Operando Surface Characterization of InP Nanowire p-n Junctions.

We present an in-depth analysis of the surface band alignment and local potential distribution of InP nanowires containing a p-n junction using scanning probe and photoelectron microscopy techniques. The depletion region is localized to a 15 nm thin surface region by scanning tunneling spectroscopy and an electronic shift of up to 0.5 eV between the n- and p-doped nanowire segments was observed and confirmed by Kelvin probe force microscopy. Scanning photoelectron microscopy then allowed us to measure the intrinsic chemical shift of the In 3d, In 4d, and P 2p core level spectra along the nanowire and the effect of operating the nanowire diode in forward and reverse bias on these shifts. Thanks to the high-resolution techniques utilized, we observe fluctuations in the potential and chemical energy of the surface along the nanowire in great detail, exposing the sensitive nature of nanodevices to small scale structural variations.

X-ray Photoelectron Spectroscopy Studies of Nanoparticles Dispersed in Static Liquid.

For nanoparticles active for chemical and energy transformations in static liquid environment, chemistries of surface or near-surface regions of these catalyst nanoparticles in liquid are crucial for fundamentally understanding their catalytic performances at a molecular level. Compared to catalysis at a solid-gas interface, there is very limited information on the surface of these catalyst nanoparticles under a working condition or during catalysis in liquid. Photoelectron spectroscopy is a surface-sensitive technique; however, it is challenging to study the surfaces of catalyst nanoparticles dispersed in static liquid because of the short inelastic mean free path of photoelectrons traveling in liquid. Here, we report a method for tracking the surface of nanoparticles dispersed in static liquid by employing graphene layers as an electron-transparent membrane to separate the static liquid containing a solvent, catalyst nanoparticles, and reactants from the high-vacuum environment of photoelectron spectrometers. The surfaces of Ag nanoparticles dispersed in static liquid sealed in such a graphene membrane liquid cell were successfully characterized using a photoelectron spectrometer equipped with a high vacuum energy analyzer. With this method, the surface of catalyst nanoparticles dispersed in liquid during catalysis at a relatively high temperature up to 150 °C can be tracked with photoelectron spectroscopy.

Chemical waves in the O2 + H2 reaction on a Rh(111) surface alloyed with nickel. II. Photoelectron spectroscopy and microscopy.

Chemical waves in the H2 + O2 reaction on a Rh(111) surface alloyed with Ni [ΘNi < 1.5 monolayers (ML)] have been investigated in the 10-7 and 10-6 mbar range at T = 773 K using scanning photoelectron microscopy and x-ray photoelectron spectroscopy as in situ methods. The local intensity variations of the O 1s and the Ni 2p signal display an anticorrelated behavior. The coincidence of a high oxygen signal with a low Ni 2p intensity, which seemingly contradicts the chemical attraction between O and Ni, has been explained with a phase separation of the oxygen covered Rh(111)/Ni surface into a 3D-Ni oxide and into a Ni poor metallic phase. Macroscopic NiO islands (≈1 µm size) formed under reaction conditions have been identified as 2D-Ni oxide. Titration experiments of the oxygen covered Rh(111)/Ni surface with H2 demonstrated that the reactivity of oxygen is decreased by an order of magnitude through the addition of 0.6 ML Ni. An excitation mechanism is proposed in which the periodic formation and reduction of NiO modulate the catalytic activity.

Chemical activity of oxygen vacancies on ceria: a combined experimental and theoretical study on CeO2(111).

The chemical activity of oxygen vacancies on well-defined, single-crystal CeO2(111)-surfaces is investigated using CO as a probe molecule. Since no previous measurements are available, the assignment of the CO ν1 stretch frequency as determined by IR-spectroscopy for the stoichiometric and defective surfaces are aided by ab initio electronic structure calculations using density functional theory (DFT).

XPS investigation of a CdS-based photoresistor under working conditions: operando-XPS.

A noncontact chemical and electrical measurement X-ray photoelectron spectroscopy (XPS) technique is performed to investigate a CdS-based photoresistor during its operation. The main objective of the technique is to trace chemical- and location-specified surface potential variations as shifts of the XPS Cd 3d(5/2) peak position without and under photoillumination with four different lasers. The system is also modeled to extract electrical information. By analyzing the measured potential variations with this model, location-dependent resistance values are represented (i) two dimensionally for line scans and (ii) three dimensionally for areal measurements. In both cases, one of the dimensions is the binding energy. The main advantage of the technique is its ability to assess an element-specific surface electrical potential of a device under operation based on the energy deviation of core level peaks in surface domains. Detection of the variations in electrical potentials and especially their responses to the energy of the illuminating source in operando, is also shown to be capable of detecting, locating, and identifying the chemical nature of structural and other types of defects.

