Thin Solid Films 519 (2011) 7364–7368

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Thin Solid Films

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / t s f

All-chemically deposited Bi2S3/PbS solar cells

Harumi Moreno-García, M.T.S. Nair, P.K. Nair ⁎
Centro de Investigación en Energía, Universidad Nacional Autónoma de México, Colonia Centro, Temixco, Morelos-62580, México

a r t i c l e i n f o a b s t r a c t

Available online 20 January 2011 We report on solar cells with a cross-sectional layout: TCO/window/Bi2S3/PbS, in which a commercial SnO2
transparent conductive oxide (TCO-PPG Sungate 500); chemically deposited window layers of CdS, ZnS or
Keywords: their oxides; n-type Bi2S3 (100 nm) and p-type PbS (360–550 nm) absorber films constitute the cell
PbS thin film structures. The crystalline structure, optical, and electrical properties of the constituent films are presented.
Bismuth sulfide thin film The open circuit voltage (Voc) and short-circuit current density (Jsc), for 1000 W/m2 solar radiation, of these
PbS
solar cells depend on the window layers, and vary in the range, 130–310 mV and 0.5–5 mA/cm2, respectively.
Bi2S3
Thin film solar cells
The typical fill factors (FF) of these cells are 0.25–0.42, and conversion efficiency, 0.1–0.4%.
Chemical deposition © 2011 Elsevier B.V. All rights reserved.

1. Introduction 2. Experimental details

We have recently advanced sequential chemical deposition of
semiconductor thin films as a simple approach to produce solar cell
structures. Basically this effort resulted from previous reports on the
utilization of PbS in thin film solar cell structures investigated in the
past by other groups: CdS/PbS [1] and ZnxCd1 − xS/PbS [2], which
produced open circuit voltages (Voc) 400–500 mV and short circuit
current density (Jsc) b 0.1 mA/cm2. Our own experience with these cell
structures is that even though chemically deposited cells of CdS/PbS
do show Voc of above 400 mV, the cells degrade fast due to reasons not
yet investigated [3]. However, the addition of a chemically deposited
Sb2S3 [4] or Sb2Se3 [5] interlayer in this cell structure was found to
result in stable solar cell structures with Voc 540–640 mV, and
conversion efficiencies (η), above 0.5%. In this work we open-up the
options for this type of cell structures through the addition of a Bi2S3
thin film.
The cell structures are developed on clear sheet glass of 3 mm
thickness with a commercial transparent conductive oxide (TCO of
SnO2) coating (PPG-Sungate 500 architectural glass). While the
simplest stable cell structure here would be TCO/n-Bi2S3/p-PbS, the
addition of a window film of chemically deposited CdS [6] or ZnS [7] or
their partially converted oxide films CdS/CdO [6,8] or ZnS/ZnO [7] is
seen to offer a choice of cell designs with comparable parameters. We
shall present the basic characteristics of the films which form the cell
structures, and describe the parameters of the different solar cells
normalized under solar radiation (1000 W/m2).
⁎ Corresponding author.
E-mail address: pkn@cie.unam.mx (P.K. Nair).
There is a choice of chemical deposition methods available [9] to
prepare each of the constituent films described below to constitute
the cell structures. However, we shall confine to the bath mixture,
deposition conditions and post-deposition thermal processing, which
were reported from our laboratory previously, and cited below.
2.1. Substrates
We used Corning microscope glass slides (75 mm× 25 mm of 1 mm
thickness) to deposit the films to study their characteristics and a
transparent conductive oxide (TCO) coating of electrically conductive
SnO2 with a sheet resistance of about 20 Ω on a 3 mm sheet glass (PPG
Sungate-500 low-emissivity architectural glass, PPG, PA), cut to this size
to deposit the cell structures. The substrates were cleaned in a neutral
detergent solution, rinsed in de-ionized water and dried prior to
depositing the films.
2.2. Window layer films
CdS films of 100–300 nm of predominantly hexagonal crystalline
structure were deposited from a mixture of solutions containing
cadmium chloride, sodium citrate, ammonia (aq.), and thiourea.
When the deposition is made at 80 °C, the film thickness is 100 nm
after 1 h and 300 nm in about 5 h [6]. When this film is heated at
450 °C in air for 30 min, a CdO surface layer is formed [8]. ZnS films of
100–200 nm thickness were deposited at 60 °C in 2–4 h from a bath
mixture constituted with solutions of zinc chloride, triethanolamine
(TEA), pH 10 buffer, and thioacetamide [7]. When this film is heated in
air for 15 or 60 min at 450 °C, a surface layer of ZnO is formed.

