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In diverse applications employing very thin, single-crystalline semiconductor sheets, including flexible electronics and photonics, energy-storage devices, and solar cells, the impacts of surfaces and interfaces on charge transport need to be understood. The authors study the electrical conductance of very thin Si(001) sheets using a special, sensitive back-gating method, to quantify the influence of H termination on conductance for sheets of different thickness, and confirm that surface states play a dominant role in these conductance properties. Their approach is extensible to other important systems, $e.g.$ $I\phantom{\rule{0}{0ex}}I\phantom{\rule{0}{0ex}}I-V$ semiconductors and transition-metal dichalcogenides.

We report the observation of a large enhancement of the wavelength-dependent photocurrent in ultrathin silicon nanomembranes (SiNM) decorated with colloidal CdSe/ZnS nanocrystal quantum dots (NQDs). Back-gated, field-effect transistor structures based on 75 nm-thick SiNMs are functionalized with self-assembled monolayers (SAMs) preventing surface oxidation and minimizing the surface defect densities. NQDs are drop cast on the active region of the device and the photocurrent is measured as a function of the excitation wavelength across the NQD absorption region. Photocurrent enhancement on the order of several hundred nA's is observed for NQD/SAM/SiNM devices compared to reference SAM/SiNM structures, with the device peak response closely correlated to the NQD absorption peak. We propose light-induced gating of the surface electrostatic potential and forward self-biasing of the FET channel as the two key mechanisms leading to the large photocurrent increase. Our findings open the possibility of employing silicon-nanocrystal hybrid structures for light sensing applications.

The fluorination of graphite/graphite oxide (GO) and their derivatives has been widely investigated for how fluorine interacts with sp2/sp3 carbon; however, the mechanism of this interaction has not yet been elucidated. Fluorination of GO (FGO) at either 10 or 15 psi for 24 h, produced two new absorption bands at ∼743 cm−1 and 482 cm−1, and are attributed to the presence of out-of-plane surface fluorine bonds in FGO (absent in fluorographite – FG). IR studies confirmed the stability of the formed C–F bonds and defect formation due to the introduction of oxyfluorinated species into the graphitic carbon through fluorination of epoxides. Fluorination of GO resulted in ∼4–5 times more fluorine incorporation in bulk as compared to FG. (4.57 vs. 0.8 at.% and 6.64 vs. 1.4 at.% at 10 and 15 psi, respectively). PXRD analyses also showed that the interlayer spacing of FGO expanded in the presence of intercalated C–F species and a defect formation was observed with the evidence of increase of the ID/IG ratio from Raman spectra. To this end, understanding the origin of surface C–F bonds and structural changes in FGO therefore leads to new applications such as implementation of FGO for sensing, nano-electronics and energy storage.

We demonstrate efficient excitonic sensitization of crystalline Si nanomembranes via combined effects of radiative (RET) and nonradiative (NRET) energy transfer from a proximal monolayer of colloidal semiconductor nanocrystals. Ultrathin, 25-300 nm Si films are prepared on top of insulating SiO(2) substrates and grafted with a monolayer of CdSe/ZnS nanocrystals via carboxy-alkyl chain linkers. The wet chemical preparation ensures that Si surfaces are fully passivated with a negligible number of nonradiative surface state defects and that the separation between nanocrystals and Si is tightly controlled. Time-resolved photoluminescence measurements combined with theoretical modeling allow us to quantify individual contributions from RET and NRET. Overall efficiency of ET into Si is estimated to exceed 85% for a short distance of about 4 nm from nanocrystals to the Si surface. Effective and longer-range radiative coupling of nanocrystal's emission to waveguiding modes of Si films is clearly revealed. This demonstration supports the feasibility of an advanced thin-film hybrid solar cell concept that relies on energy transfer between strong light absorbers and adjacent high-mobility Si layers.

The electrical properties of nanostructures are extremely sensitive to their surface condition. In very thin two-dimensional crystalline-semiconductor sheets, termed nanomembranes, the influence of the bulk is diminished, and the electrical conductance becomes exquisitely responsive to the structure of the surface and the type and density of defects there. Its understanding therefore requires a precise knowledge of the surface condition. Here we report measurements, using nanomembranes, that demonstrate direct charge transport through the π* band of the clean reconstructed Si(001) surface. We determine the charge carrier mobility in this band. These measurements, performed in ultra-high vacuum to create a truly clean surface, lay the foundation for a quantitative understanding of the role of extended or localized surface states, created by surface structure, defects or adsorbed atoms/molecules, in modifying charge transport through semiconductor nanostructures. As the electrical properties of nanostructures are strongly influenced by their surface, a thorough understanding of the surface properties is desirable. The authors demonstrate the use of charge transport in silicon nanomembranes to perform spectroscopy of the electronic structure of the surface states.

