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Sample records for commensurate monolayer films

  1. Faceting and commensurability in crystal structures of colloidal thin films.

    PubMed

    Ramiro-Manzano, F; Meseguer, F; Bonet, E; Rodriguez, I

    2006-07-14

    This Letter investigates the influence of finite size effects on the particle arrangement of thin film colloidal crystals. A rich variety of crystallographic faceting with large single domain microcrystallites is shown. Optical reflectance experiments together with scanning electron microscopy permit the identification of the crystal symmetry and the facet orientation, as well as the exact number of monolayers. When the cell thickness is not commensurable with a high symmetry layering, particles arrange themselves in a periodic distribution of (111)- and (100)-orientated face centered cubic (fcc) microcrystallites separated by planar defects. These structures can be described as a fcc ordering orientated along a vicinal surface, modified by a periodic distribution of fcc (111) stacking faults.

  2. Faceting and commensurability in crystal structures of colloidal thin films.

    PubMed

    Ramiro-Manzano, F; Meseguer, F; Bonet, E; Rodriguez, I

    2006-07-14

    This Letter investigates the influence of finite size effects on the particle arrangement of thin film colloidal crystals. A rich variety of crystallographic faceting with large single domain microcrystallites is shown. Optical reflectance experiments together with scanning electron microscopy permit the identification of the crystal symmetry and the facet orientation, as well as the exact number of monolayers. When the cell thickness is not commensurable with a high symmetry layering, particles arrange themselves in a periodic distribution of (111)- and (100)-orientated face centered cubic (fcc) microcrystallites separated by planar defects. These structures can be described as a fcc ordering orientated along a vicinal surface, modified by a periodic distribution of fcc (111) stacking faults. PMID:16907485

  3. Effective and accurate approach for modeling of commensurate-incommensurate transition in krypton monolayer on graphite.

    PubMed

    Ustinov, E A

    2014-10-01

    Commensurate-incommensurate (C-IC) transition of krypton molecular layer on graphite received much attention in recent decades in theoretical and experimental researches. However, there still exists a possibility of generalization of the phenomenon from thermodynamic viewpoint on the basis of accurate molecular simulation. Recently, a new technique was developed for analysis of two-dimensional (2D) phase transitions in systems involving a crystalline phase, which is based on accounting for the effect of temperature and the chemical potential on the lattice constant of the 2D layer using the Gibbs-Duhem equation [E. A. Ustinov, J. Chem. Phys. 140, 074706 (2014)]. The technique has allowed for determination of phase diagrams of 2D argon layers on the uniform surface and in slit pores. This paper extends the developed methodology on systems accounting for the periodic modulation of the substrate potential. The main advantage of the developed approach is that it provides highly accurate evaluation of the chemical potential of crystalline layers, which allows reliable determination of temperature and other parameters of various 2D phase transitions. Applicability of the methodology is demonstrated on the krypton-graphite system. Analysis of phase diagram of the krypton molecular layer, thermodynamic functions of coexisting phases, and a method of prediction of adsorption isotherms is considered accounting for a compression of the graphite due to the krypton-carbon interaction. The temperature and heat of C-IC transition has been reliably determined for the gas-solid and solid-solid system.

  4. Effective and accurate approach for modeling of commensurate-incommensurate transition in krypton monolayer on graphite.

    PubMed

    Ustinov, E A

    2014-10-01

    Commensurate-incommensurate (C-IC) transition of krypton molecular layer on graphite received much attention in recent decades in theoretical and experimental researches. However, there still exists a possibility of generalization of the phenomenon from thermodynamic viewpoint on the basis of accurate molecular simulation. Recently, a new technique was developed for analysis of two-dimensional (2D) phase transitions in systems involving a crystalline phase, which is based on accounting for the effect of temperature and the chemical potential on the lattice constant of the 2D layer using the Gibbs-Duhem equation [E. A. Ustinov, J. Chem. Phys. 140, 074706 (2014)]. The technique has allowed for determination of phase diagrams of 2D argon layers on the uniform surface and in slit pores. This paper extends the developed methodology on systems accounting for the periodic modulation of the substrate potential. The main advantage of the developed approach is that it provides highly accurate evaluation of the chemical potential of crystalline layers, which allows reliable determination of temperature and other parameters of various 2D phase transitions. Applicability of the methodology is demonstrated on the krypton-graphite system. Analysis of phase diagram of the krypton molecular layer, thermodynamic functions of coexisting phases, and a method of prediction of adsorption isotherms is considered accounting for a compression of the graphite due to the krypton-carbon interaction. The temperature and heat of C-IC transition has been reliably determined for the gas-solid and solid-solid system. PMID:25296827

  5. Zone-center phonons of bulk, few-layer, and monolayer 1 T -TaS2 : Detection of commensurate charge density wave phase through Raman scattering

    NASA Astrophysics Data System (ADS)

    Albertini, Oliver R.; Zhao, Rui; McCann, Rebecca L.; Feng, Simin; Terrones, Mauricio; Freericks, James K.; Robinson, Joshua A.; Liu, Amy Y.

    2016-06-01

    We present first-principles calculations of the vibrational properties of the transition-metal dichalcogenide 1 T -TaS2 for various thicknesses in the high-temperature (undistorted) phase and the low-temperature commensurate charge density wave (CDW) phase. We also present measurements of the Raman spectra for bulk, few-layer, and monolayer samples at temperatures well below that of the bulk transition to the commensurate phase. Through our calculations, we identify the low-frequency folded-back acoustic modes as a convenient signature of the commensurate CDW structure in vibrational spectra. In our measured Raman spectra, this signature is clearly evident in all of the samples, indicating that the commensurate phase remains the ground state as the material is thinned, even down to a single layer. This is in contrast to some previous studies, which suggest a suppression of the commensurate CDW transition in thin flakes. We also use polarized Raman spectroscopy to probe c -axis orbital texture in the low-T phase, which has recently been suggested to play a role in the metal-insulator transition that accompanies the structural transition to the commensurate CDW phase.

  6. Commensurability condition and hierarchy of fillings for FQHE in higher Landau levels in conventional 2DEG systems and in graphene—monolayer and bilayer

    NASA Astrophysics Data System (ADS)

    Jacak, Janusz; Jacak, Lucjan

    2016-01-01

    The structure of the filling rate hierarchy referred to as the fractional quantum Hall effect is studied in higher Landau levels using the commensurability condition. The hierarchy of fillings that are derived in this manner is consistent with the experimental observations of the first three Landau levels in conventional semiconductor Hall systems. The relative poverty of the fractional structure in higher Landau levels compared with the lowest Landau level is explained using commensurability topological arguments. The commensurability criterion for correlated states for higher Landau levels (with n≥slant 1) including the paired states at half fillings of the spin-subbands of these levels is formulated. The commensurability condition is applied to determine the hierarchy of the fractional fillings of Landau levels in the monolayer and bilayer graphene. Good agreement with current experimental observations of fractional quantum Hall effect in the graphene monolayer and bilayer is achieved. The presence of even denominator rates in the hierarchy for fractional quantum Hall effect in the bilayer graphene is also explained.

  7. Covalently networked monolayer-protected nanoparticle films.

    PubMed

    Tognarelli, D J; Miller, Robert B; Pompano, Rebecca R; Loftus, Andrew F; Sheibley, Daniel J; Leopold, Michael C

    2005-11-22

    Covalently networked films of nanoparticles can be assembled on various substrates from functionalized monolayer-protected clusters (MPCs) via ester coupling reactions. Exposure of a specifically modified substrate to alternating solutions of 11-mercaptoundecanoic acid exchanged and 11-mercaptoundecanol exchanged MPCs, in the presence of ester coupling reagents, 1,3-dicyclohexylcarbodiimide and 4-(dimethylamino)pyridine, results in the formation of a multilayer film with ester bridges between individual nanoparticles. These films can be grown in a controlled manner to various thicknesses and exhibit certain properties that are consistent with films having other types of interparticle connectivity, including chemical vapor response behavior and quantized double layer charging. Ester coupling of MPCs into assembled films is a straightforward and highly versatile approach that results in robust films that can endure harsher chemical environments than other types of films. The stability of these covalent films is assessed and compared to other more traditional MPC film assemblies.

  8. Zone-Folded Phonons and the Commensurate-Incommensurate Charge-Density-Wave Transition in 1T-TaSe2 Thin Films.

    PubMed

    Samnakay, R; Wickramaratne, D; Pope, T R; Lake, R K; Salguero, T T; Balandin, A A

    2015-05-13

    Bulk 1T-TaSe2 exhibits unusually high charge density wave (CDW) transition temperatures of 600 and 473 K below which the material exists in the incommensurate (I-CDW) and the commensurate (C-CDW) charge-density-wave phases, respectively. The (13)(1/2) × (13)(1/2) C-CDW reconstruction of the lattice coincides with new Raman peaks resulting from zone-folding of phonon modes from middle regions of the original Brillouin zone back to Γ. The C-CDW transition temperatures as a function of film thickness are determined from the evolution of these new Raman peaks, and they are found to decrease from 473 to 413 K as the film thicknesses decrease from 150 to 35 nm. A comparison of the Raman data with ab initio calculations of both the normal and C-CDW phases gives a consistent picture of the zone-folding of the phonon modes following lattice reconstruction. The Raman peak at ∼154 cm(-1) originates from the zone-folded phonons in the C-CDW phase. In the I-CDW phase, the loss of translational symmetry coincides with a strong suppression and broadening of the Raman peaks. The observed change in the C-CDW transition temperature is consistent with total energy calculations of bulk and monolayer 1T-TaSe2. PMID:25927475

  9. Sub-monolayer film growth of a volatile lanthanide complex on metallic surfaces

    PubMed Central

    Chen, Jinjie; Edelmann, Kevin; Wulfhekel, Wulf

    2015-01-01

    Summary We deposited a volatile lanthanide complex, tris(2,2,6,6-tetramethyl-3,5-heptanedionato)terbium(III), onto metal surfaces of Cu(111), Ag(111) and Au(111) in vacuum and observed well-ordered sub-monolayer films with low temperature (5 K) scanning tunneling microscopy. The films show a distorted three-fold symmetry with a commensurate structure. Scanning tunneling spectroscopy reveals molecular orbitals delocalized on the ligands of the molecule. Our results imply that this complex can be transferred onto the metal substrates without molecular decomposition or contamination of the surface. This new rare-earth-based class of molecules broadens the choice of molecular magnets to study with scanning tunneling microscopy. PMID:26733215

  10. Lateral Interactions in Monolayer Thick Mercury Films

    NASA Astrophysics Data System (ADS)

    Kime, Yolanda Jan

    An understanding of lateral adatom-adatom interactions is often an important part of understanding electronic structure and adsorption energetics in monolayer thick films. In this dissertation I use angle-resolved photoemission and thermal desorption spectroscopies to explore the relationship between the adatom-adatom interaction and other characteristics of the adlayer, such as electronic structure, defects, or coexistent structural phases in the adlayer. Since Hg binds weakly to many substrates, the lateral interactions are often a major contribution to the dynamics of the overlayer. Hg adlayer systems are thus ideal for probing lateral interactions. The electronic structures of Hg adlayers on Ag(100), Cu(100), and Cu_3Au(100) are studied with angle-resolved ultraviolet photoemission. The Hg atomic 5d_{5/2} electronic band is observed to split into two levels following adsorption onto some surfaces. The energetic splitting of the Hg 5d_{5/2} level is found to be directly correlated to the adlayer homogeneous strain energy. The existence of the split off level also depends on the order or disorder of the Hg adlayer. The energetics of Hg adsorption on Cu(100) are probed using thermal desorption spectroscopy. Two different ordered adlayer structures are observed for Hg adsorption on Cu(100) at 200 K. Under some adsorption conditions and over a range of exposures, the two phases are seen to coexist on the surface prior to the thermal desorption process. A phase transition from the more dense to the less dense phase is observed to occur during the thermal desorption process. Inherent differences in defect densities are responsible for the observed differences between lateral interactions measured previously with equilibrium (atom beam scattering) and as measured by the non-equilibrium (thermal desorption) technique reported here. Theoretical and experimental evidence for an indirect through-metal interaction between adatoms is also discussed. Although through

  11. Infrared spectroscopy of self-assembled monolayer films on silicon

    NASA Astrophysics Data System (ADS)

    Rowell, N. L.; Tay, Lilin; Boukherroub, R.; Lockwood, D. J.

    2007-07-01

    Infrared vibrational spectroscopy in an attenuated total reflection (ATR) geometry has been employed to investigate the presence of organic thin layers on Si-wafer surfaces. The phenomena have been simulated to show there can be a field enhancement with the presented single-reflection ATR (SR-ATR) approach which is substantially larger than for conventional ATR or specular reflection. In SR-ATR, a discontinuity of the field normal to the film contributes a field enhancement in the lower index thin film causing a two order of magnitude increase in sensitivity. SR-ATR was employed to characterize a single monolayer of undecylenic acid self-assembled on Si(1 1 1) and to investigate a two monolayer system obtained by adding a monolayer of bovine serum albumin protein.

  12. The influence of the surface composition of mixed monolayer films on the evaporation coefficient of water.

    PubMed

    Miles, Rachael E H; Davies, James F; Reid, Jonathan P

    2016-07-20

    We explore the dependence of the evaporation coefficient of water from aqueous droplets on the composition of a surface film, considering in particular the influence of monolayer mixed component films on the evaporative mass flux. Measurements with binary component films formed from long chain alcohols, specifically tridecanol (C13H27OH) and pentadecanol (C15H31OH), and tetradecanol (C14H29OH) and hexadecanol (C16H33OH), show that the evaporation coefficient is dependent on the mole fractions of the two components forming the monolayer film. Immediately at the point of film formation and commensurate reduction in droplet evaporation rate, the evaporation coefficient is equal to a mole fraction weighted average of the evaporation coefficients through the equivalent single component films. As a droplet continues to diminish in surface area with continued loss of water, the more-soluble, shorter alkyl chain component preferentially partitions into the droplet bulk with the evaporation coefficient tending towards that through a single component film formed simply from the less-soluble, longer chain alcohol. We also show that the addition of a long chain alcohol to an aqueous-sucrose droplet can facilitate control over the degree of dehydration achieved during evaporation. After undergoing rapid gas-phase diffusion limited water evaporation, binary aqueous-sucrose droplets show a continued slow evaporative flux that is limited by slow diffusional mass transport within the particle bulk due to the rapidly increasing particle viscosity and strong concentration gradients that are established. The addition of a long chain alcohol to the droplet is shown to slow the initial rate of water loss, leading to a droplet composition that remains more homogeneous for a longer period of time. When the sucrose concentration has achieved a sufficiently high value, and the diffusion constant of water has decreased accordingly so that bulk phase diffusion arrest occurs in the monolayer

  13. The influence of the surface composition of mixed monolayer films on the evaporation coefficient of water.

    PubMed

    Miles, Rachael E H; Davies, James F; Reid, Jonathan P

    2016-07-20

    We explore the dependence of the evaporation coefficient of water from aqueous droplets on the composition of a surface film, considering in particular the influence of monolayer mixed component films on the evaporative mass flux. Measurements with binary component films formed from long chain alcohols, specifically tridecanol (C13H27OH) and pentadecanol (C15H31OH), and tetradecanol (C14H29OH) and hexadecanol (C16H33OH), show that the evaporation coefficient is dependent on the mole fractions of the two components forming the monolayer film. Immediately at the point of film formation and commensurate reduction in droplet evaporation rate, the evaporation coefficient is equal to a mole fraction weighted average of the evaporation coefficients through the equivalent single component films. As a droplet continues to diminish in surface area with continued loss of water, the more-soluble, shorter alkyl chain component preferentially partitions into the droplet bulk with the evaporation coefficient tending towards that through a single component film formed simply from the less-soluble, longer chain alcohol. We also show that the addition of a long chain alcohol to an aqueous-sucrose droplet can facilitate control over the degree of dehydration achieved during evaporation. After undergoing rapid gas-phase diffusion limited water evaporation, binary aqueous-sucrose droplets show a continued slow evaporative flux that is limited by slow diffusional mass transport within the particle bulk due to the rapidly increasing particle viscosity and strong concentration gradients that are established. The addition of a long chain alcohol to the droplet is shown to slow the initial rate of water loss, leading to a droplet composition that remains more homogeneous for a longer period of time. When the sucrose concentration has achieved a sufficiently high value, and the diffusion constant of water has decreased accordingly so that bulk phase diffusion arrest occurs in the monolayer

  14. Heat Capacity of Dilute 3He-4He Monolayer Films

    NASA Astrophysics Data System (ADS)

    Morishita, Masashi

    2016-05-01

    The heat capacities of a small amount of 3He dissolved in monolayer 4He films are measured to clarify natures of monolayer 4He films. With increasing areal density, the measured heat capacities gradually increase and subsequently gradually decrease. With further increase in areal density, the measured heat capacity rapidly decreases to zero over a very narrow areal density range near that of the sqrt{3} × sqrt{3} phase. These slightly complex areal-density variations and dependence on 3He concentration are discussed from the viewpoint of the known properties of 4He films. The behaviors can be explained. However, the expected two-dimensional gas-liquid or gas-solid coexistence is not observed in this study.

  15. Monolayer-Mediated Patterning of Electroceramic Thin Films

    SciTech Connect

    Clem, P.G.; Payne, D.A.

    1998-10-11

    Integrated electroceramic thin film devices on semiconductor and insulator substrates feature a variety of attractive attributes, including high capacitance density, nonvolatile memory, sensor/actuator ability, and other unique electronic and optical properties. The ability to pattern such ceramic materials atop semiconductor substrates, thus, is a critical technology. Patterned oxide thin film devices are typically formed by uniform film deposition followed by somewhat complicated post-deposition ion-beam or chemical etching in a controlled environment. We review here the development of an ambient atmosphere technique which allows selective deposition of electroceramic thin layers without such post-deposition etching. In this method, substrate surfaces are selectively functionalized with hydrophobic self-assembled monolayer to modify the adhesion of subsequently deposited solution-derived electroceramics. The selective fictionalization is achieved through microcontact printing (v-CP) of self-assembled monolayer of the chemical octadecyltrichlorosilane on substrates of technical interest. Subsequent sol-gel deposition of ceramic oxides on these functionalized substrates, followed by lift-off from the monolayer, yields high quality, patterned oxide thin layers only on the unfunctionalized regions. A variety of micron- scale dielectric oxide devices have been fabricated using this process, with lateral resolution as fine as 0.5Lm. In this paper, we review the monolayer patterning and electrical behavior of several patterned electroceramic thin films, including Pb(Zr,Ti)03 [PZT], LiNb03, and Ta205. An applied device example is also presented in combination with selective MOCVD deposition of metal electrodes: integrated, fully monolayer-patterned Pt//PZT//PSi(Si(100) ferroelectric memory cells.

  16. Controlled electrodeposition of Au monolayer film on ionic liquid

    NASA Astrophysics Data System (ADS)

    Ma, Qiang; Pang, Liuqing; Li, Man; Zhang, Yunxia; Ren, Xianpei; Liu, Shengzhong Frank

    2016-05-01

    Gold (Au) nanoparticles have been attractive for centuries for their vibrant appearance enhanced by their interaction with sunlight. Nowadays, there have been tremendous research efforts to develop them for high-tech applications including therapeutic agents, sensors, organic photovoltaics, medical applications, electronics and catalysis. However, there remains to be a challenge to fabricate a monolayer Au coating with complete coverage in controlled fashion. Here we present a facile method to deposit a uniform Au monolayer (ML) film on the [BMIM][PF6] ionic liquid substrate using an electrochemical deposition process. It demonstrates that it is feasible to prepare a solid phase coating on the liquid-based substrate. Moreover, the thickness of the monolayer coating can be controlled to a layer-by-layer accuracy.

  17. Phase behavior of mixed Ar-Kr, Ar-Xe and Kr-Xe monolayer films on graphite: a Monte Carlo study.

    PubMed

    Patrykiejew, A

    2013-01-01

    Using Monte Carlo simulation methods in the grand canonical ensemble we have studied the behavior of mixed Ar-Kr, Ar-Xe and Kr-Xe monolayer films on the graphite basal plane. We have considered the adsorption of the lighter component, either argon or krypton, under the condition of a fixed chemical potential of the heavier component (krypton or xenon), as well as on the graphite surface with preadsorbed small amounts of a heavier noble gas. In both types of simulation the composition of the adsorbed layer is not conserved. We discuss the phase behavior of mixed films emerging from both types of 'computer experiment'. We also demonstrate that Monte Carlo simulation allows us to estimate the effects of preadsorbed xenon on the commensurate-incommensurate transition in the krypton monolayer film and gives the results that are in good quantitative agreement with experimental data.

  18. Ubiquitous pentacene monolayer on metals deposited onto pentacene films.

    PubMed

    Jaeckel, B; Sambur, J B; Parkinson, B A

    2007-11-01

    Photoelectron spectroscopy (XPS and UPS) was used to study the deposition of metal layers (Ag, Cu, and Au) onto pentacene films. Very low work functions were measured (PhiAg = 3.91 eV, PhiCu = 3.93 eV, and PhiAu = 4.3 eV) for all of the metals, in agreement with results from the literature. The intensities of the C 1s core-level signals from pentacene that were monitored during stepwise metal deposition leveled off at a value of about 30% of a thick pentacene film. This C 1s intensity is comparable to that of one monolayer of pentacene deposited onto the respective metal. The valence band spectra of metals deposited onto pentacene and spectra collected for pentacene deposited onto bare metal surfaces are very similar. These findings lead to the conclusion that approximately one monolayer of pentacene is always present on top of the freshly deposited metal film, which explains the very low work function of the metals when they are deposited onto organic films. We expect similar behavior with other nonreactive metals deposited onto stable organic layers.

  19. Surface energetics of freely suspended fluid molecular monolayer and multilayer smectic liquid crystal films

    PubMed Central

    Nguyen, Zoom Hoang; Park, Cheol Soo; Pang, Jinzhong; Clark, Noel A.

    2012-01-01

    A study of the surface energetics of the thinnest substrate-free liquid films, fluid molecular monolayer and multilayer smectic liquid crystal films suspended in air, is reported. In films having monolayer and multilayer domains, the monolayer areas contract, contrary to predictions from the van der Waals disjoining pressure of thin uniform slabs. This discrepancy is accounted for by modeling the environmental asymmetry of the surface layers in multilayer films, leading to the possibility that preferential end-for-end polar ordering of the rod shaped molecules can reduce the surface energy of multilayers relative to that of the monolayer, which is inherently symmetric. PMID:22826264

  20. Control of Magnetic Order in Monolayer Films by Substrate Tuning

    NASA Astrophysics Data System (ADS)

    Heinze, Stefan; Ferriani, Paolo; Turek, Ilja; Bihlmayer, Gustav; Blügel, Stefan

    2007-03-01

    Surprisingly, antiferromagnetic order has recently been observed in a monolayer (ML) film of Fe on W(001) [1] and a novel, nanoscale magnetic structure has been discovered for a ML Fe on Ir(111) [2] showing the crucial influence of the substrate. Here, we therefore propose to tailor exchange interactions in magnetic monolayer films by tuning the adjacent non-magnetic substrate. Using first-principles calculations based on density functional theory, we demonstrate a ferromagnetic-antiferromagnetic phase transition for one ML Fe on a Tax W1-x(001) surface as a function of the Ta concentration. At the Ta concentration of the transition, the nearest-neighbor exchange interaction becomes negligible and exchange terms beyond nearest-neighbors and higher order spin interactions beyond the Heisenberg Hamiltonian become crucial. In this regime, the accessible magnetic phase space is dramatically enhanced, and we study complex magnetic order such as spin-spiral states, multiple-q states, or even disordered local moment states. [1] A. Kubetzka, et al., Phys. Rev. Lett.94, 087204 (2005). [2] K. von Bergmann, et al., Phys. Rev.Lett. 96, 167203 (2006).

  1. Particle zips: vertical emulsion films with particle monolayers at their surfaces.

    PubMed

    Horozov, Tommy S; Aveyard, Robert; Clint, John H; Neumann, Bernd

    2005-03-15

    Vertical emulsion films with particle monolayers at their surfaces have been studied by direct microscope observations. The effects of particle wettability and surface coverage on the structure and stability of water films in octane and octane films in water have been investigated. Monodisperse silica particles (3 microm in diameter) hydrophobized to different extents have been used. It is found that the structure and stability of emulsion films strongly depend on the film type (water-in-oil or oil-in-water), the particle contact angle, the interactions between particles from the same and the opposite monolayer, and the monolayer density. Stable films are observed only when the particle wettability fulfills the condition for stable particle bridges--in agreement with the concept that hydrophilic particles can give stable oil-in-water emulsions, whereas hydrophobic ones give water-in-oil emulsions. In the case of water films with dilute disordered monolayers at their surfaces, the hydrophilic particles are expelled from the film center toward its periphery, giving a dimple surrounded by a ring of particles bridging the film surfaces. In contrast, the thinning of octane films with dilute ordered monolayers at their surfaces finally leads to the spontaneous formation of a dense crystalline monolayer of hydrophobic particles bridging both surfaces at the center of the film. The behaviors of water and octane films with dense close-packed particle monolayers at their surfaces are very similar. In both cases, a transition from bilayer to bridging monolayer is observed at rather low capillary pressures. The implications of the above finding for particle stabilized emulsions are discussed.

  2. Monolayer graphene films through nickel catalyzed transformation of fullerol and graphene quantum dots: a Raman spectroscopy study

    NASA Astrophysics Data System (ADS)

    Prekodravac, J. R.; Jovanović, S. P.; Holclajtner-Antunović, I. D.; Peruško, D. B.; Pavlović, V. B.; Tošić, D. D.; Todorović-Marković, B. M.; Marković, Z. M.

    2014-09-01

    In this paper we present synthesis of monolayer graphene islands. These films are deposited through nickel catalyzed transformation of fullerol and graphene quantum dots. Carbon doped nickel films are produced by autocatalytic chemical deposition. Upon rapid thermal annealing, graphene films are formed. Different characterization techniques are applied: Raman spectroscopy, scanning electron and atomic force microscopy. Raman spectroscopy analysis confirmed the formation of monolayer graphene films. Microscopy analysis revealed formation of monolayer islands.

  3. Superconducting Gap Anisotropy in Monolayer FeSe Thin Film.

    PubMed

    Zhang, Y; Lee, J J; Moore, R G; Li, W; Yi, M; Hashimoto, M; Lu, D H; Devereaux, T P; Lee, D-H; Shen, Z-X

    2016-09-01

    Superconductivity originates from pairing of electrons near the Fermi energy. The Fermi surface topology and pairing symmetry are thus two pivotal characteristics of a superconductor. Superconductivity in one monolayer (1 ML) FeSe thin film has attracted great interest recently due to its intriguing interfacial properties and possibly high superconducting transition temperature over 65 K. Here, we report high-resolution measurements of the Fermi surface and superconducting gaps in 1 ML FeSe using angle-resolved photoemission spectroscopy. Two ellipselike electron pockets are clearly resolved overlapping with each other at the Brillouin zone corner. The superconducting gap is nodeless but moderately anisotropic, which puts strong constraint on determining the pairing symmetry. The gap maxima locate on the d_{xy} bands along the major axis of the ellipse and four gap minima are observed at the intersections of electron pockets. The gap maximum location combined with the Fermi surface geometry deviate from a single d-wave, extended s-wave or s_{±} gap function, suggesting an important role of the multiorbital nature of Fermi surface and orbital-dependent pairing in 1 ML FeSe. The gap minima location may be explained by a sign change on the electron pockets, or a competition between intra- and interorbital pairing. PMID:27661715

  4. Superconducting Gap Anisotropy in Monolayer FeSe Thin Film

    NASA Astrophysics Data System (ADS)

    Zhang, Y.; Lee, J. J.; Moore, R. G.; Li, W.; Yi, M.; Hashimoto, M.; Lu, D. H.; Devereaux, T. P.; Lee, D.-H.; Shen, Z.-X.

    2016-09-01

    Superconductivity originates from pairing of electrons near the Fermi energy. The Fermi surface topology and pairing symmetry are thus two pivotal characteristics of a superconductor. Superconductivity in one monolayer (1 ML) FeSe thin film has attracted great interest recently due to its intriguing interfacial properties and possibly high superconducting transition temperature over 65 K. Here, we report high-resolution measurements of the Fermi surface and superconducting gaps in 1 ML FeSe using angle-resolved photoemission spectroscopy. Two ellipselike electron pockets are clearly resolved overlapping with each other at the Brillouin zone corner. The superconducting gap is nodeless but moderately anisotropic, which puts strong constraint on determining the pairing symmetry. The gap maxima locate on the dx y bands along the major axis of the ellipse and four gap minima are observed at the intersections of electron pockets. The gap maximum location combined with the Fermi surface geometry deviate from a single d -wave, extended s -wave or s± gap function, suggesting an important role of the multiorbital nature of Fermi surface and orbital-dependent pairing in 1 ML FeSe. The gap minima location may be explained by a sign change on the electron pockets, or a competition between intra- and interorbital pairing.

  5. Self-assembly of defect-free particle monolayers on flexible films

    NASA Astrophysics Data System (ADS)

    Hossain, Md. Shahadat; Dalal, Bhavin; Gurupatham, Sathishkumar; Fischer, Ian; Singh, Pushpendra; Aubry, Nadine

    2013-03-01

    We have recently shown that the capillarity-based process for self-assembling particle monolayers on fluid-liquid interfaces can be improved by applying an electric field in the direction normal to the interface. The electric field gives rise to repulsive dipole-dipole forces amongst the particles causing them to move apart, and thus allowing them to move freely without blocking one another. The latter is important in the formation of virtually defect-free monolayers with long-range order. In this talk, we present a technique for freezing these expanded monolayers onto the surface of a flexible thin film. The technique involves assembling the monolayer on the interface between a UV-curable resin and a fluid which can be air or another liquid, and then curing the resin by applying UV light. The monolayer becomes embedded on the surface of the solidified resin film.

  6. Morphology and Composition of Structured, Phase-Separated Behenic Acid-Perfluorotetradecanoic Acid Monolayer Films.

    PubMed

    Rehman, Jeveria; Araghi, Hessamaddin Younesi; He, Anqiang; Paige, Matthew F

    2016-05-31

    The phase separation of immiscible surfactants in mixed monolayer films provides an approach to physically manipulate important properties of thin films, including surface morphology, microscale composition, and mechanical properties. In this work, we predict, based upon existing miscibility studies and their thermodynamic underpinnings described in the literature, the miscibility and film morphology of mixed monolayers comprised of behenic acid (C21H43COOH) and perfluorotetradecanoic acid (C13F27COOH) in various molar ratios. Predictions are tested using a combination of experimental surface characterization methods for probing miscibility and film morphology at the solid/air and air/water interfaces. Film components were immiscible and phase-separated into chemically well-defined domains under a variety of experimental conditions, with monolayer morphology consistent with initial predictions. The extensibility of these basic predictions to other systems is discussed in the context of using these works for different perfluorinated surfactant molecules. PMID:27163482

  7. Functionalized self-assembled monolayers as templates for mineral oxide thin film deposition

    NASA Astrophysics Data System (ADS)

    Collins, Rochael Jeannine

    Alkyl-trichlorosilanes functionalized with thioacetate and nitrate groups were synthesized and deposited to form Self-Assembled Monolayers (SAMs). In situ transformation of the thioacetate and nitrate moieties yielded monolayers functionalized with sulfonate and alcohol groups, respectively. Percent conversion was determined to be 98% by X-ray photoelectron spectroscopy (XPS) for the thioacetate to sulfonate transformation, and 100% by XPS and IR for the nitrate to alcohol transformation. The as-deposited and transformed monolayers were characterized by wettability, XPS and ellipsometry. The alcohol terminated films were investigated as templates for the deposition of subsequent self-assembled monolayers. Multilayers, up to three layers, were demonstrated for nitrate films, with each layer adding an average of 2.25 nm to the overall film thickness. A fourth layer of octadecyltrichlorosilane was deposited and was found to add an additional 1.31 nm to the structure. Analysis of the multilayer constructions revealed increasing disorder as the number of layers increases. Other in situ functionalizations of alcohol terminated monolayers were demonstrated. Transformation to electrophilic, haloacetyl films was accomplished, and their reactivity with thiol nucleophiles was examined. In addition, the alcohol terminated SAMs were functionalized, in situ, with sulfate and phosphate groups. These films were characterized by wettability, XPS and ellipsometry. Furthermore, photopatterning of terminal functional groups was accomplished by irradiation through a mask. Patterned monolayers consisting of regions of thioacetate (masked)/sulfonate (irradiated) and nitrate (masked)/alcohol (irradiated) were demonstrated. Characterization of the patterned monolayers was carried out by XPS and SEM. A variety of terminal functional groups on the SAM were investigated as templates for bioinspired deposition of mineral oxide films. Thin films of FeOOH, SiOsb2,\\ TiOsb2,\\ Ysb2Osb3,\\ ZrOsb2

  8. Monolayer-Mediated Growth of Organic Semiconductor Films with Improved Device Performance.

    PubMed

    Huang, Lizhen; Hu, Xiaorong; Chi, Lifeng

    2015-09-15

    Increased interest in wearable and smart electronics is driving numerous research works on organic electronics. The control of film growth and patterning is of great importance when targeting high-performance organic semiconductor devices. In this Feature Article, we summarize our recent work focusing on the growth, crystallization, and device operation of organic semiconductors intermediated by ultrathin organic films (in most cases, only a monolayer). The site-selective growth, modified crystallization and morphology, and improved device performance of organic semiconductor films are demonstrated with the help of the inducing layers, including patterned and uniform Langmuir-Blodgett monolayers, crystalline ultrathin organic films, and self-assembled polymer brush films. The introduction of the inducing layers could dramatically change the diffusion of the organic semiconductors on the surface and the interactions between the active layer with the inducing layer, leading to improved aggregation/crystallization behavior and device performance. PMID:25992464

  9. Strictly monolayer large continuous MoS2 films on diverse substrates and their luminescence properties

    NASA Astrophysics Data System (ADS)

    Mohapatra, P. K.; Deb, S.; Singh, B. P.; Vasa, P.; Dhar, S.

    2016-01-01

    Despite a tremendous interest on molybdenum disulfide as a thinnest direct band gap semiconductor, single step synthesis of a large area purely monolayer MoS2 film has not yet been reported. Here, we report a CVD route to synthesize a continuous film of strictly monolayer MoS2 covering an area as large as a few cm2 on a variety of different substrates without using any seeding material or any elaborate pretreatment of the substrate. This is achieved by allowing the growth to take place in the naturally formed gap between a piece of SiO2 coated Si wafer and the substrate, when the latter is placed on top of the former inside a CVD reactor. We propose a qualitative model to explain why the MoS2 films are always strictly monolayer in this method. The photoluminescence study of these monolayers shows the characteristic excitonic and trionic features associated with monolayer MoS2. In addition, a broad defect related luminescence band appears at ˜1.7 eV. As temperature decreases, the intensity of this broad feature increases, while the band edge luminescence reduces.

  10. Comparative study of normal and branched alkane monolayer films adsorbed on a solid surface. I. Structure

    NASA Astrophysics Data System (ADS)

    Enevoldsen, A. D.; Hansen, F. Y.; Diama, A.; Criswell, L.; Taub, H.

    2007-03-01

    The structure of a monolayer film of the branched alkane squalane (C30H62) adsorbed on graphite has been studied by neutron diffraction and molecular dynamics (MD) simulations and compared with a similar study of the n-alkane tetracosane (n-C24H52). Both molecules have 24 carbon atoms along their backbone and squalane has, in addition, six methyl side groups. Upon adsorption, there are significant differences as well as similarities in the behavior of these molecular films. Both molecules form ordered structures at low temperatures; however, while the melting point of the two-dimensional (2D) tetracosane film is roughly the same as the bulk melting point, the surface strongly stabilizes the 2D squalane film such that its melting point is 91K above its value in bulk. Therefore, squalane, like tetracosane, will be a poor lubricant in those nanoscale devices that require a fluid lubricant at room temperature. The neutron diffraction data show that the translational order in the squalane monolayer is significantly less than in the tetracosane monolayer. The authors' MD simulations suggest that this is caused by a distortion of the squalane molecules upon adsorption on the graphite surface. When the molecules are allowed to relax on the surface, they distort such that all six methyl groups point away from the surface. This results in a reduction in the monolayer's translational order characterized by a decrease in its coherence length and hence a broadening of the diffraction peaks. The MD simulations also show that the melting mechanism in the squalane monolayer is the same footprint reduction mechanism found in the tetracosane monolayer, where a chain melting drives the lattice melting.

  11. Comparative study of normal and branched alkane monolayer films adsorbed on a solid surface. I. Structure.

    PubMed

    Enevoldsen, A D; Hansen, F Y; Diama, A; Criswell, L; Taub, H

    2007-03-14

    The structure of a monolayer film of the branched alkane squalane (C30H62) adsorbed on graphite has been studied by neutron diffraction and molecular dynamics (MD) simulations and compared with a similar study of the n-alkane tetracosane (n-C24H52). Both molecules have 24 carbon atoms along their backbone and squalane has, in addition, six methyl side groups. Upon adsorption, there are significant differences as well as similarities in the behavior of these molecular films. Both molecules form ordered structures at low temperatures; however, while the melting point of the two-dimensional (2D) tetracosane film is roughly the same as the bulk melting point, the surface strongly stabilizes the 2D squalane film such that its melting point is 91 K above its value in bulk. Therefore, squalane, like tetracosane, will be a poor lubricant in those nanoscale devices that require a fluid lubricant at room temperature. The neutron diffraction data show that the translational order in the squalane monolayer is significantly less than in the tetracosane monolayer. The authors' MD simulations suggest that this is caused by a distortion of the squalane molecules upon adsorption on the graphite surface. When the molecules are allowed to relax on the surface, they distort such that all six methyl groups point away from the surface. This results in a reduction in the monolayer's translational order characterized by a decrease in its coherence length and hence a broadening of the diffraction peaks. The MD simulations also show that the melting mechanism in the squalane monolayer is the same footprint reduction mechanism found in the tetracosane monolayer, where a chain melting drives the lattice melting.

  12. Rapid permeation measurement system for the production control of monolayer and multilayer films

    NASA Astrophysics Data System (ADS)

    Botos, J.; Müller, K.; Heidemeyer, P.; Kretschmer, K.; Bastian, M.; Hochrein, T.

    2014-05-01

    Plastics have been used for packaging films for a long time. Until now the development of new formulations for film applications, including process optimization, has been a time-consuming and cost-intensive process for gases like oxygen (O2) or carbon dioxide (CO2). By using helium (He) the permeation measurement can be accelerated from hours or days to a few minutes. Therefore a manometric measuring system for tests according to ISO 15105-1 is coupled with a mass spectrometer to determine the helium flow rate and to calculate the helium permeation rate. Due to the accelerated determination the permeation quality of monolayer and multilayer films can be measured atline. Such a system can be used to predict for example the helium permeation rate of filled polymer films. Defined quality limits for the permeation rate can be specified as well as the prompt correction of process parameters if the results do not meet the specification. This method for process control was tested on a pilot line with a corotating twin-screw extruder for monolayer films. Selected process parameters were varied iteratively without changing the material formulation to obtain the best process parameter set and thus the lowest permeation rate. Beyond that the influence of different parameters on the helium permeation rate was examined on monolayer films. The results were evaluated conventional as well as with artificial neuronal networks in order to determine the non-linear correlation between all process parameters.

  13. Cholesterol mediates chitosan activity on phospholipid monolayers and Langmuir-Blodgett films.

    PubMed

    Pavinatto, Felippe J; Pacholatti, Cauê P; Montanha, Erica A; Caseli, Luciano; Silva, Heurison S; Miranda, Paulo B; Viitala, Tapani; Oliveira, Osvaldo N

    2009-09-01

    The polysaccharide chitosan has been largely used in many biological applications as a fat and cholesterol reducer, bactericide agent, and wound healing material. While the efficacy for some of such uses is proven, little is known about the molecular-level interactions involved in these applications. In this study, we employ mixed Langmuir and Langmuir-Blodgett (LB) films of negatively charged dimyristoyl phosphatidic acid (DMPA) and cholesterol as cell membrane models to investigate the role of cholesterol in the molecular-level action of chitosan. Chitosan does not remove cholesterol from the monolayer. The interaction with chitosan tends to expand the DMPA monolayer due to its interpenetration within the film. On the other hand, cholesterol induces condensation of the DMPA monolayer. The competing effects cause the surface pressure isotherms of mixed DMPA-cholesterol films on a chitosan subphase to be unaffected by the cholesterol mole fraction, due to distinct degrees of chitosan penetration into the film in the presence of cholesterol. By combining polarization-modulated infrared reflection absorption spectroscopy (PM-IRRAS) and sum-frequency generation spectroscopy (SFG), we showed that chitosan induces order into negatively charged phospholipid layers, whereas the opposite occurs for cholesterol. In conclusion, chitosan has its penetration in the film modulated by cholesterol, and electrostatic interactions with negatively charged phospholipids, such as DMPA, are crucial for the action of chitosan.

  14. Novel top-contact monolayer pentacene-based thin-film transistor for ammonia gas detection.

    PubMed

    Mirza, Misbah; Wang, Jiawei; Li, Dexing; Arabi, S Atika; Jiang, Chao

    2014-04-23

    We report on the fabrication of an organic field-effect transistor (OFET) of a monolayer pentacene thin film with top-contact electrodes for the aim of ammonia (NH3) gas detection by monitoring changes in its drain current. A top-contact configuration, in which source and drain electrodes on a flexible stamp [poly(dimethylsiloxane)] were directly contacted with the monolayer pentacene film, was applied to maintain pentacene arrangement ordering and enhance the monolayer OFET detection performance. After exposure to NH3 gas, the carrier mobility at the monolayer OFET channel decreased down to one-third of its original value, leading to a several orders of magnitude decrease in the drain current, which tremendously enhanced the gas detection sensitivity. This sensitivity enhancement to a limit of the 10 ppm level was attributed to an increase of charge trapping in the carrier channel, and the amount of trapped states was experimentally evaluated by the threshold voltage shift induced by the absorbed NH3 molecular analyte. In contrast, a conventional device with a 50-nm-thick pentacene layer displayed much higher mobility but lower response to NH3 gas, arising from the impediment of analyte penetrating into the conductive channel, owing to the thick pentacene film.

  15. Wafer-Scale Monolayer Films of Semiconducting Metal Dichalcogenides for High-Performance Electronics

    NASA Astrophysics Data System (ADS)

    Xie, Saien; Kang, Kibum; Huang, Lujie; Han, Yimo; Huang, Pinshane; Mak, Kin Fai; Kim, Cheol-Joo; Muller, David; Park, Jiwoong

    2015-03-01

    Two-dimensional semiconducting transition metal dichalcogenides (TMDs) have shown their potential in electronics, optoelectronic and valleytronis. However, large-scale growth methods reported to date have only produced materials with limited structural and electrical uniformity, hindering further technological applications. Here we present a 4-inch scale growth of continuous monolayer molybdenum disulfide (MoS2) and tungsten disulfide (WS2) films that show excellent structural and electrical uniformity over the entire wafer using metal-organic chemical vapor deposition. The resulting monolayer films show high mobility of 30 cm2/Vs at room temperature, as well as the phonon-limited transport for MoS2, regardless of the channel length and device location. They allow for the batch fabrication of monolayer MoS2 field effect transistors with a 99% yield, which display spatially-uniform n-type transistor operation with a high on/off ratio. We further demonstrate the multi-level growth and fabrication of vertically-stacked monolayer MoS2 films and devices, which could enable the development of novel three-dimensional circuitry and device integration.

  16. Self-assembled monolayer films of C[sub 60]/on cysteamine-modified gold

    SciTech Connect

    Caldwell, W.B.; Chen, K.; Mirkin, C.A.; Babinec, S.J. Dow Chemical Company, Midland, MI )

    1993-08-01

    Self-assembled monolayer films (SAMs) of C[sub 60] on cysteamine-modified and cysteamine/ethanethiol-modified Au are reported. The monolayers were characterized via contact angle measurements, X-ray photoelectron spectroscopy, electrochemistry, and quartz crystal microbalance (QCM) measurements. C[sub 60] surface coverage (2.0 [times] 10[sup [minus]10] mol/cm[sup 2]) for a film formed on pure cysteamine was determined by QCM measurements and compares remarkably well with monolayer coverage (1.9 [times] 10[sup [minus]10] mol/cm[sup 2]) predicted by a model based on crystallographic data for C[sub 60]. These experiments demonstrate the utility of the QCM in characterizing and monitoring the growth of fullerene SAMs. C[sub 60] SAMs formed on pure cysteamine yield strikingly different electrochemical responses than those formed on prelayers consisting of varying ratios of ethanethiol and cysteamine and previously reported monolayers of C[sub 60] on (aminopropyl)silanized oxide surfaces. Although the C[sub 60] SAMs are stable under ambient conditions, the fullerenes may be desorbed from the surface through electrochemical reduction of the films for extended periods of time (> 10 min). 11 refs., 2 figs.

  17. Manipulating the Assembly of Spray-Deposited Nanocolloids: In Situ Study and Monolayer Film Preparation.

    PubMed

    Zhang, Peng; Santoro, Gonzalo; Yu, Shun; Vayalil, Sarathlal K; Bommel, Sebastian; Roth, Stephan V

    2016-05-01

    Fabrication of nanoparticle arrays on a substrate is one of the most concerned aspects for manipulating assembly of nanoparticles and preparing functional nanocomposites. Here, we studied in situ the assembly kinetics of polystyrene nanocolloids by using grazing incidence small-angle X-ray scattering. The structure formation of the nanoparticle film is monitored during air-brush spraying, which provides a rapid and scalable preparation. By optimizing the substrate temperature, the dispersion of the nanocolloids can be tailored to prepare monolayer film. The success of the monolayer preparations is attributed to the fast solvent evaporation which inhibits the aggregation of the nanocolloids. The present study may open a new avenue for the manufacture-friendly preparation of well-dispersed nanoparticle thin films. PMID:27070283

  18. Polymorphism of dioctyl-terthiophene within thin films: The role of the first monolayer

    NASA Astrophysics Data System (ADS)

    Lercher, Christoph; Röthel, Christian; Roscioni, Otello Maria; Geerts, Yves Henri; Shen, Quan; Teichert, Christian; Fischer, Roland; Leising, Günther; Sferrazza, Michele; Gbabode, Gabin; Resel, Roland

    2015-06-01

    The origins of specific polymorphic phases within thin films are still not well understood. The polymorphism of the molecule dioctyl-terthiophene is investigated during the presence of a silicon-oxide surface during the crystallisation process. It is found that a monolayer of molecules forms two-dimensional crystals on the surface. In the case of thicker films crystalline islands are formed, a comparison of the three polymorphic phases observed within thin films and the thermodynamically more stable single crystal phases reveals distinct differences which can be related to an adaption of the molecular packing with the flat surface of the substrate.

  19. ADO-phosphonic acid self-assembled monolayer modified dielectrics for organic thin film transistors

    NASA Astrophysics Data System (ADS)

    Zhefeng, Li; Xianye, Luo

    2014-10-01

    This study explores a strategy of using the phosphonic acid derivative (11-((12-(anthracen-2-yl)dodecyl)oxy)-11-oxoundecyl) phosphonic acid (ADO-phosphonic acid) as self-assembled monolayers (SAMs) on a Si/SiO2 surface to induce the crystallization of rubrene in vacuum deposited thin film transistors, which showed a field-effect mobility as high as 0.18 cm2/(V·s). It is found that ADO-phosphonic acid SAMs play a unique role in modulating the morphology of rubrene to form a crystalline film in the thin-film transistors.

  20. Efficient Lateral Electron Transport inside a Monolayer of Aromatic Amines Anchored on Nanocrystalline Metal Oxide Films.

    PubMed

    Bonhôte, P; Gogniat, E; Tingry, S; Barbé, C; Vlachopoulos, N; Lenzmann, F; Comte, P; Grätzel, M

    1998-02-26

    A monolayer of a phosphonated triarylamine adsorbed on nanocrystalline TiO2, ZrO2, or Al2O3 film deposited on conducting glass displays reversible electrochemical and electrochromic behavior although the redox potential of the electroactive molecules (0.80 V vs NHE) lies in the forbidden band of the semiconducting or insulating oxides. The mechanism of charge transport was found to involve hole injection from the conducting support followed by lateral electron hopping within the monolayer. The apparent diffusion coefficient ranged from 2.8 × 10(-12) m(2) s(-1) in the neat 1-ethyl-2-methylimidazolium bis(trifluoromethylsulfonyl)imide (EtMeIm(+)Tf2N(-)) to 1.1 × 10(-11) m(2) s(-1) in acetonitrile + 2 M EtMeIm(+)Tf2N(-). A percolation threshold for electronic conductivity was found at a surface coverage corresponding to 50% of a full monolayer. PMID:27577008

  1. Sputtering and secondary ion emission properties of alkali metal films and adsorbed monolayers

    SciTech Connect

    Krauss, A R; Gruen, D M

    1980-01-01

    The secondary ion emission of alkali metal adsorbed monlayer and multilayer films has been studied. Profiling with sub-monolayer resolution has been performed by Auger, x-ray photoemission and secondary ion mass spectroscopy. Characteristic differences in the sputtering yields, and ion fraction have been observed which are associated with both the surface bonding properties and the mechanism leading to the formation of secondary ions. By sputtering with a negative bias applied to the sample, positive secondary ions are returned to the surface, resulting in a reduced sputter-induced erosion rate. Comparison with the results obtained with K and Li overlayers sputtered without sample bias provides an experimental value of both the total and secondary ion sputtering yields. The first and second monolayers can be readily identified and the first monolayer exhibits a lower sputtering yield and higher secondary ion fraction. This result is related to adsorption theory and measured values are compared with those obtained by thermal desorption measurements.

  2. Substrate control for large area continuous films of monolayer MoS2 by atmospheric pressure chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Wang, Shanshan; Pacios, Merce; Bhaskaran, Harish; Warner, Jamie H.

    2016-02-01

    Growing monolayer MoS2 films that are continuous with large domain sizes by chemical vapor deposition is one of the major challenges in 2D materials research at the moment. Here, we explore how atmospheric pressure CVD can be used to grow centimeter scale continuous films of monolayer MoS2 films directly on Si substrates with an oxide layer whilst also obtaining large domain sizes exceeding 20 μm within the films. This is achieved by orientating the growth substrate in a vertical position to improve the uniformity of precursor feed-stock compared to horizontally orientated growth substrates. This leads to continuous films of monolayer MoS2 over a significantly larger area without the need for low-pressure vacuum systems or volatile precursors. This provides important insights into novel approaches for maximizing domain sizes within MoS2 films, with concomitant large area uniform coverage.

  3. Substrate control for large area continuous films of monolayer MoS2 by atmospheric pressure chemical vapor deposition.

    PubMed

    Wang, Shanshan; Pacios, Merce; Bhaskaran, Harish; Warner, Jamie H

    2016-02-26

    Growing monolayer MoS2 films that are continuous with large domain sizes by chemical vapor deposition is one of the major challenges in 2D materials research at the moment. Here, we explore how atmospheric pressure CVD can be used to grow centimeter scale continuous films of monolayer MoS2 films directly on Si substrates with an oxide layer whilst also obtaining large domain sizes exceeding 20 μm within the films. This is achieved by orientating the growth substrate in a vertical position to improve the uniformity of precursor feed-stock compared to horizontally orientated growth substrates. This leads to continuous films of monolayer MoS2 over a significantly larger area without the need for low-pressure vacuum systems or volatile precursors. This provides important insights into novel approaches for maximizing domain sizes within MoS2 films, with concomitant large area uniform coverage.

  4. Single Crystalline Film of Hexagonal Boron Nitride Atomic Monolayer by Controlling Nucleation Seeds and Domains

    PubMed Central

    Wu, Qinke; Park, Ji-Hoon; Park, Sangwoo; Jung, Seong Jun; Suh, Hwansoo; Park, Noejung; Wongwiriyapan, Winadda; Lee, Sungjoo; Lee, Young Hee; Song, Young Jae

    2015-01-01

    A monolayer hexagonal boron nitride (h-BN) film with controllable domain morphology and domain size (varying from less than 1 μm to more than 100 μm) with uniform crystalline orientation was successfully synthesized by chemical vapor deposition (CVD). The key for this extremely large single crystalline domain size of a h-BN monolayer is a decrease in the density of nucleation seeds by increasing the hydrogen gas flow during the h-BN growth. Moreover, the well-defined shape of h-BN flakes can be selectively grown by controlling Cu-annealing time under argon atmosphere prior to h-BN growth, which provides the h-BN shape varies in triangular, trapezoidal, hexagonal and complex shapes. The uniform crystalline orientation of h-BN from different nucleation seeds can be easily confirmed by polarized optical microscopy (POM) with a liquid crystal coating. Furthermore, seamlessly merged h-BN flakes without structural domain boundaries were evidence by a selective hydrogen etching after a full coverage of a h-BN film was achieved. This seamless large-area and atomic monolayer of single crystalline h-BN film can offer as an ideal and practical template of graphene-based devices or alternative two-dimensional materials for industrial applications with scalability. PMID:26537788

  5. Biotinylated polyalkylthiophene thin films and monolayers that specifically incorporate phycobiliproteins: toward smart materials

    NASA Astrophysics Data System (ADS)

    Ayyagari, Madhu S. R.; Pande, Rajiv; Lim, Jeong O.; Kamath, Manohar; Beladakere, Nagendra; Gao, Harry H.; Marx, Kenneth A.; Tripathy, Sukant K.; Kumar, Jayant; Samuelson, Lynne A.; Akkara, Joseph A.; Kaplan, David L.

    1994-05-01

    We are investigating thin film and monolayer systems that involve conjugated conducting polymers and specific biological macromolecules. One class of conducting polymers, polyalkylthiophenes, are derivatized with biotin. These biotinylated polymers form the basis for a generic cassette system of attachment for any biological molecule through biotinylation or interaction with streptavidin. The high affinity of the biotin-streptavidin system, used in sequential steps, forms the basis of the cassette method. We have formed both monolayers and thin films (a few nanometers) of the cassette assembly in which phycobiliproteins are incorporated. We are investigating the optical signal transduction properties of specific phycobiliproteins (phycoerythrin, phycocyanin and allophycocyanain) using the cassette system on the inner surface of glass capillaries and on optical fiber surfaces. Phycobiliprotein photocurrent signals in conducting polymer matrices on microelectrodes are also being investigated. Our aim is to integrate the signal transduction mechanisms of the phycobiliproteins within monolayers or thin films of the conducting polymers to create biosensors and related smart materials for applications in biomedicine and biotechnology.

  6. Single Crystalline Film of Hexagonal Boron Nitride Atomic Monolayer by Controlling Nucleation Seeds and Domains.

    PubMed

    Wu, Qinke; Park, Ji-Hoon; Park, Sangwoo; Jung, Seong Jun; Suh, Hwansoo; Park, Noejung; Wongwiriyapan, Winadda; Lee, Sungjoo; Lee, Young Hee; Song, Young Jae

    2015-01-01

    A monolayer hexagonal boron nitride (h-BN) film with controllable domain morphology and domain size (varying from less than 1 μm to more than 100 μm) with uniform crystalline orientation was successfully synthesized by chemical vapor deposition (CVD). The key for this extremely large single crystalline domain size of a h-BN monolayer is a decrease in the density of nucleation seeds by increasing the hydrogen gas flow during the h-BN growth. Moreover, the well-defined shape of h-BN flakes can be selectively grown by controlling Cu-annealing time under argon atmosphere prior to h-BN growth, which provides the h-BN shape varies in triangular, trapezoidal, hexagonal and complex shapes. The uniform crystalline orientation of h-BN from different nucleation seeds can be easily confirmed by polarized optical microscopy (POM) with a liquid crystal coating. Furthermore, seamlessly merged h-BN flakes without structural domain boundaries were evidence by a selective hydrogen etching after a full coverage of a h-BN film was achieved. This seamless large-area and atomic monolayer of single crystalline h-BN film can offer as an ideal and practical template of graphene-based devices or alternative two-dimensional materials for industrial applications with scalability. PMID:26537788

  7. Comparative study of normal and branched alkane monolayer films adsorbed on a solid surface. II. Dynamics

    NASA Astrophysics Data System (ADS)

    Enevoldsen, A. D.; Hansen, F. Y.; Diama, A.; Taub, H.; Dimeo, R. M.; Neumann, D. A.; Copley, J. R. D.

    2007-03-01

    The dynamics of monolayer films of the n-alkane tetracosane (n-C24H52) and the branched alkane squalane (C30H62) adsorbed on graphite have been studied by quasielastic and inelastic neutron scattering and molecular dynamics (MD) simulations. Both molecules have 24 carbon atoms along their carbon backbone, and squalane has an additional six methyl side groups symmetrically placed along its length. The authors' principal objective has been to determine the influence of the side groups on the dynamics of the squalane monolayer and thereby assess its potential as a nanoscale lubricant. To investigate the dynamics of these monolayers they used both the disk chopper spectrometer (DCS) and the high flux backscattering spectrometer (HFBS) at the National Institute of Standards and Technology. These instruments made it possible to study dynamical processes such as molecular diffusive motions and vibrations on very different time scales: 1-40ps (DCS) and 0.1-4ns (HFBS). The MD simulations were done on corresponding time scales and were used to interpret the neutron spectra. The authors found that the dynamics of the two monolayers are qualitatively similar on the respective time scales and that there are only small quantitative differences that can be understood in terms of the different masses and moments of inertia of the two molecules. In the course of this study, the authors developed a procedure to separate out the low-frequency vibrational modes in the spectra, thereby facilitating an analysis of the quasielastic scattering. They conclude that there are no major differences in the monolayer dynamics caused by intramolecular branching. It remains to be seen whether this similarity in monolayer dynamics also holds for the lubricating properties of these molecules in confined geometries.

  8. Chemical Vapor Deposition of Fluoroalkylsilane Monolayer Films for Adhesion Control in Microelectromechanical Systems

    SciTech Connect

    MAYER,THOMAS M.; DE BOER,MAARTEN P.; SHINN,NEAL D.; CLEWS,PEGGY J.; MICHALSKE,TERRY A.

    2000-01-26

    We have developed a new process for applying a hydrophobic, low adhesion energy coating to microelectromechanical (MEMS) devices. Monolayer films are synthesized from tridecafluoro-1,1,2,2-tetrahydrooctyltrichlorosilane (FOTS) and water vapor in a low-pressure chemical vapor deposition process at room temperature. Film thickness is self-limiting by virtue of the inability of precursors to stick to the fluorocarbon surface of the film once it has formed. We have measured film densities of {approx}3 molecules nm{sup 2} and film thickness of {approx}1 nm. Films are hydrophobic, with a water contact angle >110{sup o}. We have also incorporated an in-situ downstream microwave plasma cleaning process, which provides a clean, reproducible oxide surface prior to film deposition. Adhesion tests on coated and uncoated MEMS test structures demonstrate superior performance of the FOTS coatings. Cleaned, uncoated cantilever beam structures exhibit high adhesion energies in a high humidity environment. An adhesion energy of 100 mJ m{sup -2} is observed after exposure to >90% relative humidity. Fluoroalkylsilane coated beams exhibit negligible adhesion at low humidity and {<=} 20 {micro}J m{sup -2} adhesion energy at >90% relative humidity. No obvious film degradation was observed for films exposed to >90% relative humidity at room temperature for >24 hr.

  9. Nanostructured Ceramic Films Formation on Self-Assembled Monolayers via a Biomimetic Approach

    SciTech Connect

    Zhang, Guangneng; Blom, Douglas Allen; Coffey, Dorothy W; Allard Jr, Lawrence Frederick; Cho, Junghyun

    2006-01-01

    A biomimetic approach is employed to deposit ceramic films on organic self-assembled monolayers (SAMs) coated substrates. Specifically, zirconia (ZrO{sub 2}) films are grown in a zirconium sulfate precursor solution at near room temperatures ({approx}70 C). This process, directed by the nanoscale organic template, mimics the controlled nucleation and growth of the biominerals such as bones and teeth. The resultant zirconia films consist of nanosized particles (5-10 nm) that are precipitated out in a supersaturated precursor solution. Cross-sectional TEM and STEM works were performed to quantitatively analyze the film structure and chemistry, as well as interfacial region of the ceramic-SAM films. A stepwise deposition process was developed to avoid excessive formation of aggregation. Further, the dynamic nanoindentation testing was employed to assess the thickness and film-only intrinsic mechanical properties for direct comparison among the films processed with different processing parameters and microstructures. The films with finer particulate structure displayed higher intrinsic modulus than did those with coarser structure.

  10. Physical and monolayer film properties of potential fatty ester biolubricants

    SciTech Connect

    Yao, Linxing; Hammond, Earl G; Wang, Tong; Bu, Wei; Vaknin, David

    2014-04-03

    The desire to replace petroleum-based lubricants with alternatives that are environmentally friendly and made from sustainable sources has encouraged the development of biolubricants based on vegetable oils. To be good lubricants, the materials should have low melting points, appropriate viscosity and oxidative stability. In this paper, we report the melting point and viscosity of oleate esters of ethylene glycol, 1,2-propanediol, 2,3-butanediol, and pentaerythritol as well as the decanoate esters of 2,3-butanediol and the 12-methyltetradecanoate esters of 1,2-propanediol. Polyol esters that have a free hydroxy group had lower melting points than the completely esterified polyols, but the completely esterified polyol esters exhibited less change in viscosity with temperature than those having a free hydroxy group. 2, 3-Butanediol monooleate, which melted at -48.6°C shows promise as a biolubricant, but its viscosity index was estimated to be 100. Pentaerythritol oleate esters, with melting points below -10°C and viscosity indices in the range of 170–197, may be suitable candidates as biolubricants. The behavior of esters spread as a monomolecular film at air/water interface may provide insight into the way they behave when spread on metal or polar surfaces, so the pressure-area isotherms of 2,3-butanediol monoleate and selected esters are also reported.

  11. Characterization of Monolayer Formation on Aluminum-Doped Zinc Oxide Thin Films

    SciTech Connect

    Rhodes,C.; Lappi, S.; Fischer, D.; Sambasivan, S.; Genzer, J.; Franzen, S.

    2008-01-01

    The optical and electronic properties of aluminum-doped zinc oxide (AZO) thin films on a glass substrate are investigated experimentally and theoretically. Optical studies with coupling in the Kretschmann configuration reveal an angle-dependent plasma frequency in the mid-IR for p-polarized radiation, suggestive of the detection of a Drude plasma frequency. These studies are complemented by oxygen depletion density functional theory studies for the calculation of the charge carrier concentration and plasma frequency for bulk AZO. In addition, we report on the optical and physical properties of thin film adlayers of n-hexadecanethiol (HDT) and n-octadecanethiol (ODT) self-assembled monolayers (SAMs) on AZO surfaces using reflectance FTIR spectroscopy, X-ray photoelectron spectroscopy (XPS), contact angle, and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Our characterization of the SAM deposition onto the AZO thin film reveals a range of possible applications for this conducting metal oxide.

  12. Smooth cubic commensurate oxides on gallium nitride

    SciTech Connect

    Paisley, Elizabeth A.; Gaddy, Benjamin E.; LeBeau, James M.; Shelton, Christopher T.; Losego, Mark D.; Mita, Seiji; Collazo, Ramón; Sitar, Zlatko; Irving, Douglas L.; Maria, Jon-Paul; Biegalski, Michael D.; Christen, Hans M.

    2014-02-14

    Smooth, commensurate alloys of 〈111〉-oriented Mg{sub 0.52}Ca{sub 0.48}O (MCO) thin films are demonstrated on Ga-polar, c+ [0001]-oriented GaN by surfactant-assisted molecular beam epitaxy and pulsed laser deposition. These are unique examples of coherent cubic oxide|nitride interfaces with structural and morphological perfection. Metal-insulator-semiconductor capacitor structures were fabricated on n-type GaN. A comparison of leakage current density for conventional and surfactant-assisted growth reveals a nearly 100× reduction in leakage current density for the surfactant-assisted samples. HAADF-STEM images of the MCO|GaN interface show commensurate alignment of atomic planes with minimal defects due to lattice mismatch. STEM and DFT calculations show that GaN c/2 steps create incoherent boundaries in MCO over layers which manifest as two in-plane rotations and determine consequently the density of structural defects in otherwise coherent MCO. This new understanding of interfacial steps between HCP and FCC crystals identifies the steps needed to create globally defect-free heterostructures.

  13. Probing Thin Films and Monolayers on Gold with Large Amplitude Temperature Jumps

    NASA Astrophysics Data System (ADS)

    Sun, Yuxiao; Berg, Christopher M.; Dlott, Dana

    2014-06-01

    A methodology to probe localized vibrational transitions of self-assembled monolayers (SAMs) adsorbed on gold films using vibrational sum-frequency generation (SFG) is described. The gold film is subjected to heating from a 400nm pump laser, exposing the adsorbed molecules to a temperature jump in the 30-175° K range, calibrated using ultrafast reflectance measurements of the gold compared to steady state oven heating . SAMs of alkyl thiols as well as nitro functionalized aryl thiols were deposited and temperature jumped while be observed with SFG, monitoring the symmetric and asymmetric methyl vibrations as well as nitro vibrations. The amplitude, center, and width of the transitions were measured and provide information about delay and orientation of the molecules, as well as providing an indicator of the overall monolayer state. All transitions probed exhibited overshoot decay plateau patterns, attributed to a fast hot electron process directly exciting the probed transitions, followed by a slower bulk heating process causing monolayer disordering. This leads to a shift in the average angle of the terminal methyl, manifesting itself as a change in the amplitude of the vibration. These techniques will be applied to thin films of energetic materials to study reactions to temperature jumps. HMX is known to have a peak in sensitivity as δ-HMX transitions to β-HMX at high temperatures, but fairly little information about the reason for this is known. This technique should be able to probe that process and provide data that can be used with computational models to gain some understanding of the process.

  14. Ultrafast electron diffraction optimized for studying structural dynamics in thin films and monolayers

    PubMed Central

    Badali, D. S.; Gengler, R. Y. N.; Miller, R. J. D.

    2016-01-01

    A compact electron source specifically designed for time-resolved diffraction studies of free-standing thin films and monolayers is presented here. The sensitivity to thin samples is achieved by extending the established technique of ultrafast electron diffraction to the “medium” energy regime (1–10 kV). An extremely compact design, in combination with low bunch charges, allows for high quality diffraction in a lensless geometry. The measured and simulated characteristics of the experimental system reveal sub-picosecond temporal resolution, while demonstrating the ability to produce high quality diffraction patterns from atomically thin samples. PMID:27226978

  15. Synthesis of linked carbon monolayers: Films, balloons, tubes, and pleated sheets

    PubMed Central

    Schultz, Mitchell J.; Zhang, Xiaoyu; Unarunotai, Sakulsuk; Khang, Dahl-Young; Cao, Qing; Wang, Congjun; Lei, Changhui; MacLaren, Scott; Soares, Julio A. N. T.; Petrov, Ivan; Moore, Jeffrey S.; Rogers, John A.

    2008-01-01

    Because of their potential for use in advanced electronic, nanomechanical, and other applications, large two-dimensional, carbon-rich networks have become an important target to the scientific community. Current methods for the synthesis of these materials have many limitations including lack of molecular-level control and poor diversity. Here, we present a method for the synthesis of two-dimensional carbon nanomaterials synthesized by Mo- and Cu-catalyzed cross-linking of alkyne-containing self-assembled monolayers on SiO2 and Si3N4. When deposited and cross-linked on flat surfaces, spheres, cylinders, or textured substrates, monolayers take the form of these templates and retain their structure on template removal. These nanomaterials can also be transferred from surface to surface and suspended over cavities without tearing. This approach to the synthesis of monolayer carbon networks greatly expands the chemistry, morphology, and size of carbon films accessible for analysis and device applications. PMID:18508969

  16. Langmuir monolayers and newton black films: Two-dimensional systems investigated by X-ray reflectivity

    NASA Astrophysics Data System (ADS)

    Benattar, J. J.; Daillant, J.; Belorgey, O.; Bosio, L.

    1991-03-01

    Amphiphilic molecules and water are the basic components of many different systems, their morphology and topology conditions depend on many physical and chemical parameters mainly concentration. These systems may be either three dimensional (vesicles, micelles) or two dimensional (membranes). In this paper, we investigate Langmuir monolayers on water by means of X-ray reflectivity, with the aim to characterize the liquid expanded/liquid condensed and liquid condensed/solid transitions. We also study the structure of the Newton black film (i.e., the ultimate stage of the thinning of a soap film). The main result for the latter problem is the complete lack of water and the two-dimensional crystallization of this “inverted membrane”.

  17. Antibacterial activity of large-area monolayer graphene film manipulated by charge transfer

    PubMed Central

    Li, Jinhua; Wang, Gang; Zhu, Hongqin; Zhang, Miao; Zheng, Xiaohu; Di, Zengfeng; Liu, Xuanyong; Wang, Xi

    2014-01-01

    Graphene has attracted increasing attention for potential applications in biotechnology due to its excellent electronic property and biocompatibility. Here we use both Gram-positive Staphylococcus aureus (S. aureus) and Gram-negative Escherichia coli (E. coli) to investigate the antibacterial actions of large-area monolayer graphene film on conductor Cu, semiconductor Ge and insulator SiO2. The results show that the graphene films on Cu and Ge can surprisingly inhibit the growth of both bacteria, especially the former. However, the proliferation of both bacteria cannot be significantly restricted by the graphene film on SiO2. The morphology of S. aureus and E. coli on graphene films further confirms that the direct contact of both bacteria with graphene on Cu and Ge can cause membrane damage and destroy membrane integrity, while no evident membrane destruction is induced by graphene on SiO2. From the viewpoint of charge transfer, a plausible mechanism is proposed here to explain this phenomenon. This study may provide new insights for the better understanding of antibacterial actions of graphene film and for the better designing of graphene-based antibiotics or other biomedical applications. PMID:24619247

  18. Antibacterial activity of large-area monolayer graphene film manipulated by charge transfer

    NASA Astrophysics Data System (ADS)

    Li, Jinhua; Wang, Gang; Zhu, Hongqin; Zhang, Miao; Zheng, Xiaohu; di, Zengfeng; Liu, Xuanyong; Wang, Xi

    2014-03-01

    Graphene has attracted increasing attention for potential applications in biotechnology due to its excellent electronic property and biocompatibility. Here we use both Gram-positive Staphylococcus aureus (S. aureus) and Gram-negative Escherichia coli (E. coli) to investigate the antibacterial actions of large-area monolayer graphene film on conductor Cu, semiconductor Ge and insulator SiO2. The results show that the graphene films on Cu and Ge can surprisingly inhibit the growth of both bacteria, especially the former. However, the proliferation of both bacteria cannot be significantly restricted by the graphene film on SiO2. The morphology of S. aureus and E. coli on graphene films further confirms that the direct contact of both bacteria with graphene on Cu and Ge can cause membrane damage and destroy membrane integrity, while no evident membrane destruction is induced by graphene on SiO2. From the viewpoint of charge transfer, a plausible mechanism is proposed here to explain this phenomenon. This study may provide new insights for the better understanding of antibacterial actions of graphene film and for the better designing of graphene-based antibiotics or other biomedical applications.

