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Materials Science and Engineering R 62 (2008) 135

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Ferromagnetism and possible application in spintronics of

transition-metal-doped ZnO lms
F. Pan *, C. Song, X.J. Liu, Y.C. Yang, F. Zeng
Laboratory of Advanced Materials, Department of Materials Science and Engineering, Tsinghua University, Beijing 100084, PR China


Keywords: This review article rst presents a summary of current understanding of the magnetic properties and
Diluted magnetic oxide intrinsic ferromagnetism of transition-metal (TM)-doped ZnO lms, which are typical diluted magnetic
ZnO oxides used in spintronics. The local structure and magnetic behavior of TM-doped ZnO are strongly
Local structure
sensitive to the preparation parameters. In the second part, we discuss in detail the effects of doping
elements and concentrations, oxygen partial pressure, substrate and its orientation and temperature,
deposition rate, post-annealing temperature and co-doping on the local structure and subsequent
ferromagnetic ordering of TM-doped ZnO. It is unambiguously demonstrated that room-temperature
ferromagnetism is strongly correlated with structural defects, and the carriers involved in carrier-
mediated exchange are by-products of defects created in ZnO. The third part focuses on recent progress in
TM-doped ZnO-based spintronics, such as magnetic tunnel junctions and spin eld-effect transistors,
which provide a route for spin injection from TM-doped ZnO to ZnO. Thus, TM-doped ZnO materials are
useful spin sources for spintronics.
2008 Elsevier B.V. All rights reserved.


1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Experimental procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1. Film growth of TM-doped ZnO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2. Characterization techniques. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3. Local structure and ferromagnetism of TM-doped ZnO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1. Effect of doping concentration on structure and magnetization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.1.1. Effect of doping concentration on magnetic ordering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.1.2. Formation of a secondary phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.2. Substrate effects on magnetization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.2.1. Substrate-dependent local structure and magnetic behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.2.2. Substrate orientation-induced distinct magnetization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.3. Effects of substrate temperature and lm deposition rate on magnetization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.4. Inuence of oxygen partial pressure on magnetic ordering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.5. Strain-induced ferromagnetism enhancement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3.6. Inuence of post-annealing on magnetization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.7. Effect of co-doping on magnetic properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.8. Comparison of ZnO doped with Sc, Ti, V, Cr, Mn, Fe, Co, Ni and Cu . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4. Origin of ferromagnetism in TM:ZnO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4.1. Computational work. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
4.2. Experimental work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.2.1. Secondary phases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.2.2. Carrier exchange interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21

* Corresponding author. Tel.: +86 10 62772907; fax: +86 10 62771160.

E-mail address: (F. Pan).

0927-796X/$ see front matter 2008 Elsevier B.V. All rights reserved.
2 F. Pan et al. / Materials Science and Engineering R 62 (2008) 135

4.2.3. Defect-based BMP . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21

4.3. Effect of bandgap on the Curie temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
5. TM-doped ZnO-based prototype spintronics and multi-functional materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
5.1. Co-doped ZnO-based magnetic tunnel junctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
5.1.1. Spin-polarized transport in (Zn,Co)O/ZnO/(Zn,Co)O junctions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
5.1.2. Anomalous TMR in (Zn,Co)O-based junctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
5.2. TM-doped ZnO-based spin eld-effect transistors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
5.3. Ferroelectricity and giant piezoelectric d33 in V and Cr-doped ZnO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
6. Conclusions and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32

1. Introduction spintronics, but also owing to the excellent physical properties. So

far, RTFM has commonly been obtained in ZnO systems doped with
A diluted magnetic semiconductor (DMS) is a compound with TM elements such as Sc [23,24], Ti [23,25], V [2628], Cr
properties intermediate between a non-magnetic semiconductor [11,23,29,30], Mn [3140], Fe [4143], Co [8,23,4461], Ni
and a magnetic element, and is obtained by doping a non-magnetic [62,63], and Cu [6468], and co-doping such as CoFe [69,70] and
semiconductor with transition-metal (TM) elements (e.g., Sc, Ti, V, MnCo [71,72], for which Co- and Mn-doped ZnO are the most
Cr, Mn, Fe, Co, Ni and Cu), including TM-doped IIIV (GaAs and popular systems. Many groups have reported that TM-doped ZnO
InAs) [14], IIVI (CdTe) [5] or group IV (Ge and Si) types [6]. lms exhibit FM ordering at a TC much lower than RT, such as 83 K
However, most DMSs have a low Curie temperature (TC), which [73] and 110 K [74] for Mn-doped ZnO. Many previous publications
limits their use in practical applications [7,8]. In 2000, Dietl et al. indicate that TM ions at Zn sites is a necessary but not sufcient
[9] theoretically predicted that the TC of DMSs could be increased condition for FM in true TM:ZnO DMOs. Some ZnO lms doped
above room temperature (RT) for p-type DMSs, and ferromagnet- with Ti [75], V [27], Mn [42], Co [76,77] and Cu [78] only exhibited
ism (FM) was stable in DMSs based on wide-bandgap semicon- paramagnetism or superparamagnetism as well as spin glass
ductors, i.e., ZnO and GaN. Using rst-principle calculations, Sato behavior [79].
and Katayama-Yoshida [10] theoretically demonstrated that a ZnO Although a considerable amount of experimental data and
matrix doped with TM atoms such as V, Cr, Fe, Co and Ni exhibited corresponding mechanisms has been accumulated since the rst
FM ordering, whereas doping with Ti and Cu resulted in a report of RTFM [11,1620], the origin of FM ordering in DMOs,
paramagnetic state, which opened a window for experimental including TM-doped ZnO, is still a matter of debate, i.e., whether
attempts to prepare DMSs with room temperature ferromagnetism carrier-mediated exchange based on TM2+ replacement of Zn2+
(RTFM). FM semiconductors with O2 anions, such as TM-doped [16,17] or the formation of secondary phases [18,69,80] is
ZnO, are also termed diluted magnetic oxides (DMOs). involved. Thus, it is critical to distinguish true FM semiconductors
Soon after that, consecutive experimental reports revealed that from those that merely show magnetic hysteresis. Even more
TM-doped ZnO and TiO2 exhibited intrinsic RTFM [11,12]. These ambiguously, distinct results are frequently obtained in rather
observations prompted extensive experimental work and theore- similar TM-doped ZnO lms in the case of Co2+ substitution for
tical studies on RTFM DMOs, driven both by an urge to understand Zn2+ [11,81,82], indicating that the magnetization of TM-doped
the mechanisms involved and by the demand for better materials. ZnO is strongly dependent on the preparation parameters, and that
In fact, interest in TM-doped ZnO has increased because of the preparation process is not easily reproduced from one growth
promising applications in the eld of semiconductor spintronics, run to another.
which seeks to extend the properties and applications of In this rather contradictory context, several experiments and
established electronic devices by using the spin of electrons in calculations have been performed to elucidate the nature of RTFM
addition to their charge [7,1315]. Electron spin can potentially be
used to provide efcient injection of spin-polarized carriers for
spintronics and to fabricate transparent magnetic materials for
spintronics [1622]. There are two major criteria for selecting the
most promising materials for semiconductor spintronics. First, the
intrinsic FM should be retained at practical temperatures (i.e.
>300 K). Second, it is a major advantage if there is existing
technology for the material in other applications [14]. Fortunately,
TM-doped ZnO satises these two criteria. Following the
theoretical prediction of RTFM ascribed to a carrier-mediated
mechanism in ZnO-based DMOs [9], TM-doped ZnO has been
intensively investigated to achieve magnetic ordering above RT
and promising magneto-transport properties [11,14,1620]. As a
low-cost, wide-band gap (Eg = 3.37 eV) semiconductor, ZnO itself
has been the focus of renewed research for applications such as UV
light-emitters, transparent high-power electronics, surface acous-
tic wave devices, piezoelectric transducers and window materials
for display and solar cells [21,22].
Recently, a surge in research into TM:ZnO DMOs has been
observed, as shown in Fig. 1, indicating that this area is attracting Fig. 1. Publications per year on TM:ZnO DMOs according to the Web of Science:
increasing interest not only because of promising applications in
F. Pan et al. / Materials Science and Engineering R 62 (2008) 135 3

[8,31,44,83]. Mechanism proposed include a bound magnetic including direct current (dc) reactive [44,45,94] and radio-
polaron (BMP) mechanism involving defects, including oxygen frequency (rf) [32,9698], combinatorial laser molecular-beam
vacancies (VO) and Zn interstitials (Zni) [8,44,57], hole doping epitaxy [50,51], chemical vapor deposition (metalorganic
involving Zn vacancies [34,49,84], and the formation of FM [34,52,53,99,100], ultrasonic-assisted solution [57] and plasma-
secondary phases (e.g., Mn2xZnxO3d via Zn diffusion into the enhanced [101]), ion-beam implantation [35,42], ion-beam
Mn oxide [31]) and TM-rich nanocrystals [83]. Moreover, ab initio sputtering [54,55], and solgel methods [39,56]. Although the
calculations predicted that competition between FM and anti-FM magnetic behavior of TM-doped ZnO lms is sensitive to the
coupling existed in DMOs [84]. However, there is ongoing debate deposition conditions [1618], there is no conclusion on which
about these systems. In addition, a trace amount of an external deposition method is best for FM ordering of the lms. For
pollutant would also lead to a hysteresis loop during magnetiza- example, Co-doped ZnO lms deposited by PLD [11,77] or
tion measurements, further adding to the difculties in determin- magnetron sputtering [74,94], two widely used deposition
ing true DMOs [20,85,86]. So far, publications, including reviews methods, could alternatively exhibit RTFM and RT paramagnetism.
[1620], have commonly focused on a summary and comparison of Therefore, magnetron sputtering is increasingly popular for
DMOs obtained by different groups and the different experimental growing TM-doped ZnO lms owing to its low cost, high efciency,
conditions used (e.g., preparation methods and parameters). The and easy control, and its production of uniform lms of large size.
resulting macroscopic magnetic properties, which are critically The substrate generally used is Al2O3(0 0 1) for low mismatch
dependent on growth and processing conditions, are diverse between the lm and the substrate (2%) after a 308 in-plane
without any common characterizations. It is therefore difcult to rotation [21], which is suitable for ZnO lms exhibiting high
identify a consistent mechanism to effectively understand the crystallinity. Some other substrates suitable for the deposition of
origin of FM ordering merely by comparison of experimental TM-doped ZnO lms are Si [37,58,62,67,102], fused quartz [33],
results achieved by different groups. glass [54,68,103,104], ZnO [51,105], ScAlMgO4 [106], LiNbO3 [44],
Half a decade has already passed since the rst report of RFTM LiTaO3 [107], MgO [40], SiO2 [108] and NaCl [94]. Fig. 2 presents
for TM-doped ZnO. Efforts are increasingly shifting not only to the typical cross-sectional high-resolution transmission electron
rational design of methods to evaluate this system, but also to the microscopy (HRTEM) images of Co-doped ZnO lms grown by
development of TM-doped ZnO-based prototype spintronics dc reactive magnetron co-sputtering on Al2O3(0 0 1), Si(1 1 1),
[14,85]. When successfully combined with semiconductor func- SiO2(1 0 1) and LiNbO3(1 0 4) substrates. In contrast to the
tionalities, spintronics will have a considerable impact on future epitaxial growth of Co-doped ZnO lm on Al2O3 substrate
electronic device applications [15]. Spin injection from a TM-doped (Fig. 2a), the lms deposited on Si, SiO2 and LiNbO3 exhibit an
ZnO layer to pure ZnO and other conventional semiconductors is an (0 0 2) preferred orientation with structural defects (e.g., edge
important long-term goal of the continuing research into ZnO dislocations, marked by ?) in Fig. 2bd. Large- and small-angle
DMOs [87,88]. This concept has been realized in a representative grain boundaries are observed in the lms on Si (Fig. 2b)/LiNbO3
spintronics application, TM:ZnO-based magnetic tunnel junction (Fig. 2d) and SiO2 (Fig. 2c), respectively. Moreover, the (0 0 2)
(MTJs), which exhibit superior spin-polarized transport, such as a planes are not parallel to the surface of the LiNbO3 substrate;
large half voltage (V1/2, at which the tunnel magnetoresistance instead, the pillar-like grains tend to grow in two directions, as
ratio becomes half of the maximum) [88,89], compared to highlighted by the arrows in Fig. 2d. These observations reveal that
conventional magnetic metals and magnetic TM-oxide-based the substrate affects the microstructure and the formation of
MTJs with AlOx and MgO barriers [90]. Another typical application defects in TM-doped ZnO lm, which are expected to play an
is the spin eld effect transistor (spin-FET) proposed by Datta and important role in FM ordering in this system [94].
Das [91]. The core idea of this device is to induce spin precession by For PLD and rf magnetron sputtering techniques, lms were
the Rashba spinorbit interaction in a two-dimensional electron deposited using a ceramic target prepared using standard ceramic
gas and to use spin-dependent materials. Although a working techniques from ZnO and TMO or TM2O3 powders of 4N purity [23].
prototype of the DattaDas spin-FET has not yet been fabricated, For example, ZnO and MnO2 were mixed together, ground and
the relevant conditions necessary for the desired spin-FET calcined for 8 h at 400 8C and sintered at 600900 8C for 12 h in air
operation and simplied devices have been obtained [92,93]. to obtain Zn1xMnxO(0  x  0.1) ceramic pellets [33], whereas
In this review, to study the nature of FM ordering at high TC, our ZnO and CoO/Co3O4 powders were used to prepare a
main aim was to extract a single variable from a series of Zn1xCoxO(0  x  0.1) target. An alternative way to synthesize
experiments. An example is substrate variation [94], which is of TM-doped ZnO lms starts from pure metal targets of Zn and TM
great interest owing to its potential to provide direct information [44,59,94] or alternate deposition of TM/ZnO [54,55]. The relative
regarding the factors that affect FM ordering. Moreover, since ZnO sputtering area of TM chips attached to a Zn target was adjusted to
is a multi-functional material, recent signicant advances for this control the TM composition in TM-doped ZnO lms grown by dc
system are described, including ferroelectric, piezoelectric, optical, reactive magnetron co-sputtering [44]. Although it is hard to
and electric properties, which play important roles in spintronics precisely control the TM content in the lm to the same as that in
applications of TM-doped ZnO [21]. We summarize recent progress the target [59], the doping concentration in the lm can be
in TM-doped ZnO-based prototype spintronics, such as MTJs and estimated using extrapolated data, i.e., 5 at.% Co in a ZnO target
spin-FETs. It should be pointed out that it is almost impossible to corresponded to 6 at.% Co-doped ZnO in lms prepared by PLD
describe all the work performed around the world owing to the [25]. In general, the doping concentration ranges from 1 to 10 at.%,
rapid pace of studies in this eld, and therefore some references producing typical DMOs exhibiting good crystal quality and strong
may have been overlooked. magnetization; lower doping amounts lead to weak magnetiza-
tion, whereas higher amounts tend to result in the appearance of
2. Experimental procedure secondary phases, depending on the TM elements [50,56,69,80].
The typical deposition conditions for laser ablated lms are a
2.1. Film growth of TM-doped ZnO temperature of 400600 8C, oxygen partial pressure close to
1  105 to 5  105 torr and laser energy of 13 J cm2
TM-doped ZnO lms are commonly deposited by pulsed laser [11,25,33,41,4651,95]. A relatively low (<600 8C) growth tem-
deposition (PLD) [11,33,41,4649,95], magnetron co-sputtering, perature leads to homogeneous wurtzite TM-doped ZnO lms,
4 F. Pan et al. / Materials Science and Engineering R 62 (2008) 135

Fig. 2. (a) HRTEM image of Zn0.96Co0.04O/Al2O3 in cross-section. The inset shows the corresponding SAED pattern. (b) Representative columnar crystal grain of 15 nm in
diameter along the ZnO(0 0 2) growth direction in Co:ZnO lm grown on Si substrate. (c) HRTEM image of the 1010 zone for Zn0.96Co0.04O grown on SiO2. (d) Cross-sectional
HRTEM image of Co:ZnO/128LN. The arrows show the growth direction along ZnO(0 0 2) planes. Typical edge dislocations are marked by white symbols (?).

whereas higher temperatures increase the possibility of an matrix can be observed from the XRD pattern. (2) Small
inhomogeneous lm containing secondary phases, such as nanoclusters present in the lm can be observed in HRTEM
hexagonal Co, CoO and Co3O4 phases [17,33,109,110]. For lms images. (3) Electron energy loss spectroscopy (EELS) combined
grown by magnetron sputtering, the substrate temperature (200 with HRTEM [33,108] and X-ray photoelectron spectroscopy (XPS)
400 8C) during deposition is typically lower than that for PLD [44,52] can be used to determine the valence state. (4) X-ray
[44,68,111], and a high substrate temperature (650 8C) results in absorption spectroscopy (XAS), including TM K-edge
the appearance of secondary phases [111]. The working gas is a [34,44,55,115], TM L-edge [97,116118] and O K-edge
mixture of argon and oxygen at various pressures, which greatly [37,39,97,109], and its interpretation are used to elucidate the
affects the local structure and the electric and magnetic properties local structure. This technique is currently attracting great interest
of ZnO lms [112114]. It was found that high oxygen partial owing to its potential to provide local chemical information for
pressure (>3  103 torr) resulted in insulating Co-doped ZnO complex materials and its sensitivity to subtle differences in local
lms (>105 V cm), which could provide a reference for elucidation arrangement [119,120]. (5) Most importantly, DMOs should not
of the nature of RTFM [112,113]. only have a strong magnetic circular dichroism (MCD) signal, but
should also exhibit an MCD spectral shape that reects the band
2.2. Characterization techniques structure of the TM-doped ZnO, which is considered the most
useful tool to determine whether TM-doped ZnO is a real DMO or
Highly sensitive characterization techniques are critical for not [37,47,52,60,85,121]. (6) Electron spin resonance (ESR)
understanding the local structure and the corresponding [122,123] and Mossbauer spectroscopy [42,124] are carried out
magnetic behavior of TM-doped ZnO and to accurately detect to determine the local structure. (7) Measurement of optical
chemical information for doping elements at very low concen- properties using Raman spectroscopy and optical transmittance
trations. X-ray diffraction (XRD) in the BraggBrentano, rocking (absorption) spectrophotometry are effective in identifying the
curve, and pole gure geometries is frequently applied to local structure of the TM dopant [48,108,109,111]. If the state of a
characterize the lm structure and crystalline quality of TM- trace amount of TM dopant cannot be determined using a single
doped ZnO, and to compare the position of diffraction peaks characterization technique, the best way to investigate the local
between doped and undoped ZnO lms to predict the state and TM structure may be to use several different methods.
site of doping elements [11,41,44,48,59,94]. Moreover, HRTEM, Magnetization studies are carried out using a superconducting
eld-emission scanning electron microscopy (FE-SEM) and quantum interference device (SQUID) magnetometer in the
selected-area electron diffraction (SAED) were used in most temperature range 5350 K. High-temperature magnetization
DMO studies to identify interface bonding and structural (300 < T < 800 K) was recorded using a vibrating sample magnet-
characteristics and to observe whether small nanoclusters were ometer (VSM), which has also been used to measure TC
present in the lms [36,44,48,94,110]. [11,44,59,125,126]. RTFM can also be examined using other
During the past 5 years of DMO research, many methods have methods, such as alternating gradient magnetometry (AGM).
been introduced to identify the local structure of doping elements, Furthermore, the average atomic magnetic moment is an inter-
which is considered essential information for elucidating the esting parameter in evaluating and understanding DMOs. It is
intrinsic FM and judging whether a system is a genuine DMO. (1) therefore important to determine the accurate TM content in
Diffraction peaks due to secondary phases in a TM-doped ZnO samples. X-ray uorescence (XRF) [103], energy-dispersive X-ray
F. Pan et al. / Materials Science and Engineering R 62 (2008) 135 5

