A solvothermal route to wurtzite ZnSe nanoparticles

J.H. Zhan, X.G. Yang, W.X. Zhang, D.W. Wang, Y. Xie, and Y.T. Qiana)
Structure Research Laboratory and Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, Peoples Republic of China (Received 17 May 1999; accepted 8 December 1999)

Zinc powder reacts with equivalent elemental selenium in solvent ethylenediamine at 120 C for 6 h to form a complex, which is converted to ZnSe nanoparticles by pyrolysis or protonization. X-ray diffraction results suggest that the as-formed products have wurtzite structure. Transmission electron microscopy observation show that particles with spherical and laminar morphology were produced by pyrolysis and protonization, respectively. The formation of ZnSe nanoparticles is also investigated by infrared and thermal analysis.
I. INTRODUCTION

The wide band gap IIVI nanoscale semiconductors are of current interest for optoelectronic applications such as blue lasers, light emitting diodes and optical devices.13 An important direct band gap material, ZnSe has been called a promising material for the fabrication of visible light-emitting devices.4 Recently, ZnSe-based laser diodes have been successfully demonstrated to operate in a continuous-wave (cw) mode at room temperature.5 IIVI compounds can be prepared in a variety of ways. Molecular precursor routes have been developed by a number of groups for bulk materials or coatings.68 The straightforward method is a combination of the elements at elevated temperatures, but it is difficult to get nanoscale materials by this traditional solid state reaction. A low-energy approach is the precipitation of metal chalcogenides from aqueous solutions of the metal cations by use of H2E (E S, Se or Te).9 The elemental reactions between zinc or copper with sulfur at reflux in a strongly coordinating solvent such as pyridine and Nmethyimidazole, has been reported to form complexes, which can be thermally decomposed at 500 C to form binary chalcogenides.1012 Parkin et al. reported that the metal chalcogenides can be obtained through the reaction of selenium or tellurium with elemental metals in liquid ammonia at room temperature in a pressure vessel.13,14 As-formed zinc selenide is amorphous powder, which can be crystallized to stilleite by annealing (300 C for 2 h). Li reported another elemental reaction route to produce nanocrystalline ZnSe with zincblende structure in pyridine at 180 C in an autoclave.15 Recently, an important organometallic synthetic route has been implied

to the synthesis of colloid zincblende ZnSe nanocrystals with UV-blue luminescence up to 360 nm,16 similar to that route reported by Murray et al.17 Despite these developments in the preparation of zinc selenide nanocrystallites, stilleite ZnSe with cubic structure was generally reported to form by these methods and few reports touched the synthesis of wurtzite ZnSe nanoparticles. As a member of IIVI compounds, ZnSe crystallize in either zincblende or wurtzite structure. Frequently, ZnSe exists in cubic structure as stilleite in natural mines.18 On the other hand, hexagonal structure for ZnSe is a metastable phase, which has been observed by Pashinskin.19 In this paper, we describe a solvothermal process in ethylenediamine to produce wurtzite ZnSe nanocrystallites with various morphologies. The solvent ethylenediamine takes an important place in the formation of ZnSe hexagonal structure.
II. EXPERIMENTAL SECTION

a)

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J. Mater. Res., Vol. 15, No. 3, Mar 2000

A stoichiometric amount of zinc powder (99.99%) and elemental selenium powder (99.9%) was ground together in agate roller. This mixture was added to a Teflon-liner autoclave of 100-ml capacity, which was then filled with anhydrous ethylenediamine up to 90% of the total volume. The autoclave was maintained constantly at 120 C for 6 h and then cooled to room temperature naturally. An orange precipitate was collected. This initial product was treated in two ways. First, it was treated in an argon gas stream at 300 C. Second, it was treated with dilute HCl solution (pH 1), then washed with distilled water and anhydrous alcohol. These products were desiccated in a vacuum box at 60 C for 4 h. The samples were characterized by the x-ray powder diffraction (XRD). The XRD analysis was carried out with a Japan Rigaku D/max- rotation anode x-ray diffractometer, using Ni-filtered Cu K radiation. A scanning rate of 0.05/s was applied to record the patterns in
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J.H. Zhan et al.: A solvothermal route to wurtzite ZnSe nanoparticles