0040-6090/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2011.01.145
 H. Moreno-García et al. / Thin Solid Films 519 (2011) 7364–7368 7365

2.3. Bi2S3 thin film
A 100 ml volume of the solution mixture for the deposition of these
films contained 10 ml of 0.5 M bismuth nitrate dissolved in TEA; 8 ml
1 M thiacetamide solution and de-ionized water [10]. In about 75 min,
a thin film of 160 nm in thickness is obtained on most substrates, when
the deposition is made at 40 °C. The films were heated at 250 °C for
15 min in air or nitrogen to make them crystalline. This procedure also
results in some loss of the material, leading to a reduction in thickness
to typically 100 nm.
2.4. PbS thin films
For the deposition of these films, a 100 ml volume of the
deposition mixture was constituted by the successive addition of
the following solutions: 5 ml 1 M lead nitrate, 20 ml 1 M sodium
hydroxide, 6 ml 1 M thiourea, 4 ml 1 M TEA and de-ionized water
[3,4,11]. The film was deposited overnight (17 h) at 25 °C followed by
a second deposition for 2 h at 40 °C. The resulting film has a thickness
360 nm, which is used in cell structures. In some cases a further
deposition of the film at 40 °C was made to increase the film thickness.
A single deposition at 40 °C gives a PbS film thickness of 200 nm on a
glass substrate, which was used for structural analysis.
2.5. Cell structures
To deposit the cell structure, Bi2S3 thin films on the TCO/window
layers were taped off along the edges with a paper-based masking
tape, so that the PbS thin film is limited to a central region on the Bi2S3
film. Colloidal graphite paint (SPI-Chem) was applied on a
5 mm × 5 mm area on PbS (cell area, 0.25 mm2) and this contact
was dried in an air oven for 6 h at 60 °C. Subsequently, colloidal silver
paint (DuPont SP 480) was applied on the graphite electrode and
allowed to dry for a further 2 h at 60 °C. If silver paint is directly
applied on the PbS film, the cell degrades. This might be ascribed to
the formation of a silver sulfide layer at the Ag-electrode/PbS
interface.
2.6. Structural and optical characterization
Keithley 619 digital multimeter interfaced with a computer. These data
were converted to σd and σp for the different films. The current (I) versus
voltage (V) response of the cells was recorded in the dark and under
illumination (1000 W/m2) for TCO–substrate side incidence. The short-
circuit current (Isc) was then normalized using the value obtained for
each cell under the sun 1000 ± 50 W/m2 measured near mid-day. The
intensity of solar radiation was measured using a calibrated Kipp–Zonen
pyranometer. This produced reliable J–V data on the cells for operation
under sunlight.
3. Results and discussion
3.1. Crystalline structure
Fig. 1(a)–(d) shows the XRD patterns of the window layers of CdS,
CdS/CdO; and ZnS, ZnS/ZnO; and of the absorber layers of the Bi2S3
thin film (160 nm, as deposited) and that heated at 250 °C in air; and
of a PbS thin film of 200 nm thickness (deposited at 40 °C in 2 h). The
crystalline planes are indexed with reference to PDF 17-0320 for
Bi2S3-bismuthinite and PDF 5-592 for PbS-galena. The average
crystallite diameter for PbS is 15–20 nm, as estimated from the
(200) peak, hence making it susceptible to variation of optical band
gap (Eg) due to quantum confinement of excitons. Thin films of CdS
and ZnS/ZnO shown here are of hexagonal structure. The XRD peaks of
ZnS are not noticed in the as-deposited film, but upon heating this
film, ZnO peaks show-up. When CdS is heated, a CdO surface layer of
cubic (rock-salt) structure is formed [8].
3.2. Optical characteristics
Fig. 2(a)–(d) gives the plots of specular T and R of the window
layers and of the absorber films. The distortions in the plots appear
due to change of the detector element in the spectrophotometer. The
plots of α versus hν of the films are given in Fig. 3. Here, the Eg of the
material is the value on the hν-axis for which α → 0, as noted in this
1800
(d) PbS PDF 05-0592
1200
(220)
(200)
(111)

