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Evolution of crystalline structure in SnS thin

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DOI: 10.1016/j.solidstatesciences.2014.02.002

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 Solid State Sciences 30 (2014) 26e35

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Solid State Sciences

journal homepage: www.elsevier.com/locate/ssscie

Evolution of crystalline structure in SnS thin lms prepared by

chemical deposition
Ana Rosa Garcia-Angelmo, M.T.S. Nair*, P.K. Nair
Instituto de Energas Renovables, Universidad Nacional Autnoma de Mxico, Temixco, Morelos 62580, Mexico

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

Article history: Crystal structure and morphology undergo signicant evolution in thin lms of tin(II) sulde prepared by
Received 29 April 2013 chemical deposition, over a narrow interval of bath temperature of 20e40
C, but has not been recog-
Received in revised form nized in previous studies. The chemical bath is constituted using tin(II) chloride, triethanolamine,
24 January 2014
ammonia(aq.) and thioacetamide. At bath temperature of 20
C, the deposition rate of the lm is 10 nm/
Accepted 3 February 2014
h; and at 24 h, a lm of thickness 260 nm is obtained. This lm is compact and with a predominantly
Available online 13 February 2014
cubic (Cub-) crystalline structure. At 40
C, the deposition rate is 25 nm/h, and a lm of 600 nm in
thickness is deposited in 24 h. However, this lm has evolved into vertically stacked platelets of
Keywords:
Cubic and orthorhombic SnS thin lms
orthorhombic (OR-) crystalline structure. The transition from compact-to-platelet morphology as well as
Chemical deposition from Cub-to-OR-crystalline structure is observed near a deposition temperature, 35
C. The Cub-SnS has
Crystalline structure a characteristic high optical band gap, 1.67 eV (direct gap; forbidden transitions) with an electrical
Electrical optical properties conductivity, 107(U cm)1; both properties being un-affected when lms are heated at 300
C in a
Solar cell absorber nitrogen ambient. In OR-SnS, the band gap is 1.1 eV (indirect gap; allowed transitions). The electrical
conductivity of such lms is notably higher, 104 (U cm)1, which increases further by an order of
magnitude when the lms have been heated at 300
C in nitrogen.
2014 Elsevier Masson SAS. All rights reserved.

1. Introduction [12]. The use of a Zn(O,S) thin lm of 25e30 nm in thickness with a

SnS thin lms have been investigated for more than twenty
years as a photovoltaic absorber material. These lms mostly
crystallize in the orthorhombic (OR-) structure, when formed via
chemical deposition [1,2], electrochemical [3], spray pyrolysis [4],
thermal evaporation [5], atomic layer deposition (ALD) [6], or
plasma enhanced chemical vapor deposition [7]. However, in spe-
cic conditions of chemical deposition, lms grow also in cubic
(Cub-zinc blende) crystalline structure [8,9], which is also a case
observed in nanocrystals prepared by hydrothermal process [10].
Solar cell structures of CdS/SnS using either type of SnS reported
until 2012 lacked attractive values for the open circuit voltage (Voc)
and conversion efciency (h), with typical values of these param-
eters being: 170 mV, 0.2% [3]; 405 mV, 0.44% [11]; etc., and the best
set of values being: Voc of 260 mV, and h of 1.3%, reported in 2006
[4]. A combination of Voc of 244 mV, and h of 2.04% for active cell
area of 0.71 cm2 has been reported in 2013 for a solar cell structure,
glass/Mo/SnS/Zn(O,S)/ZnO/ITO, in which the SnS thin lm of 1.5 mm
in thickness is deposited by a pulsed-chemical vapor deposition
* Corresponding author. Tel.: 52 55 56229732; fax: 52 55 56229742.
S/Zn ratio of 0.37 is proposed to modify the conduction band off-set
of the interface to an optimum value, which reduces the interface
recombination. In this work we highlight that the crystalline
structure of the SnS lms obtained from chemical deposition is
strongly dependent on the deposition temperature, not recognized
in our previous work [1,2]. We identify here a transition tempera-
ture range of 30e35
C, above which the lms are of OR-crystalline
structure and below which the lms are of predominantly Cub-
structure. Since the two crystalline structures entail different op-
tical band gaps (Eg, 1.1 e OR, or 1.7 eV e Cub) and a distinct range of
electrical conductivity (p-type in both cases), they are both relevant
to solar cell designs.
2. Experimental
2.1. Thin lm deposition
The chemical bath for the deposition of SnS thin lms has been
established by us previously [1]: 1 g of SnCl2$2H2O is dissolved in
5 ml of acetone, and to this solution is added with stirring 12 ml of
3.7 M triethanolamine (turbid-white appearance), followed by
65 ml de-ionized water, 8 ml of 1 M tioacetamide (C2H5NS), and

http://dx.doi.org/10.1016/j.solidstatesciences.2014.02.002
1293-2558/ 2014 Elsevier Masson SAS. All rights reserved.
 A.R. Garcia-Angelmo et al. / Solid State Sciences 30 (2014) 26e35 27