the 2 range between 5 and 70. Transmission electron microscopy (TEM) was applied to determine the morphology and particle size of as-prepared products. The images were taken with a Hitachi H-800 transmission electron microscope. Differential scanning calorimetric (DSC) and thermogravimetric (TG) analysis was conducted on a Shimadzu TA-50 thermal analyzer between room temperature and 500 C in flowing N2 atmosphere. Infrared (IR) analysis of these samples were conducted on a Magna IR-750FT Spectrometer ranging from 400 to 4000 cm1 at room temperature with the samples mulled in KBr water. Absorption spectra were collected at room temperature on a Shimadzu ultraviolet-visible (UV-VIS) absorption diode array spectrometer using 1-cm Quartz cuvettes. Samples were prepared by dispersing ZnSe nanocrystallites in methanol. The luminescence spectra were measured on a Hitachi 850 fluorescence spectrometer with a Xe lamp at room temperature.

ZnSe nanoparticles could be produced by pyrolysis of the complex as indicated by the DSC. This complex decomposed at about 237.9 C until 280 C. In this preparation process, 300 C was applied to obtain pure ZnSe. The other way is treatment of the complex in acid solutions. This complex is stable in neutral aqueous solutions, but decompose at low pH. In acid solution, protonization of ethylenediamine results in ZnSe as showed with Eq. (2). An aqueous solution with a much lower pH has not been

III. RESULTS AND DISCUSSION

Zinc powder was ready to react with selenium in ethylenediamine to form an orange product, which failed to be identified from XRD pattern [Fig. 1(a)] on JCPDS cards. IR analysis was applied to determine the existence of ethylenediamine. The absorption peaks ranging from 440 to 3400 cm1 in Fig. 2(a) are mainly attributed to ethylenediamine. The elemental analysis gave a composition ZnSeC2N2H8. It is possible that zinc selenium forms a stable complex with ethylenediamine, since zinc is ready to form zinc chalcogenides with sulfur or selenium in strong donor solvents.20,21 DSC plot of this complex showed a strong endothermic peak at 239.7 C corresponding to the decomposition of the complex. The TG plot showed 30% weight loss (calculated value, 29.4%) for this complex corresponding to the loss of ethylenediamine. As treated at 300 C in flowing N2 atmosphere, this complex was converted to a yellow powder which could be identified to be hexagonal ZnSe from XRD pattern [Fig. 1(b)]. On the other hand, as the complex was treated in dilute HCl solution (pH 1), it was converted to a red-brown product, which could also be identified to be wurtzite ZnSe [Fig. 1(c)]. After refinement, the calculated cell constants a 3.98 , c 6.53 were close to the reported value.22 Therefore, there were two ways to prepare ZnSe nanoparticles after the complex was obtained by a solvothermal treatment. They can be diagramed as ZnSeC2H8N2 ZnSe + C2H8N2 ZnSeC2H8N2 ZnSe + C2H10N22+ .
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H

FIG. 1. XRD patterns for (a) the complex prepared by reaction between stoichiometric zinc and selenium in ethylenediamine, (b) ZnSe prepared by pyrolysis of the complex at 300 C, (c) ZnSe prepared by protonization of the initial product in dilute HCl solution (pH 1).

(1) (2)
FIG. 2. IR spectra of the samples: (a) the complex, (b) the product obtained by pyrolysis of the complex at 300 C, (c) the product prepared by protonization of the complex.

