J O U R N A L O F M AT E R I A L S S C I E N C E : M AT E R I A L S I N E L E C T RO N I C S 1 0 ( 1 9 9 9 ) 6 3 ± 6 6

Temperature and frequency dependent electrical

transport in thiourea and tris (thiourea)
copper (l) sulphate
B. A. EL-SAYED
Chemistry Department, Faculty of Science, Al-Azhar University, Nasr City, Cairo, Egypt
M. M. SALLAM
Physics Department, Faculty of Science, Ain Shams University, Cairo, Egypt

The d.c. conductivity of thiourea and tris (thiourea) copper sulphate have been measured as a
function of temperature, including their phase transition temperatures. The thermal
activation energy values obtained showed that the two compounds behaved as
semiconducting materials. The mechanism of the conductivity was interpreted in the light of
their molecular spectroscopic data in the infrared, ultraviolet and visible regions. The
semiconducting properties of the ligand (TU) arise as a result of electron-delocalization via p-
bond formation …C55NH, C55NH‡ 2 †, the hydrogen transfer and the highly polar resonance
hybride structural formation, and are altered by the copper ion in copper (TU) complex.
The a.c. conductivity was measured at room temperature.
# 1999 Kluwer Academic Publishers

1. Introduction sulphate solution has been added. The solid complex, as

Study of the relationship between electrical conductivity
and chemical structure of organic semiconductors and
their transition metal complexes with d-block elements
has gained more importance recently [1±8]. In the
present work, the electrical conductivity as a function
of temperature, dielectric constants at room temperature,
infrared, ultraviolet and visible spectra were studied to
clarify the role of copper ions in the semiconducting
properties of thiourea, which have already been reported
[9]. Thiourea is considered of interest as a simple
derivative of urea and crystallizes in the rhombic
bipyramidal division of the rhombic system [10]. Like
urea, it shows the capability for chelation with a variety
of transition metals [11±14]. Tris (thiourea) copper (I)
sulphate crystallizes in the tetragonal system. The crystal
structure was determined using full three-dimensional X-
ray data. The structure is ionic, with sulphate ions and
‡
in®nite spiral chains of ‰Cu…thiourea†3 Š of the usual
tetrahedral con®guration for monovalent copper by
sharing one of the three sulfur atoms of the thiourea
ligands [12].
2. Experimental
The chemicals used in this study, thiourea and copper
(II) sulphate pentahydrate, were of analar grade
(BDH). Tris (thiourea) copper (I) sulphate
‰Cu…S55C…NH2 †2 †3 Š2 SO4 2H2 O was prepared by: slowly
adding 2.5 g (0.67 mole) of copper (II) sulphate
pentahydrate in 15 ml of distilled water to 2.5 g
(0.33 mole) of thiourea dissolved in 100 ml distilled,
water with continuing stirring, until all the copper (II)
0957±4530 # 1999 Kluwer Academic Publishers
white crystals, was ®ltered off, and recrystallized by
dissolving it in a solution of thiourea (0.15 g) in 30 ml of
water containing a few drops of 1 M sulphuric acid [15].
Chemical analysis of the samples was carried out on
Perkin Elmer 2400 CHN elemental analyser before the
electrical data were collected. Anal. calcd. for thiourea:
C, 15.79; H, 5.26; found: C, 15.42; H, 5.35 and anal.
calcd. for ‰Cu…TU†3 Š2 SO4 :2H2 O: C, 10.07; H, 3.35;
found: C, 9.11; H, 3.72. Infrared (IR) spectra were
recorded at 28 + 0.1  C with a Unicam Analytical
systems, Mattson 1000 series FTIR spectrometer, as
KBr-mixed discs. Ultraviolet and visible absorption
spectra were recorded on a Unicam UV/Vis spectro-
meter, as KBr discs. The d.c. conductivity of the samples
was measured at a constant d.c. voltage using the
potential probe method [16]. The sample temperature
was measured using a calibrated nickel-chrome thermo-
couple in the range 295±440 K. The electrical
conductivity …s† was measured for the solids as
compressed discs at % 4 tons cm ÿ 2, diameter 13 mm
and thickness % 1.5 mm. The two surfaces were
polished, coated with silver paste (BDH, UK) and
checked for good contact several times at elevated
temperatures without any effect on the stability of the
silver contacts. The a.c. electrical conductivity was
measured using the four-probe technique [17]. The a.c.
conductivity …sa:c: † and the dielectric constant …e0 † in the
frequency range 1±200 kHz at room temperature were
measured, for the solids as compressed discs
at % 4 tons cm ÿ 2, diameter 13 mm. and thick-
ness % 1.5 mm, where air-dried silver paste electrical
contacts were deposited on the ¯at surfaces of the discs
63
using a Chen Hwa 1061 LCZ meter. The uncertainty in
the measured capacity was ‡ 0.006 pF, and in con-
ductivity was + 0.5%.