10 ml of 4 M NH3(aq). The starting solution has a pH of approxi-

mately 11 and appears lightly smoky. All reagents used in the work
are Baker Analyzed. Cleaned Corning microscope glass-slides
(75 mm  25 mm, 1 mm thickness) are mounted on the wall of
the beaker. Temperature of the bath is xed at 20, 25, 30, 35, 40 or
50
C. In two experiments the temperature is changed from one to
another after certain duration of deposition in the same bath. In
24 h at 20
C, a lm of 230 nm in thickness is deposited, whereas in
the same duration at 40
C a lm of 600 nm in thickness is
deposited. The lm deposited on the side of the substrates facing
the wall of the beaker is specularly reective and adherent. The lm
on the other side of the substrate is removed with cotton swabs
moistened in dilute acid. In this work we report that it is not only
the thickness or the deposition rate that changes with deposition
temperature, but most importantly also the morphology and
crystalline structure of the material, which is decisive in the optical
and electrical properties of the lms. The lms are heated at 300
C
in a nitrogen atmosphere of 10 Torr for 30 min to determine
changes that could take place. The heating does not alter the lm
morphology, crystalline structure or the band gap in a notable way, Fig. 1. Thickness of SnS thin lms deposited at different bath temperatures with
but it increases the electrical conductivity (p-type) of the lms. different durations, with regions marked for 100e160 nm (small), 230e350 nm (in-
termediate), and 500e600 nm (large) thicknesses; Inset: approximate growth rate of
lm plotted against deposition temperature.
2.2. Characterization
40
C. An increase in the initial growth rate with temperature is a
Film thickness is measured on an Ambios Technology XP-200
characteristic of chemically deposited thin lms, which is under-
step-thickness measuring equipment. A Hitachi eld effect scan-
stood in terms of thermally activated dissociation of metal com-
ning electron microscope (FESEM) 5500 is used to record the mi-
plexes and chalcogenide source. A higher deposition temperature
crographs describing the morphology of the lms. To estimate the
chemical composition of the lms, we use Hitachi SU1510 scanning
electron microscope (SEM) tted with an Oxford X-act 51-
ADD0053 energy dispersive X-ray (EDX) spectrum analyzer with a
resolution of up to 130 eV at 5.9 keV. The X-ray diffraction patterns
are recorded on a Rigaku ULTIMA-IV diffractometer using Cu-Ka
radiation in the grazing incidence (GI) X-ray diffraction (XRD) mode
with an incidence angle U (xed angle between the incident beam
and the plane of the sample) of generally 2.5
, but also of 0.5, 1.0, or
1.5
in some cases. The optical transmittance spectra (air as refer-
ence) and specular reectance spectra (front aluminized mirror as
reference) are measured using a Shimadzu UVeVISeNIR 3101
spectrophotometer. The beam of light makes incidence at the lm
side. For electrical characterization of the thin lms, pairs of silver
print (DuPont PV428) contacts of 5 mm length at 5 mm separation
are applied on the surface and allowed to dry. Photocurrent
response, current (I) against time (t), in the thin lm is measured
under tungstenehalogen radiation with an intensity of illumina-
tion of 800 W/m2 over the lm. The bias (V) applied is typically
10 V. Knowing the lm thickness (d), the Iet data are converted to
conductivity [s I/(V d)]etime (set) curve.