Communication: enhancement of dopant dependent x-ray photoelectron spectroscopy peak shifts of Si by surface photovoltage.

Binding energies measured by x-ray photoelectron spectroscopy (XPS) are influenced by doping, since electrons are transferred to (p-type) and from (n-type) samples when they are introduced into the spectrometer, or brought into contact with each other (p-n junction). We show that the barely measurable Si2p binding energy difference between moderately doped n- and p-Si samples can be enhanced by photoillumination, due to reduction in surface band-bending, which otherwise screens this difference. Similar effects are also measured for samples containing oxide layers, since the band-bending at the buried oxide-Si interfaces is manifest as photovoltage shifts, although XPS does not probe the interface directly. The corresponding shift for the oxide layer of the p-Si is almost twice that of without the oxide, whereas no measurable shifts are observable for the oxide of the n-Si. These results are all related to band-bending effects and are vital in design and performance of photovoltaics and other related systems.

Photodriven Transient Picosecond Top-Layer Semiconductor to Metal Phase-Transition in p-Doped Molybdenum Disulfide.

Visible light is shown to create a transient metallic S-Mo-S surface layer on bulk semiconducting p-doped indirect-bandgap 2H-MoS2 . Optically created electron-hole pairs separate in the surface band bending region of the p-doped semiconducting crystal causing a transient accumulation of electrons in the surface region. This triggers a reversible 2H-semiconductor to 1T-metal phase-transition of the surface layer. Electron-phonon coupling of the indirect-bandgap p-doped 2H-MoS2 enables this efficient pathway even at a low density of excited electrons with a distinct optical excitation threshold and saturation behavior. This mechanism needs to be taken into consideration when describing the surface properties of illuminated p-doped 2H-MoS2 . In particular, light-induced increased charge mobility and surface activation can cause and enhance the photocatalytic and photoassisted electrochemical hydrogen evolution reaction of water on 2H-MoS2 . Generally, it opens up for a way to control not only the surface of p-doped 2H-MoS2 but also related dichalcogenides and layered systems. The findings are based on the sensitivity of time-resolved electron spectroscopy for chemical analysis with photon-energy-tuneable synchrotron radiation.

Two-dimensional X-ray photoelectron spectroscopy for composite surface analysis.

We describe a method for obtaining two-dimensional X-ray photoelectron spectroscopic data derived from the frequency dependence of the XPS peaks recorded under electrical square-wave pulses, which control and affect the binding energy positions via the electrical potentials developed as a result of charging. By using cross-correlations between various peaks, our technique enables us to elucidate electrical characteristics of surface structures of composite samples and bring out various correlations between hidden/overlapping peaks.

Optical response of Ag-Au bimetallic nanoparticles to electron storage in aqueous medium.

Composition and structure dependence of the shift in the position of the surface plasmon resonance band upon introduction of NaBH4 to aqueous solutions of gold and silver nanoparticles are presented. Silver and gold nanoalloys in different compositions were prepared by co-reduction of the corresponding salt mixtures using sodium citrate as the reducing agent. After addition of NaBH4 to the resultant nanoalloys, the maximum of their surface plasmon resonance band, ranging between that of pure silver (ca. 400 nm) and of pure gold (ca. 530 nm), is blue-shifted as a result of electron storage on the particles. The extent of this blue shift increases non-linearly with the mole fraction of silver in the nanoparticle, parallel to the trends reported previously for both the frequency and the extinction coefficient of the plasmon band shifts. Gold(core)@silver(shell) nanoparticles were prepared by sequential reduction of gold and silver, where addition of NaBH4 results in relatively large spectral shift in the plasmon resonance band when compared with the nanoalloys having a similar overall composition. The origin of the large plasmon band shift in the core-shell is related with a higher silver surface concentration on these particles. Hence, the chemical nature of the nanoparticle emerges as the dominating factor contributing to the extent of the spectral shift as a result of electron storage in bimetallic systems.

Studies of surface of metal nanoparticles in a flowing liquid with XPS.

Studying surface of catalyst nanoparticles in a flowing liquid is important for understanding the underlying mechanism of a reaction performed in liquid. We report the design of a reaction cell system of Si3N4 window covering the flowing liquid with an electron-transmissible membrane. By using metal nanoparticles as a catalyst dispersed in a solvent, examination of the surface of catalyst nanoparticles in a flowing liquid was demonstrated by observation of Ag 3d photoemission feature when a liquid containing Ag nanoparticles was flowing through this system.