Systematic Surface Phase Transition of Ag Thin Films by Iodine Functionalization at Room Temperature: Evolution of Optoelectronic and Texture Properties.

We show a simple room temperature surface functionalization approach using iodine vapour to control a surface phase transition from cubic silver (Ag) of thin films into wurtzite silver-iodid (ß-AgI) films. A combination of surface characterization techniques (optical, electronical and structural characterization) reveal distinct physical properties of the new surface phase. We discuss the AgI thin film formation dynamics and related transformation of physical properties by determining the work-function, dielectric constant and pyroelectric behavior together with morphological and structural thin film properties such as layer thickness, grain structure and texture formation. Notable results are: (i) a remarkable increase of the work-function (by 0.9 eV) of the Ag thin layer after short a iodine exposure time (≤60 s), with simultaneous increase of the thin film transparency (by two orders of magnitude), (ii) pinning of the Fermi level at the valance band maximum upon iodine functionalization, (iii) 84% of all crystallites grain were aligned as a result of the evolution of an internal electric field. Realizing a nano-scale layer stack composed of a dielectric AgI layer on top of a metallic thin Ag layer with such a simple method has some technological implications e.g. to realize optical elements such as planar optical waveguides.

Functionalization of Silver Nanowires Surface using Ag-C Bonds in a Sequential Reductive Method.

Silver nanowires (Ag-NW) assembled in interdigitated webs have shown an applicative potential as transparent and conducting electrodes. However, upon integration in practical device designs, the presence of silver oxide, which instantaneously forms on the Ag-NW surfaces in ambient conditions, is unwanted. Here, we report on the functionalization of Ag-NWs with 4-nitrophenyl moieties through A-C bonds using a versatile two step reduction process, i.e., ascorbate reduction combined electrografting. We show that 40% of the Ag atop sites were terminated and provide high surface stability toward oxidation for more than 2 months while keeping the same intrinsic conductivity as in bulk silver.

Role of silicon nanowire diameter for alkyl (chain lengths C1-C18) passivation efficiency through Si-C bonds.

The effect of silicon nanowire (Si NW) diameter on the functionalization efficiency as given by covalent Si-C bond formation is studied for two distinct examples of 25 ± 5 and 50 ± 5 nm diameters (Si NW25 and Si NW50, respectively). A two-step chlorination/alkylation process is used to connect alkyl chains of various lengths (C1-C18) to thinner and thicker Si NWs. The shorter the alkyl chain lengths, the larger the surface coverage of the two studied Si NWs. Increasing the alkyl chain length (C2-C9) changes the coverage on the NWs: while for Si NW25 90 ± 10% of all surface sites are covered with Si-C bonds, only 50 ± 10% of all surface sites are covered with Si-C bonds for the Si NW50 wires. Increasing the chain length further to C14-C18 decreases the alkyl coverage to 36 ± 6% in thin Si NW25 and to 20 ± 5% in thick Si NW50. These findings can be interpreted as being a result of increased steric hindrance of Si-C bond formation for longer chain lengths and higher surface energy for the thinner Si NWs. As a direct consequence of these findings, Si NW surfaces have different stabilities against oxidation: they are more stable at higher Si-C bond coverage, and the surface stability was found to be dependent on the Si-C binding energy itself. The Si-C binding energy differs according to (C1-9)-Si NW > (C14-18)-Si NW, i.e., the shorter the alkyl chain, the greater the Si-C binding energy. However, the oxidation resistance of the (C2-18)-Si NW25 is lower than for equivalent Si NW50 surfaces as explained and experimentally substantiated based on electronic (XPS and KP) and structure (TEM and HAADF) measurements.

Electronic Properties of Si-Hx Vibrational Modes at Si Waveguide Interface.

