J Mater Sci: Mater Electron (2013) 24:692696 DOI 10.

1007/s10854-012-0796-4

Wurtzite ZnSe quantum dots: synthesis, characterization and PL properties

K. Senthilkumar T. Kalaivani S. Kanagesan V. Balasubramanian J. Balakrishnan

Received: 21 April 2012 / Accepted: 9 June 2012 / Published online: 21 June 2012 Springer Science+Business Media, LLC 2012

Abstract A facile method for synthesis of monodispersed, starch-capped ZnSe nanoparticles at room temperature is being reported. The nanoparticles exhibited strong quantum connement effect with respect to the bulk ZnSe. The transmission electron microscopy image indicated that the particles were well dispersed and spherical in shape. The X-ray diffraction analysis showed that the ZnSe nanoparticles were of the wurtzite structure, with average particle diameter of about 3.6 nm. The Fourier transform infrared spectrum conrmed the presence of starch as passivating agent.

1 Introduction As a result of quantum size effect and the existence of a relatively large percentage of surface atoms, semiconductor quantum dots possess unique optical and electronic properties and hence have attracted much attention in both fundamental research and technical applications over the
K. Senthilkumar (&) Department of Physics, AMET University, Chennai 603112, India e-mail: senovi2007@yahoo.co.in K. Senthilkumar T. Kalaivani Department of Physics, SRM University, Chennai 603203, India S. Kanagesan Materials Synthesis and Characterization Laboratory (MSCL), Institute of advanced technology, Universiti Putra Malaysia, Serdang 43400, Selangor, Malaysia V. Balasubramanian J. Balakrishnan Department of Chemistry, AMET University, Chennai 603112, India

past decade. These applications range from optoelectronic devices to biological labels [14]. Many synthetic methods have been developed in preparing these materials, ranging from aqueous precipitation routes [58], to high temperature hot injection methods [912]. However most of these methods involve the use sophisticated equipment with toxic and sometimes explosive starting materials which are not environmentally benign. The solubility of these materials is an essential requirement for their biological applications. This is usually achieved by surface modication techniques which are tedious, time-consuming and involve wastage of ancillary materials in addition to the rigorous condition involved in the rst step of the reaction (i.e. synthesising the organic soluble materials) before surface modication [3, 4]. There have also been direct synthesis via an aqueous solution route and many of the suitable capping agents are thiophenol, thiourea, mercapto acetate and so on which are toxic and will pollute the environment if the synthesis involves large scale production [13, 14]. Therefore in order to develop technologies that can be used to improve or protect the environment, it is desirable to design and use greener methods to synthesise nanomaterials [15, 16]. Among the various kinds of IIVI semiconductor nanocrystals, CdS, CdSe and CdTe nanocrystals are the most widely investigated, while researches on ZnSe nanocrystals are relatively few. ZnSe is an n-type semiconducting material with wider band gap of *2.7 eV at room temperature and transmittance range (0.522 lm). It exhibits tunable blue-ultraviolet (UV) luminescence. This UV range is practically unobtainable for cadmium-based systems such as CdSe, for which the toxicity of cadmium represents an additional disadvantage. Thus is more suitable for the fabrication of short-wavelength device than other IIVI semiconductor materials. For these reasons the synthesis of high quality ZnSe nanocrystals is still an

