Impurity doping of ultrasmall nanoscale (usn) silicon (Si) currently used in ultralarge scale integration (ULSI) faces serious miniaturization challenges below the 14 nm technology node such as dopant out-diffusion and inactivation by clustering in Si-based field-effect transistors (FETs). Moreover, self-purification and massively increased ionization energy cause doping to fail for Si nano-crystals (NCs) showing quantum confinement. To introduce electron- (n-) or hole- (p-) type conductivity, usn-Si may not require doping, but an energy shift of electronic states with respect to the vacuum energy between different regions of usn-Si. We show in theory and experiment that usn-Si can experience a considerable energy offset of electronic states by embedding it in silicon dioxide (SiO2) or silicon nitride (Si3N4), whereby a few monolayers (MLs) of SiO2 or Si3N4 are enough to achieve these offsets. Our findings present an alternative to conventional impurity doping for ULSI, provide new opportunities for ultralow power electronics and open a whole new vista on the introduction of p- and n-type conductivity into usn-Si.

Multiple quantum wells consisting of alternating Si and SiO2 layers were studied by means of Raman scattering. The structures were fabricated by the remote plasma enhanced chemical vapor deposition of amorphous Si and SiO2 layers on quartz substrate. The structures were subjected to a rapid thermal annealing procedure for Si crystallization. The obtained results suggest that the Si layers consist of nanocrystals embedded in an amorphous Si phase. It was found that the silicon nanocrystals inside 2nm thin layers are under high residual compressive stress. Moreover, the metastable Si III phase was detected in these samples supporting the presence of large compressive stresses in the structures. The compressive stress could be relaxed upon local laser annealing.

Conventional impurity doping of deep nanoscale silicon (dns-Si) used in ultra large scale integration (ULSI) faces serious challenges below the 14 nm technology node. We report on a new fundamental effect in theory and experiment, namely the electronic structure of dns-Si experiencing energy offsets of ca. 1 eV as a function of SiO2-vs. Si3N4-embedding with a few monolayers (MLs). An interface charge transfer (ICT) from dns-Si specific to the anion type of the dielectric is at the core of this effect and arguably nested in quantum-chemical properties of oxygen (O) and nitrogen (N) vs. Si. We investigate the size up to which this energy offset defines the electronic structure of dns-Si by density functional theory (DFT), considering interface orientation, embedding layer thickness, and approximants featuring two Si nanocrystals (NCs); one embedded in SiO2 and the other in Si3N4. Working with synchrotron ultraviolet photoelectron spectroscopy (UPS), we use SiO2-vs. Si3N4-embedded Si nanowells (NWells) to obtain their energy of the top valence band states. These results confirm our theoretical findings and gauge an analytic model for projecting maximum dns-Si sizes for NCs, nanowires (NWires) and NWells where the energy offset reaches full scale, yielding to a clear preference for electrons or holes as majority carriers in dns-Si. Our findings can replace impurity doping for n/p-type dns-Si as used in ultra-low power electronics and ULSI, eliminating dopant-related issues such as inelastic carrier scattering, thermal ionization, clustering, out-diffusion and defect generation. As far as majority carrier preference is concerned, the elimination of those issues effectively shifts the lower size limit of Si-based ULSI devices to the crystalization limit of Si of ca. 1.5 nm and enables them to work also under cryogenic conditions. *

Impurity doping in silicon (Si) ultra-large-scale integration is one of the key challenges which prevent further device miniaturization. Using ultraviolet photoelectron spectroscopy and X-ray absorption spectroscopy in the total fluorescence yield mode, we show that the lowest unoccupied and highest occupied electronic states of ≤3 nm thick SiO2-coated Si nanowells shift by up to 0.2 eV below the conduction band and ca. 0.7 eV below the valence band edge of bulk silicon, respectively. This nanoscale electronic structure shift induced by anions at surfaces (NESSIAS) provides the means for low-nanoscale intrinsic Si (i-Si) to be flooded by electrons from an external (bigger, metallic) reservoir, thereby getting highly electron- (n-) conductive. While our findings deviate from the behavior commonly believed to govern the properties of silicon nanowells, they are further confirmed by the fundamental energy gap as per nanowell thickness when compared against published experimental data. Supporting our findings further with hybrid density functional theory calculations, we show that other group IV semiconductors (diamond, Ge) do respond to the NESSIAS effect in accord with Si. We predict adequate nanowire cross-sections (X-sections) from experimental nanowell data with a recently established crystallographic analysis, paving the way to undoped ultrasmall silicon electronic devices with significantly reduced gate lengths, using complementary metal–oxide–semiconductor-compatible materials.

Articles you may be interested inPhotoluminescence properties and crystallization of silicon quantum dots in hydrogenated amorphous Si-rich silicon carbide films Dependence of band gap energy shift of In 0.2 Ga 0.8 As/GaAs multiple quantum well structures by impurity-free vacancy disordering on stoichiometry of SiO x and SiN x capping layersWe investigate the influence of layer thicknesses and interface modifications on the fundamental electronic gap of Si/ SiO 2 multilayers by a combined ab initio calculation and photoluminescence ͑PL͒ analysis. For the band gap calculations different Si/ SiO 2 interface models are studied. Experimentally investigated multiple quantum wells are prepared by remote plasma-enhanced chemical vapor deposition and rapid thermal annealing. The well-width dependence of the band gap obtained from PL measurements is much weaker than found in previous studies. This sublinear variation is in accordance with simulated electronic band gaps for hydrogen-free Si/ SiO 2 interfaces. The presence of hydrogen at the interfaces enforces the confinement effect for the band gap. Materials involved: nanocrystalline silicon, amorphous silica, ␤-cristobalite silica, and Si/ SiO 2 interface.