Open Journal of Synthesis Theory and Applications, 2013, 2, 33-37

doi:10.4236/ojsta.2013.21003 Published Online January 2013 (http://www.scirp.org/journal/ojsta)

Synthesis and Characterization of CuIn2n+1S3n+2

(with n = 0, 1, 2, 3 and 5) Powders
Naoufel Khemiri*, Dhafer Abdelkader, Bilel Khalfallah, Mounir Kanzari
Photovoltaic and Semiconductor Materials Laboratory, Tunis-El Manar University, Tunis, Tunisia
Email: *naoufel_khemiri@yahoo.fr

Received November 25, 2012; revised December 28, 2012; accepted January 5, 2013

ABSTRACT
CuIn2n+1 S3n+2 crystals were synthesized by horizontal Bridgman method using high purity copper, indium, sulfur ele-
ments. The phases and crystallographic structure of the CuIn2n+1S3n+2 crystals were analyzed by X-ray diffraction (XRD)
and the composition of the material powders was determined using the energy dispersive X-ray analysis (EDX). Meas-
urement data revealed that CuIn2n+1S3n+2 materials have not the same structure. In fact, CuInS2 and CuIn3S5 crystallize in
the chalcopyrite structure whereas CuIn5S8, CuIn7S11 and CuIn11S17 crystallize in the cubic spinel structure.

Keywords: CuIn2n+1S3n+2; Synthesis; Structural Properties

1. Introduction the presence of a single pair of the defect complex

(2V−1Cu + InCu2+) in every five units of CIS [7]. In the
Developments of thin film solar cells based on CuInS2
present study, we have investigated the structural proper-
and related alloys have made considerable progress in
ties of CuIn2n+1S3n+2 powders synthesized by the horizon-
recent years. Copper indium sulfide thin films are one of
tal Bridgman method.
the most promising absorber materials in solar cells be-
cause he has a high optical absorption coefficient (105
cm−1), and an optical band gap of 1.5 eV [1] and that’s
2. CuIn2n+1S3n+2 Materials
why CuIn2n+1S3n+2 materials attract much attention. In In order to understand the formation of ternary com-
addition, the materials do not contain any toxic elements pounds with chemical formula CuIn2n+1S3n+2, their phase
such as Ga or Se, and this may have an advantage in equilibrate can be discussed in terms of temperature or
comparison with other ternary materials like CuIn2n+1Se3n+2 composition. These compounds stabilize due to the or-
and CuGa2n+1S3n+2. They belong to I-III2n+1-VI3n+2 ternary dering of the neutral defect pairs (2V−1Cu + InCu2+) in the
materials which are receiving a great deal of attention as CuInS2 phase and this is due to its huge tolerance to
candidate materials for visible-light and IR emitters, off-stoichiometry [8]. In our knowledge, few papers [9]
high-efficiency solar cells, and other semiconductor and dealing with the physical properties of CuIn2n+1S3n+2
quantum-electronic devices [2]. Many researchers tried compounds have been reported but not much is known
to synthesize CuInS2 material by various methods be- about the fundamental properties of this system. The ter-
cause of its important properties, a new green synthesis is nary compositional triangle is the basis for analyzing the
described by some authors without using any organic composition phase behavior of these materials. In Figure
solvent [3], a new strategy has been presented to the con- 1, a schematic ternary diagram for CuIn2n+1S3n+2 com-
trollable synthesis of CuInS2 hollow nanospheres based pounds is shown. This ternary diagram can be reduced in
on the Cu2O solid nanospheres as the precursor in the a pseudo-binary diagram along the interconnection line
absence of any surfactant [4], a facile and low-cost between Cu2S and In2S3 binary materials. Indeed, by
method was developed to prepare metastable wurtzite combining these two compounds, we can obtain all ma-
copper indium sulfide (CuInS2) nanocrystals under at- terials belonging to the family with chemical formula
mospheric conditions [5] and luminescent CuInS2 nano- CuIn2n+1S3n+2 with n = 0, 1, 2, 3 and 5. The bold points
crystals were synthesized in dodecanethiol precursors [6]. along the line connecting Cu2S and In2S3 represent these
I-III2n+1-VI3n+2 ternary materials are called ordered va- materials.
cancy compound (OVC). The formation of the OVC
compound CuIn3Se5 has already been explained as due to 3. Synthesis of Materials
*
Corresponding author. The CuIn2n+1S3n+2 (with n = 0, 1, 2, 3 and 5) crystals have

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34 N. KHEMIRI ET AL.

