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Journal of Nanoscience and Nanotechnology Vol. 11, 16, 2011

Green Synthesis of Cadmium Selenide Nanocrystals: The Scope of 1,2,3-Selendiazoles in the Synthesis of Magic-Size Nanocrystals and Quantum Dots.
Rupinder K. Beri and Pawan K. Khanna
Nansocience Laboratory, Centre for Materials for Electronics Technology (C-MET), Panchwati, Off Pashan Road, Pune, 411008, Maharashtra, India A range of cadmium selenide nano-particles (the quantum dots (QDs), the magic-size nano-crystals (MSNCs) or the mixture of two) have been synthesized by the use of organoselenium reagents viz. 1,2,3-selenadiazole and metal salts in an appropriate choice of long chain fatty acids e.g., oleic acid with or without a solvent. These different types of nanocrystals can be easily obtained simply by variation in reaction temperature. The employed approach does not use any hazardous reagents and is typically non-aqueous and can be considered green. The temperature at which the reaction is carried out along with the ratio of reactants and surfactant affect the nature of products and have led to understanding of some parameters affecting the formation of either thermodynamic or kinetically stabilized products. We have obtained sub-nanosized particles (magic-sized nanocrystals), zero-dimensional quantum dots and self-assembled structures by these methods. The materials have been studied by UV-Visible spectroscopy (UV-Vis), Photoluminescence spectroscopy (PL), X-ray diffraction (XRD), Scanning electron microscopy (SEM), Energy dispersion X-ray analysis (EDAX), and Transmission electron microscopy (TEM).

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Keywords: Quantum Dots, Mazic-Sized Nano-Crystals, Semiconductors, Synthesis.

1. INTRODUCTION
IIVI semiconductor quantum dots nd extensive applications due to unique electronic and optical properties in diverse elds such as electronics, opto-electronics, and solar cells.13 CdSe is highly suited semiconductor as its absorption wavelength can be tuned to the entire visible light spectrums due to quantum connement effect. Large number of synthetic approaches have been documented in recent years and optical properties are also well understood. The most common chemical approaches are the pyrolysis of organo-metallic precursors, gas-phase synthesis, sono-chemical, and aqueous synthesizes.410 In comparison to quantum dots, size domain below 2 nm leads to different optical properties and is considered to be a hot research area within the nano-particle research. The ultra-small nanocrystals (12 nm) are reported by many researchers and these are called magic-size and /or magic-number nanocrystals or nanoclusters (MSNCs).1113 It has been argued that they have different crystal structure than the regular quantum dots and thus some reports

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show them to be elongated particles as against the spherical particles of QDs. The MSNCs thus show unique spectral properties e.g., the sharp absorptions normally at xed positions with the broad emissions.12 The broad emission makes them most desired materials for white-light emitting diodes (LEDs).5 14 CdSe nano-clusters of 12 nm dimensions were rst reported in 199615 by Plateschek et al. where they obsereved sharp HOMO-LUMO absorption peaks at 280, 360 and 410 nm. Similarly, Soloviev et al.16 showed sharp absorptions and two types of emission bands in the photoluminescence studies of CdSe nano-clusters i.e., band gap and the deep trap. We have also trapped in the recent past the early stage CdSe in commercial PMMA and have demonstrated that such early stage CdSe nano-crystals can be in-situ loaded in polymeric matrices despite the use of an aqueous selenium source.1719 A number of methods have been developed for the synthesis of CdSe quantum dots which are mostly modications of the original method developed by Bawendi et al.20 but aimed at reducing the use of hazardous chemicals. Non-aqueous methods have an advantage over the aqueous micellar methods as they produce better quality of
doi:10.1166/jnn.2011.4143

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The Scope of 1,2,3-Selendiazoles in the Synthesis of MSNCs and QDs.