3. Results and discussion

A study of the current±voltage dependence of thiourea
(TU) and its copper solid complex at room temperature,
Fig. 1, shows that the dark current id and voltage are
connected via a linear relation, in agreement with Ohm's
law. The electrical conductivities of thiourea and its
copper solid complex at applied voltages of 5, 20 and
70 V, and their thermal activation energies are collected
in Table I. The electrical conductivities of the
compounds investigated lie in the range typical of
semiconductor materials [18]. The relationship between
lns and 1/T, of the compounds under investigation Figs 2
and 3 obeyed the following equation:
s ˆ so exp…ÿ E=kT†
where so is a constant, E is the activation energy and k is
the Boltzmann constant. As expected, the total con-
Figure 2 The relation between ln s and reciprocal of the absolute
ductivity of a semiconductor results from both intrinsic temperature 1/T for thiourea (TU) at: 5 V (y), 20 V (), and 70 V ().
and extrinsic conduction, following [19]:
s ˆ so exp…ÿ DE=2kT† ‡ so…ex† exp…ÿ DE…ex† =2kT†
Therefore, the relations of ln s versus 1/T for the samples
investigated yielded different straight lines which depend
on DE and DE…ex† …DED or DEA 5DE† where DE is the
forbidden gap width, DEA : acceptor/valence band
separation and DED : donor/conduction band separation.
The data obtained show that the electrical conductivity
values of the copper solid complex over the temperature
range studied at applied voltages of 5, 20 and 70 V are
lower than those associated with the ligand (TU) itself.

Figure 3 The relation between ln s and reciprocal of the absolute

temperature 1/T for the copper solid complex at: 5 V (y), 20 V (), and
70 V ().

This may be due to the effect of copper ions …Cu2‡ † on

Figure 1 Current±voltage characteristics of thiourea (TU) () and its
copper solid complex () at room temperature.
64
the mechanism of conduction of the ligand (TU), by
decreasing the release of electrons on the nitrogen atoms
of the canonical forms II, III and IV Fig. 4 of the co-
ordinated thiourea molecules via metal sulfur bonding. In
addition, the increase in the number of delocalized
electrons due to p-bond formation …C55NH, C55NH‡ 2†
and the hydrogen transfer during the like enol formation I
Fig. 4 are expected to participate in the conduction
processes of the ligand (TU) to some extent more than
the complex.
T A B L E I Values of the electrical conductivity s and the thermal activation energy of thiourea (TU) and its copper solid complex

a a
Compound Applied TCI TCII EbI EbII EbIII sI sII
voltage (K) (K) (low) (high) at 303 K at 423 K
(V) (eV) (eV) (eV) (O ÿ 1 cm ÿ 1) (O ÿ 1 cm ÿ 1)

TU 5 330.0 392.2 0.6155 0.4788 0.1436 6:2302610710 3:198061079

20 357.8 408.2 0.9579 0.7181 0.4266 9:6954610710 3:370861076
70 348.4 Ð 0.7834 0.1959 Ð 7:53461079 7:115461076
Cu(TU)-complex 5 348.4 Ð 0.3977 0.0230 Ð 5:361610710 4:040161079
20 334.4 400.0 0.4924 0.2736 0.0862 5:2505610710 3:829661079
70 340.1 392.2 0.4924 0.3830 0.0718 5:2478610710 3:767061079

a
TC is the transition temperature
b
EI ; EII and EIII are the activation energies for the low, medium and high temperature ranges, respectively.

