Ordered arrays of II/VI diluted magnetic semiconductor quantum wires: formation within mesoporous MCM-41 silica

We present a novel way of synthesising highly ordered arrays of hollow Cd(1-x)Mn(x)S quantum wires with lateral dimensions of 3-4 nm separated by 1-2 nm SiO2 barriers by forming Cd(1-x)Mn(x)S (0 < or = x < or = 1) semiconductors inside the pore system of mesoporous MCM-41 SiO2 host structures. X-ray diffraction and transmission electron microscopy (TEM) studies reveal the hexagonal symmetry of these arrays (space group p6m) and confirm the high degree of order. Physisorption measurements show the filling of the pores of the MCM-41 SiO2. The X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), electron paramagentic resonance (EPR), and Raman studies confirm the good crystalline quality of the incorporated (Cd,Mn)S guest. The effects of reducing the lateral dimensions on the magnetic and electronic properties of the diluted magnetic semiconductor were studied by photoluminescence (PL) and PL excitation spectroscopy and by SQUID and EPR measurements in the temperature range 2-400 K. Due to the quantum confinement of the excitons in the wires, an increase of about 200 meV in the direct band gap was observed. In addition, the p-d hybridisation-related bowing of the band gap as a function of Mn concentration in the wires is much stronger than in the bulk. This effect is related to the increase in the band gap due to quantum confinement, which shifts the p-like valence band edge closer to the 3d-related states of Mn in the valence band. Thus, the p-d hybridisation and the strength of the band gap bowing are increased. Compared to bulk (II,Mn)VI compounds, antiferromagnetic coupling between the magnetic moments of the Mn2+ ions is weaker. For the samples with high Mn concentrations (x > 0.8) this leads to a suppression of the phase transition of the Mn system from paramagnetic to antiferromagnetic. This effect can be explained by the fact that the lateral dimensions of the wires are smaller than the magnetic length scale of the antiferromagnetic ordering.