3. Results and discussion

3.1. Film growth

Fig. 1 shows thickness of the tin sulde thin lms obtained at

different durations within a 24 h period of deposition at tempera-
tures of 20, 25, 30, 35 and 40
C. Three thickness ranges are
marked-off in the Figure: small, 100e160 nm; intermediate, 230e
350 nm; and large, 500e600 nm. This demarcation helps to discuss
the characteristics of the lms of comparable thickness obtained
under different deposition temperatures. Deposition of the lm at
temperatures below 20
C is possible, but it would be impracticably
slow. When the lms are deposited at temperatures above 50
C,
Fig. 2. (a) EDX-spectra of lms 20-110 deposited at 20
C and of 110 nm thickness, etc.,
they tend to be fragile to touch. The inset is a plot of growth rate of for small thicknesses; (b) EDX-spectra of lms 20-230 etc., of intermediate thicknesses.
the lms at different temperatures of deposition. This rate is 10 nm/ Plots marked H are for samples that have been heated. (c) Elemental S/Sn mole ratio
h for the deposition made at 20
C, and 25 nm/h for that done at obtained from EDX-analysis software for the lms deposited at different temperatures.
28 A.R. Garcia-Angelmo et al. / Solid State Sciences 30 (2014) 26e35
also increases the homogeneous precipitation rate, which could
reduce the nal thickness of the lms. However, such a reduction in
thickness with duration of deposition is not observed within 24 h.
3.2. Chemical composition
Fig. 2(a and b) shows relevant parts of the EDX spectra of tin
sulde thin lms of small and intermediate thicknesses. The labels
indicate the temperature of deposition (
C) and thickness of the
lms (nm) with an H included in cases where the lms are heated
prior to recording the spectra; for example, 40-160H refers to
deposition at 40
C, thickness of 160 nm, and that the lm has been
heated. The EDX spectrum of the glass substrate, Fig. 2(a), shows
only the CaeKa peak at 3.69 keV. In addition to this, the spectra of
all the lms of thickness 100e160 nm show peaks due to SeKa at
photon energy 2.31 keV and that due to SneLa at 3.44 keV. As the
lm thickness increases to intermediate range, the intensities of Se
Ka and SneLa peaks in their EDX spectra (Fig. 2b) are seen to in-
crease monotonically, and become comparable with that of CaeKa.
Heating of the lms at 300
C in nitrogen ambient of 10 Torr does
not cause any change in these intensities, as seen in the spectra of
samples 40-160 and 40-160H (Fig 2a) or of 20-230 and 20e230H or
40e300 and 40e300H (Fig 2b). Hence, the overall chemical
composition of the lms is maintained even after heating.
Fig. 2c shows the molar ratios of S/Sn in the lms deposited at the
different temperatures plotted as a function of lm thickness,
estimated using the chemical analysis software of EDX. For the 20-
110 thin lm, the ratio is 0.75, suggesting a deciency in S at small
lm thicknesses. This value rapidly increases toward 1 as the lm
thickness increases to 230 nm. For the 40e160 thin lm, this ratio is
0.61, and even at a thickness of 600 nm, it remains below 1. This
might imply the presence of hydroxide phase of tin, Sn(OH)2 or
other oxy-hydroxides in the lm.
The use of NH3(aq.) in the bath releases hydroxide ions (OH)
and maintains a pH of 11 in it. Chemical deposition of metal chal-
cogenide lms often calls for a nucleation phase involving a hy-
droxide phase of the metal. This will be taken over by the growth
phase in which the hydroxyl is displaced by sulde or selenide ions.
In the present case, such reaction is described as:
Sn(OH)2 S2 / SnS 2OH. This type of displacement is dis-
cussed in terms of the differences in solubility products Ksp and free
energy change of metal hydroxide and metal sulde or selenide
[13]. In the present case, the Ksp of Sn(OH)2 is 5  1028 (mol3/dm9)
and that of SnS is w1026 (mol2/dm6). Thus, in solutions containing
both hydroxide and sulde ions, the formation of SnS should pre-
cede that of Sn(OH)2 as the solutions can have a maximum con-
centration of free Sn(II) ions of w1013 mol dm3 or
w1010 mol dm3 before the precipitation of SnS or Sn(OH)2,
respectively, occurs. However, the hydroxide formed prior to the
availability of sulde ions by the dissociation of thioacetamide in
the solution may not be displaced completely by the sulde ions
during the deposition. This may occur particularly in cases where
the lm growth occurs through the condensation of clusters and
produces thin lms lacking in compactness, rather than by ion-by-
ion deposition process, which produces compact specularly
reective lms. Hence we expect to nd differences in the
morphology of the lms deposited at 20
C compared with that
deposited at 40
C. We note that S/Sn ratio in the lm does not alter
upon heating it at 300
C. Oxygen content in the lm (possible
through presence of hydroxide or oxy-hydroxide) is not included in
the chemical analysis, because the lms are deposited on glass
(SiO2) substrates of 1 mm thickness, and hence any variation of
oxygen content in the lm will be masked by that contained in the
substrate.
3.3. Surface morphology
Fig. 3A (aed, eeh, i, j) are the micrographs obtained from the
FESEM at low resolution and at relatively higher resolution (insets)
for the lms of small, intermediate and large thickness ranges
(described in Fig. 1), respectively. Films of thickness 110 and 230 nm
deposited at 20
C (Fig. 3A (a, e)) show reasonably compact lm
surface, compared with lms of thickness 160, 300 and 600 nm
deposited at 40
C (Fig. 3A (d, h, j)). Films deposited at 30
C (Fig. 3A
(b, f)) resemble those deposited at 20
C in morphology; and those
deposited at 35
C (Fig. 3A (c, g, i)) resemble the lms prepared at
40
C. Hence, for the given bath composition, there is a transition
from growth of a compact lm toward those consisting of vertically
organized platelets or akes of 200e400 nm in lateral size and 20e
50 nm in thickness with nearly 50% voids when the deposition
temperature is 35
C or higher. From the conclusions drawn from
Fig. 2c, the platelet-lms may result from the cluster mechanism of
deposition. Fig. 3B (e0 , f0 , h0 , and j0 ) shows the cross sectional view of
representative samples given in Fig. 3A (e, f, h, and j). These mi-
crographs illustrate the compact nature of the lm of 230 nm
thickness deposited at 20
C (e, e0 ); the vertically stacked aky
nature of the lms of 300 and 600 nm in thickness deposited at
40
C (h, h0 ; j, j0 ); and an intermediate behavior in a lm of 340 nm
in thickness deposited at 30
C (f, f0 ). The cross sectional views also
validate the lm thickness determined by the step-thickness
measurement.
3.4. Crystal structure
Fig. 4(a) shows the XRD patterns recorded using grazing inci-
dence of U 2.5
for the lms of small thickness deposited at 20e
40
C. Fig. 4(b) shows the XRD patterns of the lms of intermediate
thickness along with the peak positions and intensities reported for
cubic SnS (Cub-SnS, lattice constant a 0.58 nm) in the powder
diffraction le (PDF) 77-3356 for rock salt structure (R-SnS). Peak
positions evaluated for thin lms of zinc blende structure of SnS (Z-
SnS) for a 0.5791 nm reported by us previously [8] or for powder
diffraction pattern of Z-SnS nanocrystals [10] evaluated with
a 0.5845 nm would be very close, but the intensity ratios are
distinct. The predicted diffraction peaks for (111) planes in the Z-
SnS are at 2q approximately of 26.6
with 100% intensity; for (200)
planes at 2q of 30.8
with 40% intensity; and for (220) planes at 2q
of 44.1
with 80% intensity [8]. Fig. 4(c) shows the XRD patterns of
lms of large thickness deposited at 35 or 40
C, along with the
standard data in PDF 39-0354 for orthorhombic SnS (OR-SnS) to
which XRD peaks of SnS thin lms are more often assigned [1e7].
The peak positions marked in Fig. 4(aec) for Cub-SnS represents
both R-SnS and Z-SnS to aid visual examination. The (111) peak of
Cub-SnS near 2q of 26.5
lies between the (120) and (021) XRD
peaks of OR-SnS and similarly, (200) peak of Cub-SnS near 2q of 31

lies between the (101) and (111) XRD peaks of OR-SnS.
We consider here the recent observation made on the close
resemblance in position of simulated powder diffraction patterns of
R-SnS and Z-SnS [14]. Structure factor consideration requires that
intensity of (111) XRD peak be lower than that of (200) peak for R-
SnS, whereas (111) peak intensity would be higher than that of
(200) XRD peak for Z-SnS. When the effective electron charge
density on the two atoms constituting Z-structure is nearly equal as
in GaAs (atomic numbers of 31, 33) or InSb (: 49, 51), the (200)
peak disappears as in diamond structure; and when this happens in
R-structure, the (111) peak disappears, as in KCl (: 19, 17). In Z-SnS
(: 50, 16), the relative intensities of diffraction peaks from (111),
(200), (220), (311), and (222) planes would be comparable to that of
Z-CdS (: 48, 16) listed in PDF 10-454, which are 100%, 40%, 80%,
60%, and 20%, respectively. Values of 2q, relative intensities,
 A.R. Garcia-Angelmo et al. / Solid State Sciences 30 (2014) 26e35 29