Chemical functionalization of semiconductor surfaces, particularly silicon oxide, has enabled many technologically important applications (e.g., sensing, photovoltaics, and catalysis). For such processes, hydroxyl groups terminating the oxide surface constitute the primary reaction sites. However, their reactivity is often poor, hindering technologically important processes, such as surface phosphonation requiring a lengthy postprocessing annealing step at 140 °C with poor control of the bonding geometry. Using a novel oxide-free surface featuring a well-defined nanopatterned OH coverage, we demonstrate that hydroxyl groups on oxide-free silicon are more reactive than on silicon oxide. On this model surface, we show that a perfectly ordered layer of monodentate phosphonic acid molecules is chemically grafted at room temperature, and explain why it remains completely stable in aqueous environments, in contrast to phosphonates grafted on silicon oxides. This fundamental understanding of chemical activity and surface stability suggests new directions to functionalize silicon for sensors, photovoltaic devices, and nanoelectronics.

Because of the large surface-to-volume ratio, the conductivity of semiconductor nanostructures is very sensitive to surface chemical and structural conditions. Two surface modifications, vacuum hydrogenation (VH) and hydrofluoric acid (HF) cleaning, of silicon nanomembranes (SiNMs) that nominally have the same effect, the hydrogen termination of the surface, are compared. The sheet resistance of the SiNMs, measured by the van der Pauw method, shows that HF etching produces at least an order of magnitude larger drop in sheet resistance than that caused by VH treatment, relative to the very high sheet resistance of samples terminated with native oxide. Re-oxidation rates after these treatments also differ. X-ray photoelectron spectroscopy measurements are consistent with the electrical-conductivity results. We pinpoint the likely cause of the differences. PACS: 73.63.-b, 62.23.Kn, 73.40.Ty

Ultrathin silicon-on-insulator, composed of a crystalline sheet of silicon bounded by native oxide and a buried oxide layer, is extremely resistive because of charge trapping at the interfaces between the sheet of silicon and the oxide. After chemical modification of the top surface with hydrofluoric acid (HF), the sheet resistance drops to values below what is expected based on bulk doping alone. We explain this behavior in terms of surface-induced band structure changes combined with the effective isolation from bulk properties created by crystal thinness.

The electrical quality of functionalized, oxide-free silicon surfaces is critical for chemical sensing, photovoltaics, and molecular electronics applications. In contrast to Si/SiO2 interfaces, the density of interface states (Dit) cannot be reduced by high temperature annealing because organic layers decompose above 300 °C. While a reasonable Dit is achieved on functionalized atomically flat Si(111) surfaces, it has been challenging to develop successful chemical treatments for the technologically relevant Si(100) surfaces. We demonstrate here that recent advances in the chemical preparation of quasi-atomically-flat, H-terminated Si(100) surfaces lead to a marked suppression of electronic states of functionalized surfaces. Using a non-invasive conductance-voltage method to study functionalized Si(100) surfaces with varying roughness, a Dit as low as 2.5 × 1011 cm−2eV−1 is obtained for the quasi-atomically-flat surfaces, in contrast to >7 × 1011 cm−2eV−1 on atomically rough Si(100) surfaces. The interfaci...

A method to fabricate single-crystal Si∕SiO2 multilayer heterostructures is presented. Heterostructures are fabricated by repeated transfer of single crystal silicon nanomembranes alternating with deposition of spin-on-glass. Nanomembrane transfer produces multilayers with low surface roughness and smooth interfaces. To demonstrate interface quality, the specular reflectivities of one-, two-, and three-membrane heterostructures are measured. Comparison of the measured reflectivity with theoretical calculations shows good agreement. Nanomembrane stacking allows for the preprocessing of individual membranes with a high thermal budget before the low thermal budget assembly of the stack, suggesting a new avenue for the three dimensional integration of integrated circuits.