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attractive subject. Hines et al. [17], synthesized high quality ZnSe nanocrystals by using organometallic methods but the nanocrystals were in organic solvent and could not be dispersed in water. Murase et al. [18], synthesized blue emitting ZnSe nanocrystals in aqueous solution however, highly toxic and oxidative H2Se gas was used as the selenium precursor source. Recently Xiong et al. [19], reported synthesis of spherical cubic structure ZnSe nanoparticles but the reaction required a longer time and the selenium precursor used was unstable at room temperature. In this paper, we report a simple, economical and reproducible synthesis of starchcapped ZnSe nanoparticles at room temperature via an environmentally benign green route. In this work, starch was selected as the capping agent because it is an inexpensive, totally biodegradable polymer that is readily available from agriculture and has gained interest as a raw material for biobased products [2024]. It has a wide range of potential applications because it is abundant, renewable, safe and economic. It is a mixture of two main components: amylose formed by the a-1,4 glycosidic bonds between D-glucose units and amylopectin, a highly branched water-soluble macromolecule consisting of both a-1,4 and a-1,6 glycosidic bonds. The large number of hydroxyl groups present in glucose monomers can facilitate the complexation of metallic ions to the starch matrix, while nano-supramolecular structures formed by intermolecular and intramolecular hydrogen bonding can act as templates for nanoparticle growth. Thus making starch a good candidate for passivating QDs. Using starch as passivating agent also comes with other advantages which can help in achieving green synthesis of nanoparticles. These includes (1) the high dispersity of starch in water hence, one can completely avoid the use of organic solvents, (2) the relatively weak binding interaction between starch and nanoparticles compared to the interaction between the nanoparticles and typical thiol-based protecting groups which makes the separation of these particles feasible and (3) integration of starch-protected nanoparticles readily into systems relevant for pharmaceutical and biomedical applications. Starch-based materials have been used as substituents for petroleum-based plastic material especially in packaging industries and thus offer an alternative solution to the disposal and biodegradability problem of petroleum-based material [2224]. Since starch is biodegradable, it may also help in reducing cytotoxicity problem of quantum dots materials, a major limitation for their biological applications and could extend the application of nanoparticles materials to food and pharmaceutical products. Several authors have reported the synthesis of nanoparticles (Ag, ZnS, CdS, and CdSe) based on green synthetic method using starch as capping agent [13, 14, 2528]. Our aim is to develop an effective one-step method for the preparation of

ZnSe nanoparticles in aqueous solution using starch as capping agent. The as-synthesized ZnSe nanoparticles were characterised by UVvis absorption and PL spectroscopy, FT-IR, TEM, and XRD.

2 Materials and methods 2.1 Materials Zinc chloride, sodium borohydride (NaBH4), deionised water (HPLC grade), acetone and soluble starch were purchased from Aldrich and the selenium powder from Merck. All the chemicals were of analytical grade and used as purchased without further purication. 2.2 Synthesis of starch-capped ZnSe nanoparticles In a typical room temperature reaction, an aqueous solution of 0.4 grams of ZnCl2 was added to an aqueous solution of soluble starch (0.08 wt%) in a 100 mL one-necked roundbottom ask, under constant stirring. The pH of the solution was adjusted from 6 to 11 using 0.1 M of ammonia solution. This was followed by a slow addition of 16 9 10-3 M of colourless selenide ion stock solution prepared by reduction of 0.025 g of selenium powder in deionised water using sodiumborohydride. The colour of the solution changed immediately upon addition of selenide ion solution, indicating the formation ZnSe nanoparticles. The mixture was further stirred for 5 h and aged for 24 h followed by ltration. The precipitate was washed several times and dried at room temperature to give a material which readily disperses in water.

3 Results and discussion The reaction scheme is represented by the following equations: 4NaBH4 2Se 7H2 O ! 2NaHSe Na2 B4 O7 + 14H2 1 Zn2 HSe OH ! ZnSe H2 O 2

In aqueous solution, starch adopts a right-handed helical conformation in which the extensive number of the hydroxyl groups is expected to facilitate the complexation of metal ions to the molecular matrix. This hydroxyl group also acts as passivating centre for stabilisation and solubility of the assynthesized nanoparticles in water, while the free aldehyde group on one end of a starch polymer could also act as conjugation site for further functionalization which makes it easier for its biological applications [25, 27, 28].

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Fig. 1 XRD patterns of A pure starch and B starch-capped ZnSe nanoparticles