  19. Evanescent wave absorption sensor based on tapered multimode fiber coated with monolayer graphene film

    NASA Astrophysics Data System (ADS)

    Qiu, Hengwei; Gao, Saisai; Chen, Peixi; Li, Zhen; Liu, Xiaoyun; Zhang, Chao; Xu, Yuanyuan; Jiang, Shouzhen; Yang, Cheng; Huo, Yanyan; Yue, Weiwei

    2016-05-01

    An evanescent wave absorption (EWA) sensor based on tapered multimode fiber (TMMF) coated with monolayer graphene film for the detection of double-stranded DNA (DS-DNA) is investigated in this work. The TMMF is a silica multimode fiber (nominally at 62.5 μm), which was tapered to symmetric taper with waist diameters of ~30 μm and total length of ~3 mm. Monolayer graphene film was grown on a copper foil via chemical vapor deposition (CVD) technology and transferred onto skinless tapered fiber core via dry transfer technology. All the components of the sensor are coupled together by fusion splicer in order to eliminate the external disturbance. DS-DNA is created by the assembly of two relatively complemented oligonucleotides. The measurements are obtained by using a spectrometer in the optical wavelength range of 400-900 nm. With the increase of DS-DNA concentration, the output light intensity (OPLI) arisen an obvious attenuation. Importantly, the absorbance (A) and the DS-DNA concentrations shown a reasonable linear variation in a wide range of 5-400 μM. Through a series of comparison, the accuracy of TMMF sensor with graphene (G-TMMF) is much better than that without graphene (TMMF), which can be attributed to the molecular enrichment of graphene by π-π stacking.

  20. Chemical vapor deposition and etching of high-quality monolayer hexagonal boron nitride films.

    PubMed

    Sutter, Peter; Lahiri, Jayeeta; Albrecht, Peter; Sutter, Eli

    2011-09-27

    The growth of large-area hexagonal boron nitride (h-BN) monolayers on catalytic metal substrates is a topic of scientific and technological interest. We have used real-time microscopy during the growth process to study h-BN chemical vapor deposition (CVD) from borazine on Ru(0001) single crystals and thin films. At low borazine pressures, individual h-BN domains nucleate sparsely, grow to macroscopic dimensions, and coalescence to form a closed monolayer film. A quantitative analysis shows borazine adsorption and dissociation predominantly on Ru, with the h-BN covered areas being at least 100 times less reactive. We establish strong effects of hydrogen added to the CVD precursor gas in controlling the in-plane expansion and morphology of the growing h-BN domains. High-temperature exposure of h-BN/Ru to pure hydrogen causes the controlled edge detachment of B and N and can be used as a clean etching process for h-BN on metals.

  1. Chemical vapor deposition and etching of high-quality monolayer hexagonal boron nitride films.

    PubMed

    Sutter, Peter; Lahiri, Jayeeta; Albrecht, Peter; Sutter, Eli

    2011-09-27

    The growth of large-area hexagonal boron nitride (h-BN) monolayers on catalytic metal substrates is a topic of scientific and technological interest. We have used real-time microscopy during the growth process to study h-BN chemical vapor deposition (CVD) from borazine on Ru(0001) single crystals and thin films. At low borazine pressures, individual h-BN domains nucleate sparsely, grow to macroscopic dimensions, and coalescence to form a closed monolayer film. A quantitative analysis shows borazine adsorption and dissociation predominantly on Ru, with the h-BN covered areas being at least 100 times less reactive. We establish strong effects of hydrogen added to the CVD precursor gas in controlling the in-plane expansion and morphology of the growing h-BN domains. High-temperature exposure of h-BN/Ru to pure hydrogen causes the controlled edge detachment of B and N and can be used as a clean etching process for h-BN on metals. PMID:21793550

  2. Configuration and photochemical reaction of a bolaamphiphilic diacid with a diazo resin in monolayers and Langmuir-Blodgett films.

    PubMed

    Zhang, Li; Jiang, Siguang; Liu, Minghua

    2003-05-15

    The monolayer formation of a bolaamphiphile, 1,18-octadecanedicarboxylic acid (ODA), on pure water and the subphase containing a positively charged photoactive 2-nitro-N-methyldiphenylamine-4-diazoniumformaldehyde resin (NDR) have been investigated by pi-A isotherms, pi-t curves, and Brewster angle microscopy (BAM) measurements. It has been revealed that although an unstable monolayer was formed by ODA alone, a stable complex monolayer between ODA and NDR could be formed at the interface through electrostatic adsorption and hydrogen bonding. It has been shown that the ODA formed a U-shaped monolayer at a lower pressure and was converted to a stretched configuration upon compression to a higher surface pressure on the subphase containing NDR. Under UV irradiation at the interface photoreaction can occur in the complex monolayer, which causes shrinkage of the monolayer. Photochemical reactions can also occur in deposited Langmuir-Blodgett films. In reactions occurring at the air/water interface, the two ends of ODA can react with NDR to form an ester containing aromatic rings. This makes the compound more hydrophobic and can easily be stretched without any phase transition upon compression. When the film with U-shaped configuration was deposited onto solid substrates, the configuration could be kept even upon photoirradiation. PMID:16256551

  3. Realization of Large-Area Wrinkle-Free Monolayer Graphene Films Transferred to Functional Substrates

    PubMed Central

    Park, Byeong-Ju; Choi, Jin-Seok; Kim, Hyun-Suk; Kim, Hyun-You; Jeong, Jong-Ryul; Choi, Hyung-Jin; Jung, Hyun-June; Jung, Min-Wook; An, Ki-Seok; Yoon, Soon-Gil

    2015-01-01

    Structural inhomogeneities, such as the wrinkles and ripples within a graphene film after transferring the free-standing graphene layer to a functional substrate, degrade the physical and electrical properties of the corresponding electronic devices. Here, we introduced titanium as a superior adhesion layer for fabricating wrinkle-free graphene films that is highly applicable to flexible and transparent electronic devices. The Ti layer does not influence the electronic performance of the functional substrates. Experimental and theoretical investigations confirm that the strong chemical interactions between Ti and any oxygen atoms unintentionally introduced on/within the graphene are responsible for forming the clean, defect-free graphene layer. Our results accelerate the practical application of graphene-related electronic devices with enhanced functionality. The large-area monolayer graphenes were prepared by a simple attachment of the Ti layer with the multi-layer wrinkle-free graphene films. For the first time, the graphene films were addressed for applications of superior bottom electrode for flexible capacitors instead of the novel metals. PMID:26043868

  4. Active Antifogging Property of Monolayer SiO2 Film with Bioinspired Multiscale Hierarchical Pagoda Structures.

    PubMed

    Han, Zhiwu; Mu, Zhengzhi; Li, Bo; Wang, Ze; Zhang, Junqiu; Niu, Shichao; Ren, Luquan

    2016-09-27

    Antifogging surfaces with hydrophilic or even superhydrophilic wetting behavior have received significant attention due to their ability to reduce light scattering by film-like condensation. However, a major challenge remains in achieving high-speed antifogging performance and revealing the hydrophilic-based antifogging mechanism of glass or other transparent materials under aggressive fogging conditions. Herein, with inspiration from the fog-free property of the typical Morpho menelaus terrestris butterfly (Butler, 1866) wing scales, a monolayer SiO2 film with multiscale hierarchical pagoda structures (MHPSs) based on glass substrate was designed and fabricated using an optimized biotemplate-assisted wet chemical method without any post-treatments. The biomimetic monolayer film (BMF) composed of nanoscale SiO2 3D networks displayed excellent antifogging properties, which is superior to that of the glass substrate itself. The MHPS-based BMF even kept high transmittance (∼95%) under aggressive fog conditions, and it almost instantaneously recovered to a fog-free state (<5 s). Moreover, the underlying active antifogging strategy gathering initial fog capture and final antifog together was revealed. The fogdrops spontaneously adhered on the BMF surface and rapidly spread along the MHPSs in an anisotropic way, which made the fogdrops evaporate instantaneously to attain an initial fog-free state, leading to an efficient active antifogging performance. These properties mainly benefit from the synergistic effect of both hydrophilic chemical compositions (nanoscale SiO2) and physical structures (biomimetic MHPSs) of the BMF. High-speed active antifogging performance of the glass materials enabled the retention of a high transmittance property even in humid conditions, heralding reliable optical performance in outdoor practical applications, especially in aggressive foggy environments. More importantly, the investigations in this work offer a promising way to handily

  5. An atomic force microcopy study of the mechanical and electricalproperties of monolayer films of molecules with aromatic end groups

    SciTech Connect

    Fang, Liang; Park, J.Y.; Ma, H.; Jen, A.K.-Y.; Salmeron, M.

    2007-09-06

    The effect of intermolecular {pi}-{pi} stacking on the electrical and mechanical properties of monolayer films molecules containing aromatic groups was studied using atomic force microscopy. Two types of aromatic molecules, (4-mercaptophenyl) anthrylacetylene (MPAA) and (4-mercaptophenyl)-phenylacetylene (MPPA) were used as model systems with different {pi}-{pi} stacking strength. Monolayer films of these molecules on Au(111) surfaces exhibited conductivities differing by more than one order of magnitude, MPAA being the most conductive and MPPA the least conductive. The response to compressive loads by the AFM tip was also found to be very different for both molecules. In MPAA films distinct molecular conductivity changes are observed upon mechanical perturbation. This effect however was not observed on the MPPA film, where intermolecular {pi}-{pi} interactions are likely weaker.

  6. Easily processable highly ordered Langmuir-Blodgett films of quaterthiophene disiloxane dimer for monolayer organic field-effect transistors.

    PubMed

    Sizov, Alexey S; Anisimov, Daniil S; Agina, Elena V; Borshchev, Oleg V; Bakirov, Artem V; Shcherbina, Maxim A; Grigorian, Souren; Bruevich, Vladimir V; Chvalun, Sergei N; Paraschuk, Dmitry Yu; Ponomarenko, Sergei A

    2014-12-23

    Self-assembly of highly soluble water-stable tetramethyldisiloxane-based dimer of α,α'-dialkylquaterthiophene on the water-air interface was investigated by Langmuir, grazing incidence X-ray diffraction, and X-ray reflectivity techniques. The conditions for formation of very homogeneous crystalline monolayer Langmuir-Blodgett (LB) films of the oligomer were found. Monolayer organic field-effect transistors (OFETs) based on these LB films as a semiconducting layer showed hole mobilities up to 3 × 10(-3) cm(2)/(V s), on-off ratio of 10(5), small hysteresis, and high long-term stability. The electrical performance of the LB films studied is close to that for the same material in the bulk or in the monolayer OFETs prepared from water vapor sensitive chlorosilyl derivatives of quaterthiophene by self-assembling from solution. These findings show high potential of disiloxane-based LB films in monolayer OFETs for large-area organic electronics.

  7. Spreading of a surfactant monolayer on a thin liquid film: Onset and evolution of digitated structures

    NASA Astrophysics Data System (ADS)

    Matar, Omar K.; Troian, Sandra M.

    1999-03-01

    We describe the response of an insoluble surfactant monolayer spreading on the surface of a thin liquid film to small disturbances in the film thickness and surfactant concentration. The surface shear stress, which derives from variations in surfactant concentration at the air-liquid interface, rapidly drives liquid and surfactant from the source toward the distal region of higher surface tension. A previous linear stability analysis of a quasi-steady state solution describing the spreading of a finite strip of surfactant on a thin Newtonian film has predicted only stable modes. [Dynamics in Small Confining Systems III, Materials Research Society Symposium Proceedings, edited by J. M. Drake, J. Klafter, and E. R. Kopelman (Materials Research Society, Boston, 1996), Vol. 464, p. 237; Phys. Fluids A 9, 3645 (1997); O. K. Matar Ph.D. thesis, Princeton University, Princeton, NJ, 1998]. A perturbation analysis of the transient behavior, however, has revealed the possibility of significant amplification of disturbances in the film thickness within an order one shear time after the onset of flow [Phys. Fluids A 10, 1234 (1998); "Transient response of a surfactant monolayer spreading on a thin liquid film: Mechanism for amplification of disturbances," submitted to Phys. Fluids]. In this paper we describe the linearized transient behavior and interpret which physical parameters most strongly affect the disturbance amplification ratio. We show how the disturbances localize behind the moving front and how the inclusion of van der Waals forces further enhances their growth and lifetime. We also present numerical solutions to the fully nonlinear 2D governing equations. As time evolves, the nonlinear system sustains disturbances of longer and longer wavelength, consistent with the quasi-steady state and transient linearized descriptions. In addition, for the parameter set investigated, disturbances consisting of several harmonics of a fundamental wavenumber do not couple

  8. Spreading of a surfactant monolayer on a thin liquid film: Onset and evolution of digitated structures.

    PubMed

    Matar, Omar K.; Troian, Sandra M.

    1999-03-01

    We describe the response of an insoluble surfactant monolayer spreading on the surface of a thin liquid film to small disturbances in the film thickness and surfactant concentration. The surface shear stress, which derives from variations in surfactant concentration at the air-liquid interface, rapidly drives liquid and surfactant from the source toward the distal region of higher surface tension. A previous linear stability analysis of a quasi-steady state solution describing the spreading of a finite strip of surfactant on a thin Newtonian film has predicted only stable modes. [Dynamics in Small Confining Systems III, Materials Research Society Symposium Proceedings, edited by J. M. Drake, J. Klafter, and E. R. Kopelman (Materials Research Society, Boston, 1996), Vol. 464, p. 237; Phys. Fluids A 9, 3645 (1997); O. K. Matar Ph.D. thesis, Princeton University, Princeton, NJ, 1998]. A perturbation analysis of the transient behavior, however, has revealed the possibility of significant amplification of disturbances in the film thickness within an order one shear time after the onset of flow [Phys. Fluids A 10, 1234 (1998); "Transient response of a surfactant monolayer spreading on a thin liquid film: Mechanism for amplification of disturbances," submitted to Phys. Fluids]. In this paper we describe the linearized transient behavior and interpret which physical parameters most strongly affect the disturbance amplification ratio. We show how the disturbances localize behind the moving front and how the inclusion of van der Waals forces further enhances their growth and lifetime. We also present numerical solutions to the fully nonlinear 2D governing equations. As time evolves, the nonlinear system sustains disturbances of longer and longer wavelength, consistent with the quasi-steady state and transient linearized descriptions. In addition, for the parameter set investigated, disturbances consisting of several harmonics of a fundamental wavenumber do not couple

  9. AFM Observation of Self-Assembled Monolayer Films on GaAs (110)

    NASA Astrophysics Data System (ADS)

    Ohno, Hirotaka; Motomatsu, Makoto; Mizutani, Wataru; Tokumoto, Hiroshi

    1995-02-01

    We have confirmed that a self-assembled monolayer (SAM) film of octadecanethiol (ODT), CH3(CH2)17SH, can be formed on a cleaved GaAs (110) surface, by using an atomic force microscope (AFM) and X-ray photoelectron spectroscopy (XPS). Circular depressions were observed on the surface after film formation. The area of the circular depressions increased with immersion time, indicating that the solution oxidized the interface between ODT molecules and the GaAs surface, resulting in removal of ODT molecules. The oxidation was considerably faster in pure ethanol solution than that in ODT solution, demonstrating that the SAM film protects the GaAs surface from oxidation. High-resolution lateral force microscope (LFM) images revealed a periodic structure that had two types of lines: periodic lines 0.57 nm apart and lines rotated 55° with respect to them. A structural model of the SAM successfully explained both the features in high-resolution LFM images and the depression depth observed in AFM images.

  10. Commensurism at electronically weakly interacting phthalocyanine/PTCDA heterointerfaces

    NASA Astrophysics Data System (ADS)

    Gruenewald, Marco; Sauer, Christoph; Peuker, Julia; Meissner, Matthias; Sojka, Falko; Schöll, Achim; Reinert, Friedrich; Forker, Roman; Fritz, Torsten

    2015-04-01

    Interfaces in multilayered electronic devices are of paramount importance, especially for layer thicknesses in the nanometer range. Among the interfacial processes are charge injection or extraction and excitonic dissociation, the latter being particularly relevant if molecular components are involved. Highly ordered superstructures are preferable to prevent undesired losses of charge carriers and/or excitons. Epitaxial organic-inorganic systems have already received eminent attention, but only few studies have dealt with organic-organic heterointerfaces so far. Here, we focus on the adsorption of metal-phthalocyanines (MePc, Me = Sn or Cu) on 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) in the form of stacked monolayers (ML) on Ag(111). Using scanning tunneling microscopy and low-energy electron diffraction we reveal an initial nonordered growth for dilute SnPc submonolayers and consecutively three condensed phases at coverages ranging up to 1 ML —each possessing a distinct commensurate registry with the underlying PTCDA. By applying in situ optical differential reflectance spectroscopy and photoelectron spectroscopy we find that neither the SnPc nor the CuPc phases exhibit significant electronic or optical coupling with the PTCDA interlayer. Therefore, our results demonstrate that commensurism does not necessarily imply chemisorption, as stated previously in the literature, but that physisorption may be accompanied by commensurate superstructures.

  11. Tribological properties of self-assembled monolayers of catecholic imidazolium and the spin-coated films of ionic liquids.

    PubMed

    Liu, Jianxi; Li, Jinlong; Yu, Bo; Ma, Baodong; Zhu, Yangwen; Song, Xinwang; Cao, Xulong; Yang, Wu; Zhou, Feng

    2011-09-20

    A novel compound of an imidazolium type of ionic liquid (IL) containing a biomimetic catecholic functional group normally seen in mussel adhesive proteins was synthesized. The IL can be immobilized on a silicon surface and a variety of other engineering material surfaces via the catecholic anchor, allowing the tribological protection of these substrates for engineering applications. The surface wetting and adhesive properties and the tribological property of the synthesized self-assembled monolayers (SAMs) are successfully modulated by altering the counteranions. The chemical composition and wettability of the IL SAMs were characterized by means of X-ray photoelectron spectroscopy (XPS) and contact angle (CA) measurements. The adhesive and friction forces were measured with an atomic force microscope (AFM) on the nanometer scale. IL composite films were prepared by spin coating thin IL films on top of the SAMs. The macrotribological properties of these IL composite films were investigated with a pin-on-disk tribometer. The results indicate that the presence of IL SAMs on a surface can improve the wettability of spin-coated ionic liquids and thus the film quality and the tribological properties. These films registered a reduced friction coefficient and a significantly enhanced durability and load-carrying capacity. The tribological properties of the composite films are better than those of pure IL films because the presence of the monolayers improves the adhesion and compatibility of spin-coated IL films with substrates.

  12. Wetting transitions of simple liquid films adsorbed on selfassembled monolayer substrates: an ellipsometric study

    NASA Astrophysics Data System (ADS)

    Batchelder, D. N.; Cheng, Y. L.; Evans, S. D.; Henderson, J. R.

    We report on an ellipsometric experimental study designed to explore the relevance of the wetting phase diagram predicted by liquid state physics of basic models, to the wide class of simple organic liquid films that adsorb from saturated vapour onto planar substrates at room temperature. The wetting properties are explored by measuring adsorption isotherms in the approach to saturation, in particular, for adsorption of n -hexane on a variety of specially constructed substrates (self-assembled monolayers) spanning a wide range of surface energy, and by carrying out the microscopic equivalent of contact angle experiments at saturation. We locate a wetting transition, which in our case is continuous, and then study its properties in detail. The general prediction of the wetting phase diagram, that wetting transitions should be ubiquitous in nature and readily located via control over the substrate field, is supported by our data, but the quantitative nature of the thick film adsorption regime is not in agreement with Lifshitz theory. This conclusion supports the work of a variety of earlier related studies, but contrasts with recent results for adsorption onto the surface of water. In addition, the correlation length determined from our complete wetting adsorption isotherms is mesoscopic, suggesting that equilibrium statistical mechanics of simple models of inhomogeneous fluids cannot explain the data.

  13. In situ growth of monolayer porous gold nanoparticles film as high-performance SERS substrates

    NASA Astrophysics Data System (ADS)

    Song, Chunyuan; Wei, Yuhan; Da, Bingtao; Zhang, Haiting; Cong, Xing; Yang, Boyue; Yang, Yanjun; Wang, Lianhui

    2016-07-01

    Surface-enhanced Raman scattering (SERS) has recently received considerable attention as an ultrasensitive analytic technique. However, its wide application is limited by lack of excellent SERS-active substrates. In this work a SERS substrate with arrayed monolayer films of porous gold nanoparticles is prepared on a solid substrate by a facile, in situ and one-step growth approach. Specifically, the solid substrate was coated with a layer of dense positive charges first by layer-by-layer assembly, followed by patterned a PDMS film with arrayed wells on the substrate. Then the growth solution including chlorauric acid, cetyltrimethylammonium chloride, and ascorbic acid in a certain proportion was transferred into the wells for in situ and one-step growth of porous gold nanoparticles on the substrate. The growth time, feed ratio of the reagents, and repeat times of the in situ growth were studied systematically to obtain optimal parameters for preparing an optimal SERS substrate. The as-prepared optimal SERS substrate not only has good SERS performance with the enhancement factor up to ∼1.10 × 106, but also shows good uniformity and stability. The SERS substrate was further utilized to be ultrasensitive SERS-based chemical sensors for ppb-level detection of highly toxic dyfonate. The preliminary result indicates that the as-prepared SERS substrate has good SERS performance and shows a number of great potential applications in SERS-based sensors.

  14. Interfacial properties in Langmuir monolayers and LB films of DPPC with partially fluorinated alcohol (F8H7OH).

    PubMed

    Nakahara, Hiromichi; Hirano, Chikayo; Fujita, Ichiro; Shibata, Osamu

    2013-01-01

    Two-component interactions between (perfluorooctyl) heptanol (F8H7OH) and dipalmitoylphosphatidylcholine (DPPC), which is a major component of pulmonary surfactants in mammals, were systematically elucidated using Langmuir monolayers and Langmuir-Blodgett (LB) films of the compounds. The interactions such as the miscibility of the compounds and their phase behavior were examined from thermodynamic and morphological perspectives. The surface pressure (π)-molecular area (A) and surface potential (ΔV)-A isotherms of the binary monolayers containing F8H7OH in different mole fractions (XF8H7OH) were measured simultaneously. The excess Gibbs free energy of mixing of the two components was calculated from the π-A isotherms. The resulting isotherm data were employed to construct a two-dimensional (2D) phase diagram of the system. The phase diagram revealed that the transition pressure as well as the monolayer collapse pressure change with changes in XF8H7OH. These thermodynamic analyses suggested that the miscibility of the two components and the solidification of DPPC monolayers can be induced by the addition of F8H7OH. The phase behavior upon monolayer compression was observed morphologically in situ using Brewster angle microscopy (BAM) and fluorescence microscopy (FM), as well as ex situ using atomic force microscopy (AFM). Interestingly, the AFM-based analysis revealed the formation of monodispersed 2D micelles consisting of F8H7OH at low surface pressures.

  15. Two-component Langmuir monolayers and LB films of DPPC with partially fluorinated alcohol (F8H9OH).

    PubMed

    Nakahara, Hiromichi; Hirano, Chikayo; Shibata, Osamu

    2013-01-01

    The interaction of (perfluorooctyl)nonanol (F8H9OH) with dipalmitoylphosphatidylcholine (DPPC) was systematically studied in two-component monolayers at air-water interface. The thermodynamic property and phase morphology of the monolayers were investigated by isotherm measurements and several microscopic methods such as Brewster angle microscopy, fluorescence microscopy, and atomic force microscopy (AFM). The AFM topographies for Langmuir-Blodgett films of F8H9OH exhibit the formation of monodispersed surface micelles. In the two-component system, the incorporation of F8H9OH induces condensation (or solidification) of DPPC monolayers. The excess Gibbs free energy and interaction parameter (or energy) of the two components were calculated from the isotherm data. Both the phase transition pressure for the coexistence of ordered and disordered phases and collapse pressure of monolayers vary with the mole fraction of F8H9OH, indicating binary miscibility between F8H9OH and DPPC within a monolayer state. The miscibility is also confirmed visually by in situ and ex situ microscopy at micro- and nanometer scales.

  16. Using the Langmuir-Schaefer technique to fabricate large-area dense SERS-active Au nanoprism monolayer films.

    PubMed

    Lee, Yih Hong; Lee, Choon Keong; Tan, Baorui; Rui Tan, Joel Ming; Phang, In Yee; Ling, Xing Yi

    2013-07-21

    Interfacial self-assembly of nanoparticles is capable of creating large-area close-packed structures for a variety of applications. However, monolayers of hydrophilic cetyltrimethylammonium bromide (CTAB)-coated Au nanoparticles are challenging to assemble via interfacial self-assembly. This report presents a facile and scalable process to fabricate large-area monolayer films of ultrathin CTAB-coated Au nanoprisms at the air-water interface using the Langmuir-Schaefer technique. This is first achieved by a one-step functionalization of Au nanoprisms with poly(vinylpyrrolidone) (PVP). PVP functionalization is completed within a short time without loss of nanoprisms due to aggregation. Uniform and near close-packed monolayers of the Au nanoprisms formed over large areas (∼1 cm(2)) at the air-water interface can be transferred to substrates with different wettabilities. The inter-prism gaps are tuned qualitatively through the introduction of dodecanethiol and oleylamine. The morphological integrity of the nanoprisms is maintained throughout the entire assembly process, without truncation of the nanoprism tips. The near close-packed arrangement of the nanoprism monolayers generates large numbers of hot spots in the 2D arrays in the tip-to-tip and edge-to-edge inter-particle regions, giving rise to strong surface-enhanced Raman scattering (SERS) signals. When deposited on an Au mirror film, additional hotspots are created in the 3(rd) dimension in the gaps between the 2D nanoprism monolayers and the Au film. SERS enhancement factors reaching 10(4) for non-resonant probe molecules are achieved.

  17. Epitaxial Templating of C60 with a Molecular Monolayer.

    PubMed

    Rochford, L A; Jones, T S; Nielsen, C B

    2016-09-01

    Commensurate epitaxial monolayers of truxenone on Cu (111) were employed to template the growth of monolayer and bilayer C60. Through the combination of STM imaging and LEED analysis we have demonstrated that C60 forms a commensurate 8 × 8 overlayer on truxenone/Cu (111). Bilayers of C60 retain the 8 × 8 periodicity of templated monolayers and although Kagome lattice arrangements are observed these are explained with combinations of 8 × 8 symmetry. PMID:27540868

  18. Tracing the 4000 year history of organic thin films: From monolayers on liquids to multilayers on solidsa)

    NASA Astrophysics Data System (ADS)

    Greene, J. E.

    2015-03-01

    The recorded history of organic monolayer and multilayer thin films spans approximately 4000 years. Fatty-acid-based monolayers were deposited on water by the ancients for applications ranging from fortune telling in King Hammurabi's time (˜1800 BC, Mesopotamia) to stilling choppy waters for sailors and divers as reported by the Roman philosopher Pliny the Elder in ˜78 AD, and then much later (1774) by the peripatetic American statesman and natural philosopher Benjamin Franklin, to Japanese "floating-ink" art (suminagashi) developed ˜1000 years ago. The modern science of organic monolayers began in the late-1800s/early-1900s with experiments by Lord Rayleigh and the important development by Agnes Pockels, followed two decades later by Irving Langmuir, of the tools and technology to measure the surface tension of liquids, the surface pressure of organic monolayers deposited on water, interfacial properties, molecular conformation of the organic layers, and phase transitions which occur upon compressing the monolayers. In 1935, Katherine Blodgett published a landmark paper showing that multilayers can be synthesized on solid substrates, with controlled thickness and composition, using an apparatus now known as the Langmuir-Blodgett (L-B) trough. A disadvantage of LB films for some applications is that they form weak physisorbed bonds to the substrate. In 1946, Bigelow, Pickett, and Zisman demonstrated, in another seminal paper, the growth of organic self-assembled monolayers (SAMs) via spontaneous adsorption from solution, rather than from the water/air interface, onto SiO2 and metal substrates. SAMs are close-packed two-dimensional organic crystals which exhibit strong covalent bonding to the substrate. The first multicomponent adsorbed monolayers and multilayer SAMs were produced in the early 1980s. Langmuir monolayers, L-B multilayers, and self-assembled mono- and multilayers have found an extraordinarily broad range of applications including controlled wetting

  19. Tracing the 4000 year history of organic thin films: From monolayers on liquids to multilayers on solids

    SciTech Connect

    Greene, J. E.

    2015-03-15

    The recorded history of organic monolayer and multilayer thin films spans approximately 4000 years. Fatty-acid-based monolayers were deposited on water by the ancients for applications ranging from fortune telling in King Hammurabi's time (∼1800 BC, Mesopotamia) to stilling choppy waters for sailors and divers as reported by the Roman philosopher Pliny the Elder in ∼78 AD, and then much later (1774) by the peripatetic American statesman and natural philosopher Benjamin Franklin, to Japanese “floating-ink” art (suminagashi) developed ∼1000 years ago. The modern science of organic monolayers began in the late-1800s/early-1900s with experiments by Lord Rayleigh and the important development by Agnes Pockels, followed two decades later by Irving Langmuir, of the tools and technology to measure the surface tension of liquids, the surface pressure of organic monolayers deposited on water, interfacial properties, molecular conformation of the organic layers, and phase transitions which occur upon compressing the monolayers. In 1935, Katherine Blodgett published a landmark paper showing that multilayers can be synthesized on solid substrates, with controlled thickness and composition, using an apparatus now known as the Langmuir-Blodgett (L-B) trough. A disadvantage of LB films for some applications is that they form weak physisorbed bonds to the substrate. In 1946, Bigelow, Pickett, and Zisman demonstrated, in another seminal paper, the growth of organic self-assembled monolayers (SAMs) via spontaneous adsorption from solution, rather than from the water/air interface, onto SiO{sub 2} and metal substrates. SAMs are close-packed two-dimensional organic crystals which exhibit strong covalent bonding to the substrate. The first multicomponent adsorbed monolayers and multilayer SAMs were produced in the early 1980s. Langmuir monolayers, L-B multilayers, and self-assembled mono- and multilayers have found an extraordinarily broad range of applications including

  20. 7 CFR 1400.503 - Commensurate reduction.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ..., general partnership, or joint venture will be reduced by an amount commensurate with the direct and indirect ownership interest in the legal entity, general partnership, or joint venture of each person...

  1. Monolayer MoS2 films supported by 3D nanoporous metals for high-efficiency electrocatalytic hydrogen production.

    PubMed

    Tan, Yongwen; Liu, Pan; Chen, Luyang; Cong, Weitao; Ito, Yoshikazu; Han, Jiuhui; Guo, Xianwei; Tang, Zheng; Fujita, Takeshi; Hirata, Akihiko; Chen, Mingwei W

    2014-12-17

    The "edge-free" monolayer MoS2 films supported by 3D nanoporous gold show high catalytic activities towards hydrogen evolution reaction (HER), originating from large out-of-plane strains that are geometrically required to manage the 3D curvature of bicontinuous nanoporosity. The large lattice bending leads to local semiconductor-to-metal transition of 2H MoS2 and the formation of catalytically active sites for HER.

  2. Inorganic-organic composite nanoengineered films using self-assembled monolayers for directed zeolite film growth

    SciTech Connect

    Dye, R.C.; Hermes, R.E.; Martinez, M.G.; Peachey, N.M.

    1997-10-01

    This is the final report of a one-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). Zeolites, or molecular sieves, are aluminosilicate cage structures that are typically grown from a heterogeneous mixture of organic template molecules, inorganic salts of alumina and silica, and water. These zeolites are used in industry for catalytic cracking of hydrocarbons (gasoline manufacture from oil), and contaminant removal from chemical production processes. Within one year, we developed a viable method for the deposition of a quaternary ammonium salt amphiphile onto silicon wafer substrates. Using a biomimetic growth process, we were also able to demonstrate the first thin-film formation of a zeolite structure from such an organic template. Additionally, we synthesized the precursor to another amphiphile which was to be for further studies.

  3. Copper phthalocyanine thin films on Cu(111): Sub-monolayer to multi-layer

    NASA Astrophysics Data System (ADS)

    Stock, T. J. Z.; Nogami, J.

    2015-07-01

    Scanning tunneling microscopy (STM) has been used to observe the growth mode and crystal structure of sub-monolayer (ML) to multilayer thin films of copper phthalocyanine (CuPc) molecules on the Cu(111) surface at room temperature (RT). At sub-ML coverage the molecules are mobile on the surface. At approximately one ML coverage the molecules become sterically confined and lying flat on the Cu substrate form an ordered, multi-domained, 2D oblique lattice. As coverage is increased beyond 1 ML the molecule-substrate interaction diminishes in strength while the intermolecular interaction begins to dominate, causing the layer separation to increase, and the crystal domain size and lattice constants to shrink as the crystal structure begins to more closely resemble the bulk α-phase CuPc molecular solid. This trend continues for the layer-by-layer growth of 3 complete ML, eventually giving way to the emergence of large 3D islands at a coverage equivalent to 4 ML.

  4. Vortex phase transitions in monolayer FeSe film on SrTiO3

    NASA Astrophysics Data System (ADS)

    Zhao, Weiwei; Chang, Cui-Zu; Xi, Xiaoxiang; Mak, Kin Fai; Moodera, Jagadeesh S.

    2016-06-01

    The voltage–current (V–I) characteristics in superconducting monolayer FeSe film on SrTiO3 (100) under different magnetic fields are investigated. The zero-field V–I result exhibits signatures of a Berezinski–Kosterlitz–Thouless transition, a characteristic of two-dimensional (2D) superconductors. Under an applied magnetic field, with current density lower than the critical current density, the sheet resistance versus current density (R sq–J) dependence changes from ohmic (R sq independent of J) to non-ohmic (a nonlinear dependence of R sq on J) as the temperature decreases, indicative of a vortex phase transition/crossover. We interpret the high-temperature phase as the vortex liquid phase and the low-temperature phase as the vortex slush phase, which has short-ranged vortex lattice correlation, while long-range correlation (i.e. true superconductivity) is absent. No transition into a vortex glass phase is seen, illustrating the importance of thermal fluctuations in a perfect 2D superconductor under a magnetic field.

  5. Intercalated samarium as an agent enabling the intercalation of oxygen under a monolayer graphene film on iridium

    NASA Astrophysics Data System (ADS)

    Afanas'eva, E. Yu.; Rut'kov, E. V.; Gall', N. R.

    2016-06-01

    Using thermal desorption time-of-flight mass spectrometry and thermionic methods, it is shown that oxygen does not intercalate under a graphene monolayer grown correctly on iridium, at least at temperatures of T = 300-400 K and exposures below 12000 L. However, if the graphene film on iridium is preliminary intercalated with samarium atoms (up to coverage of θSm = 0.2-0.45), the penetration of oxygen atoms under the graphene film is observed. The oxygen atoms in the intercalated state are chemically bonded to samarium atoms and remain under graphene up to high temperatures (~2150 K).

  6. Commensurabilities between ETNOs: a Monte Carlo survey

    NASA Astrophysics Data System (ADS)

    de la Fuente Marcos, C.; de la Fuente Marcos, R.

    2016-07-01

    Many asteroids in the main and trans-Neptunian belts are trapped in mean motion resonances with Jupiter and Neptune, respectively. As a side effect, they experience accidental commensurabilities among themselves. These commensurabilities define characteristic patterns that can be used to trace the source of the observed resonant behaviour. Here, we explore systematically the existence of commensurabilities between the known ETNOs using their heliocentric and barycentric semimajor axes, their uncertainties, and Monte Carlo techniques. We find that the commensurability patterns present in the known ETNO population resemble those found in the main and trans-Neptunian belts. Although based on small number statistics, such patterns can only be properly explained if most, if not all, of the known ETNOs are subjected to the resonant gravitational perturbations of yet undetected trans-Plutonian planets. We show explicitly that some of the statistically significant commensurabilities are compatible with the Planet Nine hypothesis; in particular, a number of objects may be trapped in the 5:3 and 3:1 mean motion resonances with a putative Planet Nine with semimajor axis ˜700 au.

  7. CO Oxidation Prefers the Eley-Rideal or Langmuir-Hinshelwood Pathway: Monolayer vs Thin Film of SiC.

    PubMed

    Sinthika, S; Vala, Surya Teja; Kawazoe, Y; Thapa, Ranjit

    2016-03-01

    Using the first-principles approach, we investigated the electronic and chemical properties of wurtzite silicon carbide (2H-SiC) monolayer and thin film structures and substantiated their catalytic activity toward CO oxidation. 2H-SiC monolayer, being planar, is quite stable and has moderate binding with O2, while CO interacts physically; thus, the Eley-Rideal (ER) mechanism prevails over the Langmuir-Hinshelwood (LH) mechanism with an easily cleared activation barrier. Contrarily, 2H-SiC thin film, which exhibits a nonplanar structure, allows moderate binding of both CO and O2 on its surface, thus favoring the LH mechanism over the ER one. Comprehending these results leads to a better understanding of the reaction mechanisms involving structural contrast. Weak overlapping between the 2p(z)(C) and 3p(z)(Si) orbitals of the SiC monolayer system has been found to be the primary reason to revert the active site toward sp(3) hybridization, during interaction with the molecules. In addition, the influences of graphite and Ag(111) substrates on the CO oxidation mechanism were also studied, and it is observed that the ER mechanism is preserved on SiC/G system, while CO oxidation on the SiC/Ag(111) system follows the LH mechanism. The calculated Sabatier activities of the SiC catalysts show that the catalysts are very efficient in catalyzing CO oxidation.

  8. CO Oxidation Prefers the Eley-Rideal or Langmuir-Hinshelwood Pathway: Monolayer vs Thin Film of SiC.

    PubMed

    Sinthika, S; Vala, Surya Teja; Kawazoe, Y; Thapa, Ranjit

    2016-03-01

    Using the first-principles approach, we investigated the electronic and chemical properties of wurtzite silicon carbide (2H-SiC) monolayer and thin film structures and substantiated their catalytic activity toward CO oxidation. 2H-SiC monolayer, being planar, is quite stable and has moderate binding with O2, while CO interacts physically; thus, the Eley-Rideal (ER) mechanism prevails over the Langmuir-Hinshelwood (LH) mechanism with an easily cleared activation barrier. Contrarily, 2H-SiC thin film, which exhibits a nonplanar structure, allows moderate binding of both CO and O2 on its surface, thus favoring the LH mechanism over the ER one. Comprehending these results leads to a better understanding of the reaction mechanisms involving structural contrast. Weak overlapping between the 2p(z)(C) and 3p(z)(Si) orbitals of the SiC monolayer system has been found to be the primary reason to revert the active site toward sp(3) hybridization, during interaction with the molecules. In addition, the influences of graphite and Ag(111) substrates on the CO oxidation mechanism were also studied, and it is observed that the ER mechanism is preserved on SiC/G system, while CO oxidation on the SiC/Ag(111) system follows the LH mechanism. The calculated Sabatier activities of the SiC catalysts show that the catalysts are very efficient in catalyzing CO oxidation. PMID:26866799

  9. Charge Dynamics and Electronic Structures of Monolayer MoS2 Films Grown by Chemical Vapor Deposition

    NASA Astrophysics Data System (ADS)

    Shen, Chih-Chiang; Hsu, Yu-Te; Li, Lain-Jong; Liu, Hsiang-Lin

    2013-12-01

    THz absorption and spectroscopic ellipsometry were used to investigate the charge dynamics and electronic structures of chemical-vapor-deposited monolayer MoS2 films. THz conductivity displays a coherent response of itinerant charge carriers at zero frequency. Drude plasma frequency (˜7 THz) decreases with decreasing temperature while carrier relaxation time (˜26 fs) is almost temperature independent. The absorption spectrum of monolayer MoS2 shows a direct 1.95 eV band gap and charge transfer excitations that are ˜0.2 eV higher than those of the bulk counterpart. The ground-state exciton binding energy is found to be about 0.48 eV.

  10. The role of surface Pt on the coadsorption of hydrogen and CO on Pt monolayer film modified Ru(0001) surfaces

    NASA Astrophysics Data System (ADS)

    Diemant, T.; Hartmann, H.; Bansmann, J.; Behm, R. J.

    2016-10-01

    We have investigated the impact and role of the Pt surface modification on the coadsorption of hydrogen and CO on structurally well defined bimetallic Pt monolayer island/film modified Ru(0001) surfaces with Pt contents up to a complete Pt layer, employing temperature programmed desorption (TPD) and infrared reflection absorption spectroscopy (IRRAS). Kinetic limitations in the surface diffusion are shown to play an important role for adsorption at 90 K, and lead to profound effects of the dosing sequence on the adsorption and desorption characteristics. Furthermore, they are responsible for spill-over effects during the TPD measurements, where COad becomes mobile and can spill-over from weakly bonding Pt monolayer areas to strongly bonding Pt-free Ru(0001) areas, which displaces Dad from these surface areas. The present findings are discussed in comparison with previous results on related metallic and bimetallic adsorption and coadsorption systems.

  11. Phase Determination of Second-Order Surface Susceptibility Tensor of Liquid Crystal Monolayer Using Ultra-Thin Film Local Oscillator

    NASA Astrophysics Data System (ADS)

    Sei, Masaki; Nagayama, Kohei; Kajikawa, Kotaro; Ishii, Hisao; Seki, Kazuhiko; Kondo, Katsumi; Matsumoto, Yoshiyasu; Ouchi, Yukio

    1998-04-01

    We demonstrated full determination of second-order nonlinear susceptibility of a 4‧-n-octyl-4-cyanobiphenyl (8CB) liquid crystal (LC) monolayer adsorbed on a second-harmonic (SH) active polyimide (PI) substrate. In order to separate the SH signal of the LC film from that of the PI film, we adopted an interferometry technique of second-harmonic generation (SHG) using an ultra-thin film local oscillator. We have found a variety of phases in the components of susceptibility: those of χzii and χizi are almost the same but the phase of χzzz differs by 80° from the other two. The phases of the components of the surface susceptibility tensor are not always identical. This fact indicates that the surface SH response is more complicated than what we expected.

  12. Perforated monolayers

    SciTech Connect

    Regen, S.L.

    1989-12-01

    The goals of this DOE-sponsored program are to create novel organic thin films that possess well-defined and adjustable molecular pores; i.e. perforated monolayers,'' and to use such film for fabricating composite membranes that have unique permeation characteristics. The specific strategy that has been adopted involves (1) the synthesis of surfactant molecules bearing internal pores, i.e., porous surfactants,'' (2) the assembly of such molecules at an air--water interface, and (3) the stabilization of the resulting assembly via polymerization, before or after transfer to a macroporous support. Research that has been carried out to date has demonstrated the feasibility of using suitably designed calix(n)arene molecules as a basis for constructing perforated monolayers. Specifically, a broad range of calix(n)arenes have been mercurated with mercury trifluoracetate, and used to form polymerized and porous monolayers at the air--water interface. In related studies, p-tert- butylcalix(6)arene has been shown to produce stable monolayers at the air--water interface; removal of the p-tert-butyl groups afford a unique vesicle-forming surfactant, calix(6)arene.

  13. Effects of poly (ethylene glycol) chains conformational transition on the properties of mixed DMPC/DMPE-PEG thin liquid films and monolayers.

    PubMed

    Georgiev, Georgi As; Sarker, Dipak K; Al-Hanbali, Othman; Georgiev, Georgi D; Lalchev, Zdravko

    2007-10-01

    Foam thin liquid films (TLF) and monolayers at the air-water interface formed by DMPC mixed with DMPE-bonded poly (ethylene glycol)s (DMPE-PEG(550), DMPE-PEG(2000) and DMPE-PEG(5000)) were obtained. The influence of both (i) PEG chain size (evaluated in terms of Mw) and mushroom-to-brush conformational transition and (ii) of the liposome/micelle ratio in the film-forming dispersions, on the interfacial properties of mixed DMPC/DMPE-PEG films was compared. Foam film studies demonstrated that DMPE-PEG addition to foam TLFs caused (i) delayed kinetics of film thinning and black spot expansion and (ii) film stabilization. At the mushroom-to-brush transition, due to steric repulsion increased DMPE-PEG films thickness reached 25 nm while pure DMPC films were only 8 nm thick Newton black films. It was possible to differentiate DMPE-PEG(2000/5000) from DMPE-PEG(550) by the ability to change foam TLF formation mechanism, which could be of great importance for "stealth" liposome design. Monolayer studies showed improved formation kinetics and equilibrium surface tension decrease for DMPE-PEG monolayers compared with DMPC pure films. SEM observations revealed "smoothing" and "sealing" of the defects in the solid-supported layer surface by DMPE-PEGs adsorption, which could explain DMPE-PEGs ability to stabilize TLFs and to decrease monolayer surface tension. All effects in monolayers, foam TLFs and solid-supported layers increased with the increase of PEG Mw and DMPE-PEG concentration. However, at the critical DMPE-PEG concentration (where mushroom-to-brush conformational transition occurred) maximal magnitude of the effects was reached, which only slightly changed at further DMPE-PEG content and micelle/liposome ratio increase.

  14. Structure and dynamics of monolayer films of squalane molecules adsorbed on a solid surface

    NASA Astrophysics Data System (ADS)

    D. T Enevoldsen, A.; Hansen, F. Y.; Diama, A.; Taub, H.

    2003-03-01

    Squalane is a branched alkane (C_30H_62). It consists of a straight chain with 24 carbon atoms, as in tetracosane (C_24H_50), and has six methyl side groups. Branched polymers such as squalane are thought to be better lubricants than n-alkanes. At low temperature, our molecular dynamics (MD) simulations show that the molecules form an ordered monolayer which melts at approximately 325 K compared to the tetracosane monolayer melting point of ˜ 340 K. Our MD simulations indicate the same melting mechanism in the squalane monolayer that was found previously for tetracosane (F. Y. Hansen and H. Taub, Phys. Rev. Lett. 69, 652 (1992).) They also show that the adsorbed molecules are distorted from an all-trans carbon backbone in contrast to what was found for tetracosane. This may explain why the Bragg diffraction peaks were observed to be broader for the squalane monolayer than for tetracosane (D. Fuhrmann, A. P. Graham, L. Criswell, H. Mo, B. Matthies, K. W. Herwig, and H. Taub, Surf. Sci. 482-485, 77 (2001).). The diffusive motion in a squalane monolayer has been investigated by both quasielastic neutron scattering and MD simulations and compared to the dynamics in tetracosane monolayers. Focus will be on differences in the dynamics.

  15. Continuous ultrathin silver films deposited on SiO2 and SiNx using a self-assembled monolayer

    NASA Astrophysics Data System (ADS)

    Hafezian, Soroush; Maloney, Kate; Lefebvre, Josianne; Martinu, Ludvik; Kéna-Cohen, Stéphane

    2016-09-01

    In this letter, we study the deposition of ultrathin silver films on silicon oxide and nitride surfaces functionalized with self-assembled monolayers of (3-mercaptopropyl)-trimethoxysilane. First, we compare both solution and vapour-phase functionalization techniques and find the greatest improvement in electrical and optical properties using deposition from solution. Using X-ray photoelectron spectroscopy, we demonstrate that the formation of silver-sulfur covalent bonds is at the root of the improved wetting confirmed by ellipsometry, sheet resistance measurement, and atomic force microscopy. Second, we show that this technique can be extended to functionalize silicon nitride. Finally, we demonstrate a simple, but efficient, low-emissivity optical filter.

  16. Growth mechanism of largescale MoS2 monolayer by sulfurization of MoO3 film

    NASA Astrophysics Data System (ADS)

    Taheri, Payam; Wang, Jieqiong; Xing, Hui; Destino, Joel F.; Murat Arik, Mumtaz; Zhao, Chuan; Kang, Kaifei; Blizzard, Brett; Zhang, Lijie; Zhao, Puqin; Huang, Shaoming; Yang, Sen; Bright, Frank V.; Cerne, John; Zeng, Hao

    2016-07-01

    Monolayer two-dimensional transition metal dichalcogenides (TMDCs) such as MoS2 with broken inversion symmetry possesses two degenerate yet inequivalent valleys that can be selectively excited by circularly polarized light. This unique property renders interesting valley physics. The ability to manipulate valley degrees of freedom with light or external field makes them attractive for optoelectronic and spintronic applications. There is great demand for large area monolayer (ML) TMDCs for certain measurements and device applications. Recent reports on large area ML TDMCs focus on chemical vapor deposition growth. In this work, we report a facile approach to grow largescale continuous ML MoS2 nearly free of overgrowth and voids, by sulfurizing evaporated molybdenum trioxide ultrathin films. Photo conductivity scales with device sizes up to 4.5 mm, suggesting excellent film uniformity. The growth mechanism is found to be vaporization, diffusion, sulfurization and lateral growth, all at local micrometer scale. Our approach provides a new pathway for large-area ML TMDC growth and lithography-free device fabrication.

  17. Manipulation of the ultimate pattern of polypyrrole film on self-assembled monolayer patterned substrate by negative or positive electrodeposition

    NASA Astrophysics Data System (ADS)

    Zhou, Feng; Liu, Zhilu; Yu, Bo; Chen, Miao; Hao, Jingcheng; Liu, Weimin; Xue, Qunji

    2004-07-01

    Micro printed self-assembled monolayer may lead to different ultimate patterns of polypyrrole (PPy) by way of positive or negative deposition in guiding the electrodeposition of pyrrole. This article gives a detailed investigation of the effects of experimental conditions on the ultimate patterns of the PPy films on self-assembled monolayer (SAM)-patterned silicon and gold substrates. The effects of the substrate surface electric properties and the nature of the solvent and supporting electrolyte on the selective deposition and the PPy film morphology are also discussed. As the results, negative deposition occurs on the octadecyltrichlorosilane (OTS)-covered area of semiconductor Si surface in non-aqueous acetonitrile solution and results in positive patterns, while positive deposition occurs in aqueous solution and gives birth to negative patterns. This is attributed to the accessibility of the monomer solution to the substrate surface. The electrodeposition preferentially occurs on the exposed area of a gold substrate, though the deposition on the octadecanthiol (ODT)-covered area is unavoidable due to the hydrophobic-hydrophobic interaction. The lypophilic properties of the deposited PPy can be modified by selecting different salts as the supporting electrolytes and doping different anions during the electrodeposition. Subsequently, the morphology of the electro-deposited PPy layer can be tailored making use of the interaction between the PPy oligomer and the surfaces of different chemical functionalities.

  18. Influence of dispersion forces and ordering on the compositions of mixed monolayers of alkanoic acids on nanocrystalline TiO2 films.

    PubMed

    Kern, Meghan E; Watson, David F

    2013-11-12

    Lateral dispersion forces induce the ordering of n-alkanoic acids on nanocrystalline TiO2 films and cause the compositions of mixed monolayers to change. The equilibrium formation of single-component monolayers of n-alkanoic acids and 6-bromohexanoic acid (Br6A) on TiO2 was well-modeled by the Langmuir adsorption isotherm. Surface adduct formation constants were 10(3)-10(4) M(-1), and saturation amounts of adsorbates per projected surface area of TiO2 were on the order of 10(-7) mol cm(-2). The adsorption of n-heneicosanoic acid (21A) followed Langmuir kinetics, whereas the net rates of adsorption of shorter n-alkanoic acids and Br6A were slower than predicted by simple Langmuir kinetics, suggesting that desorption was non-negligible. At high surface coverages, n-alkanoic acids with 14 or more methylene groups formed ordered, crystalline monolayers, as evidenced by shifts of asymmetric and symmetric CH2 stretching bands in IR spectra. The extent of ordering was similar to that of self-assembled monolayers of alkanethiols on gold. The formation of ordered monolayers was well-modeled by an idealized mechanism, in which adsorption and desorption followed Langmuir kinetics and ordering was first-order with respect to the fractional surface coverage of adsorbates. Dispersion forces and ordering affected the compositions of mixed monolayers of 21A and Br6A on TiO2 films that remained in contact with mixed coadsorption solutions. When the fractional surface coverage of 21A was sufficiently high to induce ordering, it displaced Br6A from TiO2. We propose that these compositional changes were driven by the stabilization of 21A via cohesive lateral dispersion forces. Our results reveal that mixed monolayers on nanocrystalline TiO2 films are dynamic and that noncovalent intermolecular interactions can profoundly influence their compositions and properties.

  19. Excitonic resonances in thin films of WSe2: from monolayer to bulk material

    NASA Astrophysics Data System (ADS)

    Arora, Ashish; Koperski, Maciej; Nogajewski, Karol; Marcus, Jacques; Faugeras, Clément; Potemski, Marek

    2015-06-01

    We present optical spectroscopy (photoluminescence and reflectance) studies of thin layers of the transition metal dichalcogenide WSe2, with thickness ranging from mono- to tetra-layer and in the bulk limit. The investigated spectra show the evolution of excitonic resonances as a function of layer thickness, due to changes in the band structure and, importantly, due to modifications of the strength of Coulomb interactions as well. The observed temperature-activated energy shift and broadening of the fundamental direct exciton are well accounted for by standard formalisms used for conventional semiconductors. A large increase of the photoluminescence yield with temperature is observed in a WSe2 monolayer, indicating the existence of competing radiative channels. The observation of absorption-type resonances due to both neutral and charged excitons in the WSe2 monolayer is reported and the effect of the transfer of oscillator strength from charged to neutral excitons upon an increase of temperature is demonstrated.

  20. Large-roll growth of 25-inch hexagonal BN monolayer film for self-release buffer layer of free-standing GaN wafer

    PubMed Central

    Wu, Chenping; Soomro, Abdul Majid; Sun, Feipeng; Wang, Huachun; Huang, Youyang; Wu, Jiejun; Liu, Chuan; Yang, Xiaodong; Gao, Na; Chen, Xiaohong; Kang, Junyong; Cai, Duanjun

    2016-01-01

    Hexagonal boron nitride (h-BN) is known as promising 2D material with a wide band-gap (~6 eV). However, the growth size of h-BN film is strongly limited by the size of reaction chamber. Here, we demonstrate the large-roll synthesis of monolayer and controllable sub-monolayer h-BN film on wound Cu foil by low pressure chemical vapor deposition (LPCVD) method. By winding the Cu foil substrate into mainspring shape supported by a multi-prong quartz fork, the reactor size limit could be overcome by extending the substrate area to a continuous 2D curl of plane inward. An extremely large-size monolayer h-BN film has been achieved over 25 inches in a 1.2” tube. The optical band gap of h-BN monolayer was determined to be 6.0 eV. The h-BN film was uniformly transferred onto 2” GaN or 4” Si wafer surfaces as a release buffer layer. By HVPE method, overgrowth of thick GaN wafer over 200 μm has been achieved free of residual strain, which could provide high quality homo-epitaxial substrate. PMID:27756906

  1. Microwave-Accelerated Surface Modification of Plasmonic Gold Thin Films with Self-Assembled Monolayers of Alkanethiols

    PubMed Central

    Grell, Tsehai A.J.; Alabanza, Anginelle M.; Gaskell, Karen; Aslan, Kadir

    2013-01-01

    A rapid surface modification technique for the formation of self-assembled monolayers (SAMs) of alkanethiols on gold thin films using microwave heating in less than 10 min is reported. In this regard, SAMs of two model alkanethiols, 11-mercaptoundecanoic acid (11-MUDA, to generate a hydrophilic surface) and undecanethiol (UDET, a hydrophobic surface), were successfully formed on gold thin films using selective microwave heating in 1) a semi-continuous and 2) a continuous fashion and at room temperature (24 hours, control experiment, no microwave heating). The formation of SAMs of 11-MUDA and UDET were confirmed by contact angle measurements, Fourier–transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The contact angles for water on SAMs formed by the selective microwave heating and conventional room temperature incubation technique (24 hours) were measured to be similar for 11-MUDA and UDET. FT-IR spectroscopy results confirmed that the internal structure of SAMs prepared using both microwave heating and at room temperature were similar. XPS results revealed that the organic and sulfate contaminants found on bare gold thin films were replaced by SAMs after the surface modification process was carried out using both microwave heating and at room temperature. PMID:24083414

  2. Langmuir monolayers and thin films of amphifilic thiacalix[4]arenes. Properties and matrix for the immobilization of cytochrome c.

    PubMed

    Solovieva, Svetlana E; Safiullin, Roman A; Kochetkov, Evgeni N; Melnikova, Nina B; Kadirov, Marsil K; Popova, Elena V; Antipin, Igor S; Konovalov, Alexander I

    2014-12-23

    Formation and properties of Langmuir films of thiacalix[4]arene (TCA) derivatives containing N-donor groups on the lower rim (Y═O(CH2)3CN; OCH2CN; NH2; OCH2ArCN-p) in 1,3-alternate conformation on aqueous subphase and solid substrates have been studied. Only tetra-cyanopropoxy-p-tert-butylthiacalix[4]arene 1 forms a typical monomolecular layer with perpendicular orientation of the macrocycle relative to the water-air interface that is able to immobilize cytochrome c in the entire range of the surface pressure. Obtained monolayers were transferred by Langmuir-Schaefer technique onto quartz, indium-tin oxide (ITO), and silicon. It was demonstrated that protein activity is retained after immobilization on the substrate. PMID:25435075

  3. Langmuir monolayers and thin films of amphifilic thiacalix[4]arenes. Properties and matrix for the immobilization of cytochrome c.

    PubMed

    Solovieva, Svetlana E; Safiullin, Roman A; Kochetkov, Evgeni N; Melnikova, Nina B; Kadirov, Marsil K; Popova, Elena V; Antipin, Igor S; Konovalov, Alexander I

    2014-12-23

    Formation and properties of Langmuir films of thiacalix[4]arene (TCA) derivatives containing N-donor groups on the lower rim (Y═O(CH2)3CN; OCH2CN; NH2; OCH2ArCN-p) in 1,3-alternate conformation on aqueous subphase and solid substrates have been studied. Only tetra-cyanopropoxy-p-tert-butylthiacalix[4]arene 1 forms a typical monomolecular layer with perpendicular orientation of the macrocycle relative to the water-air interface that is able to immobilize cytochrome c in the entire range of the surface pressure. Obtained monolayers were transferred by Langmuir-Schaefer technique onto quartz, indium-tin oxide (ITO), and silicon. It was demonstrated that protein activity is retained after immobilization on the substrate.

  4. Molecular mobility in the monolayers of foam films stabilized by porcine lung surfactant.

    PubMed Central

    Lalchev, Z I; Todorov, R K; Christova, Y T; Wilde, P J; Mackie, A R; Clark, D C

    1996-01-01

    Certain physical properties of a range of foam film types that are believed to exist in vivo in the lung have been investigated. The contribution of different lung surfactant components found in porcine lung surfactant to molecular surface diffusion in the plane of foam films has been investigated for the first time. The influence of the type and thickness of black foam films, temperature, electrolyte concentration, and extract composition on surface diffusion has been studied using the fluorescence recovery after photobleaching technique. Fluorescent phospholipid probe molecules in foam films stabilized by porcine lung surfactant samples or their hydrophobic extracts consisting of surfactant lipids and hydrophobic lung surfactant proteins, SP-B and SP-C, exhibited more rapid diffusion than observed in films of its principal lipid component alone, L-alpha-phosphatidylcholine dipalmitoyl. This effect appears to be due to contributions from minor lipid components present in the total surfactant lipid extracts. The minor lipid components influence the surface diffusion in foam films both by their negative charge and by lowering the phase transition temperature of lung surfactant samples. In contrast, the presence of high concentrations of the hydrophillic surfactant protein A (SP-A) and non-lung-surfactant proteins in the sample reduced the diffusion coefficient (D) of the lipid analog in the adsorbed layer of the films. Hysteresis behavior of D was observed during temperature cycling, with the cooling curve lying above the heating curve. However, in cases where some surface molecular aggregation and surface heterogeneity were observed during cooling, the films became more rigid and molecules at the interfaces became immobilized. The thickness, size, capillary pressure, configuration, and composition of foam films of lung surfactant prepared in vitro support their investigation as realistic structural analogs of the surface films that exist in vivo in the lung

  5. Direct Observation of Degenerate Two-Photon Absorption and Its Saturation in WS2 and MoS2 Monolayer and Few-Layer Films.

    PubMed

    Zhang, Saifeng; Dong, Ningning; McEvoy, Niall; O'Brien, Maria; Winters, Sinéad; Berner, Nina C; Yim, Chanyoung; Li, Yuanxin; Zhang, Xiaoyan; Chen, Zhanghai; Zhang, Long; Duesberg, Georg S; Wang, Jun

    2015-07-28

    The optical nonlinearity of WS2 and MoS2 monolayer and few-layer films was investigated using the Z-scan technique with femtosecond pulses from the visible to the near-infrared range. The nonlinear absorption of few- and multilayer WS2 and MoS2 films and their dependences on excitation wavelength were studied. WS2 films with 1-3 layers exhibited a giant two-photon absorption (TPA) coefficient as high as (1.0 ± 0.8) × 10(4) cm/GW. TPA saturation was observed for the WS2 film with 1-3 layers and for the MoS2 film with 25-27 layers. The giant nonlinearity of WS2 and MoS2 films is attributed to a two-dimensional confinement, a giant exciton effect, and the band edge resonance of TPA. PMID:26135798

  6. Improved microstructure and performance of PbS thin films via in-situ thermal decomposition of lead xanthate precursors using self-assembling monolayer

    NASA Astrophysics Data System (ADS)

    Wang, Jingni; Yao, Kai; Jia, Zhenrong; Wang, Xiaofeng; Li, Fan

    2016-09-01

    Microstructure control is critical to achieve thin film-based devices with high performance. The surface properties of the substrates on which thin films grow are expected to greatly influence the morphology and the resulting performance. Generally, homogeneous, dense and highly crystalline films are required. However, "island" like structures are usually obtained mainly due to the non-uniform nucleation. In this article, the self-assembling monolayer (SAM) strategy was applied to efficiently realize the uniform nucleation and modulate the microstructure of lead sulfide (PbS) thin films, which were fabricated on the modified ZnO-coated substrates with 3-mercaptopropionic acid (MPA) SAM via in-situ thermal decomposition of lead xanthate precursors. The results showed that PbS thin films with reduced pin-holes and uniform crystalline grains were fabricated with the incorporation of MPA SAM. More importantly, PbS thin films modulated by MPA showed better photoelectric response.

  7. Cognition and order in Langmuir-Blodgett films of a 3-hexadecyl pyrrole and ferrocene-derivatized pyrrole mixed monolayer system

    SciTech Connect

    Samuelson, L.; Rahman, A.K.M.; Puglia, G.P.; Clough, S.; Tripathy, S.; Inagaki, T.; Yang, X.Q.; Skotheim, T.A.; Okamoto, Y.

    1989-01-01

    Novel, self-assembled materials have been designed and produced from first principle to possess unique structural hierarchy and electronic and optical properties. The Langmuir-Blodgett technique was used to study the molecular organization of a mixed 3-hexadecyl pyrrole (3HDP) and ferrocene-derivatized pyrrole (Fc-Py) surfactant system. The pyrrole moiety was chosen for its' well established electronic and optical properties when polymerized, while ferrocene, it is theorized, if properly oriented into a Langmuir-Blodgett monolayer film may show a layered array of transition metals which would be extremely valuable as a model for two-dimensional magnets. The ferrocene group may also provide the possibility of charge coupling between neutral ferrocene and oxidized ferricenium which could be controlled electrochemically or photochemically. It has been determined that stable monolayer films of the mixed system could be formed at the air-water interface. The growth and assembly process led to polypyrrole 2-D lattices with heretofore unsurpassed order. In fact, the process of template polymerization leads to a new crystal phase for the polypyrrole component of the thin film structure. Various monolayer and multilayer films were prepared on platinum coated substrates for surface spectroscopic characterization using synchrotron radiation. Near Edge X-Ray Absorption Fine Structure studies revealed that highly ordered multilayer structures are being formed. 8 refs., 4 figs., 1 tab.

  8. Structure and spectroscopic analysis of the graphene monolayer film directly grown on the quartz substrate via the HF-CVD technique

    NASA Astrophysics Data System (ADS)

    Mahmoud, Waleed E.; Al-Hazmi, Farag S.; Al-Ghamdi, A. A.; Shokr, F. S.; Beall, Gary W.; Bronstein, Lyudmila M.

    2016-08-01

    Direct growth of a monolayer graphene film on a quartz substrate by a hot filament chemical vapor deposition technique is reported. The monolayer graphene film prepared was characterized by Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), selected area electron diffraction (SAED), and atomic force microscopy (AFM). The optical properties were studied by spectroscopic elliposmetry. The experimental data were fitted by the Forouhi-Bloomer model to estimate the extinction coefficient and the refractive index of the monolayer graphene film. The refractive index spectrum in the visible region was studied based on the harmonic oscillator model. The lattice dielectric constant, real and imaginary dielectric constants and the ratio of the charge carrier number to the effective mass were determined. The surface and volume energy loss parameters were also found and showed that the value of the surface energy loss is greater than the volume energy loss. The determination of these optical constants will open new avenue for novel applications of graphene films in the field of wave plates, light modulators, ultrahigh-frequency signal processing and LCDs.

  9. Calcium ion interactions with insoluble phospholipid monolayer films at the A/W interface. External reflection-absorption IR studies.

    PubMed Central

    Flach, C R; Brauner, J W; Mendelsohn, R

    1993-01-01

    External reflection Fourier transform infrared (FT-IR) experiments are reported for insoluble monomolecular films of an equimolar mixture of 1,2-dipalmitoylphosphatidylcholine (DPPC) and 1,2-dipalmitoylphosphatidylserine (DPPS) at the A/W interface as a function of surface pressure and Ca2+ ion presence. The separate components showed a surface pressure-induced conformational ordering of the acyl chains. The conformational ordering occurred more cooperatively for the DPPS. Acyl chain perdeuteration of the DPPC permitted the observation of the response of the individual components in the binary mixture to changes in surface tension and to the presence of Ca2+. Plots of surface pressure versus CH2 or CD2 stretching frequencies were analyzed with a two-state model. At each surface pressure within the two-state region, the fraction of disordered form was the same for each lipid component, suggesting that they are well mixed on the surface. Calcium ion (5 mM in the subphase) produces almost no effect on the pressure-induced acyl chain ordering of the DPPC in a single component film, whereas the same levels of Ca2+ induce acyl chain ordering at all surface pressures in both components of the binary mixture. Thus, unlike the bulk phase mixture of DPPC/DPPS, the binary lipids in this mixed monolayer film appear to retain their miscibility in the presence of Ca2+. Finally, Ca(2+)-induced dehydration of the phosphate group was observed through characteristic frequency shifts in the asymmetric PO2- stretching mode. PMID:8298029

  10. Chemical stability of nonwetting, low adhesion self-assembled monolayer films formed by perfluoroalkylsilanization of copper

    NASA Astrophysics Data System (ADS)

    Hoque, E.; DeRose, J. A.; Hoffmann, P.; Bhushan, B.; Mathieu, H. J.

    2007-03-01

    A self-assembled monolayer (SAM) has been produced by reaction of 1H,1H,2H,2H-perfluorodecyldimethylchlorosilane (PFMS) with an oxidized copper (Cu) substrate and investigated by x-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), friction force microscopy (FFM), a derivative of AFM, and contact angle measurement. FFM showed a significant reduction in the adhesive force and friction coefficient of PFMS modified Cu (PFMS/Cu) compared to unmodified Cu. The perfluoroalkyl SAM on Cu is found to be extremely hydrophobic, yielding sessile drop static contact angles of more than 130° for pure water and a "surface energy" (which is proportional to the Zisman critical surface tension for a Cu surface with 0rms roughness) of 14.5mJ/m2(nM/m). Treatment by exposure to harsh conditions showed that PFMS/Cu SAM can withstand boiling nitric acid (pH=1.8), boiling water, and warm sodium hydroxide (pH =12, 60°C) solutions for at least 30min. Furthermore, no SAM degradation was observed when PFMS/Cu was exposed to warm nitric acid solution for up to 70min at 60°C or 50min at 80°C. Extremely hydrophobic (low surface energy) and stable PFMS/Cu SAMs could be useful as corrosion inhibitors in micro/nanoelectronic devices and/or as promoters for antiwetting, low adhesion surfaces or dropwise condensation on heat exchange surfaces.

  11. Chemical stability of nonwetting, low adhesion self-assembled monolayer films formed by perfluoroalkylsilanization of copper.

    PubMed

    Hoque, E; DeRose, J A; Hoffmann, P; Bhushan, B; Mathieu, H J

    2007-03-21

    A self-assembled monolayer (SAM) has been produced by reaction of 1H,1H,2H,2H-perfluorodecyldimethylchlorosilane (PFMS) with an oxidized copper (Cu) substrate and investigated by x-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), friction force microscopy (FFM), a derivative of AFM, and contact angle measurement. FFM showed a significant reduction in the adhesive force and friction coefficient of PFMS modified Cu (PFMS/Cu) compared to unmodified Cu. The perfluoroalkyl SAM on Cu is found to be extremely hydrophobic, yielding sessile drop static contact angles of more than 130 degrees for pure water and a "surface energy" (which is proportional to the Zisman critical surface tension for a Cu surface with 0 rms roughness) of 14.5 mJm2(nMm). Treatment by exposure to harsh conditions showed that PFMS/Cu SAM can withstand boiling nitric acid (pH=1.8), boiling water, and warm sodium hydroxide (pH=12, 60 degrees C) solutions for at least 30 min. Furthermore, no SAM degradation was observed when PFMS/Cu was exposed to warm nitric acid solution for up to 70 min at 60 degrees C or 50 min at 80 degrees C. Extremely hydrophobic (low surface energy) and stable PFMS/Cu SAMs could be useful as corrosion inhibitors in micro/nanoelectronic devices and/or as promoters for antiwetting, low adhesion surfaces or dropwise condensation on heat exchange surfaces.

  12. Chemical stability of nonwetting, low adhesion self-assembled monolayer films formed by perfluoroalkylsilanization of copper

    SciTech Connect

    Hoque, E.; DeRose, J. A.; Hoffmann, P.; Bhushan, B.; Mathieu, H. J.

    2007-03-21

    A self-assembled monolayer (SAM) has been produced by reaction of 1H,1H,2H,2H-perfluorodecyldimethylchlorosilane (PFMS) with an oxidized copper (Cu) substrate and investigated by x-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), friction force microscopy (FFM), a derivative of AFM, and contact angle measurement. FFM showed a significant reduction in the adhesive force and friction coefficient of PFMS modified Cu (PFMS/Cu) compared to unmodified Cu. The perfluoroalkyl SAM on Cu is found to be extremely hydrophobic, yielding sessile drop static contact angles of more than 130 degree sign for pure water and a 'surface energy' (which is proportional to the Zisman critical surface tension for a Cu surface with 0 rms roughness) of 14.5 mJ/m{sup 2}(nM/m). Treatment by exposure to harsh conditions showed that PFMS/Cu SAM can withstand boiling nitric acid (pH=1.8), boiling water, and warm sodium hydroxide (pH=12, 60 degree sign C) solutions for at least 30 min. Furthermore, no SAM degradation was observed when PFMS/Cu was exposed to warm nitric acid solution for up to 70 min at 60 degree sign C or 50 min at 80 degree sign C. Extremely hydrophobic (low surface energy) and stable PFMS/Cu SAMs could be useful as corrosion inhibitors in micro/nanoelectronic devices and/or as promoters for antiwetting, low adhesion surfaces or dropwise condensation on heat exchange surfaces.

  13. Bimetallic PdAg nanoparticle arrays from monolayer films of diblock copolymer micelles

    NASA Astrophysics Data System (ADS)

    Ehret, E.; Beyou, E.; Mamontov, G. V.; Bugrova, T. A.; Prakash, S.; Aouine, M.; Domenichini, B.; Cadete Santos Aires, F. J.

    2015-07-01

    The self-assembly technique provides a highly efficient route to generate well-ordered structures on a nanometer scale. In this paper, well-ordered arrays of PdAg alloy nanoparticles on flat substrates with narrow distributions of particle size (6-7 nm) and interparticle spacing (about 60 nm) were synthesized by the block copolymer micelle approach. A home-made PS-b-P4VP diblock copolymer was prepared to obtain a micellar structure in toluene. Pd and Ag salts were then successfully loaded in the micellar core of the PS-b-P4VP copolymer. A self-assembled monolayer of the loaded micelles was obtained by dipping the flat substrate in the solution. At this stage, the core of the micelles was still loaded with the metal precursor rather than with a metal. Physical and chemical reducing methods were used to reduce the metal salts embedded in the P4VP core into PdAg nanoparticles. HRTEM and EDX indicated that Pd-rich PdAg alloy nanoparticles were synthesized by chemical or physical reduction; UV-visible spectroscopy observations confirmed that metallic PdAg nanoparticles were quickly formed after chemical reduction; XPS measurements revealed that the PdAg alloy nanoparticles were in a metallic state after a short time of exposure to O2 plasma and after hydrazine reduction.

