We report the fabrication of degenerately doped silicon (Si) nanowires of different aspect ratios using a simple, low-cost and effective technique that involves metal-assisted chemical etching (MacEtch) combined with soft lithography or thermal dewetting metal patterning. We demonstrate sub-micron diameter Si nanowire arrays with aspect ratios as high as 180:1, and present the challenges in producing solid nanowires using MacEtch as the doping level increases in both p- and n-type Si. We report a systematic reduction in the porosity of these nanowires by adjusting the etching solution composition and temperature. We found that the porosity decreases from top to bottom along the axial direction and increases with etching time. With a MacEtch solution that has a high [HF]:[H(2)O(2)] ratio and low temperature, it is possible to form completely solid nanowires with aspect ratios of less than approximately 10:1. However, further etching to produce longer wires renders the top portion of the nanowires porous.

A two-step metal assisted chemical etching technique is used to systematically vary the sidewall roughness of Si nanowires in vertically aligned arrays. The thermal conductivities of nanowire arrays are studied using time domain thermoreflectance and compared to their high-resolution transmission electron microscopy determined roughness. The thermal conductivity of nanowires with small roughness is close to a theoretical prediction based on an upper limit of the mean-free-paths of phonons given by the nanowire diameter. The thermal conductivity of nanowires with large roughness is found to be significantly below this prediction. Raman spectroscopy reveals that nanowires with large roughness also display significant broadening of the one-phonon peak; the broadening correlates well with the reduction in thermal conductivity. The origin of this broadening is not yet understood, as it is inconsistent with phonon confinement models, but could derive from microstructural changes that affect both the optical phonons observed in Raman scattering and the acoustic phonons that are important for heat conduction. V

Thermal conductivity data for rough surface silicon nanowires suggest the breakdown of the Casimir limit which assumes completely diffuse phonon boundary scattering. We show that coherent effects in phonon transport at room temperature indeed lead to such breakdown. Correlated multiple scattering of phonons off the rough surface lead to a reduced thermal conductivity that is dependent not just on the roughness amplitude but more importantly on the roughness correlation length. A correlation length less than diameter of wire is typically necessary for lowering the thermal conductivity below the Casimir limit. Our model explains seeming anomalies in data reported for electrolessly etched and electron beam lithography defined nanowires.

This paper presents a non-lithographic approach to generate wafer-scale single crystal silicon nanowires (SiNWs) with controlled sidewall profile and surface morphology. The approach begins with silver (Ag) thin-film thermal dewetting, gold (Au) deposition and lift-off to generate a large-scale Au mesh on Si substrates. This is followed by metal-assisted chemical etching (MacEtch), where the Au mesh serves as a catalyst to produce arrays of smooth Si nanowires with tunable taper up to 13°. The mean diameter of the thus fabricated SiNWs can be controlled to range from 62 to 300 nm with standard deviations as small as 13.6 nm, and the areal coverage of the wire arrays can be up to 46%. Control of the mean wire diameter is achieved by controlling the pore diameter of the metallic mesh which is, in turn, controlled by adjusting the initial thin-film thickness and deposition rate. To control the wire surface morphology, a post-fabrication roughening step is added to the approach. This step uses Au nanoparticles and slow-rate MacEtch to produce rms surface roughness up to 3.6 nm.

Frequency dependence in phonon surface scattering is a debated topic in fundamental phonon physics. Recent experiments and theory suggest such a phenomenon, but an independent agreement between the two remains elusive. We report low-temperature dependence of thermal conductivity in silicon nanowires fabricated using a two-step, metal-assisted chemical etch. By reducing etch rates down to 0.5 nm/s from the typical >100 nm/s, we report controllable roughening of nanowire surfaces and selectively focus on moderate roughness scales rather than the extreme scales investigated previously. This critically enables direct comparison with perturbation-based spectral scattering theory. Using experimentally characterized surface roughness, we show that a multiple scattering theory provides excellent agreement and explanation of the observed low-temperature dependence of rough surface nanowires. The theory does not employ any fitting parameters. A 5-10 nm roughness correlation length is typical in metal-assisted chemical etching and resonantly scatters dominant phonons in silicon, leading to the observed ~T(1.6-2.4) behavior. Our work provides fundamental and quantitative insight into spectral phonon scattering from rough surfaces. This advances applications of nanowires in thermoelectric energy conversion.