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Met. Mater. Int., Vol. 18, No. 6 (2012), pp. 989~995 doi: 10.

1007/s12540-012-6010-7

Growth of Sb2S3 Nanowires Synthesized by Colloidal Process and Self-Assembly of Amorphous Spherical Sb2S3 Nanoparticles in Wires Formation
Ivana Lj. Validic *, Nadica D. Abazovic , and Miodrag Mitric Vin c a Institute of Nuclear Sciences, P.O. Box 522, 11001 Belgrade, University in Belgrade, Serbia
(received date: 5 September 2011 / accepted date: 25 January 2012)
We report the organic synthesis and growth of antimony sulfide (Sb2S3) amorphous nanospheres to nanowires via a simple, colloidal synthetic method. Amorphous Sb2S3 nanospheres self-assembly in wires formation was dispersed in isopropyl alcohol. With increased heating time, Sb2S3 nanospheres grew into Sb2S3 nanowires, probably involving both mechanisms of Ostwald-ripening and spherical nanoparticle self-organization through oriented-attachment of individual nanoparticles. Also, the as-synthesized Sb2S3 nanowires with different heating times (0, 5 and 10 min.) from the moment of appearance of the Sb2S3 precipitate were analyzed. The observed nanowires become longer with increased heating time and are around 100 nm in diameter and 10-20 m in length. UV-Vis absorption spectroscopy reveals that the optical band-gap energy of the Sb2S3 nanowires is independent of the heating times and is found to be ~1.5-1.6 eV. The optical band-gap energy found for amorphous Sb2S3 nanospheres was also ~1.5 eV. The structure of Sb2S3 samples was refined down to R-factors of 10.82, 11.76 and 12.08%. The refinement showed that Sb2S3 powder belongs to the orthorhombic type with space group Pbnm (no. 62) and that Sb2S3 nanowires grow along the [010] direction. Key words: semiconductors, chemical synthesis, optical properties, X-ray diffraction, scanning electron microscopy (SEM)

1. INTRODUCTION
Main-group compound V-VI materials have application in catalytic agents, thermoelectric devices, optoelectronic devices and infrared spectroscopy [1-3]. Among these compounds, Sb2S3 is an important photoconductive semiconductor that crystallizes in the orthorhombic system (pbnm space group) [4,5]. Its useful properties make it a promising candidate for important applications in diverse areas such as solar energy conversion due to its good photoconductivity, thermoelectric cooling technology, and photoelectronics in the infrared (IR) region [6]. Sb2S3 nanostructures with different morphologies and architectures were prepared by convenient methods [7-9]. For instance, Wang et al. prepared Sb2S3 nanorods with a sonochemical approach [10]. Qian et al. employed hydrothermal [11], solvothermal [12] and polyol-assisted routes [9] to synthesize Sb2S3 in either rod ribbon or wire form. Lou et al. prepared uniform Sb2S3 nanorods via a single-source precursor based solvothermal approach [13]. Until now, significant developments regarding the synthesis of this material using organic colloidal methods are very few. So far, Deng
*Corresponding author: validzic@vinca.rs KIM and Springer, Published 20 December 2012

et al. [14] reported the first synthesis of Sb2Se3-xSx nanotubes across the entire compositional range (x = 0 to 3) via a colloidal synthetic method. We report the first synthesis of the Sb2S3 nanorods/bars by a modified colloidal synthetic method [15]. On the other hand, understanding the mechanism of nanoparticle self-assembly is of critical significance for developing synthetic strategies in the purpose of forming complex nanostructures with potentially useful properties [16-19]. Moreover, developing assembly strategies is arguably more important than controlling the size and shape of individual nanoparticles through the synthesis. Thus, we believe that understanding the mechanism of self-assembly processes will provide novel synthetic controls. Here we report the organic synthesis and growth of antimony trisulfide (Sb2S3) nanospheres to nanowires by a simple colloidal process involving the injection of Sb(III)-2ethylhexanoic acid (EHA)-complex solution into a hot sulfur solution in paraffin liquid. We also showed that Ostwald-ripening and self-organization are the responsible mechanisms for the self-assembly process of Sb2S3 nanospheres. We found that the optical band-gap energies of Sb2S3 nanowires are independent of the heating times and are found to be ~1.51.6 eV, at the red part of the solar spectrum. The refinement showed that Sb2S3 powder belongs to the orthorhombic type

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with space group Pbnm and that Sb2S3 nanowires, with strong preference, grow along the [010] direction.

