Morphological, optical and photovoltaic characteristics of MoSe2/SiOx/Si heterojunctions.

This work reports the effect of different processing parameters on the structural and morphological characteristics of MoSe2 layers grown by chemical vapour deposition (CVD), using MoO3 and Se powders as solid precursors. It shows the strong dependence of the size, shape and thickness of the MoSe2 layers on the processing parameters. The morphology of the samples was investigated by field emission scanning electron microscopy (FESEM) and the thickness of the deposited layers was determined by atomic force microscopy (AFM). Raman and photoluminescence (PL) spectroscopies were used to confirm the high quality of the MoSe2 layers. Surface composition was examined by photoelectron spectroscopy (XPS). Moreover, the MoSe2/SiOx/Si heterojunctions exhibit diode behaviour, with a rectification ratio of 10, measured at ±2.0 V, which is due to the p-i-n heterojunctions formed at the p-Si/SiOx/MoSe2 interface. A photovoltaic effect was observed with a short circuit current density (Jsc), open circuit voltage (VOC) and efficiency of -0.80 mA/cm2, 1.55 V and 0.5%, respectively. These results provide a guide for the preparation of p-i-n heterojunctions based on few-layer MoSe2 with improved photovoltaic response.

Influence of annealing conditions on the formation of regular lattices of voids and Ge quantum dots in an amorphous alumina matrix.

In this work, the influence of air pressure during the annealing of Ge quantum dot (QD) lattices embedded in an amorphous Al(2)O(3) matrix on the structural, morphological and compositional properties of the film is studied. The formation of a regularly ordered void lattice after performing a thermal annealing process is explored. Our results show that both the Ge desorption from the film and the regular ordering of the QDs are very sensitive to the annealing parameters. The conditions for the formation of a void lattice, a crystalline Ge QD lattice and a disordered QD lattice are presented. The observed effects are explained in terms of oxygen interaction with the Ge present in the film.

Characterization of poly(2-hydroxyethyl methacrylate) (PHEMA) contact lens using the Langmuir monolayer technique.

The behavior of poly(2-hydroxyethyl methacrylate) (PHEMA) polymer monolayer spread on water was studied under various experimental conditions. The influence of subphase pH and temperature, compression speed, elapsed time from the deposit of the monolayer and the recording of the surface pressure-area (π-A) isotherms, as well as the number of polymer molecules deposited at the air/water surface (surface concentration) was studied. The obtained results show that PHEMA exhibits a very stable monolayer given that it is unaffected by modifications in the majority of these variables. Only the elapsed time between the spreading of the monolayer and the beginning of compression causes a small change in the π-A isotherms that consists in an increase in the area occupied by the film. This is attributed to the greater unfolding with time of the polymer's monomers at the air/water interface. The plateau that appears on π-A curves of the PHEMA monolayer is attributed to the reorientation of their hydroxyethyl polar groups through their C-O-C bonds, as well as to the reorientation of the ethylene (CH(2)) groups that link the monomers, which provokes a folding of the polymer's chains causing an accordion configuration. The existence of this structure is confirmed by the presence of numerous noise peaks in the relative thickness versus time curve corresponding to this region. In the same fashion, the images observed from Brewster angle microscopy (BAM) reveal the existence of light-dark "bands" relative to the different regions of this particular structure.

How to obtain a well-spread monolayer of lysozyme at the air/water interfaces.

The purpose of this study is to define the conditions required to obtain a complete spreading of the lysozyme monolayer at the A/W interface. To this end, using Trurnit's method, the influence of the ionic strength of the substrate, the elapsed time between the spreading of the monolayer and the beginning of its compression, and the number of lysozyme molecules spread at the interface was studied. The results obtained show that the lysozyme spreading is conditioned by the unfolding of amino acid chains which form part of its structure, so that such unfolding is hindered, either because of an excessive accumulation of lysozyme molecules on the substrate surface or because the waiting time necessary to get this unfolding is not long enough, regardless of the number of spread molecules. The complete unfolding of lysozyme, which involves the loss of tertiary and secondary structures, has been obtained in this work under certain conditions: (1) using a substrate with a high saline concentration (NaCl 3-3.5 M) and at a pH value close to the isoelectric point of lysozyme (pI=11) in order to reduce the solubility and the electrical potential of the protein, (2) increasing the elapsed time between the spreading of the protein and the beginning of its compression to 3h in order to get a complete unfolding of lysozyme, which is a very slow process, (3) using an initial spreading area of 2.1m(2)/mg or larger (equivalent to a protein surface concentration of less than 2×10(12) molec/cm(2)) to reduce the accumulation of protein molecules at the surface, thus facilitating their unfolding, and (4) using Trurnit's spreading method, although for the spreading of this protein was found to be insufficiently significant.

