles calculated from electron
diffraction rings using Eqs. (4.2 and 4.3).
Zn
x
Mn
y
O
4-
(Ref. [124]) Sintering temperature, T
s
(
o
C)
Index 2 (
o
) As-prep. 400 700
(111) 18.37 -- 17.7 17.7
-- -- 27.8
*
-- --
(220) 30.30 31.7 29.6 29.6
(311) 35.70 35.9 35.4 35.4
(400) 43.51 42.5 43.0 43.1
-- -- 46.5
*
-- --
(422) 53.93 -- 53.9 54.2
(511) 57.37 57.6 57.4 57.4
(440) 63.02 -- 61.8 62.2
*These peaks may generate from un-reacted MnO
2
.
and T
s
= 400 and 700
o
C samples. The dotted circles on the micrographs indicate the
regions where the SAED images have been recorded. As can be seen in Fig. 4.10, the
diffraction rings become brighter and sharper when increasing T
s
, revealing an
improvement in crystal quality. This result is in good agreement with the increase in
intensity of secondary XRD peaks shown in Fig. 4.1.
We have identified indices of diffraction rings observed in Fig. 4.10 based on the
relation between equations in TEM and XRD studies [122,130]. For high energy electron
diffraction, the radius of a diffraction ring (R) is given by
d
L
R
1

= , (4.2)
where L is camera length and
1
is wavelength of the electron beam (in our experiment,
the nominal camera length was 500 mm, and
1
= 0.022 for V = 250 kV). On the other
hand, for XRD the distance (d) between two planes in the reciprocal space is given by
Braggs condition

sin 2
2
= d , (4.3)
43
With
2
= 1.5406 (from Cu-k
1
), we have obtained diffraction angles (2 ) using Eqs.
4.2 and 4.3. The 2 values (shown in Table 4.2) versus the sintering temperature are in
good agreement with those in Table 4.1. This confirms that the nanoparticles are
Zn
x
Mn
y
O
4-
. Exceptionally, there are two dim diffraction rings observed for the as-
prepared sample, which may be from unreacted MnO
2
particles, and were not observed in
XRD patterns shown in Fig. 4.1, probably because the amount of MnO
2
in the samples is
too low. For the samples sintered at higher temperatures, these rings were not observed,
since MnO
2
reacts completely with ZnO to form Zn
x
Mn
y
O
4-
and Zn
1-x
Mn
x
O.
As mentioned above, when increasing T
s
above 700
o
C (i.e, T
s
800
o
C) the
nanoparticles are not in clusters but form crystals with larger particle sizes. They are
bonded to the surface of ZnO crystals, see Fig. 4.8(c,d) and Fig. 4.11. Their average size
is in the range 50-80 nm. Thus, the study the structure of these particles is really difficult
if using conventional SAED. To solve this problem, we have employed CBED, in which
the electron beam probe focused on the samples was about 20-30 nm. We have performed
CBED on many nanocrystals, such as the particles marked x in Fig. 4.11. Micro-
diffraction patterns recorded on these nanocrystals have been analyzed carefully by means
of CaRIne Crystallography (version 3.1). The results obtained reveal that the nanocrystals
have the same structure, which has been identified to be the cubic Zn
x
Mn
y
O
4-
. This is in
accordance with the XRD data as discussed above. Fig. 4.12 shows the micro-diffraction
patterns of the Zn
x
Mn
y
O
4-
nanoparticles according to five selected electron beam
directions ] 001 [ , ] 011 [ , ] 111 [ , ] 103 [ and ] 112 [ . The corresponding reflections around the
zone axis are indexed in Fig. 4.13.

Figure 4.11: Some representative micrographs of the nanoparticles (marked as "x")
attached on the surface of ZnO crystals.
44

Figure 4.12: CBED patterns recorded from the Zn
x
Mn
y
O
4-
nanoparticles sintered at 800
o
C according to five selected electron beam directions ] 001 [ , ] 011 [ , ] 111 [ , ] 103 [ and
] 112 [ . The indices are obtained by means of simulated data shown in Fig. 4.13.

Figure 4.13: Zone axis diffraction patterns of the cubic Zn
x
Mn
y
O
4-
spinel for five
selected axis zones, simulated by CaRIne Crystallography.
45
As can be seen from Fig. 4.13, for an F-centred Bravais lattice, only reflections with
h, k, l all even or all odd have non-zero structure factors (F 0). In addition, for space
group m 3 Fd reflections of type hk0 have non-zero structure factors only if the indices
satisfy the condition h + k = 4n (n is integral), as shown in Fig. 4.14. However, for zone
axes such as ] 011 [ ] 103 [ , and ] 112 [ some forbidden reflections still appear. This can be
explained by dynamical double-diffraction effects [79,130,137], which always occurs for
thick samples. For example, in the case of the ] 103 [ diffraction pattern the 0 2 0 reflection
should be absent. However, at the zone axis ] 103 [ the allowed 311 diffracted beam acts as
a new incident beam and is re-diffracted by the (311) plane. As a result, the sum of the
reciprocal lattice vectors of the two allowed reflections, ( 1 1 3 ) + ( 1 1 3 ), results in a
( 0 2 0 ) reflection, as can be seen in Fig. 4.12.
Notably, the CBED images shown in Fig. 4.12 were taken for a camera length L =
500 mm, thus only diffractions around the central 000 disk were observed. Such patterns
are termed a ZOLZ (Zero-Order Laue Zone pattern), since the permitted hkl diffraction
maxima satisfy the Weiss zone law relationship hU + kV + lW = 0 [79], where [ ] UVW is
the beam direction. By using a small convergence semiangle () and short camera length
(L = 270 mm), at the ] 001 [ zone axis we observed not only ZOLZ, but also FOLZ (First-
Order Laue Zone reflections), see Fig. 4.14. Unlike the zero layer (ZOLZ), the
intersection of the Ewald sphere with a plane creates a ring, the so-called FOLZ ring,
where the possible hkl reflections satisfy the relationship hU + kV + lW = 1 [79]. Such
features of ZOLZ and FOLZ patterns confirm that structure of the Zn
x
Mn
y
O
4-

nanoparticles belongs to the cubic space group m 3 Fd (No. 227) [137-140]. These analyses
are in good accordance with the XRD data studied above. As mentioned in previous
reports (Refs. [137,138]), we have found that the structure of Zn
x
Mn
y
O
4-
is similar to that
of MgAl
2
O
4
and Fe-Ti oxide spinels.
From micro-diffraction patterns of the zone axis ] 001 [ shown in Fig. 4.14, we
could also calculate the lattice parameter, a, of the cubic Zn
x
Mn
y
O
4-
. In this case, the
spacing (h) between two planes in the reciprocal space is given by
k
R
h
2
2
= , (4.4)
where R is the FOLZ ring radius and k = 1/. With V = 250 kV and L = 270 mm,
0.02199 and the calibration factor of EM-430 is 0.1680
-1
mm
-1
. We have measured
46
the lattice parameters for several crystals and calculated values of a ranging between 8.10
and 8.38 . This variation is due to differing Zn and Mn components in nanoparticles
(i.e., Zn
x
Mn
y
O
4-
, where x and y changes with various nanoparticles). The a values
obtained in this case is in agreement with cubic spinel compounds as investigated
previously [70,124,137]. It should be noted that the a value obtained from the XRD data
is averaged for all Zn
x
Mn
y
O
4-
nanocrystals.

Figure 4.14: CBED pattern from Zn
x
Mn
y
O
4-
nanoparticles sintered at 800
o
C for the
] 001 [ zone axis, showing reflections in both ZOLZ and FOLZ.
TEM study of the second series
Concerning the second series, which were sintered at 500 and 800
o
C (their
precursors were mixed and ground by hand without high-purity water, see Chapter 3 for
more details). Fig. 4.15 shows TEM images of the T
s
= 500
o
C sample. It is found that the
surface of crystals is rough, probably caused by the friction between particles from
mixing and grinding the precursors of ZnO and MnO
2
. It is different from the
47
microstructure observed for the first series samples. In this case, TEM images of the
sample sintered at 500
o
C do not show many nanoparticles covering the surface of ZnO
crystals (Fig. 4.15(a,b)). However, some clusters were observed with sizes with about 100
nm diameter, Fig. 4.15(c), where the size of nanoparticles is 10 - 30 nm. Taking SAED
patterns from these nanoclusters and also larger areas without nanoclusters, we have
found that the features of diffraction rings from these regions are similar, as can be seen
in Fig. 4.15(d,e). We analyzed these diffraction patterns and identified that they are all
from Mn
2
O
3
[135], their indices are indicated in Fig. 4.15(d,e). With this result, it is
reasonable to say that most nanoparticles in the T
s
= 500
o
C sample are Mn
2
O
3
, which was
caused by the decomposition process MnO
2
Mn
2
O
3
. However, the XRD data shown in
Fig. 4.5 indicates that there exist unreacted MnO
2
particles. This could be because the
particle size of MnO
2
in the sample is large and comparable to those of ZnO crystals.
Consequently, their electron diffraction includes spots instead of rings as observed in Fig.
4.15(d,e).

Figure 4.15: (a-c) TEM images of the sample sintered at 500
o
C; SAED patterns for (d) a
large area (without nanoclusters, like the figures a and b) and for (e) nanoclusters (like the
figure c).
48

Figure 4.16: TEM images of the sample sintered at 800
o
C.
TEM images for the sample sintered at 800
o
C are shown in Fig. 4.16. In
comparison with the T
s
= 500
o
C sample, the surfaces of particles have become smoother.
There are nanoparticles with 50 - 100 nm diameter attached on the surface of large
crystals of ZnO. This is similar to the situation observed for the samples annealed at
temperatures T
s
800
o
C in the first series (see Fig. 4.8 and 4.11). Based on XRD data
shown in Fig. 4.5, and on detailed analyses in Refs. [36,72,75], we suggest that the
nanoparticles in the 800
o
C sample are tetragonal Zn
z
Mn
3-z
O
4
spinels.
4.3.1.3 Energy dispersive X-ray spectroscopy microanalysis
In this subsection, we discuss EDS spectra of the first series annealed at
temperatures 400 - 1000
o
C. EDS analyses of the samples in the second series could refer
to Refs. [36,72,75], where the structure of our samples is quite similar to the structure of
samples studied in these reports.
As described above, for the first series, besides the wurtzite ZnO and cubic
Zn
x
Mn
y
O
4-
phases there exist some unreacted MnO
2
particles for the samples sintered at
low temperatures. The lattice parameters of ZnO and Zn
x
Mn
y
O
4-
crystals change with the
annealing temperature (T
s
). To get more insight into this phenomenon, we have studied
the change in Mn concentration in the crystals using energy dispersive X-ray
spectroscopy (EDS) linked with TEM. The data in the range of 0-20 keV were collected
for 240 seconds with a focused beam of about 20 nm. We have investigated statistically
hundreds of large crystals and nanoparticles. The EDS spectra obtained can be divided
into three groups with the features shown in Fig. 4.17.
49
(i) The first group corresponds to EDS spectra of the ZnO crystals, where the
intensity of Mn is low.
(ii) The second group corresponds to spectra of nanoparticles that the EDS intensity
of Mn is medium.
(iii) The other group shows spectra with a high EDS intensity of Mn, including both
large and nano-particles. The probability of finding these particles is very low, and we
have only observed them in the samples sintered at temperatures T
s
800
o
C.

5 6 7 8 9 10
Cu
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
Cu
Zn (K

)
Zn (K

)
Mn (K

)
Mn (K

)
Energy (keV)
Mn oxide
ZnO crystals
ZMO nanoparticles

Figure 4.17: EDS spectra represent to the regions ZnO crystals, Zn
x
Mn
y
O
4-
nanoparticles
and Mn oxides.
From the EDS data, we have determined the Mn concentration in crystals using an
INCA Oxford analyzer. The concentration ratio of Mn to Zn, Mn/Zn, is shown in Fig.
4.18. Clearly, there are three regions with different Mn/Zn ratios. The first and second
regions correspond to Mn/Zn ratio between 0 and 0.045 from ZnO crystals, and between
0.1 and 0.7 for Zn
x
Mn
y
O
4-
nanoparticles, respectively. The other group of spectra with
Mn/Zn between 1.05 and 2.7 is probably from unreacted MnO
2
particles. However, EDS
spectra of these particles still exhibit the presence of Zn (see Fig. 4.17). This is probably
due to the mixing of Zn
x
Mn
y
O
4-
nanoparticles as the samples sintered at low temperature
(T
s
< 700
o
C), and also due to the diffusion of Zn atoms into MnO
2
at T
s
> 700
o
C to form
Zn
z
Mn
3-z
O
4
(z 1) spinels [72]. The amount of Zn
z
Mn
3-z
O
4
in the samples is too small to
50
probe by XRD and SAED patterns. Notably, at sintering temperatures above 800
o
C, we
have not found any crystals with Mn/Zn > 1.05, since MnO
2
reacted fully with ZnO to
form Zn
1-x
Mn
x
O and Zn
x
Mn
y
O
4-
.
400 500 600 700 800 900 1000
0.0
0.5
1.0
1.5
2.0
2.5
3.0
M
n
/
Z
n

r
a
t
i
o
T
s
(
o
C)
ZnO crystals
Mn oxide
ZMO nanoparticles

Figure 4.18: The Mn/Zn ratio obtained from the crystals as a function of the sintering
temperature, T
s
.
To understand more the variation of the Mn/Zn ratio in ZnO crystals and
Zn
x
Mn
y
O
4-
nanoparticles for increasing T
s
, we re-depict Fig. 4.18 in the range 0 - 1.0, see
Fig. 4.19(a). It appears from Fig. 4.19(a) that, Mn/Zn is a function of T
s
. At temperatures
T
s
< 700
o
C, Mn/Zn seems almost unchanged. However, with increasing T
s
in the range
700 - 900
o
C, the Mn/Zn ratio of Zn
x
Mn
y
O
4-
nanoparticles increases slightly, and there
may be a small decrease of the ratio for ZnO crystals. For a further increase of T
s
above
900
o
C, Mn/Zn ratio is unchanged. These results indicate that the chemical formula of
ZnO should be written as Zn
1-x
Mn
x
O (x < 1) and Zn
x
Mn
y
O
4-
has x 2 and y 1 (i.e.
Mn/Zn ~0.5). Statistically, we obtained the Mn concentration in Zn
1-x
Mn
x
O is in the
ranges 0.3 - 3.8 at.%, and in Zn
x
Mn
y
O
4-
is in the ranges 7.0 - 36.0 at.% when T
s
is
changed, as can be seen in Fig. 4.19(b). Clearly, curves in Fig. 4.19 agree quantitatively
with variation of lattice parameter determined by XRD with T
s
. These data are considered
as important results, allowing us to understand the nature of magnetism in the ceramic
samples with respect to the sintering, as being discussed later. It should be noted that the x
value in Zn
1-x
Mn
x
O must be understood as a total concentration of Mn atoms present in
51
400 500 600 700 800 900 1000
0.00
0.02
0.04
0.06
0.2
0.4
0.6
0.8
1.0
(a)


T
s
(
o
C)
M
n
/
Z
n

r
a
t
i
o
ZnO crystals

ZMO nanoparticles
400 500 600 700 800 900 1000
0
1
2
3
4
5
10
15
20
25
30
35
40
ZMO nanoparticles
ZnO crystals
T
s
(
o
C)

M
n

c
o
n
c
e
n
t
r
a
t
i
o
n

(
a
t
.
%
)
(b)


