Self-assembly of ClAlPc molecules on moiré-patterned graphene grown on Pt(111)

Phthalocyanines are promising molecules for the development of organic electronic devices, for instance, molecular heterojunctions in organic solar cells or organic field-effect transistors. For an optimum performance of these devices, the molecular ordering on the substrate and the molecular electronic level alignment have been shown as crucial factors. In this work, the self-assembled structure and the electronic structure of chloroaluminum phthalocyanines (ClAlPc) on graphene grown on Pt(111) surfaces have been studied by scanning tunneling microscopy (STM) under ultrahigh vacuum (UHV) and low-temperature conditions. Graphene grown on Pt(111) exhibits multiple moiré patterns with different periodicities, offering a benchmark to investigate the influence of the graphene and the moiré patterns in the ClAlPc ordering. This surface allows to extend previous works performed on graphite and graphene on Cu(100), where no moiré patterns are found. Well-ordered molecular islands exhibiting rotational domains have been observed in the submonolayer regime. The orientation of individual ClAlPc molecules within the structure unit cell has been characterized pointing out to a Cl-Up configuration adopted by the molecules. Our measurements show a correlation between the molecular lattice orientation and the graphene directions, whereas no influence of the underlying moiré patterns has been found. Finally, the ClAlPc electronic structure has been characterized indicating a weak graphene-molecule interactionFinancial support from the Spanish Ministerio de Economía y Competitividad (MINECO) and Fondo Europeo de Desarrollo Regional (FEDER) under grant No. MAT2016-77852-C2-2-R and from the Spanish Ministerio de Ciencia e Innovación, through the “María de Maeztu” Programme for Units of Excellence in R&D (grant No. CEX2018-000805- M) is gratefully acknowledge

Atomic-Scale Variations of the Mechanical Response of 2D Materials Detected by Noncontact Atomic Force Microscopy

We show that noncontact atomic force microscopy (AFM) is sensitive to the local stiffness in the atomicscale limit on weakly coupled 2D materials, as graphene on metals. Our large amplitude AFM topography and dissipation images under ultrahigh vacuum and low temperature resolve the atomic and moiré patterns in graphene on Pt (111), despite its extremely low geometric corrugation. The imaging mechanisms are identified with a multiscale model based on density-functional theory calculations, where the energy cost of global and local deformations of graphene competes with short-range chemical and long-range van der Waals interactions. Atomic contrast is related with short-range tip-sample interactions, while the dissipation can be understood in terms of global deformations in the weakly coupled graphene layer. Remarkably, the observed moiré modulation is linked with the subtle variations of the local interplanar graphene-substrate interaction, opening a new route to explore the local mechanical properties of 2D materials at the atomic scaleWe thank the Marie Curie ITN Network “ACRITAS” (Grant No. FP7-PEOPLE-2012-ITN-317348) funded by the European Commission under the FP7 Marie Curie PEOPLE programme and the Spanish MINECO (Projects No. CSD2010-00024, No. MAT2011-23627, No. MAT2013-41636-P, and No. MAT2014-54484-P) for financial support. Computer time was provided by the Spanish Supercomputer Network (RES) at Marenostrum III (BSC, Barcelona) and Magerit (CesViMa, Madrid) computers. P. P. was supported by the Ramón y Cajal progra

Built-up AFM tips by metal nanoclusters engineering

The ability to probe tip-sample interactions by Atomic Force Microscopy (AFM) has recently boosted our understanding of the matter at the atomic scale, enabling the study of properties of surfaces and adsorbates which were previously inaccessible. Nevertheless, this sensitivity to forces presents some drawbacks, as the requirement of a sharp tip apex to prevent the loss of spatial resolution due to the existence of long-range interactions. In this work, we have overcome this long-standing challenge by investigating the controlled extraction of single metallic nanoclusters, selectively grown on graphene. Our results show that the successive extraction of cluster allows to grow nanotips, which minimize the long-range tip-sample interactions and greatly enhance the topographic resolution. We have demonstrated that the created nanotips are very stable, which enables exchanging the sample and using the same nanotip to explore different surfaces without loss of resolution. Since metallic clusters of very different materials and sizes can be grown and selectively extracted by AFM, ours work paves also the way to the specific functionalization of AFM-tips to sense a large variety of interactionsFinancial support from the Spanish Ministerio de Economía y Competitividad (MINECO) and Fondo Europeo de Desarrollo Regional (FEDER) under grants No. MAT2016-77852-C2-2-R and MAT2016-80907-P and by the Comunidad de Madrid NMAT2D-CM program under grant S2018/NMT-4511 is gratefully acknowledged. Financial support from the Spanish Ministerio de Ciencia e Innovacion under grant Nº PID2019-106268GB-C31 is also gratefully acknowledged. We thank Rubén Pérez and Oscar Custance for helpful discussions and Antonio J. Martínez-Galera for helpful discussions and technical assistanc

