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Growth and characterization of different structured CdO using a vapor transport M. Zaien, A. Hmood, N.M. Ahmed, Z. Hassan

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S0167-577X(13)00422-9 http://dx.doi.org/10.1016/j.matlet.2013.03.093 MLBLUE15074

Materials Letters

Received date: 6 March 2013 Revised date: 16 March 2013 Accepted date: 18 March 2013 Cite this article as: M. Zaien, A. Hmood, N.M. Ahmed, Z. Hassan, Growth and characterization of different structured CdO using a vapor transport, Materials Letters, http://dx.doi.org/10.1016/j.matlet.2013.03.093 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting galley proof before it is published in its final citable form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

Growth and characterization of different structured CdO using a vapor transport

M. Zaien a,b,*, A. Hmood a, N. M. Ahmed a, Z. Hassan a
a

Nano-Optoelectronics Research and Technology Laboratory

School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia

b

Department of Physics, College of Education for Pure Sciences, University of Anbar, Iraq Corresponding author: mustafa1973_zzz@yahoo.com H/P: 0060174596002, Fax: 00604-6579150

Abstract
Different structured of CdO ( nano- and micro ) were successfully synthesized using a vapor transport process ( solid-vapor deposition ) method for CdO powder on p-type silicon substrates at 1400 K with argon flow. Scanning electron microscopy revealed that the CdO morphology exhibited various shapes depending on the position of the Si substrates from the CdO powder in the furnace. Microstructured CdO included microrods and microcubes, microrods had diameters in the range of 600 nm to 990 nm and different lengths of more than 10 m. The X-ray diffraction pattern showed that the CdO has a cubic and polycrystalline structure. The optical properties of the different structured of CdO were investigated by photoluminescence spectroscopy. Strong emission peaks were observed at 531 nm (2.34 eV) for the nanostructured and 524 nm (2.37 eV) for the microstructured, which are ascribable to the near-band-edge emission of CdO.

Keywords: Deposition ; CdO ; Microstructure ; Polycrystalline; Optical properties 1. Introduction

Cadmium oxide is a IIVI compound semiconductor consisting of cadmium from group II and oxygen from group VI in the periodic table of elements [1]. The different structured CdO
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materials are now widely used as transparent conductive oxides (TCO) in various physical applications [2], specifically in optoelectronic devices such as solar cells because of its high transparency in the visible region of the solar spectrum [3]. These materials are also used in diodes, gas sensors and transparent electrodes [4]. CdO has a narrow direct band gap ranging from 2.2 eV to 2.5 eV [5]. In addition, it has several attractive properties, such as low resistivity, high density (8150 Kg/m3), high melting point (1500 C ), and has a cubic crystal structure [NaCl, face center cubic (fcc) type, and lattice constant a = 0.4695 nm] [6]. Numerous methods have been adopted to grow different structured CdO, such as thermal evaporation in vacuum [7], chemical bath deposition [8], vaporliquidsolid (VLS) [9]. Cadmium can be directly heated up to 900 C in air or with a trace amount of oxygen in an argon (Ar) flow [10]. In this study, different structured CdO were synthesized via a solid-vapor deposition at 1400 K with Ar flow. The morphological, structural, and optical properties of the nano- and micro-structured CdO were also studied and investigated.

2. Materials and Methodology

The different structured CdO were synthesised by solid- vapor deposition, a method was selected due to its lower cost and simplicity. The process of the Radio Corporation of America was used to remove the oxide layer from a P-type Si wafers (1 cm 1 cm 283 m) with a (111) orientation and a resistivity of 0.75 cm. CdO powder (purity: 99.99%, Aldrich) in a quartz boat was placed at the center of a horizontal quartz tube furnace ( inner diameter, 20 mm). The Si substrates were placed downstream of the flowing gas (12 cm from the CdO powder boat, with the polished side facing the source material) in another boat. The distance between the Si substrates was approximately (1 cm). Fig. 1 shows the tube furnace setup. A flow of Ar gas was initially used to purify the tube. When the temperature reached 1400 K, the CdO
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powder and Si substrates were placed inside the furnace for 2 h with an Ar flow of approximately 350 Sccm. The samples were then cooled for 2 h at room temperature. X-ray diffraction (XRD) measurements were carried out using a high- resolution X-ray diffractometer system (XPert PRO MRD PW3040, PANalytical) to determine the CdO crystallite structure. Scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) analysis (JSM-6460 LV, Japan) were conducted to determine the surface morphology and composition of the nanoand micro-structured CdO. Photoluminescence (PL) study was carried out via a spectroscopy system (HR 800UV, Jobin Yvon, USA) at room temperature using He-Cd laser ( = 325 nm).

