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Journal of Crystal Growth 354 (2012) 157163

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Journal of Crystal Growth


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Structural and morphological dependences of Sb2S3 nanobars synthesised by organo-colloidal process on precursor concentrations and reaction times
ic a,n, Nadica D. Abazovic a, S. Phillip Ahrenkiel b, Ivana A. Jankovic a Ivana Lj. Validz
a b

a Institute of Nuclear Sciences, University of Belgrade, PO Box 522, 11001 Belgrade, Serbia Vinc Nanoscience and Nanoengineering Department, South Dakota School of Mines and Technology, 501 E. Saint Joseph St., Rapid City, SD 57701, United States

a r t i c l e i n f o
Article history: Received 15 February 2012 Received in revised form 30 May 2012 Accepted 1 June 2012 Communicated by K. Deppert Available online 16 June 2012 Keywords: A1. Crystal structure A1. Growth from solutions A1. X-ray diffraction B1. Antimonides B2. Semiconducting materials

abstract
In this paper we report the synthesis of antimony sulphide (Sb2S3) nanobars performed using a simple organo-colloidal synthetic method. The as-synthesised Sb2S3 nanobars with various precursor concentrations and heating times showed differences in the morphology (open and enclosing forms) and structural parameters. UVvis absorption measurements revealed that the optical band gap energies lay in the red part of the solar spectrum. The observed band gap energies, of nearly the same values ( $ 1.6 eV), proved that precursor concentrations and heating times had no effect on them. The structure renement showed that the Sb2S3 powder belonged to the orthorhombic type with a space group Pbnm. It was found that Sb2S3 nanobars predominantly grew along the [010] direction, and that the unit cell parameters and the preferred orientation parameter (t) rened against experimental data were quite dependent on both the precursor concentration and the heating time. The optimum heating time to nicely follow the dependence of structural parameters on the precursor concentration was observed. & 2012 Elsevier B.V. All rights reserved.

1. Introduction Antimony sulphide (Sb2S3) is a semiconducting chalcogenide of the VVI groups of elements. It has a wide range of industrial applications as target material in television cameras, and in microwave, switching and optoelectronic devices, due to its attractive photo-conducting properties and high thermoelectric power [14]. Sb2S3 is an important photoconductive semiconductor that crystallises in the orthorhombic system (pbnm space group) [5,6] and some of its physical properties like photoelectric properties [7], conduction and charge carrier transport mechanism [8] have been reported in the literature. Besides, these characteristics make it a promising candidate for application in solar energy conversion industry as absorbing material [9]. Colloidal syntheses of Sb2S3 nanomaterials in organic media are very rare by dealt with in scientic papers. So far, Deng et al. [10] have described the rst synthesis of Sb2Se3-xSx nanotubes across the entire compositional range (x 03), using a colloidal synthetic method. We performed the rst synthesis of the pure Sb2S3 nanomaterial by the colloidal synthetic method [11]. Here, we report a modied colloidal synthetic route in organic media. It is the rst time oleic acid has been used as a complexing agent/ligand for the synthesis of Sb2S3 nanobars with open and

enclosing morphological forms. We followed the inuence of precursor concentration and reaction time on the morphology, band gap energies and structural parameters of the as-synthesised nanobars. Structural renement of the obtained materials reveals that Sb2S3 nanobars predominantly grow along the [010] direction, while unit cell parameters and preferred orientation parameter (t) are quite dependent on both the precursor concentration and the heating time. It was found that there was an optimum heating time for which structural parameters exhibited a pronounced dependence on the precursor concentration. No similar results concerning the band gap and structural parameter dependences of the as-synthesised Sb2S3 material have been found in the literature.