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J.H. Zhan et al.: A solvothermal route to wurtzite ZnSe nanoparticles

applied for it could make ZnSe decompose as shown by Eq. (3). In this preparation process, an acid solution (pH 1) was applied. ZnSe + 2H+ Zn2+ + H2Se (3)

IR analysis of the as-formed products was carried out to investigate attachment of ethylenediamine to ZnSe [Fig. 2(b,c)]. The absorption peaks at about 3400 and 1600 cm1, which correspond to the OH stretching vibration [ (OH)] and HOH bending vibration [(OH2)] respectively, could be due to absorption of H2O absorbed in these samples. In fact, the absorption of water is very common for powder samples with high surface area, which have been exposed to atmosphere. These results suggest the products prepared by pyrolysis and hydrolysis of the complex are pure ZnSe nanocrystallites free from ethylenediamine. The particle size and morphology of as-formed products were investigated by TEM and the typical images were shown on Fig. 3. TEM observation indicated that the preparation methods had a considerable effect on the morphology of the resulted products. The pyrolysisformed ZnSe nanoparticles have a spherical shape [Fig. 3(a)]. The particle size shown by the TEM image is larger than that estimated from the XRD pattern with DebyeScherer formula (about 18 nm). This difference may be attributed to the agglomeration of these particles. On the other hand, the protonization-formed ZnSe nanoparticles have a laminar shape [Fig. 3(b)]. These thin platelets may stack on each other to form a big particle as shown by Fig. 3(c). The small thickness may cause the breadth of these XRD reflection peaks. The different formation mechanisms could be responsible for the difference in morphology. The elemental composition of the

as-formed ZnSe was of 50:50 atomic ratio as confirmed by atomic absorption on a Perkin-Elmer 1100B atomic absorption spectrophotometer. So the preparation routes by pyrolysis or protonization had no obvious effect on the composition but on the morphology. The solvent ethylenediamine plays an important role in the formation of hexagonal wurtzite ZnSe nanoparticles. As mentioned in Ref. 14, solvothermal treatment of zinc and selenium leads to formation of cubic stilleite nanoparticles. As soon as the nucleus of hexagonal ZnSe crystallites forms, it cannot convert to cubic structure even though it is treated solvothermally in pyridine at 180 C for 6 days. If the reaction route is changed with ZnCl2 + Se + Na, the final product is the same. The UV-VIS absorption spectra of the ZnSe nanocrystals prepared by protonization are shown in Fig. 4. The onset of the absorption spectrum at about 470 nm corresponds to the band gap of ZnSe. The second transition at about 320 nm may be assigned to the second excited state within each crystallite.23 The photoluminescence (PL) spectrum, using an excitation at 233 nm with a 290-nm filter, shows a sharp PL peak at 310 nm (4.0 eV) with a shoulder peak at 330 nm as shown in Fig. 5. These results indicate that these ZnSe crystallites do not show a near band-edge emission but an emission near the second transition. A similar fluorescence was also observed in the ZnSe crystallites prepared by pyrolysis.

IV. CONCLUSION

A solvothermal method combined with pyrolysis and protonization has been successfully used to prepare ZnSe nanocrystallites. XRD results indicated that the final products were of wurtzite structure. The morphology of

FIG. 3. TEM images of ZnSe nanoparticles: (a) by pyrolysis of the complex at 300 C, (b) by protonization of the complex, (c) showing the laminar shape.
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J.H. Zhan et al.: A solvothermal route to wurtzite ZnSe nanoparticles

ACKNOWLEDGMENTS

Financial support from the National Natural Science Funds of China and National Outstanding Youth Fund is gratefully acknowledged.
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FIG. 4. UU-VIS absorption spectrum of ZnSe crystallites.

FIG. 5. Photoluminescence spectrum of ZnSe crystallites.

the final product was influenced by the post-treating methods. Spherical and laminar nanoparticles were obtained through pyrolysis and protonization of the complex respectively. An ultraviolet emission has been observed in these ZnSe nanocrystals.

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