Tunneling spectroscopy of InAs nanocrystals deposited on graphite was measured using scanning tunneling microscopy, in a double-barrier tunnel-junction configuration. The effect of the junction symmetry on the tunneling spectra is studied experimentally and modeled theoretically. When the tip is retracted, we observe resonant tunneling through the nanocrystal states without charging. Charging is regained upon reducing the tip–nanocrystal distance, making the junction more symmetric. The effect of voltage distribution between the junctions on the measured spectra is also discussed.
The surface and bulk contributions to the second-order nonlinear optical response of CdSe nanocrystals is studied. The first hyperpolarizability, βn, was measured for the nanocrystals in solution using the hyper-Rayleigh scattering method. Tri-n-octylphosphineoxide-capped nanocrystals show an enhancement in the value of the second hyperpolarizibility per unit cell, β, with reduced size. The two-state model can explain the enhancement for nanocrystals with radius down to about 1.7 nm, related with the concentration of oscillator strength, but for smaller particles the enhancement is larger than the prediction. This additional enhancement is assigned to a surface response. The contribution of surface ligands to the second harmonic signal for the nanocrystals was investigated by exchanging the tri-n-octylphosphineoxide ligands with the nonlinear chromophore nitrothiophenol. Surface exchange was evidenced through the change in particle solubility, by a substantial reduction of the fluorescence intensity, and by the vibrational spectra. The substitution to nitrothiophenol ligands leads to a size-dependent enhancement of βn compared to the original particles. The difference in βn between the surface-substituted and nonsubstituted particles scales with the number of surface sites for nanocrystals of different sizes. Surface exchange also leads to an enhancement in βn for a rod-shaped sample (aspect ratio 3.3:1). The contributions to βn for such nanocrystals can therefore be attributed to a combination of a bulk-like part arising from the nonlinear electronic response of Cd−Se bonds and a surface part effected by the nature of the ligands.
MnS nanocrystals have been prepared by a colloidal synthesis route through the reaction of MnCl2 and S[Si(CH3)3]2 in trioctylphosphineoxide. The nanocrystals were characterized using X‐ray diffraction and transmission electron microscopy. The magnetic properties were studied with SQUID magnetometry. X‐ray diffraction shows that the nanocrystals are of the thermodynamically stable α‐MnS (alabandite) structure. Size control was achieved by changing the concentration of the precursors. Nanocrystal sizes were measured by transmission electron microscopy, and three samples of average diameters 20, 40, and 80 nm were obtained, with narrow size distribution (σ˜9%). The zero field cooled magnetization curves for the 80‐, 40‐, and 20‐nm samples showed a cusp at 116 K, 97 K, and 50 K respectively, all smaller than the antiferromagnetic transition temperature, T N = 130 K, of bulk α‐MnS. Below T N the magnetization exhibits a paramagnetic behavior unlike typical antiferromagnetic materials. These results indicate that there is a mixture of paramagnetic and antiferromagnetic phases in the nanocrystals. The size dependence shows a general trend of decrease of T N with reduced particle size, indicating size dependent magnetic ordering.