2. Experimental All chemicals (antimony (III) chloride (SbCl3) (99.0% min. Alfa Aesar), sulphur powder (S) (99.999% Alfa Aesar), parafn liquid (J. T. Baker), oleic acid (OA) (C18H34O2) (65% GC Fluka), 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 were used without further purication. In a typical synthesis of Sb2S3 nanobars, Sb(III)-oleic acid-complex precursor solutions and sulphur precursor solutions were prepared simultaneously. Sb(III)-oleic acid-complex solutions were

Corresponding author. Tel.: 381 118066428; fax: 381 113408607. ic ). E-mail address: validzic@vinca.rs (I.Lj. Validz

0022-0248/$ - see front matter & 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.jcrysgro.2012.06.003

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prepared by adding 0.2 mmol (C1), 0.6 mmol (C2) or 1.8 mmol (C3) of SbCl3 to 9.6 ml oleic acid (OA). Mixtures were kept at 90 1C and stirred for 30 min until Sb (III)-complex was formed. The other asks were loaded with 0.3 mmol (C1), 0.9 mmol (C2) or 2.7 mmol (C3) of S powder, 2 ml oleylamine and 25 mL of parafn liquid. Mixtures were kept at 240 1C for about 30 minutes, i.e. until transparent yellow solutions were formed. Then, the Sb(III)-oleic acid-complex solutions were swiftly injected into the S-precursor solutions. The mixtures were kept at 240 1C, with continuous stirring. Immediately

after reaching the temperature of 240 1C, the colour of the mixed solution turned from orangeyellow to grey black, indicating the formation of the Sb2S3 species. The as-synthesised Sb2S3 precipitates (for each separate concentration C1, C2 and C3) at 240 1C were heated for 0, 5 and 10 minutes from the moment when the grey black Sb2S3 species appeared. After this time, the reaction was stopped by the injection of hexane/isopropyl mixture (1/1 v/v). The resulting solid precipitates were retrieved by centrifugation and washed/precipitated a few times with methanol/benzene mixture,

Fig. 1. SEM images of the as-synthesised Sb2S3 powders obtained for different precursor concentrations (C1, C2 and C3) and heating times: A (0 min), B (5 min) and C (10 min) compared at the same magnication.

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until the parafn liquid was removed. The nal 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 a thin layer of gold deposited by sputtering process. The Field Emission Scanning Electron Microscopy (FESEM) measurements were performed using a TESCAN Mira3 XMU at 20 kV. Selected area diffraction pattern (SAED) was acquired on a JEM-2100 LaB6 HRP transmission electron microscope (TEM) at 200 KV. Energy Dispersive X-Ray Analysis (EDX) data were acquired in the TEM using an Oxford Inca system with an X-Max silicon-drift detector. Absorption spectra of the Sb2S3 samples in isopropyl alcohol were recorded using a Perkin Elmer Lambda 9 UVvis-NIR Spectrophotometer. The X-ray Powder Diffraction (XRPD) patterns of investigated samples were obtained on a Philips PW-1050 automated diffractometer using CuKa radiation (operated at 40 kV and 30 mA). A xed 11 divergence and 0.11 receiving slits were used. Diffraction data for structural analysis were collected in the 2y range 101201, counting for 12 s in 0.021 steps. Structural analysis was done using the KOALARIE computing programme [12] based on the Rietveld full prole renement method [13]. Samples for XRPD measurements were prepared using the standard protocol [14].

It can be observed that with the increase of the concentration from C1 to C2 the length of the nanobars increases and their morphology changes from open to enclosing form. It should be emphasised here that no visible morphological differences were observed between the concentrations C2 and C3, and no signicant differences in the lengths and diameters of the nanobars.