Infrared absorption measurements give conspicuous
evidence for the complex formation via metal-sulfur
bonding. The assignment of the IR absorption bands
observed for the ligand and its copper solid complex, Fig.
5a and b, showed that the particular vibrations noted
indicate the presence of sulfur-to-metal bonds in the
copper (TU) complex, therefore, the band of thiourea
observed at 1086 cm ÿ 1 is shifted to 1113 cm ÿ 1 on
complex formation due to the considerable change in the
nature of the N2 2C bond and the C55S bond on co-
ordination of thiourea through the sulfur atom; so the
N22C22N stretching frequency is increased and the C55S
stretching frequency is decreased. On the other hand, the
absorption band observed at about 716 cm ÿ 1 in the
spectra of the metal-thiourea complex corresponds to the
732 cm ÿ 1 band of thiourea. The shift of the band to
lower frequency can be interpreted as the weakening of
the double bond character of the C55S bond. The
Figure 4 Resonance structures of thiourea (TU).
Figure 5 Infrared spectra of (a) thiourea (TU) and (b) the copper solid
complex.
formation of the S?M bonds is expected to increase the
contribution of the highly polar structure III, IV Fig. 4 to
the thiourea molecules, resulting in a greater double bond
character for the nitrogen-to-carbon bond …C5 5NH‡ 2 † and
a greater single bond character for the carbon-to-sulfur
bond. This is considered as another reason for decreasing
thep-electron delocalization sharing in the conduction
process of the co-ordinated thiourea of the complex. The
mechanism of conduction processes in the compounds
investigated was explained in the light of their electronic
absorption spectra. The data obtained showed one peak at
285 nm, corresponding to the energy gap Ea (4.4 eV) in
thiourea, and two peaks at 311 nm and 375 nm
corresponding to Ea ; 4.02 eV and 3.3 eV, respectively,
in the complex. They do, in fact, belong to different
electronic transitions corresponding to both pp (short
wavelengths) and np (long wavelengths) bands, respec-
tively. The band observed in TU at 285 nm can be
explained due to mixed pp and np states, formed by
transition of one electron in a bonding pMO to
antibonding p orbitals and by transition of a non-
bonding n electron from N and/or S atoms to antibonding
p orbitals. It is suggested that when the ligand and its
copper complex are excited by temperature (and higher
excited states are neglected), six different excited states
may appear: 1 …pp †, 3 …pp †, 1 …n; p †, 3 …n; p †, 1 …CT†,
3
…CT†, associated with different relative energy of these
states. This was revealed from the different values of the
activation energies associated with both TU and its
copper complex, and clearly the effect of the conse-
quence of the thermally activated triplet-singlet
transition and the possibility of the triplet states acting
as traps, and the role of the triplet states in the mechanism
of electronic conductance and their important in
connection with the dark conductance. The values of
sa:c: … f † as a function of frequency at room temperature
(300 K) for the samples are plotted in Fig. 6. The
frequency dependence of the conductivity shows that the
conductivity increases with increasing frequency in the
two compounds investigated, so the hopping process was
suggested as appropriate for the conduction mechanism
[20]. Also, the a.c. conductivity follows the power law
[21], sa:c: … f † ˆ Af s , where f is the frequency, A and S are
constants. The a.c. conductivity is proportional to f 0:76 in
TU and f 0:79 in the copper (TU) complex. The frequency
dependence of the dielectric constante0 Fig. 7 shows that
the dielectric constants at room temperature for both TU
and its copper solid complex decrease with increase in
the applied frequency. The loss factor …tan d† values
65
Figure 6 The relation between ln sa:c: and ln f for thiourea (TU) () and Figure 8 The relation between the loss factor tan d and ln f for thiourea
its copper solid complex () at room temperature. (TU) () and its copper solid complex () at room temperature.

