Materials Letters 61 (2007) 3605 – 3607

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Room-temperature ferromagnetism in Fe-doped, Fe- and Cu-codoped ZnO

diluted magnetic semiconductor
Hua-Wei Zhang a,b , Zhi-Ren Wei c,⁎, Zhi-Qiang Li c , Guo-Yi Dong c
a
Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
b
Graduate School of the Chinese Academy of Sciences, Beijing 100049, China
c
College of Physics Science and Technology, Hebei University, Baoding 071002, China
Received 14 July 2006; accepted 24 November 2006
Available online 20 December 2006

Abstract

Magnetic properties of Zn0.975Fe0.025O and Zn0.97Fe0.025Cu0.005O crystallites fabricated by hydrothermal method are investigated. X-ray
diffraction and Raman measurements indicate that the samples have pure ZnO wurtzite structure and Fe2+ ions have substituted Zn2+ sites.
Magnetic measurements indicate that Fe doping can induce room-temperature ferromagnetism, while codoping with Cu might enhance the
magnetic moment but reduce the Curie temperature in ZnO.
© 2006 Elsevier B.V. All rights reserved.

PACS: 75.50.Pp
Keywords: Ferromagnetism; Fe-doped ZnO; Diluted magnetic semiconductor; Hydrothermal method

1. Introduction
In the field of spintronics [1], diluted magnetic semiconduc-
tors (DMSs) are under intense investigation. DMSs are
“conventional” semiconductors doped with transition metal or
rare-earth ions which are diluted within the host matrix and
ferromagnetically aligned via an indirect magnetic coupling [2–
7]. The existence of DMSs based on Mn doped p-type ZnO has
been predicted by theory [2]. However, the origin of the
ferromagnetic order in ZnO:Mn system is quite debated [8,9].
Furthermore, currently only n-type conducting ZnO films or
single crystals are available. Ab initio calculations exhibit that
the ferromagnetic state is stable in n-type ZnO-based DMS for
Fe-, Co- and Ni-doped system [7]. Subsequently, room-
temperature ferromagnetism was observed in (110) oriented
ZnO films made from targets containing 5 at.% of Sc, Ti, V, Fe,
Co, or Ni [10]. Polyakov et al. found room-temperature
ferromagnetism by implanting Fe ions in ZnO crystal grown
by vapor phase [11]. Potzger et al. also obtained room-
temperature ferromagnetism by implanting Fe ions in hydro-
⁎ Corresponding author. Tel./fax: +86 312 5079423.
E-mail address: weizhiren-1@163.com (Z.-R. Wei).
0167-577X/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2006.11.139
thermal ZnO single crystals [12]. While Shim et al. reported the
ferromagnetic behaviors for the Fe-doped ZnO:Cu, but
ferromagnetism was attributed to secondary phase [13]. Mandal
reported magnetic glassy phase in Zn0.85Fe0.15O nanoparticles
[14].
In this contribution, we report the room-temperature
ferromagnetism of the Zn0.975Fe0.025O (ZFO) and Zn0.97Fe0.025-
Cu0.005O (ZFCO) crystallites grown by hydrothermal method.
The Cu doping can affect the magnetic properties of ZFO both
on magnetic moment and Curie temperature.
2. Experimental
ZFO and ZFCO crystallites were synthesized by a hydro-
thermal technique. Platinum lined stainless steel autoclave was
used. Compared to other chemical methods, hydrothermal
reaction proceeds in high temperature and pressure which
provide sufficient thermal energy to incorporate Fe2+ ions into
ZnO lattice. The raw material ZnO (99.99%), FeSO4·7H2O
(99.99%) and CuCl2·2H2O (99.99%) in appropriate molar ratios
were dissolved in 10 mL KOH solution. The solution was
transferred into the autoclave, and then hydrothermally treated
at 703 K for 24 h. The estimate of the reaction pressure in the
3606 H.-W. Zhang et al. / Materials Letters 61 (2007) 3605–3607
Fig. 1. Intensity of XRD vs 2θ, from the Zn0.975Fe0.025O (ZFO) and
Zn0.97Fe0.025Cu0.005O (ZFCO) crystallites. All the peaks belong to the
hexagonal structure of ZnO. The inset shows the SEM image of ZFO.
autoclave is 40 MPa. After hydrothermal treatment, the
precipitate was filtered, washed with distilled water and dried
at 353 K. The structure of the products was investigated by
XRD (Rigaku D/MAX-2200). Scanning electron microscopy
(SEM, EPMA-8705QH2) was used for microstructural analysis.
Micro-Raman scattering experiments were done with a
Renishaw micro-Raman spectroscopy system. The magnetic
properties were measured by magnetic property measurement
system (MPMS, XL-7) from Quantum Design and a vibrating
sample magnetometer (VSM, Lakeshore 7404).
3. Results and discussion
All the crystallites of Zn0.975Fe0.025O (ZFO) and Zn0.97Fe0.025-