CuInS2
S CuIn3S5
0.0 1.0

CuIn5S8
0.2 0.8
CuIn7S11
In2S3 0.4 0.6
CuIn11S17
Figure 2. Photographs showing the CuIn11S17 ingot.
0.6 0.4
Cu2S comparing the d-spacing with Joint Committee on Pow-
0.8 0.2 der Diffraction Standard (JCPDS) data files. The compo-
sition of powders was determined by means of energy
1.0 0.0 dispersive X-ray analysis (EDX) by a JEOL 6700F
In
0.0 0.2 0.4 0.6 0.8 1.0 Cu equipment which uses K-ray for Cu and L-ray for In and
S as standards.
Figure 1. The ternary system Cu-In-S including the pseu-
do-binary section Cu2S-In2S3. 4. Structural Characterization
been prepared by Bridgman horizontal method growth. 4.1. XRD Results
High purity elemental materials of copper, indium and X-ray diffraction (XRD) was used to study the structural
sulfur (Balzers 99.999%) were taken in proportions cor- properties of CuInS2, CuIn3S5, CuIn5S8, CuIn7S11 and
responding to the stoichiometric composition of the CuIn11S17 powders. Figure 3 shows the X-ray diffraction
compounds CuInS2, CuIn3S5, CuIn5S8, CuIn7S11 and (XRD) patterns of the CuIn2n+1S3n+2 materials (with n = 0,
CuIn11S17 and then loaded into five quartz ampoules. The 1, 2, 3 and 5). It is clear from Figures 3(a), (b) that the
growth of crystals was carried out in ampoules (20 cm in peak due to the 112 plane has the highest intensity for the
length with thickness 2 mm), that were pre-cleaned by CuInS2 (PDF 27-0159) and CuIn3S5 (PDF 35-1349)
chemical etching in concentrated acid HF, washed in powders while the highest intensity for CuIn5S8 (PDF
distilled water then with acetone, and finally, dried in 72-0956), CuIn7S11 (PDF 49-1383) and CuIn11S17 (PDF
oven at 150˚C during 30 minutes. The ampoules were 34-0797) powders is the peak due to the 311 plane. All
evacuated down to 10−5 mbar and were sealed off. The the diffraction peaks of the patterns shown in Figure 3
sealed ampoules containing the pure elements were could be indexed as those of CuIn2n+1S3n+2 (n = 0, 1, 2, 3
placed into a horizontal position in programmable fur- and 5) with tetragonal chalcopyrite structure for CuInS2
nace (Nabertherm-Allemagne). For the synthesis, the (space group I-42d [10]) and CuIn3S5 (space group P-42c
temperature of the furnace was increased from room [11]) and with cubic spinel structure (space group Fd3m
temperature to 600˚C with a slow rate of 10˚C/hour in [12-14]) for CuIn5S8, CuIn7S11 and CuIn11S17. This tran-
order to avoid explosions due to sulfur vapor pressure (2 sition in the crystal structure between n = 0 and 1 and n =
atm at 493˚C and 10 atm at 640˚C). The temperature was 2, 3 and 5 in the CuIn2n+1S3n+2 system can be explained
kept constant at 600˚C for 24 hours. Then, the tempera- by the migration of a part of In3+ ions towards octahedral
ture was increased with a rate of 20˚C/hour up to 1000˚C. sites when the indium atoms increase in the structure.
A complete homogenization could be obtained by keep- Indeed, the In3+ ions can be stabilized in both tetrahedral
ing the melt at 1000˚C for 48 hours. After that, the tem- and octahedral sites but tend to form bonding with octa-
perature was lowered to 800˚C at a rate of 10˚C/hour and hedral coordinations. The spinel structure is favored by
the furnace was switched off until the tube reached room increasing the indium content in the CuIn2n+1S3n+2 system
temperature. Then, the ampoules were removed from the [15]. We also note that the XRD patterns of all com-
furnace and were broken to retrieve the synthesized in- pounds do not contain extra reflections corresponding to
gots. The resulting ingots are opaque and black in color. the elements or other secondary phases, which confirms
Figure 2 represents the CuIn11S17 ingot. Finally, the the homogeneity of the synthesized materials. The lattice
CuIn2n+1S3n+2 ingots were crushed in order to obtain parameters (a) and (c) of CuInS2 and CuIn3S5 was calcu-
CuIn2n+1S3n+2 powders. The phases and crystallographic lated by using Equation (1) whereas Equation (2) was
structure of the CuIn2n+1S3n+2 powders were investigated used to calculate the lattice parameter (a) of CuIn5S8,
by X-ray diffraction (XRD) using monochromatic CuKα CuIn7S11 and CuIn11S17 [16].
(λ = 1.54052 Å) radiation in 2θ range of 20˚ - 60˚. The
operation voltage and current used are, respectively, 40 1 h2  k 2 l 2
  2 (1)
kV and 30 mA. The observed phases were determined by d2 a2 c