References
1. B . A . E L - S AY E D , M . M . S A L L A M , M . F. I S H A K and M . S .
A N TO N I O U S , accepted for Mater. Lett. (1997).
2. B . A . E L - S AY E D , S . M . S H A A B A N , A . M . H A S S A N and A . A .
S H A B A N A , Mater. Lett. 27 (1996) 65.
3. B . A . E L - S AY E D , S . M . A B D E L - WA H A B , A . M . I B R A H I M and
K . A . D A R W I S H , J. Mater. Sci. Lett. 15 (1996) 561.
4. B . A . E L - S AY E D , M . M . S A L L A M , S . M . S H A A B A N and A . A .
A . E M A R A , ibid. 15 (1996) 883.
5. B . A . E L - S AY E D , A . A . A . E M A R A , F. S . M . A B D E L -
H A M E E D and S . M . S H A A B A N , Mater. Lett. 27 (1996) 247.
6. B . A . E L - S AY E D , M . M . E L - D E S O K Y , S . M . S H A A B A N and
M . B . S AY E D , J. Mater. Sci.: Mater. Electron. 3 (1992) 124.
7. D . C . B O T T, in ``Handbook of conducting polymers'', Vol. 2,
edital by T. A. Skotheim (Marcel Dekker, New York and Basel,
1986) Ch. 33, p. 1191.
8. R . A . W E S T, in ``Solid State Chemistry and its Applications''
(John Wiley, New York, 1984), p. 498.
9. S . M . S H A A B A N , B . A . E L - S AY E D , A . A . S H A B A N A and
A . M . H A S S A N , Mater. Lett. 21 (1994) 255.
10. S . B . H E N D R I C K S , J. Am. Chem. Soc. 50 (1928) 2455.
11. D . M . A D A M S and J . B . C O R N E L L , J. Chem. Soc. A (1967) 884.
12. C . B . K N O B L E R , Y. O K AYA and R . P E P I N S K Y, Z. Kristallogr.
111 385.
Figure 7 The relation between the dielectric constant e0 and ln f for 13. R . A . B A I L E Y and T. R . P E T E R S O N , Can. J. Chem. 45 (1967)
thiourea (Tu) () and its copper solid complex () at room temperature. 1135.
14. K . S WA M I N AT H A N and H . M . N . H . I R V I N G , J. Inorg. Nucl.
associated with both TU and copper (TU) complex as a Chem. 29 (1964) 1291.
function of frequency are shown in Fig. 8. It is observed 15. G . P A S S and H . S U T C L I F F E , in ``Practical inorganic
chemistry'', 2nd Edn, (Chapman and Hall 1988) p. 78.
that the tan d exhibits a strong frequency dependence and 16. M . A . A H M E D and F. A . R A D WA N , J. Phys. Chem. Solids 49
is less pronounced at high frequency for TU. On the other (1988) 1385.
hand, tan d does not exhibit a frequency dependence in 17. S . W E M M E R , in ``Method of Measuring Earth Resistivity,
the case of the copper (TU) complex. Bulletin of the Bureau of Standards'', Vol. 12 (1916) p. 478.
In conclusion, one can safely say that the copper ions 18. R . H . B U B E , in ``Photoelectronic properties of semiconductors''
(Cambridge University Press, 1992).
retard the conduction processes of thiourea molecules in 19. M . H A N S , in ``Organic Semiconductors'', edited by H. F. Ebel
the complex by obstructing the release of the electrons on (Verlag Chemie, Weinheim, 1974), p. 50.
the nitrogen atoms of the co-ordinated thiourea mole- 20. W. B R E N I G , G . H . D O È H L E R and H . H E Y S Z E N A U , Phys. Lett.
cules and the hydrogen transfer during enol formation. A. 39 (1972) 175.
Measurements of the dielectric constants of these 21. S . R . E L L I O T T, Adv. Phys. 36 (1987) 135.

compounds as a function of temperature are now under

further investigation, and more details will be discussed Received 20 January 1998
in a separate publication. and accepted 8 October 1998

66