spectroscopy (EDS) and inductively coupled plasma (ICP) atomic The mechanism related to BMP is discussed in detail in
emission spectroscopy [44,127] have been used to determine the Section 4.2.
TM content of samples after measuring the magnetic properties. Preparing TM-doped ZnO lms with low carrier concentrations
The average magnetic moment per Co atom was then calculated, and measuring the RTFM of the samples obtained can provide
for which ICP provided more credible results for the TM content information on whether RTFM is a result of carrier-mediated
[44,94,127]. To a certain extent, the characterization techniques exchange and whether the TM-doped ZnO can actually be used in
used are keys in studying DMOs. The rather contradictory situation spintronics applications. Thus it is worth studying TM-doped
regarding DMO research means that suitable characterization oxides without carrier-mediated exchange (>105 V cm) to further
techniques are important. In contrast, incorrect measurements add our understanding of the origin of RTFM. Insulating TM-doped
further confusion to the eld, which has already been dogged by oxides with FM ordering have become a new topic of research,
conicting papers published over the past several years. It is worth namely diluted magnetic insulators (DMIs) [44,144]. On the other
pointing out that checking for basic experimental reproducibility, hand, spin ordering in tunnel junctions made of barriers that are
in addition to correct selection of characterization methods, is DMIs such as EuS has interested researchers since Esaki et al. [145]
crucial in the search for high-TC DMOs and for reliable results and observed a large magnetic eld effect [146]. The topic has attracted
discussion. renewed interest because recent experiments revealed that the
To elucidate the origin of RTFM and to identify relationships transverse and longitudinal relaxation times for electron spins in
between magnetization and the carriers in TM:ZnO, RT resistivity insulating quantum dots are in the nanosecond regime, indicating
and Hall effect measurements have been carried out using van der potential as computing elements in quantum electronics
Pauw geometry using indium metal for the contact electrodes and [147,148]. However, EuS failed in the practical sense, because its
current supplied by a dc-voltage source [109]. For some TM:ZnO TC is much lower than RT, with little hope of great improvement
lms with quite high resistance, Hall effect measurements were [7]. RTFM with a TC of 350 K was rst observed for highly
not suitable and the electric properties were determined using a TF insulating Co- and Cr-doped TiO2 [144,149,150] and TM-doped
Analyser 2000 ferroelectric testing unit and impedance spectro- SnO2 [41,151]. Interestingly, RTFM explained by the BMP
scopy [44,108,128]. mechanism has been widely observed in TM-doped ZnO DMIs
[8,30,44,75,94,108,152,153]. For example, RTFM and a high TC of
3. Local structure and ferromagnetism of TM-doped ZnO 790 K were observed in (4 at.%) Co-doped ZnO lms deposited on
1288 YX LiNbO3, which is not carrier-mediated, but co-exists with
Doped ZnO lms are either conducting or semiconducting, as the dielectric state [44]. This phenomenon can be also reproduced
characterized by strong coupling between localized d electrons of in ZnO lms doped with different Co concentrations and grown on
the TM ions and the extended s and p carriers of ZnO. Thus, the various substrates. Measurement of RTFM in Zn1xFexO (x  0.04)
carriers are spin-polarized and can mediate FM ordering of the [43] and a lack of correlation between RTFM and conductivity
magnetic moments of TM ions doped into the oxide lattice, i.e., TM [154] support this observation. Moreover, Xu et al. [155,156]
ions replace Zn2+ sites. Furthermore, additional electron doping, observed that the saturated anomalous Hall resistivity increased
such as in (Co,Al)- [49,54,129,130], (Mn,Sn)- [131] and (Cu,Ga)- with decreasing electron concentration in Co-doped ZnO. Because
doped ZnO [132], as well as hole doping, such as in (Co,Li)- the spin splitting was proportional to the macroscopic magnetiza-
[133,134], (Co,N)- [135,136], (Mn,Cu)- [125], (Fe,Cu)- [126], tion induced by the Co ions, the positive magnetoresistance
(Co,Cu)- [137] and (Mn,P)-co-doped ZnO [138], has been inves- observed and the anomalous Hall effect in the insulating regime
tigated to further examine carrier effects on RTFM. It was suggested that FM could be realized in Co:ZnO with low electron
importantly noted that additional carrier doping had no signicant concentrations [157].
impact on RTFM enhancement [125,129,131,132], and some lms As indicated above, substitutional TM ions are a necessary but
even showed RTFM with an inverse correlation between magne- not sufcient condition for FM ordering [27,42,47,79,158], and
tization and electron density [131,137,138]. Thus, inconsistent large variations in carrier concentration and magnetic properties
phenomena and conclusions have been obtained, indicating that have been reported for otherwise similar samples, indicating a
the intrinsic FM of TM-doped ZnO systems remains an open strong dependence of RTFM on the synthesis and processing
question. It is hence of vital importance to clarify the correlation, if parameters [17,159]. Indeed, there is large variability in the
any, between carriers and the mechanism of FM inherent to this magnetic behavior of TM-doped ZnO lms, and the preparation
class of DMOs. process is not easily reproduced from one growth run to another.
On the other hand, defects are supposed to play a primary The intimate correlation between carrier concentrations and
role on FM ordering in TM-doped ZnO [8]. In fact, an increasing point defects (i.e., VO and Zni) arising from a large number of
number of studies have demonstrated that the formation of VO structural defects such as edge dislocations and stacking faults
and/or Zni [30,44,57,128,139] could lead to RTFM or FM leads to difculty in elucidating the relations among carriers,
enhancement. For example, the production of VO by depositing structural defects and FM ordering. It is therefore important to
TM:ZnO lms in vacuum [44,111,117] or annealing lms in a design a series of experiments to distinguish the variation of
reducing atmosphere (such as vacuum [137,140,141] and Ar/H2 carriers and structural defects and thus to identify the nature of
[55]) could greatly enhance RTFM. Annealing of Co-doped ZnO the RTFM. We discuss the inuence of parameters including the
lms in a Zn atmosphere also resulted in FM enhancement due doping elements and concentrations, oxygen partial pressure,
to Zni [57]. A similar phenomenon was observed by Schwartz substrate and its orientation and temperature, deposition rate,
and Gamelin [142] for Co:ZnO nanocrystals. It is worth pointing post-annealing temperature and co-doping on the local structure
out that a large number of edge dislocations, which were and subsequent FM ordering of TM-doped ZnO in this section. This
directly observed by HRTEM, enhanced the concentration of VO is important for understanding the origin of RTFM in this system.
and/or Zni point defects, and thus increased the RTFM of Such understanding can reveal the potential of a class of
TM-doped ZnO lms and nanowires [58,67,94,143]. Moreover, promising magnetic materials with strong FM at the atomic
charge-compensating structural defects can form polarons by level, which is attractive for elds such as semiconductor
interaction between hydrogenic electrons and the defects, spintronics, quantum computation and magneto-optical devices
leading to coupling of the exchange between polarons [8,139]. [160].
6 F. Pan et al. / Materials Science and Engineering R 62 (2008) 135

3.1. Effect of doping concentration on structure and magnetization for Co in ZnO [50,127], much lower limits (e.g., 5 at.%) have been
reported for V, Cr, Fe, Ni and Cu are detected [30,43,50], which is
3.1.1. Effect of doping concentration on magnetic ordering consistent with Raman spectroscopic observations [161].
Incorporation of substitutional TM ions in IIVI ZnO should be Table 1 presents a list of TM-doped ZnO DMOs, including the
less difcult than incorporating them in other semiconductor substrate, TC, TM content and the corresponding magnetization
hosts, since the valence of Zn (2+) and the ionic radius can be features at 300 K. As indicated above, the magnetization of TM-
readily adopted by many 3d TM ions [19,50]. Different from TM- doped ZnO exhibits no correlation with the preparation method,
doped TiO2 [20,144], TM-doped SnO2 [41,151] and similar systems, which is therefore not listed in the table. There are many references
this favors substitution of the TM ions at the cation site and helps in for Co- and Mn-doped ZnO owing to their strong magnetization
achieving higher dopant concentrations. It also means that, in a signals and the stability of Co and Mn ion congurations [8,23,44].
perfectly stoichiometric sample, substitutional TM introduces a It is evident from Table 1 that Co-doped ZnO and Mn-doped ZnO
magnetic moment without contributing carriers. Thus, this system are the most popular systems in the literature [162166], not only
can give direct insight into the question of whether the FM because of their high thermal solubility in ZnO lms, but also
observed is carrier-mediated or not [44]. Furthermore, TM atoms because of their high magnetic moments at RT. The dopant
have different thermal solubility limits in ZnO: in general, the concentration has a denite inuence on the magnetic properties,
thermal solubility limits of Co and Mn are much higher than those with more desirable behavior often obtained at comparatively
of Ti, V, Cr, Fe, Ni and Cu [50]. In contrast to the solubility of 15 at.% lower concentrations [23,25,37,62,66], with typical concentrations

Table 1
List of TM:ZnO DMOs

System TM content (at.%) Substrate TC (K) Magnetization features Reference

Co:ZnO 5 (525) Al2O3 (1 1 2 0) >280 0.01 mB/Co [11]

Co:ZnO 25 Al2O3(0 0 0 1) Spin glass [46]
Co:ZnO 3.5 (3.511.5) Glass >350 0.21 mB/Co [103]
Co:ZnO 5 Al2O3(0 0 0 1) 300 0.7 mB/mole Co [59]
Co:ZnO 25 Al2O3(0 0 0 1) >300 1.0 mB/Co [162]
Co:ZnO 35 Al2O3(0 1 2) >300 0.1 mB/Co [52]
Co:ZnO 7 (717) Si(0 0 1) >300 0.06 mB/Co [163]
Co:ZnO 10 Al2O3(0 0 0 1) >300 105 emu [48]
Co:ZnO 5 Al2O3 (1 1 0 2) >300 2.6 mB/Co [23]
Co:ZnO 25 Al2O3(0 0 0 1) 300 0.8 mB/Co [45]
Co:ZnO 1.3 (05) Al2O3(0 0 0 1) >300 0.32 mB/Co [53]
Co:ZnO 5 Si(1 0 0) >300 1.04 mB/Co [58]
Co:ZnO 0.30.5 Al2O3 >300 3 mB/Co [164]
Co:ZnO 2 Si(1 0 0) >300 0.4 mB/Co [154]
Co:ZnO 3 (125) Al2O3 (1 1 0 2) >300 5.9 mB/Co [165]
Co:ZnO 4 LiNbO3(1 0 4) 790 6.1 mB/Co [44]
Co:ZnO 5 ZnO/Al2O3(0 0 0 1) >300 1.5 mB/Co/very weak [51]
Co:ZnO 2 (213) Al2O3(0 0 0 1) >300 0.8 mB/Co [57]
Co:ZnO 12 (831) Al2O3(0 0 0 1) >300 0.04 mB/Co [111]
Co:ZnO 10 ZnO(0 0 0 1) AF [166]
Co:ZnO 5 Si(1 0 0) >300 0.5 mB/Co [134]
Mn:ZnO 36 Al2O3(0 0 0 1) Spin glass [79]
Mn:ZnO 2 (04) Glass 425 0.16 mB/Mn [33]
Mn:ZnO 7 Al2O3(1 1 2 0) Para [32]
Mn:ZnO 2 Al2O3(0 0 0 1) 980 0.04 mB/Mn [31]
Mn:ZnO 7 Al2O3(0 0 0 1) 78 20 emu/cm3 [98]
Mn:ZnO 1 (110) Al2O3(0 0 0 1) >300 0.6 mB/Mn [140]
Mn:ZnO 7 Al2O3(0 0 0 1) 83 1.17 mB/Mn [73]
Mn:ZnO 4 Si(1 0 0) >300 1.4 mB/Mn [34]
Mn:ZnO 2 Al2O3(0 0 0 1) >300 4.36 mB/Mn [95]
Mn:ZnO 3 (315) Si(1 0 0) >300 105 emu [37]
Mn:ZnO 10 Al2O3(0 1 2) >300 0.075 mB/Mn [125]
Mn:ZnO 2.6 Al2O3(0 0 0 1) >350 4.8 mB/Mn [40]
Mn:ZnO 2 (06) Si(0 0 1) >300 0.3 mB/Mn [101]
Sc:ZnO 5 Al2O3 (1 1 0 2) >300 0.3 mB/Sc [23]
Ti:ZnO 5 Al2O3 (1 1 0 2) >300 0.5 mB/Ti [23]
Ti:ZnO 9.9 Al2O3(0 0 0 1) Para [75]
V:ZnO 15 (515) Al2O3 (1 1 2 0) >350 0.4 mB/V [26]
V:ZnO 0.120 Al2O3(0 0 0 1) Para [27]
V:ZnO 13 Al2O3 (1 1 0 2) Spin glass [28]
Cr:ZnO 5 Al2O3 (1 1 0 2) 400 0.6 mB/Cr [29]
Cr:ZnO 1.1 395 0.73 mB/Cr [30]
Fe:ZnO 4 (07) LiNbO3(1 0 4) 400 0.15 mB/Fe [43]
Ni:ZnO 1 (125) Al2O3(0 0 0 1) Para [63]
Ni:ZnO 1 (17) Si(1 0 0) >300 0.37 mB/Ni [62]
Cu:ZnO 1 (117) Al2O3(0 0 0 1) 390 0.4 mB/Cu [64]
Cu:ZnO 1 (18.3) Glass 390 1.6 mB/Cu [65]
Cu:ZnO 2 (212) Glass 350 1.8 mB/Cu [66]
Cu:ZnO 5 Si >300 0.037 mB/Cu [67]
CoFe:ZnO <15 SiO2/Si >300 15 emu/cm3 [70]
MnCo:ZnO 10 Al2O3(0 0 0 1) >300 0.11 mB [72]

Magnetization features were recorded at 300 K for the TM content listed in column 2. Para, paramagnetism; AF, anti-ferromagnetism.
F. Pan et al. / Materials Science and Engineering R 62 (2008) 135 7

Note that Co dopants at a concentration of 35 at.% can lead to

giant magnetic moments [23,44,94,165]. If carrier-mediated
exchange were the origin of RTFM, there would be no correlation
between the dopant concentration and the average magnetic
moment, because carriers are not local; instead, carriers can play a
similar role in mediating RTFM in TM-doped ZnO with different
dopant concentrations. On the contrary, if RTFM stems from BMP
on the basis of defects, the polaron percolaton threshold requires a
minimum mismatch between the dopant content and the defect
content. In this case, a certain dopant concentration is a
precondition for the appearance of a giant magnetic moment.
Suitable dopant concentrations and defects effectively couple to
form a hydrogenic orbital arising from an electron associated with
a particular defect, and the hydrogenic orbital tends to sufciently
spread out to overlap with a large number of BMPs, so that few
isolated polarons exist. More remote dopants interact too weakly
with both polarons to be of any importance. This occurs in samples
with lower doping levels, e.g., 1 at.% Co-doped ZnO, which
Fig. 3. Reported magnetic moments measured in Co-doped ZnO for different dopant produces a much lower magnetic moment for weak interaction.
concentrations. The lines are guides for the eyes.
On the other hand, for lms doped with higher levels of Co, an
increase in dopant concentration (e.g., 15 at.% Co-doped ZnO) leads
to a rapid decrease in the moment due to enhanced dopantdopant
of 5 at.% for Co-doped ZnO [11,23,51,58,59,61,128,133,134,152,
association and thus progressive orbital moment quenching
167170], and 1 at.% for Ni-doped ZnO and Cu-doped ZnO
[44,172]. In this case, anti-FM or FM appears when there are
continuous paths throughout the crystal joining nearest-neighbor
Most groups have focused on doping concentrations below the
magnetic cations [8]. This reveals how RTFM can be explained by a
solubility limit to obtain true DMOs. Although distinct magnetic
BMP model based on defects.
behaviors have been obtained by different groups owing to the
It was reported that Zn0.97Mn0.02Al0.01O lms showed RTFM
effects of the preparation method and parameters, it is worth
with 4.36 mB/Mn, for which the 2 at.% Mn doping to yield a giant
evaluating the effect of dopant concentrations on magnetization
magnetic moment is lower than the level of Co dopant required
from a series of experiments. Magnetic moments measurements
(35 at.%). Interestingly, in contrast to the Co doping concen-
reported for Co-doped ZnO at different dopant concentrations are
tration range (125 at.%) reported in many publications
shown in Fig. 3. It is interesting that Co doping in the concentration
[11,45,46,162,165,176], Mn is generally used as a dopant at a
range 35 at.% shows much stronger RTFM than other 3d TM
much lower concentration of 110 at.% [32,140], as illustrated in
dopants at the same concentrations, as well as the large solubility
Table 1. Unlike those of Co- and Mn-doped ZnO, the average
limit of Co in ZnO, which explains the many reports on 5 at.%
magnetic moment of other TM-ZnO system, such as Cr-, Ni- and
Co:ZnO in the literature [11,23,5860,95,128,133,134,152]
Cu-doped ZnO, monotonically decreases with increasing dopant
(Table 1).
concentration from 1 at.% [30,54,62,6466,71,102,177], as
Fig. 3 illustrates the Co composition dependent magnetic
shown in Fig. 4. This phenomenon may be due to the low
moment of Co:ZnO. From Fig. 3 and Table 1, one can see that
solubility of these dopants in ZnO; thus, low concentrations
TM:ZnO materials exhibit giant magnetic moments, such as
(e.g., 1 at.%) correspond to the strongest magnetization and
5.9 mB/Co and 2.6 mB/Co in semiconducting Zn0.97Co0.03O and
higher concentrations correspond to lower magnetic moments.
Zn0.95Co0.05O lms, respectively [23,165]. These are much stronger
Therefore, 35 at.% Co, 2 at.% Mn and 1 at.% Cr, Ni, and Cu doping
than for the corresponding atom in bulk metal, such as 1.7 mB/Co in
levels in ZnO show the most robust magnetic moments, which
Co metal. Similarly, 4.36 mB/Mn [95], 4.8 mB/Mn [40] and 5 mB/Mn
[171] were obtained for semiconducting Mn-doped ZnO lms.
Several studies on DMOs such as 5 at.% Co- and Cr-doped SnO2
[172,173] and 5 at.% V-doped TiO2 [174] revealed very large
magnetic moment of 7.2 mB/Co, 6.0 mB/Cr and 4.2 mB/V, respec-
tively. On the other hand, 6.1 and 3.2 mB/Co were reported for
insulating Zn0.96Co0.04O/LiNbO3 [44], which was attributed to
magnetoelectric coupling between the Co:ZnO lm and the
ferroelectric substrate and a subsequent super-coupling mechan-
ism in terms of BMPs [94], indicating that carrier-mediated
exchange is not a necessary condition for giant magnetic moments.
Using the Lande g-factor and the total angular momentum
quantum number (J) of Co2+ to evaluate the effective magnetic
moment [175] according to

meff g mB JJ 1 (1)

leads to a value of 6.6 mB/Co. In contrast, the net spin moment

calculated from the spin-only formula mmax = gmBS is 3 mB. This
phenomenon can be explained by spin and orbital angular moment Fig. 4. Reported magnetic moments measured in Cu-, Ni- and Cr-doped ZnO for
contributions [44,172174]. different dopant concentrations. The lines are guides for the eyes.
8 F. Pan et al. / Materials Science and Engineering R 62 (2008) 135

are critically dependent on the different solubility of these TM

dopants in ZnO lms.

