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Communication

Organic Synthesis with Different OA/EHA Ratios of Sb 2 S 3 Nanowires of Flower-Like Organization and [010] Orientation

In this article, organic colloidal synthesis by using different oleic acid (OA)/2-ethylhexanoic acid (EHA) ratio was reported for the first time. We found that all synthesized Sb 2 S 3 nanowires show the flower-like orga- nization and that the optical band-gap energy is independent of OA/EHA ratio. Also, Sb 2 S 3 nanowires grow predominantly along the [010] direction, and a significant decrease in unit cell parameters a, b, and c followed by decreasing the OA/EHA ratio was observed.

It seems that the shorter branched hydrocarbon chain in
´

excess leads to the better structural stability. No similar

results were found in the literature concerning the as-synthesized Sb 2 S 3 nanomaterial. All chemicals (antimony [III] chloride [SbCl 3 ] [99.0 pct min Alfa Aesar, Ward Hill, MA], sulfur powder [S] [99.999 pct Alfa Aesar], paraffin liquid [J.T. Baker, Phillipsburg, NJ], OA [C 18 H 34 O 2 ] [65 pct GC Fluka; Sigma Aldrich, St. Louis,MO], EHA [99 pct, Alfa Aesar), oleylamine techn. [70 pct Sigma 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 subsequent purification. In a typical synthesis of Sb 2 S 3 nanowires of flower-like organization, both the Sb(III)-complex precursor solution and sulfur precursor solution were prepared at the same time. The Sb(III)-complex solution was prepared by adding 1.8 mmol of SbCl 3 to a mixture containing different OA/EHA ratios [(1) 4 mL OA and 1 mL EHA, (2) 2.5 mL OA and 2.5 mL EHA, and (3) 1 mL OA and 4 mL EHA]. Mixture was kept at 363 K (90 C) and stirred for 30 minutes until Sb-fatty acid complex was formed. The other flask was loaded with 2.7 mmol of S powder, 2 mL oleylamine, and 25 mL of paraffin liquid. The mixture was kept at 513 K (240 C) for approximately 30 minutes, i.e., until transparent yellow mixture was formed. Then, a Sb- fatty acid complex was injected swiftly into the S-precursor solution. The mixture was maintained at 513 K (240 C) with continuous stirring. Immediately after reaching the temperature of 513 K (240 C), the color of the mixed solution turned from orange-yellow to gray black, indicating the formation of the Sb 2 S 3 species. The as-synthesized Sb 2 S 3 precipitates at 513 K (240 C) were heated for 6 minutes from the moment when Sb-fatty acid complex was injected. After this time, the reaction was stopped by an injection of hexane/isopropyl mixture (1/1, vol/vol). The resulting solid products were retrieved by centrifugation and washed/precipitated few times with methanol/benzene mixture, until paraffin liquid was removed. The final products were dispersible in organic solvents such as isopropyl alcohol. The scanning electron microscopy (SEM) observa- tions and measurements were performed using JEOL JSM-6460LV instrument (JEOL Ltd., Tokyo, Japan). The Sb 2 S 3 samples were coated with a thin layer of gold deposited by the sputtering process. Absorption spectra of the Sb 2 S 3 samples in isopropyl alcohol were recorded using PerkinElmer Lambda 9 UV-

VIS-NIR Spectrophotometer (PerkinElmer, Waltham, MA). The X-ray powder diffraction (XRPD) patterns of the investigated samples were obtained on a Philips

ˇ ´

IVANA Lj. VALIDZ IC , NADICA D. ABAZOVIC ,

´

and MIODRAG MITRIC

We report the first time as-synthesized antimony trisul- fide (Sb 2 S 3 ) nanowires with flower-like organization by using different oleic acid (OA)/2-ethylhexanoic acid (EHA) ratio. The resulting optical band-gap energy is 1.6 eV, and it is independent of the OA/EHA ratios. Sb 2 S 3 nanowires grow predominantly along the [010] direction, and a significant decrease in unit cell param- eters was observed. It seems that the shorter branched hydrocarbon chain leads to the better structural stability of the synthesized Sb 2 S 3 nanowires.

DOI: 10.1007/s11661-012-1097-5 The Minerals, Metals & Materials Society and ASM International 2012

One of the most interesting sulfide materials is anti- mony trisulfide (Sb 2 S 3 ) that crystallizes in the ortho-

rhombic system (pbnm space group).

It is well known

[1]

that stibnite (Sb 2 S 3 ) is a common mineral. [2] As a member

of V-VI group binary chalcogenides possessing good

photosensitivity and high thermoelectric power, it is regarded as a promising material for solar energy con- version because of its band gap that covers the range of the solar spectrum. [3] Therefore, various methods have been employed to synthesize this material at the nanoscale. [46] Sb 2 S 3 nanostructures with different morphologies and architectures were prepared by some convenient meth- ods, [68] but colloidal organic syntheses of antimony

trisulfide (Sb

) nanomaterials are rare in the scientific

papers. So far, Deng et al. [9] reported the first synthesis

2 S 3

of Sb 2 Se 3 x S x nanotubes across the entire compositional range (x = 0 to 3) via a colloidal synthetic method. We report the first synthesis of the Sb 2 S 3 nanorods/bars by

the modified colloidal synthetic method.