Figure 4.19: (a) The Mn/Zn ratio and (b) Mn concentration in ZnO crystals and
Zn
x
Mn
y
O
4-
(ZMO) nanoparticles as a function of T
s
(with 2 % error bars). The solid lines
are to guide the eye only.
52
the ZnO host lattice. Its highest value referring to the solubility of Mn in ZnO obtained is
about 4.0 %, which is in agreement with theoretical and experimental results for dilute
magnetic semiconductors [9,12,73,76].
4.3.2 Optical properties of Mn-doped ZnO ceramics
The TEM studies have shown that the ceramic samples sintered at temperatures T
s

700
o
C have poor quality, and their quality is improved significantly by sintering at higher
temperatures. To further confirm this conclusion, another effective probe is based on
optical spectroscopy techniques, such as Raman scattering and photoluminescence
spectroscopy. The spectra obtained from the first series of Mn-doped ZnO ceramics are
described below. Based on the features of the spectra, we can assess how the quality of
the sample changes with the sintering. Furthermore, the incorporation of Mn dopants into
the ZnO host matrix and the presence of secondary phases in the samples could be
deduced. All measurements were performed at room temperature.
200 300 400 500 600 700 800
T
A
+
L
O
E
1
(
L
O
)
2
B
1
(
l
o
w
)
E
2
(
h
i
g
h
)
E
1
(
T
O
)
A
1
(
T
O
)
E
2
(
h
i
g
h
)
-
E
2
(
l
o
w
)
2
T
A
T =300 K
=488 nm
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
Raman shift (cm
-1
)
Pure ZnO

Figure 4.20: The RS spectrum of pure ZnO for an excitation wavelength of 488 nm.
4.3.2.1 Raman scattering study
Firstly, we describe Raman scattering (RS) in pure ZnO. Its spectrum for an
excitation wavelength of 488 nm (2.54 eV) is shown in Fig. 4.20. This energy level is
below the band gap of ZnO (3.37 eV), thus the spectrum corresponds to normal Raman
scattering [108,141,142]. It is similar to earlier studies Refs. [107,110,111], where the RS
spectrum of pure ZnO consists of conventional vibration modes centred at 203, 332, 383,
53
411, 438, 540, 583 and 663 cm
-1
, which correspond to the processes 2TA (or 2E
2
(low)),
E
2
(high)-E
2
(low), A
1
(TO), E
1
(TO), E
2
(high), 2B
1
(low) (or 2LA), E
1
(LO) and TA+LO,
respectively (see Table 4.3 for more details). The presence of these modes proves that
ZnO has high quality. We have not observed the A
1
(LO) mode at about 574 cm
-1
(a
phonon is polarized parallel to the z axis) [107], this is probably due to its very low
intensity or the polycrystalline nature of pure ZnO in our case.
Figure 4.21 shows RS spectra from the first series, including the as-prepared sample
and the samples sintered at temperatures T
s
= 400 - 1000
o
C. When compared with the
spectrum from pure ZnO, the RS spectra of Mn-doped ZnO ceramics show not only the
modes associated with wurtzite ZnO (i.e., Zn
1-x
Mn
x
O), but also additional modes (AM) in
the frequency range 450 - 750 cm
-1
. Similar features have been observed in other ZnO
samples doped with Mn [20-22,32,33,37,42,77].
Table 4.3: Room temperature frequencies observed in our sample of pure ZnO compared
with those of Refs. [107,110,111].
Wavenumber (cm
-1
)
Our data Ref. [107] Ref. [110] Ref. [111]
Assignment
203 208 208 203 2TA; 2E
2
(low)
332 334 332 333 E
2
(high)-E
2
(low)
383 380 380 378 A
1
(TO)
411 407 408 410 E
1
(TO)
438 437 437 438 E
2
(high)
540 538 541 536 2B
1
(low); 2LA
583 583 584 590 E
1
(LO)
-- 574 574 574 A
1
(LO)
663 -- -- 666 TA+LO
In the Raman spectra for wurtzite Zn
1-x
Mn
x
O, the vibrations E
2
(high)-E
2
(low),
E
2
(high) and E
1
(LO) still persist, whereas the other modes (see Table 4.3) are invisible.
The disappearance of these modes may be due to topological and structural disorder
associated with the incorporation of Mn into ZnO, which extinguishes the weaker
54
vibrations of the host lattice. Among the visible modes, the E
2
(high) mode associated with
the motion of oxygen atoms [107] has the highest intensity, which is characteristic of the
ZnO wurtzite structure. Its peak position is always lower that in pure ZnO (even for the
as-prepared sample) and varies as a function of T
s
, see Fig. 4.22, consistent with
incorporation of Mn the ZnO host matrix. At a given T
s
value, the shift towards lower
frequencies of the E
2
(high) peak could be explained if Zn
1-x
Mn
x
O is considered as an
alloy semiconductor. The incorporation of Mn atoms into ZnO induces topological and
structural disorders. These disorders break the translation symmetry of the allowed
phonons (i. e., the q = 0 phonons, where q is the wave vector) of the host lattice and leads
to the contribution of q 0 phonons to the Raman line shape, corresponding to the finite
size effect [21,143,144]. This results in the asymmetric broadening and a shift towards
lower frequencies of the E
2
(high) mode. Within an error of about 2 cm
-1
, it is found that
increasing T
s
from 400 to 1000
o
C leads to the shift of the E
2
(high) peak towards higher
frequencies. For T
s
= 1000
o
C, the E
2
(high) frequency of the sample is close to that of
pure ZnO at 438 cm
-1
, see Fig. 4.22. This could be interpreted as consistent with the x-
value decrease in Zn
1-x
Mn
x
O for increasing T
s
, and is in good accordance with the EDS
analyses displayed in Figs. 4.18 and 4.19. Notably, the x value in Zn
1-x
Mn
x
O is the total
concentration of Mn atoms present in the ZnO crystals, as mentioned above. From the
change in peak position of E
2
(high) with respect to T
s
, it could be implied that Mn atoms
have the tendency to diffuse out of the ZnO host lattice at high sintering temperatures.
This issue will be discussed further in the context of the spin dynamics of Mn atoms in
the ZnO host versus the sintering temperature, based on photoluminescence and electron
spin resonance (ESR) studies.
For RS lines in the frequency range 450 - 750 cm
-1
, besides the E
1
(LO) mode
associated with wurtzite ZnO there are some additional ones peaked at 527, 556 and 668
cm
-1
(determined for the sample sintered at 500
o
C), labelled as AM
1
, AM
2
and AM
3
,
respectively in Fig. 4.21. Their origin has been an issue of debate [22,32,33,37,77,107].
Based on the XRD and TEM studies, we suggest that the additional modes may be
associated with secondary phases (Zn
x
Mn
y
O
4-
and MnO
2
) and/or Mn-induced ZnO host
lattice defects. To identify the origin of these vibrations, we have used additionally an
ultraviolet laser with wavelength of 325 nm (3.8 eV). This excitation energy is larger than
the band gap of wurtzite Zn
1-x
Mn
x
O, and satisfies the condition for resonant Raman
scattering of ingoing and outgoing [141,142], where the incident or scattered photons
resonate with real electronic states in a material. Under such condition, only longitudinal
55
optical (LO) phonon scattering and its overtones is visible. However, Zn
x
Mn
y
O
4-
and
MnO
2
have band gap energies higher than 3.8 eV, thus the features of their RS spectra are
independent of either wavelength (488 or 325 nm). In the present case, we exclude the
possibility that the additional modes come from MnO
2
, because only a small amount of
MnO
2
exists in the samples annealed at low temperatures T
s
< 800
o
C (as confirmed by
XRD, TEM and EDS). Furthermore, we studied RS in commercial MnO
2
and found only
a very weak Raman signal.
200 300 400 500 600 700 800
As-prep
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
1000
900
800
700
600
500
400
Raman shift (cm
-1
)
ZnO
x10
Mn-ZnO ceramics
=488 nm
T
s
(
0
C)
AM
3
AM
2
AM
1


Figure 4.21: RS spectra of Mn-doped ZnO ceramics (the first series) sintered at
temperatures T
s
= 400 - 1000
o
C compared to those of ZnO; the dotted lines show ZnO-
related modes, and solid the lines show additional modes (AM) associated the Mn dopant.
The additional modes appear even for the as-prepared sample, revealing that Mn dopants
incorporated into the ZnO host lattice and that the cubic Zn
x
Mn
y
O
4-
formed soon during
mixing and milling the initial materials of ZnO and MnO
2
. More details are shown in text.
56
100 200 300 400 500 600 700 800 900 1000
425
430
435
440
445
As-prep.
2 cm
-1
438 cm
-1
ZnO
Zn
1-x
Mn
x
O phase

(
E
2

(
h
i
g
h
)
)

(
c
m
-
1
)
T
s
(
o
C)

Figure 4.22: The E
2
(high) peak position as a function of T
s
; the solid line is to guide the
eye only.
400 600 800 1000 1200 1400
AM
3
AM
1
1LO
T
s
=1000
o
C
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
Raman shift (cm
-1
)
ZnO
2LO
(b)
(a)
= 325 nm
= 488 nm
T
s
=1000
o
C


Figure 4.23: RS spectra of the sample sintered at 1000
o
C and pure ZnO under excitation
wavelengths (a) 488 nm and (b) 325 nm.
57
Figure 4.23 shows the RS spectra of the Mn-doped ZnO sample sintered at 1000
o
C and pure ZnO under excitation wavelengths of 488 and 325 nm. As excited by 325 nm,
the resonant RS spectrum of pure ZnO exhibits only two lines coming from the first and
second LO phonons (i.e., 1LO and 2LO). However, for the Mn-doped sample besides the
LO-phonon lines there is an additional mode with the peak position matching with that of
AM
3
(as the Mn-doped sample is excited by 488 nm), see Figs. 4.23(a,b). This suggests
that AM
3
is generated from cubic Zn
x
Mn
y
O
4-
spinels, in agreement with the results
reported by Wang [21] and Cong et al. [37]; these authors also found lines at about 663
and 665 cm
-1
and suggested that these lines were from Zn
2
MnO
4
and ZnMnO
3
,
respectively. However, the AM
1
and AM
2
modes were not observed in the resonant RS
spectra of the Mn-doped ZnO samples. This confirms that the AM
1
and AM
2
lines, which
appear only in the normal RS spectra of the doped samples must be generated from
Zn
1-x
Mn
x
O, and not from Zn
x
Mn
y
O
4-
. According to earlier reports [20,22,24,33,42,77],
AM
1
at 527 cm
-1
is suggested to be a Mn-related local vibration. We believe that AM
1
is
associated with the incorporation of Mn
2+
ions into Zn sites in ZnO, since its scattering
intensity becomes dominant as the sample is sintered at 1000
o
C, see Fig. 4.21. The AM
2

line at about 556 cm
-1
has not been mentioned in previous studies. In our case, this line is
prominent and stable in peak position for the samples sintered at temperatures T
s
< 800
o
C, and becomes invisible for T
s
= 1000
o
C. This feature could be related to the improved
crystal quality of the samples for increasing T
s
, as observed by TEM. We interpret AM
2

as a phonon mode activated by defects and/or lattice disorder created by incorporation of
Mn atoms and/or Mn
2+
ions into the ZnO host lattice at an interstitial position. At high
sintering temperatures, Mn located in interstitial positions exhibits simultaneously two
dynamic tendencies: (i) diffusion out of ZnO crystals to form Zn
x
Mn
y
O
4-
(x 2 and y
1), and (ii) Mn
2+
substitution for Zn
2+
in ZnO. These suppositions can account for the
increase in scattering intensity of AM
1
and the decrease in the intensity of AM
2
for
increasing T
s
up to 1000
o
C. The results described below provide more evidence for these
assumptions. It should be noted that the scattering processes 2B
1
(low) (or 2LA) and
TA+LO of ZnO peaked at about 540 and 663 cm
-1
, respectively, could also contribute in
the frequency range 450 - 750 cm
-1
(see Fig. 4.21), which cause the asymmetrical RS
lines in this region [28].
4.3.2.2 Photoluminescence study
We have studied photoluminescence (PL) spectra of samples from the first series
sintered at temperatures T
s
= 400 - 1000
o
C. In this case, the luminescence is generated
58
mainly from wurtzite Zn
1-x
Mn
x
O rather than from the other phases (Zn
x
Mn
y
O
4-
and
MnO
2
). Accordingly, assessment of the quality of the samples becomes easier. Because
the Mn concentration in the ZnO crystals is variable (as can be seen in Figs. 4.18 and
4.19), for each sample we recorded PL spectra at different positions within the sample.
An ultraviolet laser with wavelength of 325 nm was used as an excitation source, and the
laser spot area on the samples was maintained at about 1.2 m
2
. Representative PL
spectra from the samples with T
s
600
0
C are shown in Fig. 4.24. The features of PL
spectra from the other samples (T
s
= 400 and 500
o
C) are similar to those of the T
s
= 600
o
C sample, but their intensity is much weaker, not shown. Compared with pure ZnO, Fig.
4.24(a), the PL spectra of the samples also show two peaks in the ultraviolet (UV) and
visible regions. The former with the strongest intensity is associated with the exciton-
related near-band-edge emission while the latter with much lower intensity is associated
with defects such as surface traps, oxygen vacancy, oxygen interstitial, zinc vacancy and
impurities [23,26,103,145]. The real origin of this visible emission remains controversial.
It appears from Fig. 4.24 that for the T
s
= 600
o
C sample the intensity of both UV
and visible emissions are weak, and the UV peak becomes broader towards longer
wavelengths. At higher sintering temperatures, T
s
= 700 and 800
o
C, the PL efficiency
improves. With increase of T
s
from 900 to 1000
o
C, however, the PL intensity decreases
remarkably, and no visible emission at about 540 nm is observed for the T
s
= 1000
o
C
sample. These features can be seen clearly in Fig. 4.25, where the PL spectrum of each
sample is an average of all the spectra shown in Fig. 4.24, and the PL intensity was
normalized to the UV peak.
Taking into account the spectral parameters of the UV emission, which could be
described by a Gaussian function, we found that with increasing T
s
from 600 to 1000
o
C
its peak position shifts towards shorter wavelengths, and the line width becomes
narrower, as shown in Figs. 4.26(a,b). For the T
s
> 800
o
C samples, the wavelength of the
UV emission is smaller than that of ZnO while the line width is close to the value of ZnO.
To explain fully the features above, we suggest that the PL spectra of the ceramic
samples are generated from wurtzite Zn
1-x
Mn
x
O; the presence of the secondary phases
usually reduces the PL intensity of the samples, due to non-radiative absorption. From
previous work, it is known that during the mixing and milling of the precursors ZnO and
MnO
2
, Mn is incorporated into the ZnO host lattice to form Zn
1-x
Mn
x
O compositions,
where the x value is the overall Mn amount present in ZnO crystals (below 4 at.%,
determined by TEM-EDS). This was also confirmed via the increase in the lattice
59
parameters (a and c) and by the low-frequency shift of the E
2
(high) vibration, as observed
for the as-prepared sample, see Figs. 4.2, 4.21 and 4.22. Here, there are two sites in the
ZnO lattice that Mn could be occupying: the first is the Zn site and the other is interstitial
sites. Mn atoms located at the interstitial sites act as defects, and are responsible for PL
emission in the visible region of ZnO [26], whereas Mn located on the Zn sites affects the
UV emission. At temperatures T
s
600
o
C, Mn is stable in the ZnO host lattice and tends
to occupy the interstitial sites rather than Zn sites. It acts as an electron trap and reduces
luminescence from the host lattice. Concurrently, the UV peak is broadened towards
longer wavelengths, as a consequence of the interaction between excited electrons and
defects with energy levels immediately below the band gap of ZnO [48]. For the sample
sintered at T
s
= 700
o
C, thermal energy is high enough to start activating motion of Mn
into the ZnO host lattice. There are two dynamic tendencies of Mn that could be taken
into account. (i) The first one is the Mn diffusion out of ZnO crystals to form cubic
Zn
x
Mn
y
O
4-
spinels (where x 2 and y 1 to form a stoichiometric cubic spinel of
Zn
2
MnO
4
with Mn/Zn 0.5, as can be seen clearly in Fig. 4.19 when T
s
is above 700
o
C),
and (ii) the other is the incorporation of Mn
2+
ions into the Zn
2+
sites, as confirmed later
by ESR. This leads to the following features observed from its PL spectrum: the PL
intensity increases, the UV peak shifts to a shorter wavelength, and the spectral line width
decreases, see Figs. 4.24 and 4.25. However, these dynamic processes of Mn are still too
small to cause the changes that are observed at higher temperatures T
s
from the Raman
spectra, lattice parameters (a and c), and Mn/Zn ratio of ZnO. When the samples are
sintered at temperatures T
s
= 800 - 1000
o
C, both these dynamic tendencies take place
strongly, in which the first process is always more dominant than the second. It means
that Mn is unstable in the interstitial position when the samples are annealed at high
temperatures (T
s
> 700
o
C). The strong diffusion of Mn out of Zn
1-x
Mn
x
O reduces defects,
resulting in the reduction of PL intensity of the visible emission (see Fig. 4.25). At T
s
=
1000
o
C, the visible emission is not observed. It proves that the crystal quality of the
samples is improved by increasing T
s
above 800
o
C, in good accordance with the TEM
studies. Furthermore, the diffusion of Mn out of Zn
1-x
Mn
x
O also leads to a decrease in the
lattice parameters and in the Mn concentration in Zn
1-x
Mn
x
O (see Figs. 4.2 and 4.19).
Concurrently, the E
2
(high) vibration shifts to higher frequencies, close to the value of
pure ZnO for T
s
= 1000
o
C (see Fig. 4.22). If considering carefully Fig. 4.19(b), it can be
seen clearly that the Mn concentration in Zn
1-x
Mn
x
O crystals with T
s
= 1000
o
C varies in

