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Journal of Crystal Growth 266 (2004) 523527

Hydrothermal synthesis and crystal structure of pyrite

R. Wua,*, Y.F. Zhenga, X.G. Zhangb, Y.F. Suna, J.B. Xua, J.K. Jianc
a Physics Department of Xinjiang University, No. 14, Shengli Road, Urumqi 830046, Peoples Republic of China College of Chemistry and Chemical Engineering, No. 14, Shengli Road, Urumqi 830046, Peoples Republic of China c Institute of Physics and Center for Condensed Matter Physics, Chinese Academy of Sciences, P.O. Box 603, Beijing 100080, Peoples Republic of China b

Received 15 September 2003; accepted 1 February 2004 Communicated by Mullin

Abstract A single-stage low-temperature hydrothermal synthesis route has been successfully developed for the preparation of pyrite FeS2. The as-prepared pyrite FeS2 was characterized by X-ray diffraction (XRD), a Rietveld renement method, scanning electron microscopy (SEM) and ultravioletvisible (UVVIS) spectrophotometry. The XRD and Rietveld structure renement indicated that the sample structure is a typical AB2 cubic of space group Pa3 with a lattice constant ( a 5:4151 A and a Wyckoff parameter u 0:3868: SEM showed that the polycrystalline pyrite was well crystallized. A possible mechanism for the formation mechanism of the pyrite is discussed. The inuences of reaction time and pH on the formation of the target compound were investigated. r 2004 Elsevier B.V. All rights reserved.
PACS: 61.50nw; 81.05.hd; 81.10. h Keywords: A1. Crystal morphology; A1. Crystal structure; A2. Hydrothermal crystal growth; B2. Semiconducting materials

1. Introduction Pyrite has been investigated for several years as a potential absorber material for photovoltaic thin solar cells because of its favorable basic properties [1,2]. The band gap energy Eg is about 0.95 eV from the interpretation of the schematic densityof-state curves [3] and is comparable to that of silicon but its optical absorption coefcient a 5 105 cm1 for lo750 nm is much higher. In addition, pyrite is composed of nontoxic
*Corresponding author. Tel./fax: +86-99-1858-3183. E-mail address: wurong1022@163.com (R. Wu).

elements that are very abundant, cheap and that are prerequisites for large-scale production of thin lm solar cells [4]. Traditionally, pyrite was synthesized by thermal sulfuration of iron [5,6]. Iron lms were isothermally annealed in H2S or S atmosphere at high temperature. Recently, Nakamura et al. reported that they have prepared pyrite thin lms by spray pyrolysis [7] and an eletrodeposition method [8], but they could not obtain stoichiometric pyrite in a single-stage process; they also needed additional sulfur in order to convert other phases such as FeS or FeS2x into pyrite. Therefore, there is a need to design a low-temperature synthesis route. Recently, the

0022-0248/$ - see front matter r 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.jcrysgro.2004.02.020

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hydrothermal process has opened a fruitful route for the synthesis of advanced inorganic materials that are difcult or impossible to obtain by high-temperature solid-state reaction. However, no reports concerning a hydrothermal method for the growth of pyrite have so far been published. In this paper, we have designed a new way to synthesize pyrite, using FeSO4, Na2S2O3 and S by a single stage hydrothermal method without introducing any further sulfur. Compared with other papers, it simplies the working process and is easily controlled.

3. Results and discussion 3.1. Structural analysis Fig. 1 shows the XRD pattern of products prepared using FeSO4 7H2O(0.01 mol), Na2S2O3 (0.01 mol) and S(0.01 mol) at 200 C for 24 h. The sharp diffraction peaks of the powders implied their good crystallinity. Its XRD pattern reveals that the as-prepared FeS2 consisted mainly of pyrite FeS2 with a small amount of marcasite FeS2. The main phase is pyrite FeS2 with lattice parameters close to PDF 42-1340. The impurity phase can be indexed as marcasite FeS2 (PDF 37475). A key point in the preparation of semiconducting pyrite is the phase purity [9]. FeS2 can crystallize not only into a cubic pyrite structure but also into an orthorhombic metastable marcasite structure [8]. The quantity of marcasite was calculated to be 5% of the total product from using Rietveld renement. The least-squares structure renements were undertaken using a full-prole Rietveld-type program DBWS-9006PC. As an example of one renement detailed Rietveld renement parameters are presented for the main phase pyrite FeS2 prepared at 200 C for 24 h. The quantities used to estimate the agreement between the observations and the model during the course of
8000

2. Experiments All reagents were of analytical grade and were used without further purication. In a typical process, FeSO4 7H2O(0.01 mol), Na2S2O3 (0.01 mol) and S(0.01 mol) were measured into a PTFE- line stainless steel autoclave of 40 ml capacity and lled with distilled water up to 80% of the total volume. The autoclave was sealed and maintained at a temperature in the range 90280 C for a period of 6 to 48 h. It was then cooled to room temperature naturally. The precipitates were ltered off and washed sequentially with distilled water, CS2 and dilute acid to remove the residual impurities. After being dried at 60 C for 4 h, the dark gray powder were collected for characterization. Some 40 experimental runs have been carried out in this way. The X-ray powder diffraction patterns were recorded on a Japan Mac Science 18 kW rotation anode X-ray diffractometer with Cuk a1 radiation in the 2y range of 1090 , graphite monochromatic, working at 40 kV and 200 mA. Diagrams were collected using a 0.02 stepscanning mode. The morphology and particle size of the products were investigated by scanning electronic microscopy (SEM) the images being taken with a German leo1430vp scanning electronic microscope. Absorption spectra were collected on a TU-1221 ultravioletvisible (UVvis) spectrophotometer.

