Cryst. Res. Technol. 44, No. 2, 153 – 158 (2009) / DOI 10.1002/crat.200800271
© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Synthesis and characterization of nano ZnS doped with Mn
P. Vinotha Boorana Lakshmi, K. Sakthi Raj, and K. Ramachandran*
School of Physics, Madurai Kamaraj University, Madurai, Tamil Nadu-625021, India
Received 3 April 2008, revised 29 May 2008, accepted 24 July 2008
Published online 25 August 2008
Key words diluted magnetic semiconductors, X-ray diffraction, EPR, ferromagnetism.
PACS 61.46.+w, 61.10.-I, 76.30.-v, 76.50.+g
Nanocrystalline samples of Zn
1-x
Mn
x
S (x = 0.0, 0.02, 0.04) were synthesized by chemical precipitation
method and characterized for magnetism. EPR studies showed an evidence of ferromagnetism around room
temperature. Hysterisis from vibrating sample magnetometer supports the observation.
© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1 Introduction
Zinc sulphide (ZnS), a II-VI semiconductor with a direct band gap of 3.6eV at room temperature and 40meV as
exciton binding energy, is a very good luminescence material used in displays, sensors and lasers apart from
applications in photocatalysis [1,2]. Nanodimensional ZnS is found to exhibit excellent optical and
optoelectronic properties which differ greatly from the bulk ZnS [3-5]. ZnS doped with Mn is also an equally
important electroluminescent material. Bhargava et al. [6] first reported luminescence properties of Mn-doped
ZnS nanocrystals prepared by a chemical process at room temperature, which initiated investigation on this
topic [7-9]. However, when magnetic Mn
2+
ions are introduced into nanoparticles of nonmagnetic ZnS
semiconductor, then interesting magnetic and magneto-optical properties are imminent.
Wang et al. [10] observed spin-glass behaviour at T
c
= 15 K in Zn
1-x
Mn
x
S at a high concentration x = 0.32
but a paramagnetic behaviour at a low concentration x = 0.16. Heidrich [11] concluded that there is an
antiferromagnetic coupling at the Neel temperature of T
N
=152 K ,whereas Tsujii et al. [12] found no
antiferromagnetic behaviour in ZnS:Mn systems. Yuan et al. [13] reported paramagnetic behaviour in ZnS:Mn
nanosystems prepared by co-precipitation method. Apart from these, there is not much work on ZnS:Mn,
particularly, on magnetic properties and most of the papers are focused on the efficient luminescent properties.
Even the reported magnetic works on ferromagnetism are in the cryogenic temperature. After the work of Dietl
et al. [14] attention is towards finding new spintronic materials exhibiting room temperature ferromagnetism.
Keeping this mind, the present work on ZnS:Mn nanosystem was carried out.
2 Synthesis
Although various methods are available for the synthesis of nano ZnS, chemical precipitation is widely being
used for the preparation of colloidal nanoparticles as the possibility of cluster formation is very less in this
method when compared to the other methods. Here, 0.5126 M ZnSO
4
solution and 0.069 M Na
2
S solution were
prepared in deionized water and were first refluxed for an hour separately. 6 ml Na
2
S solution was then added
to the 50 ml ZnSO
4
, which was continuously refluxed to get a colloidal form of ZnS. The colloidal sample was
refluxed for another 20 min at 80°C for uniform distribution of the particles. Then this was filtered out and
washed with distilled water and ethanol for removing the additional impurities formed during the preparation
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* Corresponding author: e-mail: : thirumalchandran@yahoo.com