2. EXPERIMENTAL PROCEDURES
All chemicals (antimony (III) chloride (SbCl3) (99.0% min Alfa Aesar), sulfur powder (S) (99.999% Alfa Aesar), paraffin liquid (J. T. Baker), 2-ethylhexanoic acid (EHA) (99% Alfa Aesar), oleylamine techn. (70% Aldrich), hexan (J. T. Baker), isopropyl alcohol (J. T. Baker), methanol (J. T. Baker) and benzene (J. T. Baker)) were of the highest purity available and they were used without further purification. In a typical synthesis of Sb2S3 nanowires, both the Sb(III)2-ethylhexanoic acid (EHA)- complex precursor solution and sulfur precursor solution were prepared at the same time. First, Sb(III)-2-ethylhexanoic acid (EHA)-complex solution was prepared by adding 1.8 mmol of SbCl3 to 5 ml EHA in a flask, kept at 90 C and stirred for 30 min until a uniform mixture was formed. Second, a sulfur solution was prepared in a separate flask, where 2.7 mmol of S powder was mixed with 2 ml oleylamine, 25 mL paraffin liquid, kept at 240 C, and then stirred for 30 min. Third, Sb(III)-2-ethylhexanoic acid (EHA)-complex precursor solution was swiftly injected into the S-precursor solution. The mixture was maintained at 240 C under continuous stirring. The color of the mixed solution turned from yellow (with no Sb present) to orange (immediately after adding Sb(III)- 2-ethylhexanoic acid (EHA)complex precursor solution), red (after 1 min. of heating), maroon (3 min. of heating) to gray black (5 min. of heating) indicating the formation of the Sb2S3 species. The as-synthesized Sb2S3 precipitates at 240 C were heated for different times (0, 5 and 10 min.), from the moment of appearance of gray-black Sb2S3. After the reaction, hexane and isopropyl alcohol were added, and the resulting solid products were retrieved by centrifugation with constant washing with a mixture of methanol and benzene (paraffin liquid is soluble in benzene). The final products were dispersible in organic solvents such as isopropyl alcohol. The scanning electron microscopy (SEM) observations and measurements were performed using a JEOL JSM-6460LV instrument (Tokyo, Japan). The Sb2S3 samples were coated with thin a layer of gold deposited by sputtering. Absorption spectra of the Sb2S3 samples in isopropyl alcohol were recorded using a Perkin Elmer Lambda 9 UV-VISNIR Spectrophotometer. The X-ray Powder Diffraction (XRPD) patterns of the investigated samples were obtained on a Philips PW-1050 automated diffractometer using CuK radiation (operated at 40 kV and 30 mA). A fixed 1 divergence and 0.1 receiving slits were used. Diffraction data for structural analysis were collected in the 2 range 10-120, counting for 12s in 0.02 steps. Structure analysis was done by the use of the KOALARIE computing program [20] based on the Rietveld full profile

refinement method [21]. This program is suitable for obtaining microstructural parameters such as crystallite size, micro strain, R-factor and the preferred orientation parameter [20]. Samples for XRPD measurements were prepared using standard protocol [22].

3. RESULTS AND DISCUSSION


Figure 1A shows phases of colloidal synthetic route for preparation of Sb2S3 nanowires on the time scale step by step. The current synthetic method is a modified well-developed technique for colloidal synthesis established by Deng et al. by using green and low-cost paraffin liquid as the solvent [23]. This technique avoids the use of TOP, as TOP is unstable, hazardous, expensive and environmentally harmful solvent, whereas paraffin liquid is a nontoxic, environmentally friendly and stable solvent with a boiling point above 300 C. The synthesis shown on Fig. 1A involves the next step: (A) yellow S-paraffin liquid solution at the temperature of 240 C, (B) orange liquid solution obtained immediately after injection of Sb(III)-2-ethylhexanoic acid-complex into the S-paraffin liquid solution, (C) red solution obtained after 1 min of heating, (D) maroon solution obtained after 3 minutes of heating and (E) gray-black solution forming after 5 min of heating. It is important to emphasize here that in all the above described solutions precipitate is present, except for situation (A) where Sb(III)-2-ethylhexanoic acid-complex is not injected yet. The changing in color of the mixed solution from yellow to gray-black indicated the formation of Sb2S3 species. The precipitates completely released from paraffin were taken from steps (B), (C) and (D) and corresponding SEM micrographs and XRD patterns with assigned planes (JCPDS 03-065-2432) are shown in Fig. 1A. As can be seen in the initial stages (B) and (C), noncrystalline and deformed nanospheres were obtained. In stage (D) quite perfect and homogeneous nanospheres with diameters around 100 nm, with well defined diffraction peaks on the still visible amorphous base, were observed. The final stage, (E), contains crystalline Sb2S3 nanowires as the end product and their optical and morphological dependence is the function of the heating time we discuss further in the text. Large scale self-assembly of nanostructured building components has attracted significant interest for device fabrication as a validated bottom-up technique. Various self-assembly processes based on different driving mechanism have been proved to be possible [24-27]. In Fig. 1B are shown SEM micrographs of amorphous spherical Sb2S3 nanoparticles (D), a photo of amorphous spherical Sb2S3 nanoparticles completely cleaned from paraffin and dispersed in isopropyl alcohol that self-assemble in wires and corresponding UV-Vis absorption spectra with plot for determination of Eg as inset. According to our opinion, the assembly process, in the present case, can be explained considering two different