60
350 400 450 500 550 600 650 700 750
(a)
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
Wavelength (nm)
Pure ZnO

350 400 450 500 550 600 650 700 750
(d)
T
s
=800
o
C
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
Wavelength (nm)
350 400 450 500 550 600 650 700 750
(b)
T
s
=600
o
C
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)


Wavelength (nm)

350 400 450 500 550 600 650 700 750
(e)
T
s
=900
o
C
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)


Wavelength (nm)
350 400 450 500 550 600 650 700 750
(c)
T
s
=700
o
C
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
Wavelength (nm)
350 400 450 500 550 600 650 700 750
(f) T
s
=1000
o
C
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)

Wavelength (nm)
Figure 4.24: PL spectra of (a) pure ZnO and (b-f) Mn-doped ZnO ceramics (the first
series) sintered at 600, 700, 800, 900 and 1000
o
C, respectively, measured statistically at
different points of the samples. The T
s
increase leads to decrease of the visible emission
and also a shift of the UV-emission peak to shorter wavelengths.
61
350 400 450 500 550 600 650 700 750
N
o
r
m
a
l
i
z
e
d

i
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
T
s
=700
o
C
800
o
C
900
o
C
1000
o
C
Wavelength (nm)

Figure 4.25: PL spectra of the samples sintered at 700 - 1000
o
C in which the spectra are
normalized to the UV-peak intensity.
375
390
405
420
600 700 800 900 1000
0
20
40
60
80
13.1 nm
pure ZnO
U
V
-
p
e
a
k

l
i
n
e
w
i
d
t
h

(
n
m
)

383.7 nm
pure ZnO
U
V

p
e
a
k

(
n
m
)

(b)
(a)

T
s
(
o
C)

Figure 4.26: The UV-peak position as a function of T
s
, the solid line is to guide the eye.
For T
s
> 800
o
C samples, their UV-peak position is below that of pure ZnO, see the dotted
line.
62
the range 0.9 - 2.3 at.%, while the other samples the Mn concentration is 0.3 - 3.8 at.%.
This provides further evidence for the diffusion of Mn out of Zn
1-x
Mn
x
O.
Regarding the second tendency for the samples sintered at temperatures T
s
= 800 -
1000
o
C, Mn
2+
ions becomes more mobile and substitute strongly into the Zn
2+
sites for
increasing T
s
. Notably, this process takes place more slowly than the first one. The
increase of Mn
2+
concentration on the Zn
2+
sites in the ZnO lattice leads to a rapid
decrease of the PL intensity, particularly for the samples with T
s
= 900 and 1000
o
C (see
Figs. 4.24 and 4.25). This situation is also observed in some Zn-Mn-O materials as the
Mn-doping concentration is increased [23,25,26]. On the other hand, the increase in Mn
2+

concentration in the Zn sites causes the blue shift of the UV emission, and the narrowing
of the spectral line width (which is close to the value of pure ZnO for T
s
= 900 and 1000
o
C), as shown in Figs. 4.26. Here, the shift of the UV peak towards shorter wavelengths
compared to pure ZnO is related to the broadening of the optical band gap
[23,82,146,147]. Meanwhile, the reduction of spectral line width for samples with T
s
=
900 and 1000
o
C towards the value of pure ZnO is interpreted as a reduction of the
interaction between excited electrons and defects, since Mn is less stable in the interstitial
sites for samples sintered at high temperatures. This is consistent with the improved
quality of the samples.
4.3.3 Magnetic properties of Mn-doped ZnO ceramics
This section presents the magnetic behaviour of the ceramic samples based on
electron spin resonance (ESR) and a quantum-design vibrating sample magnetometer
(PPMS-6000). The problems related to the spin dynamics of Mn and nature of magnetism
in the samples with respect to the sintering temperature are considered carefully.
4.3.3.1 Electron spin resonance study
ESR is one of the most sensitive methods for detecting ferromagnetic order as well
as the possible existence of other magnetic species. The existence of any paramagnetic
phase can be detected by ESR. The only reservation would be the possible existence of
other phases that are neither paramagnetic nor ferromagnetic, then resonance experiments
would not detect their presence [76,148-150].
Here, we have employed ESR spectroscopy to study spin dynamics of Mn in
samples of the first series annealed at temperatures between 400 and 1000
o
C. As a result,
ESR signals from pure ZnO and MnO
2
powders were not observed. The ESR signals
recorded in our case are generated from Mn in the ZnO lattice (i.e., Zn
1-x
Mn
x
O) and/or
Zn
x
Mn
y
O
4-
. Thus, any variation in ESR features of the samples is related to the change in
63
Mn concentration in the above compounds. Figure 4.27 shows ESR spectra for the
samples. It is found that following sintering, the ESR spectra for the samples change
remarkably. There are three characteristic regions with 400 T
s
600
o
C, 700 T
s
900
o
C and T
s
> 900
o
C where we can see clearly these changes. The following discussion
analyses the spectral characteristics of each region.
2000 2500 3000 3500 4000 4500
1000
The first series
Sample holder
T
s
(
o
C)


400
R
e
g
i
o
n

3
R
e
g
i
o
n

2
R
e
g
i
o
n

1

500
600
Field (Oe)
E
S
R

i
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)

700

800

900




Figure 4.27: Room-temperature ESR spectra of samples in the first series as a function of
T
s
. At low sintering temperatures, ESR signals of the samples are weak, and thus the
signal from the sample holder becomes visible. It is invisible as T
s
> 700
o
C, where the
ESR signal from the samples increases.
For the first region of 400 T
s
600
o
C, their ESR signals are weak and consist of
an asymmetrically single broad line, which could be from Mn dopants in compositions of
Zn
1-x
Mn
x
O and Zn
x
Mn
y
O
4-
. Among these, the ESR signal from Zn
x
Mn
y
O
4-
leads to the
asymmetry of this line, due to its partly ferromagnetic contribution when the samples are
annealed at temperatures T
s
< 600
o
C. With increasing T
s
from 400 to 600
o
C, the spectral
intensity decreases, in good agreement with our previous study [27]. We believe that the
diffusion of Mn out of Zn
1-x
Mn
x
O (i.e., the x value decreases) and/or the change of the
Mn concentration in Zn
x
Mn
y
O
4-
with increasing T
s
leads to the decrease in ESR intensity.
64
These changes are small, and not observable by other experimental techniques (XRD,
EDS, RS and PL).
For the second region, 700 T
s
900
0
C: the ESR spectra consist of a single broad
line (referred to as the background line) and the hyperfine lines generated from isolated
Mn
2+
ions distributed randomly in the ZnO matrix. Similar features were observed in
some Mn-doped ZnO and GaN materials [17,19,23,24,30,34,35,37-39,74,76,78,124,151].
In our case, the separation of the two spectral parts could be carried out by fitting the
background line to a Lorentzian function, as can be seen in Fig. 4.27 for the T
s
= 900
o
C
sample. It appears from Fig. 4.27 that with increasing T
s
from 700 to 900
o
C, the intensity
of the background line and the number of Mn
2+
hyperfine lines increases. Meanwhile, the
position of the hyperfine lines shifts downwards by ~100 Oe (note: 1.0 Oe = 1.0 G), and
their linewidth increases. For the hyperfine lines, this situation is certainly due to the
change in crystal-field parameters [148,149,151], such as the spectral splitting (or the
coupling constant), A, and the Lande factor, g. For the T
s
= 700
o
C sample, A and g
determined from spectra are about 74 Oe (69.0x10
-4
cm
-1
) and 1.972, respectively, while
those for the T
s
= 800 and 900
o
C samples are 76 Oe (70.9x10
-4
cm
-1
) and 2.014,
respectively. These values are close to those reported previously for Mn-doped ZnO
materials [17,19,23,30,34,35,38,78], revealing that Mn
2+
ions are located in a tetrahedral
environment. In other words, Mn
2+
ions substitute into the Zn sites in the ZnO host
matrix. The diffusion process starts taking place at T
s
= 700
o
C, and becomes stronger at
higher sintering temperatures, which is not mentioned in the earlier studies. Particularly,
in the absence of ESR studies (which is a sensitive probe for Mn
2+
ions) the authors of
Refs. [36,72,75] suggested that Mn ions could not diffuse into ZnO crystals. Notably, the
sextet (6 lines) observed for the T
s
= 700
o
C sample is the -1/2 1/2 transition, while
three sextet packs (18 lines) observed for the T
s
= 800 and 900
o
C samples are -3/2 -
1/2, -1/2 +1/2, and +1/2 +3/2 transition, see Fig. 4.29. They are the allowed
transitions (M
s
= 1) [149,151].
In regard to the broad background line, its intensity increases with increasing T
s
.
This feature was also found in Mn-doped ZnO nanoparticles, and attributed to an impurity
phase (Zn
1-x
Mn
x
)Mn
2
O
4
[30]. Based on XRD and TEM analyses, we claim that this line is
from Zn
x
Mn
y
O
4-
spinels. The increased intensity for samples sintered at high
temperatures is due to the y value change in Zn
x
Mn
y
O
4-
, which is confirmed from the
EDS analyses (Figs. 4.18 and 4.19) and the analysis of RS and PL spectra.
65
2600 2800 3000 3200 3400 3600 3800 4000 4200
Mn
2+
hyperfine lines

Zn
1-x
Mn
x
O
T
s
= 900
0
C
Exp. data
Zn
x
Mn
y
O
4-

Field (Oe)
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)

Figure 4.28: The experimental ESR signal of the T
s
= 900
o
C sample is fitted to a
Lorentzian function in order to separate the two spectral parts; the hyperfine lines are
from isolated Mn
2+
ions in a ZnO crystal field and the broad background line is attributed
to Zn
x
Mn
y
O
4-
.
2700 3000 3300 3600 3900 4200
T
s
=800
o
C
T
s
=700
o
C
(-3/2, -1/2) (+1/2, +3/2)
(-1/2, +1/2)
(-1/2, +1/2)

I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
Field (Oe)


Figure 4.29: The allowed transitions of the Mn
2+
hyperfine lines for the samples sintered
at 700 and 800
o
C.
For the third region, T
s
> 900
o
C: the ESR spectrum of the T
s
= 1000
o
C sample is
still a combination of two parts, resembling that of the T
s
= 900
o
C sample. However, the
ESR-signal intensity increases rapidly and the Mn
2+
hyperfine lines become broadened
and blurred into the background line. This is due to the development of the spinel phase
66
Zn
x
Mn
y
O
4-
and dipolar interactions between Mn
2+
ions (which may occur when the Mn
2+

concentration in the ZnO host lattice is large enough, where the ZnO crystal-field
parameters are changed, and Mn
2+
ions can interact with each other [34,35]). Here, the
Mn-concentration increase in Zn
x
Mn
y
O
4-
is due to a combination of Mn from unreacted
MnO
2
particles (existed in the as-prepared sample) and from Zn
1-x
Mn
x
O (since Mn
diffuses out of ZnO when Zn
1-x
Mn
x
O is sintered at high temperatures).
Our ESR study has provided further evidence for the Mn
2+
substitution for Zn
2+
in
the ZnO matrix. This process starts taking place as T
s
= 700
o
C and become more
significant when samples are sintered at higher temperatures, in good accordance with our
discussion of the PL data. Nevertheless, at any sintering temperature the diffusion of Mn
out of Zn
1-x
Mn
x
O is always more dominant, forming cubic Zn
x
Mn
y
O
4-
. spinels. This can
explain the variation tendency of the wurtzite lattice parameters a and c and also the
E
2
(high)-peak position as shown in Figs. 4.2 and 4.22.
0 80 160 240 320 400
0
10
20
30
40
0.0
0.2
0.4
0.6
0.8
1.0
2100 2800 3500 4200 4900
I
(
T
)

(
a
r
b
.

u
n
i
t
s
)
(b)
T (K)
(a)
373 K
363
343
323
303
283
263
243
223
203
183
163
143
123
103 K
1
/
I
(
T
)

(
a
r
b
.

u
n
i
t
s
)
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)


Field (Oe)
T
s
=1000
o
C
Fitting

Figure 4.30: (a) The measurement-temperature dependence of ESR spectra for the
sample sintered at 1000
o
C; (b) the 1/I(T) data are fitted to the Curie-Weiss law.
In an attempt to assess the magnetic nature of the spinel phase characterized by the
broad background line for the samples sintered at temperatures T
s
> 700
o
C, we have
studied the dependence of ESR spectra on measurement temperature for the
representative sample with T
s
= 1000
o
C. Figure 4.30(a) shows the spectra of this sample
67
measured in a temperature range between 100 and 375 K. It is found that the shape of the
ESR spectra remains almost unchanged when the measurement temperature is varied. The
signals recorded are a combination of three spectral components coming from the spinel
phase Zn
x
Mn
y
O
4-
, dipole interactions of Mn
2+
-Mn
2+
, and also Mn
2+
hyperfine lines.
Among them, the first two parts contribute to the broad line. By fitting all the spectra to a
Lorentzian function (see Fig. 4.28), we separated the broad lines from the Mn
2+
hyperfine
lines. Taking a double integration of these broad lines [27,38,78] (where the hyperfine
signals were subtracted), their intensity versus the measurement temperature, I(T), was
determined, as shown in Fig. 4.30(b). It shows that with increasing the measurement
temperature, the resonant intensity decreases.
0 50 100 150 200 250 300 350
0.02
0.03
0.04
0.05
-100 -50 0 50 100 150 200 250 300 350
0
1
2
3
40 K
(b)
(a)
M

