* Corresponding author. E-mail: ifs@ifs.ac.

ik
Solar Energy Materials and Solar Cells 55 (1998) 283289
Deposition of thin conducting lms
of CuI on glass
K. Tennakone*, G.R.R.A. Kumara, I.R.M. Kottegoda,
V.P.S. Perera, G.M.L.P. Aponsu, K.G.U. Wijayantha
Institute of Fundamental Studies, Hanthana Road, Kandy, Sri Lanka
Received 21 January 1998
Abstract
A method is described for coating thin optically transparent conducting lms of CuI (p-type
semiconductor of band gap &3.1 eV) on glass. The dependence of the sheet resistance of the
lm on the level of iodine doping and other characteristics of the lm are described. A minimum
sheet resistance 25 /(for a lm of thickness &10 m) was obtained through an optimization
of iodine doping, sintering time and temperature. 1998 Elsevier Science B.V. All rights
reserved.
Keywords: Thin conducting lms; CuI; Glass deposition
1. Introduction
Copper (I) iodide (cuprous Iodide, CuI) is a water insoluble solid with three
crystalline phases , and [14]. The high temperature (above 392C) -phase of
cubic structure is a mixed conductor, where the charge carrier is predominantly Cu>
ions. The hexagonal -phase is also an ionic conductor [1]. The low-temperature
-phase (below 350C) again of cubic structure is a p-type semiconductor of band gap
3.1 eV, whose conductivity depends on the presence of iodine in stoichiometric excess.
Iodine atom acts as an electron acceptor that creates holes in the valence band.
Recently, one of the authors of the present paper (KT) and his collaborators have
used cuprous iodide to construct a fully solid-state dye-sensitized photovoltaic cell
0927-0248/98/$19.00 1998 Elsevier Science B.V. All rights reserved.
PII S 0 9 2 7 - 0 2 4 8 ( 9 8 ) 0 0 1 1 7 - 2
[5]. The utility of this material for the above purpose depends on optical transparency
and hole conductivity of CuI. -CuI is also a convenient material for studying
cathodic dye-sensitization and in earlier reports we have discussed methods of
depositing -CuI on conducting glass by electrolytic methods [6,7]. The present work
describes a technique for deposition of this optically transparent conducting lms of
-CuI on glass.
2. Experimental procedure
Cuprous iodide was prepared by drop-wise addition of potassium iodide (50 ml,
0.5 M) to a solution of copper sulphate (30 ml, 0.5 M) at room temperature (26C) in
the presence of sulphurous acid. Sulphurous acid removes iodine liberated in the
reaction and excess copper sulphate prevents dissolution of CuI in water in the
presence of 1\ ions. The precipitate of CuI is washed with hot water, followed by
acetone and dried in vacuum at &80C for 1 h to remove any remaining iodine.
The solubility of CuI in acetonitrile enabled us to devise the following simple
method for coating thin optically transparent lms of CuI on glass substrate. 0.73 g of
CuI was dissolved in 25 ml of moisture free acetonitrile, a glass plate (Micro slides,
Marienfeld, 2;4 cm, cleaned with NaOH and rinsed with water and propan-2-ol)
was dipped into the solution, immediately withdrawn and dried in a current of hot dry
nitrogen (95C). The lm thickness can be increased by repetition of the process. The
following method was used to estimate the thickness of the CuI lms deposited on
glass plates. CuI coating is extracted into 4 ml of 0.25 M ammonia solution and
aerated to generate the deep blue cupric ammonium ion, the concentration of which
was estimated spectrophotometrically. The thickness of the lm was calculated by
determining number of moles of CuI deposited using the literature value (3.65 g/cm)
for the density of CuI. The sheet resistance of the lm was measured by the two-probe
method using gold-plated copper contacts. The value of the sheet resistance obtained
is found to be largely independent of the size of the square suggesting that the contact
resistance is negligible.
Conductivity of CuI depends on the presence of iodine in stoichiometric excess,
prolonged heating of the lm (7080C) removes iodine from the lm, increasing the
resistance. Iodine can be incorporated into CuI by exposing the lms to iodine
vapour. The level of iodine doping was varied by the following method. The CuI-
coated lm was placed in a chamber containing argon and iodine vapour. From
a knowledge of the partial pressure of iodine, the number of molecules of I

incident
on the plate per unit time is calculated [8]. The number of molecules incident on the
surface per second () is given by "p(2mk)\, where p is the partial pressure of
iodine, m the mass of the iodine molecule and k the Boltzmanns constant. Rate of
absorption of iodine occurs at a constant rate and subsequent diusion causes
uniform doping. Thus, the doping level can be determined from the duration of
exposure of the lm to iodine vapour. Iodine can also be doped by adding known
amounts of iodine to the solution of CuI in acetonitrile. The conductivities corre-
sponding to dierent levels of doping as measured by this method are in agreement
284 K. Tennakone et al. /Solar Energy Materials and Solar Cells 55 (1998) 283289
Fig. 1. X-ray diraction spectrum of -CuI: (a) before sintering; (b) after sintering at 70C.
with the results obtained from vapour-phase deposition technique, for those samples
that are not annealed.
Absorption spectrum of the lm was ascertained using a Shimadzu Model UV-300
Spectrophotometer and diraction patterns obtained using a Shimadzu SD 7A X-ray
diractometer conrmed that the lm was -CuI (Fig. 1). Sintering of the lm at 70C
increased the peak at 25.563("2) corresponding to -CuI, indicating that the
crystallinity of the lm is improved by sintering.
3. Results and discussion
The lm of CuI deposited by a single-dip coating has a thickness of &10 m and
sheet resistance at room temperature (26C) of 12 M. Our method of preparation of
CuI, ensures removal of excess iodine and therefore the sheet resistance remains quite
high. Fig. 2 illustrates the variation of the sheet resistance of the lm during iodine
doping. It is seen that the sheet resistance rapidly drops with the increase of the level of
iodine doping and reaches a saturation level of &100 k/which is further reduced
to &5 k/if the lm is sintered (at &60C) before iodine doping. If the lm is not
sintered, decrease in the sheet resistance below the saturation level (&100 k) is not
noticeable. When the lm is sintered for 5 min at dierent temperatures and the
resistance measured at room temperature (25C), a progressive decrease in sheet
resistance (sheet resistance before sintering &2 M) is observed until the sintering
temperature is &70C (Fig. 3). At temperature above &70C rapid removal of
excess iodine increases the resistance. Fig. 4 shows the dependence of the sheet
resistance on the duration of sintering at dierent temperatures when the undoped
lm is used. Above 60C, when the duration of sintering increases, excess iodine
(incorporated during preparation of CuI) is rapidly lost increasing the resistance
K. Tennakone et al. /Solar Energy Materials and Solar Cells 55 (1998) 283289 285
Fig. 2. The variation of the sheet resistance of a lm sintered at 60C (thickness 10 m) with the level
doping (weight I

/weight CuI).
Fig. 3. The variation of the sheet resistance of a lm (thickness &10 m) when sintered for 5 min at
dierent temperatures.
286 K. Tennakone et al. /Solar Energy Materials and Solar Cells 55 (1998) 283289
Fig. 4. The dependence of the sheet resistance on duration of heating at (a) 40C, (b) 50C, (c) 60C and
(d) 70C.
Fig. 5. Absorption spectrum of CuI coated on glass.
K. Tennakone et al. /Solar Energy Materials and Solar Cells 55 (1998) 283289 287
Fig. 6. Photocurrent action spectrum of a CuI lm placed in a solution of Na

SO

(intensity of illumina-
tion &0.5 W/cm).
continuously. However, below 70C, sintering improves conductivity at least initially
(510 min), possibly because of coalescence of crystallites. A lowest sheet resistance
(for a lm of thickness &10 m made by a single lm coating) of &25 / is
obtained, when a lm sintered for 510 min at 6080 is subsequently doped with
iodine. (This lowest value for the sheet resistance was obtained by the optimization of
sintering time and the temperature.) Prolonged sintering at higher temperature seems
to fracture and loosen the lm, presumably due to dierence in expansivities of CuI
and glass.
Fig. 5 indicates the optical absorption spectrumof CuI coated glass. The edge in the
spectrum of &408 nm originates from band-gap absorption in CuI, the structure left
of this edge results from absorption in the substrate. Photocurrent action spectrum of
a lm placed in a solution of Na

SO

, with a Pt counter electrode is presented in

Fig. 6. Here again the sharp photoresponse at 408 nm corresponds to the on-set of the
band-gap excitation.
4. Conclusion
Sheet resistance of CuI lms is not as low as that of familiar transparent conducting
lms (e.g. those based on Tin or Zinc oxides). A minimumsheet resistance (for a lm of
thickness &10 m, 25 /) was obtained through an optimization of iodine doping,
sintering time and temperature. However, oxide-based conducting lms are n-type
and CuI is an example of a p-type material from which conducting lms can be
288 K. Tennakone et al. /Solar Energy Materials and Solar Cells 55 (1998) 283289
deposited. Again the low-temperature (95C) deposition technique can be adopted for
coating conducting lms of CuI on plastics and other materials that are not heat
resistant. Films are stable provided extensive exposure to UV-radiation is avoided.
UV-radiation ()band-gap radiation) seems to photodegrade CuI to some extent.
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