  14. Commensurability Effects in Viscosity of Nanoconfined Water.

    PubMed

    Neek-Amal, Mehdi; Peeters, Francois M; Grigorieva, Irina V; Geim, Andre K

    2016-03-22

    The rate of water flow through hydrophobic nanocapillaries is greatly enhanced as compared to that expected from macroscopic hydrodynamics. This phenomenon is usually described in terms of a relatively large slip length, which is in turn defined by such microscopic properties as the friction between water and capillary surfaces and the viscosity of water. We show that the viscosity of water and, therefore, its flow rate are profoundly affected by the layered structure of confined water if the capillary size becomes less than 2 nm. To this end, we study the structure and dynamics of water confined between two parallel graphene layers using equilibrium molecular dynamics simulations. We find that the shear viscosity is not only greatly enhanced for subnanometer capillaries, but also exhibits large oscillations that originate from commensurability between the capillary size and the size of water molecules. Such oscillating behavior of viscosity and, consequently, the slip length should be taken into account in designing and studying graphene-based and similar membranes for desalination and filtration.

  15. Commensurability and stability in nonperiodic systems

    PubMed Central

    Fasano, Y.; De Seta, M.; Menghini, M.; Pastoriza, H.; de la Cruz, F.

    2005-01-01

    We have investigated the response of 3D Bi2Sr2CaCu2O8 vortex structures to a weak perturbation induced by 2D Fe pinning structures acting on one extremity of vortex lines. The pinning patterns were nano-engineered at the sample surface by means of either a Bitter decoration of the vortex lattice or electron-beam lithography. The commensurability conditions between 2D rigid pinning potentials and 3D elastic structures with short-range positional and long-range orientational correlation have been experimentally determined. When the 2D potential is a replica of the nonperiodic vortex structure an amplification of its interaction with the vortex structure takes place. This effect is detected only for the first matching field, becoming negligible for other matching fields. On the other hand, a periodic 2D perturbation is shown to transform the nonperiodic Bragg glass-like structure into an Abrikosov crystal with an effective Debye–Waller factor. PMID:16576763

  16. Location of the heme-Fe atoms within the profile structure of a monolayer of cytochrome c bound to the surface of an ultrathin lipid multilayer film.

    PubMed Central

    Pachence, J M; Fischetti, R F; Blasie, J K

    1989-01-01

    We have recently developed x-ray diffraction methods to derive the profile structure of ultrathin lipid multilayer films having one to five bilayers (e.g., Skita, V., W. Richardson, M. Filipkowski, A.F. Garito, and J.K. Blasie. 1987. J. Physique. 47:1849-1855). Furthermore, we have employed these techniques to determine the location of a monolayer of cytochrome c bound to the carboxyl group surface of various ultrathin lipid multilayer substrates via nonresonance x-ray diffraction (Pachence, J.M., and J.K. Blasie. 1987. Biophys. J. 52:735-747). Here an intense tunable source of x-rays (beam line X9-A at the National Synchrotron Light Source at the Brookhaven National Laboratory) was utilized to measure the resonance x-ray diffraction effect from the heme-Fe atoms within the cytochrome c molecular monolayer located on the carboxyl surface of a five monolayer arachidic acid film. Lamellar x-ray diffraction was recorded for energies above, below, and at the Fe K-absorption edge (E = 7,112 eV). An analysis of the resonance x-ray diffraction effect is presented, whereby the location of the heme-Fe atoms within the electron density profile of the cytochrome c/arachidic acid ultrathin multilayer film is indicated to +/- 3 A accuracy. PMID:2550089

  17. Inhibiting plasmon catalyzed conversion of para-nitrothiophenol on monolayer film of Au nanoparticles probed by surface enhanced Raman spectroscopy.

    PubMed

    Weng, Hua-Yi; Guo, Qing-Hua; Wang, Xing-Rong; Xu, Min-Min; Yuan, Ya-Xian; Gu, Ren-Ao; Yao, Jian-Lin

    2015-11-01

    The plasmon catalyzed surface reaction has been attracted considerable attention due to its promising application in heterogeneous catalysis. This kind of plasmon catalysis played bilateral roles in driving the unconventional reactions or destructing the surface molecule layer. The acceleration or inhibition on this catalysis is still remained significant challenge. In this paper, monolayer film of Au nanoparticles was fabricated at air/water interface as substrates both for surface enhanced Raman spectroscopy (SERS) and plasmon catalyzed surface reaction. The influence from several issues, involving surfactants, coadsorption species, the solvent and water, were systemically investigated to probe the acceleration and inhibition on the plasmon catalysis reaction. The concentration and molecular weight of surfactant polyvinylpyrrolidone (PVP) exhibited significant influence in the reactive activity for the plasmon catalyzed dimerization of para-nitrothiophenol (PNTP) to p,p'-dimercaptoazobenzene (DMAB). A suitable molecular weight of 10,000 and concentration of 10mg/mL were beneficial for improving the conversion efficiency of PNTP to DMAB. The higher molar ratio of coadsorbed 1-octanethiol and the aprotic solvents resulted in the inhibition of dimerization because 1-octanethiol occupied the surface sites to isolate the adsorbed PNTP molecules with a larger distance and lack of proton source. The plasmon catalysis occurred in ionic liquids suggested that water was essential for the dimerization of PNTP, in which it was used to accelerate the reaction rate and severed as the hydrogen source.

  18. Detection of saccharides with a fluorescent sensing device based on a gold film modified with 4-mercaptophenylboronic acid monolayer

    NASA Astrophysics Data System (ADS)

    Chen, Shu-Jen; Chang, Jui-Feng; Cheng, Nai-Jen; Yih, Jeng-Nan; Chiu, Kuo-Chi

    2013-09-01

    An extremely sensitive fluorescent sensor based on a phenylboronic acid monolayer was developed for detecting saccharide molecules. The fluorescent sensor was prepared by assembling a monolayer of 4-mercaptophenylboronic acid (4-MPBA) onto a gold-coated compact disk. The change in the fluorescence of the 4-MPBA monolayer was extremely obvious in basic methanolic buffer containing monosaccharides down to the picomolar level. The fluorescence spectra demonstrated that the 4-MPBA monolayer was sensitive to monosaccharides and disaccharides, and the affinity of the monolayer toward saccharides was in the order of glucose < fructose < mannose < galactose < maltose > lactose > sucrose. Additionally, the fluorescence intensity of 4-MPBA monolayer was restorable after cleaning with weak acid, indicating that the reported fluorescent sensor with the detection limit of glucose down to the picomolar level is reusable for sensing saccharides.

  19. Fabrication of SnO2-Reduced Graphite Oxide Monolayer-Ordered Porous Film Gas Sensor with Tunable Sensitivity through Ultra-Violet Light Irradiation

    NASA Astrophysics Data System (ADS)

    Xu, Shipu; Sun, Fengqiang; Yang, Shumin; Pan, Zizhao; Long, Jinfeng; Gu, Fenglong

    2015-03-01

    A new graphene-based composite structure, monolayer-ordered macroporous film composed of a layer of orderly arranged macropores, was reported. As an example, SnO2-reduced graphite oxide monolayer-ordered macroporous film was fabricated on a ceramic tube substrate under the irradiation of ultra-violet light (UV), by taking the latex microsphere two-dimensional colloid crystal as a template. Graphite oxide sheets dispersed in SnSO4 aqueous solution exhibited excellent affinity with template microspheres and were in situ incorporated into the pore walls during UV-induced growth of SnO2. The growing and the as-formed SnO2, just like other photocatalytic semiconductor, could be excited to produce electrons and holes under UV irradiation. Electrons reduced GO and holes adsorbed corresponding negative ions, which changed the properties of the composite film. This film was directly used as gas-sensor and was able to display high sensitivity in detecting ethanol gas. More interestingly, on the basis of SnO2-induced photochemical behaviours, this sensor demonstrated tunable sensitivity when UV irradiation time was controlled during the fabrication process and post in water, respectively. This study provides efficient ways of conducting the in situ fabrication of a semiconductor-reduced graphite oxide film device with uniform surface structure and controllable properties.

  20. Fabrication of SnO₂-reduced graphite oxide monolayer-ordered porous film gas sensor with tunable sensitivity through ultra-violet light irradiation.

    PubMed

    Xu, Shipu; Sun, Fengqiang; Yang, Shumin; Pan, Zizhao; Long, Jinfeng; Gu, Fenglong

    2015-01-01

    A new graphene-based composite structure, monolayer-ordered macroporous film composed of a layer of orderly arranged macropores, was reported. As an example, SnO2-reduced graphite oxide monolayer-ordered macroporous film was fabricated on a ceramic tube substrate under the irradiation of ultra-violet light (UV), by taking the latex microsphere two-dimensional colloid crystal as a template. Graphite oxide sheets dispersed in SnSO4 aqueous solution exhibited excellent affinity with template microspheres and were in situ incorporated into the pore walls during UV-induced growth of SnO2. The growing and the as-formed SnO2, just like other photocatalytic semiconductor, could be excited to produce electrons and holes under UV irradiation. Electrons reduced GO and holes adsorbed corresponding negative ions, which changed the properties of the composite film. This film was directly used as gas-sensor and was able to display high sensitivity in detecting ethanol gas. More interestingly, on the basis of SnO2-induced photochemical behaviours, this sensor demonstrated tunable sensitivity when UV irradiation time was controlled during the fabrication process and post in water, respectively. This study provides efficient ways of conducting the in situ fabrication of a semiconductor-reduced graphite oxide film device with uniform surface structure and controllable properties. PMID:25758292

  1. Observation of dopant-profile independent electron transport in sub-monolayer TiOx stacked ZnO thin films grown by atomic layer deposition

    NASA Astrophysics Data System (ADS)

    Saha, D.; Misra, P.; Das, Gangadhar; Joshi, M. P.; Kukreja, L. M.

    2016-01-01

    Dopant-profile independent electron transport has been observed through a combined study of temperature dependent electrical resistivity and magnetoresistance measurements on a series of Ti incorporated ZnO thin films with varying degree of static-disorder. These films were grown by atomic layer deposition through in-situ vertical stacking of multiple sub-monolayers of TiOx in ZnO. Upon decreasing ZnO spacer layer thickness, electron transport smoothly evolved from a good metallic to an incipient non-metallic regime due to the intricate interplay of screening of spatial potential fluctuations and strength of static-disorder in the films. Temperature dependent phase-coherence length as extracted from the magnetotransport measurement revealed insignificant role of inter sub-monolayer scattering as an additional channel for electron dephasing, indicating that films were homogeneously disordered three-dimensional electronic systems irrespective of their dopant-profiles. Results of this study are worthy enough for both fundamental physics perspective and efficient applications of multi-stacked ZnO/TiOx structures in the emerging field of transparent oxide electronics.

  2. 7 CFR 1400.7 - Commensurate contributions and risk.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... share of the profits or losses from the farming operation commensurate with the person's or legal entity's contribution(s) to the operation; (2) Contribution(s) to the farming operation that are at risk... farming operation. (b)...

  3. Quantitative time-resolved vibrational sum frequency generation spectroscopy as a tool for thin film kinetic studies: new insights into oleic acid monolayer oxidation.

    PubMed

    Kleber, Joscha; Laß, Kristian; Friedrichs, Gernot

    2013-08-22

    Environmental air-water interfaces are often covered by thin films of surface-active organic substances that play an important role for air-sea gas exchange and aerosol aging. Surface-sensitive vibrational sum frequency generation (VSFG) spectroscopy has been widely used to study the static structure of organic monolayers serving as simple model systems of such films. Probably due to the difficulties to correlate the SFG signal intensity with the surface concentration, corresponding time-resolved studies of surface reactions are scarce. In this study, quantitative time-resolved measurements have been performed on the oleic acid monolayer ozonolysis, which is considered a benchmark system for investigating the reactivity and fate of unsaturated natural organics. Surface concentration calibration data have been obtained by combining the pressure-area isotherm and VSFG spectra acquisition such that the 2D phase behavior of the oleic acid film could be properly taken into account. In contrast to literature reports, surface-active oxidation products were found to be negligible and do not interfere with the VSFG measurements. A pseudo-first-order kinetic analysis of the time-resolved data yielded a bimolecular rate constant of k2(oleic acid + O3 → products) = (1.65 ± 0.64) × 10(-16) cm(3) molecules(-1) s(-1), corresponding to an uptake coefficient of γ = (4.7 ± 1.8) × 10(-6). This result is in very good agreement with most recent monolayer measurements based on alternative methods and underlines the reliability of the time-resolved VSFG approach.

  4. Iso-oriented monolayer α-MoO3(010) films epitaxially grown on SrTiO3(001).

    PubMed

    Du, Yingge; Li, Guoqiang; Peterson, Erik W; Zhou, Jing; Zhang, Xin; Mu, Rentao; Dohnálek, Zdenek; Bowden, Mark; Lyubinetsky, Igor; Chambers, Scott A

    2016-02-01

    The ability to synthesize well-ordered two-dimensional materials under ultra-high vacuum and directly characterize them by other techniques in situ can greatly advance our current understanding on their physical and chemical properties. In this paper, we demonstrate that iso-oriented α-MoO3 films with as low as single monolayer thickness can be reproducibly grown on SrTiO3(001) substrates by molecular beam epitaxy ((010)(MoO3)‖(001)(STO), [100](MoO3)‖[100](STO) or [010](STO)) through a self-limiting process. While one in-plane lattice parameter of the MoO3 is very close to that of the SrTiO3 (a(MoO3) = 3.96 Å, a(STO) = 3.905 Å), the lattice mismatch along other direction is large (∼5%, c(MoO3) = 3.70 Å), which leads to relaxation as clearly observed from the splitting of streaks in reflection high-energy electron diffraction (RHEED) patterns. A narrow range in the growth temperature is found to be optimal for the growth of monolayer α-MoO3 films. Increasing deposition time will not lead to further increase in thickness, which is explained by a balance between deposition and thermal desorption due to the weak van der Waals force between α-MoO3 layers. Lowering growth temperature after the initial iso-oriented α-MoO3 monolayer leads to thicker α-MoO3(010) films with excellent crystallinity. PMID:26788784

  5. Rotation dynamics of C{sub 60} molecules in a monolayer fullerene film on the WO{sub 2}/W(110) surface near the rotational phase transition

    SciTech Connect

    Bozhko, S. I.; Levchenko, E. A.; Semenov, V. N.; Bulatov, M. F.; Shvets, I. V.

    2015-05-15

    The rotation dynamics of C{sub 60} molecules in monolayer fullerene films grown on the WO{sub 2}/W(110) surface is studied by scanning tunneling microscopy. The formation of molecule clusters, which have a high libron vibration amplitude, is detected near the rotational phase transition temperature. The energy parameters that determine a change in the molecule orientation, namely, the energy difference between the nearest minima of the C{sub 60} molecule energy (30 meV) as a function of the molecule orientation and the potential barrier between them (610 meV), are determined. The results are discussed in terms of the mean-field approximation.

  6. Rotationally Commensurate Growth of MoS2 on Epitaxial Graphene.

    PubMed

    Liu, Xiaolong; Balla, Itamar; Bergeron, Hadallia; Campbell, Gavin P; Bedzyk, Michael J; Hersam, Mark C

    2016-01-26

    Atomically thin MoS2/graphene heterostructures are promising candidates for nanoelectronic and optoelectronic technologies. Among different graphene substrates, epitaxial graphene (EG) on SiC provides several potential advantages for such heterostructures, including high electronic quality, tunable substrate coupling, wafer-scale processability, and crystalline ordering that can template commensurate growth. Exploiting these attributes, we demonstrate here the thickness-controlled van der Waals epitaxial growth of MoS2 on EG via chemical vapor deposition, giving rise to transfer-free synthesis of a two-dimensional heterostructure with registry between its constituent materials. The rotational commensurability observed between the MoS2 and EG is driven by the energetically favorable alignment of their respective lattices and results in nearly strain-free MoS2, as evidenced by synchrotron X-ray scattering and atomic-resolution scanning tunneling microscopy (STM). The electronic nature of the MoS2/EG heterostructure is elucidated with STM and scanning tunneling spectroscopy, which reveals bias-dependent apparent thickness, band bending, and a reduced band gap of ∼0.4 eV at the monolayer MoS2 edges. PMID:26565112

  7. Adsorption of metal adatoms on FeO(111) and MgO(111) monolayers: Effects of charge state of adsorbate on rumpling of supported oxide film

    NASA Astrophysics Data System (ADS)

    Goniakowski, Jacek; Noguera, Claudine; Giordano, Livia; Pacchioni, Gianfranco

    2009-09-01

    We present a theoretical density-functional theory study on the deposition of metal atoms (Ir, Pd, Pt, Ag, and Au) on FeO(111) and MgO(111) monolayers supported on Pt(111). We show the existence of a strong coupling between the charge state of the adsorbed adatom and the local polaroniclike distortion of the oxide film, and we identify two qualitatively different adsorption modes in which the distortion either reinforces the rumpling of the supported oxide film (positively charged adsorbates) or reduces or even reverses the cation-anion stacking (negatively charged adsorbates). Thus, the adsorption mode is a response to the charge state of the adsorbate and is driven mainly by the capacity of adatoms to exchange electrons with the support.

  8. Effect of Self-Assembled Monolayer Modification on Indium-Tin Oxide Surface for Surface-Initiated Vapor Deposition Polymerization of Carbazole Thin Films

    NASA Astrophysics Data System (ADS)

    Yuya Umemoto,; Seong-Ho Kim,; Rigoberto C. Advincula,; Kuniaki Tanaka,; Hiroaki Usui,

    2010-04-01

    With the aim of controlling the interface between an inorganic electrode and an organic layer, a surface-initiated vapor deposition polymerization method was employed to prepare carbazole polymer thin films that are chemically bound to an indium-tin oxide (ITO) surface. A self-assembled monolayer (SAM) that has an azo initiator as a terminal group was prepared on an ITO surface, on which carbazole acrylate monomers were evaporated under ultraviolet (UV) irradiation. The surface morphological characteristics of the films prepared with/without UV irradiation and with/without the SAM were compared. It was found that the UV irradiation leads to the polymerization of carbazole monomers irrespective of the type of substrate used. On the other hand, the surface morphological characteristics were largely dependent on the existence of the SAM. Uniform and smooth polymer thin films were obtained only when the monomers were evaporated on the SAM-modified surface under UV irradiation. A comparison of film growth characteristics on a UV-ozone-treated ITO surface suggested that the formation of uniform films was made possible not by the modification of surface energy but by the growth of the polymers chemically bound to the substrate surface.

  9. Effect of fluorocarbon self-assembled monolayer films on sidewall adhesion and friction of surface micromachines with impacting and sliding contact interfaces

    NASA Astrophysics Data System (ADS)

    Xiang, H.; Komvopoulos, K.

    2013-06-01

    A self-assembled monolayer film consisting of fluoro-octyltrichlorosilane (FOTS) was vapor-phase deposited on Si(100) substrates and polycrystalline silicon (polysilicon) surface micromachines. The hydrophobic behavior and structural composition of the FOTS film deposited on Si(100) were investigated by goniometry and X-ray photoelectron spectroscopy, respectively. The effects of contact pressure, relative humidity, temperature, and impact/sliding cycles on the adhesive and friction behavior of uncoated and FOTS-coated polysilicon micromachines (referred to as the Si and FOTS/Si micromachines, respectively) were investigated under controlled loading and environmental conditions. FOTS/Si micromachines demonstrated much lower and stable adhesion than Si micromachines due to the highly hydrophobic and conformal FOTS film. Contrary to Si micromachines, sidewall adhesion of FOTS/Si micromachines demonstrated a weak dependence on relative humidity, temperature, and impact cycles. In addition, FOTS/Si micromachines showed low and stable adhesion and low static friction for significantly more sliding cycles than Si micromachines. The adhesive and static friction characteristics of Si and FOTS/Si micromachines are interpreted in the context of physicochemical surface changes, resulting in the increase of the real area of contact and a hydrophobic-to-hydrophilic transition of the surface chemical characteristics caused by nanoscale surface smoothening and the removal of the organic residue (Si micromachines) or the FOTS film (FOTS/Si micromachines) during repetitive impact and oscillatory sliding of the sidewall surfaces.

  10. Effect of fluorocarbon self-assembled monolayer films on sidewall adhesion and friction of surface micromachines with impacting and sliding contact interfaces

    SciTech Connect

    Xiang, H.; Komvopoulos, K.

    2013-06-14

    A self-assembled monolayer film consisting of fluoro-octyltrichlorosilane (FOTS) was vapor-phase deposited on Si(100) substrates and polycrystalline silicon (polysilicon) surface micromachines. The hydrophobic behavior and structural composition of the FOTS film deposited on Si(100) were investigated by goniometry and X-ray photoelectron spectroscopy, respectively. The effects of contact pressure, relative humidity, temperature, and impact/sliding cycles on the adhesive and friction behavior of uncoated and FOTS-coated polysilicon micromachines (referred to as the Si and FOTS/Si micromachines, respectively) were investigated under controlled loading and environmental conditions. FOTS/Si micromachines demonstrated much lower and stable adhesion than Si micromachines due to the highly hydrophobic and conformal FOTS film. Contrary to Si micromachines, sidewall adhesion of FOTS/Si micromachines demonstrated a weak dependence on relative humidity, temperature, and impact cycles. In addition, FOTS/Si micromachines showed low and stable adhesion and low static friction for significantly more sliding cycles than Si micromachines. The adhesive and static friction characteristics of Si and FOTS/Si micromachines are interpreted in the context of physicochemical surface changes, resulting in the increase of the real area of contact and a hydrophobic-to-hydrophilic transition of the surface chemical characteristics caused by nanoscale surface smoothening and the removal of the organic residue (Si micromachines) or the FOTS film (FOTS/Si micromachines) during repetitive impact and oscillatory sliding of the sidewall surfaces.

  11. Electrochemical reduction of p-nitrothiophenol-self-assembled monolayer films on Au( 1 1 1 ) surface and coadsorption of anions and water molecules

    NASA Astrophysics Data System (ADS)

    Futamata, M.; Nishihara, C.; Goutev, N.

    2002-08-01

    Electrochemical reduction of p-nitrothiophenol (PNTP)-self-assembled monolayer (SAM) films on Au(1 1 1) surface was studied using attenuated total reflection-IR spectroscopy. The reduction potential was evaluated from the spectral changes, which depended on pH in electrolyte solutions, e.g. +0.05 V (pH 0.45), -0.55 V (pH 5.5) or -0.55 V (pH 13) (vs. Ag/AgCl) in accordance with voltammetric results. We found that the IR absorption bands of anions and water increases upon reduction in acidic solution at pH

    films on Au(1 1 1) surface. It suggests that the pKa of the PNTP-SAM film on the Au electrode can be evaluated from the IR spectral changes with the potential. Pronounced IR background shift observed during the PNTP reduction was discussed based on the superimposed changes from molecular structure, orientation of the SAM film and coadsorption of the anions.

  12. Characterization of heterojunctions via x-ray and uv photoemission spectroscopy: energy level implications for single and mixed monolayer SAMs, cadmium selenide nanoparticle films, and organic semiconductor depositions

    NASA Astrophysics Data System (ADS)

    Graham, Amy L.

    This work has centered on the interface dipoles arising at heterojunctions between metals, semiconductor nanoparticles, self-assembled monolayers, and organic semiconductor materials. Alkanethiol self-assembled monolayers, CdSe nanocrystals, and the organic semiconductors zinc phthalocyanine (ZnPc) and Buckminster fullerene (C60) were the basis of these investigations. UV photoemission spectroscopy has proven to be an invaluable tool to observe the vacuum level shifts for these analyses while using XPS to corroborate surface structure. With a full evaluation of these surfaces, the shifts in the vacuum level, valence ionizations, and core ionizations, the impact of these interfaces, as well as their influence on the subsequent deposition of organic semiconductor layers is established. Alkanethiols possessing varying dipole moments were examined on gold and silver substrates. The viability of these alkanethiols was demonstrated to predictively adjust the work function of these metals as a function of their intrinsic dipole moments projected to surface normal, and established differences between Ag---S and Au---S bonds. The capability of the SAMs to modify the work function of gold provided an opportunity for mixed monolayers of the alkanethiols to produce a precise range of work functions by minimal adjustments of solution concentration, which were examined with a simple point dipole model. Photoemission spectroscopy offers a thorough analysis of CdSe nanoparticle films. Despite a plethora of research on these nanocrystals, there still is controversy on the magnitude of the shift in the valence band with diameter. In our research we found the majority of the valence band shift could be attributed to the interface dipole, ignored previously. Meanwhile, the valence band tethered films was obscured by the sulfur of the thiol tether. Finally, organic semiconductor layers deposited on SAMs on gold exhibited various interface dipole effects at these heterojunctions. Charge

  13. Study of Fused Thiophene Based Organic Semiconductors and Interfacial Self-Assembled Monolayer (SAM) for Thin-Film Transistor (TFT) Application

    NASA Astrophysics Data System (ADS)

    Youn, Jangdae

    In this thesis, the molecular packing motifs of our newly designed fused thiophenes, benzo[d,d]thieno[3,2-b;4,5-b]dithiophene (BTDT) derivatives, were studied by utilizing grazing incidence wide angle X-ray scattering (GIWAXS). Considering the potential of fused thiophene molecules as an environmentally stable, high performance semiconductor building block, it must be an important groundwork to investigate their thin film structures in relation to molecular structures, single crystal structures, and organic thin-film transistors (OTFT) performances. OTFT device performance is not only determined by semiconductor materials, but also influenced by the interfacial properties. Since there are three major components in TFT structures---electrodes, semiconductors, and dielectrics, two types of major interfaces exist. One is the semiconductor-electrode interface, and the other is the semiconductor-dielectric interface. Both of these interfaces have critical roles for TFT operation. For example, the semiconductor-electrode interface determines the charge injection barrier. Before charge carriers go through the electrode (source)-semiconductor-electrode (drain) pathways, the energy gaps between the work function of the electrodes and the HOMO energy of the semiconductor materials must be overcome for hole injection, or the energy gap between the metal work function of the electrodes and the LUMO energy of the semiconductor materials must be overcome for electron injection. These charge injection barriers are largely determined by the energetic structure of the semiconductor material and work function of the electrode. However, the size of energy gap can be modified by introducing an organic self-assembled monolayer (SAM) on the surface of metal electrode. In addition, the structure of semiconductor films, especially within several monolayers right above the electrode, is greatly influenced by the SAM, and it changes charge injection property of OTFT devices. In this thesis

  14. The commensurate spin excitation in chromium: A polarised neutron investigation

    SciTech Connect

    Pynn, R. ); Stirling, W.G. . Dept. of Physics); Severing, A. )

    1991-01-01

    A polarised neutron experiment with neutron energy analysis has been performed with a single-Q sample of chromium in a large magnetic field. The 4-meV commensurate'' mode is found to involve spin fluctuations parallel to the ordered chromium moments. 8 refs., 3 figs.

  15. Commensurate Phases of Kr Adsorbed on Single-Walled Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Mbaye, Mamadou T.; Maiga, Sidi M.; Gatica, Silvina M.

    2016-10-01

    In this paper, we show that Krypton atoms form a commensurate solid (CS) phase with a fractional coverage of one krypton atom per every four carbons on zigzag carbon nanotubes. This is a unique phase, different from the √{3} × √{3}R30° CS monolayer formed on graphite, which has a lower coverage of one krypton atom per every six carbons. Our prediction disagrees with experiments that observe in nanotubes the same solid structure found on graphite. In order to address this discrepancy, we simulated adsorption of Kr on zigzag and armchair single-walled carbon nanotubes with radii ranging from 4.7 to 28.83 Å. Our simulations confirm that the CS of coverage 1/4 forms on medium-sized zigzag nanotubes. We also found the 1/6-coverage solid on graphene, which represents the infinite-radius limit of a nanotube. Our findings are key to experiments of adsorption on nanotubes where the interpretation and justification of the results are based on the monolayer coverage, such as mass or conductance isotherms measurements.

  16. Temperature effect on thin lipid film elasticity and phase separation: insights from Langmuir monolayer and fluorescence microscopy techniques

    NASA Astrophysics Data System (ADS)

    Khattari, Z.; Maghrabi, M.; Al-Abdullah, T.

    2015-07-01

    Langmuir monolayer pressure isotherms and compressibility modulus measurements of phospholipid mixtures in several Langmuir monolayer systems at the air/water interface were investigated in this study. The ultimate aim was to carry out a comparison of the elasticity modulus for monolayers with different mixtures of l,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), l,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and chicken egg yolk sphingomyelin (eSM), in the presence/absence of cholesterol (Chol). In particular, we were able to propose that the leading force beyond the phase separation into liquid expanded (LE-) and liquid condensed (LC-) phases emerges from the increasing barrier to incorporate DOPC molecules into a highly ordered LC-phase. In addition, our findings suggest that DOPC lipid molecules have a priority to incorporate in a disordered LE-phase, while DPPC and eSM prefer the ordered one. Also, Chol seems to split almost equally into both phases, indicating that Chol has no priority for either phase and there are no particular interactions between Chol and saturated lipid molecules.

  17. Phase behavior of mixed submonolayer films of krypton and xenon on graphite

    NASA Astrophysics Data System (ADS)

    Patrykiejew, A.; Sokołowski, S.

    2012-04-01

    Using the results of extensive Monte Carlo simulations in the canonical and grand canonical ensembles, we discuss the phase behavior of mixed submonolayer films of krypton and xenon adsorbed on the graphite basal plane. The calculations have been performed using two- and three-dimensional models of the systems studied. It has been demonstrated that out-of-plane motion does not affect the properties of the films as long as the total density is well below the monolayer completion and at moderate temperatures. For the total densities close to the monolayer completion, the promotion of particles to the second layer considerably affects the film properties. Our results are in a reasonable agreement with the available experimental data. The melting point of submonolayer films has been shown to exhibit non-monotonous changes with the film composition, and reaches minimum for the xenon concentration of about 50%. At the temperatures below the melting point, the structure of solid phases depends upon the film composition and the temperature; one can also distinguish commensurate and incommensurate phases. Two-dimensional calculations have demonstrated that for the xenon concentration between about 15% and 65% the adsorbed film exhibits the formation of a superstructure, in which each Xe atom is surrounded by six Kr atoms. This superstructure is stable only at very low temperatures and transforms into the mixed commensurate (√{3}× √{3})R30° phase upon the increase of temperature. Such a superstructure does not appear when a three-dimensional model is used. Grand canonical ensemble calculations allowed us to show that for the xenon concentration of about 3% the phase diagram topology of monolayer films changes from the krypton-like (with incipient triple point) to the xenon-like (with ordinary triple point).

  18. Phase behavior of mixed submonolayer films of krypton and xenon on graphite.

    PubMed

    Patrykiejew, A; Sokołowski, S

    2012-04-14

    Using the results of extensive Monte Carlo simulations in the canonical and grand canonical ensembles, we discuss the phase behavior of mixed submonolayer films of krypton and xenon adsorbed on the graphite basal plane. The calculations have been performed using two- and three-dimensional models of the systems studied. It has been demonstrated that out-of-plane motion does not affect the properties of the films as long as the total density is well below the monolayer completion and at moderate temperatures. For the total densities close to the monolayer completion, the promotion of particles to the second layer considerably affects the film properties. Our results are in a reasonable agreement with the available experimental data. The melting point of submonolayer films has been shown to exhibit non-monotonous changes with the film composition, and reaches minimum for the xenon concentration of about 50%. At the temperatures below the melting point, the structure of solid phases depends upon the film composition and the temperature; one can also distinguish commensurate and incommensurate phases. Two-dimensional calculations have demonstrated that for the xenon concentration between about 15% and 65% the adsorbed film exhibits the formation of a superstructure, in which each Xe atom is surrounded by six Kr atoms. This superstructure is stable only at very low temperatures and transforms into the mixed commensurate (√3×√3)R30° phase upon the increase of temperature. Such a superstructure does not appear when a three-dimensional model is used. Grand canonical ensemble calculations allowed us to show that for the xenon concentration of about 3% the phase diagram topology of monolayer films changes from the krypton-like (with incipient triple point) to the xenon-like (with ordinary triple point).

  19. Phase behavior of mixed submonolayer films of krypton and xenon on graphite.

    PubMed

    Patrykiejew, A; Sokołowski, S

    2012-04-14

    Using the results of extensive Monte Carlo simulations in the canonical and grand canonical ensembles, we discuss the phase behavior of mixed submonolayer films of krypton and xenon adsorbed on the graphite basal plane. The calculations have been performed using two- and three-dimensional models of the systems studied. It has been demonstrated that out-of-plane motion does not affect the properties of the films as long as the total density is well below the monolayer completion and at moderate temperatures. For the total densities close to the monolayer completion, the promotion of particles to the second layer considerably affects the film properties. Our results are in a reasonable agreement with the available experimental data. The melting point of submonolayer films has been shown to exhibit non-monotonous changes with the film composition, and reaches minimum for the xenon concentration of about 50%. At the temperatures below the melting point, the structure of solid phases depends upon the film composition and the temperature; one can also distinguish commensurate and incommensurate phases. Two-dimensional calculations have demonstrated that for the xenon concentration between about 15% and 65% the adsorbed film exhibits the formation of a superstructure, in which each Xe atom is surrounded by six Kr atoms. This superstructure is stable only at very low temperatures and transforms into the mixed commensurate (√3×√3)R30° phase upon the increase of temperature. Such a superstructure does not appear when a three-dimensional model is used. Grand canonical ensemble calculations allowed us to show that for the xenon concentration of about 3% the phase diagram topology of monolayer films changes from the krypton-like (with incipient triple point) to the xenon-like (with ordinary triple point). PMID:22502538

  20. Research of the relations between monolayer SiNx optical thin film processing techniques and laser-induced damage properties prepared by PECVD technology

    NASA Astrophysics Data System (ADS)

    Li, Peng; Hang, Lingxia; Li, Linjun; Huang, Fabin

    2015-02-01

    The monolayer SiNx optical thin films were prepared by Plasma Enhanced Chemical Vapor Deposition (PECVD) technology on the BK7 glass substrate, the laser-induced damage threshold was measured by laser damage testing equipment, and we also investigated the relations between processing techniques and laser-induced damage properties. The study and analysis to orthogonal experiment results show that PECVD processing techniques have an effect on the laser-induced damage properties. Among them,radio frequency has the biggest effection, temperature is the main factor, working pressure is the unimportant factor, and we also achieve the optimal processing parameters (Temperature is 350°; RF power is 250W; Working pressure is 60Pa).

  1. Frictional transition from superlubric islands to pinned monolayers

    NASA Astrophysics Data System (ADS)

    Pierno, Matteo; Bruschi, Lorenzo; Mistura, Giampaolo; Paolicelli, Guido; di Bona, Alessandro; Valeri, Sergio; Guerra, Roberto; Vanossi, Andrea; Tosatti, Erio

    2015-08-01

    The inertial sliding of physisorbed submonolayer islands on crystal surfaces contains unexpected information on the exceptionally smooth sliding state associated with incommensurate superlubricity and on the mechanisms of its disappearance. Here, in a joint quartz crystal microbalance and molecular dynamics simulation case study of Xe on Cu(111), we show how superlubricity emerges in the large size limit of naturally incommensurate Xe islands. As coverage approaches a full monolayer, theory also predicts an abrupt adhesion-driven two-dimensional density compression on the order of several per cent, implying a hysteretic jump from superlubric free islands to a pressurized commensurate immobile monolayer. This scenario is fully supported by the quartz crystal microbalance data, which show remarkably large slip times with increasing submonolayer coverage, signalling superlubricity, followed by a dramatic drop to zero for the dense commensurate monolayer. Careful analysis of this variety of island sliding phenomena will be essential in future applications of friction at crystal/adsorbate interfaces.

  2. Transverse commensurability effect for vortices on periodic pinning arrays

    SciTech Connect

    Reichhardt, Charles; Reichhardt, Cynthia J

    2008-01-01

    Using computer simulations, we demonstrate a type of commensurability that occurs for vortices moving longitudinally through periodic pinning arrays in the presence of an additional transverse driving force. As a function of vortex density, there is a series of broad maxima in the transverse critical depinning force that do not fall at the matching fields where the number of vortices equals an integer multiple of the number of pinning sites. The commensurability effects are associated with dynamical states in which evenly spaced structures consisting of one or more moving rows of vortices form between rows of pinning sites. Remarkably, the critical transverse depinning force can be more than an order of magnitude larger than the longitudinal depinning force.

  3. Probing commensurate ground states of Josephson vortex in layered superconductors.

    PubMed

    Takahashi, Y; Luo, M-B; Nishizaki, T; Kobayashi, N; Hu, X

    2014-04-01

    Because of the commensurability condition between the vortex lattice constant determined by external magnetic field and the nano-scale layered structure, interlayer Josephson vortices (JVs) in high-Tc cuprate superconductors can take various configurations. We have simulated with Langevin scheme the in-plane flux-flow dynamics of JVs subject to point-like pinning centers. Oscillation in resistivity is found with the applied magnetic field, where the resistivity peaks occur around commensurate JV configurations. We have also measured the resistivity experimentally using single crystals of underdoped YBa2Cu3Oy with the anisotropy parameter gamma approximately equal to 50. A unique JV lattice has been detected for the first time.

  4. Orthogonally Spin-Coated Bilayer Films for Photochemical Immobilization and Patterning of Sub-10-Nanometer Polymer Monolayers.

    PubMed

    Janes, Dustin W; Kim, Chae Bin; Maher, Michael J; Ellison, Christopher J

    2016-07-12

    Versatile and spatiotemporally controlled methods for decorating surfaces with monolayers of attached polymers are broadly impactful to many technological applications. However, current materials are usually designed for very specific polymer/surface chemistries and, as a consequence, are not very broadly applicable and/or do not rapidly respond to high-resolution stimuli such as light. We describe here the use of a polymeric adhesion layer, poly(styrene sulfonyl azide-alt-maleic anhydride) (PSSMA), which is capable of immobilizing a 1-7 nm thick monolayer of preformed, inert polymers via photochemical grafting reactions. Solubility of PSSMA in very polar solvents enables processing alongside hydrophobic polymers or solutions and by extension orthogonal spin-coating deposition strategies. Therefore, these materials and processes are fully compatible with photolithographic tools and can take advantage of the immense manufacturing scalability they afford. For example, the thicknesses of covalently grafted poly(styrene) obtained after seconds of exposure are quantitatively equivalent to those obtained by physical adsorption after hours of thermal equilibration. Sequential polymer grafting steps using photomasks were used to pattern different regions of surface energy on the same substrate. These patterns spatially controlled the self-assembled domain orientation of a block copolymer possessing 21 nm half-periodicity, demonstrating hierarchical synergy with leading-edge nanopatterning approaches.

  5. Synthesis of KCa₂Nb₃O₁₀ Crystals with Varying Grain Sizes and Their Nanosheet Monolayer Films As Seed Layers for PiezoMEMS Applications.

    PubMed

    Yuan, Huiyu; Nguyen, Minh; Hammer, Tom; Koster, Gertjan; Rijnders, Guus; ten Elshof, Johan E

    2015-12-16

    The layered perovskite-type niobate KCa2Nb3O10 and its derivatives show advantages in several fields, such as templated film growth and (photo)catalysis. Conventional synthesis routes generally yield crystal size smaller than 2 μm. We report a flux synthesis method to obtain KCa2Nb3O10 crystals with significantly larger sizes. By using different flux materials (K2SO4 and K2MoO4), crystals with average sizes of 8 and 20 μm, respectively, were obtained. The KCa2Nb3O10 crystals from K2SO4 and K2MoO4 assisted synthesis were protonated and exfoliated into monolayer nanosheets, and the optimal exfoliation conditions were determined. Using pulsed laser deposition, highly (001)-oriented piezoelectric stacks (SrRuO3/PbZr0.52Ti0.48O3/SrRuO3, SRO/PZT/SRO) were deposited onto Langmuir-Blodgett films of Ca2Nb3O10(-) (CNO) nanosheets with varying lateral nanosheet sizes on Si substrates. The resulting PZT thin films showed high crystallinity irrespective of nanosheet size. The small sized nanosheets yielded a high longitudinal piezoelectric coefficient d33 of 100 pm/V, while the larger sized sheets had a d33 of 72 pm/V. An enhanced transverse piezoelectric coefficient d31 of -107 pm/V, an important input parameter for the actuation of active structures in microelectromechanical systems (MEMS) devices, was obtained for PZT films grown on CNO nanosheets with large lateral size, while the corresponding value on small sized sheets was -96 pm/V. PMID:26583282

  6. Measuring mental disorders: The failed commensuration project of DSM-5.

    PubMed

    Whooley, Owen

    2016-10-01

    Commensuration - the comparison of entities according to a common quantitative metric - is a key process in efforts to rationalize medicine. The push toward evidence-based medicine and quantitative assessment has led to the proliferation of metrics in healthcare. While social scientific attention has revealed the effects of these metrics once institutionalized - on clinical practice, on medical expertise, on outcome assessment, on valuations of medical services, and on experiences of illness - less attention has been paid to the process of developing metrics. This article examines the attempt to create severity scales during the revision to the fifth edition of the Diagnostic and Statistical Manual of Mental Disorders (DSM-5) as a case of failed commensuration. Using data from interviews with participants in the DSM-5 revision (n = 30), I reconstruct the problems that emerged in the DSM-5 Task Force's effort to develop viable psychometric instruments to measure severity. Framed as a part of a "paradigm shift" in psychiatry, the revision produced ad hoc, heterogeneous severity scales with divergent logics. I focus on two significant issues of metric construction in this case - diagnostic validity and clinical utility. Typically perceived as technical and conceptual challenges of design, I show how these issues were infused with, and undermined by, professional political dynamics, specifically tensions between medical researchers and clinicians. This case reveals that, despite its association with objectivity and transparency, commensuration encompasses more than identifying, operationalizing, and measuring an entity; it demands the negotiation of extra-scientific, non-empirical concerns that get written into medical metrics themselves. PMID:27526260

  7. Measuring mental disorders: The failed commensuration project of DSM-5.

    PubMed

    Whooley, Owen

    2016-10-01

    Commensuration - the comparison of entities according to a common quantitative metric - is a key process in efforts to rationalize medicine. The push toward evidence-based medicine and quantitative assessment has led to the proliferation of metrics in healthcare. While social scientific attention has revealed the effects of these metrics once institutionalized - on clinical practice, on medical expertise, on outcome assessment, on valuations of medical services, and on experiences of illness - less attention has been paid to the process of developing metrics. This article examines the attempt to create severity scales during the revision to the fifth edition of the Diagnostic and Statistical Manual of Mental Disorders (DSM-5) as a case of failed commensuration. Using data from interviews with participants in the DSM-5 revision (n = 30), I reconstruct the problems that emerged in the DSM-5 Task Force's effort to develop viable psychometric instruments to measure severity. Framed as a part of a "paradigm shift" in psychiatry, the revision produced ad hoc, heterogeneous severity scales with divergent logics. I focus on two significant issues of metric construction in this case - diagnostic validity and clinical utility. Typically perceived as technical and conceptual challenges of design, I show how these issues were infused with, and undermined by, professional political dynamics, specifically tensions between medical researchers and clinicians. This case reveals that, despite its association with objectivity and transparency, commensuration encompasses more than identifying, operationalizing, and measuring an entity; it demands the negotiation of extra-scientific, non-empirical concerns that get written into medical metrics themselves.

  8. Perforated monolayers

    SciTech Connect

    Regen, S.L.

    1992-01-01

    Our research over this past grant period has focused on (1) developing methods for making in situ permeation measurements at the air-water interface, (2) defining the structural and conformational behavior of selected calix(4)arenes, (3) defining the metal complexation properties of certain upper-rim functionalized calix(4)arenes, and (4) synthesizing a broad series of polymerizable calixarenes, to be used for constructing perforated monolayers and multilayers.

  9. Tuning friction with an external magnetic field: A Quartz Crystal Microbalance study of physisorbed oxygen monolayers and multilayers sliding on nickel substrates

    NASA Astrophysics Data System (ADS)

    Fredricks, Z. B.; Stevens, K. M.; Acharya, B.; Krim, J.

    The sliding friction levels of oxygen monolayer and multilayer films adsorbed on nickel close to the oxygen monolayer solid-liquid melting transition temperature have been monitored by means of a Quartz Crystal Microbalance (QCM) technique in the presence and absence of a weak external magnetic field. Friction levels for the monolayers in the presence of the field were observed to be half of those observed in the absence of a field. For thick films, the reduction was proportionately less, indicating an interfacial effect as the source of the magnetic sensitivity. While the presence of the field is expected to increase the normal force between the paramagnetic oxygen overlayer and the ferromagnetic substrate, the impact of this mechanism on friction appears to be minimal, or possibly masked by more dominant mechanisms. These include magnetically induced structural reorientation (magnetostriction), and/or realignment of adlayer spins in response to the applied field, both of which would reduce the physical or magnetic interfacial commensurability, thus lowering friction levels. Work supported by NSF DMR1310456.

  10. Direct monitoring of opto-mechanical switching of self-assembled monolayer films containing the azobenzene group

    PubMed Central

    Tirosh, Einat; Benassi, Enrico; Pipolo, Silvio; Mayor, Marcel; Valášek, Michal; Frydman, Veronica

    2011-01-01

    Summary The potential for manipulation and control inherent in molecule-based motors holds great scientific and technological promise. Molecules containing the azobenzene group have been heavily studied in this context. While the effects of the cis–trans isomerization of the azo group in such molecules have been examined macroscopically by a number of techniques, modulations of the elastic modulus upon isomerization in self-assembled films were not yet measured directly. Here, we examine the mechanical response upon optical switching of bis[(1,1'-biphenyl)-4-yl]diazene organized in a self-assembled film on Au islands, using atomic force microscopy. Analysis of higher harmonics by means of a torsional harmonic cantilever allowed real-time extraction of mechanical data. Quantitative analysis of elastic modulus maps obtained simultaneously with topographic images show that the modulus of the cis-form is approximately twice that of the trans-isomer. Quantum mechanical and molecular dynamics studies show good agreement with this experimental result, and indicate that the stiffer response in the cis-form comprises contributions both from the individual molecular bonds and from intermolecular interactions in the film. These results demonstrate the power and insights gained from cutting-edge AFM technologies, and advanced computational methods. PMID:22259768

  11. The breakdown of superlubricity by driving-induced commensurate dislocations

    PubMed Central

    Benassi, A.; Ma, Ming; Urbakh, M.; Vanossi, A.

    2015-01-01

    In the framework of a Frenkel-Kontorova-like model, we address the robustness of the superlubricity phenomenon in an edge-driven system at large scales, highlighting the dynamical mechanisms leading to its failure due to the slider elasticity. The results of the numerical simulations perfectly match the length critical size derived from a parameter-free analytical model. By considering different driving and commensurability interface configurations, we explore the distinctive nature of the transition from superlubric to high-friction sliding states which occurs above the critical size, discovering the occurrence of previously undetected multiple dissipative jumps in the friction force as a function of the slider length. These driving-induced commensurate dislocations in the slider are then characterized in relation to their spatial localization and width, depending on the system parameters. Setting the ground to scale superlubricity up, this investigation provides a novel perspective on friction and nanomanipulation experiments and can serve as a theoretical basis for designing high-tech devices with specific superlow frictional features. PMID:26553308

  12. On the relationship between the structure of self-assembled carboxylic acid monolayers on alumina and the organization and electrical properties of a pentacene thin film

    NASA Astrophysics Data System (ADS)

    Lang, Philippe; Mottaghi, Daniel; Lacaze, Pierre-Camille

    2016-03-01

    The modification of insulating surfaces by self-assembled monolayers (SAMs) is an elegant way of tailoring the gate dielectric of organic field effect transistors (OFET) to pentacene and is commonly used to improve electrical performance. A SAM based on an alkylcarboxylic acid deposited on a thin layer of alumina, serving as the gate dielectric is considered. The relationship between carrier mobility and (i) the length of the carboxylic acid (CH3(CH2)nCOOH; n = 9, 14, 18), (ii) substrate preparation and (iii) the SAM and pentacene thin film structures is considered. The size and boundaries of pentacene grains are not limiting factors for carrier mobility, and the most relevant parameter, which depends on whether there is a SAM or not, is the organization of the first pentacene layers in contact with the gate dielectric. The variation of the interplanar distance d(0 0 1) of the pentacene layers close to the alumina surface is much greater without SAM than with, and this could explain the lower carrier mobility observed in the case of a bare alumina dielectric. The relationship between the disorder associated with this variation and mobility is discussed.

  13. Phase Transitions in Dipalmitoylphosphatidylcholine Monolayers.

    PubMed

    Zuo, Yi Y; Chen, Rimei; Wang, Xianju; Yang, Jinlong; Policova, Zdenka; Neumann, A Wilhelm

    2016-08-23

    A self-assembled phospholipid monolayer at an air-water interface is a well-defined model system for studying surface thermodynamics, membrane biophysics, thin-film materials, and colloidal soft matter. Here we report a study of two-dimensional phase transitions in the dipalmitoylphosphatidylcholine (DPPC) monolayer at the air-water interface using a newly developed methodology called constrained drop surfactometry (CDS). CDS is superior to the classical Langmuir balance in its capacity for rigorous temperature control and leak-proof environments, thus making it an ideal alternative to the Langmuir balance for studying lipid polymorphism. In addition, we have developed a novel Langmuir-Blodgett (LB) transfer technique that allows the direct transfer of lipid monolayers from the droplet surface under well-controlled conditions. This LB transfer technique permits the direct visualization of phase coexistence in the DPPC monolayer. With these technological advances, we found that the two-dimensional phase behavior of the DPPC monolayer is analogous to the three-dimensional phase transition of a pure substance. This study has implications in the fundamental understanding of surface thermodynamics as well as applications such as self-assembled monolayers and pulmonary surfactant biophysics. PMID:27479299

  14. Thermodynamic study of argon films adsorbed on boron nitride

    SciTech Connect

    Migone, A.D.; Alkhafaji, M.T. ); Vidali, G. ); Karimi, M. )

    1993-03-15

    We have performed a detailed adsorption isotherm study of Ar on BN for temperatures between 65 and 80 K. The isothermal compressibility of the films was obtained from adsorption data. At monolayer coverages, a small isotherm substep is present at melting. We found two isothermal compressibility peaks in the first layer: a sharp peak, corresponding to the melting substep, and a smaller, broader peak that occurs at lower pressures. At multilayer coverages we found reentrant layering occurring in the third and fourth layers of the film. We compare our layering results with predictions for the preroughening transition. We also found a series of small steps in the isotherms between the second and third layers and between the third and fourth layers of the film. These small steps are evidence of individual layer melting for the second and third layers. Our results at monolayer and at multilayer coverages are extensively compared to those found for Ar on graphite. We have also performed calculations of the rare-gas--BN interaction potentials. Our calculations indicate the substrate corrugation is smaller for the rare-gas--BN systems than it is for the same rare gases on graphite. The implications of this result for the possible existence of monolayer-commensurate solids on BN are discussed.

  15. Morphological transitions in polymer monolayers under compression.

    PubMed

    Srivastava, S; Basu, J K; Sprung, M; Wang, J

    2009-05-01

    We present a systematic investigation of morphological transitions in poly vinylacetate Langmuir monolayers. On compression, the polymer monolayer is converted to a continuous membrane with a thickness of approximately 2-3 nm. Above a certain surface concentration the monolayer, on water, undergoes a morphological transition-buckling, leading to formation of striped patterns of period of lambda(b) approximately 160 nm, as determined from in situ grazing incidence small angle x-ray scattering measurements. The obtained value is much smaller than what has been typically observed for Langmuir monolayers on water or thin films on soft substrates. Using existing theories for buckling of fluidlike films on fluid substrates, we obtain very low values of bending rigidity and Young's modulus of the polymer monolayer compared to that observed earlier for lipid or polymeric monolayers. Since buckling in these monolayers occurs only above a certain surface concentration, we have looked at the possibility that the buckling in these films occurs due to changes in their mechanical properties under compression. Using the model of Huang and Suo of buckling of solidlike films on viscoelastic substrates, we find values of the mechanical properties, which are much closer to the bulk values but still significantly lower. Although the reduction could be along the lines of what has been observed earlier for ultrathin polymer film or surface layers of polymers, the possibility of micromechanical effects also determining the buckling in such polymer monolayers cannot be ruled out. We have provided possible explanation of the buckling of the poly vinylacetate monolayers in terms of the change in isothermal compression modulus with surface concentration. PMID:19425809

  16. Monolayer graphene from a green solid precursor

    NASA Astrophysics Data System (ADS)

    Kalita, Golap; Wakita, Koichi; Umeno, Masayoshi

    2011-06-01

    Monolayer and bilayer graphene sheets are synthesized by simple control pyrolysis of solid botanical derivative camphor (C 10H 16O), a green and renewable carbon source. Raman studies show much intense 2D peak than that of G peak, signifying presence of monolayer graphene. Transmission electron microscopic study shows predominately monolayer or bilayer graphene sheets, while trilayer graphene sheet were also observed. Synthesized graphene film on copper foil is transferred to poly(ethylene terephthalate) substrate to fabricate transparent electrode. Electrical and optical measurement shows a sheet resistance of 860 Ω/sq with a transmittance of 91% at 550 nm wavelength of the graphene film. The technique to fabricate monolayer or bilayer graphene based film from camphor is both viable and scalable for potential large area electronic applications.

  17. Large Friction Anisotropy of a Polydiacetylene Monolayer

    SciTech Connect

    Burns, A.R.; Carpick, R.W.; Sasaki, D.Y.

    1999-05-11

    Friction force microscopy measurements of a polydiacetylene monolayer film reveal a 300% friction anisotropy that is correlated with the film structure. The film consists of a monolayer of the red form of N-(2-ethanol)- 10,12 pentacosadiynamide, prepared on a Langmuir trough and deposited on a mica substrate. As confirmed by atomic force microscopy and fluorescence microscopy, the monolayer consists of domains of linearly oriented conjugated backbones with pendant hydrocarbon side chains above and below the backbones. Maximum friction occurs when the sliding direction is perpendicular to the backbone. We propose that the backbones impose anisotropic packing of the hydrocarbon side chains which leads to the observed friction anisotropy. Friction anisotropy is therefore a sensitive, optically-independent indicator of polymer backbone direction and monolayer structural properties.

  18. Hierarchy of fillings for the FQHE in monolayer graphene

    PubMed Central

    Łydżba, Patrycja; Jacak, Lucjan; Jacak, Janusz

    2015-01-01

    In this paper, the commensurability conditions, which originated from the unique topology of two-dimensional systems, are applied to determine the quantum Hall effect hierarchy in the case of a monolayer graphene. The fundamental difference in a definition of a typical semiconductor and a monolayer graphene filling factor is pointed out. The calculations are undertaken for all spin-valley branches of two lowest Landau levels, since only they are currently experimentally accessible. The obtained filling factors are compared with the experimental data and a very good agreement is achieved. The work also introduces a concept of the single-loop fractional quantum Hall effect. PMID:26392385

  19. Synthesis of ZrO{sub 2} and Y{sub 2}O{sub 3}-doped ZrO{sub 2} thin films using self-assembled monolayers

    SciTech Connect

    Agarwal, M.; DeGuire, M.R.; Heuer, A.H.

    1997-12-01

    Undoped or Y{sub 2}O{sub 3}-doped ZrO{sub 2} thin films were deposited on self-assembled monolayers (SAMs) with either sulfonate or methyl terminal functionalities on single-crystal silicon substrates. The undoped films were formed by enhanced hydrolysis of zirconium sulfate (Zr(SO{sub 4}) {center_dot} 4H{sub 4}O) solutions in the presence of HCl at 70 C. Typically, these films were a mixture of two phases: nanocrystalline tetragonal- (t-) ZrO{sub 2} and an amorphous basic zirconium sulfate. However, films with little or no amorphous material could be produced. The mechanism of film formation and the growth kinetics have been explained through a coagulation model involving homogeneous nucleation, particle adhesion, and aggregation onto the substrate. Annealing of these films at 500 C led to complete crystallization to t-ZrO{sub 2}. Amorphous Y{sub 2}O{sub 3}-containing ZrO{sub 2} films were prepared from a precursor solution containing zirconium sulfate, yttrium sulfate (Y{sub 2}(SO{sub 4}){sub 3} {center_dot} 8H{sub 2}O), and urea (NH{sub 2}CONH{sub 2}) at pH 2.2--3.0 at 80 C. These films also were fully crystalline after annealing at 500 C.

  20. Nuclear spin-spin relaxation in 3He-Ne films

    NASA Astrophysics Data System (ADS)

    Sullivan, Neil S.; Stachiowak, Piotr; Parks, Charles

    2003-05-01

    NMR measurements of the nuclear spin-spin relaxation times are reported for commensurate monolayers of 3He and 3He-Ne films on boron nitride for temperatures 0.1monolayer coverage and the atom-vacancy exchange rate are also obtained from the experimental observations.

  1. Simultaneous Modification of Bottom-Contact Electrode and Dielectric Surfaces for Organic Thin-Film Transistors Through Single-Component Spin-Cast Monolayers

    SciTech Connect

    O Acton; M Dubey; t Weidner; K OMalley; T Kim; G Ting; D Hutchins; J Baio; T Lovejoy; et al.

    2011-12-31

    An efficient process is developed by spin-coating a single-component, self-assembled monolayer (SAM) to simultaneously modify the bottom-contact electrode and dielectric surfaces of organic thin-film transistors (OTFTs). This efficient interface modification is achieved using n-alkyl phosphonic acid based SAMs to prime silver bottom-contacts and hafnium oxide (HfO{sub 2}) dielectrics in low-voltage OTFTs. Surface characterization using near edge X-ray absorption fine structure (NEXAFS) spectroscopy, X-ray photoelectron spectroscopy (XPS), attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, atomic force microscopy (AFM), and spectroscopic ellipsometry suggest this process yields structurally well-defined phosphonate SAMs on both metal and oxide surfaces. Rational selection of the alkyl length of the SAM leads to greatly enhanced performance for both n-channel (C60) and p-channel (pentacene) based OTFTs. Specifically, SAMs of n-octylphos-phonic acid (OPA) provide both low-contact resistance at the bottom-contact electrodes and excellent interfacial properties for compact semiconductor grain growth with high carrier mobilities. OTFTs based on OPA modifi ed silver electrode/HfO{sub 2} dielectric bottom-contact structures can be operated using < 3V with low contact resistance (down to 700 Ohm-cm), low subthreshold swing (as low as 75 mV dec{sup -1}), high on/off current ratios of 107, and charge carrier mobilities as high as 4.6 and 0.8 cm{sup 2} V{sup -1} s{sup -1}, for C60 and pentacene, respectively. These results demonstrate that this is a simple and efficient process for improving the performance of bottom-contact OTFTs.

  2. Perforated monolayers

    SciTech Connect

    Regen, S.L.

    1992-12-01

    Goal of this research program is to create ultrathin organic membranes that possess uniform and adjustable pores ( < 7[angstrom] diameter). Such membranes are expected to possess high permeation selectivity (permselectivity) and high permeability, and to provide the basis for energy-efficient methods of molecular separation. Work carried out has demonstrated feasibility of using perforated monolayer''-based composites as molecular sieve membranes. Specifically, composite membranes derived from Langmuir-Blodgett multilayers of the calix[6]arene-based surfactant shown below plus poly[l-(trimethylsilyl)-l-propyne] (PTMSP) were found to exhibit sieving behavior towards He, N[sub 2] and SF[sub 6]. Results of derivative studies that have also been completed are also described in this report.

  3. A Sublattice Model of Appearance of an Incommensurate Phase Sandwiched by Reentrant Commensurate Phases

    NASA Astrophysics Data System (ADS)

    Ishibashi, Yoshihiro

    1986-12-01

    A two-sublattice model is presented for reproducing the normal(N)-commensurate(C)-incommensurate(IC)-commensurate(C) phase sequence phenomenologically. The temperature dependences of the transition parameters representing the homogeneous ionic displacements and the incommensurate modulated structure are obtained. The temperature dependences of a lattice constant and the soft mode frequencies are also presented.

  4. Structure and Phase Transitions of Monolayers of Intermediate-length n-alkanes on Graphite Studied by Neutron Diffraction and Molecular Dynamics Simulation

    SciTech Connect

    Taub, H.; Hansen, F.Y.; Diama, Amand; Matthies, Blake; Criswell, Leah; Mo, Haiding; Bai, M; Herwig, Kenneth W

    2009-01-01

    We present evidence from neutron diffraction measurements and molecular dynamics (MD) simulations of three different monolayer phases of the intermediate-length alkanes tetracosane (n-C(24)H(50) denoted as C24) and dotriacontane (n-C(32)H(66) denoted as C32) adsorbed on a graphite basal-plane surface. Our measurements indicate that the two monolayer films differ principally in the transition temperatures between phases. At the lowest temperatures, both C24 and C32 form a crystalline monolayer phase with a rectangular-centered (RC) structure. The two sublattices of the RC structure each consists of parallel rows of molecules in their all-trans conformation aligned with their long axis parallel to the surface and forming so-called lamellas of width approximately equal to the all-trans length of the molecule. The RC structure is uniaxially commensurate with the graphite surface in its [110] direction such that the distance between molecular rows in a lamella is 4.26 A=sqrt[3a(g)], where a(g)=2.46 A is the lattice constant of the graphite basal plane. Molecules in adjacent rows of a lamella alternate in orientation between the carbon skeletal plane being parallel and perpendicular to the graphite surface. Upon heating, the crystalline monolayers transform to a 'smectic' phase in which the inter-row spacing within a lamella expands by approximately 10% and the molecules are predominantly oriented with the carbon skeletal plane parallel to the graphite surface. In the smectic phase, the MD simulations show evidence of broadening of the lamella boundaries as a result of molecules diffusing parallel to their long axis. At still higher temperatures, they indicate that the introduction of gauche defects into the alkane chains drives a melting transition to a monolayer fluid phase as reported previously.

  5. Structure and phase transitions of monolayers of intermediate-length n-alkanes on graphite studied by neutron diffraction and molecular dynamics simulation.

    PubMed

    Diama, A; Matthies, B; Herwig, K W; Hansen, F Y; Criswell, L; Mo, H; Bai, M; Taub, H

    2009-08-28

    We present evidence from neutron diffraction measurements and molecular dynamics (MD) simulations of three different monolayer phases of the intermediate-length alkanes tetracosane (n-C(24)H(50) denoted as C24) and dotriacontane (n-C(32)H(66) denoted as C32) adsorbed on a graphite basal-plane surface. Our measurements indicate that the two monolayer films differ principally in the transition temperatures between phases. At the lowest temperatures, both C24 and C32 form a crystalline monolayer phase with a rectangular-centered (RC) structure. The two sublattices of the RC structure each consists of parallel rows of molecules in their all-trans conformation aligned with their long axis parallel to the surface and forming so-called lamellas of width approximately equal to the all-trans length of the molecule. The RC structure is uniaxially commensurate with the graphite surface in its [110] direction such that the distance between molecular rows in a lamella is 4.26 A=sqrt[3a(g)], where a(g)=2.46 A is the lattice constant of the graphite basal plane. Molecules in adjacent rows of a lamella alternate in orientation between the carbon skeletal plane being parallel and perpendicular to the graphite surface. Upon heating, the crystalline monolayers transform to a "smectic" phase in which the inter-row spacing within a lamella expands by approximately 10% and the molecules are predominantly oriented with the carbon skeletal plane parallel to the graphite surface. In the smectic phase, the MD simulations show evidence of broadening of the lamella boundaries as a result of molecules diffusing parallel to their long axis. At still higher temperatures, they indicate that the introduction of gauche defects into the alkane chains drives a melting transition to a monolayer fluid phase as reported previously.

  6. Electrochemical Deposition Of Thiolate Monolayers On Metals

    NASA Technical Reports Server (NTRS)

    Porter, Marc D.; Weissharr, Duane E.

    1995-01-01

    Electrochemical method devised for coating metal (usually, gold) surfaces with adherent thiolate monolayers. Affords greater control over location and amount of material deposited and makes it easier to control chemical composition of deposits. One important potential use for this method lies in fabrication of chemically selective thin-film resonators for microwave oscillators used to detect pollutants: monolayer formulated to bind selectively pollutant chemical species of interest, causing increase in mass of monolayer and corresponding decrease in frequency of resonance. Another important potential use lies in selective chemical derivatization for purposes of improving adhesion, lubrication, protection against corrosion, electrocatalysis, and electroanalysis.

  7. Molecular orientation of copper phthalocyanine thin films on different monolayers of fullerene on SiO{sub 2} or highly oriented pyrolytic graphite

    SciTech Connect

    Wang, Chenggong; Wang, Congcong; Liu, Xiaoliang; Xu, Xumei; Li, Youzhen; Xie, Fangyan; Gao, Yongli

    2015-03-23

    The interface electronic structures of copper phthalocyanine (CuPc) have been studied using ultraviolet photoemission spectroscopy as different monolayers of C{sub 60} were inserted between CuPc and a SiO{sub 2} or highly ordered pyrolytic graphite (HOPG) substrate. The results show that CuPc has standing up configuration with one monolayer of C{sub 60} insertion on SiO{sub 2} while lying down on HOPG, indicating that the insertion layer propagates the CuPc-substrate interaction. Meanwhile, CuPc on more than one monolayers of C{sub 60} on different substrates show that the substrate orientation effect quickly vanished. Our study elucidates intriguing molecular interactions that manipulate molecular orientation and donor-acceptor energy level alignment.

  8. Molecular orientation of copper phthalocyanine thin films on different monolayers of fullerene on SiO2 or highly oriented pyrolytic graphite

    NASA Astrophysics Data System (ADS)

    Wang, Chenggong; Liu, Xiaoliang; Wang, Congcong; Xu, Xumei; Li, Youzhen; Xie, Fangyan; Gao, Yongli

    2015-03-01

    The interface electronic structures of copper phthalocyanine (CuPc) have been studied using ultraviolet photoemission spectroscopy as different monolayers of C60 were inserted between CuPc and a SiO2 or highly ordered pyrolytic graphite (HOPG) substrate. The results show that CuPc has standing up configuration with one monolayer of C60 insertion on SiO2 while lying down on HOPG, indicating that the insertion layer propagates the CuPc-substrate interaction. Meanwhile, CuPc on more than one monolayers of C60 on different substrates show that the substrate orientation effect quickly vanished. Our study elucidates intriguing molecular interactions that manipulate molecular orientation and donor-acceptor energy level alignment.

  9. Characterization of organosulfur monolayer formation at gold electrodes

    SciTech Connect

    Tani Woods, N.

    1996-08-01

    Among the many types of organic films, covalently-attached organosulfur monolayers have attracted a great deal of attention. The authors have focused their interest on the fundamental characterization of spontaneously adsorbed organosulfur monolayers. An introductory chapter presents general aspects of monolayer preparation and characterization, followed by a few examples that illustrate the range of applications of these films. This thesis contains two papers. In the first paper, three analogous monolayer precursors are studied to determine their similarities and differences in the monolayer structure. A GC-MS analysis of products form the chemisorption process and open circuit potential measurements are used to derive possible mechanisms behind monolayer formation. The second paper focuses on monolayers formed from thioctic acid, including its characterization and application to cytochrome c electrochemistry. Although thiols and disulfides have been extensively studied as monolayer precursors, thioctic acid is particularly interesting because the disulfide functionality of this asymmetric molecule is contained in a strained five-membered ring. Given the ring strain, steric bulk and asymmetry of the molecule, the study of these monolayers lend insight into the factors important for the formation of organosulfur monolayers. This thesis concludes with a general summary and directions for future studies. 40 refs.

  10. SYNCHROTRON X - RAY OBSERVATIONS OF A MONOLAYER TEMPLATE FOR MINERALIZATION.

    SciTech Connect

    DIMASI,E.; GOWER,L.B.

    2000-11-27

    Mineral nucleation at a Langmuir film interface has been studied by synchrotron x-ray scattering. Diluted calcium bicarbonate solutions were used as subphases for arachidic and stearic acid monolayers, compressed in a Langmuir trough. Self-assembly of the monolayer template is observed directly, and subsequent crystal growth monitored in-situ.

  11. Suppression of polarization fluctuations in chromium alloys with commensurate spin-density waves

    NASA Astrophysics Data System (ADS)

    Michel, R. P.; Weissman, M. B.; Ritley, K.; Huang, J. C.; Flynn, C. P.

    1993-02-01

    We compare electrical resistance noise in commensurate and incommensurate phases of the spin-density wave (SDW) in Cr and dilute CrMn alloys. The commensurate phase gives much less polarization fluctuation noise than the incommensurate phase. The incommensurability of the SDW and the lattice in Cr may affect the SDW dynamics through the existence of weak planes in which the induced orbital moment contribution to the SDW is close to zero.

  12. A perturbative treatment of motion near the 3/1 commensurability

    NASA Technical Reports Server (NTRS)

    Wisdom, J.

    1985-01-01

    A semianalytic perturbation theory for motion near the 3/1 commensurability in the planar elliptic restricted three-body problem is presented. The predictions of the theory are in good agreement with the features found on numerically generated surfaces of section; a global understanding of the phase space is achieved. The principal cause of the large chaotic zone near the 3/1 commensurability is identified, and a new criterion for the existence of large-scale chaotic behavior is presented.

  13. Growth of rare-earth monolayers on synthetic fluorine mica

    NASA Astrophysics Data System (ADS)

    Tsui, F.; Han, P. D.; Flynn, C. P.

    1993-05-01

    We have grown single-crystal rare-earth films on cleaved faces of synthetic fluorine mica fluorophlogopite by molecular-beam-epitaxy techniques. This has made it possible to measure material properties such as magnetism in monolayer structures.

  14. Unconventional Charge-Density-Wave Transition in Monolayer 1T-TiSe2.

    PubMed

    Sugawara, Katsuaki; Nakata, Yuki; Shimizu, Ryota; Han, Patrick; Hitosugi, Taro; Sato, Takafumi; Takahashi, Takashi

    2016-01-26

    Reducing the dimension in materials sometimes leads to unexpected discovery of exotic and/or pronounced physical properties such as quantum Hall effect in graphene and high-temperature superconductivity in iron-chalcogenide atomically thin films. Transition-metal dichalcogenides (TMDs) provide a fertile ground for studying the interplay between dimensionality and electronic properties, since they exhibit a variety of electronic phases like semiconducting, superconducting, and charge-density-wave (CDW) states. Among TMDs, bulk 1T-TiSe2 has been a target of intensive studies due to its unusual CDW properties with the periodic lattice distortions characterized by the three-dimensional (3D) commensurate wave vector. Clarifying the ground states of its two-dimensional (2D) counterpart is of great importance not only to pin down the origin of CDW, but also to find unconventional physical properties characteristic of atomic-layer materials. Here, we show the first experimental evidence for the realization of 2D CDW phase without Fermi-surface nesting in monolayer 1T-TiSe2. Our angle-resolved photoemission spectroscopy (ARPES) signifies an electron pocket at the Brillouin-zone corner above the CDW-transition temperature (TCDW ∼ 200 K), while, below TCDW, an additional electron pocket and replica bands appear at the Brillouin-zone center and corner, respectively, due to the back-folding of bands by the 2 × 2 superstructure potential. Similarity in the spectral signatures to bulk 1T-TiSe2 implies a common driving force of CDW, i.e., exciton condensation, whereas the larger energy gap below TCDW in monolayer 1T-TiSe2 suggests enhancement of electron-hole coupling upon reducing dimensionality. The present result lays the foundation for the electronic-structure engineering based with atomic-layer TMDs.