(311)
Film thicknesses (d) were determined using Alfa Step 100 (Tencor,
600
CA) equipment. The X-ray diffraction (XRD) patterns of the thin films
were recorded in a Rigaku D/MAX-2000 for grazing incidence
0
configuration (incidence, 2°) using Cu-Kα (0.15604 nm) radiation. The (c)
(310)
(211)

(221)

300
(220)

optical transmittance (T) of the films (with air in the reference beam) and
(210)
(020)

specular reflectance (R) were recorded in the spectral range

Intensity (counts/s)

Bi2S3 PDF 17-0320

250–2500 nm in a Shimadzu UV–VIS–NIR 3101 PC spectrophotometer. 150
A front-aluminized mirror in the reference beam served as the standard Bi2S3 as dep.
for R=100%, and air for T =100% for light beam incident at the film-side
0
on the sample. The optical absorption coefficient (α) of the film was
200 (b)
determined for photon energies hν by considering multiple reflections in
(002)
(100)

(101)

the thin film [12]:

100 ZnO PDF 36-1451
2 qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi3
2
1 4ð1−RÞ + ð1−RÞ + ð2RT Þ 5
4 2
ZnS
∝= ln :
d 2T 0
(002)

CdO(cub) PDF 05-0640

(111)
(101)

(200)
(100)

800
(a)
CdS(hex) PDF 41-1049
(220)

2.7. Electrical characterization 400

Pairs of colloidal silver paint electrodes 5 mm long at 5 mm

0
separation were applied on the film to determine their electrical 10 20 30 40 50 60 70
conductivity in the dark (σd) and under illumination (σp) with intensity
of illumination 800 W/m2 (tungsten-halogen). For this measurement
the light is incident from the film-side. Current–time data were acquired Fig. 1. XRD patterns of: (a) CdS, CdS/CdO; (b) ZnS, ZnS/ZnO; (c) Bi2S3 (as prepared) and
every 1 s using a Keithley programmable 230 voltage source and a crystalline (X)Bi2S3; and (d) PbS thin films.
7366 H. Moreno-García et al. / Thin Solid Films 519 (2011) 7364–7368

6 1.4
90 (d) Bi2S3 PbS
1.2
60 PbS(360nm) 5

R 1.0
30 4

0
T 0.8
90 (c) 3
(X) Bi2S3 (120 nm) 0.6
60 R
2
0.4
30
T 1
T, R (%)

0.2
0
T, ZnS (130 nm) 1.61 eV 0.58 eV
90 (b) 0 0.0
1.0 1.5 2.0 0.5 1.0 1.5
60 T, ZnS/ZnO

Fig. 4. Analysis of the optical band gap of Bi2S3 and PbS thin films using the data given in
30
R, ZnS/ZnO Fig. 3.

