Daniel E. Perea

High-resolution detection of Au catalyst atoms in Si nanowires

The potential for the metal nanocatalyst to contaminate vapour-liquid-solid grown semiconductor nanowires has been a long-standing concern, because the most common catalyst material, Au, is highly detrimental to the performance of minority carrier electronic devices. We have detected single Au atoms in Si nanowires grown using Au nanocatalyst particles in a vapour-liquid-solid process. Using high-angle annular dark-field scanning transmission electron microscopy, Au atoms were observed in higher numbers than expected from a simple extrapolation of the bulk solubility to the low growth temperature. Direct measurements of the minority carrier diffusion length versus nanowire diameter, however, demonstrate that surface recombination controls minority carrier transport in as-grown n-type nanowires; the influence of Au is negligible. These results advance the quantitative correlation of atomic-scale structure with the properties of nanomaterials and can provide essential guidance to the development of nanowire-based device technologies.

Direct measurement of dopant distribution in an individual vapour–liquid–solid nanowire

Semiconductor nanowires show promise for many device applications, but controlled doping with electronic and magnetic impurities remains an important challenge. Limitations on dopant incorporation have been identified in nanocrystals, raising concerns about the prospects for doping nanostructures. Progress has been hindered by the lack of a method to quantify the dopant distribution in single nanostructures. Recently, we showed that atom probe tomography can be used to determine the composition of isolated nanowires. Here, we report the first direct measurements of dopant concentrations in arbitrary regions of individual nanowires. We find that differences in precursor decomposition rates between the liquid catalyst and solid nanowire surface give rise to a heavily doped shell surrounding an underdoped core. We also present a thermodynamic model that relates liquid and solid compositions to dopant fluxes.

Alternative catalysts for VSS growth of silicon and germanium nanowires

Metal impurities have been used to mediate the growth of anisotropic crystalline semiconductor nanowires for a variety of applications. A majority of efforts have employed the vapor-liquid-solid approach at growth temperatures above the metal-semiconductor eutectic. Sub-eutectic vapor-solid-solid (VSS) growth has received less attention but may provide advantages including reduced processing temperatures and more abrupt heterojunctions. We present a review of the VSS growth of Si and Ge nanowires together with new studies of Mn-mediated Ge and Si nanowires to assess the generality of sub-eutectic nanowire growth and highlight key requirements.

Relative influence of surface states and bulk impurities on the electrical properties of ge nanowires

We quantitatively examine the relative influence of bulk impurities and surface states on the electrical properties of Ge nanowires with and without phosphorus (P) doping. The unintentional impurity concentration in nominally undoped Ge nanowires is less than 2 x 10(17) cm(-3) as determined by atom probe tomography. Surprisingly, P doping of approximately 10(18) cm(-3) reduces the nanowire conductivity by 2 orders of magnitude. By modeling the contributions of dopants, impurities, and surface states, we confirm that the conductivity of nominally undoped Ge nanowires is mainly due to surface state induced hole accumulation rather than impurities introduced by catalyst. In P-doped nanowires, the surface states accept the electrons generated by the P dopants, reducing the conductivity and leading to ambipolar behavior. In contrast, intentional surface-doping results in a high conductivity and recovery of n-type characteristics.

Identification of an intrinsic source of doping inhomogeneity in vapor-liquid-solid-grown nanowires

The vapor-liquid-solid (VLS) process of semiconductor nanowire growth is an attractive approach to low-dimensional materials and heterostructures because it provides a mechanism to modulate, in situ, nanowire composition and doping, but the ultimate limits on doping control are ultimately dictated by the growth process itself. Under widely used conditions for the chemical vapor deposition growth of Si and Ge nanowires from a Au catalyst droplet, we find that dopants incorporated from the liquid are not uniformly distributed. Specifically, atom probe tomographic analysis revealed up to 100-fold enhancements in dopant concentration near the VLS trijunction in both B-doped Si and P-doped Ge nanowires. We hypothesize that radial and azimuthal inhomogeneities arise from a faceted liquid-solid interface present during nanowire growth, and we present a simple model to account for the distribution. As the same segregation behavior was observed in two distinct semiconductors with different dopants, the observed inhomogeneity is likely to be present in other VLS grown nanowires.

Correlating dopant distributions and electrical properties of boron-doped silicon nanowires

Quantitative nonuniform radial doping profiles in vapor liquid solid grown boron-doped silicon nanowires are correlated with axial variations in electrical properties. Boron concentrations measured by atom probe tomography are lower for the core material grown from a gold catalyst than for material deposited on the nanowire surface. Transistors fabricated along a single nanowire exhibit a transition from nonlinear contact-dominated behavior to linear behavior with increasing thickness of the dopant-enriched surface layer. Simple models confirm that the surface is doped to a level that enables the contact resistance to become comparable to the channel resistance, suggesting that unintentional surface doping may play a role in lowering contact resistances in some nanowire devices.