3. Results and discussion The synthetic method used in this work is a modied technique for colloidal synthesis established by Deng et al., which uses green and low-cost parafn liquid as a solvent [15]. As far as we are aware, this is the rst organo-colloidal synthesis of Sb2S3 nanobars where oleic acid is used. Dependences of the morphology, band gap energies and structural parameters of the synthesised nanobars on the concentration and heating time were followed. This technique avoids the use of TOP (trioctylphosphine), because it is an unstable, hazardous, expensive and environmentally harmful solvent. On the other hand, parafn liquid is a nontoxic, environmentally friendly solvent, stable at very high temperatures. Also, the synthesis can be carried out under nitrogen or in the open air. The morphology of Sb2S3 nanobars was checked by SEM. Fig. 1A shows the as-synthesised Sb2S3 powders obtained for different precursor concentrations C1, C2 and C3, heated for the same time (0 min from the moment of the appearance of grey black Sb2S3 species) and compared at the same magnication. As can be seen, there is a mixed morphological system for the lowest concentration (C1), composed of a small number of spherical nanoparticles and the majority of nanobars, with open morphological form. The lengths of the open nanobars range from 5 to 10 mm, with diameters around 100 nm, while the nanoparticles diameters range from 50 to150 nm. With increasing concentration (C2 and C3), only longer nanobars with enclosing morphological form were observed (nanobars that blend with each other and form an enclosing form, see explanation further in the text). The length of the nanobars exceeds 5 mm. No visible morphological differences between concentrations C2 and C3 were observed. Further, Fig. 1B shows the as-synthesised Sb2S3 powders obtained for different concentrations C1, C2 and C3, heated for 5 min (from the moment of the appearance of grey black Sb2S3 species). Compared with the previous sample, no spherical nanoparticles were observed for the sample with the lowest concentration, C1, only morphologically open form nanobars.

Fig. 2. SEM (A), FESEM (B1) and TEM (B2) images of the as-synthesised Sb2S3 powders obtained for precursor concentrations (C1 (image A) and C2 and C3 (image B1 and B2) where open (A), enclosing (B1 and B2) morphological forms of nanobars were observed.

Fig. 3. TEM images and SAED pattern for the synthesised Sb2S3 nanobars, revealing the single-crystalline orthorhombic structure. The growth direction (010) of the nanobars is perpendicular to the (102) planes indexed on the SAED pattern.

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Finally, Fig. 1C shows Sb2S3 powders obtained for different concentrations C1, C2 and C3, heated for 10 min (from the moment of the appearance of grey black Sb2S3 species). With the smallest concentration (C1), prolonged heating time leads to the formation of slightly deformed nanobars with open form morphology. The length of the nanobars increases with the increase of the concentration from C1 to C2, although a slight deformation of nanobars is still present, and

their morphology form changes from open to enclosing. With the highest concentration C3 there is no deformation. The thickness and lengths of the nanobars are mostly the same as described above. From Fig. 1A, B, and C it is obvious that the morphologies of the Sb2S3 nanobars are dependent on both the precursor concentration and the heating time. With the increase of concentration for each separate heating time, the Sb2S3 nanobars on the record

Fig. 4. EDX analysis of the Sb2S3 dispersion placed on the grid. Fe and Cu are artifacts from the grid.

Fig. 5. UVvis absorption spectra of the Sb2S3 products dispersed in isopropyl alcohol, rst derivative absorption spectra of the Sb2S3 products and corresponding plots for determination of band gap energies Eg, for each separate precursor concentration (C1 (solid line), C2 (dashed line) and C3 (dotted line)), obtained for different heating times: A (0 min), B (5 min) and C (10 min).

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grow in length. For a heating time of 5 min we found that the sample was morphologically quite homogeneous, no nanoparticles or deformed nanobars were observed. Taking into account the concentration dependence, for the highest concentration (C3) we found quite homogeneous Sb2S3 nanobars. On the heating time scale (by comparing the same concentration from the three separate images, A, B and C), the morphology changes in such a

way that for C1 we observed clearly visible nanobars with open form and spherical nanoparticles, then quite regular open form nanobars, which ended up with deformed open form nanobars. Further, for C2 we observed regular nanobars that form enclosing forms and on the heating time scale end up with deformed nanobars. Finally, the same enclosing forms composed of nanobars were observed for the highest concentration.