0
R, ZnS
(a) T, CdS/CdO which attest to the validity to the band gap analyses. It is well
90 documented that Eg in chemically deposited thin films would vary
T, CdS (100 nm) with deposition conditions because of changes in the crystalline grain
60 size [9]. In the present case, the PbS thin film deposited at 40 °C from
R, CdS the same chemical bath has an Eg of 0.49 eV. The PbS layers used in the
30 solar cell structures are sequentially deposited PbS films, first at 25 °C
R, CdS/CdO
and then at 40 °C, with a combined thickness of typically 360 nm.
0
500 1000 1500 2000 2500
3.3. Electrical characteristics

Fig. 2. Optical transmittance (T) and reflectance (R) spectra of: (a) CdS, CdS/CdO; Fig. 5 shows the σd and σp of the films. All the window layers used
(b) ZnS, ZnS/ZnO; (c) (X)Bi2S3; and (d) PbS thin films. here are of n-type electrical conductivity. In the case of chemically
deposited Bi2S3 thin, a transition from a highly resistive amorphous film
figure. The window materials involve allowed optical transitions to a crystalline film of n-type electrical conductivity occurs at a
across a direct gap. The absorber materials PbS and Bi2S3 also possess temperature above 180 °C [14]. The extent of the electrical conductivity,
direct Eg; but they involve electronic transitions that are forbidden by 10−3 to 103 Ω−1 cm−1 of the Bi2S3 thin film, is decided by the duration,
spectroscopic selection rules [13]. Plots of (αhν)2/3 versus (hν) yield temperature, and the ambient used in the thermal processing [15]. In
straight line fit in these cases, with intercepts 1.61 eV for Bi2S3 and such crystalline films, the n-type conductivity of the material is easily
0.58 eV for PbS, as illustrated in Fig. 4. The correlation factors for these ascertained by a hot-probe test, in which the hot probe attains a positive
linear fits are: 0.996 in the photon energy range 0.65 eV to 0.95 eV for potential. The p-type conductivity of the chemically deposited PbS thin
the PbS film and 0.9995 in the range 1.7 to 2.2 eV for the Bi2S3 film, films has formed the basis of its integration into solar cell structures in the
past [1–5]. Hence, a Bi2S3/PbS layer would constitute a p–n
heterojunction.

105 PbS
10-1
CdS Bi2S3

104
2.3 eV CdS/CdO

2.6 eV CdS(hex)

10-3
1.6 eV Bi2S3

ZnO CdO
0.6 eV PbS

3.4 eV ZnO
3.5 eV ZnS

-5
103 10
)-1

PbS
60 photo

0.44
60-photo

0.42
60
60

10-7
102 ZnS 0.40 60-dark 60-dark
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 Time (s)

Time (s)
Fig. 3. Optical absorption coefficients (α) of: CdS, CdS/CdO; ZnS, ZnO; (X)Bi2S3 thin
films; and of a PbS thin film of 200 nm deposited at 25 °C forming part of the cell Fig. 5. Electrical conductivity in the dark and under illumination of the thin film
structures. The values of the Eg of the materials are indicated. materials; inset: zoom-in on the PbS response.
 H. Moreno-García et al. / Thin Solid Films 519 (2011) 7364–7368 7367

Ag
Based on the value of Eg; Fermi levels evaluated from σp (by C
3
assuming typical drift mobility 0.001–0.01 m2/V-s); along with the

