An effective bottom-up technology for precisely controlling the amount of dopant atoms tethered on silicon substrates is presented. Polystyrene and poly(methyl methacrylate) polymers with narrow molecular weight distribution and end-terminated with a P-containing moiety were synthesized with different molar mass. The polymers were spin coated and subsequently end-grafted onto nondeglazed silicon substrates. P atoms were bonded to the surface during the grafting reaction, and their surface density was set by the polymer molar mass, according to the self-limiting nature of the "grafting to" reaction. Polymeric material was removed by O plasma hashing without affecting the tethered P-containing moieties on the surface. Repeated cycles of polymer grafting followed by plasma hashing led to a cumulative increase, at constant steps, in the dose of P atoms grafted to the silicon surface. P injection in the silicon substrate was promoted and precisely controlled by high-temperature thermal treatments. Sheet resistance measurements demonstrated effective doping of silicon substrate.

Doping of Si nanocrystals (NCs) has been the subject of a strong experimental and theoretical debate for more than a decade. A major difficulty in the understanding of dopant incorporation at the nanoscale is related to the fact that theoretical calculations usually refer to thermodynamic equilibrium conditions, whereas, from the experimental point of view, impurity incorporation is commonly performed during NC formation. This latter circumstance makes impossible to experimentally decouple equilibrium properties from kinetic effects. In this report, we approach the problem by introducing the dopants into the Si NCs, from a spatially separated dopant source. We induce a P diffusion flux to interact with the already-formed and stable Si NCs embedded in SiO 2 , maintaining the system very close to the thermodynamic equilibrium. Combining advanced material synthesis, multi-technique experimental quantification and simulations of diffusion profiles with a rate-equation model, we demonstrate that a high P concentration (above the P solid solubility in bulk Si) within Si NCs embedded in a SiO 2 matrix corresponds to an equilibrium property of the system. Trapping within the Si NCs embedded in a SiO 2 matrix is essentially diffusion limited with no additional energy barrier, whereas de-trapping is prevented by a binding energy of 0.9 eV, in excellent agreement with recent theoretical findings that highlighted the impact of different surface terminations (H-or O-terminated NCs) on the stability of the incorporated P atoms.

The interest toward the doping of semiconductor nanostructures has been increasing steadily, but a clear understanding must still be reached, due to challenging characterization issues. In this work, we focused on Si nanocrystals (NCs) embedded in SiO 2 , which represent the most scalable and one of the most interesting and studied systems, but where an accurate quantification of the evolution of dopant profiles is still lacking. High depth resolution time-of-flight SIMS with charge compensation has been used to extract secondary ion depth profiles relative to P and Si elements. The relative sensitivity factors of P in SiO 2 and of P in a layer containing Si NCs approximately 4.2 nm in diameter, as well as non-linearity of P intensity at high P concentrations, were determined by comparison with P dose data extracted by Rutherford backscattering spectrometry analysis. Transmission electron microscopy analyses were performed to characterize the NC size distribution and stability upon thermal annealing. As a final result, we obtained a measurement protocol able to extract with high accuracy fully calibrated P concentration profiles in the SiO 2 matrix with embedded Si NCs.

No abstract

Achieving the required control of dopant distribution and selectivity for nanostructured semiconducting building block is a key issue for a large variety of applications. A promising strategy is monolayer doping (MLD), which consists in the creation of a well-ordered monolayer of dopant-containing molecules bonded to the surface of the substrate. In this work, we synthesize a P δ-layer embedded in a SiO2 matrix by MLD. Using a multi-technique approach based on time of flight secondary ion mass spectrometry (ToF-SIMS) and Rutherford backscattering spectrometry (RBS) analyses, we characterize the tuning of P dose as a function of the processing time and temperature. We found the proper conditions for a full grafting of the molecules, reaching a maximal dose of 8.3 × 10(14) atoms/cm(2). Moreover, using 1D rate equation model, we model P diffusion in SiO2 after annealing and we extract a P diffusivity in SiO2 of 1.5 × 10(17) cm(2) s(-1).