In Situ Investigations of Al/Perovskite Interfacial Structures.

Interfacial properties of perovskite layers and metal electrodes play a crucial role in device performance and long-term stability of perovskite solar cells. In this work, we performed a comprehensive study of the interfacial structures and ion migration at the interface of a CH3NH3PbI3 perovskite layer and an Al electrode using in situ synchrotron radiation photoemission spectroscopy measurements. It was found that the Al electrode can react with the perovskite layers, leading to the formation of aluminum iodide species and the bonding between Al and N, as well as the reduction of Pb2+ ions to metallic Pb species at the interface. Moreover, during the Al deposition, iodide ions can migrate from the CH3NH3PbI3 subsurface to the Al electrode, while the reduced Pb remains at the subsurface. The depth profile photoemission measurements, made by varying the photon energies of incident synchrotron radiation X-rays, demonstrate that the reaction occurs at the Al/CH3NH3PbI3 interface at least with a thickness of ∼3.5 nm below the perovskite surface. This study provides an atomic-level fundamental understanding of the Al/CH3NH3PbI3 interfacial structures and insight into the degradation mechanisms of perovskite solar cells when using Al metal as the electrode.

Formic acid adsorption and decomposition on clean and atomic oxygen pre-covered Cu(100) surfaces.

Formic acid adsorption and decomposition on clean Cu(100) and two atomic oxygen pre-covered Cu(100) surfaces have been studied using surface science techniques including scanning tunneling microscopy, low-energy electron diffraction, x-ray photoelectron spectroscopy, and infrared reflection-absorption spectroscopy. The two atomic oxygen pre-covered Cu(100) surfaces include an O-(22 ×2)R45° Cu(100) surface and an oxygen modified Cu(100) surface with a local O-c(2 × 2) structure. The results show that the O-(22 ×2)R45° Cu(100) surface is inert to the formic acid adsorption at 300 K. After exposing to formic acid at 300 K, bidentate formate formed on the clean Cu(100) and local O-c(2 × 2) area of the oxygen modified Cu(100) surface. However, their adsorption geometries are different, being vertical to the surface plane on the former surface and inclined with respect to the surface normal with an ordered structure on the latter surface. The temperature programmed desorption spectra indicate that the formate species adsorbed on the clean Cu(100) surface decomposes into H2 and CO2 when the sample temperature is higher than 390 K. Differently, the proton from scission of the C-H bond of formate reacts with the surface oxygen, forming H2O on the oxygen modified Cu(100) surface. The CO2 signal starts increasing at about 370 K, which is lower than that on clean Cu(100), indicating that the surface oxygen affiliates formate decomposition. Combining all these results, we conclude that the surface oxygen plays a crucial role in formic acid adsorption and formate decomposition.

Supramolecular Tessellations at Surfaces by Vertex Design.

Assembly and tessellation of organic species at surfaces are important for the design of advanced materials, particularly for the development of spontaneous self-assemblies of supramolecular systems of increasing complexity. However, there are few examples where the ability to steer the system between supramolecular tessellations has been achieved. Here, we demonstrate a series of steps to reduce and then restore molecular symmetry; those variations impact vertex symmetry and thus generate a series of tessellations that reflect the molecular symmetry. We deposit 4,4'-dihydroxybiphenyl on the Ag(111) surface, then anneal at specific temperatures to achieve stepwise dehydrogenation of the terminal hydroxyls. The symmetry of tessellation vertices in the self-assembled structure also changes, as characterized by scanning tunneling microscopy and synchrotron radiation photoemission spectroscopy. This control over vertex geometry and spontaneous tessellation structure extends our understanding of supramolecular design control and advances architectural complexity for the development of functional surfaces.