(
e
m
u
)
H =50 kOe

1
*

1
0
6


(
O
e
/
e
m
u
)
T (K)

Figure 4.31: Temperature dependences of (a) magnetization and (b) inverse susceptibility
for MnO
2
; the linear line is plotted to the Curie-Weiss law, with = - 134 K.
Since the ESR intensity I(T) is directly proportional to the magnetic susceptibility,
in the high temperature limit it is commonly accepted that I(T) can be described by a
Curie-Weiss equation [19,34,78]

T
T I
1
) ( , (4.5)
where is the Curie-Weiss temperature. By extrapolating a linear-high-temperature part
of the 1/I curve to zero, see Fig. 4.30(b), is determined as about -11.7 K. This reflects
that the magnetic interactions between Mn ions responsible for the broad ESR line are
68
antiferromagnetic, which include the coupling-exchange interaction Mn
2+
-Mn
2+
in the
ZnO host and interactions between Mn ions in cubic Zn
x
Mn
y
O
4-
spinels. Earlier studies
on some ZnO materials doped with high Mn concentrations have also confirmed the
interaction Mn
2+
-Mn
2+
is antiferromagnetic [34,35,38,78].
4.3.3.2 The magnetization dependence on temperature and magnetic field
To further study influences of the sintering temperature (T
s
) and secondary phases
on magnetic properties of the samples (in the first and second series), we have measured
the change in their magnetization with respect to temperature and magnetic field. From
these data, the nature of magnetism in the samples could be understood.
It is known that both series when annealed at low temperatures show the presence of
un-reacted MnO
2
particles. Thus, we have firstly studied magnetic behaviour of this
compound. Figure 4.31 shows the temperature dependence of magnetization, M(T), for
MnO
2
under an applied field of 50 kOe. One can see that there is a peak at about 40 K,
which is assigned to the Nel temperature (T
N
). With increasing (or decreasing)
measurement temperature from T
N
, magnetization of MnO
2
decreases. By plotting the
inverse susceptibility (
-1
) and linear extrapolation of the high-temperature part down to
the
-1
= 0 axis, we estimated the Curie-Weiss temperature, -134 K. This indicates the
presence of antiferromagnetic interactions in MnO
2
, consistent with earlier studies
[31,36,152-154], see Table 4.4. At temperatures below T
N
, MnO
2
may show weak
ferromagnetic behaviour [154]. Clearly, MnO
2
is not responsible for ferromagnetism
around room temperature. The following presents in detail the magnetic properties of
each series.
Magnetization of the first series
Figure 4.32 shows magnetization dependences on magnetic field, M(H), for the as-
prepared sample measured at 5 and 300 K in the range from -50 to 50 kOe. Based on the
feature of the hysteresis loops, it is found that the material exhibits ferromagnetic
behaviour above room temperature. For the M-H curve at 300 K, besides a ferromagnetic
part for magnetic fields between -2 to 2 kOe, see the inset of Fig. 4.32(b), there is
diamagnetic response from the ZnO wurtzite-type structure [77,155,156]. The existence
of room-temperature ferromagnetism in the as-prepared samples has also been found
recently by Blythe et al. [71].
For the annealed samples, we find that the ferromagnetic ordering decreases
gradually with increasing T
s
. This behaviour can be seen in Figs. 4.33, which show the
69
M(H) curves for the representative samples with T
s
= 500, 800 and 1000
o
C. There is no
ferromagnetism observed for these samples at 300 K, see Figs. 4.33(a-c) on the right. This
result is different to the measurement for the as-prepared sample, Fig. 4.32. At 5 K,
ferromagnetism is observed, but the area of hysteresis loops become narrower with
increasing T
s
, revealing the decline of the ferromagnetic order, see Figs. 4.33(a-c) on the
left. At T
s
= 1000
o
C, the material is paramagnetic. Recently, Riyadi et al. [82] studied
Zn
1-x
Mn
x
O (0.02 x 0.08) annealed at 1200
o
C and also found the paramagnetic
behaviour at room temperature; at low temperatures samples exhibited
antiferromagnetism.
-2
-1
0
1
2
-4 -2 0 2 4
-0.3
0.0
0.3
-40 -20 0 20 40
-3
-2
-1
0
1
2
3
-4 -2 0 2 4
-0.8
-0.4
0.0
0.4
0.8
T =300 K
M
*
1
0
-
4

(
e
m
u
)
M
*
1
0
-
3

(
e
m
u
)

T =5 K
(b)
(a)
M
*
1
0
-
4

(
e
m
u
)
H (kOe)
M
*
1
0
-
3

(
e
m
u
)


H (kOe)

H (kOe)



Figure 4.32: The hysteresis loops, M-H curves, for the as-prepared sample measured at
(a) 5 and (b) 300 K; the insets show the curves on an enlarged scale.
The decrease in ferromagnetic order in the samples sintered at high temperatures
can be seen clearly by considering the magnetization dependence on the measurement
temperature, M(T) as shown in Fig. 4.34. It reveals that increasing the temperature from 5
to 300 K leads to a decrease in magnetization. For the T
s
= 500
o
C sample, there is a
ferromagnetic-to-paramagnetic phase transition at about 290 K. This feature is absent in
the samples sintered at higher temperatures (800 and 1000
o
C). All these data provide
70
further evidence that sintering improves the quality of the samples but reduce their
ferromagnetic order.
-0.4
-0.2
0.0
0.2
0.4
-8
-4
0
4
8
-0.4
-0.2
0.0
0.2
0.4
-8
-4
0
4
8
-4 -2 0 2 4
-8
-4
0
4
8
-4 -2 0 2 4
-0.4
-0.2
0.0
0.2
0.4
300 K
(c)
T
s
=1000
o
C
300 K
(b)
T
s
=800
o
C
(a)
300 K
T
s
=500
o
C



5 K
5 K
M

(
e
m
u
)
5 K


M

(
e
m
u
)









H (kOe)



Figure 4.33: Hysteresis loops for the samples sintered at (a) 500, (b) 800 and (c) 1000
o
C
measured at 5 and 300 K.
0 50 100 150 200 250 300
0
2
4
6
8
160 180 200 220 240 260 280 300
0.4
0.6
0.8
1.0
1.2


M

(
e
m
u
)
T (K)
H =50 kOe

M

(
e
m
u
)
T (K)
T
s
(
o
C)
500
800
1000

Figure 4.34: Temperature dependences of magnetization for the samples sintered at 500,
800 and 1000
o
C, under an applied field of 50 kOe.
71
There are two important questions related to magnetic properties in our samples: (i)
where ferromagnetism is generated from, and (ii) why the ferromagnetic order decreases
with increasing T
s
. Concerning the first question, there are several contradictory opinions.
Sharma et al. [9,76] believe that the ferromagnetism in low-temperature processed
samples comes from a uniform solution of Mn in the ZnO host lattice. However,
Kundaliya et al. [73] have suggested that the uniform solution of Mn in ZnO could not
occur for low-temperature processing, and therefore the ferromagnetism is generated from
a metastable oxide phase Zn
x
Mn
2-x
O
3-
. This hypothesis was widely accepted when
Garcia and Lopez-Ponce et al. [72,75] recently observed the formation of a spinel phase
Zn
x
Mn
3-x
O
4
, even for low temperature heat treatments, caused by the Zn diffusion into
MnO
2
particles. The coexistence of Mn
3+
and Mn
4+
cations in the samples led to the
ferromagnetism, since the exchange interaction between them is ferromagnetic [157].
In our case, MnO
2
is known as an antiferromagnetic material below 40 K, see Fig.
4.31 and Table 4.4. Thus, there are only two possibilities for the phases responsible for
ferromagnetism in the samples, being Zn
1-x
Mn
x
O and Zn
x
Mn
y
O
4-
. We rule out the
possibility of Zn
1-x
Mn
x
O, because this phase, even exists in the as-prepared sample (as
confirmed by TEM and optical spectroscopy), shows diamagnetic behaviour, see Fig.
32(b). Furthermore, at high sintering temperatures T
s
700
o
C, where Mn
2+
ions
substituted for Zn
2+
in the ZnO matrix, it exhibits the paramagnetic behaviour.
Consequently, only cubic Zn
x
Mn
y
O
4-
spinels are considered as the origin of the
ferromagnetism in our first series sample. The decrease in ferromagnetic order with
increasing T
s
is likely due to the increase of Mn concentration in Zn
x
Mn
y
O
4-
(see Fig.
4.19), where the additional presence of Mn ions could cause the antiferromagnetic
interactions between them. Notably, this oxide phase is metastable at low annealing
temperatures (T
s
< 800
o
C), probably because the Mn concentration in Zn
x
Mn
y
O
4-
is low;
its average value obtained is about 20 at.%. At higher sintering temperatures (T
s
800
o
C), the Mn concentration increases and reaches to about 25-27 at.%, as can be seen in
Fig. 4.19. This leads to the improvement in the quality of the samples.
Magnetization of the second series
We have studied magnetic properties of the sample in the second series sintered at
500
o
C. The dependence of magnetization on temperature and magnetic field is shown in
Fig. 4.35. The hysteresis loops, Figs. 4.35(a,b), indicate that the sample is ferromagnetic
at low temperatures, but paramagnetic at 300 K. From the M-T curve, we have realized a
72
sample exhibiting antiferromagnetic behaviour with T
N
= 80 K and = -207 K. At
temperatures above T
N
, where the material is in a paramagnetic state, magnetization
decreases gradually with increasing temperature, see Fig. 4.35(c). Notably, the increase in
magnetization at temperatures below 38 K could be related to a ferromagnetic phase.
0 50 100 150 200 250 300
1.0
1.5
2.0
-4 -2 0 2 4
-0.4
-0.2
0.0
0.2
0.4
-4 -2 0 2 4
-0.10
-0.05
0.00
0.05
0.10
38 K
80 K
300 K 10 K
H =50 kOe


M

(
e
m
u
)
T (K)
(c)
(b) (a)
M

(
e
m
u
)

M

(
e
m
u
)
Field (kOe)




Figure 4.35: Hysteresis loops measured at (a) 10 and (b) 300 K; and (c) temperature
dependence of magnetization under an applied field of 50 kOe for the second series
sintered at 500
o
C.
Unlike the magnetic data of the T
s
= 500
o
C sample in the first series (see Figs. 4.33
and 5.34) exhibiting ferromagnetism near 300 K, this sample shows ferromagnetic order
only at low temperatures. This difference between two samples provide further evidence
that ferromagnetism in Mn-doped ceramics is generated from secondary phases [158]
rather than from Mn dopants diluted in the ZnO host matrix. In Table 4.4, we have
summarized magnetic properties of some manganese-oxide compounds, which could
occur in Mn-doped ZnO ceramics. By means of these data and the magnetic features of
the second series annealed at 500
o
C, it is reasonable to assume that the low-temperature
ferromagnetic order of the sample is generated from a Mn
2
O
3
-related secondary phase.
This conclusion is in accordance with our XRD and TEM studies.

73

Table 4.4: Magnetic properties for some manganese oxides
Compound Nature of magnetism Applicable temperature (K) Reference

MnO
2
Antiferromagnetic
Antiferromagnetic
Antiferromagnetic
Weakly ferromagnetic
84
85
17
44
[153]
[36]
[154]
[154]
Mn
2
O
3
Antiferromagnetic
Ferromagnetic
80
40 - 45
[69]
[159]
Mn
3
O
4
Ferro- or ferri-magnetic 42, 46 [39], [31]
MnO
Antiferromagnetic 122
116
[153]
[39]
Antiferromagnetic 21.5 [160]
(Mn,Zn)Mn
2
O
4
Ferrimagnetic 40 [158]
ZnMnO
3
(cubic) Spin-glass -- [11]

Concerning the shape of the M-T curve in Fig. 4.35(c), there may be contributions
from several magnetic phases including Mn
2
O
3
, Zn
t
Mn
2-t
O
3
and unreacted MnO
2

particles. Amongst these phases, Zn
t
Mn
2-t
O
3
(mainly responsible to the ferromagnetism at
temperature below 38 K) is formed by the thermal diffusion of Zn atoms into MnO
2
and
the decomposition MnO
2
Mn
2
O
3
[36,72,73,75].
4.4 Conclusions
We have prepared samples of two series of Mn-doped ZnO ceramics, sintered at
temperatures between 400 and 1000
o
C. The analyses by means of XRD and TEM have
revealed that besides the main phase of wurtzite ZnO, there are some secondary phases.
The formation of these phases is related closely to fabrication conditions.
For the first series (where their precursors were wet mixed by a milling machine
using zirconia balls and high-purity water), the cubic spinel phase Zn
x
Mn
y
O
4-
is
constituted soon during mixing and milling the precursors (i.e., in the as-prepared
sample). These are nanoparticles and clustered on the surfaces of ZnO crystals. Increasing
the sintering temperature increases both the particle size and Mn concentration, but does
74
not change their structure. The crystal quality of the samples is improved when they are
sintered at temperatures T
s
800
o
C, where MnO
2
reacts completely with ZnO to form
Zn
1-x
Mn
x
O and/or Zn
x
Mn
y
O
4-
.
For the second series, their precursors were mixed and ground by hand without
high-purity water: the sample sintered at 500
o
C shows the presence of MnO
2
and Mn
2
O
3

whereas samples sintered at 800
o
C show only a tetragonal ZnMn
2
O
4
-related phase.
Our studies of the first series based on Raman, photoluminescence and ESR
spectroscopy have revealed that Mn is incorporated into the ZnO host lattice at interstitial
positions for the as-prepared sample. During the sintering at temperatures 400 - 1000
o
C,
Mn in the ZnO lattice has two dynamic tendencies, which are (i) diffusion out of ZnO
crystals to form Zn
x
Mn
y
O
4-
and (ii) Mn
2+
substitution for Zn
2+
in ZnO. These processes
take place more rapidly at temperatures T
s
700
o
C, in which the first process is always
more dominant than the other. However, the Mn
2+
substitution for Zn in ZnO and the
formation of stable oxide phases (Zn
x
Mn
y
O
4-
and/or Zn
z
Mn
2-z
O
4
) as T
s
700
o
C suppress
the ferromagnetic order in the samples, although the quality of the samples is improved.
We have found that ferromagnetism in ceramic samples processed at lower
temperatures is generated mainly from secondary phases including Zn
x
Mn
y
O
4-
and
Mn
2
O
3
(or Zn
t
Mn
2-t
O
3
). Among these, cubic Zn
x
Mn
y
O
4-
spinels dedicate the
ferromagnetic ordering around room temperature. The compositions Zn
1-x
Mn
x
O and
MnO
2
are not responsible for the ferromagnetic order. These are important conclusions
having scientific significance that have not yet clarified in previous reports (where
authors usually explained their experimental data based on magnetic properties of Mn-
doped ZnO thin films or MnO
2
/ZnO multi-layers). For the first series, the decline in
ferromagnetic order for increasing T
s
is caused by increasing Mn concentration in
Zn
x
Mn
y
O
4-
, where it goes to the stoichiometric composition of Zn
2
MnO
4
. This also leads
to the transition of Zn
x
Mn
y
O
4-
from a metastable state to stable one.
There remains an unsolved question in this research which warrants further study,
concerning the ionisation state (ions and/or atoms) of Mn in the ZnO matrix for samples
sintered below 700
o
C.
75
Chapter 5
PLD-grown Mn-doped ZnO thin films
As reviewed in Chapter 1, most Mn-doped ZnO films grown by radio-frequency
magnetron sputtering and pulsed laser deposition (PLD) exhibit ferromagnetic ordering
above room temperature. Doping with elements belonging to group V (such as N, P, and
As) should increase ferromagnetic ordering, due to the additional presence of hole carriers
in the films, as predicted by Dietl et al. [12]. To gain more insight into these problems, we
have grown Mn-doped and (Mn, P)-codoped ZnO thin films, using PLD. The structure
and quality of the films are examined carefully by XRD and TEM. The incorporation of
dopants into the host lattice and the change in their bandgap could be confirmed indirectly
by means of XRD and optical absorption spectroscopy. The magnetic properties of films
are investigated at 300 K, using a physical property measurement system (PPMS).
5.1 Sample preparation and description
In an attempt to study the influence of dopants Mn and P on the structure, optical
and magnetic properties of PLD-grown thin films, we prepared samples of Mn-doped and
(Mn, P)-codoped ZnO, including pure ZnO, Zn
0.99
Mn
0.01
O, Zn
0.98
Mn
0.02
O,
Zn
0.99
Mn
0.01
O:1 mol% Zn
3
P
2
(referred to Zn
0.99
Mn
0.01
O:P) and Zn
0.98
Mn
0.02
O:1 mol%
Zn
3
P
2
(referred to Zn
0.98
Mn
0.02
O:P), as listed in Table 5.1. Notably, the P doping from
Zn
3
P
2
is to create more hole density in Mn-doped ZnO thin films as P
3-
substituted for O
2-