Development of sample clean up methods for the analysis of Mycobacterium tuberculosis methyl mycocerosate biomarkers in sputum extracts by gas chromatography–mass spectrometry

A proof of principle gas chromatography–mass spectrometry method is presented, in combination with clean up assays, aiming to improve the analysis of methyl mycocerosate tuberculosis biomarkers from sputum. Methyl mycocerosates are generated from the transesterification of phthiocerol dimycocerosates (PDIMs), extracted in petroleum ether from sputum of tuberculosis suspect patients. When a high matrix background is present in the sputum extracts, the identification of the chromatographic peaks corresponding to the methyl derivatives of PDIMs analytes may be hindered by the closely eluting methyl ether of cholesterol, usually an abundant matrix constituent frequently present in sputum samples. The purification procedures involving solid phase extraction (SPE) based methods with both commercial Isolute-Florisil cartridges, and purpose designed molecularly imprinted polymeric materials (MIPs), resulted in cleaner chromatograms, while the mycocerosates are still present. The clean-up performed on solutions of PDIMs and cholesterol standards in petroleum ether show that, depending on the solvent mix and on the type of SPE used, the recovery of PDIMs is between 64 and 70%, whilst most of the cholesterol is removed from the system. When applied to petroleum ether extracts from representative sputum samples, the clean-up procedures resulted in recoveries of 36–68% for PDIMs, allowing some superior detection of the target analytes

Effective vanishing order of the Levi determinant

On a smooth domain in complex n space of finite D'Angelo q-type at a point, an effective upper bound for the vanishing order of the Levi determinant \text{coeff}\{\partial r \wedge \dbar r \wedge (\partial \dbar r)^{n-q}\} at that point is given in terms of the D'Angelo q-type, the dimension of the space n, and q itself. The argument uses Catlin's notion of a boundary system as well as techniques pioneered by John D'Angelo.Comment: 22 pages; typos in example from p.20 fixed in the second versio

CdS and Zn1−xSnxOy buffer layers for CIGS solar cells

Thin film solar cells based on Cu(In,Ga)Se2 (CIGS), where just the buffer layer is changed, were fabricated and studied. The effects of two different buffer layers, CdS and ZnxSn1-xOy (ZnSnO), are compared using several characterization techniques. We compared both devices and observe that the ZnSnO-based solar cells have similar values of power conversion efficiency as compared to the cells with CdS buffer layers. The ZnSnO-based devices have higher values in the short-circuit current (Jsc) that compensate for lower values in fill factor (FF) and open circuit voltage (Voc) than CdS based devices. Kelvin probe force microscopy (KPFM) results indicate that CdS provides junctions with slightly higher surface photovoltage (SPV) than ZnSnO, thus explaining the lower Voc potential for the ZnSnO sample. The TEM analysis shows a poly-crystalline ZnSnO layer and we have not detected any strong evidence of diffusion of Zn or Sn into the CIGS. From the photoluminescence measurements, we concluded that both samples are being affected by fluctuating potentials, although this effect is higher for the CdS sample.publishe