3.1.2. Formation of a secondary phase

It is considered necessary to achieve single-phase DMOs for use
in devices, in which the carriers can realize spin polarization. If
precipitates or clusters below detectable size limits are present and
responsible for the FM, and if the carriers do not mediate the FM
interaction, this then can limit the usefulness of spintronics
fabricated from such materials [18]. Therefore, it is important to
detect RTFM arising from TM2+ replacement of Zn2+ sites or
secondary phases, which is signicant for studying practical DMOs.
However, the detection of trace amounts of TM atoms requires
highly sensitive characterization techniques.
The formation of secondary phases mainly depends on the TM
solubility limit in ZnO. The thermal solubility limit for Co in ZnO is
less than 15 at.% and Co ions systematically replace Zn ions in the
lm without changing the wurtzite structure [50,127]. This is
supported by the observations of Prellier et al. [59], who reported
that the c-lattice parameter obeys Vegards law up to the solubility
limit of 10 at.% Co, after which a turning point suggests the
breakdown of Vegards law. However, different values of the
dopant solubility have been obtained; for example, limits in the
range 2550 at.% have been reported for Co-doped ZnO lms
grown by PLD. Kim et al. [178] claimed that the limit is 40 at.%,
close to the results reported by Ueda et al. [11]. This difference is
most likely attributable to the preparation process, which allows a
different distribution of Co within the ZnO wurtzite structure
[16,17,19]. The equilibrium solubility limit of Mn in ZnO was
determined by Jin et al. [50] to be 20 at.%. The high solubility of
dopants seems to result from the growth conditions. It was also Fig. 5. (a) XRD pattern of a Zn0.96Fe0.04O lm. The inset shows XPS spectra of
Zn0.96Fe0.04O (dashed line) and Zn0.93Fe0.07O (solid line). (b) XRD pattern of a
found that the formation energy of dopants can have a strong
Zn0.93Fe0.07O lm. The Fe3O4 secondary phase is marked by solid circles.
dependence on the local lattice constant, depending on the size
mismatch of the dopant and the host atom. For example, several
authors claimed that the non-equilibrium nature of the laser CoO peaks has been reported for doping concentrations above
material interaction allows doping at high Mn content (up to 25 and 22 at.% using solgel methods and reactive magnetron
36 at.%) [50,79]. Meanwhile, FM ordering has been reported for Mn co-sputtering, respectively [56,163]. The formation of Co metal
concentrations between 2.2 and 30 at.% [33,179,180], whereas nanoclusters for x  12 at.% in samples grown by solgel and rf
both the magnetic moment per Mn ion and the FM TC seem to sputtering techniques has also been observed [76]. The
decrease with increasing Mn concentration, i.e., the moment observation of a CoFe(1 1 0) diffraction peak for Zn1x(CoFe)xO
dropped from 0.71 to 0.25 emu cm3 when the Mn content O lms indicates the formation of CoFe metal particles, which
increased from 10 to 30 at.% [76]. In addition, the FM TC was above was further conrmed by a clear change in the slope of the
RT for all concentrations x  5 at.% [33,180], but was usually well d(0 0 2) variation with the CoFe content around x = 0.2 [70].
below 100 K (45 K) for higher concentrations [179]. Likewise, only a Ni(1 1 1) peak was detectable, revealing that
Besides RTFM arising from TM ion replacement of Zn2+, fcc Ni nanocrystals are highly oriented with respect to the ZnO
secondary phases such as TM metal and TM-based oxides are host matrix [181]. However, secondary phases in trace
frequently found to correspond to the magnetization measured. amounts and small clusters are hardly detected by XRD, so it
Several different methods have been used to determine the local should be remembered that the absence of evidence is not
structure of doping elements and to detect secondary phases, evidence of absence [139].
which is important for identifying whether a TM-doped ZnO is a (2) HRTEM and SEM are often performed to investigate the
genuine DMO or not. The methods for detecting secondary phases different phases that might have formed in the nanosize range
are summarized as follows. and to determine the state of Co atoms that cannot be detected
by XRD. For example, Co3O4 clusters were directly found by
(1) In the most simple approach, diffraction peaks of secondary both HRTEM [111] and FE-SEM [109] in Co-doped ZnO lms.
phases present in the TM-doped ZnO matrix can be observed in ZnCo2O4 and/or CoO clusters with a diameter of 5 nm have
the XRD pattern. In contrast to Zn1xFexO (x  0.04) samples, been observed by HRTEM [110], which was conrmed by SAD
which show a single phase with a wurtzite structure (Fig. 5a), results. Co metal clusters with an average diameter of 10 nm
as x increases to 0.07, a diffraction peak of a secondary phase have also been observed by HRTEM in 15 at.% Co-doped ZnO
appears in the XRD pattern, which is attributed to Fe3O4, as lms [76].
shown for Zn0.93Fe0.07O in Fig. 5b [43]. This observation is in (3) The valence state of a TM dopant can be determined by EELS
good agreement with the low solubility of Fe in ZnO, e.g., and XPS [33,43,44,52,108,182]. The advantage of EELS is that
<5 at.% [19,50]. In contrast, no secondary phases are found in the valence state can be measured in combination with
Co-doped ZnO, even for 10 at.%, for the same preparation observation of HRTEM images [33,108]. Wei et al. [43] observed
parameters and substrates [44], indicating the different that both the Fe 2p1/2 and 2p2/3 peaks of Zn0.93Fe0.07O were
solubility of Co and Fe in ZnO. The presence of Co3O4 and between those of Fe3+ and Fe2+, and closer to Fe3+, indicating a
F. Pan et al. / Materials Science and Engineering R 62 (2008) 135 9

slightly more intense than peak B for Zn0.96Fe0.04O, whereas

peak B0 is apparently less intense than C0 for Zn0.93Fe0.07O.
Moreover, the curve for Zn0.93Fe0.07O has all the features of
Fe3O4 [183]. It is hence concluded that when x  0.04, Fe is in
the 2+ valence state and substitutes for Zn in the wurtzite
lattice of ZnO. When x increases beyond 0.04, Fe mainly exists
in the form of Fe3O4. Moreover, Fe2+ substituting for Zn2+ in
Zn0.96Fe0.04O and the Fe3O4 secondary phase in Zn0.93Fe0.07O
are responsible for 0.15 and 1.0 mB/Fe, respectively.
(5) Most importantly, MCD (including X-ray MCD and optical
MCD) is considered the best method for evaluating whether a
TM-doped ZnO lm is a real DMO or not [85,139]. X-ray MCD
(XMCD) is commonly used, and is the difference in absorption
of left- and right-hand-circularly polarized X-rays by a
magnetized sample. Thanks to simple sum rules, XMCD can
also provide quantitative information about the distribution of
spin and orbital angular momenta. Optical MCD measures the
relative difference in the circular polarization-dependent
optical absorption under an applied magnetic eld, i.e.,
2(K  K+)/(K + K+), where K and K+ are optical absorption
coefcient for s and s+ polarizations, respectively. The optical
absorption depends on the circular polarization ascribed to
Zeeman splitting of the band structures. MCD spectroscopy
sensitively detects DMOs and reects their electronic structure
and identies secondary phases, taking the strong spd
exchange interaction of DMOs and subsequent Zeeman
splitting of the optical transitions into account [85,158]. The
part of the MCD signal that linearly increases with the magnetic
eld (H) represents the paramagnetic component, whereas the
MCD signal that persists at H = 0 Oe is the FM component. MCD
spectra showing a multiplet structure, unlike spectra of TM
metals with a single peak, reveal that TM-doped ZnO shows FM
ordering that is not due to metallic TM secondary phases, but
Fig. 6. Experimental (solid circles) and MS calculated (solid line) Fe K-edge XANES arises from TM ion substitution in Zn sites [60,121]. For
spectra of (a) Zn0.96Fe0.04O and (b) Zn0.93Fe0.07O lms. example, Mn-, Co-, Ni- and Cu-doped ZnO lms prepared by
PLD show pronounced negative optical MCD peaks near 3.4 eV
attributed to the bandgap of the host ZnO semiconductor,
mix of 2+ and 3+ valence states with predominantly Fe3+, as indicating that ZnO alloyed with Mn, Co, Ni, and Cu is a true
shown in the inset of Fig. 5a. In contrast, for a doping DMO with strong exchange interaction between sp-band
concentration of x  0.04, such as in Zn0.96Fe0.04O, the positions carriers and localized d electrons [184]. In contrast, the
of the Fe 2p1/2 and 2p2/3 peaks are apparently different from magnetic moment was observed to be 0.1 mB/Co in Co-doped
those of Zn0.93Fe0.07O (inset of Fig. 5a), revealing that Fe is in the TiO2, but the XMCD spectral line shape is nearly identical to
2+ valence state [43]. that of Co metal, showing that FM is induced by a small amount
(4) TM K-edge [34,44,55,115], L-edge [78,97,116,117] and O K- of clustered Co, consistent with the Co metal cluster observed
edge [37,97,109] XAS and its interpretation can provide a by FE-SEM [185]. Likewise, the use of advanced element and
structural ngerprint to determine TM sites in ZnO [8]. As orbital selective techniques allows researchers to observe the
discussed above, for XRD and XPS changes for different doping distinct spectral signature of Co in ionic or metallic states to
concentrations, Fe K-edge XANES can be used to determine the assign FM phases to the presence of Co metal clusters in lms
local structure of Fe in the lms and conrm the preliminary doped with Co concentrations >25 at.% [176].
conclusion. Experimental (solid squares) and full multiple- (6) ESR [99,122,123] and Mossbauer spectra [42,124] also provide
scattering (MS) ab initio calculated (solid line) XANES for information on the local structure of the TM dopant [131]. The
Zn0.96Fe0.04O and Zn0.93Fe0.07O are shown in Fig. 6a and b, ESR spectrum of Zn1xMnxO (x = 0.001) exhibits the hyperne
respectively [43]. The most interesting result here is that the and ne-structure lines of Mn2+, which broaden for higher Mn
calculated spectrum has three main features that accurately content (x = 0.035) and change to a very broad single line due to
reect those of the experimental spectrum, denoted by A (A0 ), B dipolar interactions between Mn ions at higher local concen-
(B0 ) and C (C0 ) in order of increasing photon energy in Fig. 6a trations [122]. This phenomenon indicates that ESR can reect
and b. It should be pointed out that the calculations for Fig. 6a local structure variations for a TM dopant. However, a large
and b were produced for a cluster within a sphere radius of 6 A number of TM neighbors in the ZnO lattice (n  5) have no
containing 77 atoms from the central Fe atom that replaces a effect on the line width observed [123]. Mossbauer spectra
central Zn in the ZnO atomic arrangement and 89 atoms from cannot only reveal FM (sextet) and paramagnetic (doublet)
the Fe atom that occupies a tetrahedral site in the cubic phases in Fe:ZnO, but are also useful in detecting secondary
structure of Fe3O4. There are two main differences between phases, since the Mossbauer spectrum of Fe:ZnO is different
them: (i) the curve for Zn0.96Fe0.04O has an inection at from the typical sextet of FeOx [124].
approximately EE0 = 5 eV (E0 = 7112 eV), whereas the curve (7) Optical properties (e.g., Raman spectroscopy and optical
for Zn0.93Fe0.07O is at at that position (A and A0 ); (ii) peak C is transmittance/absorption measurements) are commonly used
10 F. Pan et al. / Materials Science and Engineering R 62 (2008) 135

to characterize TM-doped ZnO because they are intimately

related to the defects and electronic structure of TM:ZnO
[48,53,108,109,111,161]. For example, spectra show character-
istic absorption edges around 567, 613 and 662 nm resulting
from the spin-orbit split ligand-eld transition of tetrahedrally
coordinated Co2+ ions due to 4A2(F) ! 2A1(G), 4A2(F) ! 4T1(P)
and 4A2(F) ! 2E(G), respectively. Once Co metallic clusters exist
in a lm, the spectrum exhibits an octahedral Co0
T1g(F) ! 4T1g(P) at approximately 513 nm [48,109]. Thakur
et al. [53] reported that for x  5 at.% in Zn1xCoxO, at which the
magnetic moment becomes negligible, broadening of the Elow 2
Raman mode was also negligible, suggesting rejection of Co
ions from Zn sites and the appearance of secondary phases. This
is consistent with the observation that a decrease in Raman
intensity indicates the formation of TM clusters [71,170].
Moreover, as the Cu concentration increased from 1 to 3 at.% in
Cu-doped ZnO, Raman spectra showed that besides a broad
asymmetric mode at 600 cm1 attributed to the E1 (LO) mode Fig. 7. Reported magnetic moment per Co atom for Co:ZnO lms grown on different
of ZnO, a distinct peak at 634 cm1 arising from the Bg mode
of CuO emerged, indicating the formation of a secondary phase
of CuO [65]. Cu-doped ZnO lms exhibited 1.6 and 1.2 mB/Cu at 300 K on quartz
and sapphire, respectively [65]. RTFM with a magnetic moment of
These methods with different physical bases have been 1.5 mB/Co was observed for Zn0.95Co0.05O lms deposited on ZnO,
demonstrated to be effective in detecting second phases. However, whereas for the lms grown on Al2O3 only weak FM signals were
it is difcult to determine a trace amount of TM dopant using a detected that could not be unambiguously separated from those of
random selection of characterization techniques. The best way to the substrate. This difference can be explained by different
investigate the state of TM dopants may be to use several methods, structural properties and defect densities in the lms [51]. Thus,
and evidence of absence can only become a reality with the advent it seems that the substrate most likely impacts the local TM
of a combination of very sensitive tools. structure and magnetization of TM-doped ZnO.
To systematically study substrate effects on the local structure
3.2. Substrate effects on magnetization and magnetic behavior of TM-doped ZnO, a series of experiments
with substrate variation was designed [94]. Substrate-dependent
3.2.1. Substrate-dependent local structure and magnetic behavior magnetization of insulating Zn1xCoxO (x = 1, 4 and 10 at.%) lms
As discussed above, several reports and reviews reveal that the has been highlighted in Fig. 8, for which the substrates were 1288
magnetic behavior of DMOs appears to be dependent on YX LiNbO3 (128LN), 648 YX LiNbO3 (64LN) and 368 YX LiTaO3
preparation conditions such as the doping concentration, substrate (36LT) ferroelectric crystals, SiO2(1 0 1) piezoelectric crystal, some
temperature, and oxygen partial pressure [11,19,44,46]. However, other single crystals [e.g., Al2O3(0 0 1), Si(1 1 1), and NaCl(1 0 0)],
few studies have directly considered the substrate-dependent and amorphous glass. It is evident that the substrate has a
magnetic behavior of DMOs [94]. The best example is a review in profound inuence on the magnetic behavior of Co-doped ZnO
which statistical data imply that the magnetization of Co-doped lms. Zn0.96Co0.04O lms are taken as an example. Interestingly,
TiO2 lms is related to the crystal structure and the substrate [19]. whereas RTFM with giant magnetic moments of 6.1, 2.5, and
For Co-doped TiO2 lms grown on Si or Al2O3 substrates, the 3.2 mB/Co is observed for Co:ZnO lms on 128LN, 64LN and LT
average magnetic moment per Co atom is <1.0 mB in all cases. For ferroelectric crystals, respectively, the lm on SiO2 piezoelectric
samples using SrTiO3 as a substrate, values were scattered over
more or less the whole range of values reported, with a slight
accumulation in the lower region. However, for lms grown on
LaAlO3 substrate with an anatase structure, most of the values
accumulated in the upper region, i.e. >1.2 mB/Co, but with some
scatter between 0.23 and 1.72 mB/Co [19].
The substrates commonly used for deposition of TM:ZnO lms
are Al2O3 [11,23,45,46,52,111,162], Si [58,67,102,134,154,163],
fused quartz [33,94,103] and ZnO [51,105,186]. The reported
magnetic moment per Co atom for Co:ZnO lms grown on different
substrates is shown in Fig. 7. As the gure shows, the substrate
inuence on magnetic ordering is not clear. The data summarized
in Fig. 7 are from results obtained by different groups using
different preparation parameters. It is known that the local
structure and magnetization of DMOs are intimately related to
experimental conditions (e.g., preparation methods and para-
meters). Therefore, the preparation method, oxygen partial
pressure, substrate and temperature are all factors that can
explain the scatter from 0 to 5.9 mB/Co and from 0.1 to 1.04 mB/Co
on Al2O3 and Si substrates, respectively. However, TM-doped ZnO Fig. 8. Room-temperature magnetic moment expressed in Bohr magnetons (mB) per
lms deposited on different substrates with the same deposition Co atom for representative Zn1xCoxO (x = 1, 4 and 10 at.%) lms grown on 128LN,
parameters show distinct magnetization. For example, (0.6 at.%) 64LN, LT, SiO2, Al2O3, Si, NaCl, and glass substrates.
F. Pan et al. / Materials Science and Engineering R 62 (2008) 135 11

crystal shows a much lower magnetic moment of 1.1 mB/Co.