Until now,

[10]

the developments regarding the synthesis of this material

are few, especially related to the growth using organic colloidal methods.

ˇ ´

IVANA Lj. VALIDZ IC , Senior Scientific Associate, and NADICA

´

D. ABAZOVIC , Scientific Associate, are with the Laboratory for Radiation Chemistry and Physics, Vincˇa Institute of Nuclear Sciences,

University of Belgrade, 11001 Belgrade, Serbia. Contact e-mail:

´

validzic@vinca.rs. MIODRAG MITRIC , Scientific Adviser, is with the Laboratory for Theoretical and Condensed Matter Physics, Vincˇa

Institute of Nuclear Sciences, University of Belgrade Manuscript submitted September 16, 2011.

METALLURGICAL AND MATERIALS TRANSACTIONS A

Sciences, University of Belgrade Manuscript submitted September 16, 2011. METALLURGICAL AND MATERIALS TRANSACTIONS A

PW-1050 automated diffractometer (Philips, Amsterdam, the Netherlands) using CuK a radiation (operated at 40 kV and 30 mA). A fixed 1 deg divergence and 0.1 deg receiving slits were used. Diffraction data for structural analysis were collected in the 2h range 10 deg to 120 deg, counting for 12 seconds in 0.02 deg steps. A structure analysis was conducted by the use of the KOALARIE computing program (http://www.ccp14.ac.uk) [11] based on the Rietveld full profile refinement method. [12] This program is suitable to obtained microstructural param- eters such as crystallite size, microstrain, R-factor, and the preferred orientation parameter. [11] Samples for XRPD measurements were prepared using standard protocol. [13] The current synthetic method is modified, well-developed technique for colloidal synthesis established by Deng et al. by using ‘‘green’’ and low-cost paraffin liquid as

the solvent.

tylphosphine (TOP), as TOP is unstable, hazardous, expensive, and environmentally harmful solvent, whereas paraffin liquid is a nontoxic, environmentally friendly, and stable solvent with boiling point above 573 K (300 C). Also, the synthesis can be carried out under nitrogen or open to air. To the best to our knowledge, this is the first colloidal synthesis of Sb 2 S 3 nanowires where the mixture of two fatty acids (nonco- ordinating solvents) was used and where nanowires of flower-like organization were observed. Low-magnification SEM micrographs of Sb 2 S 3 nanowires and Sb 2 S 3 nano- wires dispersed in isopropyl alcohol are shown on Figure 1. The initial Sb 2 S 3 nanowires are gray-black in color and stuck with each other, and therefore, they are visible to the naked eye. The morphologies of the Sb 2 S 3 nanowires of the flower-like organization were examined with an SEM. Figure 2 shows the product of the as-synthesized Sb 2 S 3 powders, which were obtained for different OA/EHA ratios: A column (OA/EHA = 4), B column (OA/ EHA = 1), and C column (OA/EHA = 0.25); all powders were heated for the same time and compared at the same magnification. No significant morphological

[14]

This technique avoids the use of trioc-

differences were observed between the samples. The lengths of the nanowires range from 5 to 10 lm and the diameters ranged from 40 to 140 nm in all the samples observed. The mixture of two fatty acids (OA:EHA = linear:branched) provided not only the growth of Sb 2 S 3 nanowires, but also what we strongly believe is respon- sible for flower-like organization. In fact, the particles that nucleated at higher temperatures have smaller radii than those nucleated at lower temperatures. This finding

indicates that nucleation is substantially faster as the temperature increases and that the growth kinetics is less strongly dependent on temperature. Primacy in the

growth kinetics takes over the solvents.

are aware, a more complex form than a flower-like organization has not been obtained to date. The Sb 2 S 3 is a direct band gap semiconductor. Optical absorption measurements were carried out to elucidate information on the band gap energy, which is one of the most important electronic parameters for semiconduc- tor nanomaterials. Because all experimental results, including XRPD and SEM observations, suggest that Sb 2 S 3 nanowires of flower-like organization are in pure,

high-quality crystalline phases, we suppose that the absorption spectrum represents the true absorption behavior of the Sb 2 S 3 nanowires. The absorption spectra of slightly turbid Sb 2 S 3 dispersions with different OA/ EHA ratios represented in Figure 3(A) were analyzed using the following well-known relation: a = k(hm)

(hm

energy, and n is equal to 1 for the direct band gap. Plots of (ahm) 2 vs (hm) for the Sb 2 S 3 samples are shown in Figure 3(B). As can be observed, all three plots are linear. The values obtained by extrapolating the straight portion to energy axis at zero absorption coefficients gave the direct band gaps of 1.6 eV for all three plots, respectively. The optical band-gap energy of the Sb 2 S 3 nanowires of flower-like organization is independent of the OA/EHA ratios. The band gap of the Sb 2 S 3 varies between 1.5 and 2.1 in the literature because of the changes in the crystallinity, size, and shape in the nano

regime.