Fig. 3. A. (aed) FESEM micrographs of lms of small thicknesses, 110e160 nm deposited at 20e40
C; (eeh) of intermediate thicknesses of 230e330 nm; (i, j) of large thicknesses, 500e
600 nm, deposited at 35 and 40
C. B. (e0 , f0 , h0 and j0 ) FESEM cross-sectional views corresponding to micrographs e, f, h and j of the lms in A. The interval between the small lines in the
scale bar is 50 nm; the formation of a thin lm of approximately the thickness (in nm) appearing as the second number in the sample label is clearly distinguished over the substrate.
30 A.R. Garcia-Angelmo et al. / Solid State Sciences 30 (2014) 26e35
Fig. 3. (continued).
calculated value of the cubic-lattice constant (a) using the diffrac-
tion peaks from (111), (200), and (220) planes observed in the XRD
patterns of the lms 20-110, 30-110, 20-230, and 30-305 given in
Fig. 4(a and b), for which Cub-SnS is the dominant phase, are given
in Table 1. The intensities of XRD peaks for (111) and (200) planes
are nearly the same in the case of the lms with thickness 100e
300 nm, but not as predicted for R-SnS (Fig. 4(b)), where (111) peak
is lower in intensity compared with (200) peak or as Z-SnS, where it
is predicted to be vice-versa: 100% for (111) peak and 40% for (200)
peak. The cubic lattice constant is determined from the 10 different
values of a in Table 1. It is 0.5792  0.0012 nm, in agreement with
our previous result [8]. The last two columns in Table 1 give the 2q
as well as the d(hkl) values estimated for the different Cub-SnS
planes. We do not evaluate the texture coefcient to quantify
preferential orientation of (200) planes for Z-SnS or of (111) planes
parallel to substrate for R-SnS, because we lack conrmation as to
which of the Cub-structure is to be considered as the standard. We
accept that the observation [14] made on a prevailing confusion in
R-SnS/Z-SnS structural assignment in the published work on thin
lm SnS may be valid. In the assignment of nano-crystals prepared
by hydrothermal synthesis to Z-SnS [10], the (200) peak of the
powder diffraction pattern is lower in intensity to (111) peak, as
expected for the zinc blende structure. However, in SnS thin lms
prepared by different chemical techniques for which zinc blende
structure has been assigned previously [8,9,15], the (111) and (200)
XRD peaks are of nearly the same intensities, similar to what is
given in Table 1. Thus, we limit here by classifying the lms
deposited at 20 and 30
C, with dominant cubic crystalline struc-
ture, as Cub-SnS, without assigning them to either R-SnS or Z-SnS.
That task is left to a future work to examine the present results and
previous work on Z-SnS [8e10,15], and to come to a reasonable
conclusion.
The orthorhombic structure, dominant in lms deposited at 35
and 40
C, is common for most SnS thin lms deposited by diverse
methods [1e7], and its standard pattern is of the mineral herzen-
bergite with lattice constants a, 0.430 nm; b, 1.157 nm; c, 0.399 nm.
The dominant peak in most cases is (111) as is in the present case,
but (040) peak could be dominant as well. A clear transition from
(040) preferential orientation for lms of 100 nm thickness to (111)
preferential orientation at lm thickness of 300 nm is reported for
OR-SnS lms deposited by ALD at substrate temperatures of 120 or
200
C [6].
From Fig. 4(a and b) we infer that the lms deposited at 20 and
30
C are of cubic crystalline structure with very little presence of
the orthorhombic phase, whereas, that deposited at 35
C and
above (Fig. 4(aec)) are of orthorhombic phase. In our previous
report on the condition for depositing Cub-SnS (assigned as Z-SnS),
the deposition temperature was found to be necessarily below
26
C, and typically 20
C [8,11]. No adherent lm was obtained at
higher temperatures. However in that case we considered that the
solution composition (containing hydrochloric and acetic acid)
rather than the temperature was responsible for the deposition of
cubic phase of the material. In our previous work [1,2] on SnS thin
lms deposited using the same bath composition as here at tem-
peratures 25e75
C, the possibility of obtaining lms with cubic
crystalline structure from baths at temperatures close to 20
C was
not investigated, mostly because of slow growth rate for the lms.
In SnS thin lms obtained via chemical deposition using Snecitrate
complex, pH of the solution is found to be critical in lm deposition
[9]. At pH 5, the deposited lm is of Z-SnS, whereas at pH 6, the
lms are OR-SnS. At the lower pH, ion-by-ion mechanism is pro-
posed to take place leading to the deposition of Z-SnS. Deposition in
these cases is done at 35
C on already existing SnS thin lm pre-
pared by successive ion layer adsorption and reaction process
which produces Z-SnS thin lms [15]. Irrespective of the cubic
crystalline structure of the base lm, deposition at the higher pH
results in lms with orthorhombic crystalline structure, establish-
ing thereby that pH is the decisive parameter.
3.4.1. Crystal structure of lms deposited at varying temperature
From the results shown in Fig. 4(aec), in which the crystalline
structure of the deposited lms is seen to alter from dominant Cub-
 A.R. Garcia-Angelmo et al. / Solid State Sciences 30 (2014) 26e35 31

(i) The deposition starts at a lower temperature (12 h at 20
C)

and once a base lm is deposited, the temperature is raised to
35
C (12 h); or alternately,
(ii) The deposition starts at 35
C or above (50
C, 4.5 h) and after
the base lm is formed the temperature is lowered to 20
C to
remain for 12 h?

