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FROM ZINC SELENATE TO ZINC SELENIDE NANOSTRUCTURES SYNTHESIZED BY REDUCTION PROCESS

Sabar D. Hutagalung1,*, Siew T. Eng1, Zainal A. Ahmad1, Ishak Mat2, and Yussof Wahab3
School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia 2 Advanced Medical and Dental Institute, Universiti Sains Malaysia, 11800 Penang, Malaysia 3 Physics Department, Universiti Teknology Malaysia, 81300 Skudai, Johor Bahru, Malaysia *Corresponding author: mrsabar@eng.usm.my
1

ABSTRACT
One-dimensional nanostructure materials are very attractive because of their electronic and optical properties depending on their size. It is well known that properties of material can be tuned by reducing size to nanoscale because at the small sizes, that they behave differently with its bulk materials and the band gap will control by the size. The tunability of the band gap makes nanostructured materials useful for many applications. As one of the wide band gaps semiconductor compounds, zinc selenide (ZnSe) nanostructures (nanoparticles, nanowires, nanorods) have received much attention for the application in optoelectronic devices, such as blue laser diode, light emitting diodes, solar cells and IR optical windows. In this study, ZnSe nanostructures have been synthesized by reduction process of zinc selenate using hydrazine hydrate (N2H4.2H2O). The reductive agent of hydrazine hydrate was added to the starting materials of zinc selenate were heat treated at 500 oC for 1 hour under argon flow to form onedimensional nanostructures. The SEM and TEM images show the formation of nanocompositelike structures, which some small nanobars and nanopellets stick to the rod. The x-ray diffraction and elemental composition analysis confirm the formation of mixture zinc oxide and zinc selenide phases.

ABSTRAK
Ekamatra nanostructure bahan-bahan amat menarik disebabkan oleh mereka elektronik dan sifat-sifat optik bergantung pada saiz mereka. Ia adalah baik dikenali ciri-ciri itu bahan boleh menalakan dengan penurunan saiz untuk nanoscale kerana pada saiz-saiz kecil itu, bahawa mereka berkelakuan secara berbeza dengan pukalnya bahan-bahan dan jurang jalur itu akan menguasai oleh saiz. Jurang kebolehan penalaan jalur itu membuat nanostructured bahanbahan berguna untuk banyak permohonan. Sebagai satu daripada celah-celah jalur lebar semikonduktor mengkompaun, zink selenida (ZnSe) nanostructures (nanoparticles, nanowires, nanorods) telah menerima banyak perhatian untuk penggunaan dalam alat-alat optoelektronik saperti diod laser biru, diod keluar cahaya, sel-sel solar dan tetingkap optic IR. Dalam kajian ini, ZnSe nanostructures telah disintesiskan oleh proses pengurangan zink selenat menggunakan hidrazina hidrat (N2H4.2H2O). Ejen reduktif hidrazina hidrat telah ditambah untuk bahan-bahan permulaan zink selenat memanaskan dirawat di hospital 500 oC untuk 1 jam di bawah aliran argon untuk membentuk ekamatra nanostructures. SEM dan TEM imejimej menunjukkan pembentukan nanocomposite seperti struktur-struktur, yang sesetengah kecil nanobars dan nanopellets berpegang rod. Belauan x-ray dan analisis komposisi unsur mengesahkan pembentukan zink oksida campuran dan zink selenida fasa-fasa. 147

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Keywords: Zinc selenide, zinc selenate, zinc oxide, nanostructures, reduction, refluxing

