Formation of high-quality CdTe, CdSe, and CdS nanocrystals using CdO as precursor.

High-quality colloidal semiconductor nanocrystals are nanometer-sized, single crystalline fragments of the corresponding bulk crystals, which have well-controlled size and size distribution and are dispersible in desired solvents/media. Recently, semiconductor nanocrystals are of great interest for both fundamental research and technical applications, 1-8 due to their strong size dependent properties and excellent chemical processibility. Synthesis of highquality semiconductor nanocrystals has been playing a critical role in this very active field. 1,9-15 As the most developed system in terms of synthesis, 1,9,10,15high-quality CdSe nanocrystals with nearly monodisperse size and shape are in active industrial development for biological labeling reagents. 5,6 Since Murray et al. 15 reported the synthesis of high quality cadmium chalcogenides nanocrystals using dimethyl cadmium (Cd(CH 3)2) as the cadmium precursor, the synthesis of CdSe nanocrystals using this precursor has been well developed. 1,9,10In comparison, the synthesis of CdTe and CdS15,16are not as advanced. For instance, there is no method to controllably vary the shape of CdTe and CdS nanocrystals. Cd(CH3)2 is extremely toxic, pyrophoric, expensive, unstable at room temperature, and explosive at elevated temperatures by releasing large amount of gas. Due to these reasons, the Cd(CH 3)2related schemes require very restricted equipments and conditions and are not suited for large-scale synthesis. In this paper, we will prove that Cd(CH3)2 can be replaced by CdO. Surprisingly, this new synthetic scheme works significantly better than the Cd(CH3)2-related ones. Without any size-sorting, the quality of quantum-confined dots and rods (quantum dots and quantum rods) of all cadmium chalcognides formed by the new method is comparable to that of the best CdSe nanocrystals reported in the literature. The new scheme is reproducible and simple and thus can be readily scaled up for industrial production. Recently, we identified that Cd(CH 3)2 decomposes in hot trioctylphosphine oxide (TOPO) and generates insoluble metallic precipitate. 9 With a strong ligand, either hexylphosphonic acid (HPA) or tetradecylphosphonic acid (TDPA), Cd(CH 3)2 is immediately converted into cadmium HPA/TDPA complex (Cd HPA/Cd-TDPA) if the cadmium to HPA/TDPA ratio is lower than 1. After the formation of the complex, an injection of Se dissolved in tributylphosphine (TBP) generates high-quality CdSe nanocrystals. This result implies that Cd(CH 3)2 may not be necessary, if we can generate the complex by other means. We first synthesized and purified Cd -HPA from CdCl 2 or Cd(CH3)2. High-quality CdSe nanocrystals were indeed yielded from this complex. This success encouraged us to develop a one-pot synthesis which does not require separated preparation of cadmium complex. We failed to make high-quality CdSe nanocrystals using CdCl2 by the one-pot approach although CdCl 2 can be dissolved in the reaction mixture at elevated temperatures. In contrast, CdO works very well for the one-pot approach. We think this is due to the low stability of CdO relative to phosphonic acids, compared to that of CdCl 2. Experimentally, CdO, TOPO, and HPA/TDPA were loaded in a three-neck flask. At about 300 °C, reddish CdO powder was dissolved and generated a colorless homogeneous solution. Introducing tellurium, selenium, and sulfur stock solutions yields high quality nanocrystals. 17 The samples for all of the measurements shown in this paper are directly from synthesis without any size separation. The growth kinetics of nanocrystals grown by the new approach possesses a pattern similar to that of the best CdSe nanocrystals formed by the Cd(CH3)2 approach (Figure 1). 10 Figure 1 and Figure 2 further reveal that the size of all three kinds of nanocrystals can be close to monodisperse, represented by the sharp absorption peaks if the growth stops in the “focusing of size distribution” regime. 10 Transmission electron microscopy (TEM) measurements indicate that these nanocrystals have very narrow distribution. The relative standard deviation of the size of the nanocrystals shown in Figure 3 (top) is about 10%. The high crystallinity of these wurtzite nanocrystals was confirmed by X-ray powder diffraction. For this CdO approach, the size of relatively monodisperse CdSe nanocrystals can be continuously tuned down to the sizes with the first absorption peak at 440 nm (see the first absorption spectrum in Figure 1). Relatively monodisperse CdSe nanocrystals with the first exciton absorption peak below 480 nm are difficult to synthesize directly with the existing Cd(CH 3)2-related approach. 10,18 (1) Peng, X. G. ; Manna, L. ; Yang, W. D. ; Wickham, J.; Scher, E. ; Kadavanich, A. ; Alivisatos, A. P. Nature2000, 404, 59-61. (2) Heath, J. R. (editor). Acc.f Chem. Res. 1999. (3) Alivisatos, A. P.Science1996, 271, 933-937. (4) Huynh, W. ; Peng, X. ; Alivisatos, A. P. AdV. Mater. 1999, 11, 923927. (5) Bruchez, M. ; Moronne, M. ; Gin, P.; Weiss, S. ; Alivisatos, A. P. Science 1998, 281, 2013-2016. (6) Chan, W. C. W. ; Nie, S. M. Science1998, 281, 2016-2018. (7) Schlamp, M. C. ; Peng, X. G. ; Alivisatos, A. P. J. Appl. Phys.1997, 82, 5837-5842. (8) Mattoussi, H. ; Radzilowski, L. H. ; Dabbousi, B. O. ; Thomas, E. L. ; Bawendi, M. G. ; Rubner, M. F. J. Appl. Phys.1998, 83, 7965-7974. (9) Peng, Z. A. ; Peng, X. G. J. Am. Chem. Soc. , in revision. (10) Peng, X. G. ; Wickham, J.; Alivisatos, A. P. J. Am. 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The temperature of the solution was cooled to 270 °C, tellurium stock solution (0.0664 g of tellurium powder dissolved i n 2 g of TOP) was injected. After injection, nanocrystals grew at 250 °C to reach desired size. (18) Bawendi, M. G. Private communication. Figure 1. Temporal evolution of size and size distribution of CdTe, CdSe, and CdS nanocrystals studied by UV -vis. 183 J. Am. Chem. Soc. 2001,123,183-184