Scanning tunneling spectroscopic studies revealed the quantum-confinement effects in Ge nanocrystals formed with ultrahigh density $(>{10}^{12}{\mathrm{cm}}^{-2})$ by Ge deposition on ultrathin Si oxide films. With decreasing crystal size, the conduction band maximum upshifted and the valence band minimum downshifted. The energy shift in both cases was about 0.7 eV with the size change from 7 to 2 nm. This shows that the energy band gaps of Ge nanocrystals increased to $\sim 1.4\mathrm{eV}$ with decreasing size. This size dependence can be explained by the quantum-confinement effect in Ge nanocrystals.

The design and fabrication of nanostructured materials to control both thermal and electrical properties are demonstrated for high-performance thermoelectric conversion. We have focused on silicon (Si) because it is an environmentally friendly and ubiquitous element. High bulk thermal conductivity of Si limits its potential as a thermoelectric material. The thermal conductivity of Si has been reduced by introducing grains, or wires, yet a further reduction is required while retaining a high electrical conductivity. We have designed two different nanostructures for this purpose. One structure is connected Si nanodots (NDs) with the same crystal orientation. The phonons scattering at the interfaces of these NDs occurred and it depended on the ND size. As a result of phonon scattering, the thermal conductivity of this nanostructured material was below/close to the amorphous limit. The other structure is Si films containing epitaxially grown Ge NDs. The Si layer imparted high electrical conductivity, while the Ge NDs served as phonon scattering bodies reducing thermal conductivity drastically. This work gives a methodology for the independent control of electron and phonon transport using nanostructured materials. This can bring the realization of thermoelectric Si-based materials that are compatible with large scale integrated circuit processing technologies.

The authors observed a quantum-confinement effect in individual ${\mathrm{Ge}}_{1-x}{\mathrm{Sn}}_x$ quantum dots (QDs) on Si (111) substrates covered with ultrathin $\mathrm{Si}{\mathrm{O}}_2$ films using scanning tunneling spectroscopy at room temperature. The quantum-confinement effect was featured by an increase in the energy band gap of $\sim 1.5\mathrm{eV}$ with a decrease in QD diameter from $35\text{to}4\mathrm{nm}$ . The peaks for quantum levels of QDs became broader with a decrease in the height-diameter aspect ratio of QDs, demonstrating the gradual emergence of two dimensionality in density of states of quasi zero-dimensional QDs with the QD flattening.

Phonon transport in Si films was controlled using epitaxially-grown ultrasmall Ge nanodots (NDs) with ultrahigh density for the purpose of developing Si-based thermoelectric materials. The Si/Ge ND stacked structures, which were formed by the ultrathin SiO₂ film technique, exhibited lower thermal conductivities than those of the conventional nanostructured SiGe bulk alloys, despite the stacked structures having a smaller Ge fraction. This came from the large thermal resistance caused by phonon scattering at the Si/Ge ND interfaces. The phonon scattering can be controlled by the Ge ND structure, which was independent of Si layer structure for carrier transport. These results demonstrate the effectiveness of ultrasmall epitaxial Ge NDs as phonon scattering sources, opening up a route for the realisation of Si-based thermoelectric materials.