Moreover, the magnetic moment decreases to 0.62, 0.66, and
0.24 mB/Co for lms deposited on Al2O3, Si, and NaCl single crystal,
respectively. The lm on the glass substrate does not exhibit any
FM signature [94]. The diamagnetic background of the substrate
has been subtracted from all of the magnetization data, indicating
that the difference in moments in Co:ZnO lms does not arise from
the substrate. A similar tendency was replicated in Co:ZnO lms
with other Co concentrations (e.g., 1 and 10 at.%).
From XPS and qualitative analysis of XANES spectra it is known
that the difference in moments cannot be ascribed to different Co
forms in Co:ZnO lms grown on different substrates, since all the
Co ions are in the 2+ valence state replacing Zn sites. The rather
robust moments on ferroelectric crystals compared to those on the
other substrates are attributed to modulation of the magnetic
moment of the Co dopant due to magnetoelectric coupling
between the Co:ZnO lm and ferroelectric crystals [94,187].
Capacitancevoltage (CV) measurements revealed that the typical
CV curve for Co:ZnO samples exhibits hysteresis with a large Fig. 9. (a) Experimental and (b) MS calculated XANES spectra of Co:ZnO lms grown
memory window of 0.6 V, which can be caused by trapping/ on 1288 YX LiNbO3 (top) and 648 YX LiNbO3 (bottom).
detrapping of charges at defect sites. Evidence of defects with
trapped electrons in Co-doped ZnO would advance our under-
standing of the BMP mechanism. direction could be explained by different CoO bond lengths [94].
The diffusion or motion of defects such as VO is then driven by Experimental Co K-edge XANES spectra of Co:ZnO lms are
the presence of stress/strain and by an electric eld effect arising compared in Fig. 9 with the ab initio calculated XANES using full
from spontaneous polarization [149] to realize an appropriate MS theory. The atomic arrangement difference between Co:ZnO on
distance between Co2+ and defects and to achieve effective 128LN and on 64LN is the difference in CoO bond length on the
interactions between them. This process of defect diffusion or basis of the lattice parameters inferred from XRD results [94]. The
motion is referred as the reorganization of defects. Only this calculated spectrum displays three main features accurately
condition is met, almost all doping Co2+ can effectively interact replicating those of experimental XANES spectra, denoted by A, B,
with the defects producing few isolated Co2+, and the giant and C in order of increasing photon energy.
magnetic moment of 6.1 mB/Co in Co:ZnO/128LN, which is slightly For Co-doped ZnO lm on 128LN, it was found that the Co
lower than the ideal magnetic moment of 6.6 mB/Co calculated photoabsorber in tetrahedral coordination is surrounded by a rst
using Eq. (1), can become a reality. In contrast, some Co2+ and shell comprising one oxygen atom at 1.820 A and three oxygen
defects with inappropriate distances (e.g., large distances) in atoms at 2.069 A. This leads to a difference of 0.03 and 0.04
Co:ZnO lms grown on non-ferroelectric substrates (without between features B and C in the normalized absorption experi-
reorganization of defects) are hard to achieve effective interac- mental and MS calculated spectra (upper spectra in Fig. 9a and b).
tions, leading to the existence of more isolated Co2+ and the However, for Co-doped ZnO lm on 64LN, the center Co is
measured magnetic moment far below the ideal one. It is known surrounded by a rst shell comprising one oxygen atom at 1.845 A
that donor spin from well-organized defects strongly correlated and three oxygen atoms at 2.097 A. This results in greater
with Co2+ within its orbit can mediate effective interactions differences of 0.08 and 0.07 for the experimental and calculated
between them based on a Heisenberg exchange Hamiltonian. The spectra (lower spectra in Fig. 9a and b). These results demonstrate
donors then tend to shape the BMP, coupling Co2+ ions within their that a slight change in CoO bond length in Co:ZnO lms has a
orbits, which try to sufciently spread out to overlap and interact profound inuence on electron movement and scattering in the
with adjacent BMPs to realize magnetic ordering, resulting in vicinity of the Co atom. Subsequently, electron spin and the
rather robust moments that can be understood in terms of a corresponding moments are likely to be sensitive to the CoO bond
supercoupling mechanism [44]. length. In fact, ab initio calculations predicted that FM coupling
It is worth pointing out that reorganization of the defects could would be affected by the MnO bond length in La0.67Ca0.33MnO3d
partly occur due to the comparatively weak polarization of the SiO2 lms [94], and that energy differences between FM and anti-FM
piezoelectric substrate, leading to a lower moment per Co atom in alignment would be very small in Co-doped ZnO systems, with
Co-doped ZnO lm, e.g., 1.1 mB/Co. Moreover, although the Co competition between FM and anti-FM coupling [84,188].
dopant exists in a 2+ state when substituting for Zn2+, randomly ZnO lms doped with different Co concentrations were deposited
distributed defects would lead to very weak moments or no RTFM on LT substrates with three different orientations [LT(1 1 0),
in Co-doped ZnO lms on other single substrates (e.g., Al2O3, Si, LT(0 1 2) and LT(0 1 8)] by dc reactive magnetron co-sputtering.
and NaCl) and glass substrate, respectively [94]. It is thus The variation in magnetic moment on different orientations as a
concluded that the substrate strongly affects the magnetization function of the Co concentration is presented in Fig. 10.
of TM-doped ZnO lms. Zn0.962Co0.038O lms deposited on LT(1 1 0), LT(0 1 2) and
LT(0 1 8) substrates exhibited different magnetization of 1.21,
3.2.2. Substrate orientation-induced distinct magnetization 2.42, 0.65 mB/Co, respectively, as shown in the inset of Fig. 10. It
An interesting point in Fig. 8 is that signicant differences in is likely that the magnetization differences for Co-doped ZnO lms
moments are observed for Co:ZnO lms grown on the same type of on three oriented LT substrates can be attributed to the lm
substrate. For example, Zn0.96Co0.04O lm grown on 64LN exhibits a microstructure and the CoO bond length, which primarily depends
comparatively lower moment of 2.5 mB/Co compared to 6.1 mB/Co on mismatch between the lm and the different oriented substrates
for lm grown on 128LN. The origin of magnetization differences on [107]. Therefore, as well as the substrate itself, its orientation has a
the same type of ferroelectric substrate with only a difference in cut profound inuence on FM ordering of TM-doped ZnO.
12 F. Pan et al. / Materials Science and Engineering R 62 (2008) 135

high Tsub exhibits the lowest saturation magnetization of

approximately 0.25 mB/Co. For the lm grown at RT, the magnetic
moment slightly increases to 0.39 mB/Co. For faster deposition
rates, much larger magnetic moments of 0.73 and 0.91 mB/Co
are observed for the samples grown with high and low Tsub,
respectively. XRD results show that the intensity of the ZnO(0 0 2)
diffraction peak decreases with increasing deposition rate and/or
decreasing substrate temperature, reecting a decrease in ZnO
crystallinity. This was demonstrated by F scans, for which
comparison of the full width at half-maximum (FWHM) intensity
for peaks with sixfold symmetry revealed a decrease in crystal
quality and an increase in structural defects with increasing
deposition rate and decreasing Tsub [109].
Experimental and calculated Co K-edge XANES spectra are
presented in Fig. 11a and b, respectively. The height difference
between the characteristic B1 and C1 peaks increases as deposition
rate increases and Tsub decreases. This is reproduced by the MS
calculation (Fig. 11b). The introduction of oxygen vacancies in the
Fig. 10. Saturated magnetization of Co:ZnO as a function of Co concentration for rst coordination sphere results in an obvious height difference
lms grown on LiTaO3 substrate in different orientations: LT(1 1 0), LT(0 1 2) and between B1 and C1 for the sample deposited with slow growth and
LT(0 1 8). The inset shows hysteresis loops of Zn0.962Co0.038O lms deposited on
low Tsub, as well as the sample grown with fast growth and high
LT(1 1 0), LT(0 1 2) and LT(0 1 8).
Tsub. For the sample prepared with fast growth and low Tsub, the
existence of oxygen vacancies in the rst coordination sphere and a
3.3. Effects of substrate temperature and lm deposition rate on Zn interstitial between the rst two coordination spheres would
magnetization result in line shapes consistent with the experimental data. This is
supported by experimental and calculated O K-edge XAS spectra
Sharma et al. [33] reported that substrate temperature affects (Fig. 11c and d, respectively). The calculations reect less of a Zn
the magnetization of Mn-doped ZnO lms. Films prepared at a low loss during deposition for the sample prepared with fast growth
processing temperature exhibited RTFM, whereas samples at and low Tsub [58], whose spectrum is similar to that of an ideal
standard high temperatures (T > 700 8C) showed clustering and no stoichiometric ZnO, and shoulder A2 at 531.2 eV appears and
RTFM. This is in agreement with work carried out by Kim et al. [46], increases in intensity from the sample prepared with slow growth
who found that a high substrate temperature of 700 8C led to the and low Tsub to the sample grown with fast growth and low Tsub,
appearance of secondary phases. In addition, Fe-doped ZnO corresponding to an increase in defect concentration in the lms, in
prepared by ion implantation at 253 K was a true DMO, whereas good agreement with microstructural characterizations [191].
preparation at 623 K led to the formation of particles inside the The magnetic moment of Co-doped ZnO lm increases with
host matrix responsible for the FM properties [42]. Very recently, it increasing structural defects and electron concentration (ne). It is
was found that Co-doped ZnO lms grown at <200 8C exhibited worth pointing out that this was the basis for the previous concept
stronger FM than those deposited at higher temperatures [111]. of carrier-mediated RTFM in DMOs, because the correlation of FM
These observations indicate that a high preparation temperature is ordering and carrier concentration was emphasized. The true
detrimental to RTFM of DMOs, and even results in the formation of origin of FM ordering, i.e., structural defects, was neglected in this
secondary phases within the host matrix. On the other hand, carrier-mediated hypothesis, which seriously misguided extensive
different from other DMOs such as TM-doped TiO2 [189,190], the research into DMOs. To determine the intrinsic FM in a Co-doped
local structure and magnetic properties of TM-doped ZnO lms are ZnO system, the sample prepared with slow growth and high Tsub
more sensitive to the substrate temperature and lm deposition was annealed for 1 h at 400 8C, resulting in an increase in ne to
rate, primarily due to temperature-dependent Zn loss during the 2.9  1019 cm3. The crystallinity of the Co-doped ZnO lm also
deposition process [58]. improved on annealing, revealing that the number of structural
Song et al. [109] investigated how the electrical properties and defects such as edge dislocations and stacking faults decreased
structural defects of TM:ZnO samples are related to FM ordering to [109]. The saturation magnetization slightly decreased from 0.25
identify factors that affect RTFM. A suitable combination of to 0.19 mB/Co, revealing that an increase in ne cannot enhance the
deposition rate and substrate temperature is key in determining magnetization of Co-doped ZnO after annealing at 400 8C. Instead,
the crystallinity and corresponding magnetization of Co-doped the magnetic moment per Co atom decreased with increasing
ZnO lms deposited by rf magnetron co-sputtering at 0.15 A/s crystallinity, which allows identication of a direct relationship
(slow growth) and 0.6 A/s (fast growth) at 573 K [high substrate between the FM of Co-doped ZnO and the presence of structural
temperature (Tsub)] and RT (low Tsub), as presented in Table 2 [109]. defects. This implies that the established theory of carrier-
For this series of lms, the sample prepared with slow growth and mediated exchange, which works well for p-type GaMnAs, is not

Table 2
Resistivity (R), electron concentration (ne) and magnetic moments (M) for Co:ZnO samples prepared by rf magnetron co-sputtering at low/high deposition rate and low/high
substrate temperature (Tsub)

Sample Rate (A/s) Tsub (K) R (V cm) ne (cm3) M (mB/Co)

Slow growth high Tsub 0.15 573 >103 No Hall signal 0.25
Slow growth low Tsub 0.15 RT 5.6 2.3  1018 0.39
Fast growth high Tsub 0.6 573 1.9  101 1.5  1019 0.73
Fast growth low Tsub 0.6 RT 1.7  102 5.2  1019 0.91
F. Pan et al. / Materials Science and Engineering R 62 (2008) 135 13

Fig. 11. (a) Experimental and (b) calculated Co K-edge XANES spectra for Co:ZnO lms (E0 = 7708.8 eV). (c) Experimental and (d) calculated O K-edge XAS for Co:ZnO lms.
Spectra correspond to samples grown with slow growth and high Tsub (LH), slow growth and low Tsub (LL), fast growth and high Tsub (HH) as well as fast growth and low Tsub
(HL) from bottom to top.

generally applicable to TM-doped ZnO. Instead, structural defects corresponding to a deposition rate of 3.0 and 2.0 nm/min,
play a primary role in RTFM of TM-doped ZnO, and carriers respectively [112]. Fig. 12 shows the PO2 -dependent RTFM and
involved in carrier-mediated exchange are natural by-products of resistivity (R) of the lms. Both the magnetization and resistivity
the creation of defects, which is demonstrated in publications with decrease with decreasing PO2 . Insulating sample 1 (0.62 mB/Co)
increasing frequency [60,76]. exhibits more robust RTFM than semiconducting sample 2
(0.45 mB/Co), revealing that an increase in carrier concentration
3.4. Inuence of oxygen partial pressure on magnetic ordering does not enhance RTFM. A similar trend was observed by
Chakraborti et al. [137] and Ivill et al. [131,138]: an increase in
In general, both the oxygen partial pressure (PO2 ) and the conductivity did not increase the magnetic moment; instead, an
substrate temperature (Tsub) play important roles in the micro- increase in carrier concentration led to weak magnetization,
structure of DMO lms, which subsequently affects the magnetic suggesting that a mechanism mediated by free carriers is not a
properties. PO2 and Tsub affect the formation of secondary phases feasible explanation for FM in TM:ZnO lms.
[46,33]. Lee et al. [98] reported that ne dramatically decreased with To interpret the intrinsic RTFM in this system, microstructural
increasing PO2 up to an Ar/O2 ratio of 1:1 for the preparation of and local structural characterizations were conducted [112]. XRD
Mn:ZnO lms by rf magnetron sputtering, which showed intrinsic spectra in BraggBretano, rocking curve and F scan geometries
FM with TC of 78 K. However, lms grown under O2 overpressure suggested that the lms were highly crystalline, as shown in
showed various secondary phases, such as ZnMn3O4, MnO2 and Fig. 13. The XRD pattern of sample 1 (Fig. 13a) has a weaker
ZnMnO3. Films deposited at lower temperature (600 8C) and Co:ZnO(0 0 2) peak than that for sample 2 (Fig. 13b). Comparison of
higher oxygen pressures (105) showed a homogeneous dis-
tribution of Zn0.75Co0.25O, leading to spin-glass behavior, whereas
mixed phases of wurtzite ZnO with rock-salt CoO and hexagonal
Co phases coexisted at higher temperatures and lower pressures,
accompanied by RTFM [46]. On the other hand, variation of PO2
can lead to a change in magnetic behavior and electric properties.
On increasing PO2 from 1.0  104 to 5 Pa, the resistivity of
Zn0.95Co0.05O lms increased from 2.15  102 to 2.06  104 V cm,
corresponding to a change in magnetization from RTFM to
paramagnetism, revealing that oxygen vacancies are absolutely
necessary to induce FM coupling in TM-doped ZnO [168]. Philip
et al. [243] observed that the electric and magnetic behavior
of Cr-doped In2O3 lms from FM metal-like to FM semiconduct-
ing to paramagnetic insulators can be controllably tuned
by P O2 . It seems that PO2 plays an important role in the
magnetization of DMOs.
A transition from DMI to DMO was realized in Zn0.96Co0.04O Fig. 12. Magnetic moment and resistivity of Zn0.96Co0.04O lms as a function of P O2 .
lms grown by dc reactive magnetron co-sputtering by decreasing The inset shows magnetic hysteresis loops (MH) for Co:ZnO lms 1 and 2 prepared
P O2 from 4.2  103 to 1.0  103 torr for samples 1 and 2, at high and low P O2 , respectively.
14 F. Pan et al. / Materials Science and Engineering R 62 (2008) 135

Fig. 13. XRD spectra of Co:ZnO lm for (a) sample 1 and (b) sample 2. X-ray rocking curves from the wurtzite (0 0 2) plane for (c) sample 1 and (d) sample 2. F scan of {1 0 1}
family peaks for (e) sample 1 and (f) sample 2.

FWHM values for X-ray rocking curves for the wurtzite(0 0 2) RTFM in Co:ZnO lms by controlling the lm thickness from 15 to
plane for samples 1 and 2 reveals an improvement in crystallinity 900 nm (15, 30, 60, 100, 150, 300, 600 and 900 nm). The lms were
of sample 2 (0.188 decrease in the FWHM value; Fig. 13c and d). The deposited on Si(1 0 0) and LiNbO3(1 0 4) substrates by rf magne-
F scan for the (1 0 1) plane of sample 2 grown at lower PO2 is tron sputtering. The thinnest lms (15 nm) with greatest lattice
similar to that of sample 1 to a certain extent, but with more strain had the highest saturated magnetic moments of 2.96 and
symmetrical peaks. These results indicate that sample 2 is more 5.52 mB/Co for Co:ZnO/Si and Co:ZnO/LiNbO3, respectively (Fig. 15)
crystalline and has fewer structural defects such as edge The saturated FM rapidly decreased with increasing lm thickness;
dislocations and stacking faults due to the comparatively slow
rate of lm growth [189,190].
Fig. 14 presents Co K-edge XANES for samples 1 and 2 and for
reference materials (Co metal, CoO, Co2O3 and Co3O4). It is evident
that Co in Co:ZnO is not in the form of Co metal or Co-based oxides
such as CoO, Co2O3 and Co3O4. The calculated spectra displays
three main features accurately replicating those of the experi-
mental spectra, denoted by A, B, and C in order of increasing photon
energy (insets a and b of Fig. 14). These spectra reveal that for
sample 1 the Co photoabsorber in tetrahedral coordination is
surrounded by a rst shell comprising four oxygen atoms, with no
difference in normalized absorption between features B and C
(upper spectra in insets a and b). For sample 2, the Co center is
surrounded by a rst shell of three oxygen atoms and a VO, leading
to an obvious difference between features B and C for the
experimental (0.13) and calculated (0.11) spectra (lower spectra in
insets a and b). It is therefore concluded that there are more VO and
thus a higher carrier concentration in sample 2 due to lower P O2 .
However, sample 1 contains more structural defects than sample 2,
resulting in stronger RTFM for sample 1, demonstrating that
structural defects are responsible for RTFM in Co-doped ZnO.

3.5. Strain-induced ferromagnetism enhancement

Strain engineering, which offers the opportunity to enhance the

physical properties of a chosen material in thin lm form by
judicious use of growth parameters, represents a new direction for
nanoscale material research [192194]. It has been found that a
slight strain-induced break in symmetry has a great inuence on
the single spin and the corresponding magnetic behavior of typical
DMSs such as Mn:GaAs [195]. Given that growing lms of different Fig. 14. Co K-edge XANES spectra for Co:ZnO and references materials Co metal,
thickness is a simple and effective method to modulate the lattice CoO, Co2O3 and Co3O4. The insets show (a) experimental and (b) MS calculated
strain within lms, Liu et al. [196] studied the effects of strain on XANES spectra for samples 1 (square) and 2 (circle).
F. Pan et al. / Materials Science and Engineering R 62 (2008) 135 15

accumulated state of strain energy due to the large lattice

mismatch (40.10%) between the lm and the Si substrate, and
the 15-nm thick Co-doped ZnO lm exhibits the greatest tensile
strain of 6.65% (Fig. 16c). As the lm thickness increases, the
accumulated strain energy progressively relaxes, i.e., the c-axis
tensile strain continuously decreases, and is only 0.69% for the 900-
nm lm, corresponding to weak FM. The FM enhancement in Co-
doped ZnO lms originates from a combination of an increase in
CoO bond length and an increase in the number of defects
induced by lattice strain [196]. These results are consistent with
the observation that lattice deformation plays a signicant role in
the high-TC FM of DMOs [197].