  15. Surface-enhanced Raman scattering of 4-mercaptobenzoic acid and hemoglobin adsorbed on self-assembled Ag monolayer films with different shapes

    NASA Astrophysics Data System (ADS)

    Zhu, Shuangmei; Fan, Chunzhen; Wang, Junqiao; He, Jinna; Liang, Erjun

    2014-06-01

    Polyvinylpyrrolidone (PVP)-protected silver nanostructures of various shapes, including nanocubes, nanospheres, and hybrid shapes with nanospheres and nanorods, on the surface of glass or Si substrates (PVP-Ag films) are prepared by using electrostatic self-assembly. With 4-mercaptobenzoic acid (4-MBA) as a probe molecule, it is demonstrated that the PVP-protected silver nanocubes films (PVP-Ag NCs) have better surface-enhanced Raman scattering (SERS) activity with an order of magnitude larger enhancement factors (EF) than the PVP-protected silver nanospheres films and the PVP-protected silver hybrid shapes films, which is confirmed by our numerical simulations. The EF of 4-MBA on the PVP-Ag NCs film are up to ~5.38 × 106, and the detection limit is at least down to ~10-8 M. The uniformity and reproducibility of the SERS signals on PVP-Ag NCs film are tested by point-to-point and batch-to-batch measurements. Meanwhile, the PVP-Ag films are also shown to be an excellent SERS substrate with good biocompatibility for hemoglobin detection. It is shown that the PVP-Ag NCs films can be used as excellent SERS substrate with good activity, uniformity, reproducibility, and biocompatibility and are promising for a myriad of chemical and biochemical sensing applications.

  16. Molecular motion in alkylsilane self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Stevens, Derrick; Scott, Mary; Guy, Laura; Bochinski, Jason; Clarke, Laura

    2008-03-01

    We have investigated intra-molecular rotation within polar-substituted alkylsilane self-assembled monolayers (SAMs) on fused silica, utilizing surface-sensitive dielectric spectroscopy. Both trichlorosilanes (which allow crosslinking within the SAM) and monochlorosilanes (attached only to the surface) are utilized to grow monolayer and submonolayer films. Dielectric loss spectra as a function of temperature have been obtained for SAMs with varying carbon chain length, surface coverage, and alkyl terminal group. As shown by ellipsometry, contact angle measurements, and AFM, monochlorosilanes form a more disordered monolayer than trichlorosilanes. This more disordered film may result in additional degrees of freedom within the monolayer, or in the language of phase transitions, a rotator phase. Issues such as uncontrolled vertical polymerization and film growth by island formation and their effect on rotational dynamics will be discussed.

  17. Molecular Dynamics in Self-Assembled Monolayers

    NASA Astrophysics Data System (ADS)

    Bochinski, Jason; Stevens, Derrick; Scott, Mary; Guy, Laura; Dedeugd, Casey; Clarke, Laura

    2007-03-01

    Silane self-assembled monolayers (SAMs) are an important tool for both scientific research and technological applications. Despite their widespread use, few experimental investigations have addressed molecular motion within these films, which offer a unique and useful physical system for fundamental scientific studies, such as observing dipolar and other glass transitions in two-dimensions. In addition, relaxations such as ``rotator'' phases where molecular groups rotate in a plane parallel to the surface have been correlated with film conductivity, adhesive, and wetting properties. We utilize surface-sensitive, dielectric relaxation spectroscopy to probe molecular motion as a function of temperature within silane chemistry-based monolayers formed upon interdigitated electrodes. Our latest results exploring a previously published motion as well as comparisons to linear polymer films will be discussed.

  18. Commensurate magnetic structure of CeRhIn4.85 Hg0.15

    SciTech Connect

    Bao, Wei C; Ronning, Filip; Bauer, Eric D; Thompson, Joe D; Gasparovic, Y; Lynn, J; Fisk, Z

    2008-01-01

    We show using neutron diffraction that the magnetic structure of CrRhIn{sub 4.85}Hg{sub 0.15} is characterized by a commensurate propagation vector (1,2,1/2,1/2). This is different from the magnetic structure in the parent compound CeRhIn{sub 5}, which orders with an incommensurate propagation vector (1/2,1/2,0.297). The special relation between the commensurate magnetic mode and unconventional superconductivity has been shown previously for this class of heavy fermion superconductors. This work provides further evidence for the ubiquity of this antiferromagnetic mode.

  19. Electromagnetic interference shielding effectiveness of monolayer graphene.

    PubMed

    Hong, Seul Ki; Kim, Ki Yeong; Kim, Taek Yong; Kim, Jong Hoon; Park, Seong Wook; Kim, Joung Ho; Cho, Byung Jin

    2012-11-16

    We report the first experimental results on the electromagnetic interference (EMI) shielding effectiveness (SE) of monolayer graphene. The monolayer CVD graphene has an average SE value of 2.27 dB, corresponding to ~40% shielding of incident waves. CVD graphene shows more than seven times (in terms of dB) greater SE than gold film. The dominant mechanism is absorption rather than reflection, and the portion of absorption decreases with an increase in the number of graphene layers. Our modeling work shows that plane-wave theory for metal shielding is also applicable to graphene. The model predicts that ideal monolayer graphene can shield as much as 97.8% of EMI. This suggests the feasibility of manufacturing an ultrathin, transparent, and flexible EMI shield by single or few-layer graphene. PMID:23085718

  20. Novel behavior of monolayer quantum gases on graphene, graphane and fluorographene.

    PubMed

    Reatto, Luciano; Galli, Davide E; Nava, Marco; Cole, Milton W

    2013-11-01

    This article discusses the behavior of submonolayer quantum films (He and H2) on graphene and newly discovered surfaces that are derived from graphene. Among these substrates are graphane (abbreviated GH), which has an H atom bonded to each C atom, and fluorographene (GF). The subject is introduced by describing the related problem of monolayer films on graphite. For that case, extensive experimental and theoretical investigations have revealed that the phase diagrams of the Bose gases (4)He and para-H2 are qualitatively similar, differing primarily in a higher characteristic temperature scale for H2 than for He. The phase behavior of these films on one side of pristine graphene, or both sides of free-standing graphene, is expected to be similar to that on graphite. We point out the possibility of novel phenomena in adsorption on graphene related to the large flexibility of the graphene sheet, to the non-negligible interaction between atoms adsorbed on opposite sides of the sheet and to the perturbation effect of the adsorbed layer on the Dirac electrons. In contrast, the behavior predicted on GF and GH surfaces is very different from that on graphite, a result of the different corrugation, i.e., the lateral variation of the potential experienced by these gases. This arises because on GF, for example, half of the F atoms are located above the C plane while the other half are below this plane. Hence, the He and H2 gases experience very different potentials from those on graphite or graphene. As a result of this novel geometry and potential, distinct properties are observed. For example, the (4)He film's ground state on graphite is a two-dimensional (2D) crystal commensurate with the substrate, the famous [Formula: see text] phase; on GF and GH, instead, it is predicted to be an anisotropic superfluid. On GF the anisotropy is so extreme that the roton excitations are very anisotropic, as if the bosons are moving in a multiconnected space along the bonds of a

  1. Reduction of interfacial friction in commensurate graphene/h-BN heterostructures by surface functionalization

    NASA Astrophysics Data System (ADS)

    Guo, Yufeng; Qiu, Jiapeng; Guo, Wanlin

    2015-12-01

    The reduction of interfacial friction in commensurately stacked two-dimensional layered materials is important for their application in nanoelectromechanical systems. Our first-principles calculations on the sliding energy corrugation and friction at the interfaces of commensurate fluorinated-graphene/h-BN and oxidized-graphene/h-BN heterostructures show that the sliding energy barriers and shear strengths for these heterostructures are approximately decreased to 50% of those of commensurate graphene/h-BN. The adsorbed F and O atoms significantly suppress the interlayer electrostatic and van der Waals energy corrugations by modifying the geometry and charge redistribution of the graphene layers. Our empirical registry index models further reveal the difference between the roles of the F and O atoms in affecting the sliding energy landscapes, and are also utilized to predict the interlayer superlubricity in a large-scale oxidized-graphene/h-BN system. Surface functionalization is a valid way to control and reduce the interlayer friction in commensurate graphene/h-BN heterostructures.

  2. Dynamic in-plane potential gradients for actively controlling electrochemical reactions: Part I. Characterization of 1- and 2-component alkanethiol monolayer gradients on thin gold films. Part II. Applications of in-plane potential gradients

    NASA Astrophysics Data System (ADS)

    Balss, Karin Maria

    The research contained in this thesis is focused on the formation and characterization of surface composition gradients on thin gold films that are formed by applications of in-plane potential gradients. Injecting milliamp currents into thin Au films yields significant in-plane voltage drops so that, rather than assuming a single value of potential, an in-plane potential gradient is imposed on the film which depends on the resistivity of the film, the cross sectional area and the magnitude of the potential drop. Furthermore, the in-plane electric potential gradient means that, relative to a solution reference couple, electrochemical reactions occurs at defined spatial positions corresponding to the local potential, V(x) ˜ E0. The spatial gradient in electrochemical potential can then produce spatially dependent electrochemistry. Surface-chemical potential gradients can be prepared by arranging the spread of potentials to span an electrochemical wave mediating redox-associated adsorption or desorption. Examples of reactions that can be spatially patterned include the electrosorption of alkanethiols and over-potential metal deposition. The unique advantage of this method for patterning spatial compositions is the control of surface coverage in both space and time. The thesis is organized into two parts. In Part I, formation and characterization of 1- and 2-component alkanethiol monolayer gradients is investigated. Numerous surface science tools are employed to examine the distribution in coverage obtained by application of in-plane potential gradients. Macroscopic characterization was obtained by sessile water drop contact angle measurements and surface plasmon resonance imaging. Gradients were also imaged on micron length scales with pulsed-force mode atomic force microscopy. Direct chemical evidence of surface compositions in aromatic thiol surface coverage was obtained by surface-enhanced Raman spectroscopy. In Part II, the applications of in-plane potential

  3. Methods of making monolayers

    DOEpatents

    Alford, Kentin L.; Simmons, Kevin L.; Samuels, William D.; Zemanian, Thomas S.; Liu, Jun; Shin, Yongsoon; Fryxell, Glen E.

    2009-09-15

    The invention pertains to methods of forming monolayers on various surfaces. The surfaces can be selected from a wide array of materials, including, for example, aluminum dioxide, silicon dioxide, carbon and SiC. The substrates can be planar or porous. The monolayer is formed under enhanced pressure conditions. The monolayer contains functionalized molecules, and accordingly functionalizes a surface of the substrate. The properties of the functionalized substrate can enhance the substrate's applicability for numerous purposes including, for example, utilization in extracting contaminants, or incorporation into a polymeric matrix.

  4. Methods of making monolayers

    DOEpatents

    Alford, Kentin L.; Simmons, Kevin L.; Samuels, William D.; Zemanian, Thomas S.; Liu, Jun; Shin, Yongsoon; Fryxell, Glen E.

    2009-12-08

    The invention pertains to methods of forming monolayers on various surfaces. The surfaces can be selected from a wide array of materials, including, for example, aluminum dioxide, silicon dioxide, carbon and SiC. The substrates can be planar or porous. The monolayer is formed under enhanced pressure conditions. The monolayer contains functionalized molecules, and accordingly functionalizes a surface of the substrate. The properties of the functionalized substrate can enhance the substrate's applicability for numerous purposes including, for example, utilization in extracting contaminants, or incorporation into a polymeric matrix.

  5. Persistent monolayer-scale chemical ordering in Si{sub 1−x}Ge{sub x} heteroepitaxial films during surface roughening and strain relaxation

    SciTech Connect

    Amatya, J. M.; Floro, J. A.

    2015-12-28

    Chemical ordering in semiconductor alloys could modify thermal and electronic transport, with potential benefits to thermoelectric properties. Here, metastable ordering that occurs during heteroepitaxial growth of Si{sub 1−x}Ge{sub x} thin film alloys on Si(001) and Ge(001) substrates is investigated. A parametric study was performed to study how strain, surface roughness, and growth parameters affect the order parameter during the alloy growth. The order parameter for the alloy films was carefully quantified using x-ray diffraction, taking into account an often-overlooked issue associated with the presence of multiple spatial variants associated with ordering along equivalent <111> directions. Optimal ordering was observed in the films having the smoothest surfaces. Extended strain relaxation is suggested to reduce the apparent order through creation of anti-phase boundaries. Ordering surprisingly persists even when the film surface extensively roughens to form (105) facets. Growth on deliberately miscut Si(001) surfaces does not affect the volume-averaged order parameter but does impact the relative volume fractions of the equivalent ordered variants in a manner consistent with geometrically necessary changes in step populations. These results provide somewhat self-contradictory implications for the role of step edges in controlling the ordering process, indicating that our understanding is still incomplete.

  6. Metastability of a Supercompressed Fluid Monolayer

    PubMed Central

    Smith, Ethan C.; Crane, Jonathan M.; Laderas, Ted G.; Hall, Stephen B.

    2003-01-01

    Previous studies showed that monomolecular films of extracted calf surfactant collapse at the equilibrium spreading pressure during quasi-static compressions but become metastable at much higher surface pressures when compressed faster than a threshold rate. To determine the mechanism by which the films become metastable, we studied single-component films of 1-palmitoyl-2-oleoyl phosphatidylcholine (POPC). Initial experiments confirmed similar metastability of POPC if compressed above a threshold rate. Measurements at different surface pressures then showed that rates of collapse, although initially increasing above the equilibrium spreading pressure, reached a sharply defined maximum and then slowed considerably. When heated, rapidly compressed films recovered their ability to collapse with no discontinuous change in area, arguing that the metastability does not reflect transition of the POPC film to a new phase. These observations indicate that in several respects, the supercompression of POPC monolayers resembles the supercooling of three-dimensional liquids toward a glass transition. PMID:14581205

  7. Ionization of covalent immobilized poly(4-vinylphenol) monolayers measured by ellipsometry, QCM and SPR

    PubMed Central

    Uppalapati, Suji; Kong, Na; Norberg, Oscar; Ramström, Olof; Yan, Mingdi

    2015-01-01

    Covalently immobilized poly(4-vinylphenol) (PVP) monolayer films were fabricated by spin coating PVP on perfluorophenyl azide (PFPA)-functionalized surface followed by UV irradiation. The pH-responsive behavior of these PVP ultrathin films was evaluated by ellipsometry, quartz crystal microbalance (QCM) and surface plasmon resonance (SPR). By monitoring the responses of these films to pH in situ, the ionization constant of the monolayer thin films was obtained. The apparent pKa value of these covalently immobilized PVP monolayers, 13.4 by SPR, was 3 units higher than that of the free polymer in aqueous solution. PMID:26097271

  8. Ionization of covalent immobilized poly(4-vinylphenol) monolayers measured by ellipsometry, QCM and SPR

    NASA Astrophysics Data System (ADS)

    Uppalapati, Suji; Kong, Na; Norberg, Oscar; Ramström, Olof; Yan, Mingdi

    2015-07-01

    Covalently immobilized poly(4-vinylphenol) (PVP) monolayer films were fabricated by spin coating PVP on perfluorophenyl azide (PFPA)-functionalized surfaces followed by UV irradiation. The pH-responsive behavior of these PVP ultrathin films was evaluated by ellipsometry, quartz crystal microbalance (QCM) and surface plasmon resonance (SPR). By monitoring the responses of these films to pH in situ, the ionization constant of the monolayer thin films was obtained. The apparent pKa value of these covalently immobilized PVP monolayers, 13.4 by SPR, was 3 units higher than that of the free polymer in aqueous solution.

  9. Surface modification of surface sol-gel derived titanium oxide films by self-assembled monolayers (SAMs) and non-specific protein adsorption studies.

    PubMed

    Advincula, Maria; Fan, Xiaowu; Lemons, Jack; Advincula, Rigoberto

    2005-04-25

    Biological events occurring at the implant-host interface, including protein adsorption are mainly influenced by surface properties of the implant. Titanium alloys, one of the most widely used implants, has shown good biocompatibility primarily through its surface oxide. In this study, a surface sol-gel process based on the surface reaction of metal alkoxides with a hydroxylated surface was used to prepare ultrathin titanium oxide (TiOx) coatings on silicon wafers. The oxide deposited on the surface was then modified by self-assembled monolayers (SAMs) of silanes with different functional groups. Interesting surface morphology trends and protein adhesion properties of the modified titanium oxide surfaces were observed as studied by non-specific protein binding of serum albumin. The surface properties were investigated systematically using water contact angle, ellipsometry, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) measurements. Results showed that the surface sol-gel process predominantly formed homogeneous, but rough and porous titanium oxide layers. The protein adsorption was dependent primarily on the silane chemistry, packing of the alkyl chains (extent of van der Waals interaction), morphology (porosity and roughness), and wettability of the sol-gel oxide. Comparison was made with a thermally evaporated TiOx-Ti/Si-wafer substrate (control). This method further extends the functionalization of surface sol-gel derived TiOx layers for possible titanium alloy bioimplant surface modification.

  10. Two-dimensional crystallization of catalase on a monolayer film of poly(1-benzyl-L-histidine) spread at the air/water interface.

    PubMed

    Sato, A; Furuno, T; Toyoshima, C; Sasabe, H

    1993-03-01

    Two-dimensional (2D) crystals of beef liver catalase were prepared by adsorption to a film of synthetic polypeptide, poly(1-benzyl-L-histidine) (PBLH), spread at the air/water interface. The crystallization experiments were carried out in the pH range of 4.8-6.4 for catalase solutions at low concentration (10 micrograms/ml). The pH-dependence suggested an electrostatic interaction in the binding of catalase to the PBLH film. At lower pH, small crystals were formed at a low binding rate, and at higher pH the binding was rapid and densely-packed 2D arrays with poor crystallinity were formed. To stimulate crystal growth, a thermal treatment was applied. One-shot heating of the interfacial catalase-PBLH film to 35-40 degrees C was remarkably effective to form larger 2D crystals. The structure of catalase 2D crystals has been analyzed by Fourier filtering of the transmission electron micrographs. The crystal form is a new one, containing four catalase molecules in the unit cell with lattice parameters of alpha = 187 A, b = 225 A and gamma = 92.8 degrees.

  11. Diamondoid monolayers as electron emitters

    DOEpatents

    Yang, Wanli; Fabbri, Jason D.; Melosh, Nicholas A.; Hussain, Zahid; Shen, Zhi-Xun

    2013-10-29

    Provided are electron emitters based upon diamondoid monolayers, preferably self-assembled higher diamondoid monolayers. High intensity electron emission has been demonstrated employing such diamondoid monolayers, particularly when the monolayers are comprised of higher diamondoids. The application of such diamondoid monolayers can alter the band structure of substrates, as well as emit monochromatic electrons, and the high intensity electron emissions can also greatly improve the efficiency of field-effect electron emitters as applied to industrial and commercial applications.

  12. Diamondoid monolayers as electron emitters

    DOEpatents

    Yang, Wanli; Fabbri, Jason D.; Melosh, Nicholas A.; Hussain, Zahid; Shen, Zhi-Xun

    2012-04-10

    Provided are electron emitters based upon diamondoid monolayers, preferably self-assembled higher diamondoid monolayers. High intensity electron emission has been demonstrated employing such diamondoid monolayers, particularly when the monolayers are comprised of higher diamondoids. The application of such diamondoid monolayers can alter the band structure of substrates, as well as emit monochromatic electrons, and the high intensity electron emissions can also greatly improve the efficiency of field-effect electron emitters as applied to industrial and commercial applications.

  13. Multifunctional self-assembled monolayers

    SciTech Connect

    Zawodzinski, T.; Bar, G.; Rubin, S.; Uribe, F.; Ferrais, J.

    1996-06-01

    This is the final report of at three year, Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The specific goals of this research project were threefold: to develop multifunctional self-assembled monolayers, to understand the role of monolayer structure on the functioning of such systems, and to apply this knowledge to the development of electrochemical enzyme sensors. An array of molecules that can be used to attach electrochemically active biomolecules to gold surfaces has been synthesized. Several members of a class of electroactive compounds have been characterized and the factors controlling surface modification are beginning to be characterized. Enzymes have been attached to self-assembled molecules arranged on the gold surface, a critical step toward the ultimate goal of this project. Several alternative enzyme attachment strategies to achieve robust enzyme- modified surfaces have been explored. Several means of juxtaposing enzymes and mediators, electroactive compounds through which the enzyme can exchange electrons with the electrode surface, have also been investigated. Finally, the development of sensitive biosensors based on films loaded with nanoscale-supported gold particles that have surface modified with the self-assembled enzyme and mediator have been explored.

  14. Controlling self assembled monolayers

    NASA Astrophysics Data System (ADS)

    Wei, Yanhu

    2007-12-01

    In this thesis, we demonstrate novel methods of controlling the morphology of self-assembled monolayers at the solution-graphite interface. Scanning tunneling microscopy is used to evaluate the capacity of chain length and weak dipolar interactions to direct packing and neighboring chain selection within monolayers. We designed and synthesized a series of 1,5-substituted anthracene derivatives and investigated the relationship between side chain structure and monolayer morphology. We report that the morphology of monolayers formed on HOPG from symmetrically substituted anthracene derivatives switches from a 2D racemate to a 2D conglomerate by the addition of a single methylene unit to each side chain, i.e., by changing the side chain lengths from even to odd. We introduced ether groups into the side chains of anthracene derivatives in an attempt to use dipolar interactions to alter monolayer morphology. We report that the insertion of electronegative oxygen atoms into the side chains of anthracene derivatives can disturb the odd - even effect of chain length and influence monolayer morphology. By introducing a proper number of ether groups at specific side chain locations, we designed two self-repelling and complementary chains: COC12OC and C2OC10OC 2. COC12OC (or C2OC10OC2) chains repel themselves but select the other C2OC10OC 2 (or COC12OC) chains as their neighbors in self-assembled monolayers. Taking into account chain length matching and dipolar complementary as mechanisms for adjacent side chain selection, we designed and synthesized two symmetrical anthracenes 12 (COC12OC-An-COC 12OC), 13 (C2OC10OC2-An-C 2OC10OC2) and two unsymmetrical anthracenes 15 (C11OC-An-COC12OC) and 16 (C 18OC2-An-C2OC10OC2). Using a mixture solution of these molecules, we prepared a highly ordered AABB monolayer pattern in which paired rows of 15 alternate with paired rows of 16, and a highly ordered AAB monolayer pattern in which rows consisting of 12 are sandwiched between paired

  15. Competition between commensurate and incommensurate magnetic ordering in Fe1+yTe

    NASA Astrophysics Data System (ADS)

    Parshall, D.; Chen, G.; Pintschovius, L.; Lamago, D.; Wolf, Th.; Radzihovsky, L.; Reznik, D.

    2012-04-01

    The Fe1+yTe1-xSex compounds belong to the family of iron-based high-temperature superconductors, in which superconductivity often appears upon doping antiferromagnetic parent compounds. Unlike other Fe-based superconductors (in which the antiferromagnetic order is at the Fermi-surface nesting wave vector [(1)/(2),(1)/(2),1]), Fe1+yTe orders at a different wave vector, [(1)/(2),0,(1)/(2)]. Furthermore, the ordering wave vector depends on y, the occupation of interstitial sites with excess iron; the origin of this behavior is controversial. Using inelastic neutron scattering on Fe1.08Te, we find incommensurate magnetic fluctuations above the Néel temperature, even though the ordered state is bicollinear and commensurate with gapped spin waves. This behavior can be understood in terms of a competition between commensurate and incommensurate order, which we explain as a lock-in transition caused by the magnetic anisotropy.

  16. Spiral Spin Structure in the Commensurate Magnetic Phase of Multiferroic RMn2O5

    NASA Astrophysics Data System (ADS)

    Kimura, Hiroyuki; Kobayashi, Satoru; Fukuda, Yoshikazu; Osawa, Toshihiro; Kamada, Youichi; Noda, Yukio; Kagomiya, Isao; Kohn, Kay

    2007-07-01

    Crystal and magnetic structure analyses have been performed for single crystals of multiferroic materials RMn2O5 (R = Y, Ho, Er) using the neutron diffraction technique. For all the compounds, the magnetic structure in the commensurate magnetic phase, where spontaneous electric polarization occurs, was determined to be a transverse spiral spin structure propagating along the c-axis. The results demonstrate that the spin configuration for Mn4+ and Mn3+ ions is essentially the same in all three materials, suggesting that the ferroelectricity of the commensurate magnetic phase originates from the spin configurations of Mn ions. By contrast, the alignment of the induced 4 f-moment of Ho3+ ions is quite different from that of Er3+ ions, which might give a rich variety of magnetic field response for magnetic and dielectric properties in the RMn2O5 system.

  17. Commensurate states on incommensurate lattices. [for superconducting arrays in magnetic fields

    NASA Technical Reports Server (NTRS)

    Grest, Gary S.; Chaikin, Paul M.; Levine, Dov

    1988-01-01

    A simple one-dimensional model related to flux quantization on superconducting networks or charged particles on a substrate is proposed to investigate whether commensurate states can exist on incommensurate lattices. For both periodic and quasi-crystalline patterns, a set of low-energy states is found which is related to decimation symmetry and periodicity. It is suggested that the present quasi-periodic arrays which possess a decimation operation can be generalized to more-dimensional quasi-crystalline systems.

  18. Monolayer phase coarsening using oscillatory flow

    NASA Astrophysics Data System (ADS)

    Leung, J.; Lopez, J. M.; Vogel, M. J.

    2005-11-01

    The co-existing phase domains of monolayers commonly observed via microscope are examined on flowing systems. Recent evidence shows that co-existing phase domains have profound effects on monolayer response to bulk flow. The present flow geometry consists of an open-top rectangular cavity in which the flow is driven by the periodic oscillation of the floor in its own plane. The oscillation of the floor dilates and compresses any film at the gas/liquid interface while still maintaining an essentially flat interface. A range of flow conditions (oscillation frequency and amplitude) is chosen so that the flow remains essentially two-dimensional. Measurements at the interface, initially covered by an insoluble monolayer (vitamin K1 or stearic acid), are made using a Brewster angle microscope system with a pulsed laser. Various phenomena such as fragmentation (breaking up of co-existing domains into finer ones) had previously been observed in sheared monolayer flows. In this new flow regime, we have seen dramatic coarsening of the domains. Interesting relaxation behavior at short and long time scales will also be discussed.

  19. Adsorption of Ions at Uncharged Insoluble Monolayers.

    PubMed

    Peshkova, Tatyana V; Minkov, Ivan L; Tsekov, Roumen; Slavchov, Radomir I

    2016-09-01

    A method is proposed for the experimental determination of the adsorption of inorganic electrolytes at a surface covered with insoluble surfactant monolayer. This task is complicated by the fact that the change of the salt concentration alters both chemical potentials of the electrolyte and the surfactant. Our method resolves the question by combining data for the surface pressure versus area of the monolayer at several salt concentrations with data for the equilibrium spreading pressure of crystals of the surfactant (used to fix a standard state). We applied the method to alcohols spread at the surface of concentrated halide solutions. The measured salt adsorption is positive and has nonmonotonic dependence on the area per surfactant molecule. For the liquid expanded film, depending on the concentration, there is one couple of ions adsorbed per each 3-30 surfactant molecules. We analyzed which ion, the positive or the negative, stands closer to the surface, by measuring the effect of NaCl on the Volta potential of the monolayer. The potentiometric data suggest that Na(+) is specifically adsorbed, while Cl(-) remains in the diffuse layer, i.e., the surface is positively charged. The observed reverse Hofmeister series of the adsorptions of NaF, NaCl, and NaBr suggests the same conclusion holds for all these salts. The force that causes the adsorption of Na(+) seems to be the interaction of the ion with the dipole moment of the monolayer. PMID:27529571

  20. Hydrolytic kinetics of biodegradable polyester monolayers

    SciTech Connect

    Lee, W.K.; Gardella, J.A. Jr.

    2000-04-04

    The rate of hydrolysis of Langmuir monolayer films of a series of biodegradable polyesters was investigated at the air/water interface. The present study investigated parameters such as degradation medium, pH, and time. The hydrolysis of polyester monolayers strongly depended on both the degradation medium used to control subphase pH and the concentration of active ions. Under the conditions studied here, polymer monolayers showed faster hydrolysis when they were exposed to a basic subphase rather than that of acidic or neutral subphase. The basic (pH = 10) hydrolysis of [poly(l-lactide)/polycaprolactone](l-PLA/PCL 1/1 by mole) blend was faster than that of each homopolymer at the initial stage. This result is explained by increasing numbers of base attack sites per unit area owing to the very slow hydrolysis of PCL, a dilution effect on the concentration of l-PLA monolayers. Conversely the hydrolytic behavior of l-lactide-co-caprolactone (1/1 by mole) was similar to that of PCL even though the chemical compositions of the blend and the copolymer are very similar to each other. The resistance of the copolymer to hydrolysis might be attributed to the hydrophobicity and the steric hindrance of caprolactone unit in the copolymer.

  1. Adsorption of Ions at Uncharged Insoluble Monolayers

    NASA Astrophysics Data System (ADS)

    Peshkova, T. V.; Minkov, I. L.; Tsekov, R.; Slavchov, R. I.

    2016-08-01

    A method is proposed for the experimental determination of the adsorption of inorganic electrolytes at a surface covered with insoluble surfactant monolayer. This task is complicated by the fact that the change of the salt concentration alters both chemical potentials of the electrolyte and the surfactant. Our method resolves the question by combining data for the surface pressure versus area of the monolayer at several salt concentrations with data for the equilibrium spreading pressure of crystals of the surfactant (used to fix a standard state). We applied the method to alcohols spread at the surface of concentrated halide solutions. The measured salt adsorption is positive and has nonmonotonic dependence on the area per surfactant molecule. For the liquid expanded film, depending on the concentration, there is one couple of ions adsorbed per each 3–30 surfactant molecules. We analyzed which ion, the positive or the negative, stands closer to the surface, by measuring the effect of NaCl on the Volta potential of the monolayer. The potentiometric data suggest that Na+ is specifically adsorbed, while Cl– remains in the diffuse layer, i.e., the surface is positively charged. The observed reverse Hofmeister series of the adsorptions of NaF, NaCl, and NaBr suggests the same conclusion holds for all these salts. The force that causes the adsorption of Na+ seems to be the interaction of the ion with the dipole moment of the monolayer.

  2. Growth of a collapsing Langmuir monolayer

    SciTech Connect

    Kundu, S.; Datta, A.; Hazra, S.

    2006-05-15

    Langmuir monolayers of stearic acid on Co ions in the aqueous subphase have been deposited at different stages of constant pressure collapse, on hydrophilic Si(001) using a modified version of the inverse Langmuir-Schaefer method of horizontal deposition. The electron density profiles (EDPs) along the depth of the deposited films, extracted from the x-ray reflectivity data, show that a monolayer to bi-molecular layer transformation takes place after collapse. The molecules in the lower monolayer have asymmetric configurations with head groups touching water and tails in air, whereas molecules in the upper layer are in symmetric configurations with tails on both sides of the heads. Atomic force microscopy images of the deposited films after collapse, however, show nearly circular islands of height more than that of the bimolecular layer observed in the EDP. As pressure increases, ridges are seen to coexist with these islands. Although the coverage of such islands and ridges is low, they play an important role in determining the growth mode. The growth of the wetting and island layers, taken together, has a striking similarity with the Stranski-Krastanow mode, observed usually for heteroepitaxial growth.

  3. Superfluid--Insulator Transition in Commensurate One-Dimensional Bosonic System with Off-Diagonal Disorder

    NASA Astrophysics Data System (ADS)

    Balabanyan, Karén; Prokof'ev, Nikolay; Svistunov, Boris

    2005-03-01

    We analyze the superfluid--insulator transition in a system of one-dimensional (1D) lattice bosons with off-diagonal disorder in the limit of large commensurate filling. We argue---in contrast to the recent prediction (E. Altman, Y. Kafri, A. Polkovnikov, and G. Refael, cond-mat/0402177) of strong- randomness fixed point for this system---that at any strength of disorder the universality class of the transition on the superfluid side coincides with that of the superfluid--Mott- insulator transition in a pure system. We present results of Monte Carlo simulations for two strongly disordered models that are in excellent agreement with the advocated scenario.

  4. Commensurate germanium light emitters in silicon-on-insulator photonic crystal slabs.

    PubMed

    Jannesari, R; Schatzl, M; Hackl, F; Glaser, M; Hingerl, K; Fromherz, T; Schäffler, F

    2014-10-20

    We report on the fabrication and characterization of silicon-on-insulator (SOI) photonic crystal slabs (PCS) with commensurately embedded germanium quantum dot (QD) emitters for near-infrared light emission. Substrate pre-patterning defines preferential nucleation sites for the self-assembly of Ge QDs during epitaxial growth. Aligned two-dimensional photonic crystal slabs are then etched into the SOI layer. QD ordering enhances the photoluminescence output as compared to PCSs with randomly embedded QDs. Rigorously coupled wave analysis shows that coupling of the QD emitters to leaky modes of the PCS can be tuned via their location within the unit cell of the PCS.

  5. Transition from superlubrically sliding islands to pinned monolayer, demonstrated in Xe/Cu(111)

    NASA Astrophysics Data System (ADS)

    Guerra, Roberto; Vanossi, Andrea; Tosatti, Erio; Trieste Nanofriction Team

    A molecular dynamics simulation case study of Xe on Cu(111) reveals unexpected information on the exceptionally smooth sliding state associated with incommensurate superlubricity which is argued to emerge in the large size limit of naturally incommensurate Xe islands. As coverage approaches a full monolayer, theory predicts an abrupt adhesion-driven two-dimensional density compression on the order of several per cent, implying a hysteretic jump from superlubric free islands to a pressurized sqrt()x sqrt()commensurate (and pinned, and therefore immobile) monolayer. These results match with recent quartz crystal microbalance data which show remarkably large slip times with increasing submonolayer coverage, signalling superlubricity, followed by a dramatic drop to zero for the dense commensurate monolayer. Careful analysis of this variety of island sliding phenomena should be essential in future applications of friction at crystal/adsorbate interfaces. Matching experimental work by M. Pierno, L. Bruschi, G. Mistura, G. Paolicelli, A. di Bona, S. Valeri. Supported by ERC Advanced Grant N. 320796 - MODPHYSFRICT.

  6. Dynamics of xenon, krypton, and methane monolayers in registry with graphite

    SciTech Connect

    Hakim, T.M.; Glyde, H.R.; Chui, S.T.

    1988-01-15

    The self-consistent phonon (SCP) theory is used to study the dynamics of monolayers of xenon, krypton, and methane adsorbed on graphite. Only the ..sqrt..3 x ..sqrt..3 solid phase is considered. It is shown that the phonon energies of the Xe monolayers are very similar to those of their floating counterparts, while the interaction of the Kr and CH/sub 4/ monolayers with the graphite significantly affects the phonon dispersion curves. The gap in the phonon dispersion curves at the center of the Brillouin zone is computed as a function of temperature. At a critical temperature, the gap goes spontaneously to zero and a transition from a locked-in commensurate phase to a floating phase takes place. This transition appears to describe the commensurate to floating transition in CH/sub 4/ well. A simple model of the floating transition is compared to the full SCP calculations. The one-phonon dynamic form factor, including the cubic anharmonic term, and phonon lifetimes are also evaluated for Kr and CH/sub 4/.

  7. Patterning Self-Assembled Monolayers on Gold: Green Materials Chemistry in the Teaching Laboratory

    ERIC Educational Resources Information Center

    McFarland, Adam D.; Huffman, Lauren M.; Parent, Kathryn, E.; Hutchison, James E.; Thompson, John E.

    2004-01-01

    An experiment demonstrating self-assembled monolayer (SAM) chemistry, organic thin-film patterning and the use of molecular functionality to control macroscopic properties is described. Several important green chemistry principles are introduced.

  8. Proximity Driven Commensurate Pinning in YBa2Cu3O7 through All-Oxide Magnetic Nanostructures.

    PubMed

    Rocci, M; Azpeitia, J; Trastoy, J; Perez-Muñoz, A; Cabero, M; Luccas, R F; Munuera, C; Mompean, F J; Garcia-Hernandez, M; Bouzehouane, K; Sefrioui, Z; Leon, C; Rivera-Calzada, A; Villegas, J E; Santamaria, J

    2015-11-11

    The design of artificial vortex pinning landscapes is a major goal toward large scale applications of cuprate superconductors. Although disordered nanometric inclusions have shown to modify their vortex phase diagram and to produce enhancements of the critical current ( MacManus-Driscoll , J. L. ; Foltyn , S. R. ; Jia , Q. X. ; Wang , H. ; Serquis , A. ; Civale , L. ; Maiorov , B. ; Hawley , M. E. ; Maley , M. P. ; Peterson , D. E. Nat. Mater. 2004 , 3 , 439 - 443 and Yamada , Y. ; Takahashi , K. ; Kobayashi , H. ; Konishi , M. ; Watanabe , T. ; Ibi , A. ; Muroga , T. ; Miyata , S. ; Kato , T. ; Hirayama , T. ; Shiohara , Y. Appl. Phys. Lett. 2005 , 87 , 1 - 3 ), the effect of ordered oxide nanostructures remains essentially unexplored. This is due to the very small nanostructure size imposed by the short coherence length, and to the technological difficulties in the nanofabrication process. Yet, the novel phenomena occurring at oxide interfaces open a wide spectrum of technological opportunities to interplay with the superconductivity in cuprates. Here, we show that the unusual long-range suppression of the superconductivity occurring at the interface between manganites and cuprates affects vortex nucleation and provides a novel vortex pinning mechanism. In particular, we show evidence of commensurate pinning in YBCO films with ordered arrays of LCMO ferromagnetic nanodots. Vortex pinning results from the proximity induced reduction of the condensation energy at the vicinity of the magnetic nanodots, and yields an enhanced friction between the nanodot array and the moving vortex lattice in the liquid phase. This result shows that all-oxide ordered nanostructures constitute a powerful, new route for the artificial manipulation of vortex matter in cuprates.

  9. Proximity Driven Commensurate Pinning in YBa2Cu3O7 through All-Oxide Magnetic Nanostructures.

    PubMed

    Rocci, M; Azpeitia, J; Trastoy, J; Perez-Muñoz, A; Cabero, M; Luccas, R F; Munuera, C; Mompean, F J; Garcia-Hernandez, M; Bouzehouane, K; Sefrioui, Z; Leon, C; Rivera-Calzada, A; Villegas, J E; Santamaria, J

    2015-11-11

    The design of artificial vortex pinning landscapes is a major goal toward large scale applications of cuprate superconductors. Although disordered nanometric inclusions have shown to modify their vortex phase diagram and to produce enhancements of the critical current ( MacManus-Driscoll , J. L. ; Foltyn , S. R. ; Jia , Q. X. ; Wang , H. ; Serquis , A. ; Civale , L. ; Maiorov , B. ; Hawley , M. E. ; Maley , M. P. ; Peterson , D. E. Nat. Mater. 2004 , 3 , 439 - 443 and Yamada , Y. ; Takahashi , K. ; Kobayashi , H. ; Konishi , M. ; Watanabe , T. ; Ibi , A. ; Muroga , T. ; Miyata , S. ; Kato , T. ; Hirayama , T. ; Shiohara , Y. Appl. Phys. Lett. 2005 , 87 , 1 - 3 ), the effect of ordered oxide nanostructures remains essentially unexplored. This is due to the very small nanostructure size imposed by the short coherence length, and to the technological difficulties in the nanofabrication process. Yet, the novel phenomena occurring at oxide interfaces open a wide spectrum of technological opportunities to interplay with the superconductivity in cuprates. Here, we show that the unusual long-range suppression of the superconductivity occurring at the interface between manganites and cuprates affects vortex nucleation and provides a novel vortex pinning mechanism. In particular, we show evidence of commensurate pinning in YBCO films with ordered arrays of LCMO ferromagnetic nanodots. Vortex pinning results from the proximity induced reduction of the condensation energy at the vicinity of the magnetic nanodots, and yields an enhanced friction between the nanodot array and the moving vortex lattice in the liquid phase. This result shows that all-oxide ordered nanostructures constitute a powerful, new route for the artificial manipulation of vortex matter in cuprates. PMID:26441137

  10. Strain relief and disorder in commensurate water layers formed on Pd(111).

    PubMed

    McBride, F; Omer, A; Clay, C M; Cummings, L; Darling, G R; Hodgson, A

    2012-03-28

    Water adsorbs and desorbs intact on Pd(111), forming a hydrogen-bonded wetting layer whose structure we examine by low energy electron diffraction (LEED) and He atom scattering (HAS). LEED shows that water forms commensurate (√3 × √3)R30° clusters that aggregate into a partially ordered, approximately (7 × 7) superstructure as the layer completes. HAS indicates that the water layer remains disordered on a local (approximately 10 Å) scale. Based on workfunction measurements and density functional theory simulations we propose that water forms small, flat domains of a commensurate (√3 × √3)R30° water network, separated by disordered domain boundaries containing largely H-down water. This arrangement allows the water layer to adapt its density and relieve the lateral strain associated with adsorbing water in the optimum flat atop adsorption site. We discuss different possibilities for the structure of these domain walls and compare this strain relief mechanism to the highly ordered, large unit cell structures formed on surfaces such as Pt(111).

  11. Stellar rotation-planetary orbit period commensurability in the HAT-P-11 system

    SciTech Connect

    Béky, Bence; Holman, Matthew J.; Noyes, Robert W.; Kipping, David M.

    2014-06-10

    A number of planet host stars have been observed to rotate with a period equal to an integer multiple of the orbital period of their close planet. We expand this list by analyzing Kepler data of HAT-P-11 and finding a period ratio of 6:1. In particular, we present evidence for a long-lived spot on the stellar surface that is eclipsed by the planet in the same position four times, every sixth transit. We also identify minima in the out-of-transit light curve and confirm that their phase with respect to the stellar rotation is mostly stationary for the 48 month time frame of the observations, confirming the proposed rotation period. For comparison, we apply our methods to Kepler-17 and confirm the findings of Bonomo and Lanza that the period ratio is not exactly 8:1 in that system. Finally, we provide a hypothesis on how interactions between a star and its planet could possibly result in an observed commensurability for systems where the stellar differential rotation profile happens to include a period at some latitude that is commensurable to the planetary orbit.

  12. Surface pressure-induced layer growth of a monolayer at the air-water interface

    SciTech Connect

    Fang, J.Y.; Uphaus, R.A. )

    1994-04-01

    Spread monolayers containing a nematic liquid crystal and stearic acid were characterized at various mole fractions by determination of surface pressure-area isotherms at the air-water interface. The surface-composition phase diagrams indicate that compression induces a new phase transition in the films, which changes from a mixed monolayer to a supermonomolecular system. X-ray diffraction and optical absorption spectra demonstrate that the supermolecular array consists of an island liquid crystal monolayer and a uniform stearic acid monolayer. 12 refs., 7 figs.

  13. Femtosecond transient absorption dynamics of close-packed gold nanocrystal monolayer arrays.

    SciTech Connect

    Eah, S.-K.; Jaeger, H. M.; Scherer, N. F.; Lin, X.-M.; Weiderrecht, G. P.; Univ. of Chicago

    2004-03-11

    Femtosecond transient absorption spectroscopy is used to investigate hot electron dynamics of close-packed 6 nm gold nanocrystal monolayers. Morphology changes of the monolayer caused by the laser pump pulse are monitored by transmission electron microscopy. At low pump power, the monolayer maintains its structural integrity. Hot electrons induced by the pump pulse decay through electron-phonon (e-ph) coupling inside the nanocrystals with a decay constant that is similar to the value for bulk films. At high pump power, irreversible particle aggregation and sintering occur in the nanocrystal monolayer, which cause damping and peak shifting of the transient bleach signal.

  14. Graphoepitaxy for Pattern Multiplication of Nanoparticle Monolayers

    NASA Astrophysics Data System (ADS)

    Ferraro, Mark E.; Bonnecaze, Roger T.; Truskett, Thomas M.

    2014-08-01

    We compute the free energy minimizing structures of particle monolayers in the presence of enthalpic barriers of a finite height βVext using classical density functional theory and Monte Carlo simulations. We show that a periodic square template with dimensions up to at least 10 times the particle diameter disrupts the formation of the entropically favored hexagonally close-packed 2D lattice in favor of a square lattice. The results illustrate how graphoepitaxy can successfully order nanoparticulate films into desired patterns many times smaller than those of the prepatterned template.

  15. Collapse of Langmuir monolayer at lower surface pressure: Effect of hydrophobic chain length

    NASA Astrophysics Data System (ADS)

    Das, Kaushik; Kundu, Sarathi

    2016-05-01

    Long chain fatty acid molecules (e.g., stearic and behenic acids) form a monolayer on water surface in the presence of Ba2+ ions at low subphase pH (≈ 5.5) and remain as a monolayer before collapse generally occurs at higher surface pressure (πc > 50 mN/m). Monolayer formation is verified from the surface pressure vs. area per molecule (π-A) isotherms and also from the atomic force microscopy (AFM) analysis of the films deposited by single upstroke of hydrophilic Si (001) substrate through the monolayer covered water surface. At high subphase pH (≈ 9.5), barium stearate molecules form multilayer structure at lower surface pressure which is verified from the π-A isotherms and AFM analysis of the film deposited at 25 mN/m. Such monolayer to multilayer structure formation or monolayer collapse at lower surface pressure is unusual as at this surface pressure generally fatty acid salt molecules form a monolayer on the water surface. Formation of bidentate chelate coordination in the metal containing headgroups is the reason for such monolayer to multilayer transition. However, for longer chain barium behenate molecules only monolayer structure is maintained at that high subphase pH (≈ 9.5) due to the presence of relatively more tail-tail hydrophobic interaction.

  16. Correlation versus commensurability effects for finite bosonic systems in one-dimensional lattices

    SciTech Connect

    Brouzos, Ioannis; Schmelcher, Peter; Zoellner, Sascha

    2010-05-15

    We investigate few-boson systems in finite one-dimensional multiwell traps covering the full interaction crossover from uncorrelated to fermionized particles. Our treatment of the ground-state properties is based on the numerically exact multiconfigurational time-dependent Hartree method. For commensurate filling, we trace the fingerprints of localization as the interaction strength increases, in several observables like reduced-density matrices, fluctuations, and momentum distribution. For a filling factor larger than 1 we observe on-site repulsion effects in the densities and fragmentation of particles beyond the validity of the Bose-Hubbard model upon approaching the Tonks-Girardeau limit. The presence of an incommensurate fraction of particles induces incomplete localization and spatial modulations of the density profiles, taking into account the finite size of the system.

  17. Psychometric Approaches for Developing Commensurate Measures Across Independent Studies: Traditional and New Models

    PubMed Central

    Bauer, Daniel J.; Hussong, Andrea

    2009-01-01

    When conducting an integrative analysis of data obtained from multiple independent studies, a fundamental problem is to establish commensurate measures for the constructs of interest. Fortunately, procedures for evaluating and establishing measurement equivalence across samples are well developed for the linear factor model and commonly used item response theory models. A newly proposed moderated nonlinear factor analysis model generalizes these models and procedures, allowing for items of different scale types (continuous or discrete) and differential item functioning across levels of categorical and/or continuous variables. The potential of this new model to resolve the problem of measurement in integrative data analysis is shown via an empirical example examining changes in alcohol involvement from age 10 to 22 across two longitudinal studies. PMID:19485624

  18. Articles including thin film monolayers and multilayers

    DOEpatents

    Li, DeQuan; Swanson, Basil I.

    1995-01-01

    Articles of manufacture including: (a) a base substrate having an oxide surface layer, and a multidentate ligand, capable of binding a metal ion, attached to the oxide surface layer of the base substrate, (b) a base substrate having an oxide surface layer, a multidentate ligand, capable of binding a metal ion, attached to the oxide surface layer of the base substrate, and a metal species attached to the multidentate ligand, (c) a base substrate having an oxide surface layer, a multidentate ligand, capable of binding a metal ion, attached to the oxide surface layer of the base substrate, a metal species attached to the multidentate ligand, and a multifunctional organic ligand attached to the metal species, and (d) a base substrate having an oxide surface layer, a multidentate ligand, capable of binding a metal ion, attached to the oxide surface layer of the base substrate, a metal species attached to the multidentate ligand, a multifunctional organic ligand attached to the metal species, and a second metal species attached to the multifunctional organic ligand, are provided, such articles useful in detecting the presence of a selected target species, as nonliear optical materials, or as scavengers for selected target species.

  19. Products and Kinetics of the Reactions of an Alkane Monolayer and a Terminal Alkene Monolayer with NO₃ Radicals

    SciTech Connect

    Gross, Simone; Bertram, Allan K.

    2009-01-27

    The reactions of an alkanethiol and a terminal alkenethiol self-assembled monolayer with NO₃ radicals (in the presence of NO₂ and O₂) were studied. For the alkane monolayer, infrared (IR) spectroscopy and time-of-flight secondary ion mass spectrometry (ToF-SIMS) confirmed the formation of organonitrates (RONO₂). The observation of organonitrates is in contrast to the recent X-ray photoelectron spectroscopy (XPS) data, which showed very little nitrogen-containing surface species. The identification of organonitrates may help explain why significant volatilization of the organic chain was not observed in recent studies of alkane monolayer oxidation by NO₃ radicals. The reactive uptake coefficient (g) of NO₃ on alkene monolayers determined in our study is higher than the values obtained in a recent study using liquid and solid alkene bulk films. A possible reason for this difference may be the location of the double bond at the interface. Using the g value determined in our studies, we show that under conditions where NO₃ is high the lifetime of an alkene monolayer in the atmosphere may be short (approximately 20 min). XPS, IR, and ToF-SIMS were used to identify surface functional groups after the oxidation of the alkene monolayers by NO₃. The results are consistent with the formation of C-O, aldehyde/ketone, carboxylic groups, and nitrogen containing species.

  20. Mechanical Properties of Monolayers on the Surface of Water

    NASA Astrophysics Data System (ADS)

    Bohanon, Thomas Michael

    Heneicosanoic acid monolayers have many phases over a temperature range of 0 to 30^circ C. The structures of these phases have been well studied. All of these phases are ordered, and two of the phases appear to have long range order. However, little is known about the molecular interactions in these phases. In this work the shear modulus and viscosity of these phases are studied using a torsion pendulum. In order to study the mechanical properties in some phases of these monolayers, it was necessary to alter the accepted manner of compressing and measuring the surface pressure of these films. Generating capillary waves with an alternating electric field gradient is a non-contact way to measure the surface tension and study the mechanical properties of monolayers. The surface elasticity can be deduced and film inhomogeneity can be determined. A fiber optic detection system has been incorporated into a capillary wave apparatus. This instrument is also used to measure anomalous viscoelastic properties of valinomycin monolayers. Capillary wave measurements have been performed on uniaxially compressed Langmuir films both parallel and perpendicular to the direction of compression. A large change in surface tension anisotropy with a small change in pH was observed, signaling a phase transition. An apparatus that radially compresses monolayers on the surface of water was constructed. This mode of compression prevents the anisotropy that is observed in films that are compressed uniaxially. The area is changed using an elastic band stretched around twelve fingers which move synchronously. Isotherms obtained using this apparatus illustrate the difference between uniaxial compression and radial compression for a heneicosanoic acid monolayer. The shear response of heneicosanoic acid monolayers at different temperatures and pressures, has been studied using a torsion pendulum. The data fit well to a stretched exponential. This suggests that there is a continuous distribution of

  1. Free exciton emission and vibrations in pentacene monolayers

    NASA Astrophysics Data System (ADS)

    He, Rui

    2011-03-01

    Pentacene is a benchmark organic semiconductor material because of its potential applications in electronic and optoelectronic devices. Recently we demonstrated that optical and vibrational characterizations of pentacene films can be carried out down to the sub-monolayer limit. These milestones were achieved in highly uniform pentacene films that were grown on a compliant polymeric substrate. Films with thickness ranging from sub- monolayer to tens of monolayers were studied at low temperatures. The intensity of the free exciton (FE) luminescence band increases quadratically with the number of layers N when N is small. This quadratic dependence is explained as arising from the linear dependence of the intensity of absorption and the probability of emission on the number of layers N. Large enhancements of Raman scattering intensities at the FE resonance enable the first observations of low-lying lattice modes in the monolayers. The measured low- lying modes (in the 20 to 100 cm-1 range) display characteristic changes when going from a single monolayer to two layers. The Raman intensities by high frequency intra-molecular vibrations display resonance enhancement double-peaks when incident or scattered photon energies overlap the FE optical emission. The double resonances are about the same strength which suggests that Franck-Condon overlap integrals for the respective vibronic transitions have the same magnitude. The interference between scattering amplitudes in the Raman resonance reveals quantum coherence of the symmetry-split states (Davydov doublet) of the lowest intrinsic singlet exciton. These results demonstrate novel venues for ultra-thin film characterization and studies of fundamental physics in organic semiconductor structures. In collaboration with Nancy G. Tassi (Dupont), Graciela B. Blanchet (Nanoterra, Cambridge, MA), and Aron Pinczuk (Columbia University).

  2. Effect of lipid composition and packing on the adsorption of apolipoproteins to lipid monolayers

    SciTech Connect

    Ibdah, J.A.; Lund-Katz, S.; Phillips, M.C.

    1987-05-01

    The monolayer system has been used to study the effects of lipoprotein surface lipid composition and packing on the affinities of apolipoproteins for the surfaces of lipoprotein particles. The adsorption of apolipoproteins injected beneath lipid monolayers prepared with pure lipids or lipoprotein surface lipids is evaluated by monitoring the surface pressure of the film and the surface concentration (Gamma) of /sup 14/C-labelled apolipoprotein. At a given initial film pressure (..pi../sub i/) there is a higher adsorption of human apo A-I to unsaturated phosphatidylcholine (PC) monolayers compared to saturated PC monolayers (e.g., at ..pi../sub i/ = 10 mN/m, Gamma = 0.35 and 0.06 mg/m/sup 2/ for egg PC and distearoyl PC, respectively, with 3 x 10/sup -4/ mg/ml apo A-I in the subphase). In addition, adsorption of apo A-I is less to an egg sphingomyelin monolayer than to an egg PC monolayer. The adsorption of apo A-I to PC monolayers is decreased by addition of cholesterol. Generally, apo A-I adsorption diminishes as the lipid molecular area decreases. Apo A-I adsorbs more to monolayers prepared with HDL/sub 3/ surface lipids than with LDL surface lipids. These studies suggest that lipoprotein surface lipid composition and packing are crucial factors influencing the transfer and exchange of apolipoproteins among various lipoprotein classes during metabolism of lipoprotein particles.

  3. Quantitative Characterization of Mechanical Property of Annealed Monolayer Colloidal Crystal.

    PubMed

    Zhang, Lijing; Wang, Weiqi; Zheng, Lu; Wang, Xiuyu; Yan, Qingfeng

    2016-01-19

    Quantitative characterization of the mechanical properties of a polystyrene (PS) monolayer colloidal crystal (MCC) annealed with solvent vapor has been performed for the first time by means of atomic force microscopy nanoindentation. The results showed that both the compressive and bending elastic modulus of PS MCC increased with the prolongation of annealing time from initial to 13 min. When the annealing time reached 15 min or even more, the PS MCC almost deformed to a planar film, and the elastic modulus of the PS MCC presented a drastic increase. These results provide a basis for tailoring the mechanical properties of a polymer colloidal monolayer via solvent vapor annealing. Such self-supported and high-mechanical-strength colloidal monolayers can be transferred to other surfaces for potential and promising applications in the bottom-up fabrication of highly ordered nanostructured materials such as nano dot arrays, photonic crystals, and many others.

  4. Self assembled monolayers of octadecyltrichlorosilane for dielectric materials

    NASA Astrophysics Data System (ADS)

    Kumar, Vijay; Puri, Paridhi; Nain, Shivani; Bhat, K. N.; Sharma, N. N.

    2016-04-01

    Treatment of surfaces to change the interaction of fluids with them is a critical step in constructing useful microfluidics devices, especially those used in biological applications. Selective modification of inorganic materials such as Si, SiO2 and Si3N4 is of great interest in research and technology. We evaluated the chemical formation of OTS self-assembled monolayers on silicon substrates with different dielectric materials. Our investigations were focused on surface modification of formerly used common dielectric materials SiO2, Si3N4 and a-poly. The improvement of wetting behaviour and quality of monolayer films were characterized using Atomic force microscope, Scanning electron microscope, Contact angle goniometer, Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) monolayer deposited oxide surface.

  5. Assembly of designed protein scaffolds into monolayers for nanoparticle patterning.

    PubMed

    Mejias, Sara H; Couleaud, Pierre; Casado, Santiago; Granados, Daniel; Garcia, Miguel Angel; Abad, Jose M; Cortajarena, Aitziber L

    2016-05-01

    The controlled assembly of building blocks to achieve new nanostructured materials with defined properties at different length scales through rational design is the basis and future of bottom-up nanofabrication. This work describes the assembly of the idealized protein building block, the consensus tetratricopeptide repeat (CTPR), into monolayers by oriented immobilization of the blocks. The selectivity of thiol-gold interaction for an oriented immobilization has been verified by comparing a non-thiolated protein building block. The physical properties of the CTPR protein thin biomolecular films including topography, thickness, and viscoelasticity, are characterized. Finally, the ability of these scaffolds to act as templates for inorganic nanostructures has been demonstrated by the formation of well-packed gold nanoparticles (GNPs) monolayer patterned by the CTPR monolayer.

  6. Quantitative Characterization of Mechanical Property of Annealed Monolayer Colloidal Crystal.

    PubMed

    Zhang, Lijing; Wang, Weiqi; Zheng, Lu; Wang, Xiuyu; Yan, Qingfeng

    2016-01-19

    Quantitative characterization of the mechanical properties of a polystyrene (PS) monolayer colloidal crystal (MCC) annealed with solvent vapor has been performed for the first time by means of atomic force microscopy nanoindentation. The results showed that both the compressive and bending elastic modulus of PS MCC increased with the prolongation of annealing time from initial to 13 min. When the annealing time reached 15 min or even more, the PS MCC almost deformed to a planar film, and the elastic modulus of the PS MCC presented a drastic increase. These results provide a basis for tailoring the mechanical properties of a polymer colloidal monolayer via solvent vapor annealing. Such self-supported and high-mechanical-strength colloidal monolayers can be transferred to other surfaces for potential and promising applications in the bottom-up fabrication of highly ordered nanostructured materials such as nano dot arrays, photonic crystals, and many others. PMID:26700374

  7. Is there a stable commensurate solid phase in the second 4He layer on graphite? - path integral Monte Carlo study

    NASA Astrophysics Data System (ADS)

    Ahn, Jeonghwan; Lee, Hoonkyung; Kwon, Yongkyung

    2015-03-01

    Existence of a stable commensurate structure in the second 4He layer on graphite has been a subject of intensive experimental and theoretical studies because of its implication in the possible realization of two-dimensional supersolidity. Earlier path-integral Monte Carlo (PIMC) calculations of Pierce and Manousakis predicted a stable C4/7 commensurate structure above the first-layer 4He atoms fixed at triangular lattice sites, but Corboz et al. later showed that no commensurate phase was stable when quantum dynamics of the first-layer 4He atoms was incorporated in the PIMC calculations. On the other hand, recent heat capacity measurements of Nakamura et al. provided a strong evidence for a commensurate solid in the second 4He layer over an extended density range. Motivated by this, we have performed new PIMC calculations for the second helium layer on graphite. Unlike previous PIMC calculations where a laterally-averaged one-dimensional substrate potential was used, we here employ an anisotropic 4He-graphite potential described by a sum of the 4He-C pair potentials. With this fully-corrugated substrate potential we make more accurate description of quantum dynamics of the first-layer 4He atoms and analyze its effects on the phase diagram of the second layer.

  8. Alkanethiols on platinum: multicomponent self-assembled monolayers.

    PubMed

    Petrovykh, Dmitri Y; Kimura-Suda, Hiromi; Opdahl, Aric; Richter, Lee J; Tarlov, Michael J; Whitman, Lloyd J

    2006-03-14

    We have studied the formation of self-assembled monolayers (SAMs) of n-alkanethiols on platinum thin films using X-ray photoelectron spectroscopy (XPS), reflection-absorption infrared spectroscopy (RAIRS), spectroscopic ellipsometry (SE), and contact angle (CA) measurements. Specifically, SAMs of 1-hexanethiol, 1-dodecanethiol, and 1-octadecanethiol were grown on polycrystalline Pt films, and the effects of Pt surface preparation, deposition conditions, and solvent treatments on the initial quality and stability of the monolayer in air were investigated. The SAMs prepared under ambient conditions on piranha-cleaned and UV/ozone-cleaned substrates were compared to monolayers formed on template-stripped Pt in an inert atmosphere. We found that alkanethiols deposited from 1 mM ethanolic solutions on piranha-cleaned Pt formed densely packed monolayers in which alkyl chains were oriented close to the surface normal. Stored in the laboratory ambient, these monolayers were unchanged over about 1 week but were largely oxidized in about 1 month. No evidence was found of molecules being weakly bound within the monolayer or having undergone C-S bond scission; however, three distinct sulfur states were observed for all samples in the XPS of the S 2p region. The lowest- and highest-binding-energy components are assigned to alkylthiolate and partially oxidized alkylthiolate species, respectively. The remaining S 2p component (approximately one-third of the sulfur layer), intermediate in binding energy between the other two components, is attributed to a chemisorbed species with a S binding configuration distinct from the majority alkylthiolate: for example, S bound to Pt bound to O, S with a different Pt coordination number, or S in an adsorbed disulfide.

  9. Improved vapor-phase deposition technique for antistiction monolayers

    NASA Astrophysics Data System (ADS)

    Ashurst, Robert W.; Carraro, Carlo; Chinn, Jeff D.; Fuentes, Victor; Kobrin, Boris; Maboudian, Roya; Nowak, Romuald; Yi, Richard

    2004-01-01

    We have developed an improved vapor-phase deposition method and an apparatus for the wafer-scale coating of monolayer films typically used in anti-stiction applications. The method consists of a surface preparation step using an O2 plasma followed by the tunable deposition of a monolayer film in the same reactor. This process has been successfully applied to MEMS test structures and has demonstrated superior anti-stiction performance. The deposition process allows tuning of the film properties by the precise metering of the precursor and a catalyst as part of the process control scheme. The anti-stiction monolayer film deposited from dimethyldichlorosilane (DDMS), tridecafluoro-1,1,2,2-tetrahydrooctyltrichlorosilane (FOTS), and heptadecafluoro-1,1,2,2-tetrahydrodecyltrichlorosilane (FDTS) were characterized using contact angle analysis, atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). The coefficient of static friction was measured using a sidewall test device and the work of adhesion using a cantilever beam array. The results showed that excellent quality, uniformity, and reproducibility could be achieved across a whole wafer using this method and equipment.

  10. Development and Evaluation of Gold-Centered Monolayer Protected Nanoparticle Stationary Phases for Gas Chromatography

    SciTech Connect

    Gross, Gwen M.; Grate, Jay W.; Synovec, Robert E.

    2004-12-10

    The current status for the development of novel open-tubular gas chromatography (GC) stationary phases consists of thin films of gold-centered monolayer protected nanoparticles (MPNs) is reported. Dodecanethiol MPNs, in which the monolayer is dodecanethiol linked to the gold nanoparticle, have shown great promise as a GC stationary phase with efficient columns having been produced in a variety of capillary i.d.'s with stationary phase film depths ranging from 10-60 nm, +/- 2 nm at a given film depth. Stationary phase operational parameters are discussed including maximum operating temperature, sample capacity, and stationary phase lifetime and robustness.

  11. COMBINING NONEXCHANGEABLE FUNCTIONAL OR SURVIVAL DATA SOURCES IN ONCOLOGY USING GENERALIZED MIXTURE COMMENSURATE PRIORS

    PubMed Central

    Murray, Thomas A.; Hobbs, Brian P.; Carlin, Bradley P.

    2015-01-01

    Conventional approaches to statistical inference preclude structures that facilitate incorporation of supplemental information acquired from similar circumstances. For example, the analysis of data obtained using perfusion computed tomography to characterize functional imaging biomarkers in cancerous regions of the liver can benefit from partially informative data collected concurrently in non-cancerous regions. This paper presents a hierarchical model structure that leverages all available information about a curve, using penalized splines, while accommodating important between-source features. Our proposed methods flexibly borrow strength from the supplemental data to a degree that reflects the commensurability of the supplemental curve with the primary curve. We investigate our method’s properties for nonparametric regression via simulation, and apply it to a set of liver cancer data. We also apply our method for a semiparametric hazard model to data from a clinical trial that compares time to disease progression for three colorectal cancer treatments, while supplementing inference with information from a previous trial that tested the current standard of care. PMID:26557211

  12. Commensurability Oscillations of Composite Fermions Induced by the Periodic Potential of a Wigner Crystal

    NASA Astrophysics Data System (ADS)

    Deng, H.; Liu, Y.; Jo, I.; Pfeiffer, L. N.; West, K. W.; Baldwin, K. W.; Shayegan, M.

    2016-08-01

    When the kinetic energy of a collection of interacting two-dimensional (2D) electrons is quenched at very high magnetic fields so that the Coulomb repulsion dominates, the electrons are expected to condense into an ordered array, forming a quantum Wigner crystal (WC). Although this exotic state has long been suspected in high-mobility 2D electron systems at very low Landau level fillings (ν ≪1 ), its direct observation has been elusive. Here we present a new technique and experimental results directly probing the magnetic-field-induced WC. We measure the magnetoresistance of a bilayer electron system where one layer has a very low density and is in the WC regime (ν ≪1 ), while the other ("probe") layer is near ν =1 /2 and hosts a sea of composite fermions (CFs). The data exhibit commensurability oscillations in the magnetoresistance of the CF layer, induced by the periodic potential of WC electrons in the other layer, and provide a unique, direct glimpse at the symmetry of the WC, its lattice constant, and melting. They also demonstrate a striking example of how one can probe an exotic many-body state of 2D electrons using equally exotic quasiparticles of another many-body state.

  13. Coherent commensurate electronic states at the interface between misoriented graphene layers

    NASA Astrophysics Data System (ADS)

    Koren, Elad; Leven, Itai; Lörtscher, Emanuel; Knoll, Armin; Hod, Oded; Duerig, Urs

    2016-09-01

    Graphene and layered materials in general exhibit rich physics and application potential owing to their exceptional electronic properties, which arise from the intricate π-orbital coupling and the symmetry breaking in twisted bilayer systems. Here, we report room-temperature experiments to study electrical transport across a bilayer graphene interface with a well-defined rotation angle between the layers that is controllable in situ. This twisted interface is artificially created in mesoscopic pillars made of highly oriented pyrolytic graphite by mechanical actuation. The overall measured angular dependence of the conductivity is consistent with a phonon-assisted transport mechanism that preserves the electron momentum of conduction electrons passing the interface. The most intriguing observations are sharp conductivity peaks at interlayer rotation angles of 21.8° and 38.2°. These angles correspond to a commensurate crystalline superstructure leading to a coherent two-dimensional (2D) electronic interface state. Such states, predicted by theory, form the basis for a new class of 2D weakly coupled bilayer systems with hitherto unexplored properties and applications.

  14. Commensurability Oscillations of Composite Fermions Induced by the Periodic Potential of a Wigner Crystal.

    PubMed

    Deng, H; Liu, Y; Jo, I; Pfeiffer, L N; West, K W; Baldwin, K W; Shayegan, M

    2016-08-26

    When the kinetic energy of a collection of interacting two-dimensional (2D) electrons is quenched at very high magnetic fields so that the Coulomb repulsion dominates, the electrons are expected to condense into an ordered array, forming a quantum Wigner crystal (WC). Although this exotic state has long been suspected in high-mobility 2D electron systems at very low Landau level fillings (ν≪1), its direct observation has been elusive. Here we present a new technique and experimental results directly probing the magnetic-field-induced WC. We measure the magnetoresistance of a bilayer electron system where one layer has a very low density and is in the WC regime (ν≪1), while the other ("probe") layer is near ν=1/2 and hosts a sea of composite fermions (CFs). The data exhibit commensurability oscillations in the magnetoresistance of the CF layer, induced by the periodic potential of WC electrons in the other layer, and provide a unique, direct glimpse at the symmetry of the WC, its lattice constant, and melting. They also demonstrate a striking example of how one can probe an exotic many-body state of 2D electrons using equally exotic quasiparticles of another many-body state. PMID:27610870

  15. Structure and Function Evolution of Thiolate Monolayers on Gold

    SciTech Connect

    Grant Alvin Edwards

    2006-05-01

    The use of n-alkanethiolate self-assembled monolayers on gold has blossomed in the past few years. These systems have functioned as models for common interfaces. Thiolate monolayers are ideal because they are easily modified before or after deposition. The works contained within this dissertation include interfacial characterization (inbred reflection absorption spectroscopy, ellipsometry, contact angle, scanning probe microscopy, and heterogeneous electron-transfer kinetics) and various modeling scenarios. The results of these characterizations present ground-breaking insights into the structure, function, and reproducible preparation of these monolayers. Surprisingly, three interfacial properties (electron-transfer, contact angle, and ellipsometry) were discovered to depend directly on the odd-even character of the monolayer components. Molecular modeling was utilized to investigate adlayer orientation, and suggests that these effects are adlayer structure specific. Finally, the electric force microscopy and theoretical modeling investigations of monolayer samples are presented, which show that the film dielectric constant, thickness, and dipole moment directly affect image contrast. In addition, the prospects for utilization of this emerging technique are outlined.

  16. Penetration of surfactin into phospholipid monolayers: nanoscale interfacial organization.

    PubMed

    Eeman, M; Berquand, A; Dufrêne, Y F; Paquot, M; Dufour, S; Deleu, M

    2006-12-19

    Atomic force microscopy (AFM) combined with surface pressure-area isotherms were used to probe the interfacial behavior of phospholipid monolayers following penetration of surfactin, a cyclic lipopeptide produced by Bacillus subtilis strains. Prior to penetration experiments, interfacial behavior of different surfactin molecules (cyclic surfactins with three different aliphatic chain lengths--S13, S14, and S15--and a linear surfactin obtained by chemical cleavage of the cycle of the surfactin S15) has been investigated. A more hydrophobic aliphatic chain induces greater surface-active properties of the lipopeptide. The opening of the peptide ring reduces the surface activity. The effect of phospholipid acyl chain length (dimyristoylphosphatidylcholine, dipalmitoylphosphatidylcholine- (DPPC), and distearoylphosphatidylcholine) and phospholipid polar head (DPPC, dipalmitoylphosphatidylethanolamine and dipalmitoylphosphatidylserine) on monolayer penetration properties of the surfactin S15 has been explored. Results showed that while the lipid monolayer thickness and the presence of electrostatic repulsions from the interfacial film do not significantly influence surfactin insertion, these parameters strongly modulate the ability of the surfactin to alter the nanoscale organization of the lipid films. We also probed the effect of surfactin structure (influence of the aliphatic chain length and of the cyclic structure of the peptide ring) on the behavior of DPPC monolayers. AFM images and isotherms showed that surfactin penetration is promoted by longer lipopeptide chain length and a cyclic polar head. This indicates that hydrophobic interactions are of main importance for the penetration power of surfactin molecules.

  17. Origin of the moiré pattern in thin Bi films deposited on HOPG

    NASA Astrophysics Data System (ADS)

    Kowalczyk, P. J.; Mahapatra, O.; Belić, D.; Brown, S. A.; Bian, G.; Chiang, T.-C.

