Free electron-driven photophysics in n-type doped silicon nanocrystals.

Although there have been extensive speculation regarding the applicability of doped silicon nanocrystals (Si NCs) in optoelectronic technologies, a quantitative analysis on the photophysical workings of introduced free carriers remains elusive. Here, we present a comprehensive study on the photophysics of ∼7.5 nm heavily phosphorous-doped Si NCs, using a combination of spectroscopic techniques. We correlate the carrier dynamics with the location of the free carriers - which we tune from NC core to surface depending on the state of oxidation. The strength of the Coulomb interactions between the photoexcited electron-hole pairs and the doping-induced free carriers depends on (1) the concentration of free carriers, (2) the location of these carriers, and (3) the diameter of the NCs. In contrast to prior studies, the photoexcited carrier dynamics in these n-type doped Si NCs are dominated by strong Coulomb interactions with doping-induced free electrons, characterized by a negative trion lifetime of around 9 ns. While radiative recombination in doped direct bandgap NCs can often still compete with trion recombination (allowing emission to be present), emission in our doped Si NCs is completely quenched due to the relatively slow radiative recombination in these indirect bandgap NCs. Furthermore, multi-exciton interaction times are slightly shortened compared to those of intrinsic Si NCs, which we attribute to an increased number of free electrons, enhancing the oscillator strength of Auger recombination. These results constitute a framework for the optimization of doped Si NC synthesis techniques and device engineering directions for future doped-Si NC-based optoelectronic and photovoltaic applications.

Oxidatively stable nanoporous silicon photocathodes with enhanced onset voltage for photoelectrochemical proton reduction.

Stable and high-performance nanoporous "black silicon" photoelectrodes with electrolessly deposited Pt nanoparticle (NP) catalysts are made with two metal-assisted etching steps. Doubly etched samples exhibit an ∼300 mV positive shift in photocurrent onset for photoelectrochemical proton reduction compared to oxide-free planar Si with identical catalysts. We find that the photocurrent onset voltage of black Si photocathodes prepared from single-crystal planar Si wafers by an Ag-assisted etching process increases in oxidative environments (e.g., aqueous electrolyte) owing to a positive flat-band potential shift caused by surface oxidation. However, within 24 h, the surface oxide layer becomes a kinetic barrier to interfacial charge transfer that inhibits proton reduction. To mitigate this issue, we developed a novel second Pt-assisted etch process that buries the Pt NPs deep into the nanoporous Si surface. This second etch shifts the onset voltage positively, from +0.25 V to +0.4 V versus reversible hydrogen electrode, and reduces the charge-transfer resistance with no performance decrease seen for at least two months. PEC performance was stable owing to Pt NP catalysts that were buried deeply in the photoelectrode by the second etch, below a thick surface layer comprised primarily of amorphous SiO2 along with some degree of remaining crystalline Si as observed by scanning and transmission electron micrographs. Electrochemical impedance studies reveal that the second etch leads to a considerably smaller interfacial charge-transfer resistance than samples without the additional etch, suggesting that burying the Pt NPs improves the interfacial contact to the crystalline silicon surface.