Silicon nanocrystals (Si NCs) are intensively studied for optoelectronic and biological applications due to having highly attractive features such as band engineering. Although doping is often used to control the optical and electrical properties, the related structural properties of solely doped and codoped Si NCs are not well-understood. In this study, we report the boron (B) and/or phosphorus (P) distribution in Si NCs embedded in borosilicate glass (BSG), phosphosilicate glass (PSG), and borophosphosilicate glass (BPSG) using atom probe tomography (APT). We compared solely and codoped Si NCs grown at different temperatures so that we may compare the effects of codoping and temperature on the B and/or P distribution. Proximity histograms and cluster analyses reveal that there exist boron-rich layers surrounding Si NCs and also B–P clusters within the Si NCs. Raman spectra also show a structural change between codoped Si NCs in solids and free-standing codoped Si NCs. These results lead us to understand that codoped Si NCs disperse in polar solvents.
Developing highly efficient and durable electrocatalysts for hydrogen evolution reaction (HER) under both alkaline and acidic media is crucial for the future development of a hydrogen economy. However, state-of-the-art high-performance electrocatalysts recently developed are based on carbon carriers mediated by binding noble elements and their complicated processing methods are a major impediment to commercialization. Here, inspired by the high-entropy alloy concept with its inherent multinary nature and using a glassy alloy design with its chemical homogeneity and tunability, we present a scalable strategy to alloy five equiatomic elements, PdPtCuNiP, into a high-entropy metallic glass (HEMG) for HER in both alkaline and acidic conditions. Surface dealloying of the HEMG creates a nanosponge-like architecture with nanopores and embedded nanocrystals that provides abundant active sites to achieve outstanding HER activity. The obtained overpotentials at a current density of 10 mA cm −2 are 32 and 62 mV in 1.0 m KOH and 0.5 m H 2 SO 4 solutions, respectively, outperforming most currently available electrocatalysts. Density functional theory reveals that a lattice distortion and the chemical complexity of the nanocrystals lead to a strong synergistic effect on the electronic structure that further stabilizes hydrogen proton adsorption/desorption. This HEMG strategy establishes a new paradigm for designing compositionally complex alloys for electrochemical reactions.
n -type β-FeSi2/p-type Si heterojunctions were fabricated from β-FeSi2 films epitaxially grown on Si(111) by facing-target direct-current sputtering. Sharp film-substrate interfaces were confirmed by scanning electron microscopy. The current-voltage and photoresponse characteristics were measured at room temperature. They exhibited good rectifying properties and a change of approximately one order of magnitude in the current at a bias voltage of −1 V under illumination by a 6 mW, 1.31 μm laser. The estimated detectivity was 1.5×109 cm √Hz W at 1.31 μm. The results suggest that the β-FeSi2/Si heterojunctions can be used as near-infrared photodetectors that are compatible with silicon integrated circuits.
Strengthening of magnesium (Mg) is known to occur through dislocation accumulation, grain refinement, deformation twinning, and texture control or dislocation pinning by solute atoms or nano-sized precipitates. These modes generate yield strengths comparable to other engineering alloys such as certain grades of aluminum but below that of high-strength aluminum and titanium alloys and steels. Here, we report a spinodal strengthened ultralightweight Mg alloy with specific yield strengths surpassing almost every other engineering alloy. We provide compelling morphological, chemical, structural, and thermodynamic evidence for the spinodal decomposition and show that the lattice mismatch at the diffuse transition region between the spinodal zones and matrix is the dominating factor for enhancing yield strength in this class of alloy.