Cd and Cu interdiffusion in Cu(In,Ga)Se2/CdS hetero-interfaces

We report a detailed characterization of an industry-like prepared Cu(In,Ga)Se2 (CIGS)/CdS heterojunction by scanning transmission electron microscopy (STEM) and photoluminescence (PL). Energy dispersive x-ray spectroscopy (EDS) shows the presence of several regions in the CIGS layer that are Cu deprived and Cd enriched, suggesting the segregation of Cd-Se. Concurrently, the CdS layer shows Cd-deprived regions with the presence of Cu, suggesting a segregation of Cu-S. The two types of segregations are always found together, which, to the best of our knowledge, is observed for the first time. The results indicate that there is a diffusion process that replaces Cu with Cd in the CIGS layer and Cd with Cu in the CdS layer. Using a combinatorial approach we identified that this effect is independent of focused-ion beam sample preparation and of the TEM-grid. Furthermore, photoluminescence measurements before and after an HCl etch indicate a lower degree of defects in the post-etch sample, compatible with the segregates removal. We hypothesize that Cu2-xSe nanodomains react during the chemical bath process to form these segregates since the chemical reaction that dominates this process is thermodynamically favourable. These results provide important additional information about the formation of the CIGS/CdS interface.publishe

Detection of Mycobacterium tuberculosis in Sputum by Gas Chromatography-Mass Spectrometry of Methyl Mycocerosates Released by Thermochemolysis

Tuberculosis requires rapid diagnosis to prevent further transmission and allow prompt administration of treatment. Current methods for diagnosing pulmonary tuberculosis lack sensitivity are expensive or are extremely slow. The identification of lipids using gas chromatography- electron impact mass spectrometry (GC-EI/MS) could provide an alternative solution. We have studied mycocerosic acid components of the phthiocerol dimycocerosate (PDIM) family of lipids using thermochemolysis GC-EI/MS. To facilitate use of the technology in a routine diagnostic laboratory a simple extraction procedure was employed where PDIMs were extracted from sputum using petroleum ether, a solvent of low polarity. We also investigated a method using methanolic tetramethylammonium hydroxide, which facilitates direct transesterification of acidic components to methyl esters in the inlet of the GC-MS system. This eliminates conventional chemical manipulations allowing rapid and convenient analysis of samples. When applied to an initial set of 40 sputum samples, interpretable results were obtained for 35 samples with a sensitivity relative to culture of 94% (95%CI: 69.2,100) and a specificity of 100% (95%CI: 78.1,100). However, blinded testing of a larger set of 395 sputum samples found the assay to have a sensitivity of 61.3% (95%CI: 54.9,67.3) and a specificity of 70.6% (95%CI: 62.3,77.8) when compared to culture. Using the results obtained we developed an improved set of classification criteria, which when applied in a blinded re-analysis increased the sensitivity and specificity of the assay to 64.9% (95%CI: 58.6,70.8) and 76.2% (95%CI: 68.2,82.8) respectively. Highly variable levels of background signal were observed from individual sputum samples that inhibited interpretation of the data. The diagnostic potential of using thermochemolytic GC-EI/MS of PDIM biomarkers for diagnosis of tuberculosis in sputum has been established; however, further refinements in sample processing are required to enhance the sensitivity and robustness of the test

Epitaxial CuInSe2 thin films grown by molecular beam epitaxy and migration enhanced epitaxy

While CuInSe2 chalcopyrite materials are mainly used in their polycrystalline form to prepare thin film solar cells, epitaxial layers have been used for the characterization of defects. Typically, epitaxial layers are grown by metal-organic vapor phase epitaxy or molecular beam epitaxy (MBE). Here we present epitaxial layers grown by migration enhanced epitaxy (MEE) and compare the materials quality to MBE grown layers. CuInSe2 layers were grown on GaAs (001) substrates by co-evaporation of Cu, In, and Se using substrate temperatures of 450 ºC, 530 ºC, and 620 ºC. The layers were characterized by high resolution X-ray diffraction (HR-XRD), high-resolution transmission electron microscopy (HRTEM), Raman spectroscopy, and atomic force microscopy (AFM). HR-XRD and HR-TEM show a better crystalline quality of the MEE grown layers, and Raman scattering measurements confirm single phase CuInSe2. AFM shows the previously observed faceting of the (001) surface into {112} facets with trenches formed along the [110] direction. The surface of MEE-grown samples appears smoother compared to MBE-grown samples, a similar trend is observed with increasing growth temperature.The authors would like to acknowledge the CAPES (CAPES-INL 04/14), CNPq, and FAPEMIG funding agencies for financial support. We acknowledge the collaboration project with IMMCSIC (AIC-B-2011-0806). P.M.P.S. acknowledges financial support from EU through the FP7 Marie Curie IEF 2012 Action No. 327367.info:eu-repo/semantics/publishedVersio