6000

intensity

4000

2000

-2000 10 30 50 70 90

2 theta (deg)

Fig. 1. A FeS2 polycrystalline powder X-ray diffraction pattern and a Rietveld renement plot. The upper shows the observed X-ray diffraction intensity data as . And the rst solid line shows the calculated pyrite phase and the second state line shows the calculated marcasite phase. The lower trace is the difference: observed minus calculated.

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R. Wu et al. / Journal of Crystal Growth 266 (2004) 523527 Table 1 Comparison of calculated and ideal structure of pyrite a u d(FeS) Tetrahedron d(FeFe) PD42-1340 Sample 5.4180 5.4151 0.3860 0.3868 2.2664 2.2669 3.8311 3.8291 d(SS) 2.1396 2.1227 y(FeSFe) 115.38 115.24 y(FeSS) 102.60 102.79 Octahedron d(SS) 3.3211 3.3209 d(SS) 3.0839 3.0865 y(SFeS) 94.26 94.19 y(SFeS) 85.74 85.81 525

Table 2 Structure renement parameters of pyrite polycrystalline powder Phase Space group Z ( a(A) Atoms position coordination and occupation Ion Pyrite Pa3 4 5.4151 Fe S
2+

wyck 4a 8C

X 0 0.3868

Y 0 0.3868

Z 0 0.3868

N 0.1667 0.3272

Fig. 2. Crystal structure of pyrite with Fe2+ octahedron and S tetrahedron coordination.

Rietveld renement were the pattern R-factor Rp 10:83; the weighted pattern R-factor Rwp 14:50: The goodness of the t S 2:1: Table 1 summarizes the interatomic bond lengths and bond angles. The distributions of the cations over positions are listed in Table 2. Pyrite unit cell (illustrated as Fig. 2) can be constructed using the above information, Fe2+ ions are octrahedrically coordinated by six S ions while the S ions are tetrahedrally coordinated by three Fe2+ ions and one S ion. Compared with the ideal pyrite structure PDF 42-1340, the measured octahedron slightly deforms whilst the tetrahedron also slightly

diminishes. In the tetrahedron d (SS) that is inconcurrent neighbors octahedron the nearest neighbors d (SS) variation is more remarkable than others, which relatively tighten up the neighbor octahedral distances. Hence the lattice constant a is compressed. The Wyckoff parameter variation may be related to the adjustment of the unit cell to accommodate these differences in the relative effective radii of the cation and anion in the octahedral and tetrahedral sites, respectively. These conclusions are in agreement with the work of de las Heras [9]. Polycrystalline aggregates known as pyrite framboids which are about several microns in size are displayed in Fig. 3a. Similar behavior is observed in Refs. [10,11] and these kinds of aggregates are more common in natural pyrite [12]. Magnifying it, Fig. 3b reveals that aggregates consisted of a lot of ne clearly identiable particles or grains. The average grain size of the sample is about 500 nm from the SEM Fig. 3b determination. 3.2. The growth process Whilst it is not possible to be certain of the actual growth mechanism for the formation of FeS2 the following observations suggest a potential process. Measurements of the pH value of the

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526 R. Wu et al. / Journal of Crystal Growth 266 (2004) 523527

as follows: Na2 S2 O3 H2 O H2 SmNa2 SO4 : 2 H2S dissolve in water to form a saturated solution, in which there exists: H2 S$H HSHS- $H S2- ; 3 S also can be deoxidized in hydrosulphuric acid to release H2S: S 2H 2e$H2 Sm: 4 As for FeSO4 it dissolves in water and releases its Fe2+ ions. The formation of FeS occurs once the ionic product of Fe2+ and S2 exceeds the product of FeS. The solubility of H2S in water is limited to 0.1 mol/l, so the majority of the H2S is still present as a gas. This could drive the following reaction which results in pyrite: H2 S FeS FeS2 H2 : 5 In our experiments, the inuence of pH value has been considered. A basic medium with pH>7.0 results in Fe(OH) 2 precipitation. When the pH is too low there is S2 O2- H $S HSO- : 3 3 6 Adding an excess of sulfur would prevent the forward reaction shown as Eq. (6). The reaction could result in a nal mixture of FeSx and give birth to an acidic medium. Hence, it is appropriate that we select a weak acid condition in order to grow pyrite. A relatively long reaction time of 24 h favors the growth of FeS2 crystals. This has been proved by our contrasting experiments. Using an appropriate pH value and a reaction time of 6 h phase peaks for FeS and other FeS compounds were found in the XRD pattern of the products. By further elongation of the reaction time to 24 h, a high yield of FeS2 was achieved without any FeS2x. The inuence of reaction temperature on the formation of the sample was also investigated. It indicated that the reaction temperature is not a sensitive factor in the formation of FeS2. The suitable reaction temperature ranged from 90 to 280 C. With increasing temperature, the second phase marcasite FeS2 decreased slightly. If the temperature exceed 200 C, there was no obvious effect on the nal composition of the compound. However,

