Materials Letters 67 (2012) 2831

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

A simple and novel route for the synthesis of water soluble ZnSe quantum dots using the Nano-Se as the reaction intermediate
Hongyi Qin a, c, Wenping Jian a, Yinan Zhang a, Taesung Kim c, Zhenhua Jiang a, Dong Jiang a,, Dahui Sun b
a b c

Engineering Research Center of High Performance Plastics, Ministry of Education; College of Chemistry, JiLin University, Changchun 130021, China First Hospital, Jilin University, Changchun 130021, China School of Mechanical Engineering, Sungkyunkwan University, Suwon 440-746, Republic of Korea

a r t i c l e

i n f o

a b s t r a c t
A new and simple synthesis method for water soluble and low toxic ZnSe QDs is presented in this paper. Nacetyl-L-cysteine (NAC) is chosen as the stabilizer of ZnSe QDs and reducing agent of Na2SeO3 in one reaction system. The reaction intermediate Nano-Se generated by the redox reaction between NAC and Na2SeO3 is used as the Se source. The water soluble ZnSe QDs obtained by our synthesis method show blue-green light emission. The effects of the pH, stabilizer concentration and synthesis time on the photoluminescence (PL) intensity of ZnSe QDs are also investigated. This new synthesis method simplies the reaction steps, enhances the utilization rate of chemicals and reduces the cost. 2011 Elsevier B.V. All rights reserved.

Article history: Received 25 April 2011 Accepted 8 September 2011 Available online 16 September 2011 Keywords: Particles Nanosize ZnSe quantum dots Water soluble Nano Se Nanocrystalline materials

1. Introduction In recent years, the highly stable quantum dots (QDs) or semiconductor nanocrystals have been of great interest. Highly uorescent QDs have been synthesized by pyrolyzing organometallic reagents in hot coordinating solvents, which requires oil-soluble ligands and high temperature (typically 200360 C) [1, 2]. Unfortunately, this approach is neither cost-effective nor environment-friendly. Furthermore, the heavy metal Cd 2+ QDs stabilized by hydrophobic capping molecules are disadvantageous in applications requiring water soluble and nontoxic QDs, such as biologic applications [3]. In order to overcome the existing disadvantages, we demonstrate a novel method of direct synthesis of water-soluble and low toxic ZnSe QDs in aqueous media. Thiol ligand N-acetyl-L-cysteine (NAC) was chosen as the ideal stabilizer, which is an antioxidant and therapeutic drug [4]. NAC, as a derivative of L-cysteine, is water soluble, biocompatible, nontoxic and low-cost, whose thiol group has excellent reduction ability by formation of the disulde bond, and this redox process is widely used in biotechnology [5, 6]. This redox principle is wisely utilized to reduce Na2SeO3 and form Nano-Se which is the Se source of ZnSe QDs in our method.

2. Experimental 2.1. Synthesis of ZnSe QDs All chemicals were acquired from China National Medicines Corp., LTD and were analytically pure. 10 ml ZnSO4 (0.1 M) and 10 ml fresh NAC (0.4 M) solutions were loaded into a three-neck ask. The mixture was adjusted to pH = 11 by stepwise addition of 1.0 M NaOH at room temperature under vigorous stirring. The air in the system was then pumped out and replaced with N2 for about 10 min. The system was heated to 100 C, and then 10 ml Na2SeO3 (0.5 M) solution was added through a syringe into the Zn precursor solution at this temperature. The molar ratio Zn:NAC:Na2SeO3 was set at 1:4:0.5. After 1 min, the three-neck ask was taken into an ice-water bath quickly and cooled to 0 C. Subsequently, the solution was diluted with acetone until the solution became cloudy, which indicated nanocrystal precipitation. The precipitate was spun down in a centrifuge at 3500 rpm for 10 min, the supernatant was then decanted, and the resulting nanocrystals were dissolved in 5 ml DI water. Unless mentioned otherwise, all ZnSe ODs suspensions described below had a 0.25 M nominal concentration. 2.2. Characterization of ZnSe QDs UVvis absorbance and uorescence measurement were obtained using Shimadzu UV-2501 and Shimadzu RF-5301 PC spectrouorimeter, respectively. FT-IR spectra were measured using the NicoletMagna 560 spectrophotometer. The transmission electron microscopy

Corresponding author. Tel.: + 86 431 87835760; fax: + 86 431 87835760. E-mail addresses: jiangdonghxy@163.com, zhangmeisdh@sina.com (D. Jiang). 0167-577X/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.matlet.2011.09.033

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(TEM) image was recorded by JEOL JEM-1200EX at acceleration of 80 kV, and the X-ray diffraction (XRD) measurement was acquired using a Siemens D5005 diffractometer. All the measurements were carried out at room temperature. 3. Results and discussion The chemical reaction of this method is described as below Eqs. (1)(5) [711] and Fig. 1, where RSH is the NAC molecule. The key point of this method is the use of NAC as the reductant of Na2SeO3 and stabilizer of ZnSe QDs at the same reaction regime. When the Na2SeO3 solution was injected into the Zn precursor solution (Eq. (1)), the color became baby pink immediately (Eqs. (2), (3)), which was the result of the formation of Nano-Se [8, 9]. These highly reactive ultrane Nano-Se particles produced in situ form Se 2 much easier than commercial Se powders do (Eq. (4)) [11], therefore, before the Nano-Se particles grew to sufcient size, they reacted with the Zn precursor and formed ZnSe QDs coated by the NAC (Eq. (5)). When this reaction occurred, the color of the Nano-Se solution also faded away. Moreover, the ZnSe QDs reaction rate and crystal nucleation rate are increased greatly due to the high-surfaceenergy of Nano-Se, which are advantageous for reducing surface defects and increasing the quality of ZnSe QDs.