Attenuated total reflectance (ATR) and X-ray photoelectron spectroscopy in suite with Kelvin probe were conjugated to explore the electronic properties of Si-Hx vibrational modes by developing Si waveguide with large dynamic detection range compared with conventional IR. The Si 2p emission and work-function related to the formation and elimination of Si-Hx bonds at Si surfaces are monitored based on the detection of vibrational mode frequencies. A transition between various Si-Hx bonds and thus related vibrational modes is monitored for which effective momentum transfer could be demonstrated. The combination of the aforementioned methods provides for results that permit a model for the kinetics of hydrogen termination of Si surfaces with time and advanced surface characterizing of hybrid-terminated semiconducting solids.

Direct observation of phonon emission from hot electrons: spectral features in diamond secondary electron emission.

In this work we use high-resolution synchrotron-based photoelectron spectroscopy to investigate the low kinetic energy electron emission from two negative electron affinity surfaces of diamond, namely hydrogenated and lithiated diamond. For hydrogen-terminated diamond electron emission below the conduction band minimum (CBM) is clearly observed as a result of phonon emission subsequent to carrier thermalization at the CBM. In the case of lithiated diamond, we find the normal conduction band minimum emission peak is asymmetrically broadened to higher kinetic energies and argue the broadening is a result of ballistic emission from carriers thermalized to the CBM in the bulk well before the onset of band-bending. In both cases the spectra display intensity modulations that are the signature of optical phonon emission as the main mechanism for carrier relaxation. To our knowledge, these measurements represent the first direct observation of hot carrier energy loss via photoemission.

Kinetic study of H-terminated silicon nanowires oxidation in very first stages.

Oxidation of silicon nanowires (Si NWs) is an undesirable phenomenon that has a detrimental effect on their electronic properties. To prevent oxidation of Si NWs, a deeper understanding of the oxidation reaction kinetics is necessary. In the current work, we study the oxidation kinetics of hydrogen-terminated Si NWs (H-Si NWs) as the starting surfaces for molecular functionalization of Si surfaces. H-Si NWs of 85-nm average diameter were annealed at various temperatures from 50°C to 400°C, in short-time spans ranging from 5 to 60 min. At high temperatures (T ≥ 200°C), oxidation was found to be dominated by the oxide growth site formation (made up of silicon suboxides) and subsequent silicon oxide self-limitation. Si-Si backbond oxidation and Si-H surface bond propagation dominated the process at lower temperatures (T < 200°C).

Hydrogen-terminated diamond electrodes. I. Charges, potentials, and energies.

Hydrogen-terminated intrinsic diamond is a most unusual insulator since in contact with air or electrolyte it develops a hole accumulation layer just below the surface. When immersed in electrolyte the hole concentration responds to ionic charges and potentials and this response can be monitored by measuring the conductance of the hole accumulation layer without interference form the bulk conductivity. This feature has been widely used for chemical sensors in the form of solution-gate field effect transistors (SGFET). Here we analyze the charge and the potential profiles in the diamond and the electrolyte, as well as the static differential capacitance of the diamond electrode under controlled potential conditions. From this analysis we derive expressions for the transfer characteristics of diamond-based SGFET's that faithfully describe experimental data presented here as well. This holds in particular for the threshold region of the transfer characteristics that can only be modeled if the unusual semiconducting properties of the diamond electrode are taken into account properly. From fits to our data we derive (among other things) a value of chi=-0.50+/-0.02eV for the electron affinity of the hydrogen-terminated diamond surface in contact with aqueous electrolyte.

Hydrogen-terminated diamond electrodes. II. Redox activity.

One of the most attractive features of diamond is its robust p -type surface conductivity that develops spontaneously under atmospheric conditions on hydrogen-terminated samples. An electrochemical charge transfer between diamond and an air-borne redox couple has been suggested to be responsible for the spontaneous appearance of surface-near holes. We present direct proof for the redox activity of the diamond surface by measuring pH -dependent open circuit potentials and quasistatic polarization curves for hydrogen-terminated and partially oxidized diamond electrodes. Under open circuit conditions we find in fact a mixed (or corrosion) potential that is consistent with the simultaneous equilibriation of the electrode versus both the hydrogen-hydronium and the oxygen-hydroxyl redox couple. Our data show extremely long-time constants for establishing the redox equilibrium and very low exchange current densities making the identification and characterization of the redox process a demanding experimental task.