Muonium in nano-crystalline II–VI semiconductors

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Abstract

The effect of quantum confinement on shallow-donor muonium states and their ionization in nanocrystalline colloidal II–VI semiconductors was studied by the transverse- and longitudinal-field μSR techniques. Evidence is found for the formation of surface muon states on nanocrystalline ZnO with hydrogen passivated surfaces. On nanocrystalline CdSe capped with organic molecules the muons probably form states at the surface or substitute for hydrogen in the organic materials. The results obtained so far on nc-CdTe are suggestive of formation of a muonium state inside the nanocrystals, but further studies are needed to find a definitive proof.

Introduction

Quantum confinement in colloidal semiconductor nanocrystals (ncs) results in a set of discrete valence hole and conduction electron energy levels, instead of bands. As a consequence, the optical and electrical properties of such systems depend strongly on the nanocrystal size, leading to extensive research [1], [2]. A compelling question that has received a lot of interest recently is whether small nanocrystals can be doped with donor (acceptor) atoms, permitting wide applications of nanocrystal materials in electronic functional devices [3]. The incorporation of hydrogen into ZnO nanocrystals has been hypothesized to be important for the transport properties of ZnO nanocrystal assemblies [4], [5].

μSR is a powerful method to study the isolated hydrogen (muonium) states in semiconductors. In particular, the formation and ionisation of a muonium shallow-donor state in some II–VI semiconductors in the bulk has been extensively studied [6], [7], [8], [9].

In this work we present the first results of a μSR survey of muonium states in nanocrystalline (nc) II–VI semiconductors, focusing on those where the shallow muonium is formed in the bulk. By using the transverse- and longitudinal-field techniques we searched for signs of the different states that might be forming inside, on the surface, or in the space between the nanocrystal cores. The temperature dependences of the signals are compared with that observed in bulk samples for the ionisation of the shallow muonium state.

Section snippets

Experimental details

Colloidal CdSe and CdTe nanocrystals used for these experiments were prepared by high-temperature organometallic synthesis. CdSe nanocrystals were prepared following de Mello Donega et al. [10], while CdTe particles were synthesized following the recipe of Wuister et al. [11]. The syntheses and subsequent steps are carried out in the inert atmosphere of an argon-purged glove box. This procedure yields small (3nm in diameter) particles with a narrow size distribution (<10% standard deviation).

Results

The low-temperature TF spectra have the same general traits for all samples studied, with a broad component and a central line, not well separated in most cases, as seen in Fig. 1 for the case of nc-CdTe.

Fig. 2 shows plots of the temperature variation of the parameters characterising the line shape of the spectra obtained for nc-CdTe and nc-ZnO. A single component was used for the fits to the nc-ZnO data and two component fits were used for nc-CdTe. These simple models do not reproduce the line

Conclusions

We have observed strong evidence in nc-ZnO of formation of surface states with dipolar interaction with nearby protons passivating dangling bonds. The plausibility of formation of states inside the nanocrystals is very low in the studied samples.

The data obtained for nc-CdSe also show strong evidence of dipolar interaction, presumably with N atoms of the HDA capping at the surface of the nanocrystals. A deep muonium state is formed, as expected for a substitution of hydrogen in the capping

Acknowledgements

This work was partially supported by the European Commission under the 6th Framework Programme through the Key Action: Strengthening the European Research Area, Research Infrastructures. Contract no. HII3-CT-2003-505925. J.M.G., J.S.L., J.L.G. and S.F.J.C. have benefited from the Treaty of Windsor Grants B-2/05 and B-55/07. The Coimbra team (CEMDRX) was also supported by FCT and FEDER funds under Portuguese Contract SFA/2-30.

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