In Fig. 5(a) we present the result of case (i), and in Fig. 5(b) that
of case (ii). To analyze variation in the crystalline structure from the
surface layer toward the depth into the glass substrate, we use the
GIXRD technique. The penetration depth (PD) and sampling depth
(SD) for the X-rays into SnS are estimated using the procedure re-
ported previously to analyze multilayer lms [16,17]. The mass
absorption coefcient (M) for CueKa radiation (0.15406 nm;
0.008 MeV) in SnS is 1509 cm1 and hence the penetration depth
(PD 1/M) is 6630 nm. The sampling depths (SD PD sin U) in SnS
(without considering any distinction among OR, and Cub crystalline
phases) are approximately 60, 115, 175, and 290 nm for U of 0.5, 1.0,
1.5, and 2.5
, respectively, as labeled in Fig. 5(a) and (b).

Case (i): A 12 h deposition at 20
C would produce a Cub-SnS

thin lm of 120 nm in thickness, and a subsequent 12 h more
in the same bath with its temperature raised to 35
C would add
about 130 nm of OR-SnS lm, taking the total lm thickness to
nearly 250 nm (Fig. 1 inset). It would occur this way only if the
deposition at the higher temperature does not follow the crys-
talline structure of the base lm. In Fig. 5(a) bottom plot for
grazing incidence at 0.5
, we see the XRD peaks of the top 60 nm
(SD) of the lm. The (111) XRD peak near 2q of 31
of OR-SnS is

Fig. 4. GIXRD patterns of lms: (a) of small thicknesses 20-110 and 30-110 of pre-
dominantly cubic structure and 35-120 and 40-160 of predominantly orthorhombic
structure; (b) of intermediate thickness 20-230, 30-305, etc.; and (c) of large thickness
35-500, 40-510, and 40-600. Standard powder diffraction les for cubic phase (Cub-
SnS) and orthorhombic phase (OR-SnS) tin(II) sulde are also given.

SnS to dominant OR-SnS at deposition temperatures of 35
C or

above, a question arises e what happens to the crystalline structure
of the lms if:

Table 1
Cubic lattice constant (a) evaluated from Fig. 4(a) and (b), which gives an average
a 0.5792  0.0012 nm. The last two columns give 2q(hkl) and inter-planar distances
d(hkl) evaluated from this average value for specic (hkl).

Cub-SnS 2q (
); I (%) 2q (
); I (%) 2q (
); I (%) (hkl) 2q(hkl) d(hkl)

Figure a (nm) a (nm) a (nm) (
) (nm)

20-110 26.56; 100 30.79; 95 e (111) 26.64 0.3344

Fig. 4(a) 0.5808 0.5803
30-110 26.63; 100 30.97; 90 e (200) 30.85 0.2896
Fig. 4(a) 0.5793 0.5770
Fig. 5. GIXRD patterns of: (a) SnS lm of 250 nm thickness deposited at 20
C for 12 h
20-230 26.69; 100 30.97; 95 44.38; 20 (220) 44.19 0.2048
and subsequently at 35
C for 12 h in the same bath, showing the grazing incidence
Fig. 4(b) 0.5780 0.5785 0.5779
angle (0.5
) and corresponding sampling depth (60 nm) labeled as 0.5
e60, etc.; (b)
30-305 26.58; 100 30.80; 90 44.18; 20 (311) 52.35 0.1746
SnS lm of 300 nm thickness deposited rst at 50
C for 4.5 h and subsequently at
Fig. 4(b) 0.5804 0.5804 0.5796
20
C for 12 h.
32 A.R. Garcia-Angelmo et al. / Solid State Sciences 30 (2014) 26e35

seen almost double in intensity with respect to the (111) peak
near 2q of 26.6
of Cub-SnS. As the sampling depth increases
toward 290 nm (top plot for U 2.5
), the intensities of Cub-SnS
(111) and (200) peaks increase, and become as strong as that of
(111) peak of OR-SnS. We may conclude that the thin lm made
through procedure (i) is composed of a bottom layer of 125 nm
Z-SnS on which OR-SnS of nearly the same thickness is depos-
ited. Note that in the plot 2.5
e290, a background intensity at 2q
of 20e30
is present due to the glass substrate, attesting to the
fact that the GIXRD is analyzing beyond the entire lm thickness
of 250 nm.
Case (ii): The deposition rate extrapolated for 50
C in Fig. 1
(inset) is >30 nm/h. Hence during a 4.5 h period, OR-SnS thin
lm of approximately 150 nm in thickness is deposited on the
glass substrate. During a further 12 h at 20
C, a lm of 120 nm is
deposited, taking the total lm thickness toward 300 nm, since
in the 30 min cooling down period from 50 to 20
C, deposition
proceeds at some variable intermediate rate (30e10 nm/h). In
this case we fail to observe Cub-SnS as a top layer in the 0.5e
60 nm GIXRD pattern, or at any depth into the lm. The material
is dominantly OR-SnS. From the surface morphology of the lms
seen in Fig. 3A (a) and (d), the deposition at 20
C on OR-SnS
lms deposited at 40
C or higher temperature would proceed
within the voids as well as along the thickness. However, such
deposition at 20
C follows the OR-SnS structure of the base lm,
rather than the Cub-SnS which would be deposited on bare glass
substrate. In the 2.5
e290 plot, the amorphous background of
the glass substrate is seen, and hence the GIXRD engages the
entire lm thickness.
illustrated in Fig. 6(a) for a lm with 200 nm thickness deposited at
30
C of predominantly the Cub-SnS phase; and in Fig. 6(b) for a
lm with 300 nm thickness deposited at 40
C, which is of pre-
dominantly OR-SnS phase. Ratio of the peak areas OR(111)/
Cub(200) is considered indicative of the relative abundance of the
two phases in the lm or the layer within the lm in case of GIXRD
results shown in Fig. 5. We have ignored any overlap from the
OR(101) to the left of the Cub(200) peak, because a strong (111)
orientation (usually of 100% intensity) is prevalent in the OR-SnS
phase, at the expense of all other planes including (101), which in
randomly oriented sample has a 70% intensity e 2nd in intensity,
after the (111) peak. Crystallite diameter is evaluated from the full
width at half maximum of the diffraction peaks using Scherrer
formula. Following general conclusions are drawn from the data in
Table 2: crystallite diameters D are 10e20 nm; increase in D with
lm thickness is small e by 1e3 nm even when the lm thickness
increases by a factor of 3e4. At temperature 20e30
C, the abun-
dance of Cub-SnS phase is generally more than twice that of OR-
SnS, and the ratio is reversed at deposition temperatures 35e
50
C. Why this should happen within a small temperature interval
of 30e35
C is a question not taken up now. A combination of thin
lm deposition parameters such as temperature, solution compo-
sition and pH may play a role.
3.5. Optical absorption and band gap
A value for Eg of approximately 1.7 eV is reported for Cub-SnS
[8,9,15], classied under Z-SnS, whereas it is about 1.1 eV for OR-
SnS [18]. In Fig. 7(a) are shown the specular optical reectance