INTRODUCTION Nanoparticles or quantum dots with three dimension confinement structures are very attractive because of their electronic and optical properties depending on their size. Quantum dots are unique class of semiconductor because at the small sizes, they behave differently with its bulk materials and the band gap will control by the size of the particle or dot. The tunability of the band gap makes quantum dot useful for many applications. As one of the wide band gaps II-VI group semiconductor compounds, ZnSe nanostructures (nanoparticles, nanowires, quantum dots) have received much attention for the application in optoelectronic devices, such as blue laser diode, light emitting diodes, solar cells and IR optical windows (Pejova and Grozdanov, 2005). There are many methods to synthesize ZnSe nanostructures such as pulsed laser deposition (Li and Nogami, 1994), chemical bath (Lipovskii et al., 1998) and sol-gel method (Leppert et al., 1998; Jiang et al., 2004). Besides, a single-source molecular precursor was also introduced by Revaprasadu et al. (1998) for preparation of ZnSe quantum dots. They have been found that obtained nanoparticles show quantum size effects in their optical spectra and exhibit near bandedge luminescence (Hao et al., 2001). Some researchers have also attempt to synthesize ZnSe hollow microspheres by using template-free solution approach (Wang et al., 2005) and hydrothermal route (Wang and Du, 2006). A novel oleic acid-controlled hydrothermal route was applied to produce ZnSe quantum dots in stable solution (Jiao et al., 2007). Meanwhile, Jiang et al. (2004) and Wang et al. (2004) have been successfully prepared ZnSe quantum dots in silica thin films via sol-gel process. On the other hand, reduction process was applied to prepare ZnSe nanoparticles (Che et al., 2004; Jun et al., 2000). The nanocrystalline of ZnSe obtained from zinc selenate by reduction process using carbon monoxide gas. In the present work, ZnSe nanostructures (nanoparticles) were synthesized via co-pricipitation process from zinc acetate dehydrate and selenoic acid as Zn- and Se-source materials, respectively. When zinc acetate dihydrate reacts with selenoic acid formed the zinc selenate. The hydrogen gas was used as reductive agent to form ZnSe nanoparticles.

EXPERIMENTAL A zinc source of 0.1 mol/L zinc acetate dihydrate (Zn(Ac)2.2H2O) and selenium source of 0.1 mol/L selenoic acid (H2SeO3) were added into the solvent (ethanol) at room temperature in a beaker. Then they were mixed and stirred with high speed for 2 hours to form zinc selenate (ZnSeO3). The product was put in a flask and dehydrated under vacuum at 60 oC for 3 hours to form zinc selenate (ZnSeO3) powder. The ZnSeO3 powder was dried in vacuum using rotary evaporator. The ZnSeO3 powder was put into a quartz boat and placed in a tube furnace. The tube furnace was sealed off and air was removed by a vacuum pump. After 30 min pumping, the hydrogen gas (with composition of 20% H2 and 80% N2) was introduced into tube furnace. After 10 min gas flowing, the tube furnace was begun to heat up with the rate of 5 oC/min under hydrogen gas flow. The heat treatment temperatures are 400, 450, and 500 oC with soaking time 1 hour. The phase formation of ZnSe was analyzed by x-ray diffraction (XRD). A field emission scanning electron microscopy (FESEM) equipped with energy dispersive x-ray (EDX) spectrometer (Zeiss SUPRA 35VP) was used for determination of microstructure and elemental 148

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composition products. The particle sizes were determined using transmission electron microscopy (TEM).

RESULTS AND DISCUSSION Figure 1 shows EDX analysis result performed on the powder before heat treatment. EDX result shows the elemental composition of 23.65 at% Zn, 22.03 at% Se and 54.32 at% O (Zn:Se:O = 1.2:1.1:2.7), which is close to the phase-formation of zinc selenate (ZnSeO3). The raw materials of zinc acetate dehydrate (Zn(Ac)2.2H2O) reacts with selenoic acid (H2SeO3) to form zinc selenate via chemical reaction as follow:

Zn2+ + SeO32- = ZnSeO3

(1)