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 N. KHEMIRI ET AL. 35

Bragg angle 2θ˚ Bragg angle 2θ˚

(a) (b)

Bragg angle 2θ˚

(c)

Bragg angle 2θ˚ Bragg angle 2θ˚

(d) (e)

Figure 3. XRD patterns of the synthesized: (a) CuInS2 (b) CuIn3S5 (c) CuIn5S8 (d) CuIn7S11 and (e) CuIn11S17 powders.

1 h2  k 2  l 2 (where θ is Bragg angle) is calculated and the Nel-

 (2) son-Riley plot is represented for different reflections. In
d2 a2
this method, the value of lattice parameter is determined
where d is interplanar spacing determined using Bragg’s by extrapolating Nelson-Riley functions to f(θ) → 0.
equation and h, k, l are the miller indices of the lattice Figure 4 represents the Nelson-Riley plots for CuInS2
planes. The corrected values of lattice parameters are and CuIn7S11 powders. The calculated values of lattice
estimated from Nelson-Riley [17] method. Consequently, parameters were collected in Table 1.
Nelson-Riley function [18]:
1  cos 2  cos 2   4.2. EDX Results
f ( )     (3)
2  sin   
The atomic ratios of Cu, In and S elements and the

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36 N. KHEMIRI ET AL.

chemical composition of the prepared powders have been 5. Conclusion

determined using the energy dispersive X-ray analysis In summary, CuIn2n+1S3n+2 (n = 0, 1, 2, 3 and 5) materials
(EDX). The EDX analysis is made at several zones of the were successfully synthesized using the horizontal
powders in order to obtain an average atomic concentra- Bridgman method. The XRD spectra of the powders in-
tion. The atomic ratios of the elements and the composi- dicate that the CuIn2n+1S3n+2 powders can be formed in
tion of powders are presented in Table 2. The uncer- different structures. Indeed, for n = 0 and 1, the powders
tainty of the present measurements is about 5%. As is crystallize in the chalcopyrite structure with the preferen-
seen in Table 2, the compositions of CuIn2n+1S3n+2 (n = 0, tial orientation along 112 plane. On the passage to n = 2,
1, 2, 3 and 5) powders is fairly close to the ideal theo- 3 and 5, CuIn5S8, CuIn7S11 and CuIn11S17 powders crys-
retical values of the starting composition. We also note tallize in the spinel structure with the preferential orient-
that all powders were deficient in sulfur. tation along 311 plane. The compositions of CuIn2n+1S3n+2

13 312

12

116

220

004

103
112
11
Lattice parameters (Å)

10 cc == 11,15
11.15 ÅÅ
9
CuInS2

7
aa = 5,53
5.53 ÅÅ
6

4
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
f(θ)

Figure 4. Nelson-Riley plots for calculation of corrected lattice parameters of CuInS2 and CuIn7S11 powders.

Table 1. Lattice parameters of CuIn2n+1S3n+2 (n = 0, 1, 2, 3 and 5) powders.

CuInS2 CuIn3S5 CuIn5S8 CuIn7S11 CuIn11S17

a (Å) 5.53 5.50 10.47 10.58 10.70

c (Å) 11.15 10.85 - - -

Table 2. Chemical compositions of CuIn2n+1S3n+2 (n = 0, 1, 2, 3 and 5) powders.

At% CuInS2 CuIn3S5 CuIn5S8 CuIn7S11 CuIn11S17

Cal. 25.00 11.11 7.14 5.26 3.44

Cu
Obs. 25.58 12.65 7.39 5.32 3.54

Cal. 25.00 33.33 35.71 36.84 37.93

In
Obs. 23.54 30.75 36.61 37.67 37.98

Cal. 50.00 55.55 57.14 57.89 58.62

S
Obs. 50.88 56.59 56.00 57.00 58.48

Compositions Cu1.03In0.93S2.04 Cu1.13In2.78S5.09 Cu1.03In5.13S7.84 Cu1.01In7.15S10.84 Cu1.02In11.01S16.95

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 N. KHEMIRI ET AL. 37

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