3.4.2. Crystalline parameters

Table 2 gives the crystallite diameter (D) for the OR-SnS and
Cub-SnS phases and an estimate for the relative abundance of the
phases (Cub/OR) in the lms obtained from data in Figs. 4 and 5. For
these evaluations it is necessary to de-convolute close-lying
Cub(200) and OR(111) peaks near 2q of 31
. This procedure is

Table 2
Crystallite diameters in the cubic (Cub) and orthorhombic (OR) phases of SnS
constituting the thin lms of different thicknesses deposited at different tempera-
tures evaluated from data presented in Figs. 4 and 5. The last column, OR(111)/
Cub(200) represents a measure of the relative abundance of the OR-SnS component
in the lm with respect to the Cub-SnS component.

Temperature (
C) Film thickness Crystallite diameter OR(111)/

or SD (nm) (nm) Cub(200)

Cub(200) OR(111)

20 110 12 e 0.1
230 18 16 0.3
30 110 13 13 0.6
200 14 15 0.5
305 20 17 0.4
35 120 13 14 1.1
340 15 15 2
500 15 17 2.7
40 160 9 16 1.1
300 13 16 2.8
500 14 17 3.8
600 14 17 3.8
20
C SD: 60 11 13 1.1
(12 h) 35
C (12 h) SD: 115 10 19 0.6
SD: 175 11 19 0.4
SD: 290 10 16 0.5
50
C SD: 60 11 15 2.4
(4.5 h) 20
C (12 h) SD: 115 11 15 2.2
SD: 175 13 14 2.9
Fig. 6. De-convolution of the GIXRD peaks of cubic and orthorhombic phases to aid
SD: 290 13 15 2.8
evaluation of parameters given in Table 1.
 A.R. Garcia-Angelmo et al. / Solid State Sciences 30 (2014) 26e35
Fig. 7. (a) Optical transmittance T and reectance R spectra of SnS thin lm of cubic
structure deposited at 20
C; (b) T and R spectra of SnS thin lm of orthorhombic
structure deposited at 40
C; (c) variation of optical absorption coefcient (a) with
photon energy, demonstrating the band gap type for cubic-SnS in inset (d) and that for
OR-SnS in inset (e).
and transmittance spectra of Cub-SnS thin lm of 230 nm in
thickness deposited during 24 h at 20
C and in Fig. 7(b) those of an
OR-SnS thin lm of 300 nm thickness deposited during 10 h at
40
C. The Cub-SnS lm has a compact morphology, as shown in
Fig. 2(e), and hence is specular. The T R values of this lm remain
above 90% from the infrared toward the red, and then strong optical
absorption sets-in. An approximate value for the wavelength (lg) at
which the strong (valence-to-conduction band) optical transitions
set-in may be identied as 745 nm. This would correspond to an Eg
(in eV 1240/lg-nm) of 1.66 eV. The OR-SnS lm has a morphology
shown in Fig. 2(h) with platelet dimension of 200e500 nm com-
parable with wavelength in the visible region. This causes optical
scattering loss, and hence the T R values continuously descend
33
from >90% at a wavelength 2500 nm toward 70% near 1000 nm.
Now, stronger optical absorption due to band-to-band transitions
begins. An approximate lg of 1130 nm and a corresponding Eg of
1.1 eV may be proposed for this lm. Optical absorption coefcients
(a) for the materials are estimated by considering multiple re-
ections within the lm [19]. Values of a for Cub-SnS and OR-SnS,
versus photon energy (hn) are plotted in Fig. 7(c). There is a clear
distinction between the two materials in the values of Eg, which is
in accordance with previous reports: close to 1.7 eV for Cub-SnS
[8,9,15] and to 1.1 eV for OR-SnS [9,18]. The plot for band gap
analysis in Fig. 7 inset (d) for Cub-SnS shows that a direct Eg of
1.67 eV with forbidden optical transitions may be assigned to this
material [20]. Inset (e) in Fig 7 shows that OR-SnS, the most studied
of SnS thin lms [1e7], has an indirect Eg of 1.1 eV with allowed
optical transitions, in agreement with earlier published work. The
crystallite grain diameter for the dominant crystalline phases in
both lms is 16e18 nm (Table 2), and hence any difference in Eg
between the materials of the lms is ascribed to difference in the
crystal structure and not to quantum connement. Effort to un-
derstand such difference among three crystal structures of SnS:
orthorhombic, zinc blende, and rock salt [21] in the context of band
alignment of CdS/SnS solar cells through rst principle density
functional pseudo-potential method has been a rst step [22]. Wide
range of optical band gaps are reported for the OR-SnS and classi-
ed under direct or indirect optical gap, even though an indirect Eg
of 1.1 eV is an often concluded value [1e7,18]. Experimental and
theoretical studies on SnS often disagree [14]. However, a recent
theoretical study on OR-SnS has assigned an indirect band gap of
1.07 eV to it [23], in agreement with the value seen in Fig. 7 inset
(e).
3.6. Electrical conductivity
In-plane electrical conductivity of SnS thin lms of intermediate
thicknesses deposited at 20 and 30
C of Cub-SnS and at 35 and
40
C of OR-SnS is shown in Fig. 8. All the samples show photo-
induced response in conductivity. Data on samples maintained
for the rst 30 s under the dark; followed by another 30 s with
800 W/m2 of illumination; and the next 40 s with the illumination
shut-off, show that the electrical conductivity increases by a factor
of 1.5e12 under illumination, depending on the sample. The plots
labeled H are for the lms heated at 300