3.6. Inuence of post-annealing on magnetization

Annealing has a great effect on the magnetization of TM-doped

ZnO, largely because it can change the microstructure and local
structure of lms [38,52,55,57,73,109,140,141,154]. It is com-
Fig. 15. Saturated magnetization as a function of thickness for Co:ZnO lms monly observed that annealing in vacuum or a reducing atmo-
deposited on Si and LiNbO3 substrates measured at room temperature. The inset
sphere results in enhanced FM of the samples due to the
shows the hysteresis loop for the 15-nm thick Co:ZnO/LiNbO3 lm.
introduction of VO [52,55,140,141], with Zni critical for RTFM in
TM-doped ZnO [30,57,141,154,198]. For example, a study of
the results for the 900-nm lm was 0.02 mB/Co, which is annealing effects on the local structure and magnetism of Co-
approximately two orders of magnitude lower than for the 15- doped ZnO lms under air, Ar, and Ar/H2 atmospheres revealed
nm thick lm. that lm annealed in Ar/H2 had a pronounced pre-edge Zn K-edge
Fig. 16a shows XRD patterns for Co:ZnO/Si lms of different XANES peak and contained more VO (1  1021 cm3) and stronger
thickness. Comparison of the (0 0 2) peaks reveals a shift from RTFM, indicating that RTFM is strongly dependent on VO [55].
33.848 for the 15-nm lm to 34.458 for unstrained ZnO, Furthermore, a change in Raman spectra (appearance/disappear-
corresponding to a change in c-axis lattice constant from 5.207 ance of an additional broad vibrational mode) for Co-doped ZnO
to 5.553 A, indicating that the unit cell in the Co:ZnO lm is lms on alternate annealing in air/high vacuum suggested that VO
elongated along the c axis. With increasing lm thickness, the is crucial in the development of RTFM [100]. Using alternate
ZnO(0 0 2) peak position shifts towards the value for unstrained annealing of Co-doped ZnO lms in air and Zn vapor, Kittilstved
ZnO. The c-axis lattice constant and calculated lattice strain are et al. [198] demonstrated quantitative reversible cycling of
plotted as a function of lm thickness in Fig. 16b and c. The c-axis saturated magnetic moments, and direct correlation between
lattice constant decreases slightly with increasing thickness. Thus, oxidative FM quenching and the diffusion and oxidation of Zni.
the initial stage of Co-doped ZnO growth represents a strongly Similarly, annealing of lms in different oxidation atmospheres in

Fig. 16. (a) XRD patterns of Co:ZnO/Si lms of 15900 nm in thickness. (b) Lattice constant and (c) c-axis lattice strain as a function of lm thickness.
16 F. Pan et al. / Materials Science and Engineering R 62 (2008) 135

the presence or absence of Zn vapor revealed that RTFM is not

linked to conductivity and that a small level of Zni defects is
important in mediating RTFM in TM:ZnO [154,102]. Similar
phenomena have been observed for TM-doped ZnO nanocrystals
[20,199,142]. In contrast, a decrease in VO concentration due to
high-temperature annealing in oxygen had a large detrimental
effect on FM, which tends to disprove a mechanism involving free
carriers [200,177]. These experimental annealing results demon-
strate that the magnetic behavior observed is directly related to the
presence of intrinsic defects, notably VO and Zni. Electrons locally
trapped by these defects occupy an orbital overlapping with the d
shells of TM neighbors to form a BMP, which accounts for the
nature of intrinsic RTFM.
The microstructure and magnetic properties of Zn0.92Co0.08O
lms annealed at different temperatures (200, 400 and 600 8C) in
vacuum and air were systematically investigated by Liu et al. [141].
The magnetic moment increased after annealing in vacuum and
decreased after annealing in air at the same temperature. A typical
plot of hysteresis loops for as-grown lm and lms annealed in air
and vacuum at 400 8C is shown in Fig. 17. The vacuum-annealed
lm shows saturation magnetization (Ms) of approximately
0.45 mB/Co, which is slightly greater than for the as-grown lm
(0.34 mB/Co), whereas the value for the air-annealed lm (0.21 mB/
Co) is much lower than Ms of the as-grown lm. The value of Ms
increases with annealing temperature up to 400 8C due to the
creation of VO during annealing in vacuum [149]. However,
annealing at 600 8C greatly decreased the FM of Co-doped ZnO
lms, likely due to an improvement in crystal quality and a
corresponding decrease in structural defects in the lm [141]. This
is supported by the result indicating that FM ordering increased
with annealing of Zn0.88Co0.12O lms in vacuum up to 500 8C,
whereas a higher annealing temperature resulted in a decrease in
magnetization [111].
On annealing in air at high temperature (>700 8C), Mn2+ and
Co ions may segregate from the crystal and form impurity phases
Fig. 18. (a) Co K-edge XANES spectra for as-deposited and annealed (750 8C) sample
or precipitates, which can lead to a decrease in Raman peak LH, Co metal, CoO and Co3O4 (E0 = 7708.8 eV). The inset shows an FE-SEM image of
intensity [71]. The XANES spectrum of Co:ZnO lm annealed at LH after annealing at 750 8C. (b) Magnetization of as-deposited and annealed
750 8C differs from that of an as-deposited lm, but closely (750 8C) LH.
matches that of Co3O4 (Fig. 18a) in terms of a similar absorption
edge, characteristic peaks, and normalized absorption intensity.
This can be ascribed to a transition from Co2+ replacement of Zn2+ in size from 60 to 120 nm. This transition in local structure (from
to the formation of Co3O4-based compounds. This is consistent Co2+ replacement of Zn2+ to Co3O4-based compounds) during
with a FE-SEM image showing small islands of precipitates 750 8C annealing means that the behavior of Co-doped ZnO lms
(Fig. 18a inset) that are almost randomly distributed and range changes from RTFM to paramagnetism, as illustrated in Fig. 18b.
These phenomena observed after annealing are consistent with the
principles described for substrate temperature-dependent mag-
netization. A combination of a comparatively low temperature
(400 8C) and a reducing atmosphere increases defects (VO or Zni)
and enhances FM ordering [33,94], whereas high-temperature
processing results in a decrease in RTFM.

3.7. Effect of co-doping on magnetic properties

Controlling the experimental parameters, e.g., decrease in P O2 ,

can increase the carrier concentration and thus enhances FM
[11,48,62,95,103,152,201]. However, some researchers have
reported that the creation of free carriers is not sufcient for FM
interactions [77,202]. Moreover, several groups observed RTFM in
the absence of free carriers [8,30,41,44,45,75,94,108,109,152,
To elucidate whether the carrier concentration can enhance
RTFM or if there is a correlation between them, co-doping has been
applied to generate additional electron/hole doping, as presented
Fig. 17. Hysteresis loops for as-grown and vacuum- and air-annealed (400 8C) in Table 3. The possible effects of co-doping, i.e., simultaneous
Zn0.92Co0.08O thin lms measured at room temperature. doping of ZnO with two or more TM ions, are interesting. Typical
F. Pan et al. / Materials Science and Engineering R 62 (2008) 135 17

Table 3
List of co-doped ZnO systems, including lms, bulk and nanocrystals

System Content (at.%) Methods Magnetism Reference

CoAl 9/1 PLD 0 ! 0.1 mB [52]

CoAl 10/(0,1.6) PLD 0.33 ! 0.11 mB [186]
CoAl 5/(00.5) rf sputtering 1.7 ! 3.36 mB [129]
CoAl 5/(03) Solgel 0.30 ! 0.48 mB [206]
CoAl 5/(02) PLD 0.88 ! 1.6 mB [95]
MnAl 2/(04) PLD 0.1 ! 4.36 mB [95]
MnSn (3,5)/ Ion implantation 5.5  105 emu [35]
MnSn 3/(00.1) PLD 0.1 ! 0.5 mB [131]
CuGa 5/1 PLD 1.45 ! 0 mB [132]
CoLi (510)/(010) Solgel 50 ! 375 emu/mole [133]
CoLi 5/5 Spin-coating 0 ! 0.5 mB [134]
CoLi 5/10 Solgel 0.009 ! 0.048 mB [203]
CoN 1.5/ rf sputtering 0.085 ! 0.129 mB [204]
CuN 10/ dc sputtering 0.36 ! 0.15 mB [66]
MnN 4/ ICP-CVD 0.3 ! 1.4 mB [205]
MnN 5/7 rf sputtering 0 ! 0.3 mB [135]
MnN 3/ rf sputtering 0 ! 0.92 mB [136]
MnP 3/2 PLD 0.2 ! 0.07 mB [138]
MnCu 10/(0,5) PLD 0.075 ! 0.1 mB [125]
FeCu 5/(01) Solid state reaction 0 ! 0.75 mB [126]
CoCu 5/(010) PLD 5 ! 15 emu/cm3 [137]

Content is presented as x/y for the main TM element/additional dopant. Magnetism results indicate the change in parameter before ! after co-doping.

electron doping elements in TM-doped ZnO are Al, Sn and Ga FM enhancement arising from an increase in donor defects or
[52,95,129,131,132,186,35], whereas N, Li, and Cu are used for hole electron carrier concentration is ambiguous because these two
doping [125,126,129,203205]. It has been reported that an factors coexist in most doped ZnO systems and are hard to
increase in carrier concentration due to trace amounts of distinguish. It is hence of vital importance to design an experiment
additional dopants can greatly enhance RTFM [95,126,206]. that can separate the two factors [129,204]. Zn0.95xCo0.05AlxO
Additional hole doping, using Li or N promotes strong hybridiza- (x = 0, 0.001, 0.002, 0.004, 0.005) thin lms were deposited on
tion of Mn 3d/N 2p states and long-range FM coupling, as it brings Si(1 0 0) substrates by rf magnetron co-sputtering [129]. Fig. 19
the d electron/TM closer to the optical values for double exchange shows XRD spectra of Zn0.95xCo0.05AlxO (x = 0, 0.002) lms. The
[133,134], although some authors reported that co-doping plays a peak corresponding to ZnO(0 0 2) changes little except for a
negligible role in enhancing the magnetic moment [125]. Ivill et al. decrease in intensity after additional Al doping in the Zn0.95Co0.05O
[131] designed a series of experiments on (Mn,Sn)-co-doped ZnO thin lm, implying a decrease in crystalline quality and an increase
with varying Sn concentration (00.1 at.%). They found that the in structural defects on inclusion of a trace amount of Al. This was
lms exhibited FM, with an inverse correlation between magne- conrmed by optical transmittance spectra of pure ZnO and
tization and electron density, as a function of the Sn doping. This Zn0.95xCo0.05AlxO (0  x  0.005) [129].
phenomenon is most consistent with the BMP model in which Fig. 20 shows curves of the magnetization versus magnetic eld
bound acceptors mediate FM doping. In this case, an increase in (MH) for Zn0.95xCo0.05AlxO (0  x  0.005) thin lms. The Al
electron density decreases the acceptor concentration and thus concentration dependence of Ms and ne is shown in the inset. It is
quenches the FM exchange. Similar conclusions have been evident that a trace amount of Al can enhance the magnetic
reported for (Mn,P)- and (Cu,Ga)-co-doped ZnO [132,138]. moment per Co ion of Co:ZnO lms. The increase in Ms with

Fig. 20. Electron carrier concentration and saturation magnetization as a function of

Fig. 19. Comparison of XRD patterns for pure ZnO, Zn0.95Co0.05O and Al concentration. The inset shows magnetization hysteresis curves of
Zn0.95xCo0.05AlxO (x = 0, 0.002) thin lms on Si(1 0 0) substrates. Zn0.95xCo0.05AlxO thin lms measured at RT.
18 F. Pan et al. / Materials Science and Engineering R 62 (2008) 135

additional Al doping, combined with the increase in ne, reveals that value for x = 0.004 (ne/nAl = 0.95), implying a greater number of
the free carrier concentration is important, as expected for DMOs. donor defects in the former lm and corresponding to the stronger
However, it should be noted that ne (1.597  1020 cm3) is greater Ms of 2.71 mB/Co, indicating that donor defects most likely play a
and Ms (2.34 mB/Co) is smaller for the Zn0.95xCo0.05AlxO (x = 0.004) critical role in governing FM ordering.
lm than for the Zn0.95xCo0.05AlxO (x = 0.001) lm A systematic study by Mokhtari et al. [207] revealed that
(ne = 4.597  1019 cm3, Ms = 2.71 mB/Co), indicating that elec- additional doping could ionize other defects, which played an
trons are not the real mediators of FM exchange. It is clear that important role in FM enhancement. Fig. 21 presents the change in
additional Al doping leads to a decrease in both the crystalline carrier density as a function of the Al concentration in (a) Co- and
quality and the number of crystal grains in Co:ZnO lms, indicating (b) Mn-doped lms. Data obtained for lms prepared by PLD at
that a large number of structural defects are introduced, mainly 0.05 mtorr and by magnetron sputtering are denoted by black and
located in grain boundary areas in the samples. In addition, the red circles, respectively. The circles around the data points indicate
concentration of donor defects (notably VO and Zni) increases to a the magnitude of the magnetic moment measured at RT. The solid
certain extent [58,109], accounting for the FM enhancement. lines correspond to addition of one carrier per Al atom. It is evident
It is noted that the ne dramatically increases up to x = 0.002 and that all data lie signicantly above this line, indicating that the
then remains relatively constant with further increases in Al presence of Al has ionized other defects, perhaps some Co2+ and
concentration, implying that Al is not the only candidate Mn2+, which provides carriers in the lms.
responsible for introducing electron carriers, as shown in Acceptor co-doping using Li and N has also been extensively
Fig. 21a (red circle). It is well known that ZnO is a natural n- studied to determine the origin of RTFM [134,204]. Fig. 22 shows
type semiconductor owing to the existence of native defects such unpolarized Raman scattering spectra measured at RT for
as VO and Zni. An increase in structural defects could enhance the (Co,N):ZnO lms. Vibrational modes are evident at 273, 470,
concentrations of point defects such as VO and Zni in the lms. Such 639, 691 and 854 cm1, in addition to the host phonons of ZnO,
an increase in point defects, as well as the native defects, is indicating the substitutional behavior of N3 for O2 and an
regarded as another primary donor source of electron carriers. increase in donor defects for (Co,N)-co-doped ZnO lms [204]. The
Since free electrons can be introduced into Co:ZnO lms not only higher intensity of the vibrational mode at 577 cm1 indicates a
by additional Al doping, but also by an increase in donor defects, higher concentration of donor defects in (Co, N):ZnO lms than in
the ratio of the carrier concentration to the Al density (ne/nAl) is an Co:ZnO lms. Acceptor doping with nitrogen compensates the
indirect measure of the number of defects in a lm, with a larger ne/ electron carriers and hence decreases ne [135]. Magnetization
nAl value indication a greater number of donor defects. For measurements reveal that co-doping increases Ms for (Co,N)-co-
Zn0.95xCo0.05AlxO (x = 0.001), ne/nAl = 1.09 is greater than the doped ZnO (0.129 mB/Co) compared to Co:ZnO (0.085 mB/Co)

Fig. 21. Carrier density of (a) Zn0.95xCo0.05AlxO and (b) Zn0.98xMn0.02AlxO lms. The solid line corresponds to addition of one carrier per Al atoms. Films were grown by PLD at
0.05 mtorr (black) [207] and magnetron sputtering (red), respectively [129]. The thickness of the circles indicates the magnetic moment in Bohr magnetons. The circles lie
signicantly above the line, indicating that the presence of Al has ionized other defects and also possibly some of the Co2+. (For interpretation of the references to color in this
gure legend, the reader is referred to the web version of the article.)
F. Pan et al. / Materials Science and Engineering R 62 (2008) 135 19

relate this difference directly to the magnetization of ZnO doped

with different TM dopants.
The Lande g-factor can be expressed as [175]:

3 1 LL 1  SS 1
g  ; (2)
2 2 JJ 1

where J is the total angular momentum, including the spin (S) and
orbit (L) angular momentum. The Lande g-factor and J can be used
to evaluate the effective magnetic moment of TM ions in TM:ZnO
lms. For Co2+ in Co:ZnO, the Lande g-factor is 4/3, the effective
magnetic moment calculated using Eq. (1) is 6.6 mB/Co and the net
spin moment calculated from the spin-only formula mmax g mB S
is 3 mB. Similarly, Mn2+ has both an effective and net spin magnetic
moment of 5 mB. These different ideal magnetic values for TM ions
are most likely one of the reason for different moments of TM:ZnO.
On the other hand, it is generally considered that Co is more
soluble than other TM atoms in ZnO lms [11,44,105]. In terms of
concentration-dependent magnetization, the largest moments
Fig. 22. Raman spectra of ZnO, Co:ZnO and (Co,N):ZnO lms. ZnO and silicon
substrate modes are marked by (*) and (#), respectively.
have been observed for ZnO doped with different TM concentra-
tions, i.e., 35 at.% for Co [44,58,103], 2 at.% for Mn [33,95], and
1 at.% for Cr, Ni and Cu [62,64,66], and ZnO lms with other dopant
[204]. Combined with FM enhancement, donor defects other than contents tend to show much lower magnetic moments. Therefore,
electron carriers are responsible for RTFM in TM-doped ZnO lms. besides ideal moment discrepancies for these TM ions in ZnO lms,
different solubility and different maximum dopant concentration-
3.8. Comparison of ZnO doped with Sc, Ti, V, Cr, Mn, Fe, Co, Ni and Cu dependent magnetization would also account for different
magnetic moments in 5 at.% TM-doped ZnO lms.
More than 800 reports on TM-doped ZnO DMOs have been
published from 2000 to date. A large number of these focus on Co-
[8,11,23,4455,5860,97,103,111,126,141,152,154,164,165,198] 4. Origin of ferromagnetism in TM:ZnO
and Mn-doped ZnO lms [3137,39,40,73,98,117,140,186]. There
have also been numerous experiments on ZnO lms doped with As discussed in Section 3, almost all of the publications that
other TM elements, including Sc [23,24], Ti [23,25], V [2628], Cr reported magnetization of TM:ZnO referred to the origin of
[11,23,29,30,208], Fe [4143,124], Ni [62,63] and Cu [6467,132]. magnetic ordering. This is very important not only for under-
Some of the magnetic moments measured at room temperature standing the nature of TM:ZnO, but also for applications in useful
reported for 5 at.% TM-doped ZnO lms are summarized in Fig. 23. spintronics. Many points and mechanisms have been proposed for
ZnO lms doped with 5 at.% Co commonly exhibit much stronger intrinsic magnetic ordering. However, it is hard to experimentally
RTFM than ZnO doped with other TM elements. This is consistent characterize and quantitatively analyze the nature of RTFM
with results obtained by Ueda et al. [11] and Venkatesan et al. [23] because so many factors affect the magnetic behavior of TM-
for ZnO doped with a series of TM elements; such studies can doped ZnO, including the microstructure, local structure, electro-
exclude the inuence of the preparation parameters on magnetic nic structure, coupling between localized magnetization, and trace
ordering. It is evident that ZnO lms doped with different TMs amounts of TM dopant atoms in complicated oxide lms. On the
exhibit RTFM with different Ms values, as well as very small other hand, FM values reported seem to be rather weak, often
magnetic moments indicating negligible FM. It is tempting to many orders of magnitude smaller than the expected spin-only
saturation moments. The samples that exhibit FM often do so at
levels low enough so that no technique other than magnetization
itself can reveal whether the phenomenon is intrinsic or arises
from impurities [209]. Magnetization is measured using a SQUID
magnetometer with a high sensitivity of 108 emu; trace FM
contamination of the substrate can lead to lms with magnetiza-
tion signals, which means that measurements may be ambiguous.
Detection of the local structure and electronic structure of TM
elements in TM:ZnO lms is generally limited by the sensitivity
and efciency of the equipment used [85,139], which can lead to
false conclusions. Reports that cast doubt on the very existence of
any type of long-range magnetic order in clean samples of TM-
doped ZnO at low doping concentrations are also appearing with
increasing frequency [209]. There is ongoing debate about these
systems. Therefore, from the broad spread of experimental data it
is difcult to draw general conclusions about the nature of
magnetic interactions in TM-doped ZnO. The confusing situation
clearly calls for a critical and even subjective position to be taken
on this topic. So far, the most popular mechanisms suggested for
magnetic ordering in TM-doped ZnO are carrier-mediated
Fig. 23. Magnetic moments reported for (5 at.%) TM:ZnO at room temperature. exchange (electron and hole carriers), and the BMP model with
20 F. Pan et al. / Materials Science and Engineering R 62 (2008) 135