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Fig. 1. (A) Synthetic route for preparation of Sb2S3 nanowires on the time scale: A (without Sb- complex solution), B (immediately after injection of Sb(III)- 2-ethylhexanoic acid (EHA)-complex solution), C (after 1 min of heating), D (after 3 min of heating), E (Sb2S3 precipitate forming after 5 min of heating), corresponding SEM micrographs and XRD patterns for Samples B, C and D (with corresponding planes (JCPDS 03-0652432)). (B) SEM micrograph of amorphous spherical Sb2S3 (D) nanoparticles, photo of amorphous spherical Sb2S3 nanoparticles dispersed in isopropyl alcohol that self-assemble into wires and corresponding UV-Vis absorption spectra with plot for determination of Eg as inset.

growth mechanisms: (i) Ostwald-Ripening (diffusion/dissolution) where small crystals or sol particles dissolve and redeposit onto larger crystals or sol particles, because larger particles are more energetically favored than smaller particles (see Fig. 1A (C) and (D)), based on transformation that we believe happened in samples (C) to (D) where we observed large and small nanoparticles that end up in quite regular and only large particles, and (ii) self-organization of spherical nanoparticles through oriented-attachment of individual nanoparticles leading to the formation of nanowires (Fig. 2). Probably, after attaining some critical size by Ostwald-ripening, an entire nanoparticle can act as a building block for the

crystallization by oriented-attachment. This is exactly what we have observed at the transition from sample (D) to (E) (SEM micrographs of nanowires observed in Sample E and further their dependence with increased heating time are shown in Fig. 2). It is important to emphasize here that spherical nanoparticle diameter depicted in stage (D) corresponds to the nanowires diameters, a-fact that supports the oriented-attachment mechanism. The results obtained from UV-Vis absorption spectra will be discussed further in the text. The morphologies of the Sb2S3 nanowires were examined with a SEM. Figure 2 shows the product of the as-synthesized Sb2S3 powders, obtained for different heating times,

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Fig. 2. SEM images of the as-synthesized Sb2S3 powders obtained for different heating times A column (0 min), B column (5 min) and C column (10 min), and compared on the same magnification.

from the moment of appearance of the Sb2S3 precipitate at 240 C, A column (0 min.), B Column (5 min.) and C column (10 min.) and compared at the same magnification. As seen in Column A, the lengths of the product range from 3 to 10 m and diameters from 80 to 120 nm. Further, Columns B and C show the products heated for 5 and 10 min, and contain nanowires that became longer with heating. The lengths of the product range from 5 to 20 m with diameters around 100 nm. No real differences in diameters and no significant morphological differences between the last two samples heated for 5 and 10 min have been observed. Thus, the longer the heating time, the longer the lengths of the produced nanowires. For heating time above 5 min, saturation in the nanowires lengths occurs. Briefly, nanowires arise and grow only in

the first 5 min from the moment of appearance of gray-black Sb2S3, while prolonged heating does not have any visible effects on theirs morphology. An optical absorption experiment has been carried out using the UV-visible spectra, which provide a simple and effective method for explaining some features concerning the band structure. Since all experimental results, including XRPD and SEM observations, suggest that Sb2S3 nanowires are in pure high-quality crystalline phases, we suppose that the absorption spectrum represents the true absorption behavior of Sb2S3 nanowires. Figure 3(a) shows the typical UV-visible absorption spectra taken from slightly turbid Sb2S3 dispersions obtained for different heating times: a (0 min), b (5 min) and c (10 min). One of the common ways of extracting

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Fig. 3. (a) UV-Vis absorption spectra of the Sb2S3 products dispersed in isopropyl alcohol and obtained for different heating times: solid line (0 min), dash line (5 min) and dot line (10 min). Inset: plots for determination of Eg. (b) First derivative absorption spectra of the Sb2S3 products heated for 0 min (solid line), 5 min (dash line) and 10 min (dot line).

