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Current Applied Physics 8 (2008) 134–137

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The dc and ac properties of potassium trioxalatoferrate (III) trihydrate

A.A. Dakhel
College of Science, University of Bahrain, P.O. Box 32038, Bahrain

Received 3 April 2006; accepted 12 June 2007

Available online 4 July 2007

Abstract

The complex potassium trioxalatoferrate (III) trihydrate {K3(Fe(C2O4)3 Æ 3H2O)} was synthesised and characterised by energy disper-
sion X-ray fluorescence (XRF) and X-ray diffraction (XRD). The electrical and dielectric properties of the complex pellet were studied by
ac- and dc-techniques in room temperature and in a temperature range of 293–373 K. The data of the ac conductivity as a function of
frequency in a frequency range of 1–100 kHz follow the correlated barrier hopping CBH model and the parameters of the model were
determined and connecting them with the optical properties. The temperature dependence of dc conductivity shows that the semicon-
ducting behaviour of conduction phenomenon in the complex is realised by hopping mechanism between localised states and the min-
imum hopping distance was determined. High relative permittivity of about 30 at 100 kHz was obtained for the complex, which can find
technological applications like alternative for the SiO2 insulator in MOS devices.
 2007 Published by Elsevier B.V.

PACS: 77.55.+f; 72.20.I; 78.70.En

Keywords: Insulating materials; Potassium ferric oxalate; K3(Fe(C2O4)3 Æ 3H2O); Dielectric phenomena; CBH model

1. Introduction found in nature as a mineral under name minguzzite [7].

The studies of structural, electrical and optical proper-
ties of charge-transfer (CT) complex salts, based on differ-
ent types of donor–acceptor pairs, have attracted much
attention due to their possible applications in electronic
and optical devices. Their physical properties like conduc-
tivity and optical nonlinearity are strongly dependent on
the nature of the CT interaction [1]. CT complexes are col-
ourised due to their absorption bands in the ultraviolet
region with tails in the visible region [2]. A great variety
of such complexes have now been characterised, with elec-
tronic conductivities spanning the whole range from insula-
tor to semiconductor to organic metal [3–5]. Among the
CT salts is the green photosensitive crystalline potassium
trioxalatoferrate (III) trihydrate {K3(Fe(C2O4)3 Æ 3H2O)}.
This complex has an octahedral geometry and is coordi-
nated with three bi-dentate oxalate (C2O4) ligands [6]. This
complex can be synthesised in the laboratory or can be
E-mail address: adakhil@sci.uob.bh
In the present work, we report on the electrical and dielec-
tric properties of the complex. Reports on such study, to
our knowledge, were not presented yet.
2. Experimental details
The green powder of potassium ferric oxalate (PFO)
{K3(Fe(C2O4)3 Æ 3H2O)} was synthesised by a traditional
well-known procedure discussed in details in Ref. [6] from
the reaction of potassium oxalate hydrate [K2C2O4 Æ H2O]
and ferric chloride [FeCl3].
The samples were prepared in form of cylindrical pellets
of diameter 13 mm and thickness about 2 mm from the
powder submitted to a pressure of 750 MPa for 10 min.
The density of the sample was measured to be 2.0 g/cm3,
which is 0.94 of the known bulk density [7]. Aluminum film
of thickness about 150 nm and area 4p mm2 was vacuum
evaporated on one face of the pellet while the counter face
was totally covered with the Al film. The Fe to Mn compo-
sition of the prepared powder was studied by the energy

1567-1739/$ - see front matter  2007 Published by Elsevier B.V.