Phosphorus doping of silicon nanostructures is a non-trivial task due to problems with confinement, self-purification and statistics of small numbers. Although P-atoms incorporated in Si nanostructures influence their optical and electrical properties, the existence of free majority carriers, as required to control electronic properties, is controversial. Here, we correlate structural, optical and electrical results of size-controlled, P-incorporating Si nanocrystals with simulation data to address the role of interstitial and substitutional P-atoms. Whereas atom probe tomography proves that P-incorporation scales with nanocrystal size, luminescence spectra indicate that even nanocrystals with several P-atoms still emit light. Current-voltage measurements demonstrate that majority carriers must be generated by field emission to overcome the P-ionization energies of 110-260 meV. In absence of electrical fields at room temperature, no significant free carrier densities are present, which disproves the concept of luminescence quenching via Auger recombination. Instead, we propose non-radiative recombination via interstitial-P induced states as quenching mechanism. Since only substitutional-P provides occupied states near the Si conduction band, we use the electrically measured carrier density to derive formation energies of ~400 meV for P-atoms on Si nanocrystal lattice sites. Based on these results we conclude that ultrasmall Si nanovolumes cannot be efficiently P-doped.Since the first reports about (heavy) P-doping of silicon nanocrystals (Si NCs), luminescence quenching was often attributed to non-radiative exciton recombination with P-induced free carriers (Auger recombination) 1 . Only few works addressed alternative quenching mechanisms like defects 2-4 . We note that a direct proof of successful P-doping is nontrivial since a true free carrier is not generated due to its confinement in the quantum dot (QD). One important parameter in the investigation of P-doped, oxide-embedded Si NCs is the excess Si concentration that determines the size and separation of NCs as well as the degree of agglomeration. While isolated and mainly spherical NCs are formed at low Si concentrations, excess Si contents above the percolation threshold form highly irregular agglomerated Si NC networks. The threshold that separates these regimes is SiO x≈0.6 for very thin films in a superlattice (SL) and SiO x≲1 for thick bulk films [5][6][7] . While the investigation of P-doping of small and well-separated Si NCs remains a challenging task, it does not come as a surprise that extended Si NC networks can be doped successfully 8,9 . Another important parameter is the dopant concentration and the term doping itself. The latter requires a disambiguation for crystallites at the bottom end of the nanoscale where it is often used deceptively for: (i) the bare incorporation of P-atoms into nanocrystals, (ii) the observation of optical or electrical effects caused by P-incorporation, and (iii) the actual generation of free majority charge carr...
n -Type β-FeSi2/intrinsic-Si/p-type Si heterojunctions, prepared by facing-targets direct-current sputtering, were evaluated as near-infrared photodetectors. The built-in potential was estimated to be approximately 1 V from capacitance-voltage characteristics. Diodes with a junction area of 0.03 mm2 exhibited a junction capacitance of 4.4 pF at zero bias. At room temperature, the devices exhibited responsivity of 140 mA/W and external quantum efficiency of 13% at a bias voltage of −5 V. The detectivity at zero bias was estimated to be 2.8×109 cm√Hz/W at the wavelength of 1.31 μm. These results indicate their high application potential as near-infrared photodiodes integrated with Si.
Boron (B) doping of silicon nanocrystals requires the incorporation of a B-atom on a lattice site of the quantum dot and its ionization at room temperature. In case of successful B-doping the majority carriers (holes) should quench the photoluminescence of Si nanocrystals via non-radiative Auger recombination. In addition, the holes should allow for a non-transient electrical current. However, on the bottom end of the nanoscale, both substitutional incorporation and ionization are subject to significant increase in their respective energies due to confinement and size effects. Nevertheless, successful B-doping of Si nanocrystals was reported for certain structural conditions. Here, we investigate B-doping for small, well-dispersed Si nanocrystals with low and moderate B-concentrations. While small amounts of B-atoms are incorporated into these nanocrystals, they hardly affect their optical or electrical properties. If the B-concentration exceeds ~1 at%, the luminescence quantum yield is significantly quenched, whereas electrical measurements do not reveal free carriers. This observation suggests a photoluminescence quenching mechanism based on B-induced defect states. By means of density functional theory calculations, we prove that B creates multiple states in the bandgap of Si and SiO2. We conclude that non-percolated ultra-small Si nanocrystals cannot be efficiently B-doped.
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