We investigate magnetron-sputtered In2(OxS1−x)3 compounds acting as an alternative buffer system to the solution-grown CdS or Zn(O,S) buffer layers in Cu(In,Ga)Se2 (CIGS) thin-film solar cells. The influence of the oxygen content on the solar cell performance, microstructure of the mixed systems, bandgap, and band offsets to CIGS is investigated experimentally and also characterized by calculations based on density functional theory. Samples in a series with different chemical compositions ranging from In2S3 to In2O3 are either directly deposited from ceramic targets or from a pure In2S3 target by reactive sputtering by adding O2 in the Ar sputtering gas. The binary compounds In2S3 and In2O3 sputtered at 220 °C substrate temperature from ceramic targets exhibit a crystalline structure, whereas the ternary In2(O,S)3 compounds are either nanocrystalline in the case of In2(O0.25S0.75)3 or amorphous for In2(O0.5S0.5)3 and In2(O0.75S0.25)3. For [O]/([O] + [S]) ratios above 0.25, the cell efficiencies decrease drastically, mainly due to lower open-circuit voltages (VOC). This behavior can be explained by an increase of the negative conduction band offset between the CIGS absorber and the oxygen-rich In2(OxS1−x)3 or In2O3 buffer, resulting in pronounced VOC losses. Adding oxygen to In2S3 with optical bandgap energies of around 2 eV results in a bowing of the values to below 2 eV and finally reaching values of around 2.7 eV for In2O3 if an indirect band transition is assumed. In summary, our results reveal that pronounced oxygen incorporation in In2S3 is not beneficial in terms of CIGS device efficiency because oxygen is electronically inactive and poorly miscible.

Graphene is inherently sensitive to vicinal dielectrics and local charge distributions, a property that can be probed by the position of the Dirac point in graphene field-effect transistors. Exploiting this as a useful sensing principle requires selectivity; however, graphene itself exhibits no molecule-specific interaction. Complementarily, metal-organic frameworks can be tailored to selective adsorption of specific molecular species. Here, a selective ethanol sensor is demonstrated by growing a surface-mounted metal-organic framework (SURMOF) directly onto graphene field-effect transistors (GFETs). Unprecedented shifts of the Dirac point, as large as 15 V, are observed when the SURMOF/GFET is exposed to ethanol, while a vanishingly small response is observed for isopropanol, methanol, and other constituents of the air, including water. The synthesis and conditioning of the hybrid materials sensor with its functional characteristics are described and a model is proposed to explain the origin, magnitude, and direction of the Dirac point voltage shift. Tailoring multiple SURMOFs to adsorb specific gases on an array of such devices thus generates a versatile, selective, and highly sensitive platform for sensing applications.

Electron transport in graphene is dominated by its Dirac-like charge carriers. Grain boundaries add a geometric aspect to the transport behavior by coupling differently oriented grains. In the phase coherent limit this aspect allows to relate the transport properties to two factors: the electronic structure of individual grains around the Dirac points and the orientation relation of the Dirac cones within the grain boundary Brillouin zone. Based on this picture it is possible to quantify the size and strain modulation of transport gaps without the need for explicit transport calculations within the non-equilibrium Green functions formalism. In this work we present a semi-analytical method that exploits this picture. Our method can explore arbitrary grain misorientations in the presence of an external strain providing valuable information about the electronic properties of individual grain boundaries.

Two-dimensional carbides/nitrides, typically called MXenes, are an emerging member of the ever-growing family of two-dimensional materials. The prediction of a ferromagnetic groundstate in chromium-containing MXenes has triggered growing interest in their chemical exfoliation from Cr-based MAX phases. However, the exfoliation poses serious difficulties using standard etching agents such as hydrofluoric acid (HF). Here, we investigate the exfoliability of Cr2GaC particles by chemical etching with aqueous HF both experimentally and theoretically. Structural and microstructural analyses show that the Cr2GaC particles decompose into chromium carbide and oxide without the formation of a Cr-based MXene. A thermodynamic analysis based on ab initio electronic structure calculations reveals that the exfoliation of Cr-based MXene from Cr2GaC by HF-etching is inhibited by more favorable competing reactions. This result confirms the experimental finding and suggests that HF is an unsuitable etching agent for a successful exfoliation of Cr2GaC.

Graphene grown by large-scale synthesis methods usually contains grain boundaries. They can strongly affect the electronic and mechanical properties of graphene and it is promising to exploit them for the design of electronic components and sensors. Here, we consider semiconducting graphene bicrystals and study how grain boundary structure variations influence electron transport using density functional theory in conjunction with the nonequilibrium Green function method. We find that the size of the transport gap in these bicrystals is not changed by structure variations. Interestingly however, electron transport outside the transport gap is very sensitive to modifications of the grain boundary. We show that these results can be understood within the ballistic transport approximation and by inspecting the electronic density of states resolved in energy-momentum space. Our findings suggest that the electronic response of graphene bicrystals can be controlled not only by grain misorientation but also by manipulation of the grain boundary structure.

Graphitization of a polymer layer provides a convenient route to synthesize nanocrystalline graphene on dielectric surfaces. The transparent and conducting wafer scale material is of interest as a membrane and a coating, and for the generation and detection of light, or strain sensing. In this work, we study the formation of nanocrystalline graphene on germanium, a surface which promotes the CVD synthesis of monocrystalline graphene. The surprising result that we obtained through graphitization is the formation of cavities in germanium, over which nanocrystalline graphene is suspended. Depending on the crystallographic orientation of the germanium surface, either trenches in (110)-Ge or pits in (111)-Ge are formed, and their dimensions depend on the graphitization temperature. Using Raman spatial imaging, we can show that nanocrystalline graphene is formed across the entire wafer in spite of the cavity formation. Interestingly, the Raman intensity is suppressed when the material is supported by germanium and is enhanced when the material is suspended. Through simulations, we can show that these effects are induced by the high refractive index of germanium and by interferences of the light field depending on the spacing between graphene and germanium. Using atomic force and scanning electron microscopy, we determined that ripples in the suspended material are induced by the mismatch of thermal expansion coefficients. Our results provide a new route to lithography-free fabrication of suspended membranes.