    2015-01-01

    Thin Bi(110) films deposited on highly oriented pyrolytic graphite (HOPG) exhibit a pronounced moiré pattern; here the origin of the moiré pattern is investigated using scanning tunneling microscopy (STM) and spectroscopy (STS), high-resolution transmission electron microscopy (HR-TEM), and density functional theory (DFT). It is shown that the moiré pattern forms only on islands which are misoriented by ˜30∘ with respect to the usual substrate symmetry direction. Two models of the moiré pattern are presented: (i) a commensurate monolayer construction (CMC) for rectangular overlayer symmetry on hexagonal substrates and (ii) a qualitative model based on simple superposition of a Bi overlayer on graphene. The CMC model has previously been applied only to systems with pure hexagonal symmetry. Both models generate moiré patterns with key parameters (period, angles of the pattern measured with respect to the main HOPG and Bi crystal directions) that are consistent with the experimental results, but development of a fully predictive/quantitative model remains an outstanding challenge. The electronic structure of the moiré pattern is investigated using STS and DFT, and it is found that the local density of states (LDOS) is modulated by the moiré pattern. These results are consistent with a picture in which a small distortion of Bi atomic positions at the film-substrate interface results in periodic modulation of the LDOS, hence allowing observation of the moiré pattern in STM images.

  18. Producing air-stable monolayers of phosphorene and their defect engineering

    PubMed Central

    Pei, Jiajie; Gai, Xin; Yang, Jiong; Wang, Xibin; Yu, Zongfu; Choi, Duk-Yong; Luther-Davies, Barry; Lu, Yuerui

    2016-01-01

    It has been a long-standing challenge to produce air-stable few- or monolayer samples of phosphorene because thin phosphorene films degrade rapidly in ambient conditions. Here we demonstrate a new highly controllable method for fabricating high quality, air-stable phosphorene films with a designated number of layers ranging from a few down to monolayer. Our approach involves the use of oxygen plasma dry etching to thin down thick-exfoliated phosphorene flakes, layer by layer with atomic precision. Moreover, in a stabilized phosphorene monolayer, we were able to precisely engineer defects for the first time, which led to efficient emission of photons at new frequencies in the near infrared at room temperature. In addition, we demonstrate the use of an electrostatic gate to tune the photon emission from the defects in a monolayer phosphorene. This could lead to new electronic and optoelectronic devices, such as electrically tunable, broadband near infrared lighting devices operating at room temperature. PMID:26794866

  19. Producing air-stable monolayers of phosphorene and their defect engineering

    NASA Astrophysics Data System (ADS)

    Pei, Jiajie; Gai, Xin; Yang, Jiong; Wang, Xibin; Yu, Zongfu; Choi, Duk-Yong; Luther-Davies, Barry; Lu, Yuerui

    2016-01-01

    It has been a long-standing challenge to produce air-stable few- or monolayer samples of phosphorene because thin phosphorene films degrade rapidly in ambient conditions. Here we demonstrate a new highly controllable method for fabricating high quality, air-stable phosphorene films with a designated number of layers ranging from a few down to monolayer. Our approach involves the use of oxygen plasma dry etching to thin down thick-exfoliated phosphorene flakes, layer by layer with atomic precision. Moreover, in a stabilized phosphorene monolayer, we were able to precisely engineer defects for the first time, which led to efficient emission of photons at new frequencies in the near infrared at room temperature. In addition, we demonstrate the use of an electrostatic gate to tune the photon emission from the defects in a monolayer phosphorene. This could lead to new electronic and optoelectronic devices, such as electrically tunable, broadband near infrared lighting devices operating at room temperature.

  20. Producing air-stable monolayers of phosphorene and their defect engineering.

    PubMed

    Pei, Jiajie; Gai, Xin; Yang, Jiong; Wang, Xibin; Yu, Zongfu; Choi, Duk-Yong; Luther-Davies, Barry; Lu, Yuerui

    2016-01-22

    It has been a long-standing challenge to produce air-stable few- or monolayer samples of phosphorene because thin phosphorene films degrade rapidly in ambient conditions. Here we demonstrate a new highly controllable method for fabricating high quality, air-stable phosphorene films with a designated number of layers ranging from a few down to monolayer. Our approach involves the use of oxygen plasma dry etching to thin down thick-exfoliated phosphorene flakes, layer by layer with atomic precision. Moreover, in a stabilized phosphorene monolayer, we were able to precisely engineer defects for the first time, which led to efficient emission of photons at new frequencies in the near infrared at room temperature. In addition, we demonstrate the use of an electrostatic gate to tune the photon emission from the defects in a monolayer phosphorene. This could lead to new electronic and optoelectronic devices, such as electrically tunable, broadband near infrared lighting devices operating at room temperature.

  1. Effect of surface charge distribution on the adsorption orientation of proteins to lipid monolayers.

    PubMed

    Tiemeyer, Sebastian; Paulus, Michael; Tolan, Metin

    2010-09-01

    The adsorption orientation of the proteins lysozyme and ribonuclease A (RNase A) to a neutral 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and a negatively charged stearic acid lipid film was investigated by means of X-ray reflectivity. Both proteins adsorbed to the negatively charged lipid monolayer, whereas at the neutral monolayer, no adsorption was observed. For acquiring comprehensive information on the proteins' adsorption, X-ray reflectivity data were combined with electron densities obtained from crystallographic data. With this method, it is possible to determine the orientation of adsorbed proteins in solution underneath lipid monolayers. While RNase A specifically coupled with its positively charged active site to the negatively charged lipid monolayer, lysozyme prefers an orientation with its long axis parallel to the Langmuir film. In comparison to the electrostatic maps of the proteins, our results can be explained by the discriminative surface charge distribution of lysozyme and RNase A.

  2. Effect of surface charge distribution on the adsorption orientation of proteins to lipid monolayers.

    PubMed

    Tiemeyer, Sebastian; Paulus, Michael; Tolan, Metin

    2010-09-01

    The adsorption orientation of the proteins lysozyme and ribonuclease A (RNase A) to a neutral 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and a negatively charged stearic acid lipid film was investigated by means of X-ray reflectivity. Both proteins adsorbed to the negatively charged lipid monolayer, whereas at the neutral monolayer, no adsorption was observed. For acquiring comprehensive information on the proteins' adsorption, X-ray reflectivity data were combined with electron densities obtained from crystallographic data. With this method, it is possible to determine the orientation of adsorbed proteins in solution underneath lipid monolayers. While RNase A specifically coupled with its positively charged active site to the negatively charged lipid monolayer, lysozyme prefers an orientation with its long axis parallel to the Langmuir film. In comparison to the electrostatic maps of the proteins, our results can be explained by the discriminative surface charge distribution of lysozyme and RNase A. PMID:20707324

  3. Producing air-stable monolayers of phosphorene and their defect engineering.

    PubMed

    Pei, Jiajie; Gai, Xin; Yang, Jiong; Wang, Xibin; Yu, Zongfu; Choi, Duk-Yong; Luther-Davies, Barry; Lu, Yuerui

    2016-01-01

    It has been a long-standing challenge to produce air-stable few- or monolayer samples of phosphorene because thin phosphorene films degrade rapidly in ambient conditions. Here we demonstrate a new highly controllable method for fabricating high quality, air-stable phosphorene films with a designated number of layers ranging from a few down to monolayer. Our approach involves the use of oxygen plasma dry etching to thin down thick-exfoliated phosphorene flakes, layer by layer with atomic precision. Moreover, in a stabilized phosphorene monolayer, we were able to precisely engineer defects for the first time, which led to efficient emission of photons at new frequencies in the near infrared at room temperature. In addition, we demonstrate the use of an electrostatic gate to tune the photon emission from the defects in a monolayer phosphorene. This could lead to new electronic and optoelectronic devices, such as electrically tunable, broadband near infrared lighting devices operating at room temperature. PMID:26794866

  4. Phenomenological Modeling for Langmuir Monolayers

    NASA Astrophysics Data System (ADS)

    Baptiste, Dimitri; Kelly, David; Safford, Twymun; Prayaga, Chandra; Varney, Christopher N.; Wade, Aaron

    Experimentally, Langmuir monolayers have applications in molecular optical, electronic, and sensor devices. Traditionally, Langmuir monolayers are described by a rigid rod model where the rods interact via a Leonard-Jones potential. Here, we propose effective phenomenological models and utilize Monte Carlo simulations to analyze the phase behavior and compare with experimental isotherms. Research reported in this abstract was supported by UWF NIH MARC U-STAR 1T34GM110517-01.

  5. Calixarene monolayers as quartz crystal microbalance sensing elements in aqueous solution.

    PubMed

    Cygan, M T; Collins, G E; Dunbar, T D; Allara, D L; Gibbs, C G; Gutsche, C D

    1999-01-01

    We have examined p-tert-butylcalix[4]arenetetrathiolate (BCAT) monolayers for their potential use as molecular recognition elements for in situ aqueous chemical sensors. Spectroscopic and wetting studies of BCAT monolayers on Au{111} reveal that the calixarene molecules exist in monolayers, preferentially oriented with their phenyl rings parallel to the surface normal axis. Using quartz crystal microbalance (QCM) sensors with gold-coated electrodes, the chemical specificity of monolayers and thin films to a variety of aromatic and aliphatic analytes in aqueous solution was examined. The response of BCAT sensors was compared to the responses of p-tert-butylcalix[4]arene (BCA)- and decanethiolate (DT)-coated QCM electrodes. BCAT is very selective for alkylbenzenes, much more so than either its spray-coated thin-film analogue, BCA, or the highly ordered DT monolayer. From these measurements, the factors behind molecular differentiation in each film are explored. Drawing upon these findings, the roles of cavitation and film order in molecular recognition for calixarene films are discussed. PMID:21662936

  6. Atomic force microscopy studies of domain structures in phase-separated monolayers

    NASA Astrophysics Data System (ADS)

    Xiao, Shou-Jun; Wu, Hai-Ming; Yang, Xiao-Min; Wei, Yu; Tai, Zi-Hou; Sun, Xing-Zhong

    1994-10-01

    Domain structures were studied with atomic force microscopy (AFM) in binary phase-separated monolayer films composed of 5, 10, 15-triphenyl-20-(4-dl-α-phenylalanylamindo) phenyl porphyrin (TPPP) and one of a series of fatty acids which are arachidic acid (AA), palmitic acid (PA), and lauric acid (LA). The liquid-condensed (LC) domain structures of AA and PA were observed in their corresponding mixed monolayers. However, instead of the fatty acid domain, a liquid-expanded (LE) domain structure of TPPP appears in the mixed monolayer of LA/TPPP.

  7. Self assembly of highly-ordered nanoparticle monolayers.

    SciTech Connect

    Bigioni, T. P.; Lin, X.-M.; Nguyen, T. T.; Corwin, E. I.; Witten, T. A.; Jaeger, H. M.; Univ. of Chicago

    2006-01-01

    When a drop of a colloidal solution of nanoparticles dries on a surface, it leaves behind coffee-stain-like rings of material with lace-like patterns or clumps of particles in the interior. These non-uniform mass distributions are manifestations of far-from-equilibrium effects, such as fluid flows and solvent fluctuations during late-stage drying. However, recently a strikingly different drying regime promising highly uniform, long-range-ordered nanocrystal monolayers has been found. Here we make direct, real-time and real-space observations of nanocrystal self-assembly to reveal the mechanism. We show how the morphology of drop-deposited nanoparticle films is controlled by evaporation kinetics and particle interactions with the liquid-air interface. In the presence of an attractive particle-interface interaction, rapid early-stage evaporation dynamically produces a two-dimensional solution of nanoparticles at the liquid-air interface, from which nanoparticle islands nucleate and grow. This self-assembly mechanism produces monolayers with exceptional long-range ordering that are compact over macroscopic areas, despite the far-from-equilibrium evaporation process. This new drop-drying regime is simple, robust and scalable, is insensitive to the substrate material and topography, and has a strong preference for forming monolayer films. As such, it stands out as an excellent candidate for the fabrication of technologically important ultra thin film materials for sensors, optical devices and magnetic storage media.

  8. Perforated monolayers: Design and synthesis of porous and cohesive monolayers from mercurated calix(n)arenes

    SciTech Connect

    Markowitz, M.A.; Janout, V.; Regen, S.L. ); Castner, D.G. )

    1989-10-11

    Mercuration of a series of O-alkylated calix(n)arenes (produced via reaction of tetrahydroxycalix(4)arene, pentahydroxylcalix(5)arene, hexahydroxycalix(6)arene, and heptahydroxycalix(7)arene with n-bromobutane and with n-bromohexadecane) afford an homologous series of calixarene-based surfactants that form stable monolayers at the air-water interface. Surface pressure-area isotherms, measured for each calixarene, yield limiting areas that are in excellent agreement with values predicted from space-filling models, if it is assumed that the base of each calixarene is parallel and the alkyl chains are perpendicular to the water surface. Introduction of malonic acid to the aqueous subphase results in a substantial increase in the cohesiveness of films derived from calix(4)arene-, calix(5)arene-, and calix(6)arene-based surfactants, as judged by changes in surface viscosity. X-ray photoelectron spectroscopic analysis of a Langmuir-Blodgett film, produced from a malonic acid stabilized calix(6)arene monolayer, shows a carboxylate/mercury ratio of 0.9.

  9. Icelike water monolayer adsorbed on mica at room temperature

    SciTech Connect

    Miranda, P.B.; Xu, L.; Shen, Y.R.; Salmeron, M.

    1998-10-01

    The structure of a water film formed on mica at room temperature, in equilibrium with water vapor at various relative humidities (RH), was studied using sum-frequency-generation (SFG) vibrational spectroscopy and scanning polarization force microscopy (SPFM). Analysis of the O-D stretch modes in the SFG spectra of D{sub 2}O on mica indicates that as RH increases, the submonolayer water structure evolves into a more ordered hydrogen-bonding network. At full monolayer coverage ({approximately} 90% RH), the SFG spectrum suggests an icelike film with no dangling O-D groups, in agreement with a recent molecular dynamics simulation.

  10. FRET study of G-quadruplex forming fluorescent oligonucleotide probes at the lipid monolayer interface

    NASA Astrophysics Data System (ADS)

    Swiatkowska, Angelika; Kosman, Joanna; Juskowiak, Bernard

    2016-01-01

    Spectral properties and G-quadruplex folding ability of fluorescent oligonucleotide probes at the cationic dioctadecyldimethylammonium bromide (DODAB) monolayer interface are reported. Two oligonucleotides, a 19-mer bearing thrombin binding aptamer sequence and a 21-mer with human telomeric sequence, were end-labeled with fluorescent groups (FAM and TAMRA) to give FRET probes F19T and F21T, respectively. The probes exhibited abilities to fold into a quadruplex structure and to bind metal cations (Na+ and K+). Fluorescence spectra of G-quadruplex FRET probes at the monolayer interface are reported for the first time. Investigations included film balance measurements (π-A isotherms) and fluorescence spectra recording using a fiber optic accessory interfaced with a spectrofluorimeter. The effect of the presence of DODAB monolayer, metal cations and the surface pressure of monolayer on spectral behavior of FRET probes were examined. Adsorption of probe at the cationic monolayer interface resulted in the FRET signal enhancement even in the absence of metal cations. Variation in the monolayer surface pressure exerted rather modest effect on the spectral properties of probes. The fluorescence energy transfer efficiency of monolayer adsorbed probes increased significantly in the presence of sodium or potassium ion in subphase, which indicated that the probes retained their cation binding properties when adsorbed at the monolayer interface.

  11. Superconductivity, Faraday effect, and optical absorption in the commensurate flux phase of the t-J model

    NASA Astrophysics Data System (ADS)

    Rodriguez, J. P.; Douçot, B.

    1992-01-01

    Using a large-N slave-boson formulation of the t-J model on the square lattice that has explicit spinon-holon decoupling of the correlated electron, we study the stability and electromagnetic response of the commensurate flux phase in the limit near half filling. A region of stability for the flux phase is found located between a dimer phase region near half filling and a fluxless metallic phase region far from half filling. The commensurate flux phase itself is found to be a superconductor of the anyon type. Furthermore, it is shown that the parity-time-reversal-violating characteristic of this phase results in a frequency-dependent Faraday effect. This effect manifests itself as a zero-field Hall effect in the low-frequency limit, where the off-diagonal conductance scales with the hole concentration. Associated with this result, it is also found that the commensurate flux phase supports a series of optical absorption peaks at energies on the order of J. Lastly, inclusion of instanton tunneling events in the effective gauge-field action results in the confinement of the spinon and holon degrees of freedom. This confinement effect, however, weakens exponentially as one approaches the Mott transition. The present results are discussed in the context of the high-Tc superconducting oxides.

  12. Structural and topographical characteristics of adsorbed WPI and monoglyceride mixed monolayers at the air-water interface.

    PubMed

    Patino, Juan M Rodríguez; Fernández, Marta Cejudo

    2004-05-25

    In this work we have analyzed the structural and topographical characteristics of mixed monolayers formed by an adsorbed whey protein isolate (WPI) and a spread monoglyceride monolayer (monopalmitin or monoolein) on the previously adsorbed protein film. Measurements of the surface pressure (pi)-area (A) isotherm were obtained at 20 degrees C and at pH 7 for protein-adsorbed films from water in a Wilhelmy-type film balance. Since the surface concentration (1/A) is actually unknown for the adsorbed monolayer, the values were derived by assuming that the A values for adsorbed and spread monolayers were equal at the collapse point of the mixed film. The pi-A isotherm deduced for adsorbed WPI monolayer in this work is practically the same as that obtained directly by spreading. For WPI-monoglyceride mixed films, the pi-A isotherms for adsorbed and spread monolayers at pi higher than the equilibrium surface pressure of WPI are practically coincident, a phenomenon which may be attributed to the protein displacement by the monoglyceride from the interface. At lower surface pressures, WPI and monoglyceride coexist at the interface and the adsorbed and spread pi-A isotherms (i.e., the monolayer structure of the mixed films) are different. Monopalmitin has a higher capacity than monoolein for the displacement of protein from the air-water interface. However, some degree of interactions exists between proteins and monoglycerides and these interactions are higher for adsorbed than for spread films. The topography of the monolayer corroborates these conclusions.

  13. Monolayer behavior of asymmetrical ester-type tartaric gemini amphiphiles.

    PubMed

    Kawase, Tokuzo; Saito, Isao; Oida, Tatsuo

    2013-01-01

    The ester-type asymmetrical tartaric gemini amphiphiles (C(m)-C(n), where m and n are the number of carbon atoms of hydrophobic alkanoyl group, m+n=28) bearing two carboxyl groups and two different alkanoyl groups were prepared from L-tartaric acid, and the pressure-area (π-A) isotherms for a series of asymmetrical tartaric gemini amphiphiles were studied.The π-A isotherms of asymmetrical C(m)-C(n) monolayers were classified into two groups. Group 1: The asymmetry was small (n/m <1.55), and a phase transition of the monolayer from the liquid-expanded to the liquid condensed state, and a subsequent transition to solid phases were observed. Group 2: The asymmetry was large (n/m >1.8), and only liquid-expanded state of the monolayer film was observed. Based on the subphase temperature (T(sub)) dependence of monolayer static elasticity, es, the melting temperature (T(L)) of asymmetrical C(m)-C(n) monolayer was estimated to be T(L) = 31.7°C and 50.6°C for C₁₃-C₁₅ and C₁₂-C₁₆, respectively. Furthermore, assuming that asymmetrical C₁₃-C₁₅ can be viewed as an equimolar mixture of symmetrical 2C₁₃ and 2C₁₅, the temperature dependence of monolayers of 2C₁₃ and 2C₁₅ mixture at various ratios were also studied. As a result, all TL values of 2C14, C₁₃-C₁₅ and an equimolar mixture of 2C₁₃ and 2C₁₅ were almost the same. However, the variation of T(L) with the molar fraction of 2C₁₅ (X(2C15)) was remarkably different from that of solid melting point T(m) with X(2C15).

  14. Platinum monolayer electrocatalyst on gold nanostructures on silicon for photoelectrochemical hydrogen evolution.

    PubMed

    Kye, Joohong; Shin, Muncheol; Lim, Bora; Jang, Jae-Won; Oh, Ilwhan; Hwang, Seongpil

    2013-07-23

    Pt monolayer decorated gold nanostructured film on planar p-type silicon is utilized for photoelectrochemical H2 generation in this work. First, gold nanostructured film on silicon was spontaneously produced by galvanic displacement of the reduction of gold ion and the oxidation of silicon in the presence of fluoride anion. Second, underpotential deposition (UPD) of copper under illumination produced Cu monolayer on gold nanostructured film followed by galvanic exchange of less-noble Cu monolayer with more-noble PtCl6(2-). Pt(shell)/Au(core) on p-type silicon showed the similar activity with platinum nanoparticle on silicon for photoelectrochemical hydrogen evolution reaction in spite of low platinum loading. From Tafel analysis, Pt(shell)/Au(core) electrocatalyst shows the higher area-specific activity than platinum nanoparticle on silicon demonstrating the significant role of underlying gold for charge transfer reaction from silicon to H(+) through platinum catalyst. PMID:23750804

  15. Utilization of monolayer MoS2 in Bragg stacks and metamaterial structures as broadband absorbers

    NASA Astrophysics Data System (ADS)

    Mukherjee, Bablu; Simsek, Ergun

    2016-06-01

    We numerically study the possibility of using atomically thin transition metal dichalcogenides (TMDs) for applications requiring broadband absorption in the visible range of the electromagnetic spectrum. We demonstrate that when monolayer TMDs are positioned into a finite-period of multilayer Bragg stack geometry, they make broadband, wide-angle, almost polarization-independent absorbers. In our study, we consider molybdenum disulfide (MoS2) and silicon dioxide (SiO2) as semiconducting and dielectric thin film of alternate high- and low- index films, respectively. By optimizing the thickness of the SiO2 film, we find that monolayer MoS2 based Bragg stacks can absorb 94.7% of the incident energy in the visible (350-700 nm). Similar structures can be engineered to make perfect reflectors for saturable absorption applications. We also demonstrate that bandwidth of metamaterial absorbers can be expanded using monolayer TMDs.

  16. Commensurability effects in one-dimensional Anderson localization: Anomalies in eigenfunction statistics

    SciTech Connect

    Kravtsov, V.E.; Yudson, V.I.

    2011-07-15

    Highlights: > Statistics of normalized eigenfunctions in one-dimensional Anderson localization at E = 0 is studied. > Moments of inverse participation ratio are calculated. > Equation for generating function is derived at E = 0. > An exact solution for generating function at E = 0 is obtained. > Relation of the generating function to the phase distribution function is established. - Abstract: The one-dimensional (1d) Anderson model (AM), i.e. a tight-binding chain with random uncorrelated on-site energies, has statistical anomalies at any rational point f=(2a)/({lambda}{sub E}) , where a is the lattice constant and {lambda}{sub E} is the de Broglie wavelength. We develop a regular approach to anomalous statistics of normalized eigenfunctions {psi}(r) at such commensurability points. The approach is based on an exact integral transfer-matrix equation for a generating function {Phi}{sub r}(u, {phi}) (u and {phi} have a meaning of the squared amplitude and phase of eigenfunctions, r is the position of the observation point). This generating function can be used to compute local statistics of eigenfunctions of 1d AM at any disorder and to address the problem of higher-order anomalies at f=p/q with q > 2. The descender of the generating function P{sub r}({phi}){identical_to}{Phi}{sub r}(u=0,{phi}) is shown to be the distribution function of phase which determines the Lyapunov exponent and the local density of states. In the leading order in the small disorder we derived a second-order partial differential equation for the r-independent ('zero-mode') component {Phi}(u, {phi}) at the E = 0 (f=1/2 ) anomaly. This equation is nonseparable in variables u and {phi}. Yet, we show that due to a hidden symmetry, it is integrable and we construct an exact solution for {Phi}(u, {phi}) explicitly in quadratures. Using this solution we computed moments I{sub m} = N< vertical bar {psi} vertical bar {sup 2m}> (m {>=} 1) for a chain of the length N {yields} {infinity} and found an

  17. Convective microsphere monolayer deposition

    NASA Astrophysics Data System (ADS)

    Gilchrist, James

    2011-03-01

    There is perhaps no simpler way of modifying surface chemistry and morphology than surface deposition of particles. Micron-sized microspheres were deposited into thin films via rapid convective deposition, similar to the `coffee ring effect' using a similar method to that studied by Prevo and Velev, Langmuir, 2003. By varying deposition rate and blade angle, the optimal operating ranges in which 2D close-packed arrays of microspheres existed were obtained. Self-assembly of colloidal particles through a balance of electrostatic and capillary forces during solvent evaporation was revealed. These interactions were explored through a model comparing the residence time of a particle in the thin film and the characteristic time of capillary-driven crystallization to describe the morphology and microstructure of deposited particles. Co-deposition of binary suspensions of micron and nanoscale particles was tailored to generate higher-quality surface coatings and a simple theory describes the immergence of instabilities that result in formation of stripes. Optical and biomedical applications that utilize the described nanoscale control over surface morphology will also be discussed.

  18. Bursting of soap films

    NASA Astrophysics Data System (ADS)

    Chowdhury, Debashish; Stauffer, Dietrich

    1992-07-01

    Soap films consist of thin films of water in between two monolayers of amphiphilic molecules. Newton black films (NBFs) are the thinnest possible soap films. We have developed a microscopic model of NBFs; this model is a variant of the Widom model for microemulsions. By carrying out Monte Carlo simulations of this model, we have investigated the dependence of the lifetime of the NBFs on (a) the initial concentration of the amphiphilic molecules, (b) the temperature and (c) the bending rigidity of the constituent amphiphilic monolayers. We compare our results with the corresponding experimental observations and suggest further specific experiments. We establish that the “edge energy” of the model bilayer tends to stabilize the NBF; a similar mechanism leads to the well known phenomenon of “self-healing” of small enough holes in pierced vesicles. We also review the laws of growth of holes in soap films during rupture. Finally, we speculate on some other possible applications of our ideas.

  19. Monolayer coated aerogels and method of making

    DOEpatents

    Zemanian, Thomas Samuel; Fryxell, Glen; Ustyugov, Oleksiy A.

    2006-03-28

    Aerogels having a monolayer coating are described. The aerogel and a monolayer forming precursor are provided in a supercritical fluid, whereupon the aerogel and the monolayer forming precursor are reacted in said supercritical fluid to form a covalent bond between the aerogel and the monolayer forming precursor. Suitable aerogels are ceramic oxides such as silica, alumina, aluminosilicate, and combinations thereof. Suitable monolayer forming precursors include alkyl silanes, chlorosilanes, boranes, chloroboranes, germanes, and combinations thereof. The method may also include providing a surface preparation agent such as water, or hydroetching an aerogel to enhance the coating of the monolayer.

  20. Topography and instability of monolayers near domain boundaries

    SciTech Connect

    Diamant, H.; Witten, T. A.; Ege, C.; Gopal, A.; Lee, K. Y. C.

    2001-06-01

    We theoretically study the topography of a biphasic surfactant monolayer in the vicinity of domain boundaries. The differing elastic properties of the two phases generally lead to a nonflat topography of {open_quotes}mesas,{close_quotes} where domains of one phase are elevated with respect to the other phase. The mesas are steep but low, having heights of up to 10 nm. As the monolayer is laterally compressed, the mesas develop overhangs and eventually become unstable at a surface tension of about K({delta}c{sub 0}){sup 2} ({delta}c{sub 0} being the difference in spontaneous curvature and K a bending modulus). In addition, the boundary is found to undergo a topography-induced rippling instability upon compression, if its line tension is smaller than about K{delta}c{sub 0}. The effect of diffuse boundaries on these features and the topographic behavior near a critical point are also examined. We discuss the relevance of our findings to several experimental observations related to surfactant monolayers: (i) small topographic features recently found near domain boundaries; (ii) folding behavior observed in mixed phospholipid monolayers and model lung surfactants; (iii) roughening of domain boundaries seen under lateral compression; (iv) the absence of biphasic structures in tensionless surfactant films.

  1. Electromelting of Confined Monolayer Ice

    NASA Astrophysics Data System (ADS)

    Qiu, Hu; Guo, Wanlin

    2013-05-01

    In sharp contrast to the prevailing view that electric fields promote water freezing, here we show by molecular dynamics simulations that monolayer ice confined between two parallel plates can melt into liquid water under a perpendicularly applied electric field. The melting temperature of the monolayer ice decreases with the increasing strength of the external field due to the field-induced disruption of the water-wall interaction induced well-ordered network of the hydrogen bond. This electromelting process should add an important new ingredient to the physics of water.

  2. Electromelting of confined monolayer ice.

    PubMed

    Qiu, Hu; Guo, Wanlin

    2013-05-10

    In sharp contrast to the prevailing view that electric fields promote water freezing, here we show by molecular dynamics simulations that monolayer ice confined between two parallel plates can melt into liquid water under a perpendicularly applied electric field. The melting temperature of the monolayer ice decreases with the increasing strength of the external field due to the field-induced disruption of the water-wall interaction induced well-ordered network of the hydrogen bond. This electromelting process should add an important new ingredient to the physics of water. PMID:23705718

  3. Reflectivity of a disordered monolayer estimated by graded refractive index and scattering models.

    PubMed

    Diamant, Ruth; Garcí-Valenzuela, Augusto; Fernández-Guasti, Manuel

    2012-09-01

    Reflectivity of a random monolayer, consisting of transparent spherical particles, is estimated using a graded refractive index model, an effective medium approach, and two scattering models. Two cases, a self-standing film and one with a substrate, are considered. Neither the surrounding medium nor the substrate are absorbing materials. Results at normal incidence, with different particle sizes, covering ratios and refractive indexes, are compared. The purpose of this work is to find under which circumstances, for reflectivity at normal incidence, a particle monolayer behaves as a graded refractive index film. PMID:23201948

  4. Mechanical properties of water-assembled graphene oxide Langmuir monolayers: Guiding controlled transfer

    SciTech Connect

    Harrison, Katharine L.; Biedermann, Laura B.; Zavadil, Kevin R.

    2015-08-24

    Liquid-phase transfer of graphene oxide (GO) and reduced graphene oxide (RGO) monolayers is investigated from the perspective of the mechanical properties of these films. Monolayers are assembled in a Langmuir–Blodgett trough, and oscillatory barrier measurements are used to characterize the resulting compressive and shear moduli as a function of surface pressure. GO monolayers are shown to develop a significant shear modulus (10–25 mN/m) at relevant surface pressures while RGO monolayers do not. The existence of a shear modulus indicates that GO is acting as a two-dimensional solid driven by strong interaction between the individual GO sheets. The absence of such behavior in RGO is attributed to the decrease in oxygen moieties on the sheet basal plane, permitting RGO sheets to slide across one another with minimum energy dissipation. Knowledge of this two-dimensional solid behavior is exploited to successfully transfer large-area, continuous GO films to hydrophobic Au substrates. The key to successful transfer is the use of shallow-angle dipping designed to minimize tensile stress present during the insertion or extraction of the substrate. A shallow dip angle on hydrophobic Au does not impart a beneficial effect for RGO monolayers, as these monolayers do not behave as two-dimensional solids and do not remain coherent during the transfer process. As a result, we hypothesize that this observed correlation between monolayer mechanical properties and continuous film transfer success is more universally applicable across substrate hydrophobicities and could be exploited to control the transfer of films composed of two-dimensional materials.

  5. Mechanical properties of water-assembled graphene oxide Langmuir monolayers: Guiding controlled transfer

    DOE PAGES

    Harrison, Katharine L.; Biedermann, Laura B.; Zavadil, Kevin R.

    2015-08-24

    Liquid-phase transfer of graphene oxide (GO) and reduced graphene oxide (RGO) monolayers is investigated from the perspective of the mechanical properties of these films. Monolayers are assembled in a Langmuir–Blodgett trough, and oscillatory barrier measurements are used to characterize the resulting compressive and shear moduli as a function of surface pressure. GO monolayers are shown to develop a significant shear modulus (10–25 mN/m) at relevant surface pressures while RGO monolayers do not. The existence of a shear modulus indicates that GO is acting as a two-dimensional solid driven by strong interaction between the individual GO sheets. The absence of suchmore » behavior in RGO is attributed to the decrease in oxygen moieties on the sheet basal plane, permitting RGO sheets to slide across one another with minimum energy dissipation. Knowledge of this two-dimensional solid behavior is exploited to successfully transfer large-area, continuous GO films to hydrophobic Au substrates. The key to successful transfer is the use of shallow-angle dipping designed to minimize tensile stress present during the insertion or extraction of the substrate. A shallow dip angle on hydrophobic Au does not impart a beneficial effect for RGO monolayers, as these monolayers do not behave as two-dimensional solids and do not remain coherent during the transfer process. As a result, we hypothesize that this observed correlation between monolayer mechanical properties and continuous film transfer success is more universally applicable across substrate hydrophobicities and could be exploited to control the transfer of films composed of two-dimensional materials.« less

  6. Mechanical Properties of Water-Assembled Graphene Oxide Langmuir Monolayers: Guiding Controlled Transfer.

    PubMed

    Harrison, Katharine L; Biedermann, Laura B; Zavadil, Kevin R

    2015-09-15

    Liquid-phase transfer of graphene oxide (GO) and reduced graphene oxide (RGO) monolayers is investigated from the perspective of the mechanical properties of these films. Monolayers are assembled in a Langmuir-Blodgett trough, and oscillatory barrier measurements are used to characterize the resulting compressive and shear moduli as a function of surface pressure. GO monolayers are shown to develop a significant shear modulus (10-25 mN/m) at relevant surface pressures while RGO monolayers do not. The existence of a shear modulus indicates that GO is acting as a two-dimensional solid driven by strong interaction between the individual GO sheets. The absence of such behavior in RGO is attributed to the decrease in oxygen moieties on the sheet basal plane, permitting RGO sheets to slide across one another with minimum energy dissipation. Knowledge of this two-dimensional solid behavior is exploited to successfully transfer large-area, continuous GO films to hydrophobic Au substrates. The key to successful transfer is the use of shallow-angle dipping designed to minimize tensile stress present during the insertion or extraction of the substrate. A shallow dip angle on hydrophobic Au does not impart a beneficial effect for RGO monolayers, as these monolayers do not behave as two-dimensional solids and do not remain coherent during the transfer process. We hypothesize that this observed correlation between monolayer mechanical properties and continuous film transfer success is more universally applicable across substrate hydrophobicities and could be exploited to control the transfer of films composed of two-dimensional materials.

  7. Superlubric-pinned Aubry transition of two dimensional monolayers in optical lattices

    NASA Astrophysics Data System (ADS)

    Mandelli, Davide; Vanossi, Andrea; Manini, Nicola; Tosatti, Erio

    Two-dimensional (2D) crystalline colloidal monolayers sliding over a laser-induced optical lattice ``corrugation'' potential emulate friction between ideal crystal surfaces. Static friction is always present when the monolayer and the optical lattices are commensurate, but when they are incommensurate the presence or absence of static friction depends upon the system parameters. In 1D, at the Aubry dynamical phase transition the static friction goes continuously from zero (superlubricity) to finite as the periodic corrugation strength is increased. We look for the Aubry-like transition in the more realistic 2D case of a monolayer in an incommensurate periodic potential using molecular dynamics simulations. Results confirm a clear and sharp 2D superlubric-pinned transition upon increasing corrugation strength. Unlike the 1D Aubry transition which is continuous, the 2D transition is first-order, with a jump of static friction. At the 2D Aubry transition there is no change of symmetry, a sudden rise of the colloid-colloid interaction energy, and a compensating drop of the colloid-corrugation energy. The observability of the superlubric-pinned colloid transition is proposed and discussed. This work has been supported by ERC Advanced Grant N. 320796 MODPHYSFRICT.

  8. NMR Studies of Quantum Tunneling in Monolayers of Helium Three

    NASA Astrophysics Data System (ADS)

    Parks, Charles; Stachowiak, Piotr; Sullivan, Neil

    2002-03-01

    The results of NMR studies of the nuclear spin-spin relaxation are reported for commensurate monolayers of helium three adsorbed on hexagonal boron nitride. The measurements were made using pulsed NMR techniques for low temperatures, 0.01 < T < 5.0 K, and for moderately high magnetic fields (up to 6 T). The relaxation rate is independent of temperature at low temperatures, 0.12 < T < 0.85 K, and this behavior is interpreted in terms of particle-particle exchange motions of the adsorbed helium atoms. The effective exchange rates were observed to change significantly on replacing a fraction of the helium atoms with relatively immobile neon atoms. This is understood if there is a significant 3-particle exchange in addition to 2-particle exchange. The analyses of the experimental results indicate that the 3-spin exchange term in the exchange Hamiltonian is of opposite sign to that of the 2-spin exchange and also has a larger amplitude. At high temperatures, 0.8 < T < 5.0 K, an exponential temperature dependence of the rate is observed that is attributed to the thermal activation of vacancies.

  9. Competing Interactions in the S=3/2 Kagome Staircase Co3V2O8: Evolution of the Commensurate and Incommensurate Phases in a Magnetic Field

    NASA Astrophysics Data System (ADS)

    Helton, Joel; Chen, Ying; Lynn, Jeffrey; Bychkov, Georgii; Barilo, Sergei; Rogado, Nyrissa; Cava, Robert

    2012-02-01

    Single crystal neutron diffraction studies have been performed on the S = 3/2 kagome staircase compound Co3V2O8 with a magnetic field applied along the magnetization easy-axis (H || a). Previous zero-field measurements reported incommensurate, transversely polarized spin density wave (SDW) phases [with a temperature dependent propagation vector of k = (0 δ 0)] interspersed with multiple commensurate lock-in transitions at temperatures above the ferromagnetic ground state. For small applied fields along a, μ0H 0.05 T, the commensurate lock-in phases are destabilized in favor of the incommensurate SDW, while slightly larger applied fields restore the commensurate lock-in phase with δ = 1/2 and yield a new commensurate phase with δ = 2/5. For measurements in an applied field, higher-order scattering is observed that corresponds to the second-harmonic.

  10. Molecular organization of a water-insoluble iridium(III) complex in mixed monolayers.

    PubMed

    Giner-Casares, Juan J; Pérez-Morales, Marta; Bolink, Henk J; Muñoz, Eulogia; de Miguel, Gustavo; Martín-Romero, María T; Camacho, Luis

    2007-11-01

    In this work, organized mixed monolayers containing a cationic water-insoluble iridium(III) complex, Ir-dye, [Ir(ppy)(2)(tmphen)]PF(6), (tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline, and ppy = 2-phenylpyridine), and an anionic lipid matrix, DMPA, dimyristoyl-phosphatidic acid, with different molar proportions, were formed by the co-spreading method at the air-water interface. The presence of the dye at the interface, as well as the molecular organization of the mixed films, is deduced from surface techniques such as pi-A isotherms, Brewster angle microscopy (BAM) and reflection spectroscopy. The results obtained remark the formation of an equimolar mixed film, Ir-dye/DMPA = 1:1. BAM images reveal a whole homogeneous monolayer, with gradually increasing reflectivity along the compression process up to reaching the collapse of this equimolecular monolayer at pi approximately equal to 37 mNm(-1). Increasing the molar ratio of DMPA in the mixture, the excess of lipid molecules organizes themselves forming dark flower-like domains of pure DMPA at high surface pressures, coexisting with the mixed Ir-dye/DMPA = 1:1 monolayer. On the other hand, unstable mixed monolayers are obtained by using an initial dye surface concentration higher than the equimolecular one. These mixed Langmuir monolayers have been successfully transferred onto solid substrates by the LB (Langmuir-Blodgett) technique. PMID:17618641

  11. Molecular organization of a water-insoluble iridium(III) complex in mixed monolayers.

    PubMed

    Giner-Casares, Juan J; Pérez-Morales, Marta; Bolink, Henk J; Muñoz, Eulogia; de Miguel, Gustavo; Martín-Romero, María T; Camacho, Luis

    2007-11-01

    In this work, organized mixed monolayers containing a cationic water-insoluble iridium(III) complex, Ir-dye, [Ir(ppy)(2)(tmphen)]PF(6), (tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline, and ppy = 2-phenylpyridine), and an anionic lipid matrix, DMPA, dimyristoyl-phosphatidic acid, with different molar proportions, were formed by the co-spreading method at the air-water interface. The presence of the dye at the interface, as well as the molecular organization of the mixed films, is deduced from surface techniques such as pi-A isotherms, Brewster angle microscopy (BAM) and reflection spectroscopy. The results obtained remark the formation of an equimolar mixed film, Ir-dye/DMPA = 1:1. BAM images reveal a whole homogeneous monolayer, with gradually increasing reflectivity along the compression process up to reaching the collapse of this equimolecular monolayer at pi approximately equal to 37 mNm(-1). Increasing the molar ratio of DMPA in the mixture, the excess of lipid molecules organizes themselves forming dark flower-like domains of pure DMPA at high surface pressures, coexisting with the mixed Ir-dye/DMPA = 1:1 monolayer. On the other hand, unstable mixed monolayers are obtained by using an initial dye surface concentration higher than the equimolecular one. These mixed Langmuir monolayers have been successfully transferred onto solid substrates by the LB (Langmuir-Blodgett) technique.

  12. Pt monolayer coating on complex network substrate with high catalytic activity for the hydrogen evolution reaction

    PubMed Central

    Li, Man; Ma, Qiang; Zi, Wei; Liu, Xiaojing; Zhu, Xuejie; Liu, Shengzhong (Frank)

    2015-01-01

    A deposition process has been developed to fabricate a complete-monolayer Pt coating on a large-surface-area three-dimensional (3D) Ni foam substrate using a buffer layer (Ag or Au) strategy. The quartz crystal microbalance, current density analysis, cyclic voltammetry integration, and X-ray photoelectron spectroscopy results show that the monolayer deposition process accomplishes full coverage on the substrate and the deposition can be controlled to a single atomic layer thickness. To our knowledge, this is the first report on a complete-monolayer Pt coating on a 3D bulk substrate with complex fine structures; all prior literature reported on submonolayer or incomplete-monolayer coating. A thin underlayer of Ag or Au is found to be necessary to cover a very reactive Ni substrate to ensure complete-monolayer Pt coverage; otherwise, only an incomplete monolayer is formed. Moreover, the Pt monolayer is found to work as well as a thick Pt film for catalytic reactions. This development may pave a way to fabricating a high-activity Pt catalyst with minimal Pt usage. PMID:26601247

  13. Preparation and tribological study of a peptide-containing alkylsiloxane monolayer on silicon.

    PubMed

    Song, Shiyong; Ren, Sili; Wang, Jinqing; Yang, Shengrong; Zhang, Junyan

    2006-07-01

    A peptide-containing alkylsilane self-assembled monolayer on silicon surface has been prepared successfully by a simple one-step strategy. The formation and structure of the peptide-containing SAMs were characterized by means of contact angle measurement, ellipsometry, FT-IR, and AFM morphology observation. It was found that the water content in the hydrolysis solution plays a key role in determining the quality of the monolayers. The micro-tribological properties of various films were evaluated by using AFM, while the macro-tribological study was performed on a ball-on-plate tribometer. It was found that the peptide-containing monolayers possess excellent friction-reduction and antiwear ability, which was attributed to its amide-containing structure. In other words, the interchain hydrogen bonds among the molecules enhance the stability of the monolayers against rubbing the counterpart ball and thus endow it an outstanding antiwear ability.

  14. Exploring the relative bending of a CVD graphene monolayer with gap-plasmons.

    PubMed

    Min, Young Hwan; Park, Won-Hwa

    2014-08-21

    We report a spectroscopic indicator showing the bending of a chemical vapor deposition (CVD) graphene monolayer on Cu foil or an arbitrary substrate after transfer. Using a Au nanoparticle (NP)-graphene monolayer-Au thin film (TF) junction system, the Radial Breathing-Like Mode (RBLM) Raman signal from the sandwiched graphene monolayer is evidently observed by employing a local z-polarized incident field formed at the Au NP-Au TF junction. We also utilized the RBLM intensity as a quantitative tool with a wide dynamic range (∼300%) compared to the 2D peak width (∼35%) for determining the relative degree of bending on the Au TF substrate. The RBLM signal from the CVD graphene monolayer is anticipated to be used as a valuable marker in exploring out-of-plane directional properties.

  15. Fruit and vegetable films and uses thereof

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The present invention is directed to monolayer, bilayer, and multilayer films made from fruit, vegetable or a combination thereof, which films have the thinness, strength, flexibility and crispness to serve as alternates or substitutes for seaweed-based films such as nori, while providing nutrition ...

  16. Mysterious Lattice Rotations in Adsorbed Monolayers

    NASA Astrophysics Data System (ADS)

    Diehl, Renee D.

    1997-03-01

    Lattice rotations due to a mismatch in structure have been observed in film growth for many years, probably beginning in the 1930's with the Nishiyama-Wasserman and Kurdjumov-Sachs orientations observed when fcc(111) films grow on bcc(110) surfaces, or vice versa. Early analysis of this problem was carried out with the aid of Moiré patterns and the observation that the preferred lattice orientations are those which maximize the Moiré fringe spacing. Later energy calculations indicated that the structures which were predicted by the the Moiré technique actually do correspond to energy minima. Epitaxial rotation in adsorbed monolayers is a conceptually simpler problem since in principle it involves only two planes of atoms, and it was first observed in 1977 for Ar on a graphite surface(C. G. Shaw, M. D. Chinn, S. C. Fain, Jr. Phys. Rev. Lett. 41 (1978) 955.). This observation came only a few months after a new theory, based on the expected elastic behavior of an overlayer, was developed by A. D. Novaco and J. P. McTague(A. D. Novaco and J. P. McTague, Phys. Rev. Lett. 38 (1977) 1286.), and the agreement with the experimental results was remarkable. It was later shown that a few symmetry principles similar to those used for the film growth studies sometimes can also predict the observed structures. However, the situation for incommensurate layers physisorbed on metal surfaces currently looks bleak. None of the existing theories or models appears to describe the experimental results. New data for physisorbed gases on metal surfaces will be presented, along with some half-baked (and probably wrong) ideas for what might be happening. This work was supported by NSF.

  17. Exploring the relative bending of a CVD graphene monolayer with gap-plasmons

    NASA Astrophysics Data System (ADS)

    Min, Young Hwan; Park, Won-Hwa

    2014-07-01

    We report a spectroscopic indicator showing the bending of a chemical vapor deposition (CVD) graphene monolayer on Cu foil or an arbitrary substrate after transfer. Using a Au nanoparticle (NP)-graphene monolayer-Au thin film (TF) junction system, the Radial Breathing-Like Mode (RBLM) Raman signal from the sandwiched graphene monolayer is evidently observed by employing a local z-polarized incident field formed at the Au NP-Au TF junction. We also utilized the RBLM intensity as a quantitative tool with a wide dynamic range (~300%) compared to the 2D peak width (~35%) for determining the relative degree of bending on the Au TF substrate. The RBLM signal from the CVD graphene monolayer is anticipated to be used as a valuable marker in exploring out-of-plane directional properties.We report a spectroscopic indicator showing the bending of a chemical vapor deposition (CVD) graphene monolayer on Cu foil or an arbitrary substrate after transfer. Using a Au nanoparticle (NP)-graphene monolayer-Au thin film (TF) junction system, the Radial Breathing-Like Mode (RBLM) Raman signal from the sandwiched graphene monolayer is evidently observed by employing a local z-polarized incident field formed at the Au NP-Au TF junction. We also utilized the RBLM intensity as a quantitative tool with a wide dynamic range (~300%) compared to the 2D peak width (~35%) for determining the relative degree of bending on the Au TF substrate. The RBLM signal from the CVD graphene monolayer is anticipated to be used as a valuable marker in exploring out-of-plane directional properties. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr01586j

  18. A Brief Review of the Relationships Between Monolayer Viscosity, Phase Behavior, Surface Pressure and Temperature Using a Simple Monolayer Viscometer

    PubMed Central

    Alonso, Coralie

    2008-01-01

    The two-dimensional surface shear viscosity, η, of fatty acid monolayers of different chain lengths, measured using a simple magnetic needle viscometer, strongly correlates with the molecular organization in condensed phases and the absolute temperature. η can increase by orders of magnitude at phase boundaries associated with tilted to untilted molecular order, providing the underlying order is semi-crystalline. Hence, untilted, long-range ordered CS phases are the most viscous films. However, despite being untilted, the LS rotator phase is less viscous than certain laterally ordered tilted phases, suggesting a decrease of the Van der Waals interactions due to molecular rotation. In certain regions of the L2 phase, η reaches a maximum before the L2-LS transition, an anomalous behavior correlated with the change in the lattice symmetry of the head group. Surface shear viscosity, even when measured with a macroscopic probe, is particularly sensitive to the microscopic organization of monolayers. PMID:17078656

  19. Preparation and photophysical properties of thin films of coumarin dyes

    NASA Astrophysics Data System (ADS)

    Ibrayev, N. Kh.; Seliverstova, E. V.; Alekseeva, V. I.; Marinina, L. E.; Savvina, L. P.

    2013-07-01

    The results from investigating the photophysical properties of new coumarin dyes synthesized and incorporated into Langmuir-Blodgett films are presented. A method for forming monolayers on the surface of a water/air interface is proposed. The phase states of mixed monolayers on a water surface are studied. It is found that mixed monolayers of amphiphilic polyampholyte and dye allow us to obtain more stable and condensed films, relative to films of single components. The spectral and luminescent properties of synthesized dyes in solution and in Langmuir-Blodgett films are studied.

  20. The rheological properties of beta amyloid Langmuir monolayers: Comparative studies with melittin peptide.

    PubMed

    Caruso, Benjamín; Ambroggio, Ernesto E; Wilke, Natalia; Fidelio, Gerardo Daniel

    2016-10-01

    We determined the rheological properties of β-amyloid Langmuir films at the air/water interface, a peptide whose interfacial structure is extended β-sheet, and compared them with those of films composed of Melittin (Mel), which adopts an α-helical conformation at neutral pH. To determine the dilatational and shear moduli we evaluated the response of pure peptide monolayers to an oscillatory anisotropic compressive work. Additionally, a micro-rheological characterization was performed by tracking the diffusion of micrometer sized latex beads onto the interface. This technique allowed us the detection of different rheological behaviour between monolayers presenting a low shear response. Monolayers of the β-sheet structure-adopting peptides, such as β-amyloid peptides, exhibited a marked shear (elastic) modulus even at low surface pressures. In contrast, Mel monolayers exhibited negligible shear modulus and the micro-rheological shear response was markedly lower than that observed for either Aβ1-40 or Aβ1-42 amyloid peptides. When Mel monolayers were formed at the interface of an aqueous solution at pH 11, we observed an increase in both the lateral stability and film viscosity as detected by a slower diffusion of the latex beads, in keeping with an increase in β-sheet structure at this high pH (verified by ATR and FT-IR measurements). We suggest that the interactions responsible for the marked response upon shear observed for β-amyloid peptide monolayers are the hydrogen bonds of the β-sheet structure that can form an infinite planar network at the interface. Conversely, α-helical Mel peptide lack of these inter-molecular interactions and, therefore the shear contribution was negligible. We propose that the secondary structure is important for modulating the rheological behavior of short peptide monolayers regardless of the mass density or surface charge at the surface.

  1. Single-monolayer in situ modulus measurements using a SAW device: Photocrosslinking of a diacetylenic thiol-based monolayer

    SciTech Connect

    Ricco, A.J.; Staton, A.W.; Crooks, R.M.; Kim, Taisun

    1997-10-01

    We report direct measurement of the modulus change that accompanies the crosslinking of a single molecular monolayer. We measured a change in elastic modulus of 5 x 10{sup 10} dyn/cm{sup 2} as a result of ultraviolet-induced photocrosslinking of a single surface-confined monolayer of the conjugated diacetylenic thiol HS(CH{sub 2}){sub 10}C{triple_bond}CC{triple_bond}C(CH{sub 2}){sub 10}COOH, designated {open_quotes}DAT{close_quotes} hereafter. The modulus measurement was made on a monolayer of DAT chemisorbed upon a gold film on the surface of a 97-MHz ST-quartz surface acoustic wave delay line. The ratio of the changes recorded in SAW velocity and attenuation, approximately 4:1, suggests that the measured effect is mainly a change in the elastic (real) component of the complex shear modulus, viscous changes playing a lesser role. In relation to typical polymer modulus values, the change of 5 x 10{sup 10} dyn/cm{sup 2} is consistent with a change from a rubbery material (G{prime} {approximately} 10{sup 7} - 10{sup 8} dyn/cm{sup 2}) to a fairly rigid, glassy material (G{prime} {approximately} 10{sup 10} dyn/cm{sup 2}), reasonable for comparison of the monolayer in its as-adsorbed and crosslinked forms. This report of the direct SAW-based measurement of the modulus change associated with the crosslinking of a single molecular monolayer is complementary to and consistent with previous in-situ measurements of this process using thickness-shear mode resonators.

  2. Phase-sensitive magnetoresistance oscillations induced by commensurate bichromatic irradiations in a two-dimensional electron system

    SciTech Connect

    Lei, X. L.; Liu, S. Y.

    2014-06-21

    We analyze a phase-sensitive contribution to the oscillating magnetoresistance induced by the combined driving of two microwave fields having commensurate frequencies ω{sub 1} and ω{sub 2} (m{sub 1}ω{sub 1} + m{sub 2}ω{sub 2} = 0 for at least a set of nonzero integers m{sub 1} and m{sub 2}), based on the balance-equation approach to magnetotransport for high-density two-dimensional electron systems. This commensurate oscillating photoresistance not only depends on the frequencies and polarizations of both microwaves, but varies drastically when changing the relative phases of two incident radiation fields. It shows up most significantly in the case of ω{sub 2}/ω{sub 1} = 3 and may lead to a phase-controllable change of more than a factor of two in the total magnetoresistivity in the vicinity of ω{sub 1}/ω{sub c} = 1.5 and 2.5 (ω{sub c} is the cyclotron frequency), when both radiation fields are linearly x-direction polarized.

  3. The origin of the Kirkwood gaps - A mapping for asteroidal motion near the 3/1 commensurability

    NASA Technical Reports Server (NTRS)

    Wisdom, J.

    1982-01-01

    A mapping of the phase space onto itself with the same low-order resonance structure as the 3/1 commensurability in the planar-elliptic restricted three-body problem is obtained. This mapping is about 1,000 times faster than the usual method of numerically integrating the averaged equations of motion. It exhibits some surprising behavior that might provide a key to the origin of the Kirkwood gaps. It is noted that a test asteroid placed in the gap may evolve for a million years with low eccentricity (less than 0.05) and then suddenly jump to large eccentricity (greater than 0.3), becoming a Mars crosser. The removal of the asteroid by a close encounter with Mars would then be possible. As a first test of this hypothesis, a distribution of 300 test asteroids in the area of the 3/1 commensurability was evolved for two million years. When the Mars crossers are removed, the distribution of initial conditions reveals a gap at the location of the 3/1 Kirkwood gap.

  4. Adhesion, Deformation and Friction for Self-Assembled Monolayers on Au and Si Surfaces

    SciTech Connect

    Houston, J.E.; Hsung, R.P.; Kiely, J.D.; Mulder, J.A.; Zhu, X.Y.

    1999-07-07

    Using Interracial Force Microscopy (IFM), we investigated the tribological behavior of hexadecanethiol monolayer on Au and films of octadecyltrichlorosilane (ODTS), perfluorodecyltrichlorosilane (PFTS) and dodecane on Si. We observe a strong correlation between hysteresis in a compression cycle (measured via nanoindentation) and friction. Additionally, we suggest that the amount of hysteresis and friction in each film is related to its detailed molecular structure, especially the degree of molecular packing.

  5. Photolithography of Dithiocarbamate-Anchored Monolayers and Polymers on Gold.

    PubMed

    Leonov, Alexei P; Wei, Alexander

    2011-03-28

    Dithiocarbamate (DTC)-anchored monolayers and polymers were investigated as positive resists for UV photolithography on planar and roughened Au surfaces. DTCs were formed in situ by the condensation of CS(2) with monovalent or polyvalent amines such as linear polyethyleneimine (PEI) under mildly basic aqueous conditions, just prior to surface passivation. The robust adsorption of the polyvalent PEI-DTC to Au surfaces supported high levels of resistance to photoablation, providing opportunities to generate thin films with gradient functionality. Treatment of photopatterned substrates with alkanethiols produced binary coatings, enabling a direct visual comparison of DTC- and thiol-passivated surfaces against chemically induced corrosion using confocal microscopy.

  6. Morphology in electrochemically grown conducting polymer films

    DOEpatents

    Rubinstein, I.; Gottesfeld, S.; Sabatani, E.

    1992-04-28

    A conducting polymer film with an improved space filling is formed on a metal electrode surface. A self-assembling monolayer is formed directly on the metal surface where the monolayer has a first functional group that binds to the metal surface and a second chemical group that forms a chemical bonding site for molecules forming the conducting polymer. The conducting polymer is then conventionally deposited by electrochemical deposition. In one example, a conducting film of polyaniline is formed on a gold electrode surface with an intermediate monolayer of p-aminothiophenol. 2 figs.

  7. Morphology in electrochemically grown conducting polymer films

    DOEpatents

    Rubinstein, Israel; Gottesfeld, Shimshon; Sabatani, Eyal

    1992-01-01

    A conducting polymer film with an improved space filling is formed on a metal electrode surface. A self-assembling monolayer is formed directly on the metal surface where the monolayer has a first functional group that binds to the metal surface and a second chemical group that forms a chemical bonding site for molecules forming the conducting polymer. The conducting polymer is then conventioonally deposited by electrochemical deposition. In one example, a conducting film of polyaniline is formed on a gold electrode surface with an intermediate monolayer of p-aminothiophenol.

  8. Molecular Packing of Functionalized Fluorinated Lipids in Langmuir Monolayers

    SciTech Connect

    Landsberg, Michael J.; Ruggles, Jeremy L.; Hussein, Waleed M.; McGeary, Ross P.; Gentle, Ian R.; Hankamer, Ben

    2012-01-20

    Fluorinated amphipaths are a fascinating class of compounds, which, despite significant challenges associated with their syntheses, have found use across a number of areas of biotechnology. Applications range from the in vitro stabilization of membrane proteins to the development of enhanced stability intravenous drug and gene delivery systems. More recently, monolayer-forming fluorinated lipids have found use in the 2D crystallization of detergent-solubilized hydrophobic or partially hydrophobic proteins at the air-water interface. In this study, we investigate the surface properties of a novel suite of monolayer forming, partially fluorinated lipids. These modular lipid structures contain a densely fluorinated insertion in the hydrocarbon tail and a synthetically modifiable headgroup. Analyses of surface-pressure area isotherms and X-ray reflectometry profiles reveal that the lipids spread into fluid monolayers and are more compressible than their non-fluorinated counterparts. Furthermore, the data support a model whereby the partially fluorinated chains of the lipid tails form a film which is fundamentally incompatible with detergents and other destabilizing amphipaths.

  9. Organization, structure and activity of proteins in monolayers.

    PubMed

    Boucher, Julie; Trudel, Eric; Méthot, Mario; Desmeules, Philippe; Salesse, Christian

    2007-08-01

    Many different processes take place at the cell membrane interface. Indeed, for instance, ligands bind membrane proteins which in turn activate peripheral membrane proteins, some of which are enzymes whose action is also located at the membrane interface. Native cell membranes are difficult to use to gain information on the activity of individual proteins at the membrane interface because of the large number of different proteins involved in membranous processes. Model membrane systems, such as monolayers at the air-water interface, have thus been extensively used during the last 50 years to reconstitute proteins and to gain information on their organization, structure and activity in membranes. In the present paper, we review the recent work we have performed with membrane and peripheral proteins as well as enzymes in monolayers at the air-water interface. We show that the structure and orientation of gramicidin has been determined by combining different methods. Furthermore, we demonstrate that the secondary structure of rhodopsin and bacteriorhodopsin is indistinguishable from that in native membranes when appropriate conditions are used. We also show that the kinetics and extent of monolayer binding of myristoylated recoverin is much faster than that of the nonmyristoylated form and that this binding is highly favored by the presence polyunsaturated phospholipids. Moreover, we show that the use of fragments of RPE65 allow determine which region of this protein is most likely involved in membrane binding. Monomolecular films were also used to further understand the hydrolysis of organized phospholipids by phospholipases A2 and C.

  10. Top-grid monolayer graphene/Si Schottkey solar cell

    SciTech Connect

    Wang, Yusheng; Chen, Caiyun; Fang, Xiao; Li, Zhipeng; Qiao, Hong; Sun, Baoquan; Bao, Qiaoliang

    2015-04-15

    Monolayer graphene/Si Schottkey solar cell was fabricated using a top-grid structure. In comparison with the prevailing “top-window” structure, the newly-designed device structure has simplified the fabrication procedures to avoid ultraviolet (UV) photolithography and SiO{sub 2}-eching. We systematically investigated the effect of chemical doping as well as device area on the device performance. It was found that a power conversion efficiency (PCE) of 5.9% can be achieved by engineering the work function of graphene through chemical doping. Our study indicates that top grid structure is suitable to make low-cost, large area and high efficiency graphene/Si Schottkey solar cell. - Graphical abstract: The engineering of the work function of graphene through chemical doping is an effective approach to improve the performance of monolayer graphene/Si Schottky solar cell. - Highlights: • Monolayer graphene/Si Schottkey solar cell was fabricated. • Chemical doping can effectively tune the work function of graphene film. • Chemical doping has significant effect on the device performance. • The top-grid device structure with graphene is promising with low-cost and high efficiency.

  11. Organization, Structure and Activity of Proteins in Monolayers

    SciTech Connect

    Boucher,J.; Trudel, E.; Methot, M.; Desmeules, P.; Salesse, C.

    2007-01-01

    Many different processes take place at the cell membrane interface. Indeed, for instance, ligands bind membrane proteins which in turn activate peripheral membrane proteins, some of which are enzymes whose action is also located at the membrane interface. Native cell membranes are difficult to use to gain information on the activity of individual proteins at the membrane interface because of the large number of different proteins involved in membranous processes. Model membrane systems, such as monolayers at the air-water interface, have thus been extensively used during the last 50 years to reconstitute proteins and to gain information on their organization, structure and activity in membranes. In the present paper, we review the recent work we have performed with membrane and peripheral proteins as well as enzymes in monolayers at the air-water interface. We show that the structure and orientation of gramicidin has been determined by combining different methods. Furthermore, we demonstrate that the secondary structure of rhodopsin and bacteriorhodopsin is indistinguishable from that in native membranes when appropriate conditions are used. We also show that the kinetics and extent of monolayer binding of myristoylated recoverin is much faster than that of the nonmyristoylated form and that this binding is highly favored by the presence polyunsaturated phospholipids. Moreover, we show that the use of fragments of RPE65 allow determine which region of this protein is most likely involved in membrane binding. Monomolecular films were also used to further understand the hydrolysis of organized phospholipids by phospholipases A2 and C.

  12. Assembly of citrate gold nanoparticles on hydrophilic monolayers

    NASA Astrophysics Data System (ADS)

    Vikholm-Lundin, Inger; Rosqvist, Emil; Ihalainen, Petri; Munter, Tony; Honkimaa, Anni; Marjomäki, Varpu; Albers, Willem M.; Peltonen, Jouko

    2016-08-01

    Self-assembled monolayers (SAMs) as model surfaces were linked onto planar gold films thorough lipoic acid or disulfide groups. The molecules used were polyethylene glycol (EG-S-S), N-[tris-(hydroxymethyl)methyl]acrylamide polymers with and without lipoic acid (Lipa-pTHMMAA and pTHMMAA) and a lipoic acid triazine derivative (Lipa-MF). All the layers, but Lipa-MF with a primary amino group were hydroxyl terminated. The layers were characterized by contact angle measurements and atomic force microscopy, AFM. Citrate stabilized nanoparticles, AuNPs in water and phosphate buffer were allowed to assemble on the layers for 10 min and the binding was followed in real-time with surface plasmon resonance, SPR. The SPR resonance curves were observed to shift to higher angles and become increasingly damped, while also the peaks strongly broaden when large nanoparticles assembled on the surface. Both the angular shift and the damping of the curve was largest for nanoparticles assembling on the EG-S-S monolayer. High amounts of particles were also assembled on the pTHMMAA layer without the lipoic acid group, but the damping of the curve was considerably lower with a more even distribution of the particles. Topographical images confirmed that the highest number of particles were assembled on the polyethylene glycol monolayer. By increasing the interaction time more particles could be assembled on the surface.

  13. Metal Nanoparticles Protected with Monolayers: Applications for Chemical Vapor Sensing and Gas Chromatography

    SciTech Connect

    Grate, Jay W.; Nelson, David A.; Skaggs, Rhonda L.; Synovec, Robert E.; Gross, Gwen M.

    2004-03-31

    Nanoparticles and nanoparticle-based materials are of considerable interest for their unique properties and their potential for use in a variety of applications. Metal nanoparticles, in which each particle’s surface is coated with a protective organic monolayer, are of particular interest because the surface monolayer stabilizes them relative to aggregation and they can be taken up into solutions.(1-4) As a result they can be processed into thin films for device applications. We will refer to these materials as monolayer-protected nanoparticles, or MPNs. Typically the metal is gold, the organic layer is a self-assembled thiol layer, and this composition will be assumed throughout the remainder of this chapter. A diversity of materials and properties is readily accessible by straightforward synthetic procedures, either by the structures of the monolayer-forming thiols used in the synthesis or by post-synthetic modifications of the monolayers. A particularly promising application for these materials is as selective layers on chemical vapor sensors. In this role, the thin film of MPNs on the device surface serves to collect and concentrate gas molecules at the sensor’s surface. Their sorptive properties also lend them to use as new nanostructured gas chromatographic stationary phases. This chapter will focus on the sorptive properties of MPNs as they relate to chemical sensors and gas chromatography.

  14. Thermal stability and molecular ordering of organic semiconductor monolayers: effect of an anchor group.

    PubMed

    Jones, Andrew O F; Knauer, Philipp; Resel, Roland; Ringk, Andreas; Strohriegl, Peter; Werzer, Oliver; Sferrazza, Michele

    2015-06-01

    The thermal stability and molecular order in monolayers of two organic semiconductors, PBI-PA and PBI-alkyl, based on perylene derivatives with an identical molecular structure except for an anchor group for attachment to the substrate in PBI-PA, are reported. In situ X-ray reflectivity measurements are used to follow the stability of these monolayers in terms of order and thickness as temperature is increased. Films have thicknesses corresponding approximately to the length of one molecule; molecules stand upright on the substrate with a defined structure. PBI-PA monolayers have a high degree of order at room temperature and a stable film exists up to 250 °C, but decomposes rapidly above 300 °C. In contrast, stable physisorbed PBI-alkyl monolayers only exist up to 100 °C. Above the bulk melting point at 200 °C no more order exists. The results encourage using anchor groups in monolayers for various applications as it allows enhanced stability at the interface with the substrate.

  15. Characterization and reactivity of organic monolayers on gold and platinum surfaces

    SciTech Connect

    Wu, Chien-Ching

    1995-12-06

    Purpose is to understand how the mobilization, dielectric, orientation, composition, coverage, and structure of self-assembled organic monolayers on metal surfaces affects the surface reactivities and properties of these films in order to facilitate the construction of desired films. Two model systems were used: tiols at Au and aromatic acids at Pt. Surface analysis methods, including contact angle, electrochemistry, ellipsometry, infrared reflection absorption spectroscopy (IRRAS), and x-ray photospectroscopy, were used to study the self-assembled organic monolayers on Au and Pt. IRRAS, contact angle, and electrochemistry were used to determine the surface pK{sub a} of phenylcarboxylic acids and pyridylcarboxylic acids monolayers on Pt. These techniques were also used to determine the orientation of polymethylene chain axis and the carboxylic follow the structural evolution of the chains and end group of the thiolate monolayers during formation. IRRAS was also used to assess the carboxylic acid group in terms of its possible existence as the non-hydrogen-bonded species, the hydrogen-bonded dimeric group, and the hydrogen-bonded polymeric group. These different forms of the end group were also followed vs coverage, as well as the reactivity vs solution pH. IRRAS and contact angle were used to calculate the rate constant of the esterification of carboxylic acid-terminated monolayers on Au.

  16. Electrochemical and scanning probe microscopic characterization of spontaneously adsorbed organothiolate monolayers at gold

    SciTech Connect

    Wong, Sze-Shun Season

    1999-12-10

    This dissertation presented several results which add to the general knowledge base regarding organothiolates monolayer spontaneously adsorbed at gold films. Common to the body of this work is the use of voltammetric reductive resorption and variants of scanning probe microscopy to gain insight into the nature of the monolayer formation process as well as the resulting interface. The most significant result from this work is the success of using friction force microscopy to discriminate the end group orientation of monolayer chemisorbed at smooth gold surfaces with micrometer resolution (Chapter 4). The ability to detect the differences in the orientational disposition is demonstrated by the use PDMS polymer stamp to microcontact print an adlayer of n-alkanethiolate of length n in a predefine pattern onto a gold surface, followed by the solution deposition of a n-alkanethiol of n {+-} 1 to fill in the areas on the gold surface intentionally not coated by the stamping process. These two-component monolayers can be discriminated by using friction force microscopy which detects differences in friction contributed by the differences in the orientation of the terminal groups at surfaces. This success has recently led to the detection of the orientation differences at nanometer scale. Although the substrates examined in this work consisted entirely of smooth gold films, the same test can be performed on other smooth substrates and monolayer materials.

  17. Phase transition to a commensurate magnetic structure in PrMn{sub 2}O{sub 5} oxide

    SciTech Connect

    Men’shenin, V. V.

    2015-06-15

    On the basis of the experimentally obtained structure of the magnetic phase of the PrMn{sub 2}O{sub 5} oxide, it is found that in the temperature interval from 18 to 25 K, a transition to this phase should be analytically described by a two-component order parameter and that the effective Hamiltonian of the system should contain two independent fourth-order invariants with respect to the components of this parameter. With the use of the results of renormalization group analysis of phase transitions with this effective Hamiltonian, which are known from the literature, it is established that a second-order transition occurs. It is shown that the commensurate antiferromagnetic phase resulting from this transition has no electric polarization because this polarization is forbidden by the symmetry of the system.

  18. Spin- and valley-dependent commensurability oscillations and electric-field-induced quantum Hall plateaux in periodically modulated silicene

    SciTech Connect

    Shakouri, Kh.; Peeters, F. M.; Vasilopoulos, P.; Vargiamidis, V.; Hai, G.-Q.

    2014-05-26

    We study the commensurability oscillations in silicene subject to a perpendicular electric field E{sub z}, a weak magnetic field B, and a weak periodic potential V=V{sub 0}cos(Cy),C=2π/a{sub 0} with a{sub 0} its period. The field E{sub z} and/or the modulation lift the spin degeneracy of the Landau levels and lead to spin and valley resolved Weiss oscillations. The spin resolution is maximal when the field E{sub z} is replaced by a periodic one E{sub z}=E{sub 0}cos(Dy),D=2π/b{sub 0}, while the valley one is maximal for b{sub 0} = a{sub 0}. In certain ranges of B values, the current is fully spin or valley polarized. Additional quantum Hall conductivity plateaux arise due to spin and valley intra-Landau-level transitions.