Interactions in monolayers: a study of the behavior of poly(methyl methacrylate)-lysozyme mixed films from surface pressure-area and ellipsometric measurements.

Mixed monolayers of PMMA-lysozyme show the existence of negative deviations from the additivity of the molecular areas (A(m)) when the composition of polymer mixtures is less than X(PMMA) 0.6, regardless of the surface pressure of the monolayers. The maximum deviation occurs in the mixed monolayer with composition X(PMMA) 0.25, which is attributed to the formation of a complex consisting of one polymer molecule and three protein molecules (1:3 stoichiometry), stabilized by hydrogen bonds between the NH groups of the protein and the CO groups of the polymer as well as by van der Waals attractive forces between the hydrocarbon chains of both components. When the relative proportion of the components in the mixed films significantly differs from the value corresponding to the stoichiometry of the complex (as in mixtures with X(PMMA) > 0.6), this complex cannot be formed, causing an immiscible system where the values of the experimental molecular areas coincide with those corresponding to ideal behavior. Measurements of monolayer thickness and BAM images allow confirmation on the microscopic level of the structural characteristics deduced from the π-A isotherms.

Approach to knowledge of the interaction between the constituents of contact lenses and ocular tears: mixed monolayers of poly(methyl methacrylate) and dipalmitoyl phosphatidyl choline.

Mixed monolayers of poly(methyl methacrylate) (PMMA), the main component of hard contact lenses, and dipalmitoyl phosphatidyl choline (DPPC), a characteristic phospholipidic constituent of ocular tear films, were selected as an in vitro model in order to observe the behavior of contact lenses on the eye. Using Langmuir monolayer and Brewster angle microscopy (BAM) techniques, the interaction between both components was analyzed from the data of surface pressure-area isotherms, compressional modulus-surface pressure, and relative film thickness versus time elapsed from the beginning of compression, together with BAM images. Regardless of the surface pressure at which the molecular/monomer areas (A(m)) were recorded, the A(m) mole fractions of PMMA (X(PMMA)) plots show that the experimental results match the theoretical values calculated from additivity rule A(m) = X(PMMA)A(PMMA) + X(DPPC)A(DPPC). The application of the Crisp phase rule to the phase diagram of the PMMA-DPPC system can explain the existence of a mixed monolayer made up of miscible components with ideal behavior at surface pressures below 25 mN/m. However, at very high surface pressures, when collapse is reached (at 60 mN/m), the single collapsed components are segregated into two independent phases. These results allows us to argue that PMMA hard contact lenses in the eye do not alter the structural characteristics of the phospholipid (DPPC) in tears.

Interactions between polymers and lipid monolayers at the air/water interface: surface behavior of poly(methyl methacrylate)-cholesterol mixed films.

The behavior of mixed monolayers of cholesterol and poly(methyl methacrylate) (PMMA) with molecular weights of M(w) = 120,000 g/mol and M(w) = 15,000 g/mol was investigated at the air/water interface using Langmuir and Brewster angle microscopy techniques. From the data of surface pressure (pi)-area (A) isotherms, compressional modulus-surface pressure (C(s)(-1)-pi) curves, and film thickness, complemented with Brewster angle microscopy images, the interaction between the components was analyzed. Regardless of the surface pressure (pi = 10, 20, or 30 mN/m) at which the mean molecular/monomer areas (Am) were calculated, the Am-mole fraction plots (corresponding to X(PMMA) = 0.1, 0.3, 0.5, 0.7, and 0.9) show that all the experimental points obtained are placed on the theoretical straight line calculated according to the additivity rule. This fact, together with the existence of two collapses in the mixed monolayers and with the fact that the surface pressure of the liquid-expanded LE-L'E phase transition of PMMA does not change with the monolayer composition, demonstrates the immiscibility of the film components at the interface. The application of the Crisp phase rule to the phase diagram of PMMA-cholesterol mixed monolayers helps to explain the existence of a biphasic system, regardless of their composition and surface pressure. Besides, Brewster angle microscopy (BAM) images showed the existence of heterogeneous cholesterol domains with high reflectivity immersed in a homogeneous polymer separate phase with low reflectivity.

