The C 1s signal from ubiquitous carbon contamination on samples forming during air exposure, so called adventitious carbon (AdC) layers, is the most common binding energy (BE) reference in X-ray photoelectron spectroscopy studies. We demonstrate here, by using a series of transition-metal nitride films with different AdC coverage, that the BE of the C 1s peak E_{\mathrm{B}}^{\mathrm{F}} varies by as much as 1.44 eV. This is a factor of 10 more than the typical resolvable difference between two chemical states of the same element, which makes BE referencing against the C 1s peak highly unreliable. Surprisingly, we find that C 1s shifts correlate to changes in sample work function {?}_{\mathrm{S}\mathrm{A}} , such that the sum E_{\mathrm{B}}^{\mathrm{F}}+{?}_{\mathrm{S}\mathrm{A}} is constant at 289.50±0.15 eV, irrespective of materials system and air exposure time, indicating vacuum level alignment. This discovery allows for significantly better accuracy of chemical state determination than offered by the conventional methods. Our findings are not specific to nitrides and likely apply to all systems in which charge transfer at the AdC/substrate interface is negligible.

There is a growing concern within the surface science community that the massive increase in the number of XPS articles over the last few decades is accompanied by a decrease in work quality including in many cases meaningless chemical bond assignment. Should this trend continue, it would have disastrous consequences for scientific research. While there are many factors responsible for this situation, the lack of insight of physical principles combined with seeming ease of XPS operation and insufficient training are certainly the major ones. To counter that, we offer a comprehensive tutorial written in the form of a step-by-step guide starting from experimental planning, through sample selection and handling, instrument setup, data acquisition, spectra analysis, and results presentation. Six application examples highlight the broad range of research questions that can be answered by XPS. The topic selection and the discussion level are intended to be accessible for novices yet challenging possible preconceptions of experienced practitioners. The analyses of thin film samples are chosen for model cases as this is from where the bulk of XPS reports presently emanate and also where the author's key expertise lies. At the same time, the majority of discussed topics is applicable to surface science in general and is, thus, of relevance for the analyses of any type of sample and material class. The tutorial contains ca. 160 original spectra and over 290 references for further reading. Particular attention is paid to the correct workflow, development of good research practices, and solid knowledge of factors that impact the quality and reliability of the obtained information. What matters in the end is that the conclusions from the analysis can be trusted. Our aspiration is that after reading this tutorial each practitioner will be able to perform error-free data analysis and draw meaningful insights from the rich well of XPS.

Intercalated layered materials offer distinctive properties and serve as precursors for important two-dimensional (2D) materials. However, intercalation of non–van der Waals structures, which can expand the family of 2D materials, is difficult. We report a structural editing protocol for layered carbides (MAX phases) and their 2D derivatives (MXenes). Gap-opening and species-intercalating stages were respectively mediated by chemical scissors and intercalants, which created a large family of MAX phases with unconventional elements and structures, as well as MXenes with versatile terminals. The removal of terminals in MXenes with metal scissors and then the stitching of 2D carbide nanosheets with atom intercalation leads to the reconstruction of MAX phases and a family of metal-intercalated 2D carbides, both of which may drive advances in fields ranging from energy to printed electronics.

Boridene: a 2D boride: A range of two-dimensional (2D) materials, including graphene and hexagonal boron nitride, have been synthesized and studied because of the unusual properties that occur when one dimension becomes very small. MXenes are a family of materials made of layers of inorganic transition metal carbides and nitrides that are a few atoms thick and are manufactured by selective etching. Attempts to make similar boridene materials have been challenging because of the reactive nature of boride phases and because the parent materials tend to dissolve rather than selectively etch. Zhou et al . synthesized boridene in the form of single-layer 2D molybdenum boride sheets by selective etching in aqueous hydrofluoric acid to produce sheets with ordered metal vacancies, opening up an additional family of materials for study. —MSL

Herein, we report on the phase stabilities and crystal structures of two newly discovered ordered, quaternary MAX phases—Mo₂TiAlC₂ and Mo₂Ti₂AlC₃—synthesized by mixing and heating different elemental powder mixtures of mMo:(3-m)Ti:1.1Al:2C with 1.5 ≤ m ≤ 2.2 and 2Mo: 2Ti:1.1Al:2.7C to 1600 °C for 4 h under Ar flow. In general, for m ≥ 2 an ordered 312 phase, (Mo₂Ti)AlC₂, was the majority phase; for m < 2, an ordered 413 phase (Mo₂Ti₂)AlC₃, was the major product. The actual chemistries determined from X-ray photoelectron spectroscopy (XPS) are Mo₂TiAlC_1.7 and Mo₂Ti_1.9Al_0.9C_2.5, respectively. High resolution scanning transmission microscopy, XPS and Rietveld analysis of powder X-ray diffraction confirmed the general ordered stacking sequence to be Mo-Ti-Mo-Al-Mo-Ti-Mo for Mo₂TiAlC₂ and Mo-Ti-Ti-Mo-Al-Mo-Ti-Ti-Mo for Mo₂Ti₂AlC₃, with the carbon atoms occupying the octahedral sites between the transition metal layers. Consistent with the experimental results, the theoretical calculations clearly show that M layer ordering is mostly driven by the high penalty paid in energy by having the Mo atoms surrounded by C in a face-centered configuration, i.e., in the center of the M_n+1X_n blocks. At 331 GPa and 367 GPa, respectively, the Young's moduli of the ordered Mo₂TiAlC₂ and Mo₂Ti₂AlC₃ are predicted to be higher than those calculated for their ternary end members. Like most other MAX phases, because of the high density of states at the Fermi level, the resistivity measurement over 300 to 10 K for both phases showed metallic behavior.

We report a new fullerenelike material consisting of cross-linked nano-onions of C and N. Growth of the onion shells takes place atom by atom on a substrate surface and yields thin solid films during magnetron sputter deposition. Electron microscopy and energy loss spectroscopy show that the core shell contains up to $20\mathrm{at}.\mathrm{}\%$ N corresponding to ${\mathrm{C}}_{48}{\mathrm{N}}_{12}$ aza-fullerene composition. Nanoindentation of this nanostructured material gives high resilience with hardness 7 GPa, Young's modulus 37 GPa, and complete elastic recovery after loading with 0.5 mN to a depth of 75 nm. Total energy calculations show the stability of ${\mathrm{C}}_{60-2n}{\mathrm{N}}_{2n}$ aza-fullerenes and suggest the existence of a novel ${\mathrm{C}}_{48}{\mathrm{N}}_{12}$ molecule.