C in a nitrogen atmo-
sphere for 30 min, prior to the measurement. Even though heating
is not found to alter the chemical composition (Fig. 2), morphology
or crystalline structure of the lm, in general it improves the dark-
as well as photo-conductivity. In Fig. 3 A(e and f), we see that the
lms deposited at 20 and 30
C have a compact surface, whereas
samples (g and h) deposited at 35 and 40
C have voids of up to 50%
in volume. This feature does not inhibit the electrical conductivity
of the latter samples, which is higher than the former by 2e3 orders
of magnitude. Thus, the charge carrier mobility and/or carrier
concentration in the lms deposited at 35e40
C are higher by
orders of magnitude. This compensates for the loss of conductive
path in the layers. The electrical conductivity in all the lms shown
in Fig. 8 is p-type. This is ascertained in hot-probe test on the
relatively more conductive (as-prepared and heated) lms depos-
ited at 35e40
C. This apparently contradicts the results of EDX in
the lms in Fig. 2(c) where S/Sn ratio is <1 in lms deposited at 30e
40
C. The p-type conductivity in metal chalcogenide semi-
conductors in the absence of deliberate doping may be explained
on the basis of vacancies at metal sites, or anti-site substitution, or
manifestation of variable vacancies [24]. In the present case, the
s2p2 electronic conguration of tin (Sn) provides many of these
options, among them Sn-substitution of S-sites which carries s2p4
electronic conguration thus lacking in electrons at the site. Films
34 A.R. Garcia-Angelmo et al. / Solid State Sciences 30 (2014) 26e35
Fig. 8. Electrical conductivity data of SnS lms of intermediate thickness deposited at
different temperatures measured with samples kept rst in the dark for 30 s, next
under illumination with 800 W/m2 tungsten-halogen light for 30 s, and nally in the
dark for 40 s for decay of the photoconductivity; H-plots are for the samples that are
heated at 300
C for 30 min in nitrogen ambient.
with many crystalline phases of SnS, as well as SnS2, Sn2S3, SnO or
SnO2 which could exist as minor components in the lm have been
prepared via chemical solution and vapor deposition [25,26]. They
present an overall complex picture of mechanisms to choose from
for a given case. We consider that the sulfur-deciency apparent in
S/Sn being <1 in Fig. 2(c) must not be mistaken for the S-site va-
cancy or S-site substitution by Sn, which are required only at part-
per-million level to account for the observed p-type conductivity
and not at percentage level detected in chemical composition an-
alyzes. The excess Sn seen in the EDX chemical analyses may arise
from segregated tin-oxy-hydroxide species or clusters present in
the lms, but not participating in the electrical conductivity.
3.7. Relevance of tin sulde as solar cell absorbers
The p-type electrical conductivity of all the samples in Fig. 8 as
well as their optical properties presented in Fig. 7 qualify both types
of SnS as optical absorbers in thin lm solar cells. Fig. 9 shows the
light generated current density (JL) as a function of lm thickness in
these absorbers when exposed to air mass 1.5 global (AM1.5G) solar
radiation of 1000 W/m2 in intensity. These values are estimated as
described previously [27,28]. It is also possible to estimate the
values for variable band gap absorber such as the material
described in Fig. 5(a), where light is incident through a window/
buffer layer (considered non-absorbing) on Cub-SnS (absorber-1,
Eg-1) of a certain thickness d1 followed by OR-SnS (absorber-2, Eg-2)
of thickness d2 [28,29]. Value of JL sets the upper limit of the short
circuit current density (Jsc). In good quality solar cells, the two
values are nearly equal [27]. In order to achieve this, the crystalline
grain diameter of the present SnS absorbers must be improved by a
factor of 10 e much beyond the 15e20 nm of either material
(Table 2). This requires appropriate re-crystallization techniques. A
smaller Eg of 1.1 eV of OR-SnS provides signicantly higher JL of
26 mA/cm2 for a thickness of 250 nm, compared with a JL of 17 mA/
cm2 for Cub-SnS. The maximum JL obtainable at a larger thickness
in OR-SnS is approximately double (41 mA/cm2) compared with
that in Cub-SnS (22 mA/cm2). However, the open circuit voltage
(Voc) of the solar cell is related to the logarithm of the inverse of the
reverse saturation current (Jo). Jo is many orders of magnitude lower
for the absorber with a higher Eg because the minority carrier
concentration (np n2i /pp) is considerably lower for the same
electrical conductivity (or for the same majority carrier concen-
tration, pp) since the intrinsic concentration (ni) exponentially
Fig. 9. Estimate for upper limit of light generated current density (JL) as a function of
lm thickness for air mass 1.5 global solar radiation (1000 W/m2) for the Cub- and OR-
SnS thin lms in the absence of reection or recombination losses. Values of JL at a lm
thickness of 250 nm and of maxima at large thicknesses are marked.
decreases with Eg. Hence, as of now both these SnS materials hold