Cu0.005O (ZFCO) are in French grey color. Fig. 1 shows the XRD
pattern of ZFO and ZFCO crystallites. All the peaks of XRD pattern
belong to the hexagonal lattice of ZnO, and no trace of secondary phase
Fig. 2. Room-temperature micro-Raman spectra of the ZFO and ZFCO, in
contrast with pure ZnO crystallites. The 514.5 nm Ar+ laser is used as an
excitation source.
Fig. 3. Magnetic moment as a function of external field (M–H) at T = 5 K for
ZFO and ZFCO. The vertical scale (magnetic moment/Fe2+) was converted from
measured values, assuming homogeneous magnetic states.
is found. A peak shift related to lattice spacing changes is clearly
observed when the concentration of Fe was varied (not shown), which
indicates that doped Fe atoms substitute for Zn atoms. The inset of Fig.
1 shows a typical SEM photo of the as-grown ZFO crystallites. The
crystallite size is about 1 μm.
Typical room-temperature Raman spectra of the as-prepared
products are performed and confirmed that Fe2+ ions are incorporated
into ZnO lattice as shown in Fig. 2. The peaks at 97, 201, 330, 379 and
437 cm− 1 are assigned to Elow TO
2 , 2-TA(M), 2-LA(M), A1 and E2
high
of
the ZnO lattice vibrations, respectively. Two vibration modes at 538
and 580 cm− 1 are LO modes with A1 symmetry. The 658 cm− 1
vibration is an intrinsic mode of ZnO and related to oxygen vacancies,
zinc interstitials, antisite oxygen, etc. Compared with the vibration
modes of ZnO crystallites, additional vibration modes are observed
at 513 (515), 559 (559), 621 (618), 642 (645) cm− 1 in ZFC (ZFCO)
crystallites. Bundesmann et al. observed some additional vibration
modes at 513, 624, 644 cm− 1 in Fe-doped ZnO films and proposed that
they were related to a single dopant and might be used as indicators to
identify incorporation [15]. The additional vibration modes are
associated with Fe dopant, because they do not appear in pure ZnO
Fig. 4. Room-temperature M–H curves of ZFO and ZFCO. The vertical scale
(magnetic moment/Fe2+) was converted from measured values, assuming
homogeneous magnetic states.
 H.-W. Zhang et al. / Materials Letters 61 (2007) 3605–3607
Fig. 5. Magnetization vs. temperature at 1000 Gs for ZFO and ZFCO crystallites
fabricated under hydrothermal condition.
−1
or in experiment. Furthermore, the modes of E2 (low) (99 cm ), 2E2
(M) (331 cm− 1) and E2 (high) (437 cm− 1) in ZnO shift to a lower
wavenumber in ZFO and ZFCO. Due to larger Fe2+ ionic radius, when
Fe2+ ions occupy the Zn2+ sites, lattice constant is changed and some
new lattice defects are introduced or intrinsic host-lattice defects
become activated.
Fig. 3 shows magnetic hysteresis (M–H) curves of ZFO and ZFCO
crystallites measured at 5 K. There is an apparent ferromagnetic
hysteresis loop in ZFO and ZFCO. Very high coercive field (4.0 kOe
for ZFO and 4.5 kOe for ZFCO) is observed, which is about one order
of magnitude much higher than that of Fe implanted ferromagnetic
ZnO crystal [11]. The saturation magnetization (Ms) is 1.8 μB/Fe2+ and
2.7 μB/Fe2+ for ZFO and ZFCO, respectively. When the measurement
temperature is increased to 300 K, the hysteresis is still evident as
shown in Fig. 4. As can be seen, the Ms and coercive field of ZFCO are
larger than those of ZFO.
The magnetization of ZFCO and ZFO as a function of temperature
is shown in Fig. 5. The magnetization of ZFO clearly shows that a
transition to a paramagnetic state occurs near 470 K. The transition
temperature of ZFCO is 320 K and the magnetization increases sharply
below Curie temperature (TC). Both of their TC are high enough for the
purpose of device applications at room temperature.
4. Conclusion
In conclusion, the room-temperature ferromagnetism is
obtained in both ZFO and ZFCO crystallites prepared by
3607
hydrothermal method. The Cu doping changes the magnetiza-
tion and TC of Fe-doped ZnO crystallites because Cu ions
introduce relatively deep donor levels in the energy gap.
Conduction from deep donors is due to impurity band and/or
hopping conduction, opposed to conventional free electrons
excited to the conduction band. Any carrier-mediated processes
would be dependent on the relevant conduction mechanisms.
Future work will focus on understanding the effect of carrier
density and kind of transition metal on magnetization behavior.
Acknowledgment
This work was financially supported by the National Natural
Science Foundation of China (NSFC, No. 50472037).
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