Beri and Khanna

quantum dots in terms of dispersity, stability and quantum yield. Different methods for obtaining magic-size nanocrystals (MSNCs) and regular quantum dots (QDs) have been reported. Low temperature inverse water-oil micellular and organometallic methods have been considered attractive. Although the nano-crystals prepared at high temperature showed better optical properties, in practice is not always benecial to the researchers. Often times, one encounters that the toxic reagents such as alkyl phosphines and amines as well as pains-taking single source organo-precursors which need high temperature has been employed for their synthesis. Use of simple air-stable organo-selenium precursors can simplify the complexed quantum dots synthesis. In this regard, we have earlier reported the synthesis of magic-sized nanocrystals by use of organo-selenium precursor i.e., cyclo-hexeno-1,2,3-selenadiazole. In addition, we have exclusively employed these alkeno selenadiazoles for quantum dots of IIVI semiconductors. The distinct advantage of using 1,2,3-selendiazole lies in its relative simple synthesis from the corresponding semicarbazone. Apart from this it allows the synthesis of quantum dots to be achieved at moderate temperatures <200 C and denes processes which are green in their avoidance of hazardous reagents such as trioctylphosphine oxide or dimethyl cadmium. Extending our research in this led, we herein present the simple, green synthesis of QDs and MSNCs of CdSe and other metal selenides by either direct thermal reactions. By adopting desired experimental conditions, metal selenides in general and CdSe quantum dots and magicsized nanocrystals in particularly, can be obtained at low temperature thermolysis of a cyclo-alkeno-1,2,3selenadiazole via a reasonably green approach avoiding the use of highly toxic reagents. The elongation along one direction in case of MSNCs differentiate them from the regular dots. Broad or narrow UV-Visible peaks and bands resulting into similar emission bands makes them suitable candidate for many optical applications. Analysis of such nano-particles can be easily performed by using absorption spectroscopy (UV-Vis) and photoluminescence (PL) which showed huge blue shift and enhanced band-gap energy due to efcient size quantization effect. The other metal selenides e.g., silver and cooper have also been successfully synthesized.

performed in solution on HITACHI F-2500 uorescence spectrophotometer. Powder X-ray diffraction patterns were measured using Cu-K ( = 1 5406 ) radiation on Mini Flex Rigaku X-ray diffractometer. Transmission Electron Microscopy (TEM) images were taken on a Technai G-20 transmission electron microscope with an acceleration voltage of 200 kV. 2.2. General Synthesis of CdSe Quantum Dots and Magic-Sized Nanocrystals and Metal Selenides Cadmium acetate and long carbon chain carboxylic acid can be heated between 100200 C in high boiling solvent e.g., diphenyl ether and pre-dissolved cyclo-alkeno1,2,3-selenadiazole or open chain 1,2,3-selenadiazoles e.g., 4-Phenyl-1,2,3-selenadiazole was then added as per desired ratios with respect to the Cd or other metal source. The reaction mixture can be heated for 26 h and the work-up is normally done by addition of ethanol. The centrifugation of the red, orange or black suspension yielded the quantum dots, magic size nano-crystals of CdSe and nano-crystal of silver or copper selenide in about 5080% yield. In a typical synthesis, cadmium acetate (0.7 g, 2.63 mmol) was added to oleic acid (15 ml, 47.8 mmol) and diphenyl ether (DPE) (20 ml) and heated to 200 C under inert atmosphere. After 10 min, 4-phenyl-1,2,3selenadiazole (0.5 g, 2.39 mmol) dissolved in DPE (5 ml) was added at the same temperature and the reaction was continued at the same temperature with constant stirring for 6 hours. After 6 hours the heating was stopped and the reaction was allowed to attain room temperature before the addition of precipitating solvent ethanol or methanol (50 ml), precipitate was aged overnight. Centrifugation and washing with same solvent provides red solid that is ltered and dried at 60 C to obtain free-owing powder (0.6 g) dispersible in toluene.

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3. RESULTS AND DISCUSSION

When cadmium acetate and oleic acid in diphenyl ether are heated together in the temperature range 100200 C and reacted further with cyclo-alkeno-1,2,3-selenadiazole dissolved in the same solvent, the solution darkens from pale-yellow to orange and then red indicating the formation of CdSe QDs or Magic sized nano-crystals depending on the reaction temperature and time. However in case of transition metals selenides such as silver and copper these turned instantly black to lead a black/brown powder. The main focus of current discussion can be aimed at CdSe so as to understand usefulness of Se-precursor for green synthesis more clearly. The isolated CdSe particles when re-dissolved in toluene or hexane showed the absorption maxima at 535560 nm in case of QDs and at about 360400 nm in case
J. Nanosci. Nanotechnol. 11, 16, 2011

2. EXPERIMENTAL DETAILS
2.1. General The Se-precursor 1,2,3-selendiazoles was prepared and puried as described in the literature.19b Solvents and chemicals were of reagent grade and were used as received. UV-Visible absorption spectra were measured on a JASCO V-570UV/VIS/NIR spectrophotometer at room temperature. Photoluminescence (PL) measurements were 2

Beri and Khanna

(a)

The Scope of 1,2,3-Selendiazoles in the Synthesis of MSNCs and QDs.

(b)

Fig. 1.