  19. Alkanephosphonates on hafnium-modified gold: a new class of self-assembled organic monolayers.

    PubMed

    Jespersen, Michael L; Inman, Christina E; Kearns, Gregory J; Foster, Evan W; Hutchison, James E

    2007-03-14

    A new method for assembling organic monolayers on gold is reported that employs hafnium ions as linkers between a phosphonate headgroup and the gold surface. Monolayers of octadecylphosphonic acid (ODPA) formed on gold substrates that had been pretreated with hafnium oxychloride are representative of this new class of organic thin films. The monolayers are dense enough to completely block assembly of alkanethiols and resist displacement by alkanethiols. The composition and structure of the monolayers were investigated by contact angle goniometry, XPS, PM-IRRAS, and TOF-SIMS. From these studies, it was determined that this assembly strategy leads to the formation of ODPA monolayers similar in quality to those typically formed on metal oxide substrates. The assembly method allows for the ready generation of patterned surfaces that can be easily prepared by first patterning hafnium on the gold surface followed by alkanephosphonate assembly. Using the bifunctional (thiol-phosphonate) 2-mercaptoethylphosphonic acid (2-MEPA), we show that this new assembly chemistry is compatible with gold-thiol chemistry and use TOF-SIMS to show that the molecule attaches through the phosphonate functionality in the patterned region and through the thiol in the bare gold regions. These results demonstrate the possibility of functionalizing metal substrates with monolayers typically formed on metal oxide surfaces and show that hafnium-gold chemistry is complementary and orthogonal to well-established gold-thiol assembly strategies.

  20. Well-ordered monolayers of alkali-doped coronene and picene: Molecular arrangements and electronic structures

    SciTech Connect

    Yano, M.; Endo, M.; Hasegawa, Y.; Okada, R.; Yamada, Y. Sasaki, M.

    2014-07-21

    Adsorptions of alkali metals (such as K and Li) on monolayers of coronene and picene realize the formation of ordered phases, which serve as well-defined model systems for metal-intercalated aromatic superconductors. Upon alkali-doping of the monolayers of coronene and picene, scanning tunneling microscopy and X-ray absorption spectroscopy revealed the rearrangement of the entire molecular layer. The K-induced reconstruction of both monolayers resulted in the formation of a structure with a herringbone-like arrangement of molecules, suggesting the intercalation of alkali metals between molecular planes. Upon reconstruction, a shift in both the vacuum level and core levels of coronene was observed as a result of a charge transfer from alkali metals to coronene. In addition, a new density of states near the Fermi level was formed in both the doped coronene and the doped picene monolayers. This characteristic electronic feature of the ordered monolayer has been also reported in the multilayer picene films, ensuring that the present monolayer can model the properties of the metal-intercalated aromatic hydrocarbons. It is suggested that the electronic structure near the Fermi level is sensitive to the molecular arrangement, and that both the strict control and determinations of the molecular structure in the doped phase should be important for the determination of the electronic structure of these materials.

  1. Structure and shear response of lipid monolayers

    SciTech Connect

    Dutta, P.; Ketterson, J.B.

    1990-02-01

    Organic monolayers and multilayers are both scientifically fascinating and technologically promising; they are, however, both complex systems and relatively inaccessible to experimental probes. In this Progress Report, we describe our X-ray diffraction studies, which have given us substantial new information about the structures and phase transitions in monolayers on the surface of water; our use of these monolayers as a unique probe of the dynamics of wetting and spreading; and our studies of monolayer mechanical properties using a simple but effective technique available to anyone using the Wilhelmy method to measure surface tension.

  2. Nucleation control for large, single crystalline domains of monolayer hexagonal boron nitride via Si-doped Fe catalysts.

    PubMed

    Caneva, Sabina; Weatherup, Robert S; Bayer, Bernhard C; Brennan, Barry; Spencer, Steve J; Mingard, Ken; Cabrero-Vilatela, Andrea; Baehtz, Carsten; Pollard, Andrew J; Hofmann, Stephan

    2015-03-11

    The scalable chemical vapor deposition of monolayer hexagonal boron nitride (h-BN) single crystals, with lateral dimensions of ∼0.3 mm, and of continuous h-BN monolayer films with large domain sizes (>25 μm) is demonstrated via an admixture of Si to Fe catalyst films. A simple thin-film Fe/SiO2/Si catalyst system is used to show that controlled Si diffusion into the Fe catalyst allows exclusive nucleation of monolayer h-BN with very low nucleation densities upon exposure to undiluted borazine. Our systematic in situ and ex situ characterization of this catalyst system establishes a basis for further rational catalyst design for compound 2D materials.

  3. Nucleation Control for Large, Single Crystalline Domains of Monolayer Hexagonal Boron Nitride via Si-Doped Fe Catalysts

    PubMed Central

    2015-01-01

    The scalable chemical vapor deposition of monolayer hexagonal boron nitride (h-BN) single crystals, with lateral dimensions of ∼0.3 mm, and of continuous h-BN monolayer films with large domain sizes (>25 μm) is demonstrated via an admixture of Si to Fe catalyst films. A simple thin-film Fe/SiO2/Si catalyst system is used to show that controlled Si diffusion into the Fe catalyst allows exclusive nucleation of monolayer h-BN with very low nucleation densities upon exposure to undiluted borazine. Our systematic in situ and ex situ characterization of this catalyst system establishes a basis for further rational catalyst design for compound 2D materials. PMID:25664483

  4. Improved aging performance of vapor phase deposited hydrophobic self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Gnanappa, Arun Kumar; O'Murchu, Cian; Slattery, Orla; Peters, Frank; O'Hara, Tony; Aszalós-Kiss, Balázs; Tofail, Syed A. M.

    2011-02-01

    A hydrophobic self-assembled monolayer (SAM) of fluoro-octyl-trichloro-silane (FOTS) was deposited on silicon using a vapor phase technique. The aging of the hydrophobic layer was examined using water contact angle measurements. It has been found that while such monolayer films suffer from a loss of hydrophobicity with time, pre-immersion nitrogen annealing can significantly improve the aging characteristics of these monolayers. The effect of nitrogen annealing on the improved aging properties of SAM coatings has been investigated by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The hydrolytic stability and the effect of nitrogen annealing were studied by morphological evolution during immersion. A spontaneous formation of silane mounds on the surface of the monolayers was found by AFM. These mounds have been irreversibly transformed from initially uniform hydrophobic surface layers. It is highly probable that the compliance of these mounds can reasonably allow hydrophilic sites to be located around the mounds. Interestingly, the density of these mounds formation is very less on the annealed samples. XPS reveals a higher level of coverage by the N2-annealed film due to agglomeration. A relative abundance of CF3 and CF2 moieties in the annealed film may explain the enhancement of the hydrophobicity as revealed by higher level of water contact angle. This hydrophobicity was found to be significantly stable in water. This novel finding explains the improved hydrophobic stability of FOTS monolayers as primarily a morpho-chemical effect that originates from the densification of the monolayers upon annealing.

  5. Cell adhesion on a polymerized peptide-amphiphile monolayer.

    PubMed

    Biesalski, Markus A; Knaebel, Alexandra; Tu, Raymond; Tirrell, Matthew

    2006-03-01

    We report the synthesis and characterization of a stable polymerized monolayer of peptide-amphihiles on a planar solid support that promotes mouse fibroblast cell adhesion and spreading. Peptide-amphiphiles consisting of a polymerizable fatty acid attached to a short RGD containing peptide sequence are self-assembled and polymerized at the water-air interface by means of the Langmuir- Blodgett technique. The surface concentration of the peptide-amphiphile is varied by co-spreading the peptide-amphiphile with an analogous non-modified polymerizable amphiphile at the water/air interface, prior to UV light-induced polymerization. The polymerized monolayer is transferred onto a hydrophobized smooth mica surface and the resulting surfaces have been investigated with respect to directing the cell adhesion and spreading of mouse fibroblast cells in a serum-free medium. Fibroblast cells adhere and spread on surfaces exposing the bioactive ligand but do not spread on reference surfaces without peptide. We find a maximum number of adherent cells at rather high peptide surface concentrations of about 10 mol% in the mixed monolayer, equivalent to more than 50 pmol/cm2 peptide on the surface of the film. We attribute this finding to a limited accessibility of the ligands by the integrins. Because of the stability of the polymerized peptide-amphiphile monolayer, these surfaces can be re-seeded multiple times with cells, i.e. adherent cells can be removed from the surface, the surface can be sterilized and cells can be re-attached. PMID:16157369

  6. Influence of calcium on ceramide-1-phosphate monolayers

    PubMed Central

    Brezesinski, Gerald; Hill, Alexandra; Gericke, Arne

    2016-01-01

    Summary Ceramide-1-phosphate (C1P) plays an important role in several biological processes, being identified as a key regulator of many protein functions. For instance, it acts as a mediator of inflammatory responses. The mediation of the inflammation process happens due to the interaction of C1P with the C2 domain of cPLA2α, an effector protein that needs the presence of submicromolar concentrations of calcium ions. The aim of this study was to determine the phase behaviour and structural properties of C1P in the presence and absence of millimolar quantities of calcium in a well-defined pH environment. For that purpose, we used monomolecular films of C1P at the soft air/liquid interface with calcium ions in the subphase. The pH was varied to change the protonation degree of the C1P head group. We used surface pressure versus molecular area isotherms coupled with other monolayer techniques as Brewster angle microscopy (BAM), infrared reflection–absorption spectroscopy (IRRAS) and grazing incidence X-ray diffraction (GIXD). The isotherms indicate that C1P monolayers are in a condensed state in the presence of calcium ions, regardless of the pH. At higher pH without calcium ions, the monolayer is in a liquid-expanded state due to repulsion between the negatively charged phosphate groups of the C1P molecules. When divalent calcium ions are added, they are able to bridge the highly charged phosphate groups, enhancing the regular arrangement of the head groups. Similar solidification of the monolayer structure can be seen in the presence of a 150 times larger concentration of monovalent sodium ions. Therefore, calcium ions have clearly a strong affinity for the phosphomonoester of C1P. PMID:26977381

  7. Toward Ferroelectric Control of Monolayer MoS2.

    PubMed

    Nguyen, Ariana; Sharma, Pankaj; Scott, Thomas; Preciado, Edwin; Klee, Velveth; Sun, Dezheng; Lu, I-Hsi Daniel; Barroso, David; Kim, SukHyun; Shur, Vladimir Ya; Akhmatkhanov, Andrey R; Gruverman, Alexei; Bartels, Ludwig; Dowben, Peter A

    2015-05-13

    The chemical vapor deposition (CVD) of molybdenum disulfide (MoS2) single-layer films onto periodically poled lithium niobate is possible while maintaining the substrate polarization pattern. The MoS2 growth exhibits a preference for the ferroelectric domains polarized "up" with respect to the surface so that the MoS2 film may be templated by the substrate ferroelectric polarization pattern without the need for further lithography. MoS2 monolayers preserve the surface polarization of the "up" domains, while slightly quenching the surface polarization on the "down" domains as revealed by piezoresponse force microscopy. Electrical transport measurements suggest changes in the dominant carrier for CVD MoS2 under application of an external voltage, depending on the domain orientation of the ferroelectric substrate. Such sensitivity to ferroelectric substrate polarization opens the possibility for ferroelectric nonvolatile gating of transition metal dichalcogenides in scalable devices fabricated free of exfoliation and transfer.

  8. Icelike Water Monolayer Adsorbed on Mica at Room Temperature

    SciTech Connect

    Miranda, P.B.; Xu, L.; Shen, Y.R.; Salmeron, M.

    1998-12-01

    The structure of a water film formed on mica at room temperature, in equilibrium with water vapor at various relative humidities (RH), was studied using sum-frequency-generation (SFG) vibrational spectroscopy and scanning polarization force microscopy (SPFM). Analysis of the O-D stretch modes in the SFG spectra of D{sub 2}O on mica indicates that as RH increases, the submonolayer water structure evolves into a more ordered hydrogen-bonding network. At full monolayer coverage ({approximately} 90{percent} RH) , the SFG spectrum suggests an icelike film with no dangling O-D groups, in agreement with a recent molecular dynamics simulation. {copyright} {ital 1998} {ital The American Physical Society}

  9. Surface Characterization of Bovine Milk Phospholipid Monolayers by Langmuir Isotherms and Microscopic Techniques

    PubMed Central

    Gallier, Sophie; Gragson, Derek; Jiménez-Flores, Rafael; Everett, David W.

    2015-01-01

    Monolayers were prepared from phospholipids extracted from bovine milk and used as a model system to mimic the native milk fat globule membrane (MFGM) surface structure in various microscopic experiments. The natural complex mixtures of phospholipids were isolated from bovine raw milk, raw cream, processed whole milk and buttermilk powder by total lipid extraction and solid-phase extraction. A Langmuir film balance mounted on an epifluorescence microscope was used to analyze the physical behavior of the monolayer films and the phase coexistence resulting from the formation of phospholipid microdomains within these films. Atomic force microscopy was used for nanometer scale topographic resolution of the microdomains. This study allowed us to compare the behavior of phospholipid monolayers from dairy products at different stages of processing, to analyze the formation of microdomains, and to study the effect of milk processing on lipid-lipid interactions and phase coexistence. We observe that milk processing changes the physical behavior of phospholipid monolayers by altering the phospholipid profile and the fatty acid distribution. PMID:21067228

  10. Ab initio study of ZrO2 monolayers epitaxial on Si

    NASA Astrophysics Data System (ADS)

    Dogan, Mehmet; Kumah, Divine; Ahn, Charles; Walker, Frederick; Ismail-Beigi, Sohrab

    Growing thin films of crystalline metal oxides on semiconductors has been of much scientific interest because of their applications in electronic devices. One research goal is to achieve ferroelectricity in a crystalline and thin oxide film that is epitaxial on a semiconductor. This would enable the realization of non-volatile field-effect transistors where the state is encoded in the polarization direction of the oxide. We study oxides that are not ferroelectric in the bulk but become ferroelectric as an ultra-thin film on a semiconductor. Recent advances in epitaxial growth methods permit fabrication of such systems. We use density functional theory to study the interface between ZrO2 monolayers and Si (001). These monolayers have multiple metastable states. We present an analysis of these configurations and energy barriers between them. We consider the likely experimental situation where different configurations coexist to form a multi-domain system, and investigate domain dynamics. Furthermore, we demonstrate that the ZrO2 monolayers can be used as a buffer layer to induce ferroelectricity in perovskite oxides such as SrTiO3 on Si. We also show that these monolayers modify the transport properties of Si which would allow for the desired device applications. This work is supported by the National Science Foundation through Grant MRSEC NSF DMR-1119826.

  11. Assembly of amorphous clusters under floating monolayers: a comparison of in situ and ex situ techniques.

    PubMed

    Uysal, Ahmet; Stripe, Benjamin; Lin, Binhua; Meron, Mati; Dutta, Pulak

    2013-11-26

    We report synchrotron X-ray scattering studies of biomimetic crystallization of hydroxyapatite (the primary constituent of bone), using monolayers of fatty acid molecules floating on simulated body fluid (SBF) as well as aqueous solutions of calcium phosphate. A ∼10 Å thick film of amorphous material is observed to form immediately at the molecular monolayer, consistent with the proposed formation of "Posner clusters". This layer becomes denser but not significantly thicker as the subphase concentration and the temperature approach physiological conditions. The amorphous films do not crystallize within 24 h, in contrast to prior reports of more rapid crystallization using electron microscopy on ex situ samples. However, crystallization occurs almost immediately after our films are transferred onto solid substrates. These results illustrate the importance of in situ measurements for model biomineralization experiments. PMID:24164244

  12. Mechanism of iron inhibition by stearic acid Langmuir-Blodgett monolayers

    SciTech Connect

    Xing, W.; Shan, Y.; Guo, D.; Lu, T.; Xi, S.

    1995-01-01

    Many organic compounds can be adsorbed onto the interface of a metal and solution to form a thin film that inhibits the corrosion process according to a blocking and/or negative catalytic effect. Using the Langmuir-Blodgett (LB) technique, stearic acid (SA) monolayers were deposited onto the surface of an iron (Fe) electrode to study the inhibition effect and the mechanism of SA in a neutral medium. Molecular orientation and the number of deposited monolayers of SA were shown to have marked effects on inhibition of Fe corrosion. The inhibition mechanism depended mainly on blocking.

  13. Electron-beam-induced alteration of the dielectric properties of sandwiched self-assembled organic monolayers

    NASA Astrophysics Data System (ADS)

    Balaur, Eugeniu; Peele, Andrew G.

    2010-04-01

    Electrical transport through octadecyltrichlorosilane self-assembled monolayers sandwiched between a silicon substrate and an aluminum film was altered using electron-beams (e-beams) with different energies and doses. Under certain e-beam conditions, improvement of the dielectric performance was observed compared with the unmodified monolayers. This was ascribed to partial "healing" of the gauche defects within the alkyl chains under the electron flux. It was also possible to vary the barrier height between 2 and 2.35 eV, an effect attributed to the creation of amorphous carbon under prolonged exposure times. Factors that influenced these effects were identified and discussed.

  14. Preparation, characterization, and photoelectric properties of a covalently self-assembled monolayer of ferrocenyl hemicyanine.

    PubMed

    Li, Lin-Ying; Chen, Xi; Xu, Meng-Yun; Zhang, Qian-Jin; Wang, Ke-Zhi

    2011-11-01

    A monolayer of a ferrocenyl hemicyanine was covalently self-assembled on an indium tin oxide (ITO)-coated glass substrate, and was characterized by UV/Vis absorption and X-ray photoelectron spectroscopy, and cyclic voltammetry. The photoelectrochemical properties and mechanism of photocurrent generation have also been studied. This monolayer film was found to exhibit a large anodic photocurrent density of 0.13 microA/cm2 with the highest photoelectric yield of 3.32% under irradiation of white light (730 nm > lambda > 325 nm) at a bias potential of +0.4 V versus saturated calomel electrode.

  15. Binary functionalization of H:Si(111) surfaces by alkyl monolayers with different linker atoms enhances monolayer stability and packing.

    PubMed

    Arefi, Hadi H; Nolan, Michael; Fagas, Giorgos

    2016-05-14

    Alkyl monolayer modified Si forms a class of inorganic-organic hybrid materials with applications across many technologies such as thin-films, fuel/solar-cells and biosensors. Previous studies have shown that the linker atom, through which the monolayer binds to the Si substrate, and any tail group in the alkyl chain, can tune the monolayer stability and electronic properties. In this paper we study the H:Si(111) surface functionalized with binary SAMs: these are composed of alkyl chains that are linked to the surface by two different linker groups. Aiming to enhance SAM stability and increase coverage over singly functionalized Si, we examine with density functional theory simulations that incorporate vdW interactions, a range of linker groups which we denote as -X-(alkyl) with X = CH2, O(H), S(H) or NH(2) (alkyl = C6 and C12 chains). We show how the stability of the SAM can be enhanced by adsorbing alkyl chains with two different linkers, e.g. Si-[C, NH]-alkyl, through which the adsorption energy is increased compared to functionalization with the individual -X-alkyl chains. Our results show that it is possible to improve stability and optimum coverage of alkyl functionalized SAMs linked through a direct Si-C bond by incorporating alkyl chains linked to Si through a different linker group, while preserving the interface electronic structure that determines key electronic properties. This is important since any enhancement in stability and coverage to give more densely packed monolayers will result in fewer defects. We also show that the work function can be tuned within the interval of 3.65-4.94 eV (4.55 eV for bare H:Si(111)).

  16. Photocatalytic Nanolithography of Self-Assembled Monolayers and Proteins

    PubMed Central

    2013-01-01

    Self-assembled monolayers of alkylthiolates on gold and alkylsilanes on silicon dioxide have been patterned photocatalytically on sub-100 nm length-scales using both apertured near-field and apertureless methods. Apertured lithography was carried out by means of an argon ion laser (364 nm) coupled to cantilever-type near-field probes with a thin film of titania deposited over the aperture. Apertureless lithography was carried out with a helium–cadmium laser (325 nm) to excite titanium-coated, contact-mode atomic force microscope (AFM) probes. This latter approach is readily implementable on any commercial AFM system. Photodegradation occurred in both cases through the localized photocatalytic degradation of the monolayer. For alkanethiols, degradation of one thiol exposed the bare substrate, enabling refunctionalization of the bare gold by a second, contrasting thiol. For alkylsilanes, degradation of the adsorbate molecule provided a facile means for protein patterning. Lines were written in a protein-resistant film formed by the adsorption of oligo(ethylene glycol)-functionalized trichlorosilanes on glass, leading to the formation of sub-100 nm adhesive, aldehyde-functionalized regions. These were derivatized with aminobutylnitrilotriacetic acid, and complexed with Ni2+, enabling the binding of histidine-labeled green fluorescent protein, which yielded bright fluorescence from 70-nm-wide lines that could be imaged clearly in a confocal microscope. PMID:23971891

  17. Computational study of low-friction quasicrystalline coatings via simulations of thin film growth of hydrocarbons and rare gases

    NASA Astrophysics Data System (ADS)

    Setyawan, Wahyu

    Quasicrystalline compounds (QC) have been shown to have lower friction compared to other structures of the same constituents. The abscence of structural interlocking when two QC surfaces slide against one another yields the low friction. To use QC as low-friction coatings in combustion engines where hydrocarbon-based oil lubricant is commonly used, knowledge of how a film of lubricant forms on the coating is required. Any adsorbed films having non-quasicrystalline structure will reduce the self-lubricity of the coatings. In this manuscript, we report the results of simulations on thin films growth of selected hydrocarbons and rare gases on a decagonal Al73Ni10Co17 quasicrystal (d-AlNiCo). Grand canonical Monte Carlo method is used to perform the simulations. We develop a set of classical interatomic many-body potentials which are based on the embedded-atom method to study the adsorption processes for hydrocarbons. Methane, propane, hexane, octane, and benzene are simulated and show complete wetting and layered films. Methane monolayer forms a pentagonal order commensurate with the d-AlNiCo. Propane forms disordered monolayer. Hexane and octane adsorb in a close-packed manner consistent with their bulk structure. The results of hexane and octane are expected to represent those of longer alkanes which constitute typical lubricants. Benzene monolayer has pentagonal order at low temperatures which transforms into triangular lattice at high temperatures. The effects of size mismatch and relative strength of the competing interactions (adsorbate-substrate and between adsorbates) on the film growth and structure are systematically studied using rare gases with Lennard-Jones pair potentials. It is found that the relative strength of the interactions determines the growth mode, while the structure of the film is affected mostly by the size mismatch between adsorbate and substrate's characteristic length. On d-AlNiCo, xenon monolayer undergoes a first-order structural

  18. Stilling Waves with Ordered Molecular Monolayers

    ERIC Educational Resources Information Center

    Vitz, Ed

    2008-01-01

    A demonstration of the damping effect of an oil monolayer on water waves is described. The history of this remarkable demonstration--with a 2000 (or more) year span--and a brief explanation in terms of the properties of water and the monolayer are presented. If a layer of olive oil, one molecule thick (about one-ten millionth of a centimeter), is…

  19. Mechanism of Pb Adsorption to Fatty Acid Langmuir Monolayers Studied by X-ray Absorption Fine Structure Spectroscopy

    SciTech Connect

    Boyanov, M.I.; Kmetko, J.; Shibata, T.; Datta, A.; Dutta, P.; Bunker, B.A.

    2010-09-30

    The local atomic environment of lead (Pb) adsorbed to a CH{sub 3}(CH{sub 2}){sub 19}COOH Langmuir monolayer was investigated in situ using grazing-incidence X-ray absorption fine structure (GI-XAFS) spectroscopy at the Pb L{sub III} edge. Measurements were performed at pH 6.5 of the 10{sup -5} M PbCl{sub 2} solution subphase, a condition under which grazing incidence diffraction (GID) revealed a large-area commensurate superstructure underneath the close-packed organic monolayer. The XAFS results indicate covalent binding of the Pb cations to the carboxyl headgroups, and the observed Pb-Pb coordination suggests that the metal is adsorbed as a hydrolysis polymer, rather than as individual Pb{sup 2+} ions. The data are consistent with a bidentate chelating mechanism and a one Pb atom to one carboxyl headgroup binding stoichiometry. We discuss how this adsorption model can explain the peculiarities observed with Pb in previous metal-Langmuir monolayer studies. A systematic study of lead perchlorate and lead acetate aqueous solutions is presented and used in the analysis. XAFS multiple scattering effects from alignment of the Pb-C-C atoms in the lead acetate solutions are reported.

  20. Pulmonary surfactant proteins SP-B and SP-C in spread monolayers at the air-water interface: I. Monolayers of pulmonary surfactant protein SP-B and phospholipids.

    PubMed Central

    Taneva, S; Keough, K M

    1994-01-01

    The effects of pulmonary surfactant protein SP-B on the properties of monolayers of dipalmitoylphosphatidylcholine (DPPC) and dipalmitoylphosphatidylglycerol (DPPG), and a mixture of DPPC:DPPG (7:3, mol:mol) were studied using spread films at the air-water interface. The addition of SP-B to the phospholipid monolayers gave positive deviations from additivity of the mean areas in the films. At low protein concentrations (less than 45% amino acid residues which corresponds to 0.5 mol% or 10 weight% SP-B) monolayers of SP-B/DPPC, SP-B/DPPG and SP-B/(DPPC:DPPG) collapsed at surface pressures of about 70 mN.m-1, comparable to those of the lipids alone. At higher concentrations of SP-B in the protein-lipid monolayers, kink points appeared in the isotherms at about 40-45 mN.m-1, implying possible exclusion of material from the films, hence, changes in the original monolayer compositions. Calculated analyses of the monolayer compositions as a function of surface pressure indicated that nearly pure SP-B, associated with small amounts of phospholipid (2-3 lipid molecules per SP-B dimer), was lost from SP-B/DPPC, SP-B/DPPG, and SP-B/(DPPC:DPPG) films at surface pressures higher than 40-45 mN.m-1. The results are consistent with a low effectiveness of SP-B in removing saturated phospholipids, DPPC or DPPG, from the spread SP-B/phospholipid films. PMID:8038385

  1. Evolution of the commensurate and incommensurate magnetic phases of the S = 3/2 kagome staircase Co3V2O8 in an applied field

    NASA Astrophysics Data System (ADS)

    Helton, Joel S.; Chen, Ying; Bychkov, Georgii L.; Barilo, Sergei N.; Rogado, Nyrissa; Cava, Robert J.; Lynn, Jeffrey W.

    2012-01-01

    Single crystal neutron diffraction studies have been performed on the S = 3/2 kagome staircase compound Co3V2O8 with a magnetic field applied along the magnetization easy-axis (\\vec{H}\\Vert \\vec{a}). Previous zero-field measurements (Chen Y et al 2006 Phys. Rev. B 74 014430) reported a rich variety of magnetic phases, with a ferromagnetic ground state as well as incommensurate, transversely polarized spin density wave (SDW) phases (with a propagation vector of \\vec{k}=(0~\\delta ~0)) interspersed with multiple commensurate lock-in transitions. The magnetic phase diagram with \\vec{H}\\Vert \\vec{a} adds further complexity. For small applied fields, μ0H ≈ 0.05 T, the commensurate lock-in phases are destabilized in favor of the incommensurate SDW ones, while slightly larger applied fields restore the commensurate lock-in phase with δ = 1/2 and yield a new commensurate phase with δ = 2/5. For measurements in an applied field, higher-order scattering is observed that corresponds to the second harmonic.

  2. ALD resist formed by vapor-deposited self-assembled monolayers.

    PubMed

    Hong, Junsic; Porter, David W; Sreenivasan, Raghavasimhan; McIntyre, Paul C; Bent, Stacey F

    2007-01-30

    A new process of applying molecular resists to block HfO2 and Pt atomic layer deposition has been investigated. Monolayer films are formed from octadecyltrichlorosilane (ODTS) or tridecafluoro-1,1,2,2-tetrahydrooctyltrichlorosilane (FOTS) and water vapor on native silicon oxide surfaces and from 1-octadecene on hydrogen-passivated silicon surfaces through a low-pressure chemical vapor deposition process. X-ray photoelectron spectroscopy data indicates that surfaces blocked by these monolayer resists can prevent atomic layer deposition of both HfO2 and Pt successfully. Time-dependent studies show that the ODTS monolayers continue to improve in blocking ability for as long as 48 h of formation time, and infrared spectroscopy measurements confirm an evolution of packing order over these time scales.

  3. 2D attenuated total reflectance infrared spectroscopy reveals ultrafast vibrational dynamics of organic monolayers at metal-liquid interfaces

    NASA Astrophysics Data System (ADS)

    Kraack, Jan Philip; Lotti, Davide; Hamm, Peter

    2015-06-01

    We present two-dimensional infrared (2D IR) spectra of organic monolayers immobilized on thin metallic films at the solid liquid interface. The experiments are acquired under Attenuated Total Reflectance (ATR) conditions which allow a surface-sensitive measurement of spectral diffusion, sample inhomogeneity, and vibrational relaxation of the monolayers. Terminal azide functional groups are used as local probes of the environment and structural dynamics of the samples. Specifically, we investigate the influence of different alkyl chain-lengths on the ultrafast dynamics of the monolayer, revealing a smaller initial inhomogeneity and faster spectral diffusion with increasing chain-length. Furthermore, by varying the environment (i.e., in different solvents or as bare sample), we conclude that the most significant contribution to spectral diffusion stems from intra- and intermolecular dynamics within the monolayer. The obtained results demonstrate that 2D ATR IR spectroscopy is a versatile tool for measuring interfacial dynamics of adsorbed molecules.

  4. 2D attenuated total reflectance infrared spectroscopy reveals ultrafast vibrational dynamics of organic monolayers at metal-liquid interfaces.

    PubMed

    Kraack, Jan Philip; Lotti, Davide; Hamm, Peter

    2015-06-01

    We present two-dimensional infrared (2D IR) spectra of organic monolayers immobilized on thin metallic films at the solid liquid interface. The experiments are acquired under Attenuated Total Reflectance (ATR) conditions which allow a surface-sensitive measurement of spectral diffusion, sample inhomogeneity, and vibrational relaxation of the monolayers. Terminal azide functional groups are used as local probes of the environment and structural dynamics of the samples. Specifically, we investigate the influence of different alkyl chain-lengths on the ultrafast dynamics of the monolayer, revealing a smaller initial inhomogeneity and faster spectral diffusion with increasing chain-length. Furthermore, by varying the environment (i.e., in different solvents or as bare sample), we conclude that the most significant contribution to spectral diffusion stems from intra- and intermolecular dynamics within the monolayer. The obtained results demonstrate that 2D ATR IR spectroscopy is a versatile tool for measuring interfacial dynamics of adsorbed molecules.

  5. Direct Structural Identification of Gas Induced Gate-Opening Coupled with Commensurate Adsorption in a Microporous Metal-Organic Framework.

    PubMed

    Banerjee, Debasis; Wang, Hao; Plonka, Anna M; Emge, Thomas J; Parise, John B; Li, Jing

    2016-08-01

    Gate-opening is a unique and interesting phenomenon commonly observed in flexible porous frameworks, where the pore characteristics and/or crystal structures change in response to external stimuli such as adding or removing guest molecules. For gate-opening that is induced by gas adsorption, the pore-opening pressure often varies for different adsorbate molecules and, thus, can be applied to selectively separate a gas mixture. The detailed understanding of this phenomenon is of fundamental importance to the design of industrially applicable gas-selective sorbents, which remains under investigated due to the lack of direct structural evidence for such systems. We report a mechanistic study of gas-induced gate-opening process of a microporous metal-organic framework, [Mn(ina)2 ] (ina=isonicotinate) associated with commensurate adsorption, by a combination of several analytical techniques including single crystal X-ray diffraction, in situ powder X-ray diffraction coupled with differential scanning calorimetry (XRD-DSC), and gas adsorption-desorption methods. Our study reveals that the pronounced and reversible gate opening/closing phenomena observed in [Mn(ina)2 ] are coupled with a structural transition that involves rotation of the organic linker molecules as a result of interaction of the framework with adsorbed gas molecules including carbon dioxide and propane. The onset pressure to open the gate correlates with the extent of such interaction.

  6. Commensurate magnetic structures of RMn2O5 (R=Y,Ho,Bi) determined by single-crystal neutron diffraction

    NASA Astrophysics Data System (ADS)

    Vecchini, C.; Chapon, L. C.; Brown, P. J.; Chatterji, T.; Park, S.; Cheong, S.-W.; Radaelli, P. G.

    2008-04-01

    Precise magnetic structures of RMn2O5 , with R=Y,Ho,Bi in the commensurate and/or ferroelectric regime, have been determined by single-crystal neutron diffraction. For each system, the integrated intensities of a large number of independent magnetic Bragg reflections have been measured, allowing unconstrained least-squares refinement of the structures. The analysis confirms the previously reported magnetic configuration in the ab plane, in particular, the existence of zigzag antiferromagnetic chains. For the Y and Ho compounds, additional weak magnetic components parallel to the c axis were detected, which are modulated in phase quadrature with the a-b components. This component is extremely small in the BiMn2O5 sample, therefore supporting symmetric exchange as the principal mechanism inducing ferroelectricity. For HoMn2O5 , a magnetic ordering of the Ho moments was observed, which is consistent with a superexchange interaction through the oxygens. For all three compounds, the point symmetry in the magnetically ordered state is m2m , allowing the polar b axis found experimentally.

  7. Large-area synthesis of high-quality and uniform monolayer WS2 on reusable Au foils

    PubMed Central

    Gao, Yang; Liu, Zhibo; Sun, Dong-Ming; Huang, Le; Ma, Lai-Peng; Yin, Li-Chang; Ma, Teng; Zhang, Zhiyong; Ma, Xiu-Liang; Peng, Lian-Mao; Cheng, Hui-Ming; Ren, Wencai

    2015-01-01

    Large-area monolayer WS2 is a desirable material for applications in next-generation electronics and optoelectronics. However, the chemical vapour deposition (CVD) with rigid and inert substrates for large-area sample growth suffers from a non-uniform number of layers, small domain size and many defects, and is not compatible with the fabrication process of flexible devices. Here we report the self-limited catalytic surface growth of uniform monolayer WS2 single crystals of millimetre size and large-area films by ambient-pressure CVD on Au. The weak interaction between the WS2 and Au enables the intact transfer of the monolayers to arbitrary substrates using the electrochemical bubbling method without sacrificing Au. The WS2 shows high crystal quality and optical and electrical properties comparable or superior to mechanically exfoliated samples. We also demonstrate the roll-to-roll/bubbling production of large-area flexible films of uniform monolayer, double-layer WS2 and WS2/graphene heterostructures, and batch fabrication of large-area flexible monolayer WS2 film transistor arrays. PMID:26450174

  8. Large-area synthesis of high-quality and uniform monolayer WS2 on reusable Au foils

    NASA Astrophysics Data System (ADS)

    Gao, Yang; Liu, Zhibo; Sun, Dong-Ming; Huang, Le; Ma, Lai-Peng; Yin, Li-Chang; Ma, Teng; Zhang, Zhiyong; Ma, Xiu-Liang; Peng, Lian-Mao; Cheng, Hui-Ming; Ren, Wencai

    2015-10-01

    Large-area monolayer WS2 is a desirable material for applications in next-generation electronics and optoelectronics. However, the chemical vapour deposition (CVD) with rigid and inert substrates for large-area sample growth suffers from a non-uniform number of layers, small domain size and many defects, and is not compatible with the fabrication process of flexible devices. Here we report the self-limited catalytic surface growth of uniform monolayer WS2 single crystals of millimetre size and large-area films by ambient-pressure CVD on Au. The weak interaction between the WS2 and Au enables the intact transfer of the monolayers to arbitrary substrates using the electrochemical bubbling method without sacrificing Au. The WS2 shows high crystal quality and optical and electrical properties comparable or superior to mechanically exfoliated samples. We also demonstrate the roll-to-roll/bubbling production of large-area flexible films of uniform monolayer, double-layer WS2 and WS2/graphene heterostructures, and batch fabrication of large-area flexible monolayer WS2 film transistor arrays.

  9. Coadsorption of ferrocene-terminated and unsubstituted alkanethiols on gold: Electroactive self-assembled monolayers

    SciTech Connect

    Chidsey, C.E.D.; Bertozzi, C.R.; Putvinski, T.M.; Mujsce, A.M. )

    1990-05-23

    Self-assembled monolayers provide an ideal system for disentangling the fundamental events in interfacial electron transfer. Coadsorption of ferrocene-terminated alkanethiols with unsubstituted n-alkanethiols on evaporated gold films yields stable, electroactive self-assembled monolayers. Monolayers containing low concentrations of alkanethiols linked to ferrocene by a polar ester group (FcCO{sub 2}(CH{sub 2}){sub n}SH, Fc = ({eta}{sup 5}-C{sub 5}H{sub 5})Fe({eta}{sup 5}-C{sub 5}H{sub 4})) show thermodynamically ideal surface electrochemistry in 1 M HClO{sub 4}, indicating the ferrocene groups to be homogeneous and noninteracting. Higher surface concentrations or use of alkanethiols linked directly to the nonpolar ferrocene group (Fc(CH{sub 2}){sub n}SH) lead to broadened electrochemical features, indicating interactions among ferrocene groups or inhomogeneous sites. Longer chain lengths and lower ferrocene surface concentrations result in slower electron-transfer kinetics with the ferrocene groups. A fraction of the thiols in a monolayer exchange with thiols in an ethanol solution, but much of the monolayer remains unequilibrated after 10 days.

  10. Assembling and compressing a semifluorinated alkane monolayer on a hydrophobic surface: Structural and dielectric properties

    SciTech Connect

    El Abed, Abdel I.; Ionov, Radoslav; Daoud, Mohamed; Abillon, Olivier

    2004-11-01

    We investigate the dynamic behavior upon lateral compression of a semifluorinated alkane F(CF{sub 2}){sub 8}(CH{sub 2}){sub 18}H (denoted F{sub 8}H{sub 18}), spread on the hydrophobic top of a suitable amphiphilic monolayer: namely, a natural {alpha}-helix alamethicin peptide (alam). We show, in particular, the formation of an asymmetric flat bilayer by compressing at the air-water interface a mixed Langmuir film made of F{sub 8}H{sub 18} and alam. The particular chemical structure of F{sub 8}H{sub 18}, the suitable structure of the underlying alam monolayer and its collapse properties, allow for a continuous compression of the upper F{sub 8}H{sub 18} monolayer while the density of the lower alam monolayer remains constant. Combining grazing incidence x-ray reflectivity, surface potential, and atomic force microscopy data allow for the determination of the orientation and dielectric constant of the upper F{sub 8}H{sub 18} monolayer.

  11. Film Balance Studies of Membrane Lipids and Related Molecules

    ERIC Educational Resources Information Center

    Cadenhead, D. A.

    1972-01-01

    Discusses apparatus, techniques, and measurements used to determine cell membrane composition. The use of a film balance to study monolayer membranes of selected lipids is described and results reported. (TS)

  12. Structural prediction for scandium carbide monolayer sheet

    NASA Astrophysics Data System (ADS)

    Ma, Hong-Man; Wang, Jing; Zhao, Hui-Yan; Zhang, Dong-Bo; Liu, Ying

    2016-09-01

    A two-dimensional tetragonal scandium carbide monolayer sheet has been constructed and studied using density functional theory. The results show that the scandium carbide sheet is stable and exhibits a novel tetracoordinated quasiplanar structure, as favored by the hybridization between Sc-3d orbitals and C-2p orbitals. Calculations of the phonon dispersion as well as molecular dynamics simulations also demonstrate the structural stability of this scandium carbide monolayer sheet. Electronic properties show that the scandium carbide monolayer sheet is metallic and non-magnetic.

  13. Drug induced `softening' in phospholipid monolayers

    NASA Astrophysics Data System (ADS)

    Basak, Uttam Kumar; Datta, Alokmay; Bhattacharya, Dhananjay

    2015-06-01

    Compressibility measurements on Langmuir monolayers of the phospholipid Dimystoryl Phospatidylcholine (DMPC) in pristine form and in the presence of the Non-steroidal Anti-inflammatory Drug (NSAID) Piroxicam at 0.025 drug/lipid (D/L) molecular ratio at different temperatures, show that the monolayer exhibits large increase (and subsequent decrease) in compressibility due to the drug in the vicinity of the Liquid Expanded - Liquid Condensed (LE-LC) phase transition. Molecular dynamics simulations of the lipid monolayer in presence of drug molecules show a disordering of the tail tilt, which is consistent with the above result.

  14. Enhancement of resistive switching under confined current path distribution enabled by insertion of atomically thin defective monolayer graphene

    PubMed Central

    Lee, Keundong; Hwang, Inrok; Lee, Sangik; Oh, Sungtaek; Lee, Dukhyun; Kim, Cheol Kyeom; Nam, Yoonseung; Hong, Sahwan; Yoon, Chansoo; Morgan, Robert B.; Kim, Hakseong; Seo, Sunae; Seo, David H.; Lee, Sangwook; Park, Bae Ho

    2015-01-01

    Resistive random access memory (ReRAM) devices have been extensively investigated resulting in significant enhancement of switching properties. However fluctuations in switching parameters are still critical weak points which cause serious failures during ‘reading’ and ‘writing’ operations of ReRAM devices. It is believed that such fluctuations may be originated by random creation and rupture of conducting filaments inside ReRAM oxides. Here, we introduce defective monolayer graphene between an oxide film and an electrode to induce confined current path distribution inside the oxide film, and thus control the creation and rupture of conducting filaments. The ReRAM device with an atomically thin interlayer of defective monolayer graphene reveals much reduced fluctuations in switching parameters compared to a conventional one. Our results demonstrate that defective monolayer graphene paves the way to reliable ReRAM devices operating under confined current path distribution. PMID:26161992

  15. Interlayer correlation between two 4He monolayers adsorbed on both sides of α -graphyne

    NASA Astrophysics Data System (ADS)

    Ahn, Jeonghwan; Park, Sungjin; Lee, Hoonkyung; Kwon, Yongkyung

    2015-07-01

    Path-integral Monte Carlo calculations have been performed to study the 4He adsorption on both sides of a single α -graphyne sheet. For investigation of the interlayer correlation between the upper and the lower monolayers of 4He adatoms, the 4He-substrate interaction is described by the sum of the 4He-C interatomic pair potentials for which we use both Lennard-Jones and Yukawa-6 anisotropic potentials. When the lower 4He layer is a C4 /3 commensurate solid, the upper-layer 4He atoms are found to form a kagome lattice structure at a Mott-insulating density of 0.0706 Å-2 and a commensurate solid at an areal density of 0.0941 Å-2 for both substrate potentials. The correlation between upper- and lower-layer pseudospins, which were introduced in Kwon et al. [Phys. Rev. B 88, 201403(R) (2013)], 10.1103/PhysRevB.88.201403 for two degenerate configurations of three 4He atoms in a hexagonal cell, depends on the substrate potential used; with the substrate potential based on the anisotropic Yukawa-6 pair potentials, the Ising pseudospins of both 4He layers are found to be antiparallel to each other whereas the parallel and antiparallel pseudospin alignments between the two 4He layers are nearly degenerate with the Lennard-Jones potentials. This is attributed to the difference in the interlayer distance, which is ˜4 Å with the Yukawa-6 substrate potential but as large as ˜4.8 Å with the Lennard-Jones potential.

  16. Covalently anchored carboxyphenyl monolayer via aryldiazonium ion grafting: a well-defined reactive tether layer for on-surface chemistry.

    PubMed

    Lee, Lita; Ma, Haifeng; Brooksby, Paula A; Brown, Simon A; Leroux, Yann R; Hapiot, Philippe; Downard, Alison J

    2014-06-24

    Electrografting of aryl films to electrode surfaces from diazonium ion solutions is a widely used method for preparation of modified electrodes. In the absence of deliberate measures to limit film growth, the usual film structure is a loosely packed multilayer. For some applications, monolayer films are advantageous; our interest is in preparing well-defined monolayers of reactive tethers for further on-surface chemistry. Here, we describe the synthesis of an aryl diazonium salt with a protected carboxylic acid substituent. After electrografting to glassy carbon electrodes and subsequent deprotection, the layer is reacted with amine derivatives. Electrochemistry and atomic force microscopy are used to monitor the grafting, deprotection, and subsequent coupling steps. Attempts to follow the same procedures on gold surfaces suggest that the grafted layer is not stable in these reaction conditions. PMID:24874712

  17. Laser-Induced Spallation of Microsphere Monolayers.

    PubMed

    Hiraiwa, Morgan; Stossel, Melicent; Khanolkar, Amey; Wang, Junlan; Boechler, Nicholas

    2016-08-01

    The detachment of a semiordered monolayer of polystyrene microspheres adhered to an aluminum-coated glass substrate is studied using a laser-induced spallation technique. The microsphere-substrate adhesion force is estimated from substrate surface displacement measurements obtained using optical interferometry, and a rigid-body model that accounts for the inertia of the microspheres. The estimated adhesion force is compared with estimates obtained using an adhesive contact model together with interferometric measurements of the out-of-plane microsphere contact resonance, and with estimated work of adhesion values for the polystyrene-aluminum interface. Scanning electron microscope images of detached monolayer regions reveal a unique morphology, namely, partially detached monolayer flakes composed of single hexagonal close packed crystalline domains. This work contributes to the fields of microsphere adhesion and contact dynamics, and demonstrates a unique monolayer delamination morphology. PMID:27409715

  18. Accurate Molecular Dimensions from Stearic Acid Monolayers.

    ERIC Educational Resources Information Center

    Lane, Charles A.; And Others

    1984-01-01

    Discusses modifications in the fatty acid monolayer experiment to reduce the inaccurate moleculary data students usually obtain. Copies of the experimental procedure used and a Pascal computer program to work up the data are available from the authors. (JN)

  19. Multicellular density fluctuations in epithelial monolayers

    NASA Astrophysics Data System (ADS)

    Zehnder, Steven M.; Wiatt, Marina K.; Uruena, Juan M.; Dunn, Alison C.; Sawyer, W. Gregory; Angelini, Thomas E.

    2015-09-01

    Changes in cell size often accompany multicellular motion in tissue, and cell number density is known to strongly influence collective migration in monolayers. Density fluctuations in other forms of active matter have been explored extensively, but not the potential role of density fluctuations in collective cell migration. Here we investigate collective motion in cell monolayers, focusing on the divergent component of the migration velocity field to probe density fluctuations. We find spatial patterns of diverging and converging cell groups throughout the monolayers, which oscillate in time with a period of approximately 3-4 h. Simultaneous fluorescence measurements of a cytosol dye within the cells show that fluid passes between groups of cells, facilitating these oscillations in cell density. Our findings reveal that cell-cell interactions in monolayers may be mediated by intercellular fluid flow.

  20. Nonequilibrium bubbles in a flowing langmuir monolayer.

    PubMed

    Muruganathan, Rm; Khattari, Z; Fischer, Th M

    2005-11-24

    We investigate the nonequilibrium behavior of two-dimensional gas bubbles in Langmuir monolayers. A cavitation bubble is induced in liquid expanded phase by locally heating a Langmuir monolayer with an IR-laser. At low IR-laser power the cavitation bubble is immersed in quiescent liquid expanded monolayer. At higher IR-laser power thermo capillary flow around the laser-induced cavitation bubble sets in. The thermo capillary flow is caused by a temperature dependence of the gas/liquid line tension. The slope of the line tension with temperature is determined by measuring the thermo capillary flow velocity. Thermodynamically stable satellite bubbles are generated by increasing the surface area of the monolayer. Those satellite bubbles collide with the cavitation bubble. Upon collision the satellite bubbles either coalesce with the cavitation bubble or slide past the cavitation bubble. Moreover we show that the satellite bubbles can also be produced by the emission from the laser-induced cavitation bubbles.

  1. Morphology control of perovskite light-emitting diodes by using amino acid self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Wang, Nana; Cheng, Lu; Si, Junjie; Liang, Xiaoyong; Jin, Yizheng; Wang, Jianpu; Huang, Wei

    2016-04-01

    Amino acid self-assembled monolayers are used in the fabrication of light-emitting diodes based on organic-inorganic halide perovskites. The monolayers of amino acids provide modified interfaces by anchoring to the surfaces of ZnO charge-transporting layers using carboxyl groups, leaving the amino groups to facilitate the nucleation of MAPbBr3 perovskite films. This surface-modification strategy, together with chlorobenzene-assisted fast crystallization method, results in good surface coverage and reduced defect density of the perovskite films. These efforts lead to green perovskite light emitting diodes with a low turn-on voltage of 2 V and an external quantum efficiency of 0.43% at a brightness of ˜5000 cd m-2.

  2. Understanding the collapse mechanism in Langmuir monolayers through polarization modulation-infrared reflection absorption spectroscopy.

    PubMed

    Goto, Thiago Eichi; Caseli, Luciano

    2013-07-23

    The collapse of films at the air-water interface is related to a type of 2D-to-3D transition that occurs when a Langmuir monolayer is compressed beyond its stability limit. Studies on this issue are extremely important because defects in ultrathin solid films can be better understood if the molecular mechanisms related to collapse processes are elucidated. This paper explores how the changes of vibration of specific groups of lipid molecules, as revealed by polarization modulation-infrared reflection absorption spectroscopy (PM-IRRAS), are affected by the monolayer collapse. Different mechanisms of collapse were studied, for those lipids that undergo constant-area collapse (such as stearic acid) and for those that undergo constant-pressure collapse (such as DPPC, DPPG, and DODAB). Lipid charges also affect the mechanism of collapse, as demonstrated for two oppositely charged lipids.

  3. Conversion of linear time-invariant time-delay feedback systems into delay-differential equations with commensurate delays

    NASA Astrophysics Data System (ADS)

    Yamazaki, Tatsuya; Hagiwara, Tomomichi

    2014-08-01

    A new stability analysis method of time-delay systems (TDSs) called the monodromy operator approach has been studied under the assumption that a TDS is represented as a time-delay feedback system consisting of a finite-dimensional linear time-invariant (LTI) system and a pure delay. For applying this approach to TDSs described by delay-differential equations (DDEs), the problem of converting DDEs into representation as time-delay feedback systems has been studied. With regard to such a problem, it was shown that, under discontinuous initial functions, it is natural to define the solutions of DDEs in two different ways, and the above conversion problem was solved for each of these two definitions. More precisely, the solution of a DDE was represented as either the state of the finite-dimensional part of a time-delay feedback system or a part of the output of another time-delay feedback system, depending on which definition of the DDE solution one is talking about. Motivated by the importance in establishing a thorough relationship between time-delay feedback systems and DDEs, this paper discusses the opposite problem of converting time-delay feedback systems into representation as DDEs, including the discussions about the conversion of the initial conditions. We show that the state of (the finite-dimensional part of) a time-delay feedback system can be represented as the solution of a DDE in the sense of one of the two definitions, while its 'essential' output can be represented as that of another DDE in the sense of the other type of definition. Rigorously speaking, however, it is also shown that the latter representation is possible regardless of the initial conditions, while some initial condition could prevent the conversion into the former representation. This study hence establishes that the representation of TDSs as time-delay feedback systems possesses higher ability than that with DDEs, as description methods for LTI TDSs with commensurate delays.

  4. A computer simulation of thin film nucleation and growth: The Volmer-Weber case

    NASA Technical Reports Server (NTRS)

    Salik, J.; Ghose, H. M.

    1985-01-01

    The computer simulation of thin film nucleation and growth, which was previously performed for the case of single monolayer, was modified to include multilayer growth via the Volmer-Weber mechanism. The simulation results show that: (1) the kinetics of multilayer film growth is nearly identical to that of monolayer growth; (2) when no reevaporation takes place, the cluster density resulting from multilayer growth is higher at high coverage than that resulting from monolayer growth; (3) when reevaporation does take place, the cluster density resulting from multilayer growth is nearly identical to that resulting from monolayer growth. This is not due, however, to similarity in microstructure.

  5. Mass spectrometric analysis of monolayer protected nanoparticles

    NASA Astrophysics Data System (ADS)

    Zhu, Zhengjiang

    Monolayer protected nanoparticles (NPs) include an inorganic core and a monolayer of organic ligands. The wide variety of core materials and the tunable surface monolayers make NPs promising materials for numerous applications. Concerns related to unforeseen human health and environmental impacts of NPs have also been raised. In this thesis, new analytical methods based on mass spectrometry are developed to understand the fate, transport, and biodistributions of NPs in the complex biological systems. A laser desorption/ionization mass spectrometry (LDI-MS) method has been developed to characterize the monolayers on NP surface. LDI-MS allows multiple NPs taken up by cells to be measured and quantified in a multiplexed fashion. The correlations between surface properties of NPs and cellular uptake have also been explored. LDI-MS is further coupled with inductively coupled plasma mass spectrometry (ICP-MS) to quantitatively measure monolayer stability of gold NPs (AuNPs) and quantum dots (QDs), respectively, in live cells. This label-free approach allows correlating monolayer structure and particle size with NP stability in various cellular environments. Finally, uptake, distribution, accumulation, and excretion of NPs in higher order organisms, such as fish and plants, have been investigated to understand the environmental impact of nanomaterials. The results indicate that surface chemistry is a primary determinant. NPs with hydrophilic surfaces are substantially less toxic and present a lower degree of bioaccumulation, making these nanomaterials attractive for sustainable nanotechnology.

  6. Monolayers and multilayers of chlorophyll [correction of chlorophyl] a on a mercury electrode.

    PubMed

    Moncelli, M R; Becucci, L; Dolfi, A; Tadini Buoninsegni, F; Agostiano, A

    2002-05-15

    A novel experimental technique used to investigate chlorophyll films on a hanging mercury drop electrode is described. Two different procedures are employed to prepare self-assembled chlorophyll monolayers and multilayers on the mercury electrode. Upon illuminating the chlorophyll a (Chl)-coated mercury electrode with an appropriate light source, the photocurrents generated by the Chl aggregates are measured under short-circuit conditions in the absence of photoartefacts. The preliminary results obtained by this novel technique are presented. PMID:12009465

  7. Protein-Induced Surface Structuring in Myelin Membrane Monolayers

    PubMed Central

    Rosetti, Carla M.; Maggio, Bruno

    2007-01-01

    Monolayers prepared from myelin conserve all the compositional complexity of the natural membrane when spread at the air-water interface. They show a complex pressure-dependent surface pattern that, on compression, changes from the coexistence of two liquid phases to a viscous fractal phase embedded in a liquid phase. We dissected the role of major myelin protein components, myelin basic protein (MBP), and Folch-Lees proteolipid protein (PLP) as crucial factors determining the structural dynamics of the interface. By analyzing mixtures of a single protein with the myelin lipids we found that MBP and PLP have different surface pressure-dependent behaviors. MBP stabilizes the segregation of two liquid phases at low pressures and becomes excluded from the film under compression, remaining adjacent to the interface. PLP, on the contrary, organizes a fractal-like pattern at all surface pressures when included in a monolayer of the protein-free myelin lipids but it remains mixed in the MBP-induced liquid phase. The resultant surface topography and dynamics is regulated by combined near to equilibrium and out-of-equilibrium effects. PLP appears to act as a surface skeleton for the whole components whereas MBP couples the structuring to surface pressure-dependent extrusion and adsorption processes. PMID:17905850

  8. The effect of β-sitosterol on the properties of cholesterol/phosphatidylcholine/ganglioside monolayers--the impact of monolayer fluidity.

    PubMed

    Hąc-Wydro, Katarzyna

    2013-10-01

    In this paper the influence of one of phytosterols, namely β-sitosterol on cholesterol (Chol)/phosphatidylcholine (PC)/ganglioside (GM3) monolayers was examined to find the correlation between the properties of model system and the effect of phytocompound. The studied monolayers differed in condensation and fluidity, which were modified by the structure of phosphatidylcholine. It was found that the incorporation of β-sitosterol into cholesterol/phosphatidylcholine/ganglioside films changes their morphology, condensation and interactions between the lipids. The substitution of cholesterol more strongly decreased the condensation and stability of the film containing PC molecules having monounsaturated chains than more densely packed monolayer composed of saturated phosphatidylcholine. However, thorough analysis of data obtained so far suggests that the magnitude of β-sitosterol effect is determined by the composition of the system rather than its fluidity itself. Moreover, the results collected herein correlate well with the findings that phytosterol more strongly inhibits the growth of cancer cells, which at a given proportion of cholesterol to phospholipids in membranes, have more unsaturated fatty acids within phospholipids molecules.

  9. Effects of irradiated biodegradable polymer in endothelial cell monolayer formation

    NASA Astrophysics Data System (ADS)

    Arbeitman, Claudia R.; del Grosso, Mariela F.; Behar, Moni; García Bermúdez, Gerardo

    2013-11-01

    In this work we study cell adhesion, proliferation and cell morphology of endothelial cell cultured on poly-L-lactide acid (PLLA) modified by heavy ion irradiation. Thin films of PLLA samples were irradiated with sulfur (S) at energies of 75 MeV and gold (Au) at 18 MeV ion-beams. Ion beams were provided by the Tandar (Buenos Aires, Argentina) and Tandetron (Porto Alegre, Brazil) accelerators, respectively. The growth of a monolayer of bovine aortic endothelial cells (BAEC) onto unirradiated and irradiated surfaces has been studied by in vitro techniques in static culture. Cell viability and proliferation increased on modified substrates. But the results on unirradiated samples, indicate cell death (necrosis/apoptosis) with the consequent decrease in proliferation. We analyzed the correlation between irradiation parameters and cell metabolism and morphology.

  10. Tuning the trion photoluminescence polarization in monolayer WS2

    NASA Astrophysics Data System (ADS)

    Hanbicki, A. T.; McCreary, K. M.; Currie, M.; Kioseoglou, G.; Hellberg, C. S.; Friedman, A. L.; Jonker, B. T.

    Monolayer transition metal dichalcogenides (TMDs) such as MoS2 or WS2 are semiconductors with degenerate, yet inequivalent k-points labeled K and K' that define the direct gap. The valence band maximum in each valley has only one spin state of opposite sense for K and K'. Consequently, one can selectively populate each valley independently with circularly polarized light, and determine the valley populations via the polarization of emitted light. Optical emission is dominated by neutral and charged exciton (trion) features, and changes in emitted polarization provide insight into the fundamental processes of intervalley scattering. We prepare single-layer WS2 films such that the photoluminescence is from the negatively charged trion and observe a room temperature optical polarization in excess of 40 This work was supported by core programs at NRL and the NRL Nanoscience Institute, and by the Air Force Office of Scientific Research #AOARD 14IOA018-134141.

  11. Crossbar nanoarchitectonics of the crosslinked self-assembled monolayer

    PubMed Central

    2014-01-01

    A bottom-up approach was devised to build a crossbar device using the crosslinked SAM of the 5,5′-bis (mercaptomethyl)-2,2′-bipyridine-Ni2+ (BPD- Ni2+) on a gold surface. To avoid metal diffusion through the organic film, the author used (i) nanoscale bottom electrodes to reduce the probability of defects on the bottom electrodes and (ii) molecular crosslinked technology to avoid metal diffusion through the SAMs. The properties of the crosslinked self-assembled monolayer were determined by XPS. I-V characteristics of the device show thermally activated hopping transport. The implementation of this type of architecture will open up new vistas for a new class of devices for transport, storage, and computing. PMID:24994952

  12. Determination of preferential molecular orientation in porphyrin-fullerene dyad ZnDHD6ee monolayers by the X-ray standing-wave method and X-ray reflectometry

    SciTech Connect

    Seregin, A. Yu. D'yakova, Yu. A.; Yakunin, S. N.; Makhotkin, I. A.; Alekseev, A. S.; Klechkovskaya, V. V.; Tereschenko, E. Yu.; Tkachenko, N. V.; Lemmetyinen, H.; Feigin, L. A.; Kovalchuk, M. V.

    2013-11-15

    Monolayers of porphyrin-fullerene dyad molecules with zinc atoms incorporated into the porphyrin ring (ZnDHD6ee) on the surface of aqueous subphase and on Si substrates have been investigated by the X-ray standing-wave method and X-ray reflectometry. The experiments have been performed under laboratory conditions and on synchrotron radiation sources (KMC-2 station of BESSY II (Berlin) and Langmuir station at the National Research Centre 'Kurchatov Institute'). Depth distributions of Zn atoms and electron density in the monolayer film are calculated. On the basis of the analysis of these distributions, it is concluded that ZnDHD6ee dyad molecules in monolayers have preferential orientation. The data obtained indicate that the molecules in monolayer film retain their orientation when the monolayer is transferred from a liquid subphase surface onto a solid substrate.

  13. Nanoscale dynamics and protein adhesivity of alkylamine self-assembled monolayers on graphene.

    PubMed

    O'Mahony, S; O'Dwyer, C; Nijhuis, C A; Greer, J C; Quinn, A J; Thompson, D

    2013-06-18

    Atomic-scale molecular dynamics computer simulations are used to probe the structure, dynamics, and energetics of alkylamine self-assembled monolayer (SAM) films on graphene and to model the formation of molecular bilayers and protein complexes on the films. Routes toward the development and exploitation of functionalized graphene structures are detailed here, and we show that the SAM architecture can be tailored for use in emerging applications (e.g., electrically stimulated nerve fiber growth via the targeted binding of specific cell surface peptide sequences on the functionalized graphene scaffold). The simulations quantify the changes in film physisorption on graphene and the alkyl chain packing efficiency as the film surface is made more polar by changing the terminal groups from methyl (-CH3) to amine (-NH2) to hydroxyl (-OH). The mode of molecule packing dictates the orientation and spacing between terminal groups on the surface of the SAM, which determines the way in which successive layers build up on the surface, whether via the formation of bilayers of the molecule or the immobilization of other (macro)molecules (e.g., proteins) on the SAM. The simulations show the formation of ordered, stable assemblies of monolayers and bilayers of decylamine-based molecules on graphene. These films can serve as protein adsorption platforms, with a hydrophobin protein showing strong and selective adsorption by binding via its hydrophobic patch to methyl-terminated films and binding to amine-terminated films using its more hydrophilic surface regions. Design rules obtained from modeling the atomic-scale structure of the films and interfaces may provide input into experiments for the rational design of assemblies in which the electronic, physicochemical, and mechanical properties of the substrate, film, and protein layer can be tuned to provide the desired functionality.

  14. Atomic force microscopy study of the adsorption of protein molecules on transferred Langmuir monolayer

    SciTech Connect

    Gainutdinov, R. V. Tolstikhina, A. L.; Stepina, N. D.; Novikova, N. N.; Yur'eva, E. A.; Khripunov, A. K.

    2010-09-15

    Ordered protein films have been obtained by the adsorption of protein molecules on a Langmuir monolayer, which had previously formed on a silicon substrate, using the Langmuir-Blodgett and molecular self-organization methods. A mixture of cholesterol with dipalmitoylphosphatidylcholine (DPPC) and a polymer-cellulose acetopivalinate-were used as immobilization materials. Protein molecules (catalase and alkaline phosphatase) immobilized on solid substrates have been investigated by atomic force micros-copy. It was shown that the developed combined technique provides a deposition of homogeneous ultrathin protein films with a high degree of filling.

  15. Enhanced near-field heat flow of a monolayer dielectric island.

    PubMed

    Worbes, Ludwig; Hellmann, David; Kittel, Achim

    2013-03-29

    We have investigated the influence of thin films of a dielectric material on the near-field mediated heat transfer at the fundamental limit of single monolayer islands on a metallic substrate. We present spatially resolved measurements by near-field scanning thermal microscopy showing a distinct enhancement in heat transfer above NaCl islands compared to the bare Au(111) film. Experiments at this subnanometer scale call for a microscopic theory beyond the macroscopic fluctuational electrodynamics used to describe near-field heat transfer today. The method facilitates the possibility of developing designs of nanostructured surfaces with respect to specific requirements in heat transfer down to a single atomic layer.

  16. Attenuated total reflection surface-enhanced infrared absorption spectroscopy of carboxyl terminated self-assembled monolayers on gold.

    PubMed

    Goutev, Nikolay; Futamata, Masayuki

    2003-05-01

    A new recipe for surface-enhanced infrared absorption (SEIRA) active island Au films with improved adhesion in aqueous solution, low resistivity, and enhancement of the infrared (IR) absorption of about 300 was developed. The Au films prepared were utilized in studies of the ionization of self-assembled monolayers of 11-mercaptoundecanoic acid in Na2SO4 aqueous solutions by attenuated total reflection surface-enhanced infrared absorption (ATR-SEIRA) spectroscopy. It was found that the carboxyl end groups of the self-assembled monolayer turn into carboxylate anions on going from anodic to cathodic potentials or from acidic to alkaline pH. The water molecules close to the self-assembled monolayer in acidic solutions or at anodic potentials are preferentially aligned with their dipole moments parallel to the interface. This type of alignment can be ascribed to the dipole-dipole interaction between the carboxyl groups and the water molecules. On the other hand, in alkaline solutions or at cathodic potentials the structure of water close to the self-assembled monolayer is essentially bulk-like, with randomly oriented water molecules. This observation suggests that in alkaline solutions or at cathodic potentials the charge of the carboxylate anions is almost completely compensated for by strongly adsorbed counter cations. As a result, the electric field close to the surface of the ionized self-assembled monolayer is weak and has little influence on the orientation and hydrogen bonding of the water molecules.

  17. Dynamics driven by lipophilic force in Langmuir monolayers: In-plane and out-of-plane growth

    NASA Astrophysics Data System (ADS)

    Basak, Uttam Kumar; Datta, Alokmay

    2015-04-01

    While monolayer area fraction versus time (An-t ) curves obtained from surface pressure-area (π -A ) isotherms for desorption-dominated (DD) processes in Langmuir monolayers of fatty acids represent continuous loss, those from Brewster angle microscopy (BAM) also show a two-dimensional (2D) coalescence. For nucleation-dominated (ND) processes both techniques suggest competing processes, with BAM showing 2D coalescence alongside multilayer formation. π enhances both DD and ND processes with a lower cutoff for ND processes, while temperature has a lower cutoff for DD but negligible effect on ND processes. Hydrocarbon chain length has the strongest effect, causing a crossover from DD to ND dynamics. Imaging ellipsometry of horizontally transferred films onto Si(100) shows Stranski-Krastanov-like growth for ND process in an arachidic acid monolayer resulting in successive stages of monolayer, trilayer, and multilayer islands, ridges from lateral island coalescence, and shallow wavelike structures from ridge coalescence on the film surface. These studies show that lipophilic attraction between hydrocarbon chains is the driving force at all stages of long-term monolayer dynamics.

  18. Phase diagram of mixed monolayers of stearic acid and dimyristoylphosphatidylcholine. Effect of the acid ionization.

    PubMed

    Mercado, Franco Vega; Maggio, Bruno; Wilke, Natalia

    2011-07-01

    The aim of this work is to study the phase diagram of mixed monolayers composed of dimyristoylphosphatidylcholine (DMPC) and stearic acid (SA) at different ionic strength and bulk pH of the aqueous subphase. In this way, the effect of ionization of SA on the interaction and thus on phase separation with the DMPC matrix can be analyzed. To this purpose, we first determined the ionization state of pure SA monolayers as a function of the bulk subphase pH. The SA monolayers are nearly fully ionized at pH 10 and essentially neutral at pH 4 and the mixture of DMPC and SA was studied at those two pHs. We found that the DMPC-enriched phase admits more SA if the SA monolayer is in a liquid-expanded state, which is highly related to the acid ionization state, and thus to the bulk pH and ionic strength. At pH 4 the molecules hardly mix while at pH 10 the mixed monolayer with DMPC can admit between 30 and 100% of SA (depending on the lateral pressure) before phase separation is established. The addition of calcium ions to the subphase has a condensing effect on SA monolayers at all pHs and the solubility of SA in the DMPC matrix does not depend on the bulk pH in these conditions. The observed phase diagrams are independent on the manner in which the state of the mixed film is reached and may thus be considered states of apparent equilibrium.

  19. Lupane-type pentacyclic triterpenes in Langmuir monolayers: a synchrotron radiation scattering study.

    PubMed

    Broniatowski, Marcin; Flasiński, Michał; Wydro, Paweł

    2012-03-20

    Lupane-type pentacyclic triterpenes (lupeol, betulin, and betulinic acid) are natural products isolated from various plant sources. The terpenes exhibit a vast spectrum of biological activity and are applied in therapies for different diseases, among which the anticancer, anti-HIV, antihypercholesteremic, and antiinflammatory are the most promising. These chemicals possess amphiphilic structure and were proved to interact strongly with biomembranes, which can be the key stage in their mechanism of action. In our studies, we applied Langmuir monolayers as versatile models of biomembranes. It turned out that the three investigated terpenes are capable of stable monolayer formation; however, these monolayers differ profoundly regarding their physicochemical characteristics. In our research, we applied the Langmuir technique (surface pressure-mean molecular area (π-A) isotherm registration) coupled with Brewster angle microscopy (BAM), but the main focus was on the synchrotron radiation scattering method, grazing incidence X-ray diffraction (GIXD), which provides information on the amphiphilic molecule ordering in the angström scale. It was proved that all the investigated terpenes form crystalline phases in their monolayers. In the case of lupeol, only the closely packed upright phase was observed, whereas for betulin and betulinic acid, the phase situation was more complex. Betulinic acid molecules can be organized in an upright phase, which is crystalline, and in a tilted phase, which is amorphous. The betulin film is a conglomerate of an upright crystalline monolayer phase, tilted amorphous monolayer phase, and a crystalline tilted bilayer. In our paper, we discuss the factors leading to the formation of the observed phases and the implications of our results to the therapeutic applications of the native lupane-type triterpenes.

  20. Interaction of methionine-enkephalins with raft-forming lipids: monolayers and BAM experiments.

    PubMed

    Tsanova, A; Jordanova, A; Dzimbova, T; Pajpanova, T; Golovinsky, E; Lalchev, Z

    2014-05-01

    Enkephalins (Tyr-Gly-Gly-Phe-Met/Leu) are opioid peptides with proven antinociceptive action in organism. They interact with opioid receptors belonging to G-protein coupled receptor superfamily. It is known that these receptors are located preferably in membrane rafts composed mainly of sphingomyelin (Sm), cholesterol (Cho), and phosphatidylcholine. In the present work, using Langmuir's monolayer technique in combination with Wilhelmy's method for measuring the surface pressure, the interaction of synthetic methionine-enkephalin and its amidated derivative with 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC), Sm, and Cho, as well as with their double and triple mixtures, was studied. From the pressure/area isotherms measured, the compressional moduli of the lipids and lipid-peptide monolayers were determined. Our results showed that the addition of the synthetic enkephalins to the monolayers studied led to change in the lipid monolayers characteristics, which was more evident in enkephalinamide case. In addition, using Brewster angle microscopy (BAM), the surface morphology of the lipid monolayers, before and after the injection of both enkephalins, was determined. The BAM images showed an increase in surface density of the mixed surface lipids/enkephalins films, especially with double and triple component lipid mixtures. This effect was more pronounced for the enkephalinamide as well. These observations showed that there was an interaction between the peptides and the raft-forming lipids, which was stronger for the amidated peptide, suggesting a difference in folding of both enkephalins. Our research demonstrates the potential of lipid monolayers for elegant and simple membrane models to study lipid-peptide interactions at the plane of biomembranes.