respect to defects, including VO and Zni, and Zn vacancies, which in the absence of free carriers. Since the total energy calculated is
are described in detail in this section. very close for FM and anti-FM orders [84,210], actual TM-doped
ZnO systems observed in experiments may remain in different
4.1. Computational work metastable states that exhibit FM, anti-FM, and spin-glass
behavior, depending on subtle differences in experimental
Computational work based on ab initio calculations can provide conditions, even for similar lms.
some initial predictions and explanations of the electronic More recently, Ye et al. [211] found that the FM state was
structure and the nature of FM ordering in TM-doped ZnO. To 43 meV lower than the anti-FM state, and thus 12.5 at.% Cu-doped
simulate realistic dopant concentrations, calculation are required ZnO was predicted to be in the ground state with a net magnetic
for supercells containing a large number of atoms, in which the moment of 1 mB/Cu and an estimated TC of 380 K. In contrast, it
doping concentrations are usually higher than 5 at.% [84,210]. was found that the close case for Mn:ZnO favors an anti-FM state,
Hence, computational results for TM:ZnO have been produced whereas the separated conguration tends to be an FM state, stable
using a range of electronic structure implementations, generally by only 0.01 eV [216]. Furthermore, different geometries with
using a density functional theory (DFT) approach based on FM, ferrimagnetic and anti-FM congurations were found to be
pseudopotentials with localized atomic-orbital basis sets, in which nearly energetically degenerate for both bulk V:ZnO and subsur-
the total energy of a many-electron system is described as a face layers of the lms, where V atoms couple ferromagnetically
function of the electron density [19,84,210,211]. This method when they occupy surface sites of the lms [210]. On the other
combines accuracy with low computational cost, particularly hand, Lee and Chang [188] calculated the energy difference
compared to other approaches such as plane-wave pseudopoten- between FM and anti-FM alignments for two Co atoms substituted
tial or all-electron methods [84]. The most widely used approx- in ZnO using the GGA approximation in supercells of 2  2  1,
imation is the local density approximation (LDA) exchange 2  1  2 and 4  1  1 to allow different CoCo distances. The
correlation function [10]. Relaxation of the constraint of an equal total energy difference between the FM and anti-FM states was
occupation of spin-up and spin-down states and minimization of <3 meV per Co atom, indicating that competition between FM and
the total energy with respect to spin occupancy results in the local anti-FM coupling exists in Co-doped ZnO and that spontaneous
spin-density approximation (LSDA) [19,133]. magnetization is not possible in intrinsic Co-doped ZnO, which
It is known that LDA or LDSA calculations fail in predicting the theoretically supports FM at 300 K in some Co-doped ZnO lms,
insulating behavior of many TM oxides, but produce the metallic but the reproducibility was less than 10% [11]. Meanwhile, high
ground state. Incorporation of the effective on-site Coulomb concentrations of both Co ions and electron carriers are needed to
interaction, characterized by Hubbard U (LDA + U), between TM 3d achieve FM [188,217]. These diverse magnetic behaviors predicted
electrons into LDA or LDSA calculations greatly improves the by calculations could be one of the main reasons for the conicting
interaction for TM oxides [212,213]. On the other hand, the highly experimental results reported.
precise projected augmented wave (PAW) method within the However, for both Co- and Mn-doped ZnO, the FM state was
generalized gradient approximation (GGA) or GGA + U scheme, stabilized by the introduction of holes, such as the creation of Zn
which includes an explicit dependence of exchange-correlation vacancies in (Co,Cu)-doped ZnO. Following this prediction, the
energy on the electron density gradient, has also been used in effects of Zn vacancies on FM were experimentally and theore-
calculations [33,10,214,215]. tically investigated [34,218,219]. Some groups demonstrated that
In 2000, Dietl et al. [9] theoretically predicted that p-type ZnO Zn vacancies promote the appearance of RTFM by rst-principle
doped with 5 at.% Mn and similar TM-doped wide-bandgap calculations [34,218,219]. Comparison of experimental and
semiconductors would show RTFM, which focused much attention calculated O K-edge XANES revealed that Zn vacancies indeed
on TM:ZnO research. The prediction used a mean eld approach, exist in Mn-doped ZnO lms and account for the RTFM. Likewise,
assuming hole-mediated FM interactions between Mn local the presence of Fe3+ is a signature of hole doping induced by Zn
moments. TC was then determined from competition between vacancies. A deep acceptor trap due to Zn vacancies with thermal
this long-range carrier-mediated FM coupling and short-range activation energy of 0.815 eV has also been detected by deep-level
MnMn anti-FM exchange interactions. Following this prediction, transient spectroscopy [49]. Karmakar et al. [218] revealed
Sato and Katayama-Yoshida [10] used the KorringaKohn experimentally and theoretically that hole doping is crucial in
Rostoker (KKR) Green function method based on LDA of density promoting FM in Fe-doped ZnO systems, and the presence of Fe3+ is
functional theory to calculate the properties of ZnO doped with a signature of hole doping induced by Zn vacancies. Furthermore,
TMs such as V, Cr, Mn, Fe, Co, and Ni. Additional holes were Yan et al. [34] recently demonstrated that Zn vacancies favor RTFM
introduced by replacing O with N, and electrons were added by in Mn-doped ZnO lms using simulations of O K-edge XANES and
replacing some of the Zn atoms with Ga. The energy difference rst-principle calculations; similar calculations and results were
between FM and anti-FM ordering was taken as the upper TC limit. reported by Iusan et al. [219]. To elucidate the effects of co-doping
This energy difference (EFM  EAFM) was in the region of 0.2 eV, and defects on magnetic ordering in TM-doped ZnO, Gopal and
which corresponds to a high TC. An FM ground state would be Spaldin [213] systematically investigated four cases: (a) single-TM
favored at a doping level of 25 at.% V, Cr, Fe, Co, or Ni in ZnO (Cr, Mn, Fe, Co, Ni and Cu) substitution at Zn sites; (b)
without additional dopants to provide carriers, whereas Mn-doped substitutional magnetic TM ions combined with additional Cu
ZnO was anti-FM. and Li dopants; (c) substitutional magnetic TM ions combined with
Spaldin [84] identied potential FM ground states within VO; and (d) pairs of magnetic ions (Co and Fe, Co and Mn). The
(Zn,Co)O or (Zn,Mn)O using the DFT approach with an LSDA results indicate that FM ordering of TM ions is not induced by
exchange-correlation function. This is achieved for 32-atom addition of substitutional TM impurities or VO. Incorporation of
supercells containing two dopant ions in different positional interstitial or substitutional Li is favorable for FM, as are Zn
arrangements: a close conguration in which TM atoms were vacancies, which is consistent with experimental results for
separated by a single O ion, and a separated conguration in (Co,Li)-co-doped ZnO [133,134].
which they were connected by an OZnO bond. The calcula- We cannot draw denite conclusions regarding intrinsic RTFM
tions show that the energy difference between the anti-FM and FM from the computational work carried out. Electron carriers
spin orders was only a few meV, producing paramagnetic behavior [188,220] and hole doping [49,84,133,134,213,221] seem to be
F. Pan et al. / Materials Science and Engineering R 62 (2008) 135 21

necessary for FM ordering. Gopal and Spaldin [213] proposed that effect (AHE) [226], which was previously considered an indicator of
the calculated magnetic behavior is strongly dependent both on whether a doped sample was a DMO or not. AHE was observed in
the computational details (with FM disfavored by improved FM ZnO and in non-FM Cu-doped ZnO lms, indicating that AHE
convergence) and on the choice of exchange correlation function does not uniquely demonstrate FM behavior [227]. Therefore,
(with FM disfavored by the more appropriate LSDA + U method). checking for basic experimental reproducibility, in addition to
This observation explains the large spread of computational results carrying out careful high-sensitivity characterizations, is highly
in the literature. Fortunately, there is some common ground: most warranted.
publications agree that intrinsic FM does not occur in TM-doped
ZnO at reasonable doping concentrations, but in many cases the 4.2.2. Carrier exchange interactions
addition of carriers or point defects stabilizes the FM state Since RTFM arising from carrier exchange interactions has been
[222,223]. These additional carriers or point defects are in fact by- predicted for several TM-doped ZnO systems [9,10,228], a great
products of structural defects in TM-doped ZnO, which have deal of attention has been focused on doped ZnO systems as
frequently been demonstrated by recent experiments and appear potential DMOs to provide efcient injection of spin-polarized
with increasing frequency. carriers for spintronics devices. Meta-analysis reveals that early
publications (20012004) generally favored carrier exchange
4.2. Experimental work interactions [11,81,48], which are characterized by strong coupling
between localized d electrons of TM ions and the extended sp
Fueled by theoretical predictions, claims of FM at and above carriers of ZnO. The term carrier-mediated exchange refers to
room temperature in TM-doped ZnO have abounded. Unfortu- interactions between localized magnetic moments that are
nately, neither the true nature of these materials nor the physical mediated by free carriers in the system, which can be divided
causes of the magnetism have been adequately determined. It is into three cases: the RudermannKittelKasuyaYosida (RKKY)
known that it is difcult to introduce factors that may inuence interaction; Zener carrier-mediated exchange; and Zener double
RTFM, such as defects and carriers, into calculations. Moreover, it is exchange. RKKY interaction formally describes the magnetic
not easy to realize low doping concentrations (<2 at.%) in TM- exchange between a single localized magnetic moment and a free
doped ZnO supercells because of the limitation of the calculation electron gas. Zener carrier-mediated exchange proposes that
efciency of rst-principle calculations. So far, hundreds of studies carriers can mediate FM interaction between local moments in
have experimentally investigated intrinsic RTFM by focusing on the lms and both local magnetic moments and itinerant carriers
correlations among the magnetization, microstructure, local [9]. FM ordering is driven by a decrease in carrier energy due to
structure and electric properties. Besides the extrinsic origin of redistribution between spin sub-bands split by the exchange
RTFM arising from FM secondary phases, several mechanisms have interaction. Finally, the Zener double-exchange model refers to
been proposed for intrinsic magnetic ordering, including carrier- indirect coupling mediated by oxygen atoms between neighboring
mediated exchange (electron and hole carriers) and a BMP model FM ions in different states. The kinetic energy of the system
in terms of structural defects (VO and Zni), which are described in decreases if the magnetic moments align in parallel, since parallel
details in the following subsections. alignment allows electron transfer from ions in the low state to
those in the higher state [19].
4.2.1. Secondary phases In TM-doped ZnO, the addition of Al as a dopant, or a decrease in
Before elucidating the mechanisms of intrinsic FM, it must rst PO2 during lm growth, seems to increase the carrier concentration
be conrmed whether the magnetic hysteresis loops measured are and enhance FM [46,206]. This suggests the presence of carrier-
intrinsic or extrinsic. Magnetic contamination [86], measurement mediated exchange. It was found that two distinct mechanisms
errors [139] and secondary phases [31,110] are all possibilities for could give rise to FM in TM-doped ZnO prepared by PLD: magnetic
FM signals. Low levels of FM contamination in the substrate and polarons and carrier-mediated exchange, giving rise to DMI and
lm can yield magnetization signals detectable by magnetometers, DMO behavior, respectively [152]. Recently, some groups reported
which have a high sensitivity of 108 emu. The mass of a 100-nm that additional doping cannot signicantly enhance FM ordering
thick lm on a substrate of 5 mm  5 mm  0.5 mm is approxi- [109,112,125,129,131,138]. For ZnO, it is known that annealing in a
mately 1015 mg, whereas the substrate mass is 50 mg. reducing atmosphere results in the creation of VO, with the
Approximately 200 ng of FM contaminant, equivalent to a speck formation of one charge-compensating electron for every VO, thus
of radius of 20 mm, would be sufcient to produce the magnetic leading to an increase in conductivity. That is, an increase in
moment observed for a typical FM thin-lm specimen [139]. A carriers generally accompanies the production of defects, leading
common feature is that all samples tend to exhibit phase to misguided and shortsighted conclusion of a carrier-mediated
segregation at high dopant concentrations and rather high mechanism. By separating these two factors, several reports have
annealing temperatures (>700 8C in general). These secondary determined that FM enhancement is most likely due a decrease in
phases are often likely to be responsible for the FM observed, crystalline quality and an increase in structural defects with a trace
which are key points for the study of DMOs. A key requirement in amount of additional doping (e.g., Al and Sn) [129,130,138].
elucidating RFTM in TM-doped ZnO is to judge whether the
magnetism originates from substitutional dopants on Zn sites or 4.2.3. Defect-based BMP
from the formation of a secondary FM phase. Note that conducting or semiconducting TM-doped ZnO lms
A number of FM or ferrimagnetic Co-based phases have been with a perfect single-crystal structure show negligible FM, which is
detected. For example, FM Mn2xZnxO3d has been proposed as the considered to represent the absence of structural defects
origin of high-temperature FM in (Zn,Mn)O [31]. Both metals and [27,77,79,153,158,184]. There is a dramatic increase in resistivity
their oxides have been identied as being responsible for FM for Co:ZnO lms on Cu doping, but this change in resistivity does
behavior in TM-doped ZnO lms, such as Co [18,224,225], Mn not affect the magnetic moment, suggesting that a carrier-
[122], CoFe [70], CoO [56,163], Co3O4 [56,109,111,163], Fe3O4 [43], mediated mechanism is not a feasible explanation for FM in these
and CuO [65]. These types of TM-doped ZnO lms are not genuine lms [137,139]. Cu-doped ZnO lms showed RTFM with 1.45 mB/
DMOs. However, these non-magnetic semiconductors with Cu, whereas FM completely vanished when additional carriers
embedded secondary FM phases may exhibit an anomalous Hall were introduced into the lms [132]. Coey et al. [8] observed RTFM
22 F. Pan et al. / Materials Science and Engineering R 62 (2008) 135

in insulating TM:ZnO and elucidated a BMP mechanism. Further- that structural defects have a signicant inuence on magnetism in
more, an increasing number of experimental results demonstrate these systems.
that carriers are not necessary for RTFM, and FM interaction can be Under conditions in which acceptor dopants are activated,
unambiguously observed in lms without free carriers but in a leading to a decrease in free-electron density, magnetization is
dielectric state [8,30,41,44,45,75,94,108,109,152,153,186]. This enhanced. The result is consistent with hole-mediated FM in Mn-
insulating nature is signicant, in that a magnetic coupling doped ZnO, in which bound acceptors mediate the FM ordering.
interaction other than carrier-mediated exchange is apparently Increasing the electron density decreases the acceptor concentra-
operative. tion, thus quenching the FM exchange [131,138]. In addition, ZnO
In fact, many specically designed experiments appearing with and similar TM oxides show paramagnetism at RT, whereas it has
increasing frequency reveal that defects such as VO and Zni account been claimed that RTFM can be obtained in certain d0 TM oxides
for RTFM in TM:ZnO [44,58,94,167]. For example, Co:ZnO lms without a dopant [229231]. It should be pointed out that pure
annealed in Ar/H2 with a pronounced Zn K-edge XANES pre-edge HfO2 powder develops a weak magnetic moment on heating in
peak showed an increase in VO (1  1021 cm3) that was responsible vacuum, which is eliminated on annealing in oxygen [229]. Lattice
for much stronger RTFM [55]. Annealing of Zn0.92Co0.08O lms in defects are proposed to be responsible for the FM properties in
vacuum and air also demonstrated that VO and Zni are responsible for these semiconducting and insulating lms without doping. It is
the RTFM of the lms [141]. More interestingly, quantitative worth pointing out that the absence of free spin-polarized carriers
reversible cycling of magnetic moments was achieved by annealing would restrict the application of these materials in RT spintronics
TM:ZnO lms in alternating air and Zn vapor (vacuum), demon- [139,154,232].
strating a direct correlation between FM and Zni (VO) [102,154,198]. Fig. 24a shows the lattice structure of TM:ZnO, in which TM ions
By annealing lms in different oxidation atmospheres and in the are incorporated into the wurtzite lattice at Zn2+ ion sites. The
presence or absence of Zn vapor, it has been demonstrated that highly non-equilibrium process of lm deposition makes it
RTFM is not linked to conductivity and that a small level of Zni possible that structural defects in the doped lm are located
defects and consequent BMP plays a crucial role in mediating RTFM throughout the lattice at arbitrary distances with respect to Co
in TM:ZnO. Similarly, post-annealing leads to a decrease in the c sites, which can play an important role in the system, as illustrated
lattice parameter by affecting the Zni concentration, corresponding in Fig. 24b. The formation of one charge-compensating electron for
to a decrease in RTFM [57]. every VO produces a polaron. An electron associated with a
Using XAS and XMCD, Matsumura et al. [197] obtained direct particular defect is conned in a hydrogenic orbital of radius
evidence that the absence of anomalous dispersion of the atomic rH = er(m/m*)a0 and g = er(m/m*), where er is the dielectric constant,
scattering factor for Co is probably caused by signicant lattice m the electron mass, m* the effective mass of the donor electrons,
deformation of the local structure around Co due to VO, accounting and a0 is the Bohr radius (0.53 A). For Co:ZnO, m/m* = 3.57 and er is
for RTFM in Co:ZnO, whereas Co ions indeed substitute in Zn sites in the range 437 [8,44,107,141], which is dependent on the
in paramagnetic Co:ZnO thin lms [197]. This observation also fabrication method and parameters. For example, er = 10 corre-
demonstrates that VO is necessary for the appearance of RTFM. sponds to large rH and g, i.e., rH = 18.9 A and g = 35.7. Likewise, the
Elimination of defects, as well as lling up VO, would degrade the polaron size is estimated to be approximately 7.6 and 7.8 A in Co-
FM ordering [29,141,200]. For example, Cr:ZnO lms fabricated doped ZnO [8,100]. In contrast, the disappearance of RTFM after
under various conditions revealed that elimination of structural hydrogen implantation can be ascribed to the enhanced effective
defects and lling up of VO might lead to a certain level of FM mass and subsequent decrease in g, which also supports the above
degradation [29]. Likewise, annealing of Cu-doped ZnO lms in equation [38]. It should be noted that if the donor orbital extends
oxygen led to a decrease in VO and had a large detrimental effect on over a sufcient number of cations, there is nothing to be gained by
FM [177]. The large amount of edge dislocations observed would any further increase in er [8].
enhance the concentration of VO and Zni point defects, which Interestingly, an electron trapped in a defect is demonstrated by
contribute to FM ordering [58,94]. Therefore, these results imply CV measurement, which exhibits hysteresis with a large memory