Fig. 6. Final Rietveld plots of Sb2S3 powders obtained for different concentrations (C1, C2 and C3), and heating times: A (0 min), B (5 min), C (10 min) and D (the standard pattern of Sb2S3 with corresponding planes (JCPDS 03065-2432)).

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To conrm the existence of an open (C1) and enclosing (C2 and C3) morphological forms composed of nanobars, we performed high magnication SEM (A), FESEM (B1) and TEM (B2) measurements and presented them in Fig. 2A (open forms) and B1 and B2 (enclosing forms). It can clearly be seen that the nanobars presented in Fig. 2A are indeed open (this is the reason that we named them nanobars with open form), while the nanobars presented in Fig. 2B1 and B2 stick to each other, creating enclosing morphology forms. Fig. 3 shows TEM images and SAED pattern for the synthesised Sb2S3 nanobars. The SAED pattern is essentially identical along the nanobars, verifying that the nanobars are single- crystalline. SAED patterns and lattice images reveal that the lattice vector of the (102) planes is perpendicular to the (010) direction, along which the nanobars grow. These results are in agreement with those obtained from the Rietveld renements of XRPD patterns (see further in the text). EDX spectrum of the synthesised Sb2S3 material conrmed the purity of our samples, detecting only Sb and S (see Fig. 4). Fe and Cu are the peaks from the TEM grid and pole piece. Optical properties of the synthesised materials were characterised by UV/Vis absorption measurements, and presented in Fig. 5 for different heating times (A (0 min), B (5 min) and C (10 min)) and different precursor concentrations (C1 (solid line), C2 (dashed line) and C3 (dotted line)). A common way to extract band gap from absorption spectra is to get the rst derivative of absorbance with respect to photon energy and nd the maxima in the derivative spectra at the lower energy sides [16,17]. The Eg is associated with the maximum in the spectrum, i.e. where the absorbance has the maximum increase with respect to photon energy. In Fig. 5, next to the UV/Vis spectra, such derivative spectra of the samples are presented for different heating times (A (0 min), B (5 min) and C (10 min)) and different precursor concentrations (C1 (solid line), C2 (dashed line) and C3 (dotted line)). The observed band gap energies for all the samples obtained for different heating times and precursor concentrations are almost identical (with very small oscillation) and are about $ 1.68 eV. It is important to emphasise here that by performing the rst derivative of absorbance we limited energy area for determination of Eg that was used in another estimation of the band gap values by using the following well-known relation: a k(hn) 1(hn Eg)n/2, where k is the constant, hn is the photon energy and n is equal to 1 for direct band gap. The obtained (ahn)2 f(hn) plots for slightly turbid Sb2S3 dispersions for different heating times (A (0 min), B (5 min) and C (10 min)) and different precursor concentrations (C1 (solid line), C2 (dashed line)
Table 1 Structure R factors values for different precursor concentrations (C1, C2 and C3) and heating times: A (0 min), B (5 min) and C (10 min). A (0 min) R (%) C1 C2 C3 12.52 11.73 10.99 B (5 min) R (%) 12.82 12.92 11.41 C (10 min) R (%) 13.53 11.56 11.08