J (mA/cm2)
PbS(360- 550)
160-550
electron affinity χ evaluated from the electronegativity of the (X)Bi2S3(100 nm) 260-550
2 160H-360
constituent elements and Eg [16], the work function of each of the CdS,CdO (160-260nm)
TCO
constituent film may be estimated [17]. The difference in the work
1 1000 W/m
2
functions of the materials of the heterojunction would give the built-
260-360
in voltage (Vbi) of the junction. In the present case, Vbi for the Bi2S3/ 160-360 DARK 160-360
0
PbS junction is about 400 mV, but it could be higher in the presence of -0.1 0.0 0.1 0.2 0.3 0.4
a ZnS or CdS window layer. Further studies are required to ascertain
-1 V (V)
these values.
-2 FF rS
3.4. Solar cell characteristics Cell type VOC JSC
2 %
CdS(x)/PbS(x) mV mA/cm
-3 160-360 310 1.0 0.36 0.11 125
In Fig. 6 we illustrate the need for heating the Bi2S3 thin films
260-360 300 1.5 0.33 0.15 118
before adding the PbS thin film to form the junction. Without this -4 160-550 310 1.5 0.37 0.17 38
heating process (in air or nitrogen), at a temperature 150–300 °C, Jsc is 260-550 275 2.0 0.40 0.22 30
small. The values of Voc might become inferior with heating (dropping -5 160H-360 180 1.8 0.27 0.09 270
from 270 mV to 160 mV), but the cell efficiency would go up from
0.08% to 0.34%. The series resistance (rs) is typically ten times higher Fig. 7. J–V characteristics of CdS/Bi2S3/PbS cells with variable thickness (x) of CdS (160
than that of good quality solar cells; and this limitation keeps the fill or 260 nm) and PbS (360 or 550 nm) thin films, as well as of a cell with a CdS/CdO
window layer (plot 160 H-360) produced by heating a CdS film of 160 nm at 450 °C for
factor (FF) and efficiency (η) low in the present cell structures. 30 min.
Fig. 7 shows that Voc could be improved from 270 mV to 310 mV in
the cell if a CdS thin film is added to the cell structure. We consider
that this improvement comes about because the electron affinity of The characteristics of a solar cell with a partially converted
CdS (4.5 eV) is lower than that of Bi2S3 (4.68 eV), hence enabling a ZnS/ZnO window layer produced by heating a ZnS thin film of 100 nm
higher Vbi as well as a higher Voc. The best Voc of 310 mV is obtained for in air for 15 min at 450 °C, are shown in Fig. 9. This cell structure gave
a cell with a CdS window of 160 nm and a PbS film, 550 nm in the highest Jsc in the present study, 5 mA/cm2 and η of 0.4%. However,
thickness. The efficiency reaches 0.17% in this case. However, with a the Voc of this cell is inferior, 225 mV. With a ZnS thin film of 160 nm
CdS film of 260 nm, the Voc of 275 mV and a slightly higher η 0.22% are heated in the same way maintains a higher Voc, 280 mV, but the Jsc is
obtained. With a partially converted CdS/CdO window, the cell low, 3 mA/cm2 and so is η (0.2%).
performance degrades: Voc 180 mV and Jsc 1.8 mA/cm2. We consider In all these cases, we note in the inset tables that the rs of the cells
that further optimization of film thickness and thermal processing remains high, N30 Ω cm2, and the rp is rather low, 500 Ω cm2, except
would be required before this route is ruled out from the effort to in cells with a ZnS window (without heating). We consider that the
improve the cell performance. graphite-acrylic paint increases the rs and inadequate edge isolation
The addition of a ZnS window layer of 100 nm also produces a Voc lowers the shunt resistance. Future work would address these issues
of 310 mV in the cells, as shown in Fig. 8. Here Jsc (1.8 mA/cm2) is to improve upon the cell parameters reported here.
relatively higher compared with a cell with CdS window. The FF of
these cells are high, 0.42, because of a relatively high parallel 4. Conclusions
resistance (rp), 900 Ω cm2 of the cell, compared with b500 Ω cm2 for
the cells without any window layer or with a CdS window. The The main conclusion of this work is that Bi2S3/PbS solar cells can be
conversion efficiency of these cells is still low, 0.23%. A ZnS window prepared by sequential chemical deposition on a TCO-coated low-
layer of a higher thickness, N100 nm, only leads to a deterioration of emissivity glass (PPG Sungate 500). Here the substrate is an
the overall cell performance. architectural glass introduced by PPG (www.ppg.com) in 1984,
which has been tested in high efficiency double glazed windows
Ag over the years. The sheet resistance of this glass is higher than
4 C commercial tin-doped indium oxide or the F/Sb-doped tin oxide
J (mA/cm2)