in the ZnO host lattice. These films were deposited on the SiO
2
/Si (001) substrates, under
a pressure of 50 mTorr (~6.67x10
-5
bar), which was controlled by the Ar-oxygen gas
mixture with the Ar:O
2
ratio of 8:2. During growth, the substrate temperature was held at
400
o
C which was the optimal temperature to obtain films with their crystals oriented
along the c axis perpendicular to the substrate. The deposition time was 45 minutes for
pure ZnO, and was 30 minutes for the doped ZnO films. The laser power output and pulse
repetition rate were kept at 120 mJ and 10 Hz, respectively, which was transmitted
through a quartz lens and chamber window of the PLD system (transmittance of quartz is
about 0.94). With a laser spot size on the target of ~1.0 mm, the laser power density was
about 10 J/cm
2
. Detailed descriptions of experimental parameters used for growing the
76
films are shown in Table 5.1. To carry out measurements of optical absorption spectra,
the films were deposited on quartz substrates under similar growth conditions.
Table 5.1: Experimental parameters used during the growth of Mn-doped and (Mn, P)-
codoped ZnO thin films.
Experimental parameters
Name

Description Sub. temp
(
o
C)
Pressure
(mTorr)
Time
(min)
Ar:O
2
Laser power
(J/cm
2
)
Freq.
(Hz)
ZnO pure ZnO 400 50 45 8:2 10 10
N
1
Zn
0.99
Mn
0.01
O 400 50 30 8:2 10 10
N
2
Zn
0.98
Mn
0.02
O 400 50 30 8:2 10 10
N
3
Zn
0.99
Mn
0.01
O:P 400 50 30 8:2 10 10
N
4
Zn
0.98
Mn
0.02
O:P 400 50 30 8:2 10 10
It should be noted that the use of similar experimental parameters during growth of
the films allowed us to assess exactly the influences of the dopants on their structure and
physical properties. Particularly, it was essential to control extrinsic impurities which
might be associated with any change in sample preparation conditions.
The following presents studies of the structural, optical and magnetic properties of
the as-prepared films (without any processing and heat treatment). For convenience,
Zn
0.99
Mn
0.01
O, Zn
0.98
Mn
0.02
O, Zn
0.99
Mn
0.01
O:P and Zn
0.98
Mn
0.02
O:P in the text will be
referred to N
1
, N
2
, N
3
and N
4
, respectively.
5.2 Structural analysis
5.2.1 XRD study
After preparation, the structure of films ZnO and N
1
- N
4
were examined by an
X'Pert Philips diffractometer. Figures 5.1 and 5.2 show their XRD patterns in the 2
range of 30 - 40
o
. As observed for the ZnO film, XRD patterns of the doped films exhibit
only one peak at about 34.3
o
, which corresponds to the (002) plane of the ZnO wurtzite
structure. This confirms that most crystals of the films were grown along the c-axis
perpendicular to the Si substrate. There is no evidence of secondary phases related to Mn
metal and/or Mn oxides present in the films.
77
30 31 32 33 34 35 36 37 38 39 40
x =0.01 (N
1
)
x =0.02 (N
2
)
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)

2 (Degree)
ZnO
(002)
Zn
1-x
Mn
x
O

Figure 5.1: XRD patterns for PLD-grown Zn
1-x
Mn
x
O (x = 0.01 and 0.02) films on
SiO
2
/Si (001) substrates.
30 31 32 33 34 35 36 37 38 39 40
(002)
Zn
1-x
Mn
x
O:P

x =0.02 (N
4
)
x =0.01 (N
3
)
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
2 (Degree)
ZnO

Figure 5.2: XRD patterns for PLD-grown Zn
1-x
Mn
x
O:P (x = 0.01 and 0.02) films on
SiO
2
/Si (001) substrates.

78
Table 5.2: Thickness, lattice parameters and bandgap of Mn-doped and (Mn, P)-codoped
ZnO thin films grown by PLD.
Property

ZnO N
1
N
2
N
3
N
4

Thickness (nm) 330 200 200 200 200
Lattice constant, c ()

5.231 5.232 5.234 5.234 5.237
Band gap, E
g
(eV) 3.232 3.247 3.264 3.246 3.257
As measured by the position of the (002) peak, the increase of Mn concentration in
the films leads to a small shift of its peak position towards smaller diffraction angles,
equivalent to a slight increase of the lattice parameter c. The c value of the ZnO film is
5.231 while those of N
1
, N
2
, N
3
and N
4
are 5.232, 5.234, 5.234 and 5.237 ,
respectively (see Table 5.2). Clearly, the change in the c parameter is very small, about
0.004 - 0.05 % for N
1
and N
2
, and 0.06 - 0.10 % for N
3
and N
4
. This can be explained by
the substitution of Mn
2+
for Zn
2+
in Zn
1-x
Mn
x
O (i.e., N
1
and N
2
), and concurrent
substitution of Mn
2+
for Zn
2+
and P
3-
for O
2-
in Zn
1-x
Mn
x
O:P (i.e., N
3
and N
4
), because
the radius of substituting ions {Mn
2+
(0.80 ) and P
3-
(1.80 - 2.12 )}is larger than that
of substituted ions {Zn
2+
(0.74 ) and O
2-
(1.38 )} [45,62,95,161], see Table A2
(Appendix).
5.2.2 TEM study
In addition to XRD, we investigated the microstructure of films, using TEM. For
this study, both plan-view and cross-section samples were prepared. Figures 5.3 shows
plan-view images for ZnO and N
1
- N
4
with different magnifications. The morphology of
the films is quite similar, which consist of nanoparticles with the crystal size ranging from
20 - 60 nm. At the grain boundaries, there are some narrow gaps of about 5.0 nm. SAED
patterns recorded prove that the doped films have the wurtzite structure of ZnO [162,163],
see Fig. 5.4. Here, the crystals of the thin films are c-axis aligned, thus planes (hkl) with l
0 are invisible. There are no additional diffraction rings from secondary phases related
to Mn and P, in agreement with the XRD study. Recently, Zhang et al. [163] investigated
PLD-grown Zn
1-x
Mn
x
O films and found Mn-related phases developing only when Mn
concentration was higher than 3.0 %.
79

Figure 5.3: Plan-view images with different magnifications for films (a) ZnO, (b) N
1
, (c)
N
2
, (d) N
3
and (e) N
4
.
80

Figure 5.4: SAED patterns of films ZnO, N
2
and N
4
. All diffraction rings (see the
indices) are from the wurtzite-type structure of ZnO, there are no diffraction rings from
Mn-related secondary phases.
81
Comparing with ZnO, the c lattice parameter increases for the doped films, as a
consequence of the incorporation of the dopants into the ZnO host lattice. Also, individual
nanoparticles observed in plan-view images are single crystals with the hexagonal
structure, see Fig. 5.5, which grow along the c-axis perpendicular to the substrate. This
was also confirmed by cross-section images, as shown in Figs. 5.6. The crystals are
columnar and have diameters of below 60 nm. Their lengths are about 330 and 200 nm
for ZnO and N
1
- N
4
, respectively (see Table 5.2). The invisibility of columnar crystals
close to the boundary between the films and substrate for Figs. 5.6(c-e) could be related to
the thickness. Having taken micro-diffraction patterns of individual columnar crystals, we
also get the same result (as mentioned in the case of plan-view images) that crystals grow
along the c = ] 0001 [ axis (see Fig. 5.7), which is the preferred growth direction of ZnO.
In fact, to grow Mn-doped ZnO films with crystals oriented along the c-axis growth is
usually carried out on sapphire substrates; there are very few works on the SiO
2
/Si
substrate (see Table 5.4 for more details). How other substrates (such as quartz and
sapphire) influence the crystalline orientation of films will be the next step of our
research.
XRD and TEM studies demonstrate that our thin films, Mn-doped and (Mn, P)-
codoped ZnO grown on SiO
2
/Si, have good quality. The dopants Mn and O are
incorporated into the ZnO host lattice, which leads to the increase of the lattice
parameters. To the limit of experimental measurement, we have not observed additional
phases caused by the doping.

Figure 5.5: (a) A plan-view image, and (b) the ] 0001 [ -zone axis diffraction patterns
taken from individual particles (see dotted circles in Figure (a)) of the ZnO film.

82

Figure 5.6: The comparison of cross-section images for (a) ZnO, (b) N
1
, (c) N
2
, (d) N
3

and (e) N
4
grown by PLD under similar growth conditions.

83

Figure 5.7: A cross-section image of the ZnO film. The inset shows the ] 0 2 11 [ -zone axis
diffraction pattern of individual columnar crystals, which grow along the c = ] 0001 [ axis
perpendicular to the substrate (see the arrow in Figure).
5.3 Optical absorption study
To study influences of the dopants on optical properties of the thin films, we
measured their optical absorption spectra. In the wavelength range investigated, only
band-edge absorption at about 375 nm is observed, as shown in Fig. 5.8, which
corresponds to the threshold for charge transition between the highest nearly filled band
and the lowest nearly empty band. Compared with the pure ZnO film, the increase in
doping concentration leads to the shift of this band towards shorter wavelengths,
corresponding to an increase of the band gap. Similar results were found in other Mn-
doped ZnO materials [19,23]. In the absorption region, the absorption coefficient is
calculated from the following relation [52]
) 2 exp( 1
) exp( ) 1 (
2
2
d R
d R
T

= , (5.1)
where R and T are the spectral reflectance and transmittance, respectively, and d is the
film thickness. For greater optical density (d > 1), interference effects due to internal
reflections and reflectance at normal incidence are negligible, and Eq. (5.1) can be
approximated as
) exp( d T . (5.2)
The optical absorption coefficient is then given by
) ln(
1
T
d
= . (5.3)

84
330 345 360 375 390 405 420
0.0
0.2
0.4
0.6
0.8
(a) Zn
1-x
Mn
x
O
ZnO
x =0.01 (N
1
)
x =0.02 (N
2
)
A
b
s
o
r
b
a
n
c
e

(
a
r
b
.

u
n
i
t
s
)
Wavelength (nm)

330 345 360 375 390 405 420
0.0
0.2
0.4
0.6
0.8
(b)
Zn
1-x
Mn
x
O:P
A
b
s
o
r
b
a
n
c
e

(
a
r
b
.

u
n
i
t
s
)
Wavelength (nm)
ZnO
x =0.01 (N
3
)
x =0.02 (N
4
)

Figure 5.8: Optical absorption spectra of (a) Mn-doped and (b) (Mn, P)-codoped ZnO
thin films compared with the spectrum of ZnO.
85
3.10 3.15 3.20 3.25 3.30 3.35 3.40
0
2
4
6
8
(a)



Zn
1-x
Mn
x
O
(

)
2

(
a
r
b
.

u
n
i
t
s
)
h (eV)
ZnO
x =0.01 (N
1
)
x =0.02 (N
2
)

3.10 3.15 3.20 3.25 3.30 3.35 3.40
0
2
4
6
8
(b)
Zn
1-x
Mn
x
O:P
(

)
2

(
a
r
b
.

u
n
i
t
s
)
h (eV)
ZnO
x =0.01 (N
3
)
x =0.02 (N
4
)

Figure 5.9: The plot of (h)
2
versus h of (a) Mn-doped and (b) (Mn, P)-codoped ZnO
films.
From absorption spectra, the absorption coefficient can be calculated from the
absorbance (A) and film thickness (d) as follows [164]
d
A
303 . 2 = . (5.4)
In our case, d = 230 nm for ZnO and d = 200 nm for films N
1
- N
4
. According to
interband absorption theory, the band gap of the films is determined from the relation
[52,164]
n
g
E h B h ) ( = , (5.5)
86
where B is the probability parameter for the transition, E
g
is the band gap of a material, h
is the incident photon energy, and n is the transition coefficient (depending on whether
the electronic transition is direct or indirect). For semiconductors with a direct electronic
transition, the value of n is 1/2. By plotting (h)
2
versus h and taking the intersection of
extrapolated lines from the linear part of the curves (h)
2
h to the value (h)
2
= 0
for the films (see Fig. 5.9), the values of E
g
obtained are 3.232, 3.247, 3.264, 3.246 and
3.257 eV for ZnO and N
1
- N
4
, respectively (see Table 2).
0.000 0.005 0.010 0.015 0.020
3.23
3.24
3.25
3.26
E
g

(
e
V
)
x concentration (at.%)
Zn
1-x
Mn
x
O
Zn
1-x
Mn
x
O:P

Figure 5.10: Dependences of E
g
on Mn-doping concentration (x) and P. The dotted lines
are to guide the eye only. Note that Mn concentration x is values obtained from the target.
In Fig. 5.10, we plot the dependence of E
g
on Mn concentration and P doping in the
films. For Zn
1-x
Mn
x
O, E
g
increases with increasing the x value. However, the additional
presence of P in these films slightly reduces E
g
, see Fig. 5.10. According to earlier studies
[19,23,62,165], the increase in band gap of Mn-doped ZnO has been associated with the
following explanations: (i) the formation of MnO (with band gap = 4.2 eV), (ii) spatially
confined effect [19,23], and (iii) Burstein-Moss effect caused by the increase in carrier
(electron) concentration [165]. We believe that only two latter possibilities could cause
the band-gap increase in our Zn
1-x
Mn
x
O films, because XRD and TEM studies show no
evidence of secondary phases related to manganese oxides. Furthermore, the additional
doping of P into Zn
1-x
Mn
x
O (i.e., Zn
1-x
Mn
x
O:P) results in a slight decrease of E
g
, see Fig.
5.10. This could be due to the presence of holes (created by the substitution of P
3-
for O
2-

in the ZnO lattice), which make the electron concentration in Zn
1-x
Mn
x
O:P films lower
87
than that in Zn
1-x
Mn
x
O. It should be noticed that the increase of the band gap energy is
related to the carrier concentration (n
e
) through the following equation [166]
3 / 2 3 / 2
*
2
)
3
(
8
e
n
m
h
E