  1. Quantitative mechanical analysis of thin compressible polymer monolayers on oxide surfaces.

    PubMed

    Huang, Qian; Yoon, Ilsun; Villanueva, Josh; Kim, Kanguk; Sirbuly, Donald J

    2014-10-28

    A clear understanding of the mechanical behavior of nanometer thick films on nanostructures, as well as developing versatile approaches to characterize their mechanical properties, are of great importance and may serve as the foundation for understanding and controlling molecular interactions at the interface of nanostructures. Here we report on the synthesis of thin, compressible polyethylene glycol (PEG) monolayers with a wet thickness of <20 nm on tin dioxide (SnO2) nanofibers through silane-based chemistries. Nanomechanical properties of such thin PEG films were extensively investigated using atomic force microscopy (AFM). In addition, tip-sample interactions were carefully studied, with different AFM tip modifications (i.e., hydrophilic and hydrophobic) and in different ionic solutions. We find that the steric forces dominate the tip-sample interactions when the polymer film is immersed in solution with salt concentrations similar to biological media (e.g., 1x phosphate buffer solution), while van der Waals and electrostatic forces have minimal contributions. A Dimitriadis thin film polymer compression model shows that the linear elastic regime is reproducible in the initial 50% indentation of these films which have tunable Young's moduli ranging from 5 MPa for the low molecular weight films to 700 kPa for the high molecular weight PEG films. Results are compared with the same PEG films deposited on silicon substrates which helped quantify the structural properties and understand the relationship between the structural and the mechanical properties of PEG films on the SnO2 fibers. PMID:25157609

  2. Surfactant Dynamics: Spreading and Wave Induced Dynamics of a Monolayer

    NASA Astrophysics Data System (ADS)

    Strickland, Stephen Lee

    Material adsorbed to the surface of a fluid - for instance crude oil in the ocean, biological surfactant on ocular or pulmonary mucous, or emulsions - can form a 2-dimensional mono-molecular layer. These materials, called surfactants, can behave like a compressible viscous 2-dimensional fluid, and can generate surface stresses that influence the sub-fluid's bulk flow. Additionally, the sub-fluid's flow can advect the surfactant and generate gradients in the surfactant distribution and thereby generate gradients in the interfacial properties. Due to the difficulty of non-invasive measurements of the spatial distribution of a molecular monolayer at the surface, little is known about the dynamics that couple the surface motion and the evolving density field. In this dissertation, I will present a novel method for measuring the spatiotemporal dynamics of the surfactant surface density through the fluorescence emission of NBD-tagged phosphatidylcholine, a lipid, and we will compare the surfactant dynamics to the dynamics of the surface morphology.With this method, we will consider the inward and outward spreading of a surfactant on a thin fluid film as well as the advection of a surfactant by linear and non-linear gravity-capillary waves. These two types of surfactant coupled fluid flows will allow us to probe well-accepted assumptions about the coupled fluid-surfactant dynamics. In chapter 1, we review the models used for understanding the spreading of a surfactant on a thin fluid film and the motion of surfactant on a linear gravity-capillary wave. In chapter 2, we will present the experimental methods used in this dissertation. In chapter 3, we will study the outward spreading of a localized region of surfactant and show that the spreading of a monolayer is considerably different from the spreading of thicker-layered surfactant. In chapter 4, we will investigate the inward spreading of a surfactant into a circular surfactant-free region and show that hole closure and

  3. Chitosan in nanostructured thin films.

    PubMed

    Pavinatto, Felippe J; Caseli, Luciano; Oliveira, Osvaldo N

    2010-08-01

    This review paper brings an overview of the use of chitosans in nanostructured films produced with the Langmuir-Blodgett (LB) or the electrostatic layer-by-layer (LbL) techniques, with emphasis on their possible applications. From a survey in the literature one may identify three main types of study with chitosan in nanostructured films. First, the interaction between chitosans and phospholipid Langmuir monolayers has been investigated for probing the mechanisms of chitosan action in their biological applications, with the monolayers serving as cell membrane models. In the second type, chitosan serves as a matrix for immobilization of biomolecules in LB as well as in LbL films, for which chitosan is suitable to help preserve the bioactivity of such biomolecules for long periods of time even in dry, solid films. An important application of these chitosan-containing films is in sensing and biosensing. The third type of study involves exploiting the mechanical and biocompatibility properties of chitosan in producing films with enhanced properties, for example, for tissue engineering. It is emphasized that chitosans have been proven excellent building blocks to produce films with controlled molecular architecture, allowing for synergy between distinct materials. We also discuss the prospects of the field, following a critical review of the latest developments in nanostructured chitosan films. PMID:20590156

  4. Reversibly immobilized biological materials in monolayer films on electrodes

    SciTech Connect

    Weaver, P.F.; Frank, A.J.

    1991-04-08

    A method is provided for reversibly binding charged biological particles in a fluid medium to an electrode surface. The method comprises treating (e.g., derivatizing) the electrode surface with an electrochemically active material; connecting the electrode to an electrical potential; and exposing the fluid medium to the electrode surface in a manner such that the charged particles become adsorbed on the electrode surface.

  5. Reversibly immobilized biological materials in monolayer films on electrodes

    SciTech Connect

    Weaver, Paul F.; Frank, Arthur J.

    1993-01-01

    Methods and techniques are described for reversibly binding charged biological particles in a fluid medium to an electrode surface. The methods are useful in a variety of applications. The biological materials may include microbes, proteins, and viruses. The electrode surface may consist of reversibly electroactive materials such as polyvinylferrocene, silicon-linked ferrocene or quinone.

  6. Reversibly immobilized biological materials in monolayer films on electrodes

    DOEpatents

    Weaver, P.F.; Frank, A.J.

    1993-05-04

    Methods and techniques are described for reversibly binding charged biological particles in a fluid medium to an electrode surface. The methods are useful in a variety of applications. The biological materials may include microbes, proteins, and viruses. The electrode surface may consist of reversibly electroactive materials such as polyvinylferrocene, silicon-linked ferrocene or quinone.

  7. Oscillatory barrier-assisted Langmuir-Blodgett deposition of large-scale quantum dot monolayers

    NASA Astrophysics Data System (ADS)

    Xu, Shicheng; Dadlani, Anup L.; Acharya, Shinjita; Schindler, Peter; Prinz, Fritz B.

    2016-03-01

    Depositing continuous, large-scale quantum dot films with low pinhole density is an inevitable but nontrivial step for studying their properties for applications in catalysis, electronic devices, and optoelectronics. This rising interest in high-quality quantum dot films has provided research impetus to improve the deposition technique. We show that by incorporating oscillatory barriers in the commonly used Langmuir-Blodgett method, large-scale monolayers of quantum dots with full coverage up to several millimeters have been achieved. With assistance of perturbation provided by the oscillatory barriers, the film has been shown to relax towards thermal equilibrium, and this physical process has been supported by molecular dynamics simulation. In addition, time evolution of dilatational moduli has been shown to give a clear indication of the film morphology and its stability.

  8. Tuning the Reactivity of Ultrathin Oxides: NO Adsorption on Monolayer FeO(111).

    PubMed

    Merte, Lindsay R; Heard, Christopher J; Zhang, Feng; Choi, Juhee; Shipilin, Mikhail; Gustafson, Johan; Weaver, Jason F; Grönbeck, Henrik; Lundgren, Edvin

    2016-08-01

    Ultrathin metal oxides exhibit unique chemical properties and show promise for applications in heterogeneous catalysis. Monolayer FeO films supported on metal surfaces show large differences in reactivity depending on the metal substrate, potentially enabling tuning of the catalytic properties of these materials. Nitric oxide (NO) adsorption is facile on silver-supported FeO, whereas a similar film grown on platinum is inert to NO under similar conditions. Ab initio calculations link this substrate-dependent behavior to steric hindrance caused by substrate-induced rumpling of the FeO surface, which is stronger for the platinum-supported film. Calculations show that the size of the activation barrier to adsorption caused by the rumpling is dictated by the strength of the metal-oxide interaction, offering a straightforward method for tailoring the adsorption properties of ultrathin films. PMID:27346455

  9. Aging of Transition Metal Dichalcogenide Monolayers.

    PubMed

    Gao, Jian; Li, Baichang; Tan, Jiawei; Chow, Phil; Lu, Toh-Ming; Koratkar, Nikhil

    2016-02-23

    Two-dimensional sheets of transition metal dichalcogenides are an emerging class of atomically thin semiconductors that are considered to be "air-stable", similar to graphene. Here we report that, contrary to current understanding, chemical vapor deposited transition metal dichalcogenide monolayers exhibit poor long-term stability in air. After room-temperature exposure to the environment for several months, monolayers of molybdenum disulfide and tungsten disulfide undergo dramatic aging effects including extensive cracking, changes in morphology, and severe quenching of the direct gap photoluminescence. X-ray photoelectron and Auger electron spectroscopy reveal that this effect is related to gradual oxidation along the grain boundaries and the adsorption of organic contaminants. These results highlight important challenges associated with the utilization of transition metal dichalcogenide monolayers in electronic and optoelectronic devices. We also demonstrate a potential solution to this problem, featuring encapsulation of the monolayer sheet by a 10-20 nm thick optically transparent polymer (parylene C). This strategy is shown to successfully prevent the degradation of the monolayer material under accelerated aging (i.e., high-temperature, oxygen-rich) conditions.

  10. Aging of Transition Metal Dichalcogenide Monolayers.

    PubMed

    Gao, Jian; Li, Baichang; Tan, Jiawei; Chow, Phil; Lu, Toh-Ming; Koratkar, Nikhil

    2016-02-23

    Two-dimensional sheets of transition metal dichalcogenides are an emerging class of atomically thin semiconductors that are considered to be "air-stable", similar to graphene. Here we report that, contrary to current understanding, chemical vapor deposited transition metal dichalcogenide monolayers exhibit poor long-term stability in air. After room-temperature exposure to the environment for several months, monolayers of molybdenum disulfide and tungsten disulfide undergo dramatic aging effects including extensive cracking, changes in morphology, and severe quenching of the direct gap photoluminescence. X-ray photoelectron and Auger electron spectroscopy reveal that this effect is related to gradual oxidation along the grain boundaries and the adsorption of organic contaminants. These results highlight important challenges associated with the utilization of transition metal dichalcogenide monolayers in electronic and optoelectronic devices. We also demonstrate a potential solution to this problem, featuring encapsulation of the monolayer sheet by a 10-20 nm thick optically transparent polymer (parylene C). This strategy is shown to successfully prevent the degradation of the monolayer material under accelerated aging (i.e., high-temperature, oxygen-rich) conditions. PMID:26808328

  11. Real-time imaging of crystallization in polylactide enantiomeric monolayers at the air-water interface.

    PubMed

    Kim, Young Shin; Snively, Christopher M; Liu, Yujuan; Rabolt, John F; Chase, D Bruce

    2008-10-01

    A newly developed planar array infrared reflection-absorption spectrograph (PA-IRRAS) offers significant advantages over conventional approaches including fast acquisition speed, excellent compensation for water vapor, and an excellent capacity for large infrared accessories, e.g., a water trough. In this study, the origin of stereocomplexation in a polylactide enantiomeric monolayer at the air-water interface was investigated using PA-IRRAS. PA-IRRAS was used as a probe to follow the real-time conformational changes associated with intermolecular interactions of polymer chains during the compression of the monolayers. It was found that a mixture of poly(D-lactic acid) (PDLA) and poly(L-lactic acid) (PLLA) (D/L) formed a stereocomplex when the two-dimensional monolayer developed at the air-water interface before film compression, indicating that there is no direct correlation between film compression and stereocomplexation. PA-IRRAS spectra of the stereocomplex exhibited distinct band shifts in crystalline sensitive components, e.g., the vas(C-O-C, h) mode, as well as amorphous-dependent components, e.g., the vs(C-O-C) mode, when compared with the spectra of PLLA alone. On the other hand, time-resolved PA-IRRAS spectra, which were obtained as the films were being compressed, revealed that both monolayers of PLLA and mixed PLLA/PDLA stereocomplex were crystallized into a 10(3)-helix and a 3(1)-helix, respectively, with a distinct band shift in crystalline sensitive components only. Fourier self-deconvolution of the spectra demonstrated that the band shift in crystalline sensitive components is correlated with the intermolecular interaction of polymer chains. PMID:18781784

  12. Anodic passivation of tin by alkanethiol self-assembled monolayers examined by cyclic voltammetry and coulometry.

    PubMed

    Worley, Barrett C; Ricks, William A; Prendergast, Michael P; Gregory, Brian W; Collins, Ross; Cassimus, John J; Thompson, Raymond G

    2013-10-22

    The self-assembly of medium chain length alkanethiol monolayers on polycrystalline Sn electrodes has been investigated by cyclic voltammetry and coulometry. These studies have been performed in order to ascertain the conditions under which their oxidative deposition can be achieved directly on the oxide-free Sn surface, and the extent to which these electrochemically prepared self-assembled monolayers (SAMs) act as barriers to surface oxide growth. This work has shown that the potentials for their oxidative deposition are more cathodic (by 100-200 mV) than those for Sn surface oxidation and that the passivating abilities of these SAMs improve with increasing film thickness (or chain length). Oxidative desorption potentials for these films have been observed to shift more positively, and in a highly linear fashion, with increasing film thickness (~75 mV/CH2). Although reductive desorption potentials for the SAMs are in close proximity to those for reduction of the surface oxide (SnOx), little or no SnOx formation occurs unless the potential is made sufficiently anodic that the monolayers start to be removed oxidatively. Our coulometric data indicate that the charge involved with alkanethiol reductive desorption or oxidative deposition is consistent with the formation of a close-packed monolayer, given uncertainties attributable to surface roughness and heterogeneity phenomena. These experiments also reveal that the quantity of charge passed during oxidative desorption is significantly larger than what would be predicted for simple alkylsulfinate or alkylsulfonate formation, suggesting that oxidative removal involves a more complex oxidation mechanism. Analogous chronocoulometric experiments for short-chain alkanethiols on polycrystalline Au electrodes have evidenced similar oxidative charge densities. This implies that the mechanism for oxidative desorption on both surfaces may be very similar, despite the significant differences in the inherent dissolution

  13. Long-lived nanosecond spin relaxation and spin coherence of electrons in monolayer MoS2 and WS2

    NASA Astrophysics Data System (ADS)

    Yang, Luyi; Sinitsyn, Nikolai A.; Chen, Weibing; Yuan, Jiangtan; Zhang, Jing; Lou, Jun; Crooker, Scott A.

    2015-10-01

    The recently discovered monolayer transition metal dichalcogenides (TMDCs) provide a fertile playground to explore new coupled spin-valley physics. Although robust spin and valley degrees of freedom are inferred from polarized photoluminescence (PL) experiments, PL timescales are necessarily constrained by short-lived (3-100 ps) electron-hole recombination. Direct probes of spin/valley polarization dynamics of resident carriers in electron (or hole)-doped TMDCs, which may persist long after recombination ceases, are at an early stage. Here we directly measure the coupled spin-valley dynamics in electron-doped MoS2 and WS2 monolayers using optical Kerr spectroscopy, and reveal very long electron spin lifetimes, exceeding 3 ns at 5 K (two to three orders of magnitude longer than typical exciton recombination times). In contrast with conventional III-V or II-VI semiconductors, spin relaxation accelerates rapidly in small transverse magnetic fields. Supported by a model of coupled spin-valley dynamics, these results indicate a novel mechanism of itinerant electron spin dephasing in the rapidly fluctuating internal spin-orbit field in TMDCs, driven by fast inter-valley scattering. Additionally, a long-lived spin coherence is observed at lower energies, commensurate with localized states. These studies provide insight into the physics underpinning spin and valley dynamics of resident electrons in atomically thin TMDCs.

  14. Self-assembled honeycomb lattice in the monolayer of cyclic thiazyl diradical BDTDA (= 4,4′-bis(1,2,3,5-dithiadiazolyl)) on Cu(111) with a zero-bias tunneling spectra anomaly

    PubMed Central

    Yamamoto, Masayuki; Suizu, Rie; Dutta, Sudipta; Mishra, Puneet; Nakayama, Tomonobu; Sakamoto, Kazuyuki; Wakabayashi, Katsunori; Uchihashi, Takashi; Awaga, Kunio

    2015-01-01

    Scanning tunneling microscopy (STM) observation reveals that a cyclic thiazyl diradical, BDTDA (= 4,4′-bis(1,2,3,5-dithiadiazolyl)), forms a well-ordered monolayer honeycomb lattice consisting of paramagnetic corners with unpaired electrons on a clean Cu(111) surface. This BDTDA lattice is commensurate with the triangular lattice of Cu(111), with the former being 3 × 3 larger than the latter. The formation of the BDTDA monolayer structure, which is significantly different from its bulk form, is attributed to an interaction with the metal surface as well as the intermolecular assembling forces. STM spectroscopy measurements on the BDTDA molecules indicate the presence of a characteristic zero-bias anomaly centered at the Fermi energy. The origin of this zero-bias anomaly is discussed in terms of the Dirac cones inherent to the honeycomb structure. PMID:26678594

  15. Nonlinear optical techniques for surface studies. [Monolayers

    SciTech Connect

    Shen, Y.R.

    1981-09-01

    Recent effort in developing nonlinear optical techniques for surface studies is reviewed. Emphasis is on monolayer detection of adsorbed molecules on surfaces. It is shown that surface coherent antiStokes Raman scattering (CARS) with picosecond pulses has the sensitivity of detecting submonolayer of molecules. On the other hand, second harmonic or sum-frequency generation is also sensitive enough to detect molecular monolayers. Surface-enhanced nonlinear optical effects on some rough metal surfaces have been observed. This facilitates the detection of molecular monolayers on such surfaces, and makes the study of molecular adsorption at a liquid-metal interface feasible. Advantages and disadvantages of the nonlinear optical techniques for surface studies are discussed.

  16. Adherence of Mycoplasma hyopneumoniae to cell monolayers.

    PubMed

    Zielinski, G C; Young, T; Ross, R F; Rosenbusch, R F

    1990-03-01

    This work was an attempt to develop an in vitro adherence model for Mycoplasma hyopneumoniae, using monolayers of human and porcine lung fibroblasts and porcine kidney cells. Mycoplasma hyopneumoniae grown in Friis mycoplasma broth was radiolabeled with 35[S]-methionine, washed, concentrated, and inoculated on the monolayers. After 15 minutes of centrifugation to facilitate adherence, monolayers were washed 3 times, dissolved with 0.1N NaOH, and suspended in scintillation liquid, and the radioactivity was determined in a liquid scintillation counter. Adherence, measured as a percentage of counts added, varied according to the mycoplasma strain and the cell line used. Comparison of strains J, 144L, and 232 of M hyopneumoniae revealed 7.5 +/- 5.9, 31.9 +/- 13, and 9.6 +/- 5% adherence to porcine kidney cells, respectively. Slightly different, but proportionally the same relationships were obtained with swine or human fibroblasts. Adherence was decreased slightly by repeated washings of the mycoplasma-treated cell monolayers; however, a plateau was reached, indicating irreversibility of the adherence process. Pretreatment of cell monolayers with nonlabeled organisms substantially blocked adherence by labeled organisms. Dilution of labeled organisms resulted in an increased proportion adhering. Therefore, it appears that the adherence was a receptor-dependent event. Treatment of the mycoplasmas with trypsin prior to the inoculation of monolayers resulted in a marked reduction in adherence. Treatment of the mycoplasmas with hyperimmune swine serum against M hyopneumoniae or normal swine serum resulted in 80 to 90% reduction of adherence; however, no inhibition occurred when mycoplasmas were treated with purified IgG from the hyperimmune serum.

  17. The microstructure and dissolution behavior of lipid-monolayer-coated, air-filled microbubble

    NASA Astrophysics Data System (ADS)

    Pu, Gang

    Suspensions of lipid-coated microbubbles are currently being developed for use as ultrasound contrast agents, drug delivery vehicles and blood substitutes. In our study, first, we examined the effect of lipid acyl chain length and the cooling rate on the microbubble surface domain morphology. The average domain size decreased with increasing cooling rate for all acyl chain lengths. The shape factor increased with chain length for the highest cooling rate. Second, we investigated the effect of microstructure on molecular oxygen permeation through condensed phospholipid monolayers. Oxygen permeability was shown to increase linearly with domain boundary density at a constant phospholipid acyl chain length and, accordingly, was shown to decrease exponentially with increasing chain length at a constant domain boundary density. Modification of the energy barrier theory to account for microstructural effects, in terms of the domain boundary density, provides a general equation to model passive transport through polycrystalline monolayer films. Last, we demonstrated that the phase conditions and microstructure of the shell were critical to determine the dissolution behaviors of the lipid-coated microbubble. For these two-phase coexistence bubbles, a transition from primary collapse, as loss of expanded phase due to vesiculation, to secondary collapse, as the rapid propagation of monolayer folds and simultaneous deformation, was observed. For very rigid monolayers, we observed substantial surface buckling with simultaneous nucleation and growth of folds.

  18. Molecular organization in phospholipid monolayer domains by correlative fluorescence microscopy and electron diffraction.

    PubMed

    Hui, S W; Yu, H

    1994-04-01

    Lipid monolayer is a half leaflet model for lipid bilayer, which forms the basis of biological membranes. Within a certain range of surface area per molecular of phospholipid monolayers at the air-water interface, where the compressibility was nearly infinite, two phases with different molecular packings were observable by fluorescence microscopy. Mixed-phase monolayers of L-1,2-dipalmitoyl-N-monomethyl-3-phosphatidylethanolamine [DP(Me)PE] or L-1,2-dipalmitoyl-N-dimethyl-3-phosphatidyl-ethanolamine [DP(Me)2PE] were deposited on marker grids coated with Formvar films. The molecular organization in the dark and bright fluorescent areas on the grids was investigated by low dose, selected area electron diffraction. Sharp reflection arcs, at a spacing of 4.2A and arranged in a hexagon pattern, were detected from dark domains of both lipids. A diffuse reflection ring at a spacing of 4.6A was derived from the bright background areas. Diffraction patterns were obtained from neighboring areas along selected dark domains of both lipids. The orientations of diffraction patterns from areas along smooth and curving boundaries of DP(Me)2PE domains were found to turn with the boundaries. In the branching domains of DP(Me)PE, the orientations of diffraction patterns indicated that the branches were formed by twinning. Electron diffraction thus provides an unique way to sample the local molecular packing order and orientation within individual domains in phospholipid monolayers.

  19. [Surface Enhanced Raman Spectroscopic Studies on the Coupling Effect of Multilayer Au@SiO2 Film].

    PubMed

    Hu, Di-jun; Zhang, Xue-jiao; Xu, Min-min; Yao, Jian-lin; Gu, Ren-ao

    2015-05-01

    The SiO2 shell with the thickness of 4 nm was attached onto high surface enhanced Raman spectroscopy (SERS) active Au core nanoparticles to obtain Au@SiO2 core shell nanoparticles by the hydrolysis of sodium silicate solution with the boiling water bath. The inert shell of SiO2 isolated the direct interaction of Au nanoparticles and probe molecules. The stable, compact and uniform monolayer nanoparticles film was self assembled at water/oil interface, and one to six monolayers film was transferred to Si wafer as SERS substrates through layer by layer technique. The relationship between the SERS activities and layers of the monolayer nanoparticles film on Si surface was investigated. The SERS mapping was developed to determine the layers of the Au@SiO2 film. The coupling effect among the Au@SiO2 films was explored by changing the adsorption location of the probe on the multilayer films. The result revealed that the monolayer film was a favourable candidate with high-quality performances for the SERS application. The SERS signal was distributed on the surface with high uniformity at the same monolayer film, and it was enhanced in the intensity with the increase in film layers. It reached the maximun intensity as the film was over five layers. It indicated that the SERS signal was contributed mainly by the first five monolayers. The probe molecules were immobilized onto the first monolayer nanoparticles film, and the SERS signal from the probe approached to the maximum as the second monolayer covered the probe modified first nanoparticles film. It was dominated by the coupling effect ("hot spots") of the adjacent layers. The SERS signal decreased in intensity when the third layer was transferred onto the second layer, and it disappeared after the fouth layer was covered, mainly duo to the shield of the nanoparticles film to the incident laser and Raman signal. The preliminary results provided guidance for fabricating optimal SERS substrates. PMID:26415440

  20. Influence of adsorption or desorption and surface diffusion on the formation kinetics of open half-monolayer coverage.

    PubMed

    Feldman, E P; Stefanovich, L I; Terekhova, Yu V

    2014-06-01

    The formation kinetics of open half-monolayer films on solid substrates is studied by the deposition of particles from a gaseous (vapor) phase to a cold substrate (room temperature) provided the lateral interaction between the particles of adsorbed layer (adlayer) is attractive. A detailed analysis of two limiting cases is presented: when the half-monolayer film formation rate is limited by the adsorption of particles from the gas phase and when the formation of the half-monolayer film surface is determined by the rate of surface diffusion of the adsorbed particles. The asymptotic analysis of the coverage dispersion evolution and the characteristic spatial scale of coverage inhomogeneities at the early and late stages of relaxation of a submonolayer film after quenching under the spinodal is carried out. It is found that separation of the adlayer occurs, so inhomogeneities of submonolayer films at the later stages of the process tend to equilibrium values of coverage in any case. However, asymptotic and numerical analysis shows that in the second case for some relationship between the kinetic and thermodynamic parameters of the adlayer an intermediate asymptotic relaxation process can be observed. It testifies to a kinetic slowdown of the separation process at the spinodal values of coverages. This fact manifests as the appearance of the intermediate plateau in the evolution curves for the coverage dispersion and nonmonotonic change of the characteristic spatial scale of coverage inhomogeneities. Moreover, at the early stages of the coverage evolution, the incubation period is revealed in the development of its inhomogeneities. It is shown that at the later stages of the separation of the half-monolayer film, the characteristic spatial scale of coverage inhomogeneities increases with time according to the law τ {1/2} and the width of the transition region between enriched and depleted regions of adlayer decreases as 1/τ {1/2}.

  1. Monolayer Topological Insulators: Silicene, Germanene, and Stanene

    NASA Astrophysics Data System (ADS)

    Ezawa, Motohiko

    2015-12-01

    We report the recent progress on the theoretical aspects of monolayer topological insulators including silicene, germanene and stanene, which are monolayer honeycomb structures of silicon, germanium and tin, respectively. They show quantum spin Hall effects in nature due to the spin-orbit interaction. The band gap can be tuned by applying perpendicular electric field, which induces a topological phase transition. We also analyze the topological properties of generic honeycomb systems together with the classification of topological insulators. Phase diagrams of topological insulators and superconductors in honeycomb systems are explicitly determined. We also investigate topological electronics including a topological field-effect transistor, the topological Kirchhoff's law and the topological spin-valleytronics.

  2. Low temperature photoresponse of monolayer tungsten disulphide

    SciTech Connect

    Cao, Bingchen; Shen, Xiaonan; Shang, Jingzhi; Cong, Chunxiao; Yang, Weihuang; Eginligil, Mustafa E-mail: meginligil@ntu.edu.sg; Yu, Ting E-mail: meginligil@ntu.edu.sg

    2014-11-01

    High photoresponse can be achieved in monolayers of transition metal dichalcogenides. However, the response times are inconveniently limited by defects. Here, we report low temperature photoresponse of monolayer tungsten disulphide prepared by exfoliation and chemical vapour deposition (CVD) method. The exfoliated device exhibits n-type behaviour; while the CVD device exhibits intrinsic behaviour. In off state, the CVD device has four times larger ratio of photoresponse for laser on/off and photoresponse decay–rise times are 0.1 s (limited by our setup), while the exfoliated device has few seconds. These findings are discussed in terms of charge trapping and localization.

  3. Nonlinear optical studies of organic monolayers

    SciTech Connect

    Shen, Y.R.

    1988-02-01

    Second-order nonlinear optical effects are forbidden in a medium with inversion symmetry, but are necessarily allowed at a surface where the inversion summary is broken. They are often sufficiently strong so that a submonolayer perturbation of the surface can be readily detected. They can therefore be used as effective tools to study monolayers adsorbed at various interfaces. We discuss here a number of recent experiments in which optical second harmonic generation (SHG) and sum-frequency generation (SFG) are employed to probe and characterize organic monolayers. 15 refs., 5 figs.

  4. Monochromatic electron photoemission from diamondoid monolayers

    SciTech Connect

    Yang, Wanli; Yang, Wanli L.; Fabbri, J.D.; Willey, T.M.; Lee, J.R.I.; Dahl, J.E.; Carlson, R.M.K.; Schreiner, P.R.; Fokin, A.A.; Tkachenko, B.A.; Fokina, N.A.; Meevasana, W.; Mannella, N.; Tanaka, K.; Zhou, X.J.; van Buuren, T.; Kelly, M.A.; Hussain, Z.; Melosh, N.A.; Shen, Z.-X.

    2007-02-27

    We found monochromatic electron photoemission from large-area self-assembled monolayers of a functionalized diamondoid, [121]tetramantane-6-thiol. Photoelectron spectra of the diamondoid monolayers exhibited a peak at the low-kinetic energy threshold; up to 68percent of all emitted electrons were emitted within this single energy peak. The intensity of the emission peak is indicative of diamondoids being negative electron affinity materials. With an energy distribution width of less than 0.5 electron volts, this source of monochromatic electrons may find application in technologies such as electron microscopy, electron beam lithography, and field-emission flatpanel displays.

  5. Active Tensile Modulus of an Epithelial Monolayer

    NASA Astrophysics Data System (ADS)

    Vincent, Romaric; Bazellières, Elsa; Pérez-González, Carlos; Uroz, Marina; Serra-Picamal, Xavier; Trepat, Xavier

    2015-12-01

    A general trait of cell monolayers is their ability to exert contractile stresses on their surroundings. The scaling laws that link such contractile stresses with the size and geometry of constituent cells remain largely unknown. In this Letter, we show that the active tension of an epithelial monolayer scales linearly with the size of the constituent cells, a surprisingly simple relationship. The slope of this relationship defines an active tensile modulus, which depends on the concentration of myosin and spans more than 2 orders of magnitude across cell types and molecular perturbations.

  6. Pattern formation in fatty acid-nanoparticle and lipid-nanoparticle mixed monolayers at water surface

    NASA Astrophysics Data System (ADS)

    Choudhuri, M.; Datta, A.; Iyengar, A. N. Sekar; Janaki, M. S.

    2015-06-01

    Dodecanethiol-capped gold nanoparticles (AuNPs) are self-organized in two different amphiphilic monolayers one of which is a single-tailed fatty acid Stearic acid (StA) and the other a double-tailed lipid 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC). In the StA-AuNP film the AuNPs self-organize to form an interconnected network of nanoclusters on compression while in the DMPC-AuNP film the AuNPs aggregate to form random, isolated clusters in the film. The long time evolution of the films at constant surface pressure reveals ring structures in the former and diffusion limited aggregates in the latter that with time evolve into an irregular porous maze of AuNPs in the DMPC film. The difference in structure of the AuNP patterns in the two films can be attributed to a difference in the lipophilic interactions between the NPs and the amphiphilic molecules. The mean square intensity fluctuations f(ln) calculated along a typical line for the 2D structures in both the films at initial and final stages of long time evolution reflect the structural changes in the films over time.

  7. Experimental Apparatus to Search for Supersolidity in Monolayer He on Graphite

    NASA Astrophysics Data System (ADS)

    Kubota, Y.; Toda, R.; Kamada, M.; Nakamura, S.; Matsui, T.; Fukuyama, Hiroshi

    2014-04-01

    We describe some details of a new experimental setup for torsional oscillator (TO) measurement of He monolayers adsorbed on a graphite surface. This setup is designed to seek for the possible supersolid phase, in which crystalline order coexists with superfluidity, in two dimensional (2D) solid He below 300 mK. Among such 2D solids, the commensurate phase in the second layer on graphite is the most hopeful candidate for the novel supersolid phase since it is the lowest-density quantum solid ever found. An exfoliated graphite substrate we used is ZYX which has at least ten times longer surface coherence length compared to Grafoil, an exfoliated graphite most commonly used in previous experiments. The first version of TO we made has the resonant frequency of 786.8 Hz and the Q value of at mK. The resonant frequency of this particular TO without any He samples () showed unexpectedly large temperature variation and non-reproducibility below 1 K as well as sudden jumps when mechanical shocks are applied to the experimental apparatus. We found the stability of is highly correlated with the temperature stability of 1 K pot in dilution refrigerator.

  8. Computer simulations of the Adsorption of Xenon onto a C60 monolayer on Ag (111)

    NASA Astrophysics Data System (ADS)

    Gatica, Silvina; Cole, Milton; Diehl, Renee

    2007-03-01

    We performed Grand Canonical Monte Carlo simulations to study the adsorption of Xenon on a substrate composed of C60 molecules placed on top of a Ag(111) surface. The C60 molecules form a commensurate structure at a distance of 0.227 nm above the Ag surface. The interaction potential between the Xe atoms and the substrate has two contributions: from the C60 molecules and from the Ag atoms. In the simulations, the interaction with the Ag surface was computed using an ab initio van der Waals potential, varying as 1/d^3. The interaction between the Xe atoms and each C60 molecule was computed using a potential previously developed by Hernandez et.al. (E. S. Hernandez, M. W. Cole and M. Boninsegni, ``Wetting of spherical surfaces by quantum fluids'', J. Low Temp. Phys. 134, 309-314 (2004)), who integrated the Lennard Jones interaction over the surface of a spherical buckyball. The total potential has especially attractive 3-fold sites, positioned 0.4 nm above the point between each three buckyballs. The low coverage uptake populates those sites, and then continues forming a monolayer. The adsorption isotherms show several steps, typical of substrates that have distinct adsorption sites. We compare the results with the experimental data.

  9. The influence of the preparation conditions on structure and optical properties of solid films of graphene oxide

    NASA Astrophysics Data System (ADS)

    Seliverstova, E.; Ibrayev, N.; Dzhanabekova, R.; Gladkova, V.

    2016-02-01

    In this study, we investigated the physico-chemical properties of graphene oxide monolayers at the interface water-air. Monolayers were formed by the spreading of dispersion of graphene oxide in acetone and THF. It was found than graphene monolayers are in the “liquid” state on the surface of subphase. Monolayers were transferred onto solid substrates according to Langmuir-Blodgett (LB) method. SEM images show that the films have an island structure. The films obtained from acetone solutions are more uniform, which makes them more promising in terms of their use as conductive coatings. Absorption spectrum of graphene LB films exhibits a broad band in the ultraviolet and visible region of the spectrum. The optical density of the film obtained from acetone solution is greater than the optical density of the film prepared from THF. In the visible region of the spectrum both films have high transparency.

  10. Monolayer Co3 O4 Inverse Opals as Multifunctional Sensors for Volatile Organic Compounds.

    PubMed

    Lee, Chul-Soon; Dai, Zhengfei; Jeong, Seong-Yong; Kwak, Chang-Hoon; Kim, Bo-Young; Kim, Do Hong; Jang, Ho Won; Park, Joon-Shik; Lee, Jong-Heun

    2016-05-17

    Monolayers of periodic porous Co3 O4 inverse opal (IO) thin films for gas-sensor applications were prepared by transferring cobalt-solution-dipped polystyrene (PS) monolayers onto sensor substrates and subsequent removal of the PS template by heat treatment. Monolayer Co3 O4 IO thin films having periodic pores (d≈500 nm) showed a high response of 112.9 to 5 ppm C2 H5 OH at 200 °C with low cross-responses to other interfering gases. Moreover, the selective detection of xylene and methyl benzenes (xylene+toluene) could be achieved simply by tuning the sensor temperature to 250 and 275 °C, respectively, so that multiple gases can be detected with a single chemiresistor. Unprecedentedly high ethanol response and temperature-modulated control of selectivity with respect to ethanol, xylene, and methyl benzenes were attributed to the highly chemiresistive IO nanoarchitecture and to the tuned catalytic promotion of different gas-sensing reactions, respectively. These well-ordered porous nanostructures could have potential in the field of high-performance gas sensors based on p-type oxide semiconductors. PMID:27125495

  11. Phase diagram of the CF{sub 4} monolayer and bilayer on graphite

    SciTech Connect

    Thomas, Petros; Hess, George B.

    2014-05-21

    We report an experimental study of physisorbed monolayers and bilayers of CF{sub 4} on graphite using infrared reflection absorption spectroscopy supplemented by ellipsometry. The symmetric C–F stretch mode ν{sub 3} near 1283 cm{sup −1} in the gas is strongly blue shifted in the film by dynamic dipole coupling. This blue shift provides a very sensitive measure of the inter-molecular spacing in the monolayer and, less directly, in the bilayer. We find that important corrections are necessary to the volumetric coverage scales used in previous heat capacity and x-ray diffraction studies of this system. This requires quantitative and some qualitative changes to the previously proposed phase diagram. We find evidence for a new phase transition in the middle of the hexagonal incommensurate region and construct new phase diagrams in both the variables coverage-temperature and chemical potential-temperature. We determine the compressibility and thermal expansion in the low-pressure hexagonal incommensurate phase and values for the entropy change in several phase transitions. Below about 55 K there is evidence of solution of up to 7% of an impurity, most likely CO, in our monolayer but not the bilayer film.

  12. Gold Nanoparticle Monolayers from Sequential Interfacial Ligand Exchange and Migration in a Three-Phase System

    PubMed Central

    Yang, Guang; Hallinan, Daniel T.

    2016-01-01

    Using a three-phase system, centimeter-scale monolayer gold nanoparticle (Au NP) films have been prepared that have long-range order and hydrophobic ligands. The system contains an interface between an aqueous phase containing Au NPs and an oil phase containing one of various types of amine ligands, and a water/air interface. As the Au NPs diffuse to the water/oil interface, ligand exchange takes place which temporarily traps them at the water/oil interface. The ligand-exchanged particles then spontaneously migrate to the air/water interface, where they self-assemble, forming a monolayer under certain conditions. The spontaneous formation of the NP film at the air/water interface was due to the minimization of the system Helmholtz free energy. However, the extent of surface functionalization was dictated by kinetics. This decouples interfacial ligand exchange from interfacial self-assembly, while maintaining the simplicity of a single system. The interparticle center-to-center distance was dictated by the amine ligand length. The Au NP monolayers exhibit tunable surface plasma resonance and excellent spatial homogeneity, which is useful for surface-enhanced Raman scattering. The “air/water/oil” self-assembly method developed here not only benefits the fundamental understanding of NP ligand conformations, but is also applicable to the manufacture of plasmonic nanoparticle devices with precisely designed optical properties. PMID:27762394

  13. Monolayer Co3 O4 Inverse Opals as Multifunctional Sensors for Volatile Organic Compounds.

    PubMed

    Lee, Chul-Soon; Dai, Zhengfei; Jeong, Seong-Yong; Kwak, Chang-Hoon; Kim, Bo-Young; Kim, Do Hong; Jang, Ho Won; Park, Joon-Shik; Lee, Jong-Heun

    2016-05-17

    Monolayers of periodic porous Co3 O4 inverse opal (IO) thin films for gas-sensor applications were prepared by transferring cobalt-solution-dipped polystyrene (PS) monolayers onto sensor substrates and subsequent removal of the PS template by heat treatment. Monolayer Co3 O4 IO thin films having periodic pores (d≈500 nm) showed a high response of 112.9 to 5 ppm C2 H5 OH at 200 °C with low cross-responses to other interfering gases. Moreover, the selective detection of xylene and methyl benzenes (xylene+toluene) could be achieved simply by tuning the sensor temperature to 250 and 275 °C, respectively, so that multiple gases can be detected with a single chemiresistor. Unprecedentedly high ethanol response and temperature-modulated control of selectivity with respect to ethanol, xylene, and methyl benzenes were attributed to the highly chemiresistive IO nanoarchitecture and to the tuned catalytic promotion of different gas-sensing reactions, respectively. These well-ordered porous nanostructures could have potential in the field of high-performance gas sensors based on p-type oxide semiconductors.

  14. Bovine and human insulin adsorption at lipid monolayers: a comparison

    NASA Astrophysics Data System (ADS)

    Mauri, Sergio; Pandey, Ravindra; Rzeznicka, Izabela; Lu, Hao; Bonn, Mischa; Weidner, Tobias

    2015-07-01

    Insulin is a widely used peptide in protein research and it is utilised as a model peptide to understand the mechanics of fibril formation, which is believed to be the cause of diseases such as Alzheimer and Creutzfeld-Jakob syndrome. Insulin has been used as a model system due to its biomedical relevance, small size and relatively simple tertiary structure. The adsorption of insu lin on a variety of surfaces has become the focus of numerous studies lately. These works have helped in elucidating the consequence of surface/protein hydrophilic/hydrophobic interaction in terms of protein refolding and aggregation. Unfortunately, such model surfaces differ significantly from physiological surfaces. Here we spectroscopically investigate the adsorption of insulin at lipid monolayers, to further our understanding of the interaction of insulin with biological surfaces. In particular we study the effect of minor mutations of insulin’s primary amino acid sequence on its interaction with 1,2-Dipalmitoyl-sn-glycero-3-phosphoglycerol (DPPG) model lipid layers. We probe the structure of bovine and human insulin at the lipid/water interface using sum frequency generation spectroscopy (SFG). The SFG experiments are complemented with XPS analysis of Langmuir-Schaefer deposited lipid/insulin films. We find that bovine and human insulin, even though very similar in sequence, show a substantially different behavior when interacting with lipid films.

  15. Design and compressibility of Langmuir monolayers from organometallic nanocyclic complexes

    NASA Astrophysics Data System (ADS)

    Grushevskaya, H. V.; Krylova, N. G.; Lipnevich, I. V.

    2016-08-01

    We propose to control design of organometallic conducting Langmuir monolayer by utilizing geometrodynamic approach. By means of this approach the compressibility of the monolayer, which consists of molecules of thiophene-pyrrole series oligomer with covalently bound hydrophobic alkyl chain, has been analyzed for different subphase with iron salts. It has been discovered that the monolayers are polymerized and turn into monolayers of nanocyclic organometallic coordination compounds at a two-dimensional phase transition of the first order.

  16. Growth of Continuous Monolayer Graphene with Millimeter-sized Domains Using Industrially Safe Conditions

    PubMed Central

    Wu, Xingyi; Zhong, Guofang; D'Arsié, Lorenzo; Sugime, Hisashi; Esconjauregui, Santiago; Robertson, Alex W.; Robertson, John

    2016-01-01

    We demonstrate the growth of continuous monolayer graphene films with millimeter-sized domains on Cu foils under intrinsically safe, atmospheric pressure growth conditions, suitable for application in roll-to-roll reactors. Previous attempts to grow large domains in graphene have been limited to isolated graphene single crystals rather than as part of an industrially useable continuous film. With both appropriate pre-treatment of the Cu and optimization of the CH4 supply, we show that it is possible to grow continuous films of monolayer graphene with millimeter scale domains within 80 min by chemical vapour deposition. The films are grown under industrially safe conditions, i.e., the flammable gases (H2 and CH4) are diluted to well below their lower explosive limit. The high quality, spatial uniformity, and low density of domain boundaries are demonstrated by charge carrier mobility measurements, scanning electron microscope, electron diffraction study, and Raman mapping. The hole mobility reaches as high as ~5,700 cm2 V−1 s−1 in ambient conditions. The growth process of such high-quality graphene with a low H2 concentration and short growth times widens the possibility of industrial mass production. PMID:26883292

  17. Growth of Continuous Monolayer Graphene with Millimeter-sized Domains Using Industrially Safe Conditions.

    PubMed

    Wu, Xingyi; Zhong, Guofang; D'Arsié, Lorenzo; Sugime, Hisashi; Esconjauregui, Santiago; Robertson, Alex W; Robertson, John

    2016-01-01

    We demonstrate the growth of continuous monolayer graphene films with millimeter-sized domains on Cu foils under intrinsically safe, atmospheric pressure growth conditions, suitable for application in roll-to-roll reactors. Previous attempts to grow large domains in graphene have been limited to isolated graphene single crystals rather than as part of an industrially useable continuous film. With both appropriate pre-treatment of the Cu and optimization of the CH4 supply, we show that it is possible to grow continuous films of monolayer graphene with millimeter scale domains within 80 min by chemical vapour deposition. The films are grown under industrially safe conditions, i.e., the flammable gases (H2 and CH4) are diluted to well below their lower explosive limit. The high quality, spatial uniformity, and low density of domain boundaries are demonstrated by charge carrier mobility measurements, scanning electron microscope, electron diffraction study, and Raman mapping. The hole mobility reaches as high as ~5,7002 m(2) V(-1) s(-1) in ambient conditions. The growth process of such high-quality graphene with a low H2 concentration and short growth times widens the possibility of industrial mass production.

  18. Dynamic mechanical properties of a polyelectrolyte adsorbed insoluble lipid monolayer at the air-water interface.

    PubMed

    Park, Chang Young; Kim, Mahn Won

    2015-04-23

    Polymers have been used to stabilize interfaces or to tune the mechanical properties of interfaces in various contexts, such as in oil emulsions or biological membranes. Although the structural properties of these systems are relatively well-studied, instrumental limitations continue to make it difficult to understand how the addition of polymer affects the dynamic mechanical properties of thin and soft films. We have solved this challenge by developing a new instrument, an optical-tweezer-based interface shear microrheometer (ISMR). With this technique, we observed that the interface shear modulus, G*, of a dioctadecyldimethylammonium chloride (DODAC) monolayer at the air-water interface significantly increased with adsorption of polystyrenesulfonate (PSS). In addition, the viscous film (DODAC monolayer) became a viscoelastic film with PSS adsorption. At a low salt concentration, 10 mM of NaCl in the subphase, the viscoelasticity of the DODAC/PSS composite was predominantly determined by a particular property of PSS, that is, it behaves as a Gaussian chain in a θ-solvent. At a high salt concentration, 316 mM of NaCl, the thin film behaved as a polymer melt excluding water molecules. PMID:25826703

  19. Surfactant-induced phases in water-supported alkane monolayers: I. Thermodynamics.

    PubMed

    Yefet, Shai; Sloutskin, Eli; Tamam, Lilach; Sapir, Zvi; Cohen, Asaf; Deutsch, Moshe; Ocko, Benjamin M

    2014-07-15

    Alkanes longer than n = 6 carbons do not spread on the water surface, but condense in a macroscopic lens. However, adding trimethylammonium-based surfactants, C(m)TAB, in submillimolar concentrations causes the alkanes to spread and form a single Langmuir-Gibbs (LG) monolayer of mixed alkanes and surfactant tails, which coexists with the alkane lenses. Upon cooling, this LG film surface-freezes at a temperature T(s) above the bulk freezing temperature T(b). The thermodynamics of surface freezing (SF) of these LG films is studied by surface tension measurements for a range of alkanes (n = 12-21) and surfactant alkyl lengths (m = 14, 16, 18), at several concentrations c. The surface freezing range T(s)-T(b) observed is up to 25 °C, an order of magnitude larger than the temperature range of SF monolayers on the surface of pure alkane melts. The measured (n,T) surface phase diagram is accounted for well by a model based on mixtures' theory, which includes an interchange energy term ω. ω is found to be negative, implying attraction between unlike species, rather than the repulsion found for SF of binary alkane mixtures. Thus, the surfactant/alkane mixing is a necessary condition for the occurrence of SF in these LG films. The X-ray derived structure of the films is presented in an accompanying paper. PMID:24918482

  20. Spin Waves and the Origin of Commensurate Magnetism in Ba2CoGe2O7

    SciTech Connect

    Zheludev, Andrey I; Sato, T.; Masuda, Takatsugu; Uchinokura, K.; Shirane, G.; Roessli, B.

    2003-01-01

    The square-lattice antiferromagnet Ba{sub 2}CoGe{sub 2}O{sub 7} is studied by means of neutron diffraction and inelastic scattering. This material is isostructural to the well-known Dzyaloshinskii-Moriya helimagnet Ba{sub 2}CuGe{sub 2}O{sub 7} but exhibits commensurate long-range Neel order at low temperatures. Measurements of the spin wave dispersion relation reveal strong in-plane anisotropy that is the likely reason for the suppression of helimagnetism.

  1. Motion of the Jovian commensurability resonances and the character of the celestial mechanics in the asteroid zone - Implication for kinematics and structure

    NASA Technical Reports Server (NTRS)

    Torbett, M.; Smoluchowski, R.

    1982-01-01

    The motion of the Jovian commensurability resonances during the early evolution of the solar system induced by the dissipation of the accretion disk results in fundamental differences in the celestial mechanics of objects over which a resonance passes from that observed for a stationary resonance. Objects experiencing resonance passage acquire irreversible increases of average eccentricity to large values accounting for the present-day random velocities of the asteroids. Semi-major axes are similarly irreversibly decreased by amounts capable of clearing the Kirkwood gaps. The gap widths are in agreement with observation.

  2. Motion of the Jovian commensurability resonances and the character of the celestial mechanics in the asteroid zone - Implication for kinematics and structure

    NASA Astrophysics Data System (ADS)

    Torbett, M.; Smoluchowski, R.

    1982-06-01

    The motion of the Jovian commensurability resonances during the early evolution of the solar system induced by the dissipation of the accretion disk results in fundamental differences in the celestial mechanics of objects over which a resonance passes from that observed for a stationary resonance. Objects experiencing resonance passage acquire irreversible increases of average eccentricity to large values accounting for the present-day random velocities of the asteroids. Semi-major axes are similarly irreversibly decreased by amounts capable of clearing the Kirkwood gaps. The gap widths are in agreement with observation.

  3. Tidal evolution of the Uranian satellites. I - Passage of Ariel and Umbriel through the 5:3 mean-motion commensurability

    NASA Technical Reports Server (NTRS)

    Tittemore, William C.; Wisdom, Jack

    1988-01-01

    A significant chaotic zone is associated with the 5:3 mean-motion commensurability resonance through which Ariel and Umbriel would have passed, in the event that Uranus' specific dissipation function were less than 100,000; the standard theory for passage through orbital resonances would in this case be inapplicable, in view of significant changes in the probability and the mechanism of capture into the resonance. It is suggested that tidal evolution within the chaotic zone may have pushed eccentrocities to comparatively high values at which the probability of escape from resonance remained. Eccentricities sufficiently great to affect Ariel's thermal history have not been found.

  4. Glitter in a 2D monolayer.

    PubMed

    Yang, Li-Ming; Dornfeld, Matthew; Frauenheim, Thomas; Ganz, Eric

    2015-10-21

    We predict a highly stable and robust atomically thin gold monolayer with a hexagonal close packed lattice stabilized by metallic bonding with contributions from strong relativistic effects and aurophilic interactions. We have shown that the framework of the Au monolayer can survive 10 ps MD annealing simulations up to 1400 K. The framework is also able to survive large motions out of the plane. Due to the smaller number of bonds per atom in the 2D layer compared to the 3D bulk we observe significantly enhanced energy per bond (0.94 vs. 0.52 eV per bond). This is similar to the increase in bond strength going from 3D diamond to 2D graphene. It is a non-magnetic metal, and was found to be the global minima in the 2D space. Phonon dispersion calculations demonstrate high kinetic stability with no negative modes. This 2D gold monolayer corresponds to the top monolayer of the bulk Au(111) face-centered cubic lattice. The close-packed lattice maximizes the aurophilic interactions. We find that the electrons are completely delocalized in the plane and behave as 2D nearly free electron gas. We hope that the present work can inspire the experimental fabrication of novel free standing 2D metal systems.

  5. Nanotubes based on monolayer blue phosphorus

    NASA Astrophysics Data System (ADS)

    Montes, E.; Schwingenschlögl, U.

    2016-07-01

    We demonstrate structural stability of monolayer zigzag and armchair blue phosphorus nanotubes by means of molecular dynamics simulations. The vibrational spectrum and electronic band structure are determined and analyzed as functions of the tube diameter and axial strain. The nanotubes are found to be semiconductors with a sensitive indirect band gap that allows flexible tuning.

  6. Convective Assembly of a Particle Monolayer.

    PubMed

    Fleck, N A; McMeeking, R M; Kraus, T

    2015-12-29

    Recently, the steady-state process of convective assembly has emerged as a viable production route for colloidal monolayers. The present study models the regions of particle assembly: Region I comprises convective concentration of a particle suspension in a liquid below a meniscus, Region II comprises permeation of fluid through the dense particle monolayer, and Region III comprises capillary densification. For each region, the dominant physics and nondimensional groups are identified, and quantitative models are derived to describe the evolution of microstructure in terms of the main process parameters. The concentration profile within the assembly zone of Region I is predicted, including the role of a concentration-dependent diffusion constant and the shape of the meniscus. The fluid flow through the assembled monolayer is treated in Region II, along with a stability calculation to reveal that isolated particle clusters do not survive on top of the monolayer. The physics of capillary crystallization is addressed in Region III, with an emphasis on the density of cracks that emerge. The Peclet number and Capillary number both play important roles but in different regions of the assembly process.

  7. Effects of cholesterol component on molecular interactions between paclitaxel and phospholipid within the lipid monolayer at the air-water interface.

    PubMed

    Zhao, Lingyun; Feng, Si-Shen

    2006-08-01

    Cholesterol is a main component of the cell membrane and could have significant effects on drug-cell membrane interactions and thus the therapeutic efficacy of the drug. It also plays an important role in liposomal formulation of drugs for controlled and targeted delivery. In this research, Langmuir film technique, atomic force microscopy (AFM) and Fourier transform infrared spectroscopy (FTIR) are employed for a systematic investigation on the effects of cholesterol component on the molecular interactions between a prototype antineoplastic drug (paclitaxel) and 1,2-dipalmitoyl-sn-glycerol-3-phosphocholine (DPPC) within the cell membrane by using the lipid monolayer at the air-water interface as a model of the lipid bilayer membrane and the biological cell membrane. Analysis of the measured surface pressure (pi) versus molecular area (a) isotherms of the mixed DPPC/paclitaxel/cholesterol monolayers at various molar ratios shows that DPPC, paclitaxel and cholesterol can form a non-ideal miscible system at the air-water interface. Cholesterol enhances the intermolecular forces between paclitaxel and DPPC, produces an area-condensing effect and thus makes the mixed monolayer more stable. Investigation of paclitaxel penetration into the mixed DPPC/cholesterol monolayer shows that the existence of cholesterol in the DPPC monolayer can considerably restrict the drug penetration into the monolayer, which may have clinical significance for diseases of high cholesterol. FTIR and AFM investigation on the mixed monolayer deposited on solid surface confirmed the obtained results.

  8. Study of structural order in porphyrin-fullerene dyad ZnDHD6ee monolayers by electron diffraction and atomic force microscopy

    SciTech Connect

    D'yakova, Yu. A.; Suvorova, E. I.; Orekhov, Andrei S.; Orekhov, Anton S.; Alekseev, A. S.; Gainutdinov, R. V.; Klechkovskaya, V. V. Tereschenko, E. Yu.; Tkachenko, N. V.; Lemmetyinen, H.; Feigin, L. A.; Kovalchuk, M. V.

    2013-11-15

    The structure of porphyrin-fullerene dyad ZnDHD6ee monolayers formed on the surface of aqueous subphase in a Langmuir trough and transferred onto solid substrates has been studied. The data obtained are interpreted using simulation of the structure of isolated molecules and their packing in monolayer and modeling of diffraction patterns from molecular aggregates having different sizes and degrees of order. Experiments on the formation of condensed ZnDHD6ee monolayers are described. The structure of these monolayers on a water surface is analyzed using {pi}-A isotherms. The structure of the monolayers transferred onto solid substrates is investigated by electron diffraction and atomic force microscopy. The unit-cell parameters of two-dimensional domains, which are characteristic of molecular packing in monolayers and deposited films, are determined. Domains are found to be organized into a texture (the molecular axes are oriented by the [001] direction perpendicular to the substrate). The monolayers contain a limited number of small 3D domains.

  9. A computer model of engineered cardiac monolayers.

    PubMed

    Kim, Jong M; Bursac, Nenad; Henriquez, Craig S

    2010-05-19

    Engineered monolayers created using microabrasion and micropatterning methods have provided a simplified in vitro system to study the effects of anisotropy and fiber direction on electrical propagation. Interpreting the behavior in these culture systems has often been performed using classical computer models with continuous properties. However, such models do not account for the effects of random cell shapes, cell orientations, and cleft spaces inherent in these monolayers on the resulting wavefront conduction. This work presents a novel methodology for modeling a monolayer of cardiac tissue in which the factors governing cell shape, cell-to-cell coupling, and degree of cleft space are not constant but rather are treated as spatially random with assigned distributions. This modeling approach makes it possible to simulate wavefront propagation in a manner analogous to performing experiments on engineered monolayer tissues. Simulated results are compared to previously published measured data from monolayers used to investigate the role of cellular architecture on conduction velocities and anisotropy ratios. We also present an estimate for obtaining the electrical properties from these networks and demonstrate how variations in the discrete cellular architecture affect the macroscopic conductivities. The simulations support the common assumption that under normal ranges of coupling strength, tissues with relatively uniform distributions of cell shapes and connectivity can be represented using continuous models with conductivities derived from random discrete cellular architecture using either global or local estimates. The results also reveal that in the presence of abrupt changes in cell orientation, local estimates of tissue properties predict smoother changes in conductivity that may not adequately predict the discrete nature of propagation at the transition sites. PMID:20441739

  10. Controlling surface functionality through generation of thiol groups in a self-assembled monolayer.

    SciTech Connect

    Lud, S. Q.; Neppl, S.; Richter, G.; Bruno, P.; Gruen, D. M.; Jordan, R.; Feulner, P.; Stutzmann, M.; Garrido, J. A.; Materials Science Division; Technische Univ. Munchen

    2010-01-01

    A lithographic method to generate reactive thiol groups on functionalized synthetic diamond for biosensor and molecular electronic applications is developed. We demonstrate that ultrananocrystalline diamond (UNCD) thin films covalently functionalized with surface-generated thiol groups allow controlled thiol-disulfide exchange surface hybridization processes. The generation of the thiol functional head groups was obtained by irradiating phenylsulfonic acid (PSA) monolayers on UNCD surfaces. The conversion of the functional headgroup of the self-assembled monolayer was verified by using X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS), and fluorescence microscopy. Our findings indicate the selective generation of reactive thiol surface groups. Furthermore, we demonstrate the grafting of yeast cytochrome c to the thiol-modified diamond surface and the electron transfer between protein and electrode.

  11. A dielectric model of self-assembled monolayer interfaces by capacitive spectroscopy.

    PubMed

    Góes, Márcio S; Rahman, Habibur; Ryall, Joshua; Davis, Jason J; Bueno, Paulo R

    2012-06-26

    The presence of self-assembled monolayers at an electrode introduces capacitance and resistance contributions that can profoundly affect subsequently observed electronic characteristics. Despite the impact of this on any voltammetry, these contributions are not directly resolvable with any clarity by standard electrochemical means. A capacitive analysis of such interfaces (by capacitance spectroscopy), introduced here, enables a clean mapping of these features and additionally presents a means of studying layer polarizability and Cole-Cole relaxation effects. The resolved resistive term contributes directly to an intrinsic monolayer uncompensated resistance that has a linear dependence on the layer thickness. The dielectric model proposed is fully aligned with the classic Helmholtz plate capacitor model and additionally explains the inherently associated resistive features of molecular films.

  12. Strain-relief by single dislocation loops in calcite crystals grown on self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Ihli, Johannes; Clark, Jesse N.; Côté, Alexander S.; Kim, Yi-Yeoun; Schenk, Anna S.; Kulak, Alexander N.; Comyn, Timothy P.; Chammas, Oliver; Harder, Ross J.; Duffy, Dorothy M.; Robinson, Ian K.; Meldrum, Fiona C.

    2016-06-01

    Most of our knowledge of dislocation-mediated stress relaxation during epitaxial crystal growth comes from the study of inorganic heterostructures. Here we use Bragg coherent diffraction imaging to investigate a contrasting system, the epitaxial growth of calcite (CaCO3) crystals on organic self-assembled monolayers, where these are widely used as a model for biomineralization processes. The calcite crystals are imaged to simultaneously visualize the crystal morphology and internal strain fields. Our data reveal that each crystal possesses a single dislocation loop that occupies a common position in every crystal. The loops exhibit entirely different geometries to misfit dislocations generated in conventional epitaxial thin films and are suggested to form in response to the stress field, arising from interfacial defects and the nanoscale roughness of the substrate. This work provides unique insight into how self-assembled monolayers control the growth of inorganic crystals and demonstrates important differences as compared with inorganic substrates.

  13. Superhigh moduli and tension-induced phase transition of monolayer gamma-boron at finite temperatures

    PubMed Central

    Zhao, Junhua; Yang, Zhaoyao; Wei, Ning; Kou, Liangzhi

    2016-01-01

    Two dimensional (2D) gamma-boron (γ-B28) thin films have been firstly reported by the experiments of the chemical vapor deposition in the latest study. However, their mechanical properties are still not clear. Here we predict the superhigh moduli (785 ± 42 GPa at 300 K) and the tension-induced phase transition of monolayer γ-B28 along a zigzag direction for large deformations at finite temperatures using molecular dynamics (MD) simulations. The new phase can be kept stable after unloading process at these temperatures. The predicted mechanical properties are reasonable when compared with our results from density functional theory. This study provides physical insights into the origins of the new phase transition of monolayer γ-B28 at finite temperatures. PMID:26979283

  14. Robust room temperature valley polarization in monolayer and bilayer WS2.

    PubMed

    Nayak, Pramoda K; Lin, Fan-Cheng; Yeh, Chao-Hui; Huang, Jer-Shing; Chiu, Po-Wen

    2016-03-21

    We report robust room temperature valley polarization in chemical-vapor-deposition (CVD) grown monolayer and bilayer WS2via polarization-resolved photoluminescence measurements using excitation below the bandgap. We show that excitation with energy slightly below the bandgap of the multi-valleyed transition metal chalcogenides can effectively suppress the random redistribution of excited electrons and, thereby, greatly enhance the efficiency of valley polarization at room temperature. Compared to mechanically exfoliated WS2, our CVD grown WS2 films also show enhancement in the coupling of spin, layer and valley degree of freedom and, therefore, provide improved valley polarization. At room temperature, using below-bandgap excitation and CVD grown monolayer and bilayer WS2, we have reached a record-high valley polarization of 35% and 80%, respectively, exceeding the previously reported values of 10% and 65% for mechanically exfoliated WS2 layers using resonant excitation. This observation provides a new direction to enhance valley control at room temperature.

  15. Reversible modification of the structural and electronic properties of a boron nitride monolayer by CO intercalation.

    PubMed

    Ng, May Ling; Shavorskiy, Andrey; Rameshan, Christoph; Mikkelsen, Anders; Lundgren, Edvin; Preobrajenski, Alexei; Bluhm, Hendrik

    2015-04-01

    We demonstrate the reversible intercalation of CO between a hexagonal boron nitride (h-BN) monolayer and a Rh(111) substrate above a threshold CO pressure of 0.01 mbar at room temperature. The intercalation of CO results in the flattening of the originally corrugated h-BN nanomesh and an electronic decoupling of the BN layer from the Rh substrate. The intercalated CO molecules assume a coverage and adsorption site distribution comparable to that on the free Rh(111) surface at similar conditions. The pristine h-BN nanomesh is reinstated upon heating to above 625 K. These observations may open up opportunities for a reversible tuning of the electronic and structural properties of monolayer BN films. PMID:25712198

  16. Genetically improved monolayer-forming tobacco mosaic viruses to generate nanostructured semiconducting bio/inorganic hybrids.

    PubMed

    Atanasova, Petia; Stitz, Nina; Sanctis, Shawn; Maurer, Johannes H M; Hoffmann, Rudolf C; Eiben, Sabine; Jeske, Holger; Schneider, Jörg J; Bill, Joachim

    2015-04-01

    The genetically determined design of structured functional bio/inorganic materials was investigated by applying a convective assembly approach. Wildtype tobacco mosaic virus (wt TMV) as well as several TMV mutants were organized on substrates over macroscopic-length scales. Depending on the virus type, the self-organization behavior showed pronounced differences in the surface arrangement under the same convective assembly conditions. Additionally, under varying assembly parameters, the virus particles generated structures encompassing morphologies emerging from single micrometer long fibers aligned parallel to the triple-contact line through disordered but dense films to smooth and uniform monolayers. Monolayers with diverse packing densities were used as templates to form TMV/ZnO hybrid materials. The semiconducting properties can be directly designed and tuned by the variation of the template architecture which are reflected in the transistor performance. PMID:25768914

  17. Pit Formation during the Self-Assembly of Dithiol Monolayers on Au(111)

    NASA Astrophysics Data System (ADS)

    Macdairmid, A. R.; Cappello, M. L.; Keeler, W. J.; Banks, J. T.; Gallagher, M. C.

    2000-03-01

    The formation of pits one gold atom deep during the growth of alkanethiol monolayers on Au(111), has been observed previously by others. Explanations for pit formation include etching of the substrate, or mass transport of gold atom + thiol molecule on the surface, due to changes in surface energy^1. We have investigated the structure of dithiothreitol (DTT) SAMs on Au(111). Ex situ STM measurements indicate similar pitting occurs during formation of the dithiol monolayer. The degree of pitting depends on exposure time, sample temperature during formation, and subsequent annealing of the sample. Pitting is enhanced considerasbly when DTT is coordinated with Ti, in fact DTT/Ti films exhibit considerable pit motion during STM imaging. ^1 F. Teran et al. Electrochimica Acta 44, 1053 (1998).

  18. Strain-relief by single dislocation loops in calcite crystals grown on self-assembled monolayers

    PubMed Central

    Ihli, Johannes; Clark, Jesse N.; Côté, Alexander S.; Kim, Yi-Yeoun; Schenk, Anna S.; Kulak, Alexander N.; Comyn, Timothy P.; Chammas, Oliver; Harder, Ross J.; Duffy, Dorothy M.; Robinson, Ian K.; Meldrum, Fiona C.

    2016-01-01

    Most of our knowledge of dislocation-mediated stress relaxation during epitaxial crystal growth comes from the study of inorganic heterostructures. Here we use Bragg coherent diffraction imaging to investigate a contrasting system, the epitaxial growth of calcite (CaCO3) crystals on organic self-assembled monolayers, where these are widely used as a model for biomineralization processes. The calcite crystals are imaged to simultaneously visualize the crystal morphology and internal strain fields. Our data reveal that each crystal possesses a single dislocation loop that occupies a common position in every crystal. The loops exhibit entirely different geometries to misfit dislocations generated in conventional epitaxial thin films and are suggested to form in response to the stress field, arising from interfacial defects and the nanoscale roughness of the substrate. This work provides unique insight into how self-assembled monolayers control the growth of inorganic crystals and demonstrates important differences as compared with inorganic substrates. PMID:27302863

  19. Strain-relief by single dislocation loops in calcite crystals grown on self-assembled monolayers.

    PubMed

    Ihli, Johannes; Clark, Jesse N; Côté, Alexander S; Kim, Yi-Yeoun; Schenk, Anna S; Kulak, Alexander N; Comyn, Timothy P; Chammas, Oliver; Harder, Ross J; Duffy, Dorothy M; Robinson, Ian K; Meldrum, Fiona C

    2016-01-01

    Most of our knowledge of dislocation-mediated stress relaxation during epitaxial crystal growth comes from the study of inorganic heterostructures. Here we use Bragg coherent diffraction imaging to investigate a contrasting system, the epitaxial growth of calcite (CaCO3) crystals on organic self-assembled monolayers, where these are widely used as a model for biomineralization processes. The calcite crystals are imaged to simultaneously visualize the crystal morphology and internal strain fields. Our data reveal that each crystal possesses a single dislocation loop that occupies a common position in every crystal. The loops exhibit entirely different geometries to misfit dislocations generated in conventional epitaxial thin films and are suggested to form in response to the stress field, arising from interfacial defects and the nanoscale roughness of the substrate. This work provides unique insight into how self-assembled monolayers control the growth of inorganic crystals and demonstrates important differences as compared with inorganic substrates. PMID:27302863

  20. Study of the aggregation of human insulin Langmuir monolayer.

    PubMed

    Liu, Wei; Johnson, Sheba; Micic, Miodrag; Orbulescu, Jhony; Whyte, Jeffrey; Garcia, Andrew R; Leblanc, Roger M

    2012-02-21

    The human insulin (HI) Langmuir monolayer at the air-water interface was systematically investigated in the presence and absence of Zn(II) ions in the subphase. HI samples were dissolved in acidic (pH 2) and basic (pH 9) aqueous solutions and then spread at the air-water interface. Spectroscopic data of aqueous solutions of HI show a difference in HI conformation at different pH values. Moreover, the dynamics of the insulin protein showed a dependence on the concentration of Zn(II) ions. In the absence of Zn(II) ions in the subphase, the acidic and basic solutions showed similar behavior at the air-water interface. In the presence of Zn(II) ions in the subphase, the surface pressure-area and surface potential-area isotherms suggest that HI may aggregate at the air-water interface. It was observed that increasing the concentration of Zn(II) ions in the acidic (pH 2) aqueous solution of HI led to an increase of the area at a specific surface pressure. It was also seen that the conformation of HI in the basic (pH 9) medium had a reverse effect (decrease in the surface area) with the increase of the concentration of Zn(II) ions in solution. From the compression-decompression cycles we can conclude that the aggregated HI film at air-water interface is not stable and tends to restore a monolayer of monomers. These results were confirmed from UV-vis and fluorescence spectroscopy analysis. Infrared reflection-absorption and circular dichroism spectroscopy techniques were used to determine the secondary structure and orientation changes of HI by zinc ions. Generally, the aggregation process leads to a conformation change from α-helix to β-strand and β-turn, and at the air-water interface, the aggregation process was likewise seen to induce specific orientations for HI in the acidic and basic media. A proposed surface orientation model is presented here as an explanation to the experimental data, shedding light for further research on the behavior of insulin as a Langmuir

  1. Characterization of 10,12-pentacosadiynoic acid Langmuir-Blodgett monolayers and their use in metal-insulator-metal tunnel devices.

    PubMed

    Sharma, Saumya; Khawaja, Mohamad; Ram, Manoj K; Goswami, D Yogi; Stefanakos, Elias

    2014-01-01

    The characterization of Langmuir-Blodgett thin films of 10,12-pentacosadiynoic acid (PDA) and their use in metal-insulator-metal (MIM) devices were studied. The Langmuir monolayer behavior of the PDA film was studied at the air/water interface using surface tension-area isotherms of polymeric and monomeric PDA. Langmuir-Blodgett (LB, vertical deposition) and Langmuir-Schaefer (LS, horizontal deposition) techniques were used to deposit the PDA film on various substrates (glass, quartz, silicon, and nickel-coated film on glass). The electrochemical, electrical and optical properties of the LB and LS PDA films were studied using cyclic voltammetry, current-voltage characteristics (I-V), and UV-vis and FTIR spectroscopies. Atomic force microscopy measurements were performed in order to analyze the surface morphology and roughness of the films. A MIM tunnel diode was fabricated using a PDA monolayer assembly as the insulating barrier, which was sandwiched between two nickel layers. The precise control of the thickness of the insulating monolayers proved critical for electron tunneling to take place in the MIM structure. The current-voltage characteristics of the MIM diode revealed tunneling behavior in the fabricated Ni-PDA LB film-Ni structures.

  2. Suppression of the coffee-ring effect by self-assembling graphene oxide and monolayer titania

    NASA Astrophysics Data System (ADS)

    Sun, Pengzhan; Ma, Renzhi; Wang, Kunlin; Zhong, Minlin; Wei, Jinquan; Wu, Dehai; Sasaki, Takayoshi; Zhu, Hongwei

    2013-02-01

    The in situ self-assembly of two types of typical two-dimensional (2D) nanomaterials (i.e., graphene oxide (GO) and monolayer titania (TO)) is realized using a simple drop-casting method. Within the as-prepared hybrid films, the GO and TO nanosheets arrange alternately into a lamellar structure. Notably, the hybridization of GO and TO suppresses the formation of coffee-rings when drop-cast, which is attributed to the strong interactions between the GO and TO nanosheets. Finally, the mechanism for the in situ hybridization of these two types of nanosheets into heterogeneous lamellar films and the suppression of the coffee-ring effect are discussed. These results demonstrate the potential applications of drop-cast hybrid films for high-quality membrane deposition from liquid phases.