So, the direct band gap energy of each

where k is the constant, hm is the photon

[15]

As far as we

1

E g ) n/2

[1,46,9,16]

] As far as we 1 E g ) n /2 [ 1 , 4 –

Fig. 1—Low-magnification SEM micrograph and photographs of Sb 2 S 3 nanowires dispersed in isopropyl alcohol.

METALLURGICAL AND MATERIALS TRANSACTIONS A

Fig. 2—SEM images of the as-synthesized Sb 2 S 3 powders obtained for different OA/EHA

Fig. 2—SEM images of the as-synthesized Sb 2 S 3 powders obtained for different OA/EHA ratios: A column (OA/EHA = 4), B column (OA/EHA = 1), and C column (OA/EHA = 0.25) heated for the same time and compared using the same magnification.

sample at 1.6 eV corresponds to the optical transitions expected for Sb 2 S 3 in the literature. The refinement of the diffraction data showed that Sb 2 S 3 powder belongs to the orthorhombic type of

METALLURGICAL AND MATERIALS TRANSACTIONS A

structure, where all diffraction peaks could be indexed to a pure phase of Sb 2 S 3 (JCPDS 03-065-2432). The structure refinements were done in the space group Pnma (no.62). The results of the final Rietveld refinements for

Fig. 3—Ultraviolet-Vis absorption spectra ( A ) and plots for determination of E g (

Fig. 3—Ultraviolet-Vis absorption spectra (A) and plots for determination of E g (B) of the Sb 2 S 3 nanowires dispersed in isopropyl alcohol and obtained for different OA/EHA ratio: a (OA/EHA = 4), b without column (OA/EHA = 1), and c without column (OA/EHA = 0.25), heated for the same time.

c without column (OA/EHA = 0.25), heated for the same time. Fig. 4—Final Rietveld plots of

Fig. 4—Final Rietveld plots of Sb 2 S 3 powders obtained for different OA/EHA ratios: A without column (OA/EHA = 4), B without column (OA/EHA = 1), and C without column (OA/EHA = 0.25), heated for the same time, with corresponding planes (JCPDS 03-065-2432).

METALLURGICAL AND MATERIALS TRANSACTIONS A

all three samples with different OA/EHA ratios are depicted in Figure 4. The structure of antimony trisul- fide was refined down to the R-factor of 10.76 pct (Figure 4(a)), 10.87 pct (Figure 4(b)), and 10.49 pct (Figure 4(c)). The values of estimated standard devia-

tions as well as reliability factors confirmed that these data are reliable and that the structure was well refined (not shown). The unit cell parameters are as follows:

a = 1.13230 nm, b = 0.38438 nm, and c = 1.12426 nm

(Figure 4(a)); a = 1.13192 nm, b = 0.38418 nm, and

c

= 1.12389 (Figure 4(b)); and a = 1.13191 nm,

b

= 0.38415 nm, and c = 1.12384 nm (Figure 4(c)).

As can be observed, the unit cell parameters (a, b, and c) decrease with a decreasing OA/EHA ratio, implying that the smaller unit cell dimensions are more energy favorable. At the same time, it is obvious that an excess of EHA fatty acid with the shorter branched hydrocar- bon chain better stabilizes the system than linear OA fatty acid. Also, a decrease of the OA/EHA ratio leads to a reduction of unit cell volume that is in accordance with the previous observation. The results of the

Rietveld refinements also show that the Sb 2 S 3 nanowires grow predominantly along the [010] direction, which agrees with the fact that in the Pnma setting, the rods

However,

Sb 2 S 3

structures, which often are elongated along [001]. [18] So,

it should not be unusual that the seed crystals can be

synthesized to behave in a similar fashion. The same high values of the preferred orientation parameter (s) refined against experimental data (1.60) were observed for all three samples. In principle, the nonrandom particle orientations (when the shapes are anisotropic, for example, platelet like or needle/wires like) are called the preferred orientation effects and are addressed by introducing the preferred orientation factor (T hkl ) and the preferred orientation parameter refined against experimental data (s). [10,19] It has been observed [10] that the orientation parameters s have the highest value for the longest and thinnest Sb 2 S 3 rods/bars and decrease with the heating time for shorter and thicker rods/bars. In this study, we did not find any significant morpho- logical differences in the samples, and the preferred orientation parameter (s) is high and has the same values for all the samples observed. In summary, antimony trisulfide (Sb 2 S 3 ) nanowires with a flower-like organization were synthesized suc- cessfully by an organic colloidal synthetic method for the first time using mixture of OA and EHA acids with

develops in nature as ramified crystals or wire

and wires are parallel to the [010] direction.

[17]

METALLURGICAL AND MATERIALS TRANSACTIONS A

different ratios precipitated at 513 K (240 C). We also presented that Sb 2 S 3 nanowires with flower-like organi- zation grow predominantly along the [010] direction and that an excess of EHA fatty acid with the shorter branched hydrocarbon chain better stabilizes the system structurally than linear OA fatty acid.

Financial support for this study was granted by the Ministry of Science and Technological Develop- ment of the Republic of Serbia (Project 172056 and III

45015).

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