Freestanding silicon nanocrystals (Si‐ncs) offer unique optical and electronic properties for new photovoltaic, thermoelectric, and other electronic devices. A method to fabricate Si‐ncs which is scalable to industrial usage has been developed in recent years. However, barriers to the widespread utilization of these nanocrystals are the presence of charge‐trapping defects and an oxide shell formed upon ambient atmosphere exposure hindering the charge transport. Here, we exploit low‐cost post‐growth treatment routes based on wet‐etching in hydrofluoric acid plus surface hydrosilylation or annealing enabling a complete native oxide removal and a reduction of the defect density by up to two orders of magnitude. Moreover, when compared with only H‐terminated Si‐ncs we report an enhancement of the conductivity by up to a factor of 400 for films of HF etched and annealed Si‐ncs, which retain a defect density below that of untreated Si‐ncs even after several months of air exposure. Further, we demonstrate that HF etched and hydrosilylated Si‐ncs are extremely stable against oxidation and maintain a very low defect density after a long‐term storage in air, opening the possibility of device processing in ambient atmosphere.
We demonstrate the successful covalent functionalization of n-type 6H-SiC with organosilanes. In particular, wet-chemically processed self-assembled layers of octadecyltrimethoxysilane and amino-propyldiethoxymethylsilane were investigated. The structural and chemical properties of these layers were studied by contact angle measurements, atomic force microscopy, thermal desorption, and x-ray photoelectron spectroscopy. The organic layers are smooth and wetting angles up to 100° are observed. Desorption temperatures in the range of 830K prove the covalent bonding of the organic molecules to the SiC surface. By utilizing self-assembled layers with functional end groups, attachment of complex molecules was demonstrated by immobilization of proteins on micropatterned organic layers.
Using electron paramagnetic resonance, we find that vacuum annealing at 200 °C leads to a significant reduction in the silicon dangling bond (Si-db) defect density in silicon nanoparticles (Si-NPs). The best improvement of the Si-db density by a factor of 10 is obtained when the vacuum annealing is combined with an etching step in hydrofluoric acid (HF), whereas HF etching alone only removes the Si-dbs at the Si/SiO2 interface. The reduction in the Si-db defect density is confirmed by photothermal deflection spectroscopy and photoconductivity measurements on thin Si-NPs films.
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