= , (5.6)
where h is Plancks constant and m
*
is the electron effective mass in the conduction band.
5.4 Magnetic properties
We studied the magnetic properties of the films at room temperature. In this case,
the magnetic field was applied parallel to the film plane and varied from -5 to 5 kOe.
Figure 5.11 shows hysteresis loops of pure ZnO, Mn-doped and (Mn, P)-codoped ZnO
films at 300 K, where the diamagnetic contribution from the Si substrate has been
substrated. It appears from Fig. 5.11(a) that the ZnO film also exhibits weak
ferromagnetic behaviour with a magnetic saturation (M
s
) of about 1.8 emu/cm
3
. The
ferromagnetism becomes clearer when the ZnO film doped with Mn (N
1
and N
2
). The
increase of Mn-doping concentration leads to an increase in ferromagnetic ordering, see
Fig. 5.11(b). Magnetic saturation values of N
1
and N
2
obtained are 4.5 and 10.5 emu/cm
3
,
respectively. Also, their coercive force (H
c
) increases with increasing Mn concentration,
47 Oe for sample N
1
and 68 Oe for N
2
(see Table 5.3). Interestingly, the additional doping
with phosphorous (P) into films Zn
1-x
Mn
x
O (i.e. Zn
1-x
Mn
x
O:P, for samples N
3
and N
4
)
enhances remarkably their ferromagnetic ordering, as can be seen in Fig. 5.11(c) and
Table 5.3. In particular, for sample N
4
its magnetic saturation M
s
= 22.5 emu/cm
3
is over
two times higher than that of N
2
. The magnetic moment per Mn atom was then estimated
to be between 1.17 and 2.92
B
/Mn for the samples N1 N4. Clearly, all our PLD-grown
doped ZnO films on SiO
2
/Si(001) show room-temperature ferromagnetism. Having
reviewed earlier studies, we also find that most Mn-doped ZnO films grown by PLD [72-
76,80,84-86,161,163,167-172], and RF-sputtering or reactive cosputtering
[45,46,54,61,62,83,173-177] exhibit ferromagnetism at room temperature (as summarized
in Table 5.4). From Table 5.4, one can see that ferromagnetism in Mn-doped films seems
independent of substrate types employed (such as sapphire, Si, quartz and GaN).
However, it is sensitive to impurity concentration, dopant type (i.e., donor or acceptor),
growth conditions and sample processing.

88
-4 -2 0 2 4
-3
-2
-1
0
1
2
3
(a)
pure ZnO
M

(
e
m
u
/
c
m
3
)

H (kOe)

-4 -2 0 2 4
-12
-8
-4
0
4
8
12
(b)
M

(
e
m
u
/
c
m
3
)
Zn
1-x
Mn
x
O
H (kOe)
x =0.01 (N
1
)
x =0.02 (N
2
)

-4 -2 0 2 4
-20
-10
0
10
20
(c)
Zn
1-x
Mn
x
O:P
M

(
e
m
u
/
c
m
3
)
H (kOe)
x =0.01 (N
3
)
x =0.02 (N
4
)

Figure 5.11: Hysteresis loops of (a) pure ZnO, (b) Mn-doped and (c) (Mn, P)-codoped
ZnO films measured at 300 K.
89
Table 5.3: Magnetic properties of thin films ZnO, Mn-doped and (Mn, P)-codoped ZnO
measured at 300 K.
Property ZnO N1 N2 N3 N4
Magnetic property WFM
*
FM
*
FM FM FM
Saturation, M
s

(emu/cm
3
)
1.8 4.5

10.5 5.5 22.5
Coercitivity, H
c
(Oe) -- 47 68 68 74
*Note: WFM (Weak ferromagnetic); and FM (Ferromagnetic)
For the growth process, it has been suggested that the fabrication of Mn-doped ZnO
films under a low oxygen pressure (below 10
-5
Torr) is an important key to gain room-
temperature ferromagnetic ordering [163,168,176]. As shown in Table 5.4, however,
films grown at high oxygen pressures (between 0.01 and 750 Torr) [80,84,87,167,169]
still exhibit room-temperature ferromagnetism. These results prove that some other
factors (such as growth temperature, Mn concentration, and microstructure of films) could
influence strongly their magnetic properties.
Recently, room-temperature ferromagnetism has been also found in pure PLD-
grown ZnO films [168,178] and sol-gel prepared nanoparticles [179]. This phenomenon is
not observed in bulk samples made from commercial ZnO powder and nanoparticles
[168,179]. In principle, there is no source for ferromagnetism in undoped ZnO, since both
Zn
2+
and O
2-
are nonmagnetic. It has been suggested that the ferromagnetism in reduced
dimensional systems of thin films and nanoparticles is due to intrinsic defects, such as
oxygen vacancies [180], defects on the Zn site [168] or Zn vacancies [178]. These defects
could be mainly located on nanoparticle surfaces [179] and the interface between the thin
film and substrate [168]. However, this is still an issue for debate.
Concerning our work, the thin films were prepared with similar growth conditions
(see Table 5.1), thus we believe that the room-temperature ferromagnetism could be only
generated from the following interactions: (i) intrinsic defects (for pure ZnO), probably
oxygen vacancies [180], (ii) defect-mediated exchange interaction of Mn ions (for
Zn
1-x
Mn
x
O), and (iii) defect- and hole-mediated exchange interaction of Mn ions (for
Zn
1-x
Mn
x
O:P). The detailed explanation of magnetic interaction mechanisms taking place
in these cases warrants further study.

90
For comparison, in Table 5.4 we summarize the magnetic properties of Mn-doped
ZnO films reported in recent studies. They were grown by different methods, such as
PLD, RF-sputtering, MOCVD (Metal-organic chemical vapour deposition), MBE
(Molecular-beam expitaxy). One can see that almost all thin film samples show room-
temperature ferromagnetic behaviour dependent on growth conditions, such as
temperature and working pressure, gas ambient (oxygen, argon and/or nitrogen). It is
difficult to give an exact specification for the growth conditions that induce room-
temperature ferromagnetism. Thus, in spite of many research works on Mn-doped ZnO
films, the real origin of ferromagnetism is not well understood.
5.5 Conclusions
We fabricated low dimension samples of thin films ZnO, Zn
1-x
Mn
x
O and
Zn
1-x
Mn
x
O:P (x = 0.01 and 0.02) under similar growth conditions, using PLD. The
influence of Mn concentration and P on their structure, optical and magnetic properties
were investigated. Our studies were consistent with the incorporation of dopants Mn and
P into the ZnO host lattice. This increased the lattice parameters and caused the E
g
shift of
ZnO towards higher energies. At room temperature, even the pure ZnO film exhibited
weak-ferromagnetic behaviour, which is probably generated from intrinsic defects created
during the thin-film fabrication. The ferromagnetic ordering increased remarkably when
the ZnO films were codoped with Mn and P, particular for sample N
4
(Zn
0.98
Mn
0.02
O:P).
This could be explained by hole-mediated ferromagnetic interactions taking place
between Mn ions. However, to explain fully the magnetism observed, it is necessary to
know: (i) the change in carrier concentration of the thin films induced by doping with Mn
and P; (ii) what kind of intrinsic defects (oxygen and/or zinc vacancies) are generated and
where they are located; (iii) direct evidence showing the substitution of Mn and P for Zn
and O, respectively, in the ZnO lattice. These problems should be investigated in future
research.

91
Table 5.4: Magnetic property of Mn-doped ZnO films reported in recent studies.
Compound Substrate Growth
method
Growth
temperature
(
o
C)
Oxygen
pressure
(Torr)
Magnetic
property
T
C

(K)
Magnetic
moment
Refs.
Zn
0.99
Mn
0.01
O
Zn
0.98
Mn
0.02
O
Zn
0.99
Mn
0.01
O:P
Zn
0.98
Mn
0.02
O:P

SiO
2
/Si

PLD
*

400

5x10
-2

(Ar:O
2
= 8:2)

FM

> 300

1.17-2.92
B
/Mn

Present
Zn
0.978
Mn
0.022
O Quartz PLD 400 N/A FM > 300 ~0.05 (emu/g) [76]
ZnO/Mn
3
O
4
multilayers

c-Al
2
O
3
*
PLD 700 (ZnO)
500 (Mn
3
O
4
)
5x10
-3
(ZnO)
4x10
-2
(Mn
3
O
4
)
FM > 300 ~0.45
B
/Mn [73]
Zn
0.90
Mn
0.10
O
Zn
0.85
Mn
0.10
Cu
0.05
O
r-Al
2
O
3
*
PLD 650 0.1

FM > 300 0.075
B
/Mn
0.1
B
/Mn
[84]
Zn
0.99
Mn
0.01
O c-Al
2
O
3
PLD 650 ~10
-6
FM > 300 7.0 (emu/cm
3
) [168]
Zn
0.7
(Mn
0.15
Co
0.15
)O c-Al
2
O
3
PLD 400 ~3.8x10
-7
FM > 300 0.19
B
/(Mn+Co) [161]
Zn
0.94
Mn
0.06
O c-Al
2
O
3
PLD 500 1x10
-3
FM > 300 0.2
B
/Mn [74]
Zn
1-x
Mn
x
O c-Al
2
O
3
PLD 700, 800 1x10
-3
1x10
-1
FM > 300 ~8.0 (emu/cm
3
) [85,86]
Zn
0.98
Mn
0.02
O c-Al
2
O
3
PLD N/A 0.01

FM > 300 0.1
B
/Mn [80]
Zn
0.94
Mn
0.06
O
Zn
0.90
Mn
0.10
O
c-Al
2
O
3
PLD 570 22.5x10
-3
(N
2
)
3.75x10
-5

FM
PM
> 290
--
0.03
B
/Mn [171]
Zn
98
Nd
1
Mn
1
O
100
a-Al
2
O
3
*
PLD 590 4.5x10
-3
FM > 290 1.0 (emu/cm
3
) [172]
Zn
0.95
Mn
0.05
O r-Al
2
O
3
PLD 600 0.3 - 750 FM > 300 < 0.1
B
/Mn [169]
Zn
1-x
Mn
x
O c-Al
2
O
3
PLD 500 0.15 FM > 300 0.013 (emu/g) [167]
(Mn, P)-codoped ZnO c-Al
2
O
3
PLD 450 750 1x10
-4
FM > 300 0.1 0.35
B
/Mn [170]
Zn
1x
Mn
x
O Si (001) PLD 500 5x10
-4
FM > 300 0.15
B
/Mn [163]
Zn
0.93
Mn
0.07
O a-Al
2
O
3
RF-sputtering
*
400 6x10
-3

(Ar:O
2
= 5:1)
PM -- [173]
Zn
0.93
Mn
0.07
O c-Al
2
O
3
RF-sputtering 550, 650 Ar gas FM > 300 ~1.25 (emu/cm
3
) [50]
Zn
0.93
Mn
0.07
O c-Al
2
O
3
RF-sputtering 550 0.012
(Ar:N
2
= 7:3)
FM > 300 0.92
B
/Mn

[45]
Zn
0.90
(Mn
0.03
Co
0.07
)O c-Al
2
O
3
RF-sputtering 550 12x10
-3
(Ar) FM > 300 0.11
B
/(Mn+Co) [46]
Zn
0.84
Mn
0.16
O Quartz RF-sputtering 300 7.5x10
-3

(Ar:O
2
= 4:1)
FM 62 0.42
B
/Mn [62]
Zn
0.94
Mn
0.03
Co
0.03
O c-Al
2
O
3
RF-sputtering 550 12x10
-3
(Ar) FM > 300 0.125
B
/(Mn+Co) [61]
Mn-doped ZnO c-Al
2
O
3
, GaN RF-sputtering 500 - 700 N/A FM > 300 [83]
92
Zn
1-x
Mn
x
O GaAs RF-sputtering 500 - 560 8x10
-4
(Ar) FM > 300 ~0.7 (emu/cm
3
) [175]
(Mn, N)-codoped ZnO Quartz RF-sputtering 300 7.5x10
-3

(Ar:O
2
:N
2
=
8:2:1)
FM > 300 0.35
B
/Mn [177]
Zn
0.96
Mn
0.04
O Si(001) RF-sputtering 300 4.0x10
-4

(Ar:O
2
)
FM > 300 14.3-25.1
(emu/cm
3
)
[181]
Zn
0.96
Mn
0.04
O
1-
Si (001) Cosputtering 300 2.2x10
-7

> 1.3x10
-6

FM
PM
> 300
--
3.27
B
/Mn

[176]
p-type Zn
0.99
Mn
0.01
O:P
n-type Zn
0.99
Mn
0.01
O:P
SiO
2
/Si Reactive
sputtering
500 5x10
-3

(Ar:O
2
= 5:1)
FM
PM
> 300
--
~0.45
B
/Mn [174]
Mn-doped ZnO c-Al
2
O
3
PLD and
Implantation
400 0.02 FM > 300 NA [87]
Zn
1-x
Mn
x
O c-Al
2
O
3
Laser MBE
*
400 - 640 N/A FM 35 - 45 NA [182]
(Mn, N)-codoped ZnO c-Al
2
O
3
MOCVD 400 N/A FM > 300 NA [183]
*Note: PLD (Pulsed laser deposition); RF-sputtering (Radio frequency magnetron sputtering); MOCVD (Metal-
organic chemical vapour deposition); MBE (Molecular-beam expitaxy); FM (Ferromagnetic); PM (Paramagnetic) c-
Al
2
O
3
= Al
2
O
3
(0001); a-plane Al
2
O
3
= Al
2
O
3
) 0 2 11 ( ; and r-Al
2
O
3
= Al
2
O
3
) 02 1 1 (