Coexistence of universal and topological anomalous hall effects in metal CrO2 thin films in the dirty limit.

The scaling exponent of 1.6 between anomalous Hall and longitudinal conductivity, characteristic of the universal Hall mechanism in dirty-metal ferromagnets, emerges from a series of CrO2 films as we systematically increase structural disorder. Magnetic disorder in CrO2 increases with temperature and this drives a separate topological Hall mechanism. We find that these terms are controlled discretely by structural and magnetic defect populations, and their coexistence leads to apparent divergence from exponent 1.6, suggesting that the universal term is more prevalent than previously realized.

Interactions between membrane sterols and phospholipids in model mammalian and fungi cellular membranes--a Langmuir monolayer study.

This paper is aimed at investigating sterol/phospholipid interactions in the exact proportion that occurs in fungi/mammalian cells. We have performed a thorough analysis of surface pressure (pi)-area (A) isotherms with the Langmuir monolayer technique, complemented with Brewster angle microscopy (BAM) images. The following mixtures were analysed: cholesterol (Chol)-dipalmitoyl phosphatidylcholine (DPPC), Chol-dioleoyl phosphatidylcholine (DOPC), ergosterol (Erg)-DPPC, and Erg-DOPC. For each system, two different concentrations of the sterols were used, 13 and 30%, corresponding to the range of concentration found in various natural membranes. The obtained results show the existence of attractive interactions between phospholipids and cholesterol. Mixtures with ergosterol behave quite differently, i.e. either the interactions are repulsive (mixtures with DPPC) or the system is ideal (mixtures with DOPC). The obtained results have implications in the polyene antibiotics mode of action, i.e. the polyenes may interact easier with ergosterol, present in fungi cells, as compared to cholesterol--the main sterol of the mammalian cellular membranes.

Structural and optical properties of ge nanocrystals embedded in Al2O3.

Ge nanocrystals (NCs) embedded in aluminum oxide were grown by RF-magnetron sputtering. Raman, high resolution transmission electron microscopy (HRTEM), selected area diffraction (SAD), and X-ray diffraction (XRD) techniques confirmed good cristallinity of the NCs from samples annealed at 800 degrees C. The average NC size was estimated to be around 7 nm. Photoluminescence (PL) measurements show an emission related to the NCs. The temperature dependence of the PL confirms the confinement phenomenon in the Ge NCs.

Methane detection at 1670-nm band using a hollow-core photonic bandgap fiber and a multiline algorithm.

The long interaction pathlengths provided by hollow-core photonic bandgap fibers (HC-PBFs) are especially advantageous for the detection of weakly absorbing gases such as methane (CH(4)). In this paper, we demonstrate methane sensing with a 1670-nm band HC-PBF. A multiline algorithm is used to fit the R(6) manifold (near 1645 nm) and, in this way, to measure the gas concentration. With this method, a minimum detectivity of 10 ppmv for the system configuration was estimated.

The influence of subphase temperature on miltefosine-cholesterol mixed monolayers.

Effects of the subphase temperature on the surface pressure (pi)-area (A) isotherms of mixed monolayers of miltefosine (hexadecylphosphocholine), a potential anticancer drug, and cholesterol were investigated at the air/water interface, which were supplemented with Brewster angle microscopy (BAM) observations. Comparison of the collapse pressure values, mean molecular areas, excess areas and excess free energy of mixing between the mixed monolayer at various molar ratios and the pure component monolayers showed that, regardless of the subphase temperature, the investigated miltefosine-cholesterol system is much more stable than that the pure component monolayers, suggesting strong attractive interactions between miltefosine and cholesterol in mixed monolayers. As a consequence, it was postulated that stable "complexes" of the two components could form at the interface, for which stoichiometry may vary with the subphase temperature. Such "surface complexes" should be responsible for the contraction of the mean molecular area and thus the high stability of the mixed monolayer.