3. Results and discussion

Fig. 2 (1S) shows the XRD patterns of the nanostructured CdO on the Si substrate. The diffraction peaks observed at diffraction 2 angles of 33o, 38o, 55o, 65o, 69o, and 82o corresponded to the (111), (200), (220), (311), (222), and (400) planes. These peaks also corresponded to those observed for CdO (JCPDF File No. 03-065-2908). Fig. 2 (2S and 3S) show the XRD patterns of the microstructured CdO on the Si substrates (rods and cubes). The diffraction peaks observed at diffraction 2 angles of 33o, 38o, 55o, 65o, and 82o corresponded to the (111), (200), (220), (311), and (400) planes. The spectrum indicates that the studied different structured CdO are polycrystalline in nature with a cubic structure, except for two peaks at 44.5o and 31.8o. These two different peaks are related to the Si carbide of the XRD sample holder and Cadmium element in (2S) microrods and (3S) microcubes CdO, respectively. Prominent peaks were used to calculate the average crystallite sizes of the different structured CdO using the Scherrer equation, which is expressed as follows [3,9]:
D 0.94O E COST

(1)

Where is the wavelength ( = 1.542 ) (CuK), is the full width at half maximum ( FWHM ) of the line, and is the diffraction angle. The average crystallite size decreased with an increase in the lattice constant when the distance of the substrates from the CdO powder was increased. The crystallization of the CdO and the intensity of the peaks decreased because of the structural defects in the microstructured compared with the nanostructured without any defects due to (1S sample) is near from the CdO powder at the center of a furnace tube as in Fig. 1, and there is a high temperature with a prolonged time (2 h) to improve crystallization of the CdO same the effects of annealing in the report [11]. The strain of different structured CdO grown on the Si substrates along the c-axis can be calculated using the following equation [12]:

H ZZ % 

C  CO CO

(2)

Where C represents the lattice constant of the different structured CdO estimated from XRD data, and CO is the standard lattice constant for the unstrained CdO [7]. The negative values of the strain reveal the compressive strain of the nanostructured and microrods CdO, whereas the positive value of the strain reveals the tensile strain of the microcubes CdO. These extremely low values of compressive and tensile strains suggest that the synthesized nano- and microstructured CdO have high-quality crystal geometry [3,13]. All results are presented in Table 1. Fig. 3 shows the SEM images of the surface morphology of the different structured CdO deposited on the Si substrates. The various shapes of the grown CdO structures depend on the position of the Si substrates from the CdO powder in the furnace and the prolonged reaction time (2 h). Fig. 3(1S) shows the growth of grass packs-like nanostructured CdO. Microstructured CdO included microrods and microcubes, as shown in Fig. 3(2S and 3S), respectively. Microrods had diameters ranging from 600 nm to 990 nm and various lengths greater than 10 m. The EDX
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spectrum and atomic composition of the nano- and micro-structured CdO on the Si substrates are shown on the right side of SEM images. The tabulated atomic and weight percent values of the elements in the CdO structures on the Si substrates are presented in Fig. 3. The concentrations of these elements are indicated by the peaks, which clearly shows that the elements corresponding to the peaks comprise the CdO on the Si substrate. Fig. 4 (1S, 2S, and 3S) show the photoluminescence spectroscopy of the nanostructured, microrods, and microcubes of CdO, respectively, at 325 nm excitation. The PL spectroscopy show strong emission peaks were observed at 531 nm (2.34 eV) for the nanostructured and 524 nm (2.37 eV) for the microstructured (microrods and microcubes), which are ascribable to the near-band-edge (NBE) emission of CdO [9,13]. These values indicate the quantum confinement effect of the as-synthesized nano- and micro-structured CdO. The results also revealed that the intensity of the emission peaks depends on the structure shape and the surface morphology.