93
Chapter 6
Mn-doped ZnO nanostructures
It was mentioned in Chapters 1 and 2 that ZnO shows many novel nanoscale structures
such as nanoparticles, nanorods, nanowires, nanoneedles, nanotetrapods, nanocombs,
nanorings and so forth. This discovery opens up prospective applications in biosensors,
optoelectronic devices, and energy nanogenerators. In recent years, the doping of
magnetic elements into these structures for spintronic applications also has been of
intensive interest. This chapter presents the growth process of Mn-doped ZnO
nanostructures, using different routes. Investigations basing on EDS, XRD, Raman
scattering and luminescence spectroscopy are carried out, which prove the presence of
Mn in the ZnO host lattice.
6.1 Mn-doped ZnO nanostructures prepared by direct route
For the direct route, we have grown nanorods, nanowires and nanoneedles, using
commercial powders Zn (99.9995 %) and MnCl
2
.4H
2
O (98 %) as initial materials
[55,58,59]. Weight ratios of Zn:MnCl
2
.4H
2
O = 95:5, 85:15, and 75:25 were chosen to
synthesize ZnO nanostructures with different Mn concentrations. The detailed
descriptions of the growth are shown in Chapter 3. By changing the deposition time and
temperature, and keeping the working pressure of about 150 Torr (~0.2 bar), we have
grown nanorods, nanowires and nanoneedles on the Si substrates arranged on the top of
the material source (see Fig. 3.9). Table 6.1 shows some experimental parameters
employed to grow Mn-doped ZnO nanostructures. In fact, the fabrication of these
nanostructures is like an art, meaning the repeat of the nanostructures depends remarkably
on experimenter's skills. Normally, the optimal temperature range to obtain nanorods,
nanowires and nanoneedles is between 470 and 510
o
C under a working pressure of about
0.2 bar. At higher temperatures, Mn-doped films are usually formed, whereas at lower
temperatures (< 470
o
C) there is no chemical reaction between the precursors to obtain
products. During the growth, the following reactions could be taken place
Zn (solid) Zn (vapour) (6.1)
MnCl
2
.4H
2
O MnCl
2
+ 4H
2
O Mn (vapour) + 2HCl + 2H
2
O + O
2
(6.2)
94
(1-x)Zn (vapour) + xMn(vapour) + O
2
Zn
1-x
Mn
x
O (seed) (6.3)
Zn
1-x
Mn
x
O (seed) Zn
1-x
Mn
x
O (crystal) (6.4)
For the first process (Eqs. 6.1 and 6.2), metal vapours Zn and Mn are created, due to
the evaporation of Zn and decomposition of MnCl
2
.4H
2
O under thermal activation
energy. The decomposition of MnCl
2
.4H
2
O also creates oxygen, which leads to
combustion reaction with Zn and Mn vapours in order to form Zn
1-x
Mn
x
O seeds. In
favourable conditions of temperature, pressure and substrate, Zn
1-x
Mn
x
O crystalline
nanostructures will develop directly from these seeds.
Figures 6.1, 6.2 and 6.3 show SEM images of Mn-doped ZnO nanorods, nanowires
and nanoneedles, respectively, with different magnifications. Experimentally, we could
obtain these nanostructures on Si substrates with an area of about 0.5x0.5 cm
2
, and their
diameter ranges from 20 to 700 nm (more SEM images are shown in Figs. A2 and A3,
Appendix). Our TEM studies revealed that all crystals have the wurtzite structure and
grow along c-axis. There was no evidence of Mn-related secondary phases and/or clusters
when investigating individual crystals. The following presents EDS, XRD and Raman
scattering studies for ZnO nanorods doped with different Mn concentrations. The results
obtained provide indirect evidence of the Mn incorporation into the ZnO host lattice.
Similar investigations are in preparation for other samples (nanowires and nanoneedles).
The comparison in optical and magnetic properties among these nanostructures will be
the next step of our research.
Table 6.1: Some experimental parameters used to grow Mn-doped ZnO nanostructures by
the direct route, using Zn and MnCl
2
.4H
2
O as precursors.
Nanostructure Temperature
(
o
C)
Deposition time
(minute)

Ar gas flow
(sccm)
Working pressure
(bar)
Nanorods 490 30-60 150 0.2
Nanowires 490 90 150 0.2
Nanoneedles 500 120 150 0.2
95

Figure 6.1: SEM images of Mn-doped ZnO nanorods with different magnifications.
96

Figure 6.2: SEM images of Mn-doped ZnO nanowires with different magnifications.

97

Figure 6.3: SEM images of Mn-doped ZnO nanoneedles with different magnifications.

98

Figure 6.4: A SEM-EDS spectrum of Mn-doped ZnO nanorods.
0 2 4 6 8 10 12 14
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
Cu O
Zn
Mn
Mn
Cu
Zn
Zn
Energy (keV)

Figure 6.5: A TEM-EDS spectrum taken from a single Mn-doped ZnO nanorod.
Figure 6.4 shows an EDS spectrum of Mn-doped ZnO nanorods, which was
acquired with energy dispersive X-ray spectroscopy linked with FE-SEM (JEOL-JSM
6330F). It appears from the figure that Mn is present in the samples. However, from this
measurement we do not know whether Mn is incorporated inside nanorods, since the
spectrum was taken from a large area of the samples, i.e. including hundreds of nanorods.
Dealing with this problem, we used TEM equipped with EDS (referred to as TEM-EDS).
The electron beam with size 30-50 nm was focused on each individual nanorod. TEM-
EDS spectra were recorded from different points along a nanorod. Figure 6.5 shows a
representative TEM-EDS spectrum of a single nanorod. Mn peaks in the EDS spectrum
proves that Mn locates inside ZnO nanorods. From EDS data, we determined average Mn
99
concentrations in samples grown with the ratios Zn:MnCl
2
.4H
2
O = 95:5, 85:15, and 75:25
to be about 0.83, 1.34, and 1.96 at.%, respectively. For each nanorod, the change in Mn
concentration measured at different points along the nanorod is about 5 %, exhibiting
fairly uniform distribution of Mn. Here, one can see that estimated Mn amounts in ZnO
nanorods are much lower than nominal doping rates. Such situation was also observed by
Liu el al. [59], which might be due to the loss of sublimated Mn by carrying out the
growth process at reduced pressure [59,60].
25 30 35 40 45 50 55 60 65
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
(101)
Si
(002)
2 (degree)
Mn-ZnO
nanorods
33.5 34.0 34.5 35.0

Mn (at.%)
1.96
1.34
0.83
ZnO
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
2 (degree)

Figure 6.6: XRD patterns of samples ZnO nanorods doped with different Mn
concentrations.
Figure 6.6 shows XRD patterns of ZnO nanorods doped with 0.83, 1.34 and 1.96
at.% Mn. There is a strong peak at about 34.3
o
corresponding to the (002) plane of
wurtzite ZnO. This confirms that nanorods grow along the c-axis and are mostly
perpendicular to the substrate. With increasing Mn-doping concentration, the (002) peak
shifts slightly towards lower diffraction angles. This phenomenon was also observed in
Mn-doped ZnO polycrystalline ceramics, as presented in Chapter 4. It is explained by the
substitution of Mn
2+
for Zn
2+
in the ZnO lattice, because the ionic diameter of Mn
2+
(0.80
) is larger than that of Zn
2+
(0.74 ) (see Table A2, Appendix). Based on XRD data, we
determined the lattice parameter c of 0.83, 1.34 and 1.96 %Mn-doped ZnO nanorods as
5.233, 5.235 and 5.239 , respectively, while that of pure ZnO nanorods is 5.232 .
100
200 300 400 500 600 700 800
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
=488 nm
Mn-ZnO
nanorods
Mn (at.%)
1.96
1.34
0.83
ZnO
Raman shift (cm
-1
)

Figure 6.7: Raman scattering spectra of ZnO nanorods doped with different Mn
concentrations grown directly by CVD.
In addition to XRD study, we investigated Raman scattering (RS) spectra of the
samples in the wavenumber range of 200 - 800 cm
-1
. Comparing with pure ZnO nanorods,
RS spectra of Mn-doped ZnO exhibit additional modes besides conventional modes of the
ZnO wurtzite structure (see Fig. 6.7). These modes are located in the wavenumber range
of 450 - 600 cm
-1
, which could be explained by the incorporation of Mn
2+
in the ZnO
lattice. When Mn
2+
ions with a larger ionic radius occupy Zn
2+
sites, some defects are
introduced or vibrations related to intrinsic host-lattice defects are activated. As a result,
some additional modes characteristic of dopant vibrations appear in the Raman spectra
[20,64]. The Mn doping at high concentrations (for x > 1.34 at.%, see Fig. 6.7) could also
cause lattice disorder that influences phonon vibrations of ZnO. This decreases the
intensity of some conventional modes, as can be seen in Fig. 6.7, in the range of 300 - 400
cm
-1
. Similar results were also reported by Zhang et al. [64] on CVD-grown Mn-doped
ZnO nanostructures.
Our investigation of EDS, XRD and Raman scattering prove that Mn is incorporated
into the ZnO nanorods. We believe that similar results would be obtained for the
nanowires and nanoneedles. The advantage of the direct route is that it is possible to grow
Mn-doped ZnO nanostructures with fairly uniform distribution of Mn dopant. However, it
101
is really difficult to grow other nanostructures beyond rods, wires and nanoneedles. Given
these challenges we chose another route that started from precursors of pure ZnO
nanostructures and Mn metal, because the growth of pure ZnO nanostructures is much
easier than those doped with Mn, as presented in the following sections.
6.2 Mn-doped ZnO nanostructures prepared by indirect route
Besides nanowires and nanorods, this route can create some other Mn-doped ZnO
nanostructures (such as tetrapods, multilegs and combs), which are difficult to grow by
the direct route, using precursors of Zn and MnCl
2
.4H
2
O. To synthesize Mn-doped ZnO
nanostructures by an indirect route, we used two steps: (i) grow pure ZnO nanostructures,
and (ii) dope Mn into these nanostructures using thermal diffusion. For the first step, pure
ZnO nanostructures were grown by the aqueous solution and CVD methods, as described
in detail in Chapter 3. The following presents some results obtained basing this approach.
6.2.1 Aqueous solution-grown ZnO nanorods diffused with Mn
For each growth time, this method allows us to obtain a large amount of ZnO
nanorods with equal sizes on Si substrates. The synthesis process was described in
Chapter 3, using C
6
H
12
N
4
and Zn(NO
3
)
2
.6H
2
O as initial materials. Figure 6.8 shows SEM
images of as-prepared ZnO nanorods with dimensions of about 80-200 nm diameter and
1-2 m length. They are single crystals and grow along the c-axis, which are confirmed
by TEM (see the inset of Fig. 6.8). Because the growth is carried out in solution and at a
low temperature (95
o
C), the nanorods obtained still contain remnants such as C
6
H
12
N
4
,
Zn(NO
3
)
2
and H
2
O. In order to remove these impurities, we desiccate the as-prepared
ZnO nanorods at temperatures above 300
o
C. This procedure is confirmed by thermal
gravimetric analysis (TGA) data that we studied in the temperature range of 20 - 1000
o
C,
as shown in Fig. 6.9. With increasing temperature, the weight of nanorods decreases
rapidly, particularly in the temperature range 20 - 300
o
C (the weight loss is about 6.5
wt.%). This is due to decomposition and evaporation of the remnants. At temperatures
above 300
o
C, the mass of the nanorods becomes more stable. The weight loss counted
between 300 to 1000
o
C is about 1.0 wt.%, which is comparable with that of commercial
ZnO powders (about 0.6 wt.%) in the same temperature range, see Fig. 6.9. It should be
noted that the weight loss of ZnO nanorods when heated to high temperatures (> 800
o
C)
is mainly caused by sublimation.
102

Figure 6.8: SEM images of as-prepared ZnO nanorods grown by an aqueous solution
method with different magnifications. The inset shows their SAED pattern, revealing that
the nanorods grow along the c = ] 0001 [ axis.

103
0 100 200 300 400 500 600 700 800 900 1000
92
94
96
98
100
ZnO nanorods

Temperature (
o
C)
0
20
40
60
80
100


W
e
i
g
h
t

l
o
s
s

(
%
)
C
6
H
12
N
4
20
40
60
80
100




Zn(NO
3
)
2
.6H
2
O
Commercial ZnO


Figure 6.9: TGA data of ZnO nanorods grown by an aqueous solution method in
comparison with those of commercial ZnO, Zn(NO
3
)
2
6H
2
O and C
6
H
12
N
4
in the
temperature range 20 - 1000
o
C.

After fabrication, we doped Mn into these ZnO nanorods by thermal diffusion. ZnO
nanorods on the Si substrate were covered with the smooth surface of a Mn fragment. The
separation was maintained at about 1 mm (see Fig. 3.13, Chapter 3) to avoid direct
reaction. The diffusion process was carried out in a quartz tube furnace at a vacuum
pressure of about 10
-3
Torr for 90 minutes. In order to prepare samples doped with
different Mn concentrations, we changed annealing temperature from 600 to 850
o
C. It
was found that Mn dopants started diffusing in the ZnO nanorods at about 680
o
C, and
Mn concentration in the nanorods increases with increasing annealing temperature. By
this route, we prepared samples with Mn concentrations 0.62 (ZM1), 1.15 (ZM2), 1.74
(ZM3), 2.53 (ZM4) and 4.71 at.% (ZM5), which were averaged from TEM-EDS spectra
of individual nanorods. Visually, the Mn-diffused samples have a yellowish colour,
depending on their Mn concentration. As experimental evidence, Figure 6.10 shows a
104
TEM-EDS spectrum of Mn-doped ZnO nanorods prepared by thermal diffusion, which
reveals the presence of Mn in the samples.
0 2 4 6 8 10 12 14
O
Cu
Zn
Zn
Zn
Mn
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
Energy (keV)

Figure 6.10: A TEM-EDS spectrum of Mn-diffused ZnO nanorods (sample ZM2)
prepared by thermal diffusion.
It is found that following thermal diffusion the morphology of Mn-doped ZnO
nanorods is modified {see Fig. 6.11(a,b)}, compared to the as-prepared ZnO nanorods
(Fig. 6.8) and those annealed at 800
o
C {Fig. 6.11(c)}. In Chapter 4, we noticed the
diffusion of Zn atoms into manganese oxides taking place strongly, even at low annealing
temperatures. In this case, thus, the modification in morphology of the Mn-doped ZnO
nanorods could be due to the strong diffusion of Zn atoms into manganese oxides created
on the surface of the Mn metal as heated at high temperatures. During the diffusion, if the
nanorods are in contact directly with the Mn metal, after thermal diffusion the
morphology of the nanorods is modified very much, as can be seen in Fig. 6.11(d). This is
the reason that when preparing the Mn-doped samples by thermal diffusion we
maintained the distance between the ZnO nanorods and Mn metal at about 1 mm.
105

Figure 6.11: Some SEM images: (a and b) of Mn-diffused ZnO nanorods (sample ZM4)
at different magnifications, (c) pure ZnO nanorods annealed at 800
o
C in vacuum for 90
minutes, and (d) Mn-doped ZnO nanorods obtained when the ZnO nanorods and Mn
metal are in contact during the diffusion.
The modification in morphology of nanorods could be also observed clearly by
TEM. As shown on in Fig. 6.12, there are two types of Mn-diffused nanorod shapes. The
first type corresponds to the nanorods with a very sharp tip {Fig. 6.12(a,b)} while the
other does not have this feature {Fig. 6.12(c)}. At sharp tips, the Mn concentration is
usually 20 - 30 % higher than other positions. This phenomenon is attributed to nanorods
located at the surface of samples. These nanorods are closer to the Mn fragment where the
sublimation and diffusion of Zn into manganese oxides would take place more rapidly.
Notably, the surfaces of pure and Mn-doped ZnO nanorods annealed at high temperatures
show many round patches with 5 - 40 nm diameter, probably caused by evaporation of the
remnants. The density of these traces is about 40-70/m
2
. When compared with as-
106
prepared ZnO nanorods, the surface of the Mn-diffused nanorods is rough, almost like
"saw-teeth". The surface roughness is about 13 - 19 nm, see Fig. 6.13(a). By plotting the
variation of contrast intensity along the edge of a nanorod, we obtained the distance
between two "saw-teeth" d as about 25 - 40 nm, while the width of each tooth d is 17 -
22 nm, see Fig. 6.13(b). The formation mechanism of these "saw-teeth" requires further
study.

Figure 6.12: TEM images for Mn-diffused ZnO nanorods (sample ZM4) (a,b) with and
(c) without a sharp tip.

Figure 6.13: (a) A TEM image shows the surface modification of Mn-diffused ZnO
nanorods, (b) the variation of contrast intensity taken along the edge of a nanorod in (a).
107
30 35 40 45 50 55 60 65
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
ZnO-800
o
C
0.62
1.74
2.53
4.71

2 (Degree)
ZnO as-prep.