3.1 XRD analysis Figure 1 showed the XRD pattern of the pure starch and the as prepared ZnSe nanoparticles. It was observed that the crystallites exhibited predominantly wurtzite crystal structure with distinct diffraction peaks which corresponded to the crystalline planes of hexagonal ZnSe and lattice constant of 0.397 nm, which was consistent with the JCPDS card for ZnSe (JCPDS no. 89-2840). The diffraction peak at 23.7 was attributed to starch crystalline peak [21]. The mean particle diameter of the starch-capped ZnSe as calculated from the line width of the diffraction peak using DebyeScherrer equation was 3.50 nm. The broad nature of the diffraction peaks could be attributed to the nanocrystalline nature of the particles. The stronger and narrower (002) peak in Fig. 1 indicated that the nanoparticles were elongated along the c-axis. It should be noted that syntheses of ZnSe nanoparticles at low-temperature usually yield cubic sphalerite structure while hexagonal wurtzite phase are only produced at high temperature [17 19, 2931]. This result showed that incorporation of hexagonal ZnSe phase at room temperature is possible. 3.2 TEM analysis Figure 2 shows the TEM images and particle size distribution of the starch-capped ZnSe nanoparticles. The image showed that the particles were well dispersed, small and spherical in shape. The particles are in the range 2.34.2 nm with mean particle diameter of 3.4 nm and standard deviation (r) of 0.563 nm indicating broad size distribution. This is in accordance with the XRD result. The broad size distribution is attributed to the aggregation of the smaller particles which are thermodynamically unstable in the solution as a result of their high surface energy which makes them very reactive [14, 32, 33]. The absorption and photoluminescence spectra of starchcapped ZnSe nanoparticles are shown in Fig. 3. The absorption spectrum (Fig. 3) consists of an absorption shoulder at 282 nm (4.40 eV) Signifying the monodispersity of the particles and an absorption edge at 303 nm (4.09 eV) which was blue shifted from the bulk band gap of 460 nm (2.70 eV) for bulk ZnSe. This shifting from the bulk band gap was caused by strong quantum connement and also signied small particle size. The emission spectrum (Fig. 4) was broad and showed emission maximum at 408 nm for an excitation at 260 nm which was red-shifted in relation to its absorption maximum. The unevenness of

Fig. 2 The TEM image (A) and particle size distribution (B) of starch-capped ZnSe nanoparticle

3.3 Optical analysis

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Fig. 5 FT-IR spectrum of starch-capped ZnSe nanoparticles Fig. 3 UVvis absorption spectra of starch-capped ZnSe nanoparticles

CH while the band at 1,630 cm-1 was attributed to tightly bound water present in the starch. The two characteristic bands at the ngerprint region of spectra at 1,146 and 1,075 cm-1 were attributed to the CO, CC stretching and COH bending of starch respectively while the band at 1,330 cm-1 was attributed to the angular deformation of CH. The prominent band at 992 cm-1 was attributed to the skeletal mode vibration of a 14 glycosidic linkage (COC) while the band at 757 cm-1 was attributed CC stretching.

4 Conclusions In conclusion, monodispersed ZnSe nanoparticles were successfully synthesized via a simple ans green method at room temperature using a renewable starch as capping agent. The advantages of this method are (1) it is simple, cheap, efcient and economical which takes place within a short period of time and under ambient environmental conditions.(2) Hexagonal (rather than cubic) ZnSe nanocrystallite was produced at low temperature. (3) The assynthesized material can be widely used in many applications such as luminescent probe, biomedical labelling, catalysis, food and pharmaceutical industry, and so on. This method can be extended for the preparation of other functionalised water soluble selenide nanoparticles.
Acknowledgments This work was supported by AMET University, Chennai, and SRM University, Chennai. The authors thank Faculty members of physics and Chemistry Departments in SRM and AMET University, Chennai.

Fig. 4 Photo luminescence spectra of ZnSe nanoparticles

the emission curve suggests the presence of surface defects. This could be attributed to the smaller size of the particles. As the particle size decreases the surface to volume ratio increases, thereby increasing the number of surface atoms and energy. This increased the density of the surface defects which resulted in ineffective passivation of the surface states [19, 34]. The emission spectrum further buttresses the proposition for the broad size distribution of the nanoparticles. 3.4 IR analysis The surface morphology of the as-synthesized material was investigated using FT-IR spectroscopy to conrm the capping of the particles by starch (Fig. 5). The strong band at 3,298 cm-1 was attributed to the OH stretching of starch and it width was ascribed to the formation of inter and intramolecular hydrogen bond. The band at 2,921 cm-1 was ascribed to the asymmetric stretching of

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