Optical spectra of QDs and MSNCs (a) UV-Vis and (b) PL.

of MSNCs of CdSe. Figure 1(a) shows much blue shifted absorption values when compared with the bandgap energy of the bulk CdSe. The absorption band in Figure 1(a) shows that the sample is a mixture of magic sized and regular quantum dots of CdSe. Such nanoparticles are also useful from many technological angle as these can be considered as magic-sized doped regular quantum dots generated in-situ by varying the reaction conditions or by effectively adopting a single type of experimental conditions with respect to surfactant, reaction temperature and or reaction time. When the absorption band was excited at 350400 nm ( ex = 350400 nm), the spectrum (Fig. 1(b)) showed a band-gap emission from the nano-particles. We believe that the sharp emission at about 460 is due to MSNCs and the broad emissions there after could be either due to MSNCs themselves or due to the mixture of these with regular quantum dots. The multi wavelength emission prole may result not only due to broad size distribution but also due to presence of two different type of species i.e., MSNCs and regular QDs in the present case. The sharp emission is indicative of narrow size distribution. The emission proles of the magic-sized nano-cluster is much different than the quantum dots. The absorption spectrum showed two well-dened absorptions any where between 370 nm to 400 nm (Fig. 1(a)) depending on the experimental conditions adopted as different preparation strategy leads to different types of MSNCs. Some call it
J. Nanosci. Nanotechnol. 11, 16, 2011

single family (identied by single sharp absorption peak), some call is double family (identied by absorption doublet) and some time these are termed as multiple family magic-sized nano-crystals (when the absorption peaks are more than two). Based on the literature, these absorptions can be assigned to electronic transitions 1S(e)-1S3/2 (h); 1s(e)2S3/2 (h). Similarly, the emission spectrum showed two values; the rst a sharp peak Stokes shifted from the absorption value and the second a broad band ranging from 450 to 650 nm (Fig. 1(b)). The extended thermal energy and reaction time eventually leads to formation of spherical dots (QDs) of about 35 nm due to constant nucleation and growth of the initially thermodynamically stabilized elongated particles (MSNCs). The number of atoms in these elongated particles and the exact crystal structure (cubic or hexagonal) is still a subject of great interest. The longer reaction time if pursued in different solvent, may results in formation of different sizes of quantum dots and their energy gap value may also vary due to variation in particle size and the difference in the coordinating ability of the solvent molecules. Thus the reaction in DMF yields the QDs that have absorption value at 583 nm as against the preparation carried out in DPE which shows the formation of slightly smaller sized QDs. It is opined that DMF may coordinate through the loan pair of the nitrogen atom and thus act as electron donor and this may lead to lowering in band gap energy. In other word the electron rich surfaces or the core may leads to red-shift in the absorption spectrum. It has been described21 for MSNCs of the family 408 prepared using trioctypphosphine (TOP) that this family exhibit poor band gap emission but showed signicant trap emission possibly because the product was initiated from the Cd precursor which might be a Cd-P complex. The Cd-P complexation may result from the coordination competition of TOP (which is often taken in large amount), to Cd and carboxylic acid. This clearly shows that the nature of Cd precursors plays an essential role in the formation single-sized nano particles.
3 2.5 2 QDs/DPE QDs/DMF

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Abs.

1.5 1 0.5 0 450 548 nm

583 nm

500

550

600

650

700

Wavelength in nm
Fig. 2. UV-Vsible absorption spectra of QDs of CdSe prepared in two different solvents showing the difference in band-gap energy.

The Scope of 1,2,3-Selendiazoles in the Synthesis of MSNCs and QDs.

Beri and Khanna

CdSe

Scheme 1.

Se-precusor (1) and its reaction for obtaining CdSe QDs.

A case of a particular Se-precursor i.e., 4-phenyl 1,2,3selenadiazole (1) can be discussed here in more detail for synthesis of CdSe quantum dots (Scheme 1). The monitoring of the reaction was performed by taking aliquots which shows that the growth occurs slowly and upto a period of 1 h (Fig. 3). It is reasonable to conclude from related observations with the use of cylo-alkenoselenadiazoles that use of (1) is typically a non-injection method where temperature was not the only parameter that affects the formation of quantum dots. The chemical reactivity of precursor is also an important factor which affects the precursor concentration available for formation of CdSe. Tunning of precursor concentrations can be achieved by changing the relative proportion in which the Se:Cd precursors are taken. A 1:1 ratio of Se: Cd precursor led to formation of quantum dots. The cadmium acetate is presumed to be converting in-situ to cadmium oleate which reacts with (1) to produce CdSe Qdots. The absorption maxima at 530 nm (Fig. 3(b)) shows large blue shift as a result of size quantization effect and corresponds to an increase in band-gap to 2.34 eV in comparison to band gap of bulk CdSe which is reported to be 1.74 eV.22 The use of precursor (1) thus yielded CdSe quantum dots with increased energy gap between the HOMO-LUMO by about 0.60 eV. The particle size is calculated to be 3.0 nm based on optical data using the effective mass approximation equation.23 The uorescence spectrum was recorded with excitation energy ( ex of 400 nm. Figure 3(b) (PL) shows a bang-gap emission from the solution when measured in toluene with sharp emission band at about at 569 nm with small FWHM of 38 nm and a Stokes shift of 39 nm. A FWHM of about 40 nm refers to a size distribution of 10% which is considerably smaller than organic uorophores. The quantum yield (using Rhodamine B as reference) was estimated to be 15%. We did not observe any deep-trap emission band during the measurement of the emission spectrum. The synthesized quantum dots are stable as solids and in solution (e.g., toluene). Prolonged air storage of the so-prepared QDs does not show any change in their absorption prole. The TEM micrographs (Fig. 4) demonstrate high-quality non-aggregated particles having an average diameter along 4

