Escolar Documentos
Profissional Documentos
Cultura Documentos
Materials Letters
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 / m a t l e t
a r t i c l e i n f o a b s t r a c t
Article history: We report the synthesis of antimony trisulfide (Sb2S3) nanorods/bars via a simple, low-cost and colloidal
Received 25 January 2011 synthetic method. The as-synthesized Sb2S3 nanorods/bars with different heating times from the moment of
Accepted 8 March 2011 appearance of the Sb2S3 precipitate at 240 °C are the longest and thinnest in the beginning (diameters of 50–
Available online xxxx
100 nm and lengths of 3–5 μm). UV/Vis absorption spectroscopy reveals that the optical band gap energy of
the Sb2S3 nanorods/bars slightly decreases with increasing the heating times in the range of 1.54, 1.50 to
Keywords:
Colloidal processing
1.47 eV at the red part of the solar spectrum. The structure of Sb2S3 for all free samples was refined down to
Electron microscopy the R-factor of 9.57, 5.43 and 6.19%. The refinement showed that Sb2S3 powder belongs to the orthorhombic
Semiconductors type with space group Pbnm (no. 62). It was found that Sb2S3 nanorods/bars predominantly grow along the
Solar energy materials [010] direction. The preferred orientation parameter (τ) refined against experimental data is quite high and is
X-ray technique found to be 1.42, 1.21 and 1.19 for all three samples observed. A decrease in unit cell parameter b followed by
increasing the heating times was observed.
© 2011 Elsevier B.V. All rights reserved.
1. Introduction
2. Experimental
⁎ Corresponding author. Tel.: +381 118066428; fax: +381 113408607. Fig. 1. Synthetic scheme and photographs of Sb2S3 nanorods/bars dispersed in
E-mail address: validzic@vinca.rs (I.Lj. Validžić). isopropyl alcohol.
0167-577X/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2011.03.032
1920 I.Lj. Validžić, M. Mitrić / Materials Letters 65 (2011) 1919–1922
Alfa Aesar), oleylamine (OA) techn. (70% Aldrich), hexan (J. T. Baker), the Sb2S3 species. The as-synthesized Sb2S3 precipitates at 240 °C
isopropyl alcohol (IA) (J. T. Baker), methanol (J. T. Baker) and benzene were heated for different times (0, 5 and 10 min). After the reaction,
(J. T. Baker)) were of the highest purity available and they were used hexane and IA were added, and the resulting solid products were
without further purification. retrieved by centrifugation with constant washing with mixture of
In a typical synthesis of Sb2S3 nanorods/bars, both the Sb(III)- methanol and benzene.
complex precursor solution and sulfur precursor solution were The scanning electron microscopy (SEM) observations and
prepared in the same time. Firstly, Sb(III)-complex solution was measurements were performed using JEOL JSM-6460LV instrument
prepared by adding 0.6 mmol of SbCl3 to 3.21 g PA in a flask and kept (Tokyo, Japan).
at 80 °C and stirred for 30 min until a uniform mixture was formed. Absorption spectra of the Sb2S3 samples in methanol were recorded
Secondly, sulfur solution was prepared in a separate flask, where using Perkin Elmer Lambda 9 UV/VIS/NIR Spectrophotometer.
0.9 mmol of S powder was mixed with 2 ml OA, 25 mL PL and kept at The X-ray Powder Diffraction (XRPD) patterns were obtained on a
220 °C, then stirred for 30 min. Thirdly, S-precursor solution was Philips PW-1050 using CuKα radiation with a fixed 1° divergence and
swiftly poured into the Sb(III)-complex precursor. The mixture was 0.1° receiving slits. Diffraction data were collected in the 2θ range 10–
maintained at 240 °C with continuous stirring. Immediately after 90°, counting for 12 s in 0.02° steps. Structure analysis was done by
reaching the temperature of 240 °C, the color of the mixed solution the use of the KOALARIE computing program based on the Rietveld
turned from orange–yellow to gray black, indicating the formation of full profile refinement method.
Fig. 2. SEM images of the as-synthesized Sb2S3 powders, obtained for different heating times: a and b (0 min), c and d (5 min) and e and f (10 min).
I.Lj. Validžić, M. Mitrić / Materials Letters 65 (2011) 1919–1922 1921
Fig. 4. Final Rietveld plots of Sb2S3 powders a (0 min), b (5 min), c (10 min), d (the standard pattern of Sb2S3 with corresponding planes), and the values of the preferred orientation
parameters τ.