  3. Interaction of L-Phenylalanine with a Phospholipid Monolayer at the Water-Air Interface.

    PubMed

    Griffith, Elizabeth C; Perkins, Russell J; Telesford, Dana-Marie; Adams, Ellen M; Cwiklik, Lukasz; Allen, Heather C; Roeselová, Martina; Vaida, Veronica

    2015-07-23

    The interaction of L-phenylalanine with a 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) monolayer at the air-water interface was explored using a combination of experimental techniques and molecular dynamics (MD) simulations. By means of Langmuir trough methods and Brewster angle microscopy, L-phenylalanine was shown to significantly alter the interfacial tension and the surface domain morphology of the DPPC film. In addition, confocal microscopy was used to explore the aggregation state of L-phenylalanine in the bulk aqueous phase. Finally, MD simulations were performed to gain molecular-level information on the interactions of L-phenylalanine and DPPC at the interface. Taken together, these results show that L-phenylalanine intercalates into a DPPC film at the air-water interface, thereby affecting the surface tension, phase morphology, and ordering of the DPPC film. The results are discussed in the context of biological systems and the mechanism of diseases such as phenylketonuria.

  4. Insertion Mechanism of a Poly(ethylene oxide)-poly(butylene oxide) Block Copolymer into a DPPC Monolayer

    SciTech Connect

    Leiske, Danielle L.; Meckes, Brian; Miller, Chad E.; Wu, Cynthia; Walker, Travis W.; Lin, Binhua; Meron, Mati; Ketelson, Howard A.; Toney, Michael F.; Fuller, Gerald G.

    2012-02-06

    Interactions between amphiphilic block copolymers and lipids are of medical interest for applications such as drug delivery and the restoration of damaged cell membranes. A series of monodisperse poly(ethylene oxide)-poly(butylene oxide) (EOBO) block copolymers were obtained with two ratios of hydrophilic/hydrophobic block lengths. We have explored the surface activity of EOBO at a clean interface and under 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) monolayers as a simple cell membrane model. At the same subphase concentration, EOBO achieved higher equilibrium surface pressures under DPPC compared to a bare interface, and the surface activity was improved with longer poly(butylene oxide) blocks. Further investigation of the DPPC/EOBO monolayers showed that combined films exhibited similar surface rheology compared to pure DPPC at the same surface pressures. DPPC/EOBO phase separation was observed in fluorescently doped monolayers, and within the liquid-expanded liquid-condensed coexistence region for DPPC, EOBO did not drastically alter the liquid-condensed domain shapes. Grazing incidence X-ray diffraction (GIXD) and X-ray reflectivity (XRR) quantitatively confirmed that the lattice spacings and tilt of DPPC in lipid-rich regions of the monolayer were nearly equivalent to those of a pure DPPC monolayer at the same surface pressures.

  5. Monolayer PtSe 2 , a New Semiconducting Transition-Metal-Dichalcogenide, Epitaxially Grown by Direct Selenization of Pt

    DOE PAGES

    Wang, Yeliang; Li, Linfei; Yao, Wei; Song, Shiru; Sun, J. T.; Pan, Jinbo; Ren, Xiao; Li, Chen; Okunishi, Eiji; Wang, Yu-Qi; et al

    2015-05-21

    For single-layer transition-metal dichalcogenides (TMDs) receive significant attention due to their intriguing physical properties for both fundamental research and potential applications in electronics, optoelectronics, spintronics, catalysis, and so on. Here, we demonstrate the epitaxial growth of high-quality single-crystal, monolayer platinum diselenide (PtSe2), a new member of the layered TMDs family, by a single step of direct selenization of a Pt(111) substrate. We found that a combination of atomic-resolution experimental characterizations and first-principle theoretic calculations reveals the atomic structure of the monolayer PtSe2/Pt(111). Angle-resolved photoemission spectroscopy measurements confirm for the first time the semiconducting electronic structure of monolayer PtSe2 (in contrastmore » to its semimetallic bulk counterpart). The photocatalytic activity of monolayer PtSe2 film is evaluated by a methylene-blue photodegradation experiment, demonstrating its practical application as a promising photocatalyst. Moreover, circular polarization calculations predict that monolayer PtSe2 has also potential applications in valleytronics.« less

  6. Interaction of the Antimicrobial Peptides Rhesus θ-Defensin and Porcine Protegrin-1 with Anionic Phospholipid Monolayers.

    PubMed

    Knyght, Ivana; Clifton, Luke; Saaka, Yussif; Lawrence, M Jayne; Barlow, David J

    2016-07-26

    A combination of Langmuir isotherm, Brewster angle microscopy (BAM), and neutron reflectivity studies have been performed to gain insight into the effects on model bacterial cell membranes of the antimicrobial peptides, Rhesus θ-defensin 1 (RTD-1), and porcine protegrin 1 (PG-1). The peptides were interacted with monolayers spread at the air-water interface and prepared from a 3:1 molar mixture of phosphatidylethanolamine and phosphatidylglycerol used to approximate the cell membranes of Gram positive bacteria. The Langmuir film balance measurements show that both peptides perturb the lipid monolayers causing an increase in surface pressure, and the BAM studies show that each results in the formation of small domains within the lipid films, around 5 μm diameter. The overall change in monolayer surface pressure caused by PG-1, however, is a little more pronounced than that due to RTD-1 (+8.5 mN·m(-1) vs +5.5 mN·m(-1)), and the rate of its initial interaction with the monolayer is a little more rapid than that for RTD-1. The neutron reflectivity studies also show differences for PG-1 and RTD-1, with the model fits to these data showing that the more amphiphilic PG-1 becomes fully embedded within the lipid film-causing an extension of the lipid acyl chains but leaving the thickness of the lipid headgroup layer unaffected-while RTD-1 is seen to insert less deeply-causing the same extension of the lipid acyl chains as PG-1 but also causing a significant increase in thickness of the lipid headgroup layer. The various differing effects of the two peptides on anionic lipid monolayers are discussed in the context of their differing hemolytic activities, and their proposed differing propensities to form transmembrane pores. PMID:27357217

  7. Investigation of Mixed Surfactant Films at Water Surface Using Molecular Dynamics Simulations.

    PubMed

    Habartová, Alena; Roeselová, Martina; Cwiklik, Lukasz

    2015-10-27

    Multicomponent Langmuir monolayers are important models of organic coatings of naturally occurring water-vapor interfaces such as the surfaces of oceans or aerosol particles. We investigated mixed monolayers comprised of palmitic acid, C15H31COOH (PA) and 1-bromoalkanes of different chain length (C5, C10, and C16) at the air-water interface employing classical molecular dynamics simulations. Different composition ratios and lateral compression of the monolayers were considered. The structural parameters, such as density profiles, and deuterium order parameter, evaluated as functions of composition and the lateral film packing, provide microscopic information about organization and dynamics of the mixed monolayers. Simulations demonstrate that stable and well mixed monolayers are formed by the mixtures of PA and BrC16H33 (BrCl6), whereas the two considered shorter bromoalkanes, BrC5H11 (BrC5) and BrC10H21 (BrC10), do not form stable films. This is in accord with earlier experimental studies. Under high lateral pressures, in PA/BrC10 mixed systems molecules of the bromoalkane readily flip in the monolayer and subsequently leave the film, while the molecules of the longer BrC16 are expelled from the PA film but no flipping occurs. These results suggest that the film collapse under pressure is preceded by squeezing-out of bromoalkanes from the PA monolayer. PMID:26439598

  8. Ligand Replacement Approach to Raman-Responded Molecularly Imprinted Monolayer for Rapid Determination of Penicilloic Acid in Penicillin.

    PubMed

    Zhang, Liying; Jin, Yang; Huang, Xiaoyan; Zhou, Yujie; Du, Shuhu; Zhang, Zhongping

    2015-12-01

    Penicilloic acid (PA) is a degraded byproduct of penicillin and often causes fatal allergies to humans, but its rapid detection in penicillin drugs remains a challenge due to its similarity to the mother structure of penicillin. Here, we reported a ligand-replaced molecularly imprinted monolayer strategy on a surface-enhanced Raman scattering (SERS) substrate for the specific recognition and rapid detection of Raman-inactive PA in penicillin. The bis(phenylenediamine)-Cu(2+)-PA complex was first synthesized and stabilized onto the surface of silver nanoparticle film that was fabricated by a bromide ion-added silver mirror reaction. A molecularly imprinted monolayer was formed by the further modification of alkanethiol around the stabilized complex on the Ag film substrate, and the imprinted recognition site was then created by the replacement of the complex template with Raman-active probe molecule p-aminothiophenol. When PA rebound into the imprinted site in the alkanethiol monolayer, the SERS signal of p-aminothiophenol exhibited remarkable enhancement with a detection limit of 0.10 nM. The imprinted monolayer can efficiently exclude the interference of penicillin and thus provides a selective determination of 0.10‰ (w/w) PA in penicillin, which is about 1 order of magnitude lower than the prescribed residual amount of 1.0‰. The strategy reported here is simple, rapid and inexpensive compared to the traditional chromatography-based methods. PMID:26545037

  9. Ligand Replacement Approach to Raman-Responded Molecularly Imprinted Monolayer for Rapid Determination of Penicilloic Acid in Penicillin.

    PubMed

    Zhang, Liying; Jin, Yang; Huang, Xiaoyan; Zhou, Yujie; Du, Shuhu; Zhang, Zhongping

    2015-12-01

    Penicilloic acid (PA) is a degraded byproduct of penicillin and often causes fatal allergies to humans, but its rapid detection in penicillin drugs remains a challenge due to its similarity to the mother structure of penicillin. Here, we reported a ligand-replaced molecularly imprinted monolayer strategy on a surface-enhanced Raman scattering (SERS) substrate for the specific recognition and rapid detection of Raman-inactive PA in penicillin. The bis(phenylenediamine)-Cu(2+)-PA complex was first synthesized and stabilized onto the surface of silver nanoparticle film that was fabricated by a bromide ion-added silver mirror reaction. A molecularly imprinted monolayer was formed by the further modification of alkanethiol around the stabilized complex on the Ag film substrate, and the imprinted recognition site was then created by the replacement of the complex template with Raman-active probe molecule p-aminothiophenol. When PA rebound into the imprinted site in the alkanethiol monolayer, the SERS signal of p-aminothiophenol exhibited remarkable enhancement with a detection limit of 0.10 nM. The imprinted monolayer can efficiently exclude the interference of penicillin and thus provides a selective determination of 0.10‰ (w/w) PA in penicillin, which is about 1 order of magnitude lower than the prescribed residual amount of 1.0‰. The strategy reported here is simple, rapid and inexpensive compared to the traditional chromatography-based methods.

  10. Wetting, mixing, and phase transitions in Langmuir-Gibbs films.

    PubMed

    Sloutskin, E; Sapir, Z; Bain, C D; Lei, Q; Wilkinson, K M; Tamam, L; Deutsch, M; Ocko, B M

    2007-09-28

    Millimolar bulk concentrations of the surfactant cetyltrimethylammonium bromide (CTAB) induce spreading of alkanes, H(CH(2))(n)H (denoted C(n)) 12< or =n< or =21, on the water surface, which is not otherwise wet by these alkanes. The novel Langmuir-Gibbs film (LGF) formed is a liquidlike monolayer comprising both alkanes and CTAB tails. Upon cooling, an ordering transition occurs, yielding a hexagonally packed, quasi-2D crystal. For 11< or =n< or =17 this surface-frozen LGF is a crystalline monolayer. For 18< or =n< or =21 the LGF is a bilayer with a crystalline, pure-alkane, upper monolayer, and a liquidlike lower monolayer. The phase diagram and film structure were determined by x-ray, ellipsometry, and surface tension measurements. A thermodynamic theory accounts quantitatively for the observations. PMID:17930612

  11. Fracture Characteristics of Monolayer CVD-Graphene

    PubMed Central

    Hwangbo, Yun; Lee, Choong-Kwang; Kim, Sang-Min; Kim, Jae-Hyun; Kim, Kwang-Seop; Jang, Bongkyun; Lee, Hak-Joo; Lee, Seoung-Ki; Kim, Seong-Su; Ahn, Jong-Hyun; Lee, Seung-Mo

    2014-01-01

    We have observed and analyzed the fracture characteristics of the monolayer CVD-graphene using pressure bulge testing setup. The monolayer CVD-graphene has appeared to undergo environmentally assisted subcritical crack growth in room condition, i.e. stress corrosion cracking arising from the adsorption of water vapor on the graphene and the subsequent chemical reactions. The crack propagation in graphene has appeared to be able to be reasonably tamed by adjusting applied humidity and stress. The fracture toughness, describing the ability of a material containing inherent flaws to resist catastrophic failure, of the CVD-graphene has turned out to be exceptionally high, as compared to other carbon based 3D materials. These results imply that the CVD-graphene could be an ideal candidate as a structural material notwithstanding environmental susceptibility. In addition, the measurements reported here suggest that specific non-continuum fracture behaviors occurring in 2D monoatomic structures can be macroscopically well visualized and characterized. PMID:24657996

  12. Piezoelectric monolayers as nonlinear energy harvesters.

    PubMed

    López-Suárez, Miquel; Pruneda, Miguel; Abadal, Gabriel; Rurali, Riccardo

    2014-05-01

    We study the dynamics of h-BN monolayers by first performing ab-initio calculations of the deformation potential energy and then solving numerically a Langevine-type equation to explore their use in nonlinear vibration energy harvesting devices. An applied compressive strain is used to drive the system into a nonlinear bistable regime, where quasi-harmonic vibrations are combined with low-frequency swings between the minima of a double-well potential. Due to its intrinsic piezoelectric response, the nonlinear mechanical harvester naturally provides an electrical power that is readily available or can be stored by simply contacting the monolayer at its ends. Engineering the induced nonlinearity, a 20 nm2 device is predicted to harvest an electrical power of up to 0.18 pW for a noisy vibration of 5 pN. PMID:24722065

  13. Spontaneous phase separation during self-assembly in bi-dispersed spherical iron oxide nanoparticle monolayers

    SciTech Connect

    Stanley, Jacob; Boucheron, Leandra; Shpyrko, Oleg E-mail: oshpyrko@physics.ucsd.edu; Lin, Binhua E-mail: oshpyrko@physics.ucsd.edu; Meron, Mati

    2015-04-20

    Recent developments in the synthesis of iron oxide nanoparticles have resulted in the ability to fabricate roughly spherical particles with extremely high size uniformity (low polydispersity). These particles can form self-assembled monolayer films at an air-water interface. When the polydispersity of the particles is low, these monolayers can be well-ordered over a length scale dozens of times the particle size. The van der Waals force between the particles is what drives this self-assembly. Through the use of Grazing Incidence X-Ray Diffraction we demonstrate that, when these films are formed at the liquid surface from bi-dispersed solutions containing 10 and 20 nm spherical particles suspended in chloroform, the particles phase separate into well-ordered patches during the self-assembly process. Furthermore, the domain sizes of these phase separated regions are at most 2–3 times smaller than that of a film comprising only mono-dispersed particles and their degree of disorder is comparable. This is shown for multiple solutions with differing ratios of 10 and 20 nm particles.

  14. Atomistic simulations of langmuir monolayer collapse.

    PubMed

    Lorenz, Christian D; Travesset, Alex

    2006-11-21

    Monolayers at the vapor/water interface collapse by exploring the third dimension at sufficient lateral compression, either by forming three-dimensional structures or by solubilization into the aqueous solution. In this paper, we provide an atomistic description of collapse from molecular dynamics (MD) simulations. More specifically, we investigate monolayers of arachidic acids spread on pure water and in an aqueous solution with Ca2+ ions in the subphase. In both cases, it is found that the collapsed systems generally lead to the formation of multilayer structures, which in the system with Ca2+ ions, proceeds by an intermediate regime where the monolayer exhibits significant roughness (of the order of 4 A). If no roughness is present, the system forms collapsed structures into the aqueous solution. The computational cost of atomic MD limits our simulations to relatively small system sizes, fast compression rates, and temporal scales on the order of a nanosecond. We discuss the issues caused by these limitations and present a detailed discussion of how the collapse regime proceeds at long time scales. We conclude with a summary of the implications of our results for further theoretical and experimental studies. PMID:17106994

  15. Investigation on gallium ions impacting monolayer graphene

    SciTech Connect

    Wu, Xin; Zhao, Haiyan Yan, Dong; Pei, Jiayun

    2015-06-15

    In this paper, the physical phenomena of gallium (Ga{sup +}) ion impacting monolayer graphene in the nanosculpting process are investigated experimentally, and the mechanisms are explained by using Monte Carlo (MC) and molecular dynamics (MD) simulations. Firstly, the MC method is employed to clarify the phenomena happened to the monolayer graphene target under Ga{sup +} ion irradiation. It is found that substrate has strong influence on the damage mode of graphene. The mean sputtering yield of graphene under 30 keV Ga{sup +} ion irradiation is 1.77 and the least ion dose to completely remove carbon atoms in graphene is 21.6 ion/nm{sup 2}. Afterwards, the focused ion beam over 21.6 ion/nm{sup 2} is used for the irradiation on a monolayer graphene supported by SiO2 experimentally, resulting in the nanostructures, i.e., nanodot and nanowire array on the graphene. The performances of the nanostructures are characterized by atomic force microscopy and Raman spectrum. A plasma plume shielding model is put forward to explain the nanosculpting results of graphene under different irradiation parameters. In addition, two damage mechanisms are found existing in the fabrication process of the nanostructures by using empirical MD simulations. The results can help us open the possibilities for better control of nanocarbon devices.

  16. Intrinsic structural defects in monolayer molybdenum disulfide

    SciTech Connect

    Zhou, Wu; Idrobo Tapia, Juan C

    2013-01-01

    Monolayer molybdenum disulfide (MoS2) is a two-dimensional direct band gap semiconductor with distinctive mechanical, electronic, optical and chemical properties that can be utilized for novel nanoelectronics and optoelectronics devices. The performance of these electronic devices strongly depends on the quality and defect morphology of the MoS2 layers. Yet, little is known about the atomic structure of defects present in monolayer MoS2 and their influences on the material properties. Here we provide a systematic study of various intrinsic structural defects, including point defects, grain boundaries, and edges, in chemical vapor phase grown monolayer MoS2 via direct atomic resolution imaging, and explore their energy landscape and electronic properties using first-principles calculations. We discover that one-dimensional metallic wires can be created via two different types of 60 grain boundaries consisting of distinct 4-fold ring chains. A new type of edge reconstruction, representing a transition state during growth, was also identified, providing insights into the material growth mechanism. The atomic scale study of structural defects presented here brings new opportunities to tailor the properties of MoS2 via controlled synthesis and defect engineering.

  17. Exploring atomic defects in molybdenum disulphide monolayers

    PubMed Central

    Hong, Jinhua; Hu, Zhixin; Probert, Matt; Li, Kun; Lv, Danhui; Yang, Xinan; Gu, Lin; Mao, Nannan; Feng, Qingliang; Xie, Liming; Zhang, Jin; Wu, Dianzhong; Zhang, Zhiyong; Jin, Chuanhong; Ji, Wei; Zhang, Xixiang; Yuan, Jun; Zhang, Ze

    2015-01-01

    Defects usually play an important role in tailoring various properties of two-dimensional materials. Defects in two-dimensional monolayer molybdenum disulphide may be responsible for large variation of electric and optical properties. Here we present a comprehensive joint experiment–theory investigation of point defects in monolayer molybdenum disulphide prepared by mechanical exfoliation, physical and chemical vapour deposition. Defect species are systematically identified and their concentrations determined by aberration-corrected scanning transmission electron microscopy, and also studied by ab-initio calculation. Defect density up to 3.5 × 1013 cm−2 is found and the dominant category of defects changes from sulphur vacancy in mechanical exfoliation and chemical vapour deposition samples to molybdenum antisite in physical vapour deposition samples. Influence of defects on electronic structure and charge-carrier mobility are predicted by calculation and observed by electric transport measurement. In light of these results, the growth of ultra-high-quality monolayer molybdenum disulphide appears a primary task for the community pursuing high-performance electronic devices. PMID:25695374

  18. Spin-Cast and Patterned Organophosphonate Self-Assembled Monolayer Dielectrics on Metal-Oxide-Activated Si

    SciTech Connect

    O Acton; D Hutchins; L Arnadottir; T Weidner; N Cernetic; G Ting; T Kim; D Castner; H Ma; A Jen

    2011-12-31

    An efficient process is developed for modifying Si with self-assembled monolayers (SAMs) through in situ metal oxide surface activation and microcontact printing or spin-coating of phosphonic-acid-based molecules. The utility of this process is demonstrated by fabricating self-organized and solution-processed low-voltage organic thin-film transistors enabled by patterned and spin-cast phosphonate SAM/metal oxide hybrid dielectrics.

  19. Monolayer MXenes: promising half-metals and spin gapless semiconductors

    NASA Astrophysics Data System (ADS)

    Gao, Guoying; Ding, Guangqian; Li, Jie; Yao, Kailun; Wu, Menghao; Qian, Meichun

    2016-04-01

    Half-metals and spin gapless semiconductors are promising candidates for spintronic applications due to the complete (100%) spin polarization of electrons around the Fermi level. Based on recent experimental and theoretical findings of graphene-like monolayer transition metal carbides and nitrides (also known as MXenes), we demonstrate using first-principles calculations that monolayers Ti2C and Ti2N exhibit nearly half-metallic ferromagnetism with the magnetic moments of 1.91 and 1.00μB per formula unit, respectively, while monolayer V2C is a metal with unstable antiferromagnetism, and monolayer V2N is a nonmagnetic metal. Interestingly, under a biaxial strain, there is a phase transition from a nearly half-metal to truly half-metal, spin gapless semiconductor, and metal for monolayer Ti2C. Monolayer Ti2N is still a nearly half-metal under a suitable biaxial strain. Large magnetic moments can be induced by the biaxial tensile and compressive strains for monolayer V2C and V2N, respectively. We also show that the structures of these four monolayer MXenes are stable according to the calculated formation energy and phonon spectrum. Our investigations suggest that, unlike monolayer graphene, monolayer MXenes Ti2C and Ti2N without vacancy, doping or external electric field exhibit intrinsic magnetism, especially the half-metallic ferromagnetism and spin gapless semiconductivity, which will stimulate further studies on possible spintronic applications for new two-dimensional materials of MXenes.

  20. Surface biophysics of the surface monolayer theory is incompatible with regional lung function.

    PubMed Central

    Scarpelli, E M; Mautone, A J

    1994-01-01

    The surface monolayer theory of Clements was tested on open surface films of calf lung surfactant extract in a leak-free vertical film surface balance in which alveolar area (A) changes in each lung zone were simulated in accordance with the theory. We found that: 1) physiologically necessary low surface tension (gamma), < 4 dyn/cm, was sustained only by continuous film compression ("expiration"); 2) compression from A equivalent to total lung capacity to functional residual capacity produced fleeting gamma reduction in all zones and quick reversal to high gamma with A changes that simulated tidal volume (VT) breathing at both 14 (adult) and 40 (neonatal) cpm; 3) phase differences between gamma and A axes of VT loops that indicate mixed surface film composition may be attributable to film inertia and viscoelasticity; 4) estimated alveolar retraction pressure due to gamma (P gamma) exceeds "net" transpulmonary pressure, i.e., favors alveolar collapse, under virtually all conditions of the theory in all zones; 5) return to transient, fleeting low gamma in successive VT cycles was determined by the inherent difference in compression and decompression rates, which results in exhaustion of available A in very few cycles; 6) the "sigh", which restores stable low gamma according to the theory, actually produced unstable high gamma during virtually all phases of the maneuver. In contrast, closed bubble films of the surfactant were structurally stable and produce stable near 0 gamma and P gamma. Images FIGURE 4 FIGURE 5 PMID:7811918

  1. Synthetic peptide monolayers: Probing structure, attachment, and hydration conduction with STM

    NASA Astrophysics Data System (ADS)

    Bergeron, David Joseph

    2000-10-01

    Although the scanning tunneling microscope (STM) has been used in many studies of proteins and other biological molecules, the interpretation of the data has been hampered by a limited understanding of image contrast and tip-sample interactions. It has been recognized that adsorbed water can carry the currents necessary for STM imaging, and it has been speculated that the mechanism of charge transport is based on the exchange of protons along hydrogen-bonded networks. While a water film facilitates the imaging of proteins, it hampers efforts to use STM to probe the electronic structure of redox proteins. The physics of charge transfer in proteins and the intricacies of imaging large molecules with STM can be studied using synthetic proteins. A protein designed with engineerable electron transfer properties, a hydrophilic exterior and mechanisms for attachment to surfaces has been studied using both STM and fixed-electrode conductivity measurements. The effects of immobilization strategy on image quality were investigated by preparing monolayers using self-assembly, Langmuir-Blodgett and monolayer insertion techniques and imaging these films in both humid air and vacuum. The molecules were easily imaged in humid air due to the adsorbed water film, but dehydration in vacuum introduced a conductance gap which prevented the proteins from being imaged within a wide voltage range. The molecules were subjected to large forces when the tip scanned over them without retracting from the surface and peptides were displaced in ways which reflected the strength of their attachment to the surface. In the course of these studies, new STM imaging phenomena have been observed including meniscus-limited lateral resolution, and intermittent imaging of covalently attached molecules. The conductivity of protein films deposited between fixed electrodes depended strongly on hydration, and the experimental arrangement provides a platform for further study of the mechanism of conduction

  2. Visualization of two-dimensional single chain conformations solubilized in a miscible polymer blend monolayer by atomic force microscopy.

    PubMed

    Sugihara, Kouki; Kumaki, Jiro

    2012-06-01

    Polymer Langmuir monolayers spread on a water surface are one of the best models for two-dimensional (2D) polymer and have been extensively studied. However, the most fundamental issue in understanding a 2D film, the polymer chain packing in the film, is still not well-understood, especially from the experimental point of view. Direct observation of the chain packing by microscopy at a molecular level, such as by atomic force microscopy (AFM), might be one of the most promising ways to study this issue; however, because of the limited resolution of the method, the chain packing of polymer cannot be resolved by AFM, except for especially large polymers. Here, we show that a mixed monolayer of vinyl polymers, poly(methyl methacrylate) (PMMA) and poly(n-nonyl acrylate) (PNA), was miscible at a low surface pressure, and if a small amount of PMMA chains was solubilized in a PNA monolayer, the isolated PMMA chains in the PNA monolayer were, for the first time, successfully visualized by AFM with a clear contrast, which originated from a difference of rigidities of the polymers due to their different glass transition temperatures (105 °C(PMMA) and -89 °C(PNA)). The PMMA chains were found to strongly interpenetrate into the PNA monolayer, with a radius of gyration (R(g(PMMA))) that was several times larger than that of the 2D ideal chain (segregated-chain). Furthermore, the radius scaled with the molecular weight of the PMMA (M(PMMA)) as R(g(PMMA)) ∝ M(PMMA)(0.63), which was between the scaling of the 2D ideal chain (segregated chain), R(g) ∝ M(0.5), and the 2D chain in good solvent, R(g) ∝ M(0.75). On the other hand, R(g(PMMA)) was independent of the molecular weight of the PNA matrix over a wide range. These results indicate that the PNA/PMMA monolayer is a strongly miscible system, although the R(g(PMMA)) scaling with M(PMMA) (0.63) is somewhat smaller than that expected for a 2D chain in good solvent systems (0.75). The generation of molecular level information

  3. Crystal field effect induced topological crystalline insulators in monolayer IV-VI semiconductors.

    PubMed

    Liu, Junwei; Qian, Xiaofeng; Fu, Liang

    2015-04-01

    Two-dimensional (2D) topological crystalline insulators (TCIs) were recently predicted in thin films of the SnTe class of IV-VI semiconductors, which can host metallic edge states protected by mirror symmetry. As thickness decreases, quantum confinement effect will increase and surpass the inverted gap below a critical thickness, turning TCIs into normal insulators. Surprisingly, based on first-principles calculations, here we demonstrate that (001) monolayers of rocksalt IV-VI semiconductors XY (X = Ge, Sn, Pb and Y = S, Se, Te) are 2D TCIs with the fundamental band gap as large as 260 meV in monolayer PbTe. This unexpected nontrivial topological phase stems from the strong crystal field effect in the monolayer, which lifts the degeneracy between p(x,y) and p(z) orbitals and leads to band inversion between cation pz and anion px,y orbitals. This crystal field effect induced topological phase offers a new strategy to find and design other atomically thin 2D topological materials.

  4. Synthesis and Optical Control of Circular Polarization in monolayer Tungsten Disulfide

    NASA Astrophysics Data System (ADS)

    McCreary, Kathleen; Hanbicki, Aubrey; Jonker, Berend; Currie, Marc; Kioseoglou, George

    The unique electronic band structure in single layer WS2 provides the ability to selectively populate a desired valley by exciting with circularly polarized light. The valley population is reflected through the circular polarization of photoluminescence (PL). We investigate the circularly polarized PL in WS2 monolayers synthesized using chemical vapor deposition (CVD). The resulting polarization is strongly dependent on the sample preparation. As-grown CVD WS2 (still on the growth substrate) exhibits low polarized emission, regardless of laser excitation or laser power. Removing WS2 from the growth substrate and repositioning on the same substrate significantly impacts the optical properties. In transferred films, the excitonic state is optically controlled via high-powered laser exposure such that subsequent PL is solely from either the charged exciton state or the neutral exciton state. Neutral excitonic emission exhibits zero polarization whereas the trion polarization can exceed 25% at room temperature. The removal process may modify the strain, sample-to-substrate distance, and chemical doping in the WS2 monolayer, and work is underway to determine how these factors influence the valley populations. These results demonstrate a new method to control the excitonic state and PL polarization in monolayer WS2. . Supported by core programs at NRL and the NRL Nanoscience Institute, and by the Air Force Office of Scientific Research #AOARD 14IOA018-134141.

  5. The impact of solution agglomeration on the deposition of self-assembled monolayers

    SciTech Connect

    BUNKER,BRUCE C.; CARPICK,ROBERT W.; ASSINK,ROGER A.; THOMAS,MICHAEL L.; HANKINS,MATTHEW G.; VOIGT,JAMES A.; SIPOLA,DIANA L.; DE BOER,MAARTEN P.; GULLEY,GERALD L.

    2000-04-17

    Self-assembled monolayers (SAMS) are commonly produced by immersing substrates in organic solutions containing trichlorosilane coupling agents. Unfortunately, such deposition solutions can also form alternate structures including inverse micelles and lamellar phases. The formation of alternate phases is one reason for the sensitivity of SAM depositions to factors such as the water content of the deposition solvent. If such phases are present, the performance of thin films used for applications such as minimization of friction and stiction in micromachines can be seriously compromised. Inverse micelle formation has been studied in detail for depositions involve 1H-, 1H-, 2H-, 2H-perfluorodecyltrichlorosilane (FDTS) in isooctane. Nuclear magnetic resonance experiments have been used to monitor the kinetics of hydrolysis and condensation reactions between water and FDTS. Light scattering experiments show that when hydrolyzed FDTS concentrations reach a critical concentration, there is a burst of nucleation to form high concentrations of spherical agglomerates. Atomic force microscopy results show that the agglomerates then deposit on substrate surfaces. Deposition conditions leading to monolayer formation involve using deposition times that are short relative to the induction time for agglomeration. After deposition, inverse micelles can be converted into lamellar or monolayer structures with appropriate heat treatments if surface concentrations are relatively low.

  6. Electrodeposition of gold nanoparticles on aryl diazonium monolayer functionalized HOPG surfaces.

    PubMed

    González, M C R; Orive, A G; Salvarezza, R C; Creus, A H

    2016-01-21

    Gold nanoparticle electrodeposition on a modified HOPG surface with a monolayer organic film based on aryl diazonium chemistry has been studied. This organic monolayer is electrochemically grown with the use of 2,2-diphenyl-1-picrylhydrazyl (DPPH), a radical scavenger. The electrodeposition of gold on this modified surface is highly favored resulting in an AuNP surface density comparable to that found on glassy carbon. AuNPs grow only in the areas covered by the organic monolayer leaving free clean HOPG zones. A progressive mechanism for the nucleation and growth is followed giving hemispherical AuNPs, homogeneously distributed on the surface and their sizes can be well controlled by the applied electrodeposition potential. By using AFM, C-AFM and electrochemical measurements with the aid of two redox probes, namely Fe(CN)6(4-)/Fe(CN)6(3-) and dopamine, relevant results about the electrochemical modified surface as well as the gold nanoparticles electrodeposited on them are obtained.

  7. Effect of colloidal particle size on adsorbed monodisperse and bidisperse monolayers.

    PubMed

    Rosenberg, Rachel T; Dan, Nily

    2011-07-19

    Coating hydrogel films or microspheres by an adsorbed colloidal shell is one synthesis method for forming colloidosomes. The colloidal shell allows control of the release rate of encapsulated materials, as well as selective transport. Previous studies found that the packing density of self-assembled, adsorbed colloidal monolayers is independent of the colloidal particle size. In this paper we develop an equilibrium model that correlates the packing density of charged colloidal particles in an adsorbed shell to the particle dimensions in monodisperse and bidisperse systems. In systems where the molar concentration in solution is fixed, the increase in adsorption energy with increasing particle size leads to a monotonic increase in the monolayer packing density with particle radius. However, in systems where the mass fraction of the particles in the adsorbing solutions is fixed, increasing particle size also reduces the molar concentration of particles in solution, thereby reducing the probability of adsorption. The result is a nonmonotonic dependence of the packing density in the adsorbed layer on the particle radius. In bidisperse monolayers composed of two particle sizes, the packing density in the layer increases significantly with size asymmetry. These results may be utilized to design the properties of colloidal shells and coatings to achieve specific properties such as transport rate and selectivity.

  8. MoS2 monolayers on nanocavities: enhancement in light-matter interaction

    NASA Astrophysics Data System (ADS)

    Janisch, Corey; Song, Haomin; Zhou, Chanjing; Lin, Zhong; Elías, Ana Laura; Ji, Dengxin; Terrones, Mauricio; Gan, Qiaoqiang; Liu, Zhiwen

    2016-06-01

    Two-dimensional (2D) atomic crystals and van der Waals heterostructures constitute an emerging platform for developing new functional ultra-thin electronic and optoelectronic materials for novel energy-efficient devices. However, in most thin-film optical applications, there is a long-existing trade-off between the effectiveness of light-matter interactions and the thickness of semiconductor materials, especially when the materials are scaled down to atom thick dimensions. Consequently, enhancement strategies can introduce significant advances to these atomically thick materials and devices. Here we demonstrate enhanced absorption and photoluminescence generation from MoS2 monolayers coupled with a planar nanocavity. This nanocavity consists of an alumina nanolayer spacer sandwiched between monolayer MoS2 and an aluminum reflector, and can strongly enhance the light-matter interaction within the MoS2, increasing the exclusive absorption of monolayer MoS2 to nearly 70% at a wavelength of 450 nm. The nanocavity also modifies the spontaneous emission rate, providing an additional design freedom to control the interaction between light and 2D materials.

  9. Molecular recognition on acoustic wave devices: Sorption in chemically anchored zeolite monolayers

    SciTech Connect

    Yan, Yongan; Bein, T.

    1992-11-12

    Zeolite crystals were attached to the gold electrodes of quartz crystal microbalances (QCM). Monolayers of thiol-alkoxysilanes on the gold surface served as interfacial layers for the subsequent adhesion of the zeolite crystals to the QCM. The process of anchoring the zeolite crystals via the thiol-silane monolayers was studied by reflection adsorption infrared (IR) spectroscopy, contact angle, and scanning electron microscopy (SEM). The siloxane linkages between the microporous zeolite crystals and the terminal cross-linked polysiloxane groups of the interfacial monolayer play an important role in enhancing the packing density of microporous crystals and the thermal stability (up to at least 350 {degrees}C) of the film on the gold surface. Dynamic sorption isotherms of organic vapors and nitrogen as well as the transient sorption behavior of organic vapor pulses were studied to characterize the zeolite-coated QCMs. The resonance frequency response of zeolite-coated QCMs to vapor pulses could be increased up to 500-fold compared to the bare sensor. The regular micropores (0.3-0.75 nm) of the QCM-attached zeolite crystals were found to efficiently control molecular access into the coating. Selectivity of the frequency response in excess of 100:1 toward molecules of different size and/or shape could be demonstrated. The kinetics of vapor desorption from the zeolite layers are strongly dependent on the adsorbate/zeolite combination, thus providing an additional capability for molecular recognition. 33 refs., 11 figs., 2 tabs.

  10. Tunnel magnetoresistance in Self-Assembled Monolayers Based Tunnel Junctions

    NASA Astrophysics Data System (ADS)

    Mattana, Richard; Barraud, Clément; Tatay, Sergio; Galbiati, Marta; Seneor, Pierre; Bouzehouane, Karim; Jacquet, Eric; Deranlot, Cyrile; Fert, Albert; Petroff, Frédéric

    2012-02-01

    Organic/molecular spintronics is a rising research field at the frontier between spintronics and organic chemistry. Organic molecule and semiconductors were first seen as promising for spintronics devices due to their expected long spin lifetime. But an exciting challenge has also been to find opportunities arising from chemistry to develop new spintronics functionalities. It was shown that the molecular structure and the ferromagnetic metal/molecule hybridization can strongly influence interfacial spin properties going from spin polarization enhancement to its sign control in spintronics devices. In this scenario, while scarcely studied, self-assembled monolayers (SAMs) are expected to become perfect toy barriers to further test these tailoring properties in molecular magnetic tunnel junctions (MTJs). Due to its very high spin polarization and air stability LSMO has positioned itself as the electrode of choice in most of the organic spintronics devices. We will present a missing building block for molecular spintronics tailoring: the grafting and film characterization of organic monofunctionalized long alkane chains over LSMO. We have obtained 35% of magnetoresistance in LSMO/SAMs/Co MTJs. We will discuss the unusual behaviour of the bias voltage dependence of the TMR.

  11. 2-D Pigment Langmuir Monolayer Assemblies for Light Harvesting Applications.

    NASA Astrophysics Data System (ADS)

    Gregory, Brian W.; Vaknin, David; Cotton, Therese M.; Struve, Walter S.

    1996-03-01

    The use of Coulombic forces to isolate charged, water-soluble macrocycles at the air/water interface (through their interactions with the oppositely charged headgroups of a phospholipid Langmuir monolayer) is currently being exploited in this laboratory as a means to create two-dimensional arrays of pigments for light-harvesting purposes. Significant differences have been observed in the surface pressure-molecular area (π-A) isotherms of dihexadecyl phosphate on subphases containing either tetra-(N-methylaza)- phthalocyanine (i.e., tetra-(N-methyl)-2,3-pyridinoporphyrazine) or tetra- (N-methylpyridyl)-porphyrin, both of which are cationic. In situ x-ray specular reflectivity has been employed to determine interfacial organization in these systems and to elucidate the origin of their different phase behavior at the air/water interface. In addition, electronic absorption spectra and electronic linear dichroism have been utilized to determine average pigment orientation in transferred films. * Ames Laboratory is operated by Iowa State University for the U.S. Department of Energy under Cotract No. W-4705-Eng-82.

  12. Growth and properties of self-assembled monolayers on metals

    NASA Astrophysics Data System (ADS)

    Zhuang, Y. X.; Hansen, O.; He, J. C.

    2009-03-01

    Self-assembled monolayers (SAMs) grown from organosilane are promising candidate for anti-stiction coatings. It is well know that the application of hydrocarbon- and fluorocarbon-based SAMs can significantly reduce stiction and adhesion in silicon micro/nanostructures in Micro-Electro-Mechancial System (MEMS). There are often various metals involved in MEMS, such as Au, Al, Ti, etc. In the process of growing anti-stiction SAMs on the silicon microstructures, SAM will be unavoidably deposited on the metals, which will significantly change surface properties of the materials. Therefore, it is necessary to investigate how the organosilane SAMs grow on the metals, and affect the surface properties of the materials. In this paper, CF3(CF2)5(CH2)2SiCl3 (FOTS) SAMs were grown on various metals using a vapour phase process in a home-made setup. The metals investigated are thin film Pd, Au, Ni, Al, Ti, Cr with thickness of 100 nm, which are deposited on monocrystal-silicon substrates using e-beam evaporation. The SAMs were characterized by static contact angle, surface energy, roughness, nano-scale adhesion force and friction force.

  13. Asphaltene Adsorption onto Self-Assembled Monolayers of Mixed Aromatic

    SciTech Connect

    Turgman-Cohen, S.; Smith, M; Fischer, D; Kilpatrick, P; Genzer, J

    2009-01-01

    The adsorption of asphaltenes onto flat solid surfaces modified with mixed self-assembled monolayers (SAMs) of aliphatic and aromatic trichlorosilanes with varying wettabilities, aromaticities, and thicknesses is tested. The mixed SAMs are characterized by means of contact angle to assess hydrophobicity and molecular and chemical uniformity, spectroscopic ellipsometry to measure the thickness of the films, and near edge X-ray absorption fine structure (NEXAFS) spectroscopy to assess chemical and molecular composition. The molecular characteristics of the adsorbed asphaltene layer and the extent of asphaltene adsorption are determined using NEXAFS and spectroscopic ellipsometry, respectively. The SAMs are formed by depositing phenyl-, phenethyl-, butyl-, and octadecyl- trichlorosilanes from toluene solutions onto silica-coated substrates; the chemical composition and the wettability of the SAM surface is tuned systematically by varying the trichlorosilane composition in the deposition solutions. The adsorption of asphaltenes on the substrates does not correlate strongly with the SAM chemical composition. Instead, the extent of asphaltene adsorption decreases with increasing SAM thickness. This observation suggests that the leading interaction governing the adsorption of asphaltenes is their interaction with the polar silica substrate and that the chemical composition of the SAM is of secondary importance.

  14. Embedding Ba Monolayers and Bilayers in Boron Carbide Nanowires.

    PubMed

    Yu, Zhiyang; Luo, Jian; Shi, Baiou; Zhao, Jiong; Harmer, Martin P; Zhu, Jing

    2015-11-26

    Aberration corrected high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) was employed to study the distribution of barium atoms on the surfaces and in the interiors of boron carbide based nanowires. Barium based dopants, which were used to control the crystal growth, adsorbed to the surfaces of the boron-rich crystals in the form of nanometer-thick surficial films (a type of surface complexion). During the crystal growth, these dopant-based surface complexions became embedded inside the single crystalline segments of fivefold boron-rich nanowires collectively, where they were converted to more ordered monolayer and bilayer modified complexions. Another form of bilayer complexion stabilized at stacking faults has also been identified. Numerous previous works suggested that dopants/impurities tended to segregate at the stacking faults or twinned boundaries. In contrast, our study revealed the previously-unrecognized possibility of incorporating dopants and impurities inside an otherwise perfect crystal without the association to any twin boundary or stacking fault. Moreover, we revealed the amount of barium dopants incorporated was non-equilibrium and far beyond the bulk solubility, which might lead to unique properties.

  15. Embedding Ba Monolayers and Bilayers in Boron Carbide Nanowires

    NASA Astrophysics Data System (ADS)

    Yu, Zhiyang; Luo, Jian; Shi, Baiou; Zhao, Jiong; Harmer, Martin P.; Zhu, Jing

    2015-11-01

    Aberration corrected high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) was employed to study the distribution of barium atoms on the surfaces and in the interiors of boron carbide based nanowires. Barium based dopants, which were used to control the crystal growth, adsorbed to the surfaces of the boron-rich crystals in the form of nanometer-thick surficial films (a type of surface complexion). During the crystal growth, these dopant-based surface complexions became embedded inside the single crystalline segments of fivefold boron-rich nanowires collectively, where they were converted to more ordered monolayer and bilayer modified complexions. Another form of bilayer complexion stabilized at stacking faults has also been identified. Numerous previous works suggested that dopants/impurities tended to segregate at the stacking faults or twinned boundaries. In contrast, our study revealed the previously-unrecognized possibility of incorporating dopants and impurities inside an otherwise perfect crystal without the association to any twin boundary or stacking fault. Moreover, we revealed the amount of barium dopants incorporated was non-equilibrium and far beyond the bulk solubility, which might lead to unique properties.

  16. Embedding Ba Monolayers and Bilayers in Boron Carbide Nanowires

    PubMed Central

    Yu, Zhiyang; Luo, Jian; Shi, Baiou; Zhao, Jiong; Harmer, Martin P.; Zhu, Jing

    2015-01-01

    Aberration corrected high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) was employed to study the distribution of barium atoms on the surfaces and in the interiors of boron carbide based nanowires. Barium based dopants, which were used to control the crystal growth, adsorbed to the surfaces of the boron-rich crystals in the form of nanometer-thick surficial films (a type of surface complexion). During the crystal growth, these dopant-based surface complexions became embedded inside the single crystalline segments of fivefold boron-rich nanowires collectively, where they were converted to more ordered monolayer and bilayer modified complexions. Another form of bilayer complexion stabilized at stacking faults has also been identified. Numerous previous works suggested that dopants/impurities tended to segregate at the stacking faults or twinned boundaries. In contrast, our study revealed the previously-unrecognized possibility of incorporating dopants and impurities inside an otherwise perfect crystal without the association to any twin boundary or stacking fault. Moreover, we revealed the amount of barium dopants incorporated was non-equilibrium and far beyond the bulk solubility, which might lead to unique properties. PMID:26607754

  17. Manganese Atom Ordered Monolayer on Wurtzite Gallium Nitride

    NASA Astrophysics Data System (ADS)

    Chinchore, Abhijit; Wang, Kangkang; Lin, Wenzhi; Pak, Jeongihm; Liu, Yinghao; Smith, Arthur

    2009-03-01

    While transition-metal-doped gallium nitride (GaN) thin films have been explored as potential dilute magnetic semiconductor bulk layers, the structural and magnetic effects of various transition metal adatoms on GaN surfaces are not even well understood. In this work, we investigate the sub-monolayer deposition of manganese (Mn) onto the N-polar wurtzite GaN (000-1) 1x1 surface. The growth is monitored in-situ using reflection high energy electron diffraction (RHEED). A fresh GaN(000-1) 1x1 surface is prepared by rf nitrogen plasma-assisted MBE followed by annealing to remove excess gallium adatoms. The atomically flat GaN surface, held at 200^o C, is then exposed to submonolayer doses of Mn. The deposition rate is maintained at 0.007 ML per second, and a 3x pattern develops along [10-10]; whereas, only 1x is seen along [11-20]. Analysis of the RHEED pattern and subsequent modeling indicates a 3 x3 R 30^o structure consisting of 2/3 ML Mn atoms in a row-like arrangement having spacing 3a/2 along rows and 3a/2 between rows. Scanning tunneling microscopy/spectroscopy studies are currently underway to explore this surface further. This work is supported by DOE (Grant No.DE-FG02-06ER46317) and NSF (Grant No. 0730257).

  18. Supported lipid monolayer with improved nanomechanical stability: effect of polymerization.

    PubMed

    El Zein, Racha; Dallaporta, Hervé; Charrier, Anne M

    2012-06-21

    We study the effect of polymerization on the nanomechanical stability of supported lipid monolayers consisting of 1,2-di-(10Z,12Z-tricosadiynoyl)-sn-glycero-3-phosphocholine by means of force mapping using an atomic force microscope. For both nonpolymerized and polymerized lipid monolayers, we investigate the break-through forces required to rupture the monolayers for a whole range of loading velocities. We show that the average break-through force exerted by the tip and required to penetrate the monolayer has a logarithmic dependence on the loading rate. Both Young moduli and intrinsic Gibbs energies have been determined for the nonpolymerized and polymerized lipid monolayers, and we show a drastic effect of polymerization on the nanomechanical stability of the monolayer with an increase by a factor of ∼100 for the young modulus and ∼3 for the intrinsic Gibbs activation energy.

  19. Sensitive methods for estimating the anchoring strength of nematic liquid crystals on Langmuir-Blodgett monolayers of fatty acids

    SciTech Connect

    Fazio, Valentina S. U.; Nannelli, Francesca; Komitov, Lachezar

    2001-06-01

    The anchoring of the nematic liquid crystal N-(p-methoxybenzylidene)-p-butylaniline (MBBA) on Langmuir-Blodgett monolayers of fatty acids (COOHC{sub n}H{sub 2n+1}) was studied as a function of the length of the fatty acid alkyl chain n (n=15,17,19,21). The monolayers were deposited onto glass plates coated with indium tin oxide, which were used to assemble sandwich cells of various thicknesses that were filled with MBBA in the nematic phase. The mechanism of relaxation from the flow-induced quasiplanar to the surface-induced homeotropic alignment was studied for the four aligning monolayers. It was found that the speed of the relaxation decreases linearly with increasing length of the alkyl chain n, which suggests that the Langmuir-Blodgett film plays a role in the phenomenon. This fact was confirmed by a sensitive estimation of the anchoring strength of MBBA on the fatty acid monolayers after anchoring breaking, which takes place at the transition between two electric-field-induced turbulent states, denoted as DSM1 and DSM2 (where DSM indicates dynamic scattering mode). It was found that the threshold electric field for the anchoring breaking, which can be considered as a measure of the anchoring strength, also decreases linearly as n increases. Both methods thus possess a high sensitivity in resolving small differences in anchoring strength. In cells coated with mixed Langmuir-Blodgett monolayers of two fatty acids (n=15 and n=17) a maximum of the relaxation speed was observed when the two acids were present in equal amounts. This observation suggests an efficient method for controlling the anchoring strength in homeotropic cells by changing the ratio between the components of the surfactant film.

  20. Asymmetric printing of molecules and zeolites on self assembled monolayers.

    PubMed

    Kehr, Nermin Seda; Schäfer, Andreas; Ravoo, Bart Jan; De Cola, Luisa

    2010-04-01

    Microcontact printing (mCP) is used to immobilize dyes and peptides asymmetrically, by a "peptide coupling" reaction, on monolayers of zeolite L crystals in the contact area between the stamp and the surface of the monolayer. Chemically patterned surfaces of monolayers of zeolite L crystals are obtained by using patterned stamps with different ink solutions. Additional printing of functionalized nano-objects on SAMs of zeolite L crystals is demonstrated.

  1. Cytochrome c Complexes with Cardiolipin Monolayer Formed under Different Surface Pressure.

    PubMed

    Marchenkova, Margarita A; Dyakova, Yulia A; Tereschenko, Elena Yu; Kovalchuk, Mikhail V; Vladimirov, Yury A

    2015-11-17

    The formation of the complex of cytochrome c (Cytc) with a phospholipid cardiolipin (CL) in mitochondria is a crucial event in apoptosis development. There are two viewpoints on the structure of the complex. (1) Cytc is bound on the surface of the lipid bilayer. (2) The complex is a hydrophobic nanoparticle Cytc-CL formed by Cytc molten globule, covered by CL monolayer.1 In the present work, we attempted to bridge the gap between these two structures. We investigated the interaction between Cytc and Langmuir monolayers of CL. The surface pressure increase during incorporation of Cytc into CL monolayer obeys the equation: π = π0 + Δπ∞[1 - exp(-βt)], where β is pseudo-first-order rate constant of Cytc binding, directly proportional to the initial Cytc concentration c0. Parameters Δπ∞ and the rate β measured in different conditions were virtually equal for natural bovine CL and peroxidation-resistant tetraoleoyl CL in all experiments. Surface area-surface pressure isotherms of Cytc alone and in combination with a CL monolayer were similar in shape. Apparently, the protein exposes hydrophilic groups to the water phase and hydrophobic to the air or to the hydrocarbon chains of CL. The 30% ethanol dramatically accelerated the adsorption of Cytc on the water surface. The protein-lipid surface films showed, in compression-expansion cycles, that hysteresis loops were observed always when Cytc present, reproducible in repeating cycles. Taken together, our data show that when incorporated in a lipid monolayer or after adsorption on the water-air interface, Cytc undergoes conformational transition. In that, one part of the globule sphere becomes predominantly hydrophobic and the other, hydrophilic and charged ("stratified" Cytc). We hypothesize that in CL-containing bilayer membranes, Cytc incorporation into the lipid monolayer would result in membrane folding with subsequent formation of either catalytically reactive "bubbles" inside the bilayer, formed by Cytc

  2. Method for fabricating hafnia films

    DOEpatents

    Hu, Michael Z [Knoxville, TN

    2007-08-21

    The present invention comprises a method for fabricating hafnia film comprising the steps of providing a substrate having a surface that allows formation of a self-assembled monolayer thereon via covalent bonding; providing an aqueous solution that provides homogeneous hafnium ionic complexes and hafnium nanoclusters wherein the aqueous solution is capable of undergoing homogeneous precipitation under controlled conditions for a desired period of time at a controlled temperature and controlled solution acidity for desired nanocluster nucleation and growth kinetics, desired nanocluster size, desired growth rate of film thickness and desired film surface characteristics. The method further comprising forming the self-assembled monolayer on the surface of the substrate wherein the self-assembled monolayer comprises a plurality of hydrocarbon chains cross-linked together along the surface of the substrate, the hydrocarbon chains being uniformly spaced from one another and wherein each of the hydrocarbon chains having a functional anchoring group at a first end of the chain covalently bonded with the surface of the substrate and each of the hydrocarbon chains having a functional terminating group projected away from the surface wherein the functional terminating group provides a bonding site for the hafnium film to grow; and exposing the substrate to the aqueous solution for a desired period of time at a controlled temperature wherein the hafnium ionic complexes and the hafnium nanoclusters are deposited on the bonding site of the functional terminating group thereby forming the hafnia film wherein the hafnium bonded to the hydrocarbons and to one another provide a uniform ordered arrangement defined by the uniform arrangement of the hydrocarbons.

  3. Carbon phosphide monolayers with superior carrier mobility

    NASA Astrophysics Data System (ADS)

    Wang, Gaoxue; Pandey, Ravindra; Karna, Shashi P.

    2016-04-01

    Two dimensional (2D) materials with a finite band gap and high carrier mobility are sought after materials from both fundamental and technological perspectives. In this paper, we present the results based on the particle swarm optimization method and density functional theory which predict three geometrically different phases of the carbon phosphide (CP) monolayer consisting of sp2 hybridized C atoms and sp3 hybridized P atoms in hexagonal networks. Two of the phases, referred to as α-CP and β-CP with puckered or buckled surfaces are semiconducting with highly anisotropic electronic and mechanical properties. More remarkably, they have the lightest electrons and holes among the known 2D semiconductors, yielding superior carrier mobility. The γ-CP has a distorted hexagonal network and exhibits a semi-metallic behavior with Dirac cones. These theoretical findings suggest that the binary CP monolayer is a yet unexplored 2D material holding great promise for applications in high-performance electronics and optoelectronics.Two dimensional (2D) materials with a finite band gap and high carrier mobility are sought after materials from both fundamental and technological perspectives. In this paper, we present the results based on the particle swarm optimization method and density functional theory which predict three geometrically different phases of the carbon phosphide (CP) monolayer consisting of sp2 hybridized C atoms and sp3 hybridized P atoms in hexagonal networks. Two of the phases, referred to as α-CP and β-CP with puckered or buckled surfaces are semiconducting with highly anisotropic electronic and mechanical properties. More remarkably, they have the lightest electrons and holes among the known 2D semiconductors, yielding superior carrier mobility. The γ-CP has a distorted hexagonal network and exhibits a semi-metallic behavior with Dirac cones. These theoretical findings suggest that the binary CP monolayer is a yet unexplored 2D material holding great

  4. Tidal evolution of the Uranian satellites. III - Evolution through the Miranda-Umbriel 3:1, Miranda-Ariel 5:3, and Ariel-Umbriel 2:1 mean-motion commensurabilities

    NASA Astrophysics Data System (ADS)

    Tittemore, W. C.; Wisdom, J.

    1990-06-01

    Numerical experiments have been conducted which indicate that the orbital eccentricity of Miranda may have reached a value sufficiently large to have affected its thermal evolution. There is a large chaotic zone associated with the Miranda-Ariel 5:3 mean-motion commensurability, even in the planar approximation; the orbital eccentricities of both satellites may vary chaotically for a considerable period. Since the anomalously high orbital inclination of Miranda is a consequence of passage through the 3:1 commensurability with Umbriel, the requirement that the satellites encountered this resonance places a lower limit on the Uranian specific dissipation function of 39,000.

  5. Tidal evolution of the Uranian satellites. III - Evolution through the Miranda-Umbriel 3:1, Miranda-Ariel 5:3, and Ariel-Umbriel 2:1 mean-motion commensurabilities

    NASA Technical Reports Server (NTRS)

    Tittemore, William C.; Wisdom, Jack

    1990-01-01

    Numerical experiments have been conducted which indicate that the orbital eccentricity of Miranda may have reached a value sufficiently large to have affected its thermal evolution. There is a large chaotic zone associated with the Miranda-Ariel 5:3 mean-motion commensurability, even in the planar approximation; the orbital eccentricities of both satellites may vary chaotically for a considerable period. Since the anomalously high orbital inclination of Miranda is a consequence of passage through the 3:1 commensurability with Umbriel, the requirement that the satellites encountered this resonance places a lower limit on the Uranian specific dissipation function of 39,000.

  6. Corrosion resistance of sintered NdFeB coated with SiC/Al bilayer thin films by magnetron sputtering

    NASA Astrophysics Data System (ADS)

    Huang, Yiqin; Li, Heqin; Zuo, Min; Tao, Lei; Wang, Wei; Zhang, Jing; Tang, Qiong; Bai, Peiwen

    2016-07-01

    The poor corrosion resistance of sintered NdFeB imposes a great challenge in industrial applications. In this work, the SiC/Al bilayer thin films with the thickness of 510 nm were deposited on sintered NdFeB by magnetron sputtering to improve the corrosion resistance. A 100 nm Al buffer film was used to reduce the internal stress between SiC and NdFeB and improve the surface roughness of the SiC thin film. The morphologies and structures of SiC/Al bilayer thin films and SiC monolayer film were investigated with FESEM, AFM and X-ray diffraction. The corrosion behaviors of sintered NdFeB coated with SiC monolayer film and SiC/Al bilayer thin films were analyzed by polarization curves. The magnetic properties were measured with an ultra-high coercivity permanent magnet pulse tester. The results show that the surface of SiC/Al bilayer thin films is more compact and uniform than that of SiC monolayer film. The corrosion current densities of SiC/Al bilayer films coated on NdFeB in acid, alkali and salt solutions are much lower than that of SiC monolayer film. The SiC/Al bilayer thin films have little influence to the magnetic properties of NdFeB.

  7. Diacetylene mixed Langmuir monolayers for interfacial polymerization.

    PubMed

    Ariza-Carmona, Luisa; Rubia-Payá, Carlos; García-Espejo, G; Martín-Romero, María T; Giner-Casares, Juan J; Camacho, Luis

    2015-05-19

    Polydiacetylene (PDA) and its derivatives are promising materials for applications in a vast number of fields, from organic electronics to biosensing. PDA is obtained through polymerization of diacetylene (DA) monomers, typically using UV irradiation. DA polymerization is a 1-4 addition reaction with both initiation and growth steps with topochemical control, leading to the "blue" polymer form as primary reaction product in bulk and at interfaces. Herein, the diacetylene monomer 10,12-pentacosadiynoic acid (DA) and the amphiphilic cationic N,N'-dioctadecylthiapentacarbocyanine (OTCC) have been used to build a mixed Langmuir monolayer. The presence of OTCC imposes a monolayer supramolecular structure instead of the typical trilayer of pure DA. Surface pressure, Brewster angle microscopy, and UV-vis reflection spectroscopy measurements, as well as computer simulations, have been used to assess in detail the supramolecular structure of the DA:OTCC Langmuir monolayer. Our experimental results indicate that the DA and OTCC molecules are sequentially arranged, with the two OTCC alkyl chains acting as spacing diacetylene units. Despite this configuration is expected to prevent photopolymerization of DA, the polymerization takes place without phase segregation, thus exclusively leading to the red polydiacetylene form. We propose a simple model for the initial formation of the "blue" or "red" PDA forms as a function of the relative orientation of the DA units. The structural insights and the proposed model concerning the supramolecular structure of the "blue" and "red" forms of the PDA are aimed at the understanding of the relation between the molecular and macroscopical features of PDAs.

  8. Processing of monolayer materials via interfacial reactions

    DOEpatents

    Sutter, Peter Werner; Sutter, Eli Anguelova

    2014-05-20

    A method of forming and processing of graphene is disclosed based on exposure and selective intercalation of the partially graphene-covered metal substrate with atomic or molecular intercalation species such as oxygen (O.sub.2) and nitrogen oxide (NO.sub.2). The process of intercalation lifts the strong metal-carbon coupling and restores the characteristic Dirac behavior of isolated monolayer graphene. The interface of graphene with metals or metal-decorated substrates also provides for controlled chemical reactions based on novel functionality of the confined space between a metal surface and a graphene sheet.

  9. Cell Volume Fluctuations in MDCK Monolayers

    PubMed Central

    Zehnder, Steven M.; Suaris, Melanie; Bellaire, Madisonclaire M.; Angelini, Thomas E.

    2015-01-01

    Cells moving collectively in tissues constitute a form of active matter, in which collective motion depends strongly on driven fluctuations at the single-cell scale. Fluctuations in cell area and number density are often seen in monolayers, yet their role in collective migration is not known. Here we study density fluctuations at the single- and multicell level, finding that single-cell volumes oscillate with a timescale of 4 h and an amplitude of 20%; the timescale and amplitude are found to depend on cytoskeletal activity. At the multicellular scale, density fluctuations violate the central limit theorem, highlighting the role of nonequilibrium driving forces in multicellular density fluctuations. PMID:25606673

  10. Fibrinogen monolayer characterization by colloid deposition.

    PubMed

    Nattich-Rak, Małgorzata; Adamczyk, Zbigniew; Wasilewska, Monika; Sadowska, Marta

    2013-09-24

    Colloid particle deposition was applied to characterize bovine and human fibrinogen (Fb) monolayers on mica produced by controlled adsorption under diffusion transport at pH 3.5. The surface concentration of Fb was determined by AFM enumeration of single molecules adsorbed over the substrate surface. The electrokinetic properties of Fb monolayers for various ionic strength were studied using the in situ streaming potential measurements. It was shown that Fb adsorbs irreversibly on mica for a broad range of ionic strength of 4 × 10(-4) to 0.15 M, NaCl. The overcharging of initially negative mica surface occurred for fibrinogen surface concentrations higher than 1400 μm(-2). The orientation of fibrinogen molecules in the monolayers was evaluated by the colloid deposition method involving negatively charged polystyrene latex microspheres, 820 nm in diameter. An anomalous deposition of negative latex particles on substrates exhibiting a negative zeta potential was observed, which contradicts the mean-field DLVO predictions. Measurable deposition was observed even at low ionic strength where the minimum approach distance of latex particles to the interface exceeds 70 nm (for 6 × 10(-4) M NaCl). This confirms that, at this pH, fibrinogen molecules adsorb end-on on mica assuming extended conformations with the positive charge located mostly in the end part of the αA chains. This agrees with previous experimental and theoretical results discussed in the literature (Santore, M. M.; Wertz Ch. F. Protein spreading kinetics at liquid-solid interfaces via an adsorption probe method. Langmuir 2005, 21, 10172-10178 (experimental); Adamczyk, Z.; Barbasz, J.; Cieśla, M.; Mechanisms of fibrinogen adsorption at solid substrates. Langmuir, 2011, 25, 6868-6878 (theoretical)). This unusual latex deposition on Fb monolayers was quantitatively interpreted in terms of the model developed in ref 55 (Jin, X.; Wang, N. H. L.; Tarjus, G.; Talbot, J. Irreversible adsorption on nonuniform

  11. Surface interactions, thermodynamics and topography of binary monolayers of Insulin with dipalmitoylphosphatidylcholine and 1-palmitoyl-2-oleoylphosphatidylcholine at the air/water interface.

    PubMed

    Grasso, E J; Oliveira, R G; Maggio, B

    2016-02-15

    The molecular packing, thermodynamics and surface topography of binary Langmuir monolayers of Insulin and DPPC (dipalmitoylphosphatidylcholine) or POCP (1-palmitoyl-2-oleoylphosphatidylcholine) at the air/water interface on Zn(2+) containing solutions were studied. Miscibility and interactions were ascertained by the variation of surface pressure-mean molecular area isotherms, surface compressional modulus and surface (dipole) potential with the film composition. Brewster Angle Microscopy was used to visualize the surface topography of the monolayers. Below 20mN/m Insulin forms stable homogenous films with DPPC and POPC at all mole fractions studied (except for films with XINS=0.05 at 10mN/m where domain coexistence was observed). Above 20mN/m, a segregation process between mixed phases occurred in all monolayers without squeezing out of individual components. Under compression the films exhibit formation of a viscoelastic or kinetically trapped organization leading to considerable composition-dependent hysteresis under expansion that occurs with entropic-enthalpic compensation. The spontaneously unfavorable interactions of Insulin with DPPC are driven by favorable enthalpy that is overcome by unfavorable entropic ordering; in films with POPC both the enthalpic and entropic effects are unfavorable. The surface topography reveals domain coexistence at relatively high pressure showing a striped appearance. The interactions of Insulin with two major membrane phospholipids induces composition-dependent and long-range changes of the surface organization that ought to be considered in the context of the information-transducing capabilities of the hormone for cell functioning.

  12. Surface interactions, thermodynamics and topography of binary monolayers of Insulin with dipalmitoylphosphatidylcholine and 1-palmitoyl-2-oleoylphosphatidylcholine at the air/water interface.

    PubMed

    Grasso, E J; Oliveira, R G; Maggio, B

    2016-02-15

    The molecular packing, thermodynamics and surface topography of binary Langmuir monolayers of Insulin and DPPC (dipalmitoylphosphatidylcholine) or POCP (1-palmitoyl-2-oleoylphosphatidylcholine) at the air/water interface on Zn(2+) containing solutions were studied. Miscibility and interactions were ascertained by the variation of surface pressure-mean molecular area isotherms, surface compressional modulus and surface (dipole) potential with the film composition. Brewster Angle Microscopy was used to visualize the surface topography of the monolayers. Below 20mN/m Insulin forms stable homogenous films with DPPC and POPC at all mole fractions studied (except for films with XINS=0.05 at 10mN/m where domain coexistence was observed). Above 20mN/m, a segregation process between mixed phases occurred in all monolayers without squeezing out of individual components. Under compression the films exhibit formation of a viscoelastic or kinetically trapped organization leading to considerable composition-dependent hysteresis under expansion that occurs with entropic-enthalpic compensation. The spontaneously unfavorable interactions of Insulin with DPPC are driven by favorable enthalpy that is overcome by unfavorable entropic ordering; in films with POPC both the enthalpic and entropic effects are unfavorable. The surface topography reveals domain coexistence at relatively high pressure showing a striped appearance. The interactions of Insulin with two major membrane phospholipids induces composition-dependent and long-range changes of the surface organization that ought to be considered in the context of the information-transducing capabilities of the hormone for cell functioning. PMID:26624532

  13. Long-lived nanosecond spin relaxation and spin coherence of electrons in monolayer MoS2 and WS2

    DOE PAGES

    Yang, Luyi; Sinitsyn, Nikolai A.; Chen, Weibing; Yuan, Jiangtan; Zhang, Jing; Lou, Jun; Crooker, Scott  A.

    2015-08-03

    The recently discovered monolayer transition metal dichalcogenides (TMDCs) provide a fertile playground to explore new coupled spin–valley physics. Although robust spin and valley degrees of freedom are inferred from polarized photoluminescence (PL) experiments PL timescales are necessarily constrained by short-lived (3–100 ps) electron–hole recombination9, 10. Direct probes of spin/valley polarization dynamics of resident carriers in electron (or hole)-doped TMDCs, which may persist long after recombination ceases, are at an early stage. Here we directly measure the coupled spin–valley dynamics in electron-doped MoS2 and WS2 monolayers using optical Kerr spectroscopy, and reveal very long electron spin lifetimes, exceeding 3 ns atmore » 5 K (2-3 orders of magnitude longer than typical exciton recombination times). In contrast with conventional III–V or II–VI semiconductors, spin relaxation accelerates rapidly in small transverse magnetic fields. Supported by a model of coupled spin–valley dynamics, these results indicate a novel mechanism of itinerant electron spin dephasing in the rapidly fluctuating internal spin–orbit field in TMDCs, driven by fast inter-valley scattering. Additionally, a long-lived spin coherence is observed at lower energies, commensurate with localized states. These studies provide insight into the physics underpinning spin and valley dynamics of resident electrons in atomically thin TMDCs.« less

  14. Long-lived nanosecond spin relaxation and spin coherence of electrons in monolayer MoS2 and WS2

    SciTech Connect

    Yang, Luyi; Sinitsyn, Nikolai A.; Chen, Weibing; Yuan, Jiangtan; Zhang, Jing; Lou, Jun; Crooker, Scott  A.

    2015-08-03

    The recently discovered monolayer transition metal dichalcogenides (TMDCs) provide a fertile playground to explore new coupled spin–valley physics. Although robust spin and valley degrees of freedom are inferred from polarized photoluminescence (PL) experiments PL timescales are necessarily constrained by short-lived (3–100 ps) electron–hole recombination9, 10. Direct probes of spin/valley polarization dynamics of resident carriers in electron (or hole)-doped TMDCs, which may persist long after recombination ceases, are at an early stage. Here we directly measure the coupled spin–valley dynamics in electron-doped MoS2 and WS2 monolayers using optical Kerr spectroscopy, and reveal very long electron spin lifetimes, exceeding 3 ns at 5 K (2-3 orders of magnitude longer than typical exciton recombination times). In contrast with conventional III–V or II–VI semiconductors, spin relaxation accelerates rapidly in small transverse magnetic fields. Supported by a model of coupled spin–valley dynamics, these results indicate a novel mechanism of itinerant electron spin dephasing in the rapidly fluctuating internal spin–orbit field in TMDCs, driven by fast inter-valley scattering. Additionally, a long-lived spin coherence is observed at lower energies, commensurate with localized states. These studies provide insight into the physics underpinning spin and valley dynamics of resident electrons in atomically thin TMDCs.

  15. Geometric Stability and Elastic Response of a Supported Nanoparticle Film

    SciTech Connect

    Leahy, Brian D.; Pocivavsek, Luka; Meron, Mati; Lam, Kin Lok; Salas, Desiree; Viccaro, P. James; Lee, Ka Yee C.; Lin, Binhua

    2011-09-16

    The mechanical response to compression of a self-assembled gold nanoparticle monolayer and trilayer at the air-liquid interface is examined. Analysis of the film's buckling morphology under compression reveals an anomalously low bending rigidity for both the monolayer and the trilayer, in contrast with continuum elastic plates. We attribute this to the spherical geometry of the nanoparticles and poor coupling between layers, respectively. The elastic energy of the trilayers is first delocalized in wrinkles and then localized into folds, as predicted by linear and nonlinear elastic theory for an inextensible thin film supported on a fluid.

  16. Infrared spectroelectrochemical characterization of ferrocene-terminated alkanethiolate monolayers at gold

    SciTech Connect

    Popenoe, D.D.; Deinhammer, R.S.; Porter, M.D. Iowa State Univ., Ames, IA )

    1992-10-01

    Cyclic voltammetry and in situ infrared reflection-absorption spectroscopy with electrochemical modulation were applied to the study of monolayers self-assembled from 11-mercaptoundecyl ferrocene-carboxylate (FcCOOC[sub 11]SH) at gold. Voltammetry was used to assess both the reactivity and stability of the surface film in various aqueous electrolytes. The results of these studies indicated that the ferrocenyl monolayers are relatively unstable at pH > 2, except when perchlorate is the dominant anion present. A large change in double-layer capacitance observed upon oxidation of the ferrocenyl end group was attributed to the creation of cationic sites in the diffuse layer. Compositional and structural correlations between the monolayer and the redox chemistry of the ferrocenyl end group were probed using the in situ spectroscopic technique. The features observed in the differential spectra of the oxidized form of the film were ascribed to changes in the bond strengths of the adsorbate as a result of generation of a ferricinium ion. No detectable changes in orientation of the polymethylene chains as a function of applied voltage were observed. The spectral data also suggest that the redox chemistry leads to a reorientation of the water molecules in the region near the ferrocenyl end group. Vibrational mode assignments for FcCOