Evolution of Cu-In Catalyst Nanoparticles under Hydrogen Plasma Treatment and Silicon Nanowire Growth Conditions.

We report silicon nanowire (SiNW) growth with a novel Cu-In bimetallic catalyst using a plasma-enhanced chemical vapor deposition (PECVD) method. We study the structure of the catalyst nanoparticles (NPs) throughout a two-step process that includes a hydrogen plasma pre-treatment at 200 °C and the SiNW growth itself in a hydrogen-silane plasma at 420 °C. We show that the H2-plasma induces a coalescence of the Cu-rich cores of as-deposited thermally evaporated NPs that does not occur when the same annealing is applied without plasma. The SiNW growth process at 420 °C induces a phase transformation of the catalyst cores to Cu7In3; while a hydrogen plasma treatment at 420 °C without silane can lead to the formation of the Cu11In9 phase. In situ transmission electron microscopy experiments show that the SiNWs synthesis with Cu-In bimetallic catalyst NPs follows an essentially vapor-solid-solid process. By adjusting the catalyst composition, we manage to obtain small-diameter SiNWs-below 10 nm-among which we observe the metastable hexagonal diamond phase of Si, which is predicted to have a direct bandgap.

Influence of the Electron Beam and the Choice of Heating Membrane on the Evolution of Si Nanowires' Morphology in In Situ TEM.

We used in situ transmission electron microscopy (TEM) to observe the dynamic changes of Si nanowires under electron beam irradiation. We found evidence of structural evolutions under TEM observation due to a combination of electron beam and thermal effects. Two types of heating holders were used: a carbon membrane, and a silicon nitride membrane. Different evolution of Si nanowires on these membranes was observed. Regarding the heating of Si nanowires on a C membrane at 800 °C and above, a serious degradation dependent on the diameter of the Si nanowire was observed under the electron beam, with the formation of Si carbide. When the membrane was changed to Si nitride, a reversible sectioning and welding of the Si nanowire was observed.

High Density of Quantum-Sized Silicon Nanowires with Different Polytypes Grown with Bimetallic Catalysts.

When Si nanowires (NWs) have diameters below about 10 nm, their band gap increases as their diameter decreases; moreover, it can be direct if the material adopts the metastable diamond hexagonal structure. To prepare such wires, we have developed an original variant of the vapor-liquid-solid process based on the use of a bimetallic Cu-Sn catalyst in a plasma-enhanced chemical vapor deposition reactor, which allows us to prevent droplets from coalescing and favors the growth of a high density of NWs with a narrow diameter distribution. Controlling the deposited thickness of the catalyst materials at the sub-nanometer level allows us to get dense arrays (up to 6 × 1010 cm-2) of very-small-diameter NWs of 6 nm on average (standard deviation of 1.6 nm) with crystalline cores of about 4 nm. The transmission electron microscopy analysis shows that both 3C and 2H polytypes are present, with the 2H hexagonal diamond structure appearing in 5-13% of the analyzed NWs per sample.