Surface behavior of oleoyl palmitoyl phosphatidyl ethanolamine (OPPE) and the characteristics of mixed OPPE-miltefosine monolayers.

Langmuir monolayers of oleoyl palmitoyl phosphatidyl ethanolamine (OPPE) were investigated at the air/water interface by means of surface pressure (pi)-area (A) isotherms complemented with Brewster angle microscopy images upon film compression/expansion. The characteristic phase transition appearing in the course of pi/A isotherms was attributed to the coexistence of two liquid-expanded phases of different molecular ordering. The interactions between OPPE and hexadecylphosphocholine (miltefosine) were studied at different subphase pHs (2, 6, and 10) at 20 degrees C and analyzed with mean molecular area (A12)-, excess area of mixing (Aexc)-, and excess free energy of mixing (DeltaGexc)-composition plots. The obtained results indicate that at pH 10, where both OPPE and miltefosine polar groups are negatively charged, attractive interactions are observed (reflected by negative deviations from ideality), contrary to expectation. This peculiar behavior is explained as being due both to water molecules, which surround negatively charged polar groups and increase the distance between them, weakening in this way the electrostatic repulsion forces; and to positively charged counterions present in the diffuse double layer, neutralizing their charge. In this way, the van der Waals attraction forces between hydrocarbon tails of both molecules predominate and are responsible for the observed negative deviations from ideal behavior. Similar explanations are given for the observed negative deviations at pH 2 where both polar groups are positively charged. At pH 6, the observed negative deviations at low surface pressures and positive deviations at high pressures are interpreted as being due to a change in orientation of polar groups upon monolayer compression.

Molecular organisation of amphotericin B at the air-water interface in the presence of sterols: a monolayer study.

Using the monolayer technique to study the surface behaviour of systems consisting of amphotericin B (AmB) and various sterols, the components were found to interact with each other. The interactions observed are accounted for by postulating that, at low surface pressures, AmB and different sterols form mixed films where the former lies parallel and the latter normal to the air-water interface in such a way that the polar groups in both components establish hydrogen bonds that lead to the formation of an AmB-sterol 'complex' of 2:1 stoichiometry at the interface. At high surface pressures, AmB molecules rearrange themselves normal to the interface; this gives rise to the Van der Waals interactions between non-polar chains of both components that vary with the nature and composition of the system. The occurrence of these hydrophobic interactions prevents the desorption of AmB into the subphase, which is consistent with the positive excess areas of mixing obtained under these surface pressure conditions. Among the four sterols studied, ergosterol exhibits the strongest interaction with AmB and beta-sitosterol the weakest. Cholesterol and stigmasterol show intermediate behaviour.

Study of pi-A Curves for Mixed Monolayers of Cyclosporin and Poly(dl-Lactic Acid-co-Glycolic Acid) Spread at the Air/Water Interface

Mixed monolayers of CyA and poly(dl-lactic acid-co-glycolic acid) spread at the air/water interface were studied by measuring surface pressure (pi) as a function of the area per residue (A). The pi-A curves suggest that the components are miscible below surface pressures of 10 mN/m. Also, the diagrams obtained by plotting the mean area per residue as a function of molar fraction show positive deviations from ideal, which indicate the existence of interactions between both components in the mixed films. The nature of these interactions was influenced by the pH and temperature of the subphase; however, it was not dependent on the molecular size of the polymer. Above pi = 10 mN/m mixed monolayers showed immiscible behavior with no interactions between their components. This was manifested by the obedience to the mean area additivity rule and the same value of collapse pressure present for all mixed monolayers studied.

Surface pressure-area isotherms of mixed cyclosporin-poly(isobutylcyanoacrylate) monolayers spread at the air/water interface.

The pi-A isotherms of mixed monolayers of cyclosporin and poly(isobutylcyanoacrylate) (PIBCA) show that the molecular areas of cyclosporin and PIBCA are additive regardless of the pH of the substrate or the physical state of the monolayers. All these mixed films collapse at the same surface pressure; therefore, application of the two-dimensional phase rule implies that cyclosporin and PIBCA are immiscible at the interface. This conclusion may have important implications with regard to the formulation of PIBCA-cyclosporin nanoparticles for cyclosporin administration, though further research in this direction will require consideration of the role played by the coadjuvants used for PIBCA polymerization during nanoparticle formation.