Fig. 24. (a) Lattice structure of TM:ZnO. (b) Three-polaron subsystem representing supercoupling between polarons.
F. Pan et al. / Materials Science and Engineering R 62 (2008) 135 23

window of 0.6 V [94], effectively providing evidence of a BMP

mechanism: the charge-compensating electron in each defect
forms a polaron. The formula for Co-doped ZnO can be written as
(Zn0.96Co0.04)(O&d), where & represents a donor (defect) and dp is
the defect percolation threshold [8]. For (4 at.%) Co:ZnO lms with
er = 22 and me/m  0.3, dp can be calculated from g3dp = 4.3 [8].
Using the value of dp calculated, the critical concentration of
oxygen vacancies (n&; defects) can be obtained from the relation
d = n&/no, where no is the oxygen density of no = 1.4  1022 for a
close-packed oxygen lattice in ZnO. In the present case, the defect
percolation threshold n& is thus approximately 1.6  1017 [108].
FM ordering is due to superexchange between complexes in DMI,
i.e., VO and magnetic impurities, which are stabilized by charge
transfer from vacancies to impurities. The percolation threshold for
magnetic ordering is determined by the radius of vacancy levels,
but the exchange mechanism does not require free carriers [228].
If there is a sufciently large orbital radius, overlap between a
hydrogenic electron and the cations within its orbit leads to FM Fig. 25. Theoretical Curie temperature of DMOs [9].
supercoupling between them, as shown in Fig. 24b. Interaction
between the hydrogenic electron and the cations is represented by
a Heisenberg exchange Hamiltonian [233]: increasing bandgap (Eg). It should be noted that high TC values
attributed to secondary phases are excluded from the table, such as
Hi j J i j Si s j ; (3) TC = 980 K for Mn-doped ZnO and 1180 K for Co:TiO2 due to the
ij formation of Co metal [226] and Mn2xZnxO3d [31], respectively.
In contrast to the confusion in the literature regarding magnetic
where S is the spin of Co2+ and s is the donor electron spin. The moments of DMOs, according to theoretical studies based on the
donors tend to form BMPs, coupling Co2+ within their orbits. The BMP mechanism [8,236], the TC of DMOs is commonly quantita-
Hamiltonian of a two-polaron subsystem is given by Eq. (3), where tively given by [8]:
the donor electron spin index j takes only two values, j1 and j2,
1=2 3
corresponding to the two polarons under consideration. The T C S 1s2 xd=3 Ji j f O rceff =r O =kB ; (4)
hydrogenic orbital tends to spread out sufciently to overlap with
a large number of BMPs, but some isolated polarons cannot be where S is the localized core spin, s the electron donor spin, x the
covered and thus cannot achieve macro-FM ordering. It is therefore doping concentration, d the donor concentration, Jij the sd exchange
concluded that the origin of FM in DMOs does not necessarily parameter (bandgap Eg), fO the oxygen packing fraction for the oxide,
involve free charge carriers and that RKKY-type indirect exchange rceff the effective cation radius, and kB is Boltzmanns constant.
interactions are not necessary for magnetic ordering. In contrast, Theoretical predictions according to Eq. (4) reveal that Eg and the
TM ions form deep levels in the bandgap and a certain doping and donor concentrations are important factors for TC of a
concentration of defects in the lms may play a more active role given system. For example, TC can be estimated from the following
in mediating FM exchange than in traditional RKKY systems, as parameters for Co:ZnO: S = 3/2, s = 1/2, x = 0.04, Jij = 3.6 eV [44],
increasingly supported by related publications. d = 0.01, rceff 0:20 nm 0:20 nm, and r0 = 0.14 nm [8]. The TC given

4.3. Effect of bandgap on the Curie temperature Table 4

Curie temperatures (TC) reported for DMOs

It is generally reported that TM-doped ZnO lms show FM Band gap (eV) System TC (K) Reference
ordering at or above RT (Table 1); these materials have been InAs 0.36 Mn:InAs 30 [237]
considered typical DMOs with high TC, and should be promising for
Ge 0.75 Mn:Ge 116 [238]
use in spintronics. In fact, using a mean eld approach, calculations
Mn:Ge 150 [6]
predicted TC for oxides and semiconductors, assuming hole-
mediated FM interactions between Mn local moments. TC was then GaAs 1.55 Mn:GaAs 150 [1]
Mn:GaAs 173 [2]
determined from competition between this long-range carrier-
mediated FM coupling and short-range TMTM anti-FM exchange ZnTe 2.38 Cr:ZnTe 300 [239]
interactions. The major breakthrough in such calculations is GaP 2.87 (Mn,C):GaP 300 [240]

magnetic ordering temperatures in excess of RT for Mn-doped GaN TiO2 3.0 (rutile) Fe/Co/Ni:TiO2 700 [234]
and ZnO (Fig. 25, plotted according to Ref. [9]). Given that TC is one 3.2 (anatase) Cr:TiO2 700 [190]
of the most important parameters for DMOs, many researchers ZnO 3.37 Mn:ZnO 425 [33]
have tried to enhance it and to elucidate the factors that inuence Co:ZnO 790 [44]
it. This has led to TC enhancement from much lower than RT [158] Cu:ZnO 390 [65]
to 790 K [44] for TM:ZnO and to 700 K for TM-doped TiO2 SnO2 3.4 Co: SnO2 650 [172]
[190,234], and to 110 K [3] to 173 K [235] for Mn:GaAs [236]. The Fe:SnO2 610 [41]
highest TC values for typical DMOs with intrinsic magnetization are CeO2 3.4 Co: CeO2 740875 [241]
listed in Table 4, including Mn:InAs [237], Mn:Ge [238,6], Mn:GaAs GaN 3.5 Mn:GaN 940 [242]
[1,2], Cr:ZnTe [239], (Mn,C):GaP [240], Fe/Co/Ni:TiO2 [234], In2O3 3.75 CrIn2O3 850930 [243]
Cr:TiO2 [190], Mn:ZnO [33], Co:ZnO [44], Cu:ZnO [65], Co: SnO2 LiNbO3 3.8 CoLiNbO3 710 [120]
HfO2 4.5 Co:HfO2 800 [244]
[172], Fe:SnO2 [41], Co:CeO2 [241], Mn:GaN [242], Cr:In2O3 [243],
AlN 6.2 Cr:AlN 900 [245]
Co:LiNbO3 [120], Co:HfO2 [244], Cr:AlN [245], in order of
24 F. Pan et al. / Materials Science and Engineering R 62 (2008) 135

Fig. 26. Curie temperature reported for DMOs as a function of bandgap. The correlation between them is described by a simple linear t: TC = 226.3Eg  107.4.

by Eq. (4) can then be estimated as 822 K, which is close to the accomplished under ambient conditions via optical pumping with
experimental result of 790 K for (4 at.%) Co:ZnO [44]. TC values appropriately polarized laser light [249,250]. This method is well
reported for DMOs as a function of semiconductor Eg are known and has been used to achieve the drift transport of optically
summarized in Fig. 26. Interestingly, the reported data reveal that induced spin-polarized carriers in semiconductors [251]. However,
TC is proportional to the semiconductor Eg. This correlation can be ultimate device integration will require electrical spin injection,
described by a simple linear t: TC = 226.3Eg  107.4, demonstrating which can be accomplished either by injection from a spin-
that Eg has a signicant inuence on the TC of TM-doped ZnO. This polarized source or by spin-ltering unpolarized carriers at the
relation provides an insight into the TC values measured for DMOs interface [22,246]. Several experiments have successfully demon-
lms and opens the possibility of increasing TC by modifying the Eg of strated spin injection into semiconductors and additional concepts
DMOs, especially for Mn-doped GaAs, which has potential applica- for spin lters and spin aligners have been proposed [252]. It is
tions in spintronics owing to its strong spinorbit coupling and high envisioned that the merging of electronics, photonics and
spin polarization [2]. magnetics will ultimately result in new spin-based multifunctional
devices, e.g., MTJs, spin-FETs, spin light-emitting diodes (spin-
5. TM-doped ZnO-based prototype spintronics and multi- LEDs), spin resonant tunneling devices, optical switches operating
functional materials at terahertz frequency, and modulators and quantum bits for
quantum computation and communication [7]. For example, MTJs
Spintronics is a topic that has attracted much interest in recent and spin-FETs fabricated by DMO-based transparent heterostruc-
years. Within the context of spintronics, the spin of electrons, and tures are not only effective models for studying spin transport and
not just their electrical charge, is controlled during the operation of spin injection, but are also promising in information processing
information circuits. The transport and manipulation of spin- [237]. Spin-polarized electrons are injected via an n-contact to a p-
polarized electrons or holes in semiconductors offer huge potential contact in a magnetic semiconductor-based LED with a TM-doped
for novel devices that combine non-volatile information storage ZnO n-contact and a conventional non-magnetic p-contact. ZnO is
with high processing speed at low power, which may even be expected to be one of the most promising materials for RT
useful for quantum computation [7,246]. It was the discovery of polarized light emission, but optical spin polarization in ZnO has
giant magnetoresistance (GMR) and tunnel magnetoresistance not been detected to date owing to the short spin relaxation time,
(TMR) that initiated spintronics research and guided a rst- which likely results from the Rashba effect. Possible solutions
generation device in the form of spin valves based on FM involve either cubic-phase ZnO or the use of additional stressor
multilayers, such as Co/Ru [247], which are now used in the read layers to create greater spin splitting to obtain polarized light
heads of most hard-disk storage devices. Second-generation emission from these structures, as well as the consideration of
spintronics integrating semiconductor materials and magnetic alternative semiconductors and fresh device approaches
elements involve new exible devices such as spin-FET and spin [159,253,254].
logic devices, which not only improve the capabilities of electronic Despite persistent efforts by many groups, spin injection from a
transistors, but also have new functionalities [248]. Successful conventional FM metal into a semiconductor has proved highly
realization of most spintronics applications depends critically on inefcient, and is limited to <0.1% [246,255]. Although promising
the ability to create spin-polarized charge carriers in a conven- advances in spin-injection efciency from metal contacts into
tional semiconductor in a device structure [22]. To successfully semiconductors have been recently been achieved (using injection
incorporate spin into existing semiconductor technology, technical from ohmic contacts or ballistic point contacts, tunnel injection or
issues such as efcient injection, transport, control and manipula- hot electron injection), there are generally difculties in reprodu-
tion, and detection of spin polarization and spin-polarized currents cibility [256]. Some experiments also yielded high spin-injection
have to be solved [7]. efciencies; however, other experiments revealed no unambig-
A major issue that needs to be resolved is the transfer of spin- uous results, and for many of the concepts proposed even a proof of
polarized carriers from a magnetic contact into a non-magnetic principle is still lacking [91]. In contrast, efcient spin injection has
semiconductor. Highly efcient electrical spin injection was recently been successfully demonstrated in all semiconductor
realized for the rst time in 1999 [249]. Spin injection can be tunnel diode structures using either a spin-polarized DMO as the
F. Pan et al. / Materials Science and Engineering R 62 (2008) 135 25

injector or a paramagnetic semiconductor under high magnetic paradigms. In fact, besides TM:ZnO, Ti0.95Co0.05O and (Zn,Cr)Te
eld as a spin lter [257259]. According to this concept, making with TC above RT have been used as one of the magnetic electrodes
carriers ow from DMOs to a conventional semiconductor, such as in MTJs, possessing TMR up to 180 and 250 K, respectively, but are
from TM:ZnO to ZnO, would be an effective way to realize high spin limited by inelastic tunneling conduction due to the low quality of
injection efciency because of their minimum crystal structure the amorphous AlOx barrier and/or the junction interface [270
mismatch, good chemical compatibility and similar electric 272]. The TMR temperature and spin polarization could be
properties. enhanced by optimization of the interface and barrier quality in
MTJs [264,270272], in analogy to single-crystal Fe/MgO/Fe MTJs
5.1. Co-doped ZnO-based magnetic tunnel junctions with large TMR of 180% at 300 K [273].
Based on the concepts described above, TM:ZnO-based
The main trigger for the search for spin injection was the heterostructures have been developed to study spin injection
discovery of GMR in 1988 by Grunberg [260] and Fert [261], who and spin-polarized transport [88,89,274]. In particular, (Zn,Co)O
were awarded the 2007 Nobel Prize for Physics. In the simplest was selected for fabrication of two FM electrodes, with a pure
case, a very thin, non-magnetic metal layer is sandwiched between insulating ZnO layer as the barrier, which is compatible with
two FM metal layers. Later, CoFe/Al2O3/Co and NiFe junctions were (Zn,Co)O and allows epitaxial growth [88,89]. (Zn,Co)O/ZnO/
found to show TMR of 11.8% at RT [262]. These publications (Zn,Co)O epitaxial structures satisfy two primary requirements
prompted a focus on the study of GMR and TMR [247,263,264]. for spin injection: a minimum conductance mismatch and high
TM:ZnO and similar DMOs with RTFM have been prepared to spin polarized contacts [265]. In this scenario, TMR is expected to
provide materials in which the spin freedom of electrons can be persist up to RT and exhibit high V1/2 to overcome one of the main
manipulated for spin transport electronics [16]. Steady progress is shortcomings of MTJs for technical applications: a dramatic
being made on this front, but few reports have been published on decrease in TMR with bias. Moreover, this MTJ structure indeed
spin-polarized transport in heterostructures made from doped provides an approach for spin injection from a (Zn,Co)O electrode
ZnO [88,89,265]. In fact, spin injection from a doping ZnO layer to to ZnO, detected by measuring SP tunneling into the other (Zn,Co)O
pure ZnO and other conventional semiconductors is a key long- electrode.
term goal of the extensive study of ZnO DMOs [87,88]. Fig. 27a shows a cross-sectional view of (Zn,Co)O (50 nm)/ZnO
(4 nm)/(Zn,Co)O (25 nm) junctions. The two (Zn,Co)O layers serve
5.1.1. Spin-polarized transport in (Zn,Co)O/ZnO/(Zn,Co)O junctions as the bottom (50 nm) and top (25 nm) magnetic electrodes
Large TMR at low temperature (e.g., 4 K) has been obtained in (r = 1.7  102 V cm), which are separated by an insulating ZnO
(Ga,Mn)As-based MTJs [266269]. However, the operation of these barrier with a lm thickness of 4 nm (107 V cm). For vertical
junctions is reduced to a rather low temperature (<30 K) owing to transport measurement, the ZnO barrier and the Zn0.94Co0.06O top
the low TC (170 K) of (Ga,Mn)As [1,2,235]. It is important to electrode were patterned using shadow mask into a circular
develop MTJs of high-TC DMOs (such as TM-doped ZnO) to enhance junction with a diameter of 300 mm (Fig. 27b). Fig. 27c shows a
the operation temperature, and eventually to achieve RT device typical atomic force microscopy image of the junction surface. The

Fig. 27. (a) Schematic representation of a (Zn,Co)O/ZnO/(Zn,Co)O junction. (b) SEM image of an MTJ array. (c) AFM image of junctions for a scan area of 3 mm  3 mm. (d) XRD
spectrum of the MTJ. The inset displays a pole gure for the wurtzite(1 0 1) plane.
26 F. Pan et al. / Materials Science and Engineering R 62 (2008) 135

Fig. 28. (a) Low-magnication image of MTJ cross-section. The dashed line denotes the (Zn,Co)O/Al2O3 interface and areas b and c correspond to the images in (b) and (c),
respectively. (b) HRTEM image of (Zn,Co)O/ZnO/(Zn,Co)O heterostructure. (c) Cross-sectional HRTEM image of (Zn,Co)O/Al2O3 interface. (d) SAED pattern of the junction (F,
lm; S, substrate).

root-mean-square of the surface roughness is approximately (>1 T) does not reect any specic correlation with magnetization
0.9 nm for a scan area of 3 mm  3 mm, indicating that the data. This result is supported by work carried out by Ramachan-
junction has a smooth surface. The sharp and intense wurtzite dran et al. [265], who reported that the positive TMR apparently
ZnO(0 0 2) peak observed in Fig. 27d indicates that the trilayered saturates and starts to decrease at intermediate magnetic elds,
lms are highly crystalline. This is further conrmed by a pole and that the value of this magnetic eld decreases with decreasing
gure of the lms acquired from the (1 0 1) planes, which was temperature. The positive TMR can be attributed to spin splitting of
obtained by azimuthally rotating the sample from 08 to 3608 at tilt the conduction band and a subsequent redistribution of conduc-
angles from 208 to 908. Six poles are evident, in agreement with the tion electrons when an sd exchange interaction is present [265].
sixfold symmetry of hexagonal ZnO. The low-magnication image The diffusion of Co dopes the ZnO barrier near the interface and
in Fig. 28a reveals the uniform thickness of the junction of 80 nm. likely leads to alignment of paramagnetic Co states and a decrease
The HRTEM image in Fig. 28b shows the good crystallinity of the in spin-ip scattering; subsequent suppression of spin-ip
heterostructure acquired for area b in Fig. 28a. It was found that
both the (Zn,Co)O electrodes and the ZnO barrier behave as single-
crystal structures with well-dened interfaces. A typical cross-
sectional image of the (Zn,Co)O/Al2O3 interface is shown in Fig. 28c
for area c in Fig. 28a. The SAD pattern in Fig. 28d indicates that
the orientation relationship is wurtzite(0 0 2)jjsapphire(0 0 3). It is
thus concluded that epitaxial growth of (Zn,Co)O-based MTJs
occurs from the bottom (Zn,Co)O electrode via the ZnO barrier to
the top (Zn,Co)O electrode, although some defects exist.
The spin injection and spin transport characteristics are
manifested directly in the magnetotransport properties. Fig. 29
shows the TMR dependence on the magnetic eld at four typical
temperatures. The TMR ratio is dened as TMR% = [R(H)  R(0)]/
R(0), where R(H) and R(0) are the eld-dependent resistance and
zero-eld resistance, respectively. A common feature is that all
curves show positive TMR with symmetrical behavior and a high
saturation eld >2 T. On the other hand, the TMR curves do not
exhibit a buttery shape; instead, the TMR monotonously
increases with increasing magnetic eld. It is noted that Co:ZnO
junctions have a coercivity eld of 11 mT and saturation of
0.2 T. Although the magnetization is accompanied by an increase Fig. 29. TMR curves of junctions measured at a current of 1 mA at 4, 50, 100, 200, and
in parabolic resistance, it is clear that the high TMR saturation 300 K.
F. Pan et al. / Materials Science and Engineering R 62 (2008) 135 27

scattering at or near the interface has been identied as a possible The magnitude of a TMR ratio is commonly dened using
source of high-eld TMR [88]. Jullieres formula, TMR = 2P1P2/(1  P1P2), where P1 and P2 are the
A possible explanation for the intrinsic positive TMR can be spin polarization of FM1 and FM2, respectively [276]. Thus, SP was
found by invoking spin orientations in (Zn,Co)O. In the low eld, calculated as 31% at 4 K. This is apparently lower than the value for
the entire density of states near the Fermi energy (EF) arise from (Ga,Mn)As-based MTJs [266], presumably because Co:ZnO is a
the minority spin band for (Zn,Co)O [275]; the spin (S) is parallel in controllable n-type DMO with very low spinorbit coupling. This is
the bottom and top electrodes, because both electrodes are different to GaMnAs, which is a p-type DMO with very strong spin
fabricated from the same (Zn,Co)O, as marked in Fig. 28. In this orbit coupling [41]. Interestingly, the SP is estimated to be 4% at RT,
parallel case, the electron can easily tunnel from one electrode to revealing an effective but very small spin polarization in fully
the other, giving rise to low resistance in the junction. As the eld is epitaxial (Zn,Co)O/ZnO/(Zn,Co)O junctions at RT. Clearly, higher SP
enhanced, domain rotation becomes prevalent, accompanied by and a better understanding of the physical phenomena require
rotation of S. It is noted that the domains, as well as S, in magnetic further efforts.
materials are rotated sequentially rather than simultaneously,
particularly for the bottom and top (Zn,Co)O electrodes of different 5.1.2. Anomalous TMR in (Zn,Co)O-based junctions
lm thickness in our scenario. Consequently, S in the two Fig. 30a shows non-linear currentvoltage (IV) characteristics
electrodes would not be totally parallel when applying H, leading for MTJs up to 2 V under H = 0 and 1 T at 4 K, which is expected for a
to difcult transport and producing high resistivity. Moreover, tunneling device. This is indicative of carrier injection by tunneling,
these descriptions concerning sequential rotation of S most likely taken the linear IV curve for a single (Zn,Co)O lm into account. On
correspond to a monotonic increase rather than buttery TMR the basis of IV curves obtained at H = 1 and 0 T, TMR versus bias
curves. (TMR%V) at different temperatures is plotted in Fig. 30be, where