4. Conclusion
Different structured CdO were successfully synthesized by solid-vapor deposition of CdO powder on a p-Si substrate at 1400 K. The XRD pattern showed that nano- and micro-structured CdO are polycrystalline in nature with a cubic structure. The average crystallite size decreased with an increase in the lattice constant when the distance of the substrates from the CdO powder was increased. SEM results showed that the various shapes of the grown CdO structures depend on the position of the Si substrates in the furnace. Microstructured CdO included microrods and microcubes. The direct band gaps energy were 2.34 eV for nanostructured CdO and 2.37 eV for microstructured (microrods and microcubes). These nano- and micro-structured CdO can be used in various technological applications, especially in solar cells.
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Acknowledgement: The authors gratefully acknowledge the support of the School of Physics
in Universiti Sains Malaysia.

References
[1] Ortega M, Santane G, Morales-Acevedo A. Superficies y Vacio 1999;9:294-295.

[2] Sravani C, Reddy KTR, Hussain OMd, Reddy PJ. Thin Solid Films 1994;253:339-343.

[3] Zaien M, Ahmed NM, Hassan Z. Superlattices and Microstructures 2012;52:800-806. [4] Hames Y, San SE. Solar Energy 2004;77 :291-294. [5] Senthil K, Tak Y, Soel M, Yong K. Nanoscale Res Lett 2009;4:1329-1334. [6] Reddy S, Kumara Swamy BE, Umesh Chandra, Sherigara BS, Jayadevappa H. Int J Electrochem Sci 2010;5:10-17. [7] Dantus C, Rusu RS, Rusu GI. Superlattices and Microstructures 2011;50:303-310. [8] Dhawale DS, More AM, Latthe SS, Rajpure KY, Lokhande CD. Applied Surface Science 2008;254:3269-3273. [9] Kuo Tz-Jun, Huang Michael H. J Phys Chem B 2006;110:13717-13721. [10] Liu X, Li C, Han S, Han J, Zhou C. Appl Phys Lett 2003;82:1950. [11] Vigil O, Cruz F, Morales-Acevedo A, Contreras-Puente G, Vaillant L, Santana G. Materials Chemistry and Physics 2001;68:249252.

[12] Tsay C.-Y, Fan K.-S, Chen S.-H, Tsai C.-H. J Alloys Compd 2010;495:126-130.

[13] Zaien M, Ahmed NM, Hassan Z. Chalcogenide Letters 2012;9:115-119.

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Figures Captions Fig. 1: Tube furnace setup. Fig. 2 : XRD patterns of the (1S) nanostructured CdO, (2S) microrods CdO, and (3S) microcubes CdO on silicon substrates. Fig. 3: SEM images and EDX analysis of the (1S) nanostructured CdO, (2S) microrods CdO, and (3S) microcubes CdO on silicon substrates. Fig. 4: Photoluminescence spectroscopy of the (1S) nanostructured CdO, (2S) microrods CdO, and (3S) microcubes CdO. Table caption Table 1: Values of the lattice constant (a), the crystallite size (D), and the strain (
zz)

for CdO structures at different distances of the Si substrates from the CdO

powder in the furnace. Table 1:

Highlights

>Different structured CdO were synthesized by vapor transport on Si substrate at 1400 K.> The XRD pattern showed that structured are polycrystalline in nature with a cubic structure. >SEM results showed that the CdO structures depend on the
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position of the Si substrates in the furnace.> The direct band gaps energy were 2.34 eV for nanostructured and 2.37 eV for microstructured.

Fig. 1

Figure(s)

Fig. 2

Fig. 4

Fig. 3