2RSH Zn

2OH

RSZnSR 2H2 O

4RSH SeO3

RSSR 3H2 O RSSeSR

2 3

RSSeSRRSSR Se 3Se 6OH

2Se
2

SeO3 3H2 O

4 5
Fig. 2. (a) Infrared spectra of NAC-capped ZnSe, NAC-Nano Se and free NAC, and (b) TEM image of ZnSe QDs for reaction time 1 min.

RSZnSR Se

ZnSe

In order to study the reaction mechanism in detail, the IR spectra of the free NAC, NAC-capped ZnSe QDs and NAC-capped Nano-Se are compared in Fig. 2a. The NAC-capped Nano-Se was synthesized in the same way that NAC-capped ZnSe was, except that 10 ml ZnSO4 (0.1 M) was replaced by 10 ml DI water. Apparently, the NAC thiol group peak (2454 cm 1) of the NAC-capped ZnSe disappears completely, which demonstrates that the NAC exists as a stabilizer on the surface of ZnSe QDs [4, 12]. And the IR spectrum of the NACcapped Nano-Se sample is similar with that of the NAC-capped ZnSe

Fig. 1. Schematic diagram of the formation mechanism of the NAC-ZnSe QDs, RSH is the NAC molecule.

QDs. It demonstrates that the NAC can react with the Na2SeO3 and exists as Nano-Se stabilizer. Therefore, the NAC can be used as the reductant and stabilizer in the whole reaction system. The TEM (Fig. 2b) image shows that the size of ZnSe QDs is less than 10 nm and there is no particles aggregation. However, the ZnSe QDs is not monodisperse and its size distribution is wide, from 2 nm to 10 nm, and the concentration of b 5 nm QDs is relatively larger. According to the chemical reaction equations and our study, pH is an important parameter that greatly affected the quality of QDs. As shown in Fig. 3a, when the pH increases from 5.53 to 10.55, the photoluminescence (PL) intensity increases greatly, and the PL emission position (470484 nm) and UVvisible absorption spectrum (338357 nm) show a vaguely detectable red-shift. NAC thiol group is nucleophilic and easily oxidized, and its reactivity is enhanced when the thiol group is ionized by alkali ions. The thiol and carboxyl groups of NAC exist as negatively charged thiolate and carboxylate groups under the strong alkaline condition of pH = 11 [13]. The negative charges of the carboxylate groups located on the surface of the QDs repel each other, thus preventing aggregation. Moreover, the reduction reaction rate of the negative thiolate groups is increased under the high pH condition, increasing the nucleation rate and reducing the surface defects of QDs [14], hence, better PL properties are obtained. However, the rst exciton peaks and emission peaks are wide and unobvious, they demonstrate that the size distribution of ZnSe QDs is large, and the size of ZnSe QDs with the largest distribution is about 3 nm [15].

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H. Qin et al. / Materials Letters 67 (2012) 2831

Fig. 3. (a) PL intensity and UVvisible absorption spectrum of ZnSe QDs synthesized under various pH, and (b) PL intensity and normalized PL of ZnSe QDs for different reaction time.

Fig. 4. (a) Images of ZnSe QDs with different ratios of Zn:NAC under daylight and 315 nm UV light, respectively (Zn:Se = 1:0.5), and (b) X-ray diffraction (XRD) pattern for ZnSe QDs.

The reaction time at 100 C was an important parameter and it greatly affected the size and quality of these QDs. As shown in Fig. 3b, the PL intensity peaks after 1 min, and the emission spectrum shifts to greater wavelengths over time. After 5 min under 100 C, the suspension became cloudy, indicating aggregation due to the decomposition of the NAC stabilizer. The effect of NAC concentration was also investigated according to the ratio of Zn:NAC:Na2SeO3 from 1:2.5:0.5 to 1:5.5:0.5 continuously. As shown in Fig. 4a, the Zn:NAC:Na2SeO3 = 1:2.5:0.5 sample is cloudy because the stabilizer NAC was not enough and aggregation occurred. The Zn:NAC:Na2SeO3 = 1:5.5:0.5 sample, however, is light brown under daylight and shows almost no uorescence under UV light. The amount of the stabilizer NAC exceeded that of Zn and Se sources and almost all the Zn and Se sources existed as RSZnSR and Nano-Se, hence, the chemical chain reaction process no longer continued to form ZnSe QDs and the sample showed the color of the Nano-Se solution. For the other samples, the observed emission spectra are blueshifted with the addition of the stabilizer NAC. The PL intensity of samples with Zn:NAC:Na2SeO3 = 1:3.5:0.5 and 1:4:0.5 seems to be relatively better than those of the samples with other Zn:NAC: Na2SeO3 ratios. The ZnSe QDs exhibit a diffraction pattern quite close to that of bulk cubic ZnSe (Fig. 4b), which shows that the dominant structure is the ZnSe crystal phase. However, the diffraction peaks are asymmetric, that may be related with the instrumental bias, transparency of samples and impurities in the sample.

4. Conclusion A novel and simple method was investigated to prepare water soluble ZnSe QDs by using NAC as the stabilizer and reductant, and using Nano-Se as the reaction intermediate. This synthetic process is uncomplicated, environmental friendly and economical. It increases the utilization efciency of chemicals, simplies the experimental process, and reduces cost. Furthermore, the use of low toxic and water soluble ZnSe QDs is the future trend in labeling of biological molecules and cells. We expect this method to be used in the synthesis of CdSe and other selenide QDs. As such, our method shows potential in mass production and in biological uorescence labeling. Acknowledgment This work was nancially supported by Specialized Research Fund for the Doctoral Program of Higher Education (20100061120085) and Basic Scientic Research Business Expenses of Jilin University (200903104). References
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