Fig. 30. (a) MTJ IV characteristics under applied elds of H = 0 and 1 T at 4 K. Typical bias dependence TMR curves at (b) 4, (c) 100, (d) 200, and (e) 300 K.
28 F. Pan et al. / Materials Science and Engineering R 62 (2008) 135

TMR% = [Rjun(1 T)  Rjun(0 T)]/Rjun(0 T). Although both the TMR ratio Four interesting phenomena are observed at different tempera-
and the signal-to-noise ratio drastically decrease with increasing tures: a very large V1/2 in excess of 4 V at T > 6 K; nearly constant
temperature, the parabolic TMR%V curve remains at 300 K, revealing TMR up to 2 V at T = 5 K; a combination of higher (at low voltage)
that the effects of bias on transport in the junction can persist up to and lower (at high voltage) TMR with increasing voltage at T = 3
RT. The most outstanding property of all the TMR%V curves from 4 to 4 K; and an anomalous increase in TMR with increasing voltage at
300 K is their weak bias dependence. V1/2, the voltage at which the T = 2 K. The anomalous voltage-dependent TMR can be explained
TMR ratio is half of the maximum, exceeds 2 V over a wide by the large energy separation between the Fermi level and the
temperature range (4300 K). These values are much larger than mobility edge [89]. A non-metal ! metal transition caused by the
for conventional magnetic metal and for DMO-based MTJs with AlOx, magnetic eld can bring the Fermi level above the mobility edge, so
MgO and similar barriers [270273]. The decrease in TMR with bias that the energy separation between the Fermi level and the
can be explained by inelastic scattering by magnon excitations at the mobility edge is large enough to cause the V1/2 behavior observed
FM/insulator interface [264]. The much lower bias dependence is [281].
likely due to the coherence of the (Zn,Co)O/ZnO interface owing to
both the minimum conductance mismatch and the high spin- 5.2. TM-doped ZnO-based spin eld-effect transistors
polarized contacts.
The typical V1/2 value is approximately 0.2 V [262,277]. V1/2 The most effective measurement of the quality of the DMO-
enhancement has generally been achieved by fabrication of double based FM materials is the operation of device structures such as the
barriers [278] and by improving control of the single-crystal MTJs described above, spin-FETs and photo-induced ferromagnets
barrier [273,279], yielding up to 1.44 V in fully epitaxial MgO [16,22,88,282]. The use of DMOs as the spin source in spintronics
double-barrier MTJs [280]. As discussed above, all-epitaxial could allow high spin injection efciency and long spin coherence.
(Zn,Co)O/ZnO/(Zn,Co)O junctions show a very large V1/2 far in The spin-FET proposed by Datta and Das [91] and subsequent
excess of 2 V [88]. The double-barrier junctions grown by coherent numerous clones have motivated extensive study of spin preci-
sputtering on Al2O3(0 0 1) substrate are composed of two FM sion-controlled electronic semiconductor devices [237,282284].
(Zn,Co)O electrodes (50 and 25 nm for bottom and top, respec- Huang et al. [285] claimed that a silicon spin transport device
tively) separated by a ZnO (4 nm)/(Zn,Co)O (6 nm)/ZnO (4 nm) showed output current modulation through voltage control of spin
trilayer [89]. On the basis of IV curves obtained at H = 2 and 0 T precision, with 37% electron current spin polarization after
(Fig. 31a), TMR%V at different temperature is plotted in Fig. 31. transport through 10-mm undoped silicon, but no spin-FET based

Fig. 31. (a) MTJ currentbias voltage (IV) characteristics up to 5 V under applied elds of H = 0 and 2 T at 3 K. Typical bias voltage dependence of TMR curves at (b) 20, (c) 10, (d)
6, (e) 5, (f) 4, (g) 3 and (h) 2 K.
F. Pan et al. / Materials Science and Engineering R 62 (2008) 135 29

and drain contact material, it should be possible to have a 100%

spin-polarized electron ow in the (Zn,Mn)O channel [22]. These
heterostructures could be grown by magnetron sputtering to
realize fully epitaxial growth and shadow mask patterning. By
manipulating the relative orientation of the magnetization of the
injector and detector with a different in-plane external magnetic
eld and gate voltage, the current in the detector can be changed
correspondingly, in analogy to the in-plane spin valve [93,285].
The magnetocurrent ratio is MC% ISD  ISD =ISD , where ISD is the
magnetocurrent and the superscripts P and AP refer to parallel and
Fig. 32. Schematic diagram of an all ZnO-based spin-FET [14]. antiparallel injector/detector magnetization conguration, respec-
tively. Subsequently, this magnetocurrent ratio corresponds to a
on FM semiconductors has been experimentally demonstrated yet. conduction electron current spin polarization of P ISD 
The primary obstacle to experimental achievement is the inability ISD =ISD ISD with respect to Jullieres formula [276]. The
to achieve high spin injection efciency at the interface between fabrication of TM-doped ZnO-based spin-FETs and the realization
the source and channel and high spin detection efciency at the of reliable spin detection are highly warranted and should be the
interface between the channel and drain, which are key for spin- focus of intense efforts.
FETs. It is known that the spin injection and detection efciencies
have to be of the order of 99.9995% to achieve an onoff 5.3. Ferroelectricity and giant piezoelectric d33 in V and Cr-doped ZnO
conductance ratio of 105, which is a typical value for modern
transistors [283]. However, the maximum spin injection efciency Although FM in TM-doped ZnO systems has been discussed in
demonstrated is only 90% at low temperature [249], which is far detail, ferroelectricity, which usually exists in perovskites and
below the requirement for spin-FETs. ilmenites, has also been found in these systems. Recently, Yang
Because any scattering at the interface between the ferro- et al. [286,287] reported the observation of ferroelectric behavior
magnet and the semiconductor can cause spin relaxation, a in V- and Cr-doped ZnO lms. In their experiments, ferroelectric
minimum conductance mismatch and high chemical compatibility measurements were performed on Ag/Zn1xTMxO/n-Si (TM = V,Cr)
between these layers are necessary. Fortunately, ZnO-based DMO sandwich structures in which Ag was deposited on lms as the top
heterostructures can be used to fabricate spin-FETs with potential electrodes and a conductive Si substrate served as the bottom
to show high spin injection efciency and spin transport coherence electrode. Fig. 33a and b show polarizationelectric eld (PE)
[22,93]. Following the idea of the fully epitaxial growth of hysteresis loops for V- and Cr-doped ZnO lms, respectively.
(Zn,Co)O-based MTJs and the concept of ZnO-based spin-FETs by Although the characteristics are not fully saturated, the hysteretic
Pearton et al. [22], a schematic diagram of a spin-FET on the basis of behavior still indicates the presence of ferroelectricity. The shift of
ZnO DMOs is presented in Fig. 32. In this scheme, (Zn,Mn)O can be the loop center observed for these Ag/Zn1xTMxO/n-Si structures is
a half-metallic ferromagnet, which serves as the channel, and considered to result from the asymmetric electrode structure. The
(Zn,Co)O is used to fabricate the source [30 nm (Zn,Co)O injector] ferroelectric behavior in V- and Cr-doped ZnO lms was further
and drain [60 nm (Zn,Co)O detector], as well as a thin insulating conrmed by well-shaped displacement-applied eld (DE)
ZnO layer acting as a gate oxide. Using FM (Zn,Co)O as the source buttery loops, as shown in Fig. 33c and d, respectively

Fig. 33. (a) Frequency dependence of the PE characteristics of Zn0.975V0.025O lms measured at room temperature. (b) PE characteristics of Ag/Zn0.94Cr0.06O/n-Si FET
measured at 2 kHz and room temperature. Piezoelectric hysteresis loop (black) and DV curve (red) for (c) Zn0.975V0.025O and (d) Zn0.94Cr0.06O lms. (For interpretation of the
references to color in this gure legend, the reader is referred to the web version of the article.)
30 F. Pan et al. / Materials Science and Engineering R 62 (2008) 135

Fig. 35. Effective d33 as a function of V concentration x in Zn1xVxO lms, bulk ZnO
and ZnO nanobelts.

simultaneous FM and ferroelectric ordering have attracted

extensive interest since they have potential applications in
important devices such as transducers and memory [292,293].
The piezoelectric properties of ZnO lms doped with different V
concentrations have been systematically investigated by SPM
characterization by Yang et al. [288] and Zhao et al. [294]. Fig. 35
shows the piezoelectric d33 coefcients reported for bulk ZnO and
quasi-one-dimensional nanobelts and the average d33 coefcient
as a function of vanadium concentration in Zn1xVxO lms. The d33
coefcient for bulk ZnO and a nanobelt is 9.9 and 26.7 pC/N,
respectively; the latter was the highest d33 value for ZnO-based
systems before ferroelectric TM-doped ZnO systems were found.
The d33 value measured for an undoped ZnO lm was 11.8 pC/N.
Fig. 34. (a) Room-temperature magnetic hysteresis of Zn0.985V0.015O lms. The inset However, when 2.5 at.% V was introduced, a peak d33 value of
shows the same parameters on an expanded scale. (b) Temperature dependence of 110 pC/N was obtained, approximately one order of magnitude
(&) FC and (~) ZFC magnetizations for Zn0.985V0.015O lms. The inset shows the
greater than the value for pure ZnO lm and fourfold greater than
temperature dependence of the difference between the FC and ZFC data.
for the ZnO nanobelt. A comparably high d33 value of 120 pC/N was
obtained in ferroelectric Zn0.94Cr0.06O lms. The intriguing piezo-
[287,288]. It should be noted that ferroelectricity in ZnO-based electric properties mean that V- and Cr-doped ZnO are promising
systems has also been reported for Li- and Mg-doped ZnO bulk candidates for sensors, actuators, and transducers.
and/or lms [289291]. Piezoelectric hysteresis loops (d33-applied The origin of ferroelectric behavior in ZnO-based systems has
eld) could be calculated from DE curves and clearly showed that been the subject of much discussion, with two main interpreta-
the Zn1xTMxO lms are switchable and the ferroelectricity is tions: the so-called size-mismatch model and the electronic origin
retained. More importantly, high piezoelectric d33 coefcients model. It is commonly believed that the probable reason for the
were observed for ferroelectric V- and Cr-doped ZnO lms. ferroelectric behavior is that smaller substitutes can occupy off-
The observation of ferroelectricity in V- and Cr-doped ZnO is center positions and form permanent electric dipoles, which
particularly intriguing in light of recent reports of FM in these results in spontaneous polarization. Four ZnO-based systems have
systems, suggesting the possibility of engineering a multiferroic been found to exhibit ferroelectricity so far: Li:ZnO, Mg:ZnO,
material with simultaneous FM and ferroelectricity. Fig. 34a V:ZnO, and Cr:ZnO. The ionic radius of Li+, Mg2+, V5+, and Cr3+ is 0.6,
displays a typical magnetic hysteresis loop (M versus H) for a 0.65, 0.54, and 0.63 A, respectively, which are all smaller than that
Zn0.985V0.015O lm measured at 300 K. The sample exhibits weak of Zn2+ (0.74 A) [286,287,289,295]. Some researchers have
FM and saturation magnetization of 0.13 mB/V. A coercive eld of suggested that a change in electronic conguration could also
8 mT can be observed on the expanded scale of the hysteresis be a possible reason for this novel ferroelectricity [286,295]. For
loop. Fig. 34b shows the temperature dependence of the eld- instance, the replacement of Zn2+ (1s2 2s2 2p6 3s2 3p6 3d10) by V5+
cooled (FC) and zero-eld-cooled (ZFC) magnetization for the (1s2 2s2 2p6 3s2 3p6) with no 3d electrons likely affects the 3d2p
Zn0.985V0.015O lm. The data were taken in a magnetic eld of 1500 hybridization between Zn and O in V-doped ZnO systems, which
Oe applied parallel to the lm surface. The inset shows the could change the Zn(V)O bond length and induce local dipole
magnetization difference between FC and ZFC data as a function of moments. However, both models are still assumptions and
temperature, i.e., DM(T) = MFC(T)  MZFC(T). The DMT curve convincing evidence is required for conrmation.
exhibits a decreasing trend overall, but the DM value is still XANES provides advantageous local and chemical information
reasonably positive near RT. Other mechanisms such as spin glass and is sensitive to subtle differences in local arrangement, which
effects and superparamagnetic clusters could also present hyster- can yield a better understanding of ferroelectric behavior. There-
esis, but they would exhibit a value of DM = 0 below 100 K [292]. fore, XANES was recently used to characterize ferroelectric V-
Therefore, the hysteresis arises from intrinsic FM of insulating V- doped ZnO systems [286]. Qualitative analysis of XANES V K-edge
doped ZnO, which is a special multiferroic. Multiferroics that show spectra revealed that V substitutes replacing Zn are in the 5+ state.
F. Pan et al. / Materials Science and Engineering R 62 (2008) 135 31

proposed for a V-doped ZnO system [288]. Since the dominant

effect of the electric eld in wurtzite semiconductors is to rotate
bonds that are non-collinear with the polar c-axis, i.e., Zn2O1
bonds [287], towards the direction of the applied eld, thus
producing piezoelectric strain, the electromechanical response in
wurtzite materials should be mainly governed by the ease of bond
bending [296]. In V-doped ZnO lms, since V5+ ions have a higher
positive charge than Zn2+ ions, the non-collinear VO1 bonds ought
to have a stronger polarity than Zn2O1 bonds and hence can rotate
more easily in an applied eld. On the other hand, (2 at.%) Cu-, Ni-,
Co- and Fe-doped ZnO lms have much smaller d33 values of 13.5,
9.8, 10.7 and 5.8 pC/N, respectively, which may be primarily
because the radii of Cu2+ (0.72 A) and Ni2+ (0.72 A) are almost equal
to that of Zn2+ (0.74 A), whereas those of Co2+ (0.79 A) and Fe2+
(0.76 A) are greater than that of Zn2+ [297,298], different from the
scenario for Li+, Mg2+, V5+, and Cr3+ ions.
V- and Cr-doped ZnO show simultaneous FM and ferroelec-
tricity, and are thus promising multiferroic materials. TM-doped
ZnO is also considered as a promising optical material that could be
extensively used for transparent electrodes/devices and the
window of solar cells. Some optoelectronic applications of ZnO
overlap with those of GaN, which is now widely used for LEDs.
However, ZnO has some advantages over GaN: the large exciton
binding energy (60 meV) of ZnO could lead to lasing action based
on exciton recombination, even above RT, which is widely used for
production of green, blue-UV, and white LEDs, as discussed in
numerous reviews and reports [21,22,299,300,301]. It is worth
pointing out that ZnO has much simpler crystal-growth technol-
Fig. 36. Experimental and MS calculated V K-edge XANES spectra for V:ZnO lms. ogy, resulting in potential lower costs for ZnO-based devices. The
transmittance is usually greater than 80% for TM-doped ZnO in the
visible region [48,109,129], indicating that these materials are
To verify the assumption that V5+ ions are off-center, V K-edge suitable for transparent spintronics applications with integrated
XANES spectra were calculated via the full MS ab initio method. It TM-doped ZnO layers [88,89,302,303]. Thus, ZnO could be used as
was found that three main features (peaks A, B and C) match the materials with multi-functions, including FM, ferroelectric, piezo-
experimental curve to a certain extent by simply replacing the electric, optical, and electric features, which could play important
central Zn by V in a designed V-doped ZnO cluster (Fig. 36). roles in spintronics applications of TM-doped ZnO.
However, the relative height of peaks B and C differ, and there is a
much lower pre-edge peak compared to the experimental 6. Conclusions and outlook
spectrum. Constriction of local VO4 units (C) and displacement
of V5+ ions from the cell center (D) were then introduced as In conclusion, we have presented a comprehensive review of
parameters in the calculation. Introduction of VO4 constriction the preparation parameters that affect the local TM structure and
improved the t to the experimental curve. When V5+ displace- magnetization of TM-doped ZnO-based spintronics prototypes.
ment was also considered, the closest t was obtained. This ZnO lms have been the subject of varying degrees of research
accurate replication of the characteristics of the experimental effort over recent decades. This effort has recently been intensied
spectrum implies that V5+ displacement likely occurs and is for the preparation and elucidation of TM-doped ZnO DMOs with
responsible for ferroelectricity in the V:ZnO system. Thus the RTFM and the development of spin-polarized injection, transport
XANES calculations provided a direct evidence for the size- and detection experiments on TM-doped ZnO-based heterostruc-
mismatch model and claried the ferroelectric origin in V:ZnO tures for spintronics applications. Although it is clear that TM-
system. doped ZnO systems exhibit RTFM, there are still many open
For ferroelectrics with a centrosymmetric paraelectric phase, questions regarding its origin and use in spintronics. By extracting
d33 can be expressed as follows: a single variable from a series of experiments, carriers and defects
can be separated and direct relationships between FM and the
d33 2Q eff e0 er Ps ; (5) presence of structural defects can be identied. It has been
unambiguously demonstrated that structural defects are respon-
where Qeff is the effective electrostriction coefcient, and e0 and er sible for RTFM in TM-doped ZnO, whereas carriers involved in
are the permittivity of free space and relative permittivity, carrier-mediated exchange are natural by-products of the creation
respectively. Eq. (5) indicates that the piezoresponse in ferro- of defects in ZnO. In contrast, an increase in electron density
electrics is directly dependent on Ps via a factor linking the decreases the acceptor concentration, thus quenching FM
electrostrictive characteristics and the dielectric constants. On the exchange. We have described recent signicant advances in TM-
other hand, this type of dependence also exists in ferroelectrics doped ZnO-based prototype spintronics, in which TM-doped ZnO-
with a non-centrosymmetric paraelectric phase [288]. Therefore, based MTJ structures provide a compass for the spin injection from
the giant d33 in V- and Cr-doped ZnO was attributed to the (Zn,Co)O to ZnO at RT and shows a large half voltage (>4 V). In
emergence of switchable Ps. Moreover, the relatively high er in V- addition, second generation spintronics integrating TM-doped ZnO
and Cr-doped ZnO lms induced by switchable Ps may also lms with promising ferromagnetic, ferroelectric, piezoelectric
contribute to the high d33. A microscopic explanation was also and optical properties tend to fabricate new exible devices with
32 F. Pan et al. / Materials Science and Engineering R 62 (2008) 135

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supported by the National Natural Science Foundation of China [44] C. Song, K.W. Geng, F. Zeng, X.B. Wang, Y.X. Shen, F. Pan, Y.N. Xie, T. Liu, H.T. Zhou,
(Grant nos. 50772055 and 50325105), the Ministry of Science and Z. Fan, Phys. Rev. B 73 (2006) 024405.
Technology of China (Grant no. 2006CB605201-1) and a National [45] A. Dinia, G. Schmerber, V. Pierron-Bohnes, C. Meny, P. Panissod, E. Beaurepaire, J.
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