Figure 1. EDX analysis Figure 2 shows XRD pattern of zinc selenide powder heat treated at 400, 450, and 500 oC for 1 hour by using hydrogen gas as a reductive agent, respectively. It was shown that zinc selenate (ZnSeO3) peaks (Reference code 01-075-0718) are the dominant peaks observed at 400 oC as shown in Figure 2(a). The reduction of zinc selenate (ZnSeO3) to zinc selenide (ZnSe) was not complete. Further increases annealing temperature to 450 oC, shows a better formation of ZnSe (Figure 2(b)). There are five strong peaks of (111), (220), (311), (222) and (400) have been detected belong to ZnSe (Reference code 01-088-2345). However, some ZnSeO3 peaks are still detected coexist with ZnSe. At annealing temperature of 500 oC, found the formation of zinc oxide (ZnO) phase (Reference code 01-070-8070) beside ZnSe and ZnSeO3 peaks. The hydrogen gas was used as reductive agent with purpose to form ZnSe from ZnSeO3 according to reaction as follow:

ZnSeO3 + 3H2 = ZnSe + 3H2O

(2)

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However, it is found that the formation of zinc selenide (ZnSe) not fully obtained as an expected by Eq. (2). The formation of ZnO can be explained that during annealing oxygen is more easy reacts with zinc ions to form ZnO rather then with hydrogen at high temperature. A similar result was reported by Kumaresan et al. (2002) on ZnSe thin films prepared by photochemical deposition and Lokhande et al. (1998) on ZnSe prepared via chemical bath deposition. At annealing temperature of 300 oC, they obtained ZnSe but exhibit the small XRD peaks corresponding to zinc. Upon annealing at 400 oC, the crystallinity increased further and the excess zinc was disappeared. However, some small peaks belonging to ZnO are appear in the sample, which may be due to the conversion of zinc into ZnO upon annealing.
1800 1600 1400 y x: ZnSe y: ZnSeO3 z: ZnO z y x(200) 1000 x(111) 800 y 600 400 y 200 0 20 30 40 50 60 70 y y z y y y x(220) y x(311) y z z

Relative Intensity (a.u)

1200

(c)
z

x(222)

x(400)

(b) (a)

2 (degree)

Figure 2. XRD patterns of annealed samples at (a) 400, (b) 450, and (c) 500 oC for 1 hour under H2 flow. In our experiment, hydrogen gas was used reductive agent to convert the zinc selenate to ZnSe. The other reason why incomplete formation ZnSe and excess ZnO is may be due to the oxygen impurity in gas supply system since the purity of used hydrogen gas too low (20% H2 and 80% N2). It is expected that the higher concentration of hydrogen gas will produce a better formation of ZnSe phase which is complete reduction of ZnSeO3. SEM image of annealed sample under H2 flow at 450 oC for 1 hour exhibit the spherical shape nanoparticles (Figure 3). TEM analysis was performed on the samples with different annealing temperatures to confirm size and shape of grown nanoparticles. As shown in Figure 4, all three samples produce nanoscale particle sizes. Sample annealed at 400 oC exhibit smaller particle size if compare to others. The average particle size of sample annealed at 450 oC is 40 nm. The average particle size was found to be increased with annealing temperature as shown in Figure 5.

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Figure 3. SEM image of sample annealed at 450 oC for 1 hour under H2 flow.

Fig 4 (a)

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Fig 4 (b)

Fig 4 (c)

Figure 4. TEM images of sample at different annealing temperatures (a) 400 oC, (b) 450 oC, (d) 500 oC.

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(a)

(b)

Figure 5. Particle size distribution of samples annealed at (a) 450 oC and (b) 500 oC.

CONCLUSION Zinc-based nanostructures (nanoparticles, nanorods) have been successfully synthesized by reduction process of zinc selenate using hydrogen gas and graphite powder. The SEM and TEM images show that some small nanobars or nanopellets stick to the rod and form nanocompositelike structures. The elemental composition indicates the formation of mixture phases of zinc selenide and zinc oxide.

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ACKNOWLEDGEMENT This work was supported by Fundamental Research Grant Scheme (FRGS), Ministry of Higher Education, Malaysia under project no. 203.PBAHAN.6070019.

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