Fig. 3. The SEM images of as-prepared FeS2 synthesized at 200 C for 24 h.

solution in the reaction system showed that it decreased to 3 as a result of the hydrothermal process. The nal product revealed a black gray precipitate and a white crystal. In addition there was a characteristic bad egg smell indicating the presence of H2S. SO2 and H+ ions could also be 4 detected in the residual solution after hydrothermal reaction. On the basis of this analysis and standard chemical knowledge, the overall reaction may be represented by the following equation: FeSO4 Na2 S2 O3 S H2 O FeS2 kNa2 SO4 H2 SO4 : 1

The possible mechanism for the formation of FeS2 crystal is described below. The reactions take place

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10
(ahv) (A.U)

15 12 9 6 3 0 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2.0 hv (eV)

absorbance

8 6 4 2

200 300 400 500 600 700 800 900 wavelength / nm

Fig. 4. Absorption spectra of nal product at 200 C for 24 h( insert image ahn2 2hn curve of it). Table 3 Band gap of pyrite by preparation techniques Technique OS [13] SIO [13] SVP [13] Egd (eV) 1.35 1.30 1.35

precursors in the temperature range 90280 C for 24 h. Rietveld renement gave good structure models for the Pa3 space group with unit cell ( parameters a 5:4151 A and u 0:3868: The nearest neighbors d (SS) distance in the FeS2 unit cell diminished, relatively tightening up the neighboring octahedral distance. Hence the lattice constant a was compressed. SEM showed the formation of a local polycrystalline aggregation consisting of ne and clearly identiable particles with average sample grain size of about 500 nm. The direct Egd energy gaps have been qualitatively determined by ahn2 versus photoenergy plots in order to obtain a band gap Egd 1:38 eV. A possible mechanism is proposed for the formation of pyrite. It was found that the reaction time and pH value performed important roles in the growth of pyrite crystals. Acknowledgements This project was nancially supported by the National Nature Science Foundation of China (NFSC) under Contract No.50062002. References
[1] W. Jaegermann, H. Tributsch, J. Appl. Electrochem. 13 (1983) 743. [2] A. Ennaoui, H. Tributsch, Sol. Cells 13 (1984) 197. [3] S. Ogawa, J. Appl. Phys. 50 (3) 2308. [4] A. Ennaoui, S. Fiechter, C. Pettenkofer, N. Alonso-Vante, K. Buker, M. Bronold, C. Hophfer, H. Tribusch, Sol. Energy Mater. Sol. Cells 29 (1993) 289. [5] G. Pimenta, V. Schroder, W. Kautek, Ker. Bunsenges, Phys. Chem. 95 (1991) 1470. [6] B. Rezig, H. Dahman, M. Kautek, Renewable Energy (1992) 125. [7] A. Yamamoto, M. Nakamura, A. Seki, E.L. Li, A. Hashimoto, S. Nakamura, Sol. Energy Mater. Sol. Cells 75 (2003) 451456. [8] S. Nakamura, A. Yamamoto, Sol. Energy Mater. Sol. Cells 65 (2001) 79. [9] C. de las Heras, J.L. Martin de Vidales, I.J. Ferrer, C. Scanchez, J. Mater. Res. 11 (1996) 211. [10] I.J. Ferrer, C. Sanchez, J. Appl. Phys. 70 (5) (1991) 2641. [11] R.E. Sweeney, I.R. Kaplan, Econ. Geol. 68 (1973) 618. [12] R.A. Berner, Econ. Geol. 64 (1969) 383. [13] G. Smestad, A. Ennaoui, S. Fiechter, H. Tribusch, W.K. Holhmannn, M. Birkholz, W. Kautek, Sol. Energy Mater. 20 (1990) 149.

our present understandings of the formation mechanism for FeS2 crystallization into a cubic pyrite structure or an orthorhombic metastable marcasite structure in hydrothermal process is still limited and more in-depth studies are underway. 3.3. Optical absorption The optical absorption measurement performed in the UVvis spectral range conrmed the absorbing character of pyrite as shown in Fig. 4. The direct Egd energy gaps were determined by plotting, respectively ahn2 as a function of energy hn [13]. a is determined from transmittance spectra. The band gap Egd 1:38 eV has been qualitatively determined by extrapolating the straight line to the energy axis (arrow in insert spectra). Table 3 shows Egd obtained by several preparation methods and our conclusion is very close to these.

4. Conclusion Pyrite was successfully synthesized by a hydrothermal method using FeSO4, Na2S2O3 and S as