and C3 (dotted line)) are given next to the derivative spectra of the samples. As can be seen, all nine plots (A, B and C) are quite linear. The values obtained by extrapolating the straight portion to energy axis at zero absorption coefcients gave the direct band gap energies of about $ 1.55 eV for all nine samples. The slight differences (in the second decimal place) in the values of the band gap energies are too small for drawing conclusions. To avoid the difculties of obtaining Eg from absorption spectroscopy in dispersed samples, diffuse reectance measurements (DRS) of dry powders were performed (spectra not shown). The values obtained by using the KubelkaMunk function for all nine samples were found to be $ 1.6 eV, which is in good agreement with information extracted from 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 [5,10,1821]. So, the direct band gap energy of each sample at around 1.51.7 eV corresponds to optical transitions expected for Sb2S3 in the literature. Further in the text we concentrate on the dependence of structural parameters on the concentration and reaction time of Sb2S3 nanobars. The renement of the diffraction data showed that Sb2S3 belongs to the orthorhombic structure, where all diffraction peaks could be indexed to a pure phase (JCPDS 03065-2432) (Fig. 6D). The structure renements were done in the space group Pnma (no. 62), and the results for all nine samples are depicted in Fig. 6((A) for 0 min heating time for all three concentrations, C1, C2 and C3, (B) for 5 min heating time and (C) for 10 min heating time). The structure of Sb2S3 was rened down to the R factors whose values obtained for different precursor concentrations and heating times were summarised in Table 1. Dependences of the structural lattice cell parameters (a, b and c) on both the precursor concentrations and heating times are shown in Table 2. Results of the Rietveld renements for all the samples show that the Sb2S3 nanobars predominantly grow along the (010) direction, which is in accordance with the fact that in the Pnma setting the rods and wires are parallel to the (010) direction [22]. As can be seen, the unit cell parameters a, b and c permanently increase with increasing concentration (from C1 to C3, for the samples heated for 0 and 5 min), which supports our visual statement about the enclosing form composed of nanobars (see Table 2). Very high and the same values of the preferred orientation parameter (t) rened against experimental data (around 1.50) for the samples heated for 0 and 5 min were observed. In principle, the non-random particle orientation (when the shapes are anisotropic, for example platelet-like or needle/wires-like) is called preferred orientation effect and can be dened by introducing the preferred orientation factor (Thkl) and the preferred orientation parameter rened against experimental data (t) [11,23]. For the samples heated for 10 min, the situation is slightly different. Only the unit cell parameter b permanently increases with the increase of the concentration from C1 to C3. Also, the preferred orientation parameter (t) rened against experimental data increases with increasing concentration from C1, where t 1.06 (meaning that no preferred orientation is present) over

Table 2 Structural lattice parameters (a, b and c) values for different precursor concentrations (C1, C2 and C3) and heating times: A (0 min), B (5 min) and C (10 min). A (0 min) a (nm) C1 C2 C3 1.13176 1.13187 1.13212 b (nm) 0.38398 0.38417 0.38432 c (nm) 1.12379 1.12384 1.12406 B (5 min) a (nm) 1.13159 1.13208 1.13228 b (nm) 0.38393 0.38418 0.38444 c (nm) 1.12340 1.12405 1.12423 C (10 min) a (nm) 1.13136 1.13201 1.13189 b (nm) 0.38395 0.38422 0.38427 c (nm) 1.12363 1.12407 1.12390

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C2, where t 1.41 (preferred orientation is present and very high) to C3, where t 1.72 (extremely high preferred orientation is present). The fact that no orientation is present in the sample C1 could be explained by the most deformed morphology observed, which could be related to the structure. At the end of the paper it is important to emphasise that we performed photoluminescence spectroscopy measurements as an equally important and nondestructive tool for evaluating the optical nature of the materials. No peaks were observed either in PL emission or excitation spectra for a broad spectral range, typical of this material.

4. Conclusion To summarise the work described, nanobars with different morphology (open and enclosing forms, as we name them) of Sb2S3 were synthesised by organic colloidal synthetic method in the presence of oleic acid used for the rst time for the synthesis of antimony sulphide. In our work we followed the concentration and heating time dependences of the as-synthesised Sb2S3 nanobars, showing the primary changes in the morphology and structural parameters. Dependences of the structural factors and morphology on the factors that we can control (precursor concentration and heating time) are inescapable in this analysis, and certainly can lead to a better understanding of the overall picture. On the contrary, the values of the band gap energies found are nearly the same ( $ 1.6 eV), proving that the precursor concentrations and heating times have no effect on them.

Acknowledgements Financial support for this study was granted by the Ministry of Science and Technological Development of the Republic of Serbia (Projects 172056 and 45020). References
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