doi:10.1016/j.cap.2007.06.003
 A.A. Dakhel / Current Applied Physics 8 (2008) 134–137
dispersion X-ray fluorescence (EDXRF) method. The
exciting Ni-filtered X-ray beam from the Cu anode
(35 kV and 40 mA) was incident on the pellet surface at
15. The fluorescent yield was collected at 90 by using
an Amptek XR-100CR, Si X-ray detector of energy resolu-
tion 180 eV at 5.9 keV. The crystal structure was investi-
gated with a Philips PW 1729 X-ray diffractometer of Cu
Ka radiation. Keithley 3330 LCZ meter with a signal of
50 mV was used for ac-electrical measurements and Keith-
ley 614 electrometer was used for the dc measurements.
The measurements were done in dark inside a tempera-
ture-controlled furnace.
3. Characterisation
Fig. 1 shows the EDXRF spectrum of the prepared PFO
powder. The signals are K Ka of energy 3.31 keV with a
very small shoulder of K Kb of energy 3.59 keV, Fe Ka
of energy 6.40 keV, and Fe Kb of energy 7.06 keV. There
are no other significant signals, taking into the consider-
ation that the instrumental detection limit (IDL) [8] of
the set-up is about 800 ppm at energy 5.84 keV. The weight
fraction ratio (x) of Fe to K in PFO powder was deter-
mined by the known method of micro radiographic analy-
sis [9,10] based on the measurement of the integrated
intensity of Fe Ka line and K Ka line in the reference sam-
ples and in the pellet of PFO powder. The reference sam-
ples were pure Fe and KBr pellets of thickness about
2 mm prepared from pure powders (materials are from
Fluka A.G.) submitted to a pressure of 750 MPa for
10 min. The result of measurements was x = 0.50, which
is almost identical with the theoretical value 0.476 calcu-
lated for pure bulk PFO powder.
Fig. 2 presents the X-ray diffraction (XRD) pattern of
the PFO sample. In accordance with Ref. [7], the polycrys-
talline pattern shows a monoclinic space group P21/c struc-
ture of a = 0.766 nm, b = 1.987 nm, c = 1.027 nm, and
b = 105.1. The average grain size calculated by the Scher-
rer formula [11] from the most intense (2 0 0) peak at
Fig. 1. XRF spectrum of potassium trioxalatoferrate (III) trihydrate
powder. The exciting line was Cu Ka line of energy 8.05 keV.
135
Fig. 2. X-ray diffraction of potassium ferric oxalate disc sample. The
beam was Cu Ka and the scan speed was 0.01/s.
2h = 24.63 was about 45 nm. It was observed that the cal-
cination of the sample at 100 C for 90 min creates a micro-
structural changes in the complex, which can be noticed by
changing the relative intensities of the reflections. Also,
the humidification of the complex maximises the intensity
of the (1 1 0) reflection at 12.7. These observations reflect
the great microstructural variations due to the change in
the structural humidity content in the complex, but without
change its crystalline system.
4. Electrical measurements
The linear current density–dc field (J–E) characteristic
of the pellet in the range of investigation (for fields E <
22.3 kV/cm) indicates the ohmic contact between the pellet
and Al electrode films.
The measured values of relative permittivity (RP) e0p and
electrical conductivity rp of the pellet were corrected
according to the pore fraction factor p = (D  Dp)/D
where Dp and D are the pellet sample density and bulk
PFO material density, respectively. Such correction is nec-
essary to obtain the crystalline value of RP (e 0 ) and conduc-
tivity (r). The correction was done according to the
following equations [12]:
3
e0 ¼ ðe01=3
p  pÞ =ð1  pÞ; ð1Þ
2=3
r ¼ rp f1 þ ½p=1 þ p g: ð2Þ
In the present work p was 0.06 so that the correction was
not so significant (<1%). The measurement gives the cor-
rected resistivity of 2.74 · 106 X cm in dark at room
temperature.
AC conduction: The corrected ac conductivity (rac) of
insulators is usually expressed as a sum of a dc conductivity
(rdc) and a frequency-dependent component (rac(x)) i.e.
rac = rdc + rac(x) [13]. This additive implies that the two
components arise from entirely separate mechanisms. For
the hopping conduction, the component r(x) is typically
expressed by the power law rac(x) = Arxs, where Ar is a
136 A.A. Dakhel / Current Applied Physics 8 (2008) 134–137
frequency independent factor. The appropriate theoretical
model that describes the function rac(x) in the present
work is the correlated barrier hopping (CBH) model, in
which the conductivity rac(x) follows the following relation
[14,15]:
N 2LS n7el
rac ðxÞ ¼ k xs ; ð3Þ
sb0 e5ox W 6M
where k ¼ e6 =24p3 e50 ¼ 0:415  1060 C V5 m5, WM is the
maximum barrier height for hopping in eV, NLS is the trap
concentration, nel is the number of simultaneously hopped
carriers between centres, s0 is the effective relaxation time
(about 1013 s), b = 1  s, and s is given at tempera-
ture T by the following relation: s = 16kBT[WM +
kBT ln(xs0)]1. Usually experiments show that s 6 1
depending on the microstructure of the investigated
insulator.
Fig. 3 shows the room temperature frequency depen-
dence of the corrected ac conductivity rac in the frequency
range of 1–100 kHz. We mention here that, for lower fre-
quencies than 1 kHz a larger influence of the interfacial
charges on the electrical measurements would defect the
results [16]. The analysis shows that the CBH model is con-
venient to explain the experimental data and the fitting
value of s is 0.68, which corresponds to WM  0.9 eV. This
value is almost equal to one quarter the optical absorption
edge, which was measured for the powder PFO to be
3.65 eV and shown in Fig. 4. According to the original
CBH theory [15], the value of WM is equal to the mobility