1922 I.Lj. Validžić, M. Mitrić / Materials Letters 65 (2011) 1919–1922
The refinement of the diffraction data showed that Sb2S3 belongs to highest value for the longest and thinnest rods/bars as we expected, and
the orthorhombic structure, where all diffraction peaks could be indexed decreases with the heating time for shorter and thicker rods/bars.
to a pure phase (JCPDS 03-065-2432). The structure refinements were
done in the space group Pnma (no.62), and results for all three samples 4. Conclusions
are depicted in Fig. 4. The structure of Sb2S3 was refined down to the
R-factor of 9.57(a), 5.43(b) and 6.19(c) %. The unit cell parameters are: In summary, Sb2S3 nanorods/bars were synthesized by a modified
(a) a = 1.13224 nm, b = 0.38420 nm and c = 1.12403 nm, (b) colloidal synthetic method. We also presented that the optical Eg
a=1.13176 nm, b=0.38396 nm and c=1.12368, (c) a=1.13183 nm, slightly decreases with increasing the heating time, and that Sb2S3
b=0.38385 nm and c =1.12376 nm. The unit cell parameter b perma- nanorods/bars predominantly grow along the [010] direction. The
nently decreases with increasing the heating time, implying that the preferred orientation parameter (τ) is quite high for all three samples
smaller unit cell dimensions are energy more favorable. Results of the observed and decreases with the heating time. Also, decrease in cell
refinements also show that the Sb2S3 nanorods/bars predominantly grow parameter b with increasing the heating time was found.
along the [010] direction, that is in accordance with the fact that in the
Pnma setting the rods are parallel to the [010] direction [11]. In other Acknowledgment
words, in reflection mode all the major (h0l) planes are of relatively
higher intensity compared to their reported values (see Fig. 4). In Financial support for this study was granted by the Ministry of
principle, when the shapes of crystallites are isotropic, random Science and Technological Development of the Republic of Serbia
distribution of their orientations is not a problem, and deviations from (Project 172056 and III 45015).
an ideal sample are usually negligible. However, quite often the shapes are
anisotropic (needle/rod-like) and this result in distinctly nonrandom
References
crystallite orientations. The nonrandom orientation is called preferred
orientation and is addressed by the preferred orientation factor (Thkl) and [1] Yu Y, Wang RH, Chen Q, Peng LM. J Phys Chem B 2006;109:13415–9.
the preferred orientation parameter refined against experimental data (τ) [2] Bao H, Cui X, Li CM, Song Q, Lu Z, Guo J. J Phys Chem C 2007;111:17131–5.
[3] Ota J, Srivastava SK. Cryst Growth Des 2007;7:343–7.
[12]. The radial March–Dollase function (as a part of KOALARIE computing [4] Yang J, Zeng JH, Yu SH, Yang L, Zhang YH, Qian YT. Chem Mater 2000;12:2924–9.
program) that describes the anisotropic distribution as a function of angle [5] Hu H, et al. J Cryst Growth 2003;258:106–12.
φhkl is represented in the form: Thkl =(τ2 cos2 φhkl +(1/τ) sin2 φhkl)−3/2. [6] Deng Z, Mansuripur M, Muscat A. J Nano Lett 2009;9:2015–20.
[7] Deng Z, Cao L, Tang F, Zou B. J Phys Chem B 2005;109:16671–5.
In the case of platelet-like particles, the function is stretched along
[8] Ota J, Roy P, Srivastava SK, Nayak BB, Saxena AK. Cryst Growth Des 2008;8:2019–23.
T∥(T∥ N T⊥), while in case of needles/rods, it is stretched along T⊥(T∥ N T⊥). [9] Vogel R, Hoyer P, Weller H. J Phys Chem 1994;98:3183–8.
Therefore, τ b 1 describes preferred orientation of the platelets and τN 1 [10] Lou W, Chen M, Wang X, Liu W. Chem Mater 2007;19:872–8.
describes preferred orientation of the needles/rods [12]. Fig. 4 (a, b and c) [11] Lundegaard LF, Miletich R, Balic-Zunic T, Makovicky E. Phys Chem Miner 2003;30:
463–8.
shows the high values of the preferred orientation parameter (1.42, 1.21 [12] Pecharsky VK, Zavalij PY. Fundamentals of powder diffraction and structural
and 1.19) (τ), for all three samples. The orientation parameter τ has the characterization of materials. Springer; 2009. p. 194–9. chapter 8.