1.15






Mn-diffused
ZnO nanorods


Mn (at. %)



Figure 6.14: XRD patterns of Mn-doped ZnO nanorods prepared by thermal diffusion,
compared with as-prepared ZnO nanorods and those annealed at 800
o
C.
The above investigations have revealed that the morphology and surfaces of Mn-
doped ZnO nanorods prepared by thermal diffusion were extensively modified when
compared with the as-prepared ZnO nanorods. From TEM-EDS data, we obtained Mn
concentration in the samples. Figure 6.14 shows their XRD patterns in comparison with
those of pure ZnO nanorods. One can see that all samples exhibit XRD peaks coming
from the ZnO wurtzite structure. The presence of Mn in the samples does not lead to
development of Mn-related secondary phases, see Fig. 6.14. The XRD spectra are similar
to Mn-doped samples of polycrystalline ceramics and thin films, where the increase in
Mn-doping concentration causes a slight shift (about 0.05
o
) of XRD peaks towards lower
diffraction angles. This is explained by the substitution of Mn
2+
for Zn
2+
in the ZnO
lattice.

108
240 320 400 480 560 640 720 800

ex.
=488 nm

I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)

Raman shift (cm
-1
)
ZnO


1.74
1.15
0.62

T
A
+
L
O
1
L
O
E
2
(
h
i
g
h
)
-
E
2
(
l
o
w
)
A
1
(
T
O
)
E
2
(
h
i
g
h
)
Mn-diffused
ZnO nanorods
Mn (at.%)
4.71
2.53


Figure 6.15: Raman scattering spectra of Mn-doped ZnO nanorods prepared by thermal
diffusion under an excitation wavelength of 488 nm; the dotted lines show conventional
modes associated with ZnO wurtzite.
To further confirm this conclusion, we studied Raman scattering spectra of the
nanorods excited at 488 nm. The results are shown in Fig. 6.15. It is found that Raman
scattering intensity in the wavenumber range of 480 - 600 cm
-1
increases strongly with
increasing Mn concentration, whereas the scattering intensity in the range of 300 - 400
cm
-1
decreases. Particularly, at Mn concentrations above 1.74 at.%, some conventional
modes disappear, similarly to the behavior observed in CVD-grown Mn-doped ZnO
nanorods (Fig. 6.7). Such changes are due to the incorporation of Mn into the ZnO host
lattice, which have been explained carefully in Chapter 4 and the section 6.1.
6.2.2 CVD-grown ZnO nanostructures diffused with Mn
Recently, we have grown pure ZnO nanowires and then used thermal diffusion (as
described above) to dope Mn [184]. Our study exhibited the incoporation of Mn into
nanowires at temperatures above 600
o
C, similarly to results obtained in the part 6.2.1.
We believe that it is possible to realize the Mn doping in other CVD-grown ZnO
nanostructures. In this section, we present the growth of some ZnO nanostructures,
including tetrapods and combs. The starting material of ~1.0 g Zn powder was loaded in a
109
ceramic boat and placed in the centre of the quartz tube furnace. The Si substrates were
arranged upstream on an alumina plate, near the vapour source (see Fig. 3.13). The
growth was carried out with Ar gas at atmosphere pressure at temperatures between 630 -
700
o
C for 6 - 10 hrs. Detail description of the growth procedure is given in Chapter 3.
Notably, the upstream arrangement of the Si substrates is to limit the Zn vapour flux
during the growth process, since a large vapour flux could form mixture of
nanostructures. With these conditions, we repeated many experimental times and obtained
some other nanostructures of ZnO in the temperature range 625 - 650
o
C. These structures
include ZnO nanotetrapods (Fig. 6.16) and nanocombs (Fig. 6.17) with different
morphologies. They grow above the substrate surface, revealing that Zn droplets could
play as initial nucleus for the growth.

Figure 6.16: SEM images show different morphologies of nanotetrapods grown at (a) 625
- 630
o
C, (b, c) 640
o
C, and (d) 650
o
C.
110

Figure 6.17: SEM images of ZnO comb-like nanostructures (grown at about 630
o
C) with
different magnifications
During the growth process, the following reactions took place
Zn (solid) Zn (vapour) evaporation, (6.5)
Zn (vapour) + O
2
ZnO (seed) combustion, (6.6)
ZnO (seed) ZnO (crystal) growth, (6.7)
where an oxygen source was from the residual oxygen in the reactor tube and/or in Ar
gas.
111
For many years, efforts have been made to understand the nature of crystal growth
for ZnO nanostructures in order to gain greater control. However, the large range of
parameters involved and the complexity of the system means that the growth remains
somewhat of an art rather than a science.
Based on above experimental results, we believe that it is possible to use thermal
diffusion in order to dope Mn into these nanostructures of ZnO. This is a simple and
inexpensive method. However, its weakness is the non-uniform distribution of Mn in
nanostructures. Normally, ZnO layers located near the surface have higher Mn
concentrations [60,67], because they are closer to the Mn metal.
6.3 Conclusions
We prepared ZnO nanostructures doped with different Mn concentrations, basing on
direct and indirect routes. For the direct route, Mn-doped ZnO nanorods, nanowires and
nanoneedles were grown on the Si substrates at temperatures 470 - 510
o
C, using Zn and
MnCl
2
.4H
2
O powders as starting materials. Structural, EDS and optical studies revealed
the incorporation of Mn in the ZnO host lattice. For the indirect route, we followed two
steps. The first one is to synthesis pure ZnO nanostructures (using an aqueous solution
method at about 100
o
C, and CVD at temperatures 630 - 650
o
C), while the other is to
dope Mn into these nanostructures (basing on thermal diffusion at above 680
o
C). The Mn
doping source is Mn fragments with a smooth surface. We diffused successfully Mn into
nanorods and nanowires. Studies of XRD, EDS and Raman spectra indicated the presence
of the dopant Mn in the ZnO host lattice. We believe that these results would be repeated
in other ZnO structures, such as tetrapods and comb-like nanocrystals. The finding of
optimal fabrication conditions to obtain uniform distribution of Mn in these ZnO
nanostructures and the investigation of their magnetic properties in comparison with other
Mn-doped ZnO materials requires further study.
112
Chapter 7
Conclusions and future research
We have studied the structural, optical and magnetic properties of various Mn-doped ZnO
materials, including polycrystalline ceramics, thin films and nanostructures. Samples
were prepared by solid-state reaction, PLD, CVD and aqueous chemical solution
deposition. Our work focused on some topical issues of Mn-doped ZnO materials: (i) the
influences of the Mn dopant, preparation conditions and processing on structural, optical
and magnetic properties, and (ii) the origin of ferromagnetism in these materials. The
research method was based on a combination of X-ray diffraction, scanning/transmission
electron microscopy, energy dispersive X-ray spectroscopy, photoluminescence and
Raman scattering spectroscopy, and a physical property measurement system (PPMS).
Some important results obtained for each material system (i.e., polycrystalline ceramics,
thin films and nanostructures) are presented briefly below.
7.1 Mn-doped ZnO polycrystalline ceramics
We prepared two series of samples of Mn-doped ZnO ceramics. The first series,
where their precursors were put in a sealed plastic jar and wet mixed by a milling
machine using zirconia balls and high-purity water, was sintered at temperatures between
400 and 1000
o
C. The second series were sintered at 500 and 800
o
C, in which the
precursors were mixed and ground by hand without high-purity water. The XRD and
TEM analyses revealed that besides the main phase of wurtzite ZnO, there were
secondary phases related to the Mn oxides. The mixing condition of the precursors (ZnO
and MnO
2
powders) influenced strongly the formation of these phases.
For the first series, we observed Zn
x
Mn
y
O
4-
compositions with the cubic spinel
structure, which were observed very soon, even in the as-prepared sample. This phase
grows as nanoparticles which cover the surfaces of ZnO crystals. With increasing
sintering temperature up to 1000
o
C, the particle size and Mn concentration in
cubic Zn
x
Mn
y
O
4-
spinels increased, with a corresponding change in the lattice parameter
a. At annealing temperatures T
s
800
o
C, the crystal quality of the samples, which
included both phases Zn
1-x
Mn
x
O and Zn
x
Mn
y
O
4-
, was improved. Concurrently, at these
113
temperatures MnO
2
could react completely with ZnO to form Zn
1-x
Mn
x
O and/or
Zn
x
Mn
y
O
4-
.
Concerning the second series, the sample sintered at 500
o
C revealed the presence of
MnO
2
and Mn
2
O
3
, whereas samples sintered at 800
o
C showed only tetragonal
Zn
x
Mn
2-z
O
4
spinel.
Our studies based on TEM-EDS, Raman scattering, photoluminescence and ESR
spectroscopy indicated that Mn is incorporated into the ZnO host lattice, even for the as-
prepared sample. To explain the changes of Mn concentration and lattice parameters (a
and c) of the ZnO crystals, we suggested that Mn in the as-prepared sample was located at
interstitial positions. When the samples were annealed at temperatures between 400 and
1000
o
C, Mn in the ZnO lattice is subject to two simultaneous dynamic tendencies: (i)
diffusion of Mn out of ZnO crystals to form cubic Zn
x
Mn
y
O
4-
spinels, and (ii) the
substitution of Mn
2+
for Zn
2+
in the ZnO host lattice. These processes take place rapidly at
temperatures T
s
700
o
C, in which the first process was always more dominant than the
other. The evidence for this phenomenon is the strong changes in the lattice parameters of
both Zn
1-x
Mn
x
O and Zn
x
Mn
y
O
4-
phases (in the first series) and the appearance of Mn
2+

hyperfine lines in their ESR spectra. However, the Mn
2+
substitution for Zn
2+
in ZnO and
the formation of stable oxide phases (i.e., Zn
x
Mn
y
O
4-
and/or Zn
z
Mn
2-z
O
4
) as T
s
700
o
C
suppresses the ferromagnetic ordering in the samples, although the quality of the samples
is improved.
Based on magnetic measurements, we found that ferromagnetism in samples
processed at lower temperatures is generated mainly from secondary phases related to Mn
oxides, being Zn
x
Mn
y
O
4-
(for the first series) and Mn
2
O
3
or Zn
t
Mn
2-t
O
3
(for the second
series). The compositions Zn
1-x
Mn
x
O, MnO
2
and ZnMn
2
O
4
were not responsible for the
ferromagnetic ordering. For the first series, the decline in ferromagnetic order for
increasing T
s
was caused by increasing Mn concentration in Zn
x
Mn
y
O
4-
This could also
cause the transition of Zn
x
Mn
y
O
4-
from a metastable state to a stable one mentioned in
previous studies.
7.2 Mn-doped ZnO thin films
We prepared the thin films ZnO, Zn
1-x
Mn
x
O and Zn
1-x
Mn
x
O: 1.0 mol% P (x = 0.01
and 0.02) on the SiO
2
/Si(001) substrates under similar growth conditions, using PLD. The
doping with 1.0 mol% P was designed to increase the hole density in the films. The
influences of Mn concentration and P on the structure, optical and magnetic properties of
114
the films were investigated in detail by means of TEM, XRD, optical absorption
spectroscopy and vibrating sample magnetometry. All measurements were carried out at
room temperature. Our studies revealed that the dopants Mn and P were incorporated into
the ZnO host lattice. This result was deduced indirectly from the increase of the lattice
parameters and the blue shift of band gap energy E
g
towards higher energies.
Surprisingly, the pure ZnO film exhibited weak-ferromagnetic behaviour at 300 K, which
could be generated from intrinsic defects created during the thin-film fabrication. The
ferromagnetic ordering increased when the ZnO film was doped with Mn. The additional
doping with P into the Mn-doped ZnO films enhanced remarkably the ferromagnetic
ordering, particular for sample N
4
(Zn
0.98
Mn
0.02
O:P). We believe that the substitution of
P
3-
for O
2-
in the ZnO host lattice could introduce a higher concentration of holes. As a
result, the increase of ferromagnetic ordering in Zn
1-x
Mn
x
O:P films could be explained by
hole-mediated ferromagnetic interactions taking place between Mn ions.
7.3 Mn-doped ZnO nanostructures
ZnO nanostructures (including rods, wires, needles, tetrapods and combs) doped
with different Mn concentrations were fabricated by means of direct and indirect routes.
For the direct route, Mn-doped ZnO nanorods, nanowires and nanoneedles were grown on
the Si substrates by CVD, using the starting materials of Zn and MnCl
2
.4H
2
O powders.
The nanostructures were formed at temperatures between 470 and 510
o
C. Our
investigations of structure, EDS and Raman scattering spectra revealed the incorporation
of Mn in the ZnO host lattice. This increased slightly the lattice parameters and excited
Mn-related vibrational modes of ZnO.
Using the indirect route to make Mn-doped ZnO nanostructures, we followed two
steps: (i) Synthesis of pure ZnO nanostructures based on an aqueous solution method at
about 100
o
C and CVD at temperatures 630 - 650
o
C; (ii) Mn doping into these
nanostructures, using thermal diffusion at above 680
o
C. For the second step, we used Mn
fragments with the smooth surface as the doping source. By this route, we diffused
successfully Mn into nanorods and nanowires. Control of the Mn concentration could be
carried out either by changing the diffusion temperature or the diffusion time. Our
investigations of XRD, EDS and Raman scattering indicated the presence of the dopant
Mn in the ZnO host lattice of nanorods and nanowires. We believe that these results
would be found in other ZnO tetrapod and comb-like nanocrystals.


115
7.4 Future research
In spite of the experimental results summarised above, there are still some unsolved
questions in our work that warrant further study.
For polycrystalline samples of Mn-doped ZnO ceramics; there is a need to identify
exactly the location of Mn and its ionisation state (ions and/or atoms) in the ZnO host
lattice, particularly for samples sintered at temperatures below 700
o
C.
For Mn-doped ZnO thin films: to explain fully the ferromagnetism observed, we
need to know (i) the change in carrier concentration of the thin films induced by doping
Mn and P, (ii) what kind of intrinsic defects (oxygen and/or zinc vacancies) and where
they are located; (iii) direct evidence for the substitution of Mn and P for Zn and O,
respectively, in the ZnO host lattice.
For Mn-doped ZnO nanostructures: (i) to find optimal fabrication conditions for a
uniform distribution of Mn in the ZnO nanostructures, and (ii) measure the magnetic
properties of the samples and compare them with the other Mn-doped ZnO materials.
This would assist an overall assessment of the influences of fabrication conditions,
structure and morphology on the magnetic properties of Mn-doped materials prepared by
different methods or routes.
116
Appendix
This part provides some supplemental data discussed in the main text.

Figure A1: XRD patterns of the 10% MnO
2
-90% ZnO sample sintered at different
temperatures. Dashed lines, circles, and asterisk represent the main peaks from
Zn
x
Mn
3-x
O
4
, Mn
2
O
3
, and MnO
2
, respectively Ref. [72]. An added symbol x in the
figure shows a cubic Zn
x
Mn
y
O
4
-related secondary phase which was not discussed in
Ref. [72].

Table A1: Theoretical values of the moment per transition metal ion.
Ion Ti
2+
Co
2+
V
2+
Mn
2+
Moment 2
B
3
B
3
B
5
B


Table A2: Radius of some ions [45,62,161].
Ion Zn
2+
Mn
2+
Mn
3+
Mn
4+
Co
2+
O
2-
N
3-
P
3-
Radius
()
0.74 0.80 0.66 0.54 0.72 1.38 1.46 1.80 -
2.12


117

Figure A2: SEM images of Mn-doped ZnO nanorods with diameters of (a) 50-100 nm,
and (b) 250-300 nm.

Figure A3: SEM images of Mn-doped ZnO nanowires with diameters of (a) 20-50 nm
and (b) 80-100 nm, (c) 100-200 nm, and (d) 500-700 nm.
118
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