promise as solar cell materials. In an actual solar cell structure, the
buffer/absorber interface determines the conduction band off-sets
and the interface recombination loss in current collection, as dis-
cussed in Ref. [12]. The possible presence of two (or more) types of
SnS with distinct band gaps and hence of electron afnity would
require additional attention in such analyses.
4. Conclusions
The present work offers a simple procedure of variation of
deposition temperature in the interval 20e40
C to obtain absorber
material consisting of either or both forms of SnS: compact lm of
cubic crystalline structure with band gap close to 1.7 eV and/or a
layer of vertically stacked platelets of orthorhombic crystalline
structure with band gap 1.1 eV. This possibility brings-in many
design geometries for solar cells. The electrical conductivity of the
lms can vary over a large range, 107e102 (U cm)1 and hence
help optimize the depletion layer width to ensure >90% of optical
absorption within the layer to maximize photo-carrier generation
in the cell. As is common with most chemically deposited thin lms,
the crystallite grain diameter of the lms is 15e20 nm for both
crystalline phases. For efcient thin lm solar cells, this value must
improve by a factor of 10 to reduce recombination losses. The
multivalent states of Sn(II) and Sn(IV) and their vacancies or anti-
site substitutions in SnS should be understood better to improve
the cell performance, which in most reported work has so far
remained below 1% of conversion efciency.
Acknowledgments
We are grateful to Patricia E. Altuzar Coello for GIXRD mea-
surement, Maria Luisa Ramn for assistance in XRD data, Jos
Campos for the electrical characterization and EDX measurement,
Rogelio Moran Elvira for recording FESEM data and to Oscar Gomez
Daza for general assistance in the lm preparation and in optical
characterization laboratory. This work is supported by PAPIIT-
UNAM-IN113909, IN117912, and IT100814, SEP-CONACyT CB-
101472, and LIFYCS-CONACYT 123122. ARG acknowledges graduate
fellowship from CONACYT-Mexico.
References
[1] M.T.S. Nair, P.K. Nair, Semicond. Sci. Technol. 6 (1991) 132e134.
 A.R. Garcia-Angelmo et al. / Solid State Sciences 30 (2014) 26e35
[2] P.K. Nair, M.T.S. Nair, E.A. Meyers, R.A. Zingaro, Thin Solid Films 239 (1994)
85e92.
[3] M. Gunasekaran, M. Ichimura, Sol. Energy Mater. Sol. Cells 91 (2007) 774e778.
[4] K.T.R. Reddy, N.K. Reddy, R.W. Miles, Sol. Energy Mater. Sol. Cells 90 (2006)
3041e3046.
[5] M.M. El-Nahass, H.M. Zeyada, M.S. Aziz, N.A. El-Ghamaz, Opt. Mater. 20 (2002)
159e170.
[6] P. Sinsermsuksakul, J. Heo, W. Noh, A.S. Hock, R.G. Gordon, Adv. Energy Mater.
1 (2011) 1116e1125.
[7] A. Ortiz, J.C. Alonso, M. Garcia, J. Toriz, Semicond. Sci. Technol. 11 (1996) 243e247.
[8] D. Avellaneda, M.T.S. Nair, P.K. Nair, J. Electrochem. Soc. 155 (2008) D517e
D525.
[9] C. Gao, H. Shen, L. Sun, Z. Shen, Mater. Lett. 65 (2011) 1413e1415.
[10] E.C. Greyson, J.E. Barton, T.W. Odom, Small 2 (2006) 368e371.
[11] D. Avellaneda, M.T.S. Nair, P.K. Nair, Thin Solid Films 517 (2009) 2500e2502.
[12] P. Sinsermsuksakul, K. Hartman, S.B. Kim, J. Heo, L. Sun, H.H. Park,
R. Chakraborty, T. Buonassisi, R.G. Gordon, Appl. Phys. Lett. 102 (2013)
053901-1e053901-5.
[13] G. Hodes, Chemical Solution Deposition of Semiconductor Films, Print Edition,
Marcel Dekker, Inc., New York, 2003.
[14] L.A. Burton, A. Walsh, J. Phys. Chem. C 116 (2012) 24262e24267.
[15] C. Gao, H. Shen, L. Sun, H. Huang, L. Lu, H. Cai, Mater. Lett. 64 (2010) 2177e2179.
[16] B.E. McCandless, Mater. Res. Soc. Symp. Proc. 865 (2005) F4.1.1eF4.1.12.
View publication stats
35
[17] P.K. Nair, E. Barrios-Salgado, J. Capistrn, M.L. Ramn, M.T.S. Nair, R.A. Zingaro,
J. Electrochem. Soc. 157 (2010) D528eD537.
[18] R. Poerschke, O. Madelung (Eds.), Data in Science and Technology: Semi-
conductors Other than Group IV Elements and IIIeV Compounds, rst ed.,
Springer-Verlag Berlin Heidelberg, New York, 1992.
[19] D.K. Schrder, Semiconductor Material and Device Characterization, third ed.,
John Wiley & Sons, New York, 2006.
[20] R.A. Smith, Semiconductors, second ed., Cambridge University Press, Bristol,
1978.
[21] A.N. Mariano, K.L. Chopra, Appl. Phys. Lett. 10 (1967) 282e284.
[22] M. Ichimura, Sol. Energy Mater. Sol. Cells 93 (2009) 375e378.
[23] J. Vidal, S. Lany, M. dAvezac, A. Zunger, A. Zakutayev, J. Francis, J. Tate, Appl.
Phys. Lett. 100 (2012) 032104-1e032104-4.
[24] K. Biswas, S. Lany, A. Zunger, Appl. Phys. Lett. 96 (2010) 201902-1e201902-3.
[25] R.D. Engelken, H.E. McCloud, C. Lee, M. Slayton, H. Ghoreishi, J. Electrochem.
Soc. 134 (1987) 2696e2707.
[26] L.S. Price, I.P. Parkin, A.M.E. Hardy, R.J.H. Clark, T.G. Hibbert, K.C. Molloy, Chem.
Mater. 11 (1999) 1792e1799.
[27] J. Nelson, The Physics of Solar Cells, rst ed., Imperial College Press, London,
2003.
[28] D. Becerra, M.T.S. Nair, P.K. Nair, J. Electrochem. Soc. 158 (2011) H741eH749.
[29] M. Calixto-Rodriguez, H. Moreno Garcia, M.T.S. Nair, P.K. Nair, J. Solid State Sci.
Technol. 2 (2013) Q69eQ73.