small axis of 3.2 nm. The EDAX analyses (Calcd for CdSe: Cd, 58.6; Se 41.3%, Found Cd, 58.7: Se, 41.2% respectively) is precisely consistent with a CdSe composition of 1:1. The organic portion corresponds to 25%
(a)

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(b)

Fig. 3. (a) UV-Vis showing evolution of band and growth of CdSe QDs obtained using (1) (b) Superimposed UV-visible (UV-Vis) and photoluminescence (PL) spectra ( ex = 400 nm).

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Beri and Khanna

The Scope of 1,2,3-Selendiazoles in the Synthesis of MSNCs and QDs.

(a)

Fig. 5. X-ray diffraction pattern of CdSe QDs obtained using (1).

(b)

Fig. 4.

(a) TEM and (b) HRTEM of CdSe QDs obtained using (1).

and CdSe to 75%. Analysis of almost all our samples by selected area electronic diffraction pattern (SAED) showed relevant concentric rings characteristic of cubic crystal structure of CdSe. The EDAX analyses for quantum dots was consistent in most cases with a CdSe composition of 1:1. However, in case of MSNCs the % Cd was found to be higher than %Se. The X-ray diffraction pattern (Fig. 5) conrms cubic crystal structure of CdSe.24 The diffraction peaks at 2 theta value of 25.3 , 41.9 , 49.6 , 67.7 78 corresponding to 111 220, 331, 311 and 422 are were all observed. From the pattern in Figure 4 , the presence of reections at 331 and 422 planes suggest the crystalline nature of the sample. The crystallite size was estimated to be 34 nm applying Debye Scherrers formula. Figure 6 shows the comparison of the XRD pattern of the regular quantum dots and the MSNCs. It is possible to differentiate the two on the basis of the XRD pattern as one can see the difference in peak intensity along the 220 plane. Using the Scherrers formula particle size was estimated to be about 34 nm in case of the quantum dots
J. Nanosci. Nanotechnol. 11, 16, 2011

(thick lines) but in case of MSNCs (thin lines) this calculation can not considered as accurate because of the possible distortion in the crystal structure. The Scherrer formula is particularly true for the spherical particles and therefore the estimation of the particle size of non-spherical species does not lead to correct particle size/crystallite size. Instead the particle size of the MSNCs can be correlated with the reported absorption pattern and those measured by TEM and reported in the literature. The clear elongation at 220 plane does indicate that there is certain distortion as expected. The limited number of atoms in such crystals are expected to go through certain degree of strain and thus the elongation of the structure is possible to stabilize the crystals. This assumption is supported by the suppressed intensity of 111 peak which is the highest intensity peak for QDs and the increased intensity of 200 peak. The XRD patterns therefore, indicate that the particles are elongated and not spherical. The emergence of the low intensity peaks at plane 400 is also supportive of distorted structure. Atomic force microscopy (AFM) of the CdSe (Fig. 7) QDs showed non-aggregated almost spherical particles. The AFM analysis showed that topographically the particles seems to be oval indicating that the dots are homogeneously settled on the substrate and uniformity of particles has been attained.

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Suppression of peak intensity

Appearance of 400 peak

Fig. 6. Comparison of the XRD pattern of CdSe QDs and MSNCs.

The Scope of 1,2,3-Selendiazoles in the Synthesis of MSNCs and QDs.

