A continuous flow of hot electrons that are not at thermal equilibrium with the surrounding metal atoms is generated by the absorption of photons. Here we show that hot electron flow generated on a gold thin film by photon absorption (or internal photoemission) is amplified by localized surface plasmon resonance. This was achieved by direct measurement of photocurrent on a chemically modified gold thin film of metal-semiconductor (TiO(2)) Schottky diodes. The short-circuit photocurrent obtained with low-energy photons is consistent with Fowler's law, confirming the presence of hot electron flows. The morphology of the metal thin film was modified to a connected gold island structure after heating such that it exhibits surface plasmon. Photocurrent and optical measurements on the connected island structures revealed the presence of a localized surface plasmon at 550 ± 20 nm. The results indicate an intrinsic correlation between the hot electron flow generated by internal photoemission and localized surface plasmon resonance.
Densities of interfacial and bulk defects in high-dielectrics are typically about two orders of magnitude larger than those in Si-SiO 2 devices. An asymmetry in electron and hole trapping kinetics, first detected in test capacitor devices with nanocrystalline ZrO 2 and HfO 2 dielectrics, is a significant potential limitation for Si device operation and reliability in complementary metal oxide semiconductor applications. There are two crucial issues: i) are the electron and hole traps intrinsic defects, or are they associated with processed-introduced impurities?, and ii) what are the local atomic bonding arrangements and electronic state energies of these traps? In this study, thin film nanocrystalline high-gate dielectrics, TiO 2 , ZrO 2 , and HfO 2 (group IVB TM oxides), are investigated spectroscopically to identify the intrinsic electronic structures of valence and conduction band states, as well as those of intrinsic bonding defects. A quantitative/qualitative distinction is made between crystal field and Jahn-Teller (J-T) d-state energy differences in nanocrystralline TM elemental oxides, and noncrystalline TM silicates and Si oxynitrides. It is experimentally shown and theoretically supported that a length scale for nanocrystallite size < 2-3 nm i) eliminates J-T d-state term splittings in band edge -bonded d-states, and ii) represents a transition from the observation of discrete band edge defects to band-tail defects. Additionally, -state bonding coherence can also be disrupted with similar effects on band edge and defect states in HfO 2 films which have been annealed in NH 3 at 700 C, and display Hf-N bonds in N atom K 1 edge X-ray absorption spectra.
In this study, tin sulfide thin films were obtained by atomic layer deposition (ALD) using Tetrakis(dimethylamino)tin (TDMASn, [(CH3)2N]4Sn) and hydrogen sulfide (H2S). The growth rate of the tin sulfides (SnSx) was shown to be highly dependent on the deposition temperature, and reaction times of 1 second for the TDMASn and H2S were required to reach the saturation regime. Surface morphologies were smooth or rectangular with rounded corners as observed by a field emission scanning electron microscope (FE-SEM) and were dependent on temperature. X-ray diffraction results confirmed that the crystal structure of SnSx can be tuned by changing the ALD temperature. Below 120 °C, SnSx films appeared to be amorphous. In addition, SnSx films were SnS2 hexagonal at 140 and 150 °C and SnS orthorhombic above 160 °C. Similarly, the values of the optical band gap and binding energy showed significant differences between 150 and 160 °C. The electronic structures of SnSx were extracted by UPS and absorption spectroscopy, and the unsaturated Sn 3d molecular orbital (MO) states in the band edge were found to be responsible for the great improvement in electrical conductivity. This study shows that TDMASn-H2S ALD is an effective deposition method for SnSx films, offering a simple approach to tune the physical properties.
True n-type doping of titanium oxide without formation of midgap states would expand the use of metal oxides for charge-based devices. We demonstrate that plasma-assisted fluorine insertion passivates defect states and that fluorine acts as an n-type donor in titanium oxide. This enabled us to modify the Fermi level and transport properties of titanium oxide outside the limits of O vacancy doping. The origin of the electronic structure modification is explained by ab initio calculation.
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