PbS(350) coatings on glass (TEC 8, 15 of Pilkington glass, Toledo), etc., which are
(X, ASD)Bi2S3 250A
2
TCO DARK
2 Ag
1000 W/m C
(mA/cm2)

0 4
PbS(360-550)
-0.1 0.0 0.1 0.2 0.3 0.4 (X)Bi2S3(100 nm)
ASD V (V) 2 ZnS (100-130 nm)
-2 250N TCO
250A 2
J

1000 W/m
100-360 DARK
-4 0
Cell VOC JSC FF rS -0.1 100-360 0.0 0.1 0.2 0.3 0.4
type mV mA/cm2 % 100-460 V (V)
-6 -2
ASD 260 1.1 0.28 0.08 223 Cell type VOC JSC FF rS
130-360 ZnS(x)/PbS(x) mV mA/cm2 %
250A 250 5.1 0.27 0.34 74 130-460
-8 -4 100-360 310 1.8 0.42 0.23 37
250N 130 4.8 0.25 0.15 66
130-360 300 1.7 0.38 0.20 35
100-550 310 1.9 0.40 0.23 37
Fig. 6. Current density–voltage (J–V) characteristics of Bi2S3/PbS (360 nm) cell
-6 130-550 275 1.9 0.36 0.20 34
structures using as-deposited (ASD) Bi2S3 thin film of 100 nm or (X)Bi2S3 film of
100 nm formed from it by heating them in nitrogen at 250 °C (250 N) or in air at 250 °C Fig. 8. J–V characteristics of ZnS/Bi2S3(100)/PbS cells with variable thickness (x) of ZnS
(250A). (100 or 130 nm) and PbS (360 or 550 nm) thin films.
7368 H. Moreno-García et al. / Thin Solid Films 519 (2011) 7364–7368

Ag
resistance of the cell. Further, we do not consider that optimum film
J (mA/cm2)
C
6 PbS(360) thicknesses or heat treatment for Bi2S3 or PbS absorber films as well as
(X)Bi2S3(100 nm) of the window layers has yet been identified.
ZnS/ZnO (100-160 nm)
3 TCO
2 Acknowledgments
100H15-360 DARK 1000 W/m
0
-0.1 0.0 0.1 0.2 0.3 0.4 The authors acknowledge the assistance of Maria Luisa Ramón García
V (V) in recording the XRD patterns; José Campos in the electrical character-
-3 100H60-360 100H15-360 ization of the materials and films; and Oscar Gomez-Daza in the chemical
laboratory and optical characterization. HMG acknowledges the graduate
-6 Cell type VOC JSC FF rS fellowship from CONACyT-Mexico. The work was funded through
ZnS/O-PbS mV mA/cm2 % projects: DGAPA-UNAM IN110008, CONACyT CB-79938, and ICyTDF-
100H15-360 225 5.0 0.35 0.40 72
-9 307/2009.
160H60-360 280 1.8 0.27 0.13 136

Fig. 9. J–V characteristics of ZnS/Bi2S3(100 nm)/PbS(360 nm) cells with ZnS thin film of
100 or 160 nm, with a ZnO surface layer produced by heating the films at 450 °C in air
for 15 min (100 H15-360) and heating for 60 min of ZnS thin film of 160 nm thickness
and PbS thin film of 360 nm thickness (160 H60-360).
normally used in thin film solar cell work. This adds on to the series
resistance of the cells. However, the resistance of the graphite-acrylic
electrode still dominates the series resistance of the cell. Basically, the
sequential chemical deposition of semiconductor films brings the solar
cell research to many more semiconductor materials, which have been
extensively investigated in the past for distinct purposes [9].
The improvement in the fill factor when ZnS is used as a window
layer is noteworthy toward planning future research. We consider
that a TCO/ZnS/CdS window might prove to be superior. The
optimization of the film thickness is an easy task with chemical
deposition. Doped graphite-acrylic electrodes, and/or appropriate
curing temperatures for them may be sought to reduce the series
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