bandgap for bipolarons hopping and one quarter of the
bandgap for one polaron hopping. Thus, the results in
the present case show that the conductivity at room tem-
perature is realised by hopping between molecules in a sin-
gle polaron process. The minimum (cut-off) hopping jump
(Rmin) [17] was calculated to be 0.22 nm, which is equal to
the effective intermolecular separation. We state here that
Fig. 3. Frequency dependence of the ac conductivity rac(x), the corrected
real part e 0 (x) and the corrected imaginary part e00 (x) of the relative
permittivity of potassium trioxalatoferrate (III) trihydrate pellet at room
temperature.
Fig. 4. The spectral absorbance of the prepared potassium trioxalatofer-
rate (III) trihydrate powder.
Bruetting et al. [18] have mentioned that the average mean
free path in inorganic materials is of order of intermolecu-
lar distance.
The application of the power law gives the value of rdc
(2.6 · 107 S/cm), which is almost identical with that value
measured directly by dc technique.
Finally, the fitting of the experimental data to Eq. (3)
yields the value of density of localised states or hopping
centres (NLS) to be 2.3 · 1021 cm3, which is almost equal
to the concentration of molecules (2.45 · 1021 cm3).
Real and imaginary parts of RP: The real part of the rel-
ative permittivity (RP) e 0 calculated from the capacitance
measurement decreases as the frequency increases, getting
the value 28.6 at 100 kHz, as shown in Fig. 3. This high-
e 0 value suggests the possibility of using the PFO complex
as alternative for Si oxide in manufacturing of MOS
devices for equipments work in a circumstances suitable
to the chemical and physical properties of the complex (like
its high solubility in hot water, melting point of 231 C,
photosensitive and reacts to light of k < 450 nm etc.).
Based on Kramers–Kronig (KK) relations, it was
proved that the power law follow of the ac conductivity
of an insulator leads its RP to comply with a power-depen-
0
dence on the frequency [19]; e 0 (x) / xs 1. As seen from
Fig. 3, this relation is adequate especially for high frequen-
cies with s 0 is equal to 0.47, which is different from the
value of s by about 30%.
The measured imaginary part of RP (e00 ) was corrected
due to the transfer of electrical charges from one electrode
to the other, which is related to dc conductivity (or rdc/
e0x). Therefore e00 can be obtained using the following
equation [12]:
e00 ¼ ðrac  rdc Þ=e0 x; ð4Þ
where rac is the pores-corrected ac conductivity and rdc is
the dc conductivity obtained from the application of power
law [13]. Therefore, e00 in Eq. (4), referred to as the dielectric
 A.A. Dakhel / Current Applied Physics 8 (2008) 134–137
Fig. 5. Arrhenius plot of temperature dependent of dc conductivity of
potassium trioxalatoferrate (III) trihydrate pellet.
loss, is the contribution from dipoles, defects, and localised
or bound charges. The frequency dependence of e00 is de-
picted in Fig. 3, where one can observe a maximum. Such
dependence e00 (x) corresponds to a polarisation resonance
associated with the lattice vibrations. The resonance peak
of e00 (x) at about 5 kHz corresponds to a relaxation time
s of 3.18 · 105 s. It is possible to calculate the molecular
dipole moment p by applying the well-known Debye equa-
tion for e00 [20,21]:
A=T
e00 ¼ xs; ð5Þ
1 þ x2 s2
where T is the temperature in K. The dipole strength A is
given by: A = Np2/3e0kB, where N is the dipole concentra-
tion (2.45 · 1027 m3), kB is the Boltzmann constant, and e0
is the permittivity of free space. The fitting of the e00 (x) data
to Eq. (5) around the peak gives A = 1.2 · 104 K at 293 K
and p = 4.25 · 1029 C m, which has an ordinary order on
magnitude.
Temperature dependence of dc conductivity: The temper-
ature dependence of dc conductivity r(T) and capacitance
was studied in the range of (293–373 K) and the results
are given in Fig. 5. The obtained semiconducting behaviour
of r(T) is usually expressed by a typical Arrhenius type of
activation: r = r0 exp(Er/kT), where Er is the activation
energy. The small-obtained value of the pre-exponential
r0 (3.3 · 106 S/cm) indicates that the conduction is rea-
lised by hopping between localised states and not by the
extended states [22,23]. This result is confirmed by the
applicability of CBH model and by the small value of acti-
vation energy (55.6 meV).
It was also observed that the capacitance was almost
temperature independent in the studied range of
temperatures.
137
5. Conclusion
The ac behaviour of the prepared potassium trioxalato-
ferrate (III) trihydrate {K3(Fe(C2O4)3 Æ 3H2O)} sample
shows that it follows the power law and CBH model for
conduction by a single polaron hopping between localised
states. The concentration of molecules (2.3 · 1021 cm3)
and the effective intermolecular separation (0.22 nm) were
determined from the application of the CBH model. The
obtained high-e value (around 30) at room temperature
suggests that this complex can be used as alternative for
Si oxide in manufacturing of MOS devices. Furthermore,
it was observed that e is almost temperature independent
in the used temperature range. The dielectric properties
of the complex were studies through Debye model, from
which the relaxation time for the dipoles (3.18 · 107 s)
and the dipole moment (4.25 · 1029 C m) were deter-
mined. The study of temperature dependent of dc conduc-
tivity shows that the semiconducting conduction is also
realised by hopping between localised states with activation
energy of about 55.6 meV.
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