band gaps from absorption spectra is to get first derivative with respect to photon energy and finding the maxima in the derivative spectra at the lower energy sides [28,29]. The Eg is associated to the maximum in the spectrum, i.e. where the absorbance has a maximum increase with respect to photon energy. In Fig. 3(b), such derivative spectra of the samples are presented. The observed band gap energies for all samples obtained for different heating times, are almost identical, circa 1.65 eV. By performing the first derivative of absor-

bance spectra we limited energy area for determination of Eg that was used in another band gap value estimation by using the following well-known relationship: = k(h)1(h-Eg)n/2. In the equation k is the constant, h is the photon energy and 2 n is equal to 1 for a direct band gap. Plots of (h) vs. (h) for the Sb2S3 samples are shown in Fig. 3(a) as inset. As can be seen, all three plots are quite linear. The values obtained by extrapolating the straight portion to the energy axis at zero absorption coefficients gave direct band gap energies of

Fig. 4. Final Rietveld plots of Sb2S3 powders obtained for different heating times: a (0 min), b (5 min), c (10 min) with corresponding planes for standard pattern of Sb2S3 (JCPDS 03-065-2432)).

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about 1.5 eV for all three samples. Slight differences (in the second decimal place) in the band gap energy values are too small for drawing conclusions. The band-gap found for amorphous Sb2S3 nanospheres were also around 1.5 eV (see Figure 1B), which is not so surprising due to the fact that we observed all planes assigned to the Sb2S3 phase. It is important to emphasize here that in order to avoid difficulties in obtaining Eg from absorption spectroscopy of the dispersed samples, diffuse reflectance measurements (DRS) of dry powders were performed (spectra not shown). The values were obtained by using the Kubelka-Munk equation for all three samples and were found to be 1.55 eV which agrees with information extracted from the absorption spectra. In general, Sb2S3 has a band gap that varies between 1.5 and 2.2 eV depending on the size, shape and crystallinity in the nanoscale regime [4,7,14,30-32]. So, the direct band gap energy of each sample at around 1.5-1.6 eV corresponds to optical transitions expected for Sb2S3 in the literature. The experimental values of the band gap for Sb2S3 nanowires are suitable for photovoltaic conversion, suggesting that Sb2S3 nanowires may be very promising for solar energy and photoelectronic applications. The refinement of the diffraction data showed that Sb2S3 powder belongs to the orthorhombic type structures, where all diffraction peaks could be indexed to a pure phase of Sb2S3 (JCPDS 03-065-2432). The structure refinements were done in the space group Pnma (no.62). Results of the final Rietveld refinements for all three samples with different heating times, a (0 min), b (5 min) and c (10 min) are depicted in Fig. 4. The corresponding planes for standard patterns of Sb2S3 are given in Fig. 4(a). The structure of antimony trisulfide was refined down to the R-factor of 10.82(a), 11.76(b) and 12.08(c) %. Results of the Rietveld refinements also show that the Sb2S3 nanowires predominantly grow along the [010] direction, which is accordance with the fact that in the Pnma setting, the rods and wires are parallel to the [010] direction [33]. Refined against experimental data (1.75), very high and similar values of the preferred orientation parameter (t) for all three samples were observed. In principal, the non-random particle orientation (when the shapes are anisotropic, for example, platelet-like or needle/wires-like) is called preferred orientation effect and are addressed by introducing the preferred orientation factor (Thkl) and the preferred orientation parameter refined against experimental data (t) [34].

through a colloidal organic synthetic route. We showed that amorphous spherical Sb2S3 nanoparticles that self-assemble in wires follow a two-stage process: (i) Ostwald-Ripening (diffusion/dissolution) where small crystals or sol particles dissolve, and redeposit onto larger crystals or sol particles, and (ii) self-organization of spherical nanoparticles through oriented-attachment of individual nanoparticles leading to the formation of nanowires. The found band-gaps of our nanowires and amorphous Sb2S3 nanospheres (~1.5-1.6 eV) are at the red part of the solar spectrum, thus suggesting that these nanowires may hold promise for solar energy conversion as well as for novel opto-electronics applications. We also revealed that Sb2S3 nanowires grow along the [010] direction with strong preference. We believe that it is reasonable to expect that the present methods can be extended to the synthesis of other semiconductor nanowires as well, by the suitable choice of sources and synthetic parameters.

ACKNOWLEDGMENTS
Financial support for this study was granted by the Ministry of Science and Technological Developments of the Republic of Serbia (Project 172056, III 45020 and III 45015).

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4. CONCLUSIONS
Using a simple and low-cost colloidal organic synthetic technique involving the injection of Sb(III)-2-ethylhexanoic acid (EHA) complex source solution into a hot paraffin liquid containing sulfur (S), we demonstrated growth of antimony trisulfide (Sb2S3) amorphous nanospheres into nanowires

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