Baohua Mao

Properties of Disorder-Engineered Black Titanium Dioxide Nanoparticles through Hydrogenation

The recent discovery of “black” TiO2 nanoparticles with visible and infrared absorption has triggered an explosion of interest in the application of TiO2 in a diverse set of solar energy systems; however, what a black TiO2 nanoparticle really is remains a mystery. Here we elucidate more properties and try to understand the inner workings of black TiO2 nanoparticles with hydrogenated disorders in a surface layer surrounding a crystalline core. Contrary to traditional findings, Ti3+ here is not responsible for the visible and infrared absorption of black TiO2, while there is evidence of mid-gap states above the valence band maximum due to the hydrogenated, engineered disorders. The hydrogen atoms, on the other hand, can undergo fast diffusion and exchange. The enhanced hydrogen mobility may be explained by the presence of the hydrogenated, disordered surface layer. This unique structure thus may give TiO2, one of the most-studied oxide materials, a renewed potential.

Using “Tender” X-ray Ambient Pressure X-Ray Photoelectron Spectroscopy as A Direct Probe of Solid-Liquid Interface

We report a new method to probe the solid-liquid interface through the use of a thin liquid layer on a solid surface. An ambient pressure XPS (AP-XPS) endstation that is capable of detecting high kinetic energy photoelectrons (7 keV) at a pressure up to 110 Torr has been constructed and commissioned. Additionally, we have deployed a “dip & pull” method to create a stable nanometers-thick aqueous electrolyte on platinum working electrode surface. Combining the newly constructed AP-XPS system, “dip & pull” approach, with a “tender” X-ray synchrotron source (2 keV–7 keV), we are able to access the interface between liquid and solid dense phases with photoelectrons and directly probe important phenomena occurring at the narrow solid-liquid interface region in an electrochemical system. Using this approach, we have performed electrochemical oxidation of the Pt electrode at an oxygen evolution reaction (OER) potential. Under this potential, we observe the formation of both Pt2+ and Pt4+ interfacial species on the Pt working electrode in situ. We believe this thin-film approach and the use of “tender” AP-XPS highlighted in this study is an innovative new approach to probe this key solid-liquid interface region of electrochemistry.

Direct Work Function Measurement by Gas Phase Photoelectron Spectroscopy and Its Application on PbS Nanoparticles

Work function is a fundamental property of a materials surface. It is playing an ever more important role in engineering new energy materials and efficient energy devices, especially in the field of photovoltaic devices, catalysis, semiconductor heterojunctions, nanotechnology, and electrochemistry. Using ambient pressure X-ray photoelectron spectroscopy (APXPS), we have measured the binding energies of core level photoelectrons of Ar gas in the vicinity of several reference materials with known work functions (Au(111), Pt(111), graphite) and PbS nanoparticles. We demonstrate an unambiguously negative correlation between the work functions of reference samples and the binding energies of Ar 2p core level photoelectrons detected from the Ar gas near the sample surface region. Using this experimentally determined linear relationship between the surface work function and Ar gas core level photoelectron binding energy, we can measure the surface work function of different materials under different gas environments. To demonstrate the potential applications of this ambient pressure XPS technique in nanotechnology and solar energy research, we investigate the work functions of PbS nanoparticles with various capping ligands: methoxide, mercaptopropionic acid, and ethanedithiol. Significant Fermi level position changes are observed for PbS nanoparticles when the nanoparticle size and capping ligands are varied. The corresponding changes in the valence band maximum illustrate that an efficient quantum dot solar cell design has to take into account the electrochemical effect of the capping ligand as well.

Oxidation and reduction of size-selected subnanometer Pd clusters on Al2O3 surface.

In this paper, we investigate uniformly dispersed size-selected Pd(n) clusters (n = 4, 10, and 17) on alumina supports. We study the changes of clustered Pd atoms under oxidizing and reducing (O2 and CO, respectively) conditions in situ using ambient pressure XPS. The behavior of Pd in the clusters is quite different from that of Pd foil under the same conditions. For all Pd clusters, we observe only one Pd peak. The binding energy of this Pd 3d peak is ~1-1.4 eV higher than that of metallic Pd species and changes slightly in CO and O2 environments. On the Pd foil however many different Pd species co-exist on the surface and change their oxidation states under different conditions. We find that the Pd atoms in direct contact with Al2O3 differ in oxidation state from the surface Pd atoms in a foil under reaction conditions. Compared to previous literature, we find that Pd 3d peak positions are greatly influenced by the different types of Al2O3 supports due to the combination of both initial and final state effects.

Influence of Step Geometry on the Reconstruction of Stepped Platinum Surfaces under Coadsorption of Ethylene and CO

We demonstrate the critical role of the specific atomic arrangement at step sites in the restructuring processes of low-coordinated surface atoms at high adsorbate coverage. By using high-pressure scanning tunneling microscopy (HP-STM) and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS), we have investigated the reconstruction of Pt(332) (with (111)-oriented triangular steps) and Pt(557) surfaces (with (100)-oriented square steps) in the mixture of CO and C2H4 in the Torr pressure range at room temperature. CO creates Pt clusters at the step edges on both surfaces, although the clusters have different shapes and densities. A subsequent exposure to a similar partial pressure of C2H4 partially reverts the clusters on Pt(332). In contrast, the cluster structure is barely changed on Pt(557). These different reconstruction phenomena are attributed to the fact that the 3-fold (111)-step sites on Pt(332) allows for adsorption of ethylidyne-a strong adsorbate formed from ethylene-that does not form on the 4-fold (100)-step sites on Pt(557).

Correlation between active layer thickness and ambient gas stability in IGZO thin-film transistors

Decreasing the active layer thickness has been recently reported as an alternative way to achieve fully depleted oxide thin-film transistors for the realization of low-voltage operations. However, the correlation between the active layer thickness and device resistivity to environmental changes is still unclear, which is important for the optimized design of oxide thin-film transistors. In this work, the ambient gas stability of IGZO thin-film transistors is found to be strongly correlated to the IGZO thickness. The TFT with the thinnest IGZO layer shows the highest intrinsic electron mobility in a vacuum, which is greatly reduced after exposure to O2/air. The device with a thick IGZO layer shows similar electron mobility in O2/air, whereas the mobility variation measured in the vacuum is absent. The thickness dependent ambient gas stability is attributed to a high-mobility region in the IGZO surface vicinity with less sputtering-induced damage, which will become electron depleted in O2/air due to the electron transfer to adsorbed gas molecules. The O2 adsorption and deduced IGZO surface band bending is demonstrated by the ambient-pressure x-ray photoemission spectroscopy results.