Beri and Khanna

References and Notes

1. K. S. Leschkies, R. Divakar, J. Basu, E. Enache-Pommer, J. E. Boercker, C. B. Carter, U. R. Kortshagen, D. J. Norris, and E. S. Aydil, Nano Lett. 7, 1793 (2007). 2. M. Achermann, M. A. Petruska, D. D. Koleske, M. H. Crawford, and V. I. Klimov, Nano Lett. 6, 1396 (2006). 3. P. V. Kamat, J. Phys. Chem. C 112, 18737 (2008). 4. L. Manna, C. Scher Erik, and A. Paul Alivisatos, J. Am. Chem. Soc. 122, 12700 (2000). 5. P. K. Khanna, P. More, R. Shewate, R. K. Beri, A. K. Viswanath, V. N. Singh, and B. R. Mehta, Chem. Lett. 38, 676 (2009). 6. S. J. Rosenthal, J. McBride, S. J. Pennycook, and L. C. Feldman, Surface Science Reports 62, 111 (2007). 7. T. Trindade and P. OBrein, Chem. Mater. 9, 523 (1997) 8. N. L. Pickett, F. G. Riddell, D. F. Foster, D. J. Cole-Hamilton, and J. R. Fryer, J. Mater. Chem. 7, 1855 (1997). 9. Q. Shen, L. Jiang, J. Miao, W. Hou, and J. Zhu, J. Chem. Soc., Chem. Commun. 1683 (2008) 10. L. Liu, Q. Peng, and Y. Li, Inorg. Chem. 47, 5022 (2008). 11. A. L. Rogach, D. V. Talapin, and H. Weller, Semiconductor Nanoparticles in Colloids and Colloid Assemblies, edited by F. Caruso, Wiley (2004). 12. J. Ouyang, M. B. Zaman, F. J. Yan, D. Johnston, G. Li, X. Wu, D. Leek, C. I. Ratcliffe, J. A. Ripmeester, and K. Yu, J. Phys. Chem. C 112, 13805 (2008). 13. R. K. Beri and P. K. Khanna, Cryst. Engg. Commn. (2010). 14. K. Wooseok and L. Jing, J. Am. Chem. Soc. 130, 8114 (2008). 15. V. Ptatschek, T. Schmidt, M. Lerch, G. Muller, L. Spanhel, A. Emmerling, J. Fricke, A. H. Foitzik, and E. Langer, Ber. BunsenGes. Phys. Chem. 102, 85 (1998). 16. V. N. Soloviev, A. Eichhofer, D. Fenske, and U. Banin. J. Am. Chem. Soc. 122, 2673 (2000). 17. R. K. Beri and P. K. Khanna, Unpublished results. 18. R. K. Beri, P. More, B. G. Bharate, and P. K. Khanna, Curr. Appl. Phys. 10, 553 (2010). 19. P. K. Khanna, P. More, B. G. Bharate, and A. K. Viswanath, J. Luminescence 130, 18 (2010); (b) H. Meier and E. Voigt, Tetrahedron 28, 187 (1972). 20. C. B. Murray, D. J. Norris, and M. G. Bawendi, J. Am. Chem. Soc. 115, 8706 (1993). 21. K. Yu, M. Z. Hu, R. Wang, M. L. Piolet, M. Frotey, M. B. Zaman, X. Wu, D. M. Leek, Y. Tao, D. Wilkinson, and C. Li, J. Phys. Chem. C 114, 3329 (2010). 22. P. K. Khanna, R. M. Gorte, and C. P. Morley, Mater. Lett. 57, 1464 (2003). 23. J. Hambrock, A. Birkner, and R. A. Fischer, J. Mater. Chem. 11, 3197 (2001). 24. L. Lui, Q. Peng, and Y. Li, Inorg. Chem. 47, 5022 (2008).

Fig. 7.

Atomic Force Micrograph (AFM) and TEM of CdSe QDs.

4. CONCLUSIONS
In summary, The results presented herein, demonstrate the usefulness of known but not-so-well studied and explored organoselenium compounds in the synthesis of monodisperse crystalline cubic CdSe quantum dots of 34 nm in size. Without the use phosphorous or amine ligands and by avoiding size-focussing or size sorting techniques. The two type of nano-particles can be prepared by using the same precursors and same method just by slight variation of reaction temperature and time. Acknowledgments: PKK thanks DST, Govt. of India for nancial support (Grant No. SR/S1/PC-17/2006), Dr. A. K. Vishwanath and Dr. C. V. V. V. Satyanarayana for fruitful discussion and Professor B. R. Mehta for TEM facility under Nanoscience and Nanotechnology Initiative of the DST at IIT Delhi (Project No. SR/S5/NM-22/2004).

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Received: xx Xxxx xxxx. Accepted: xx Xxxx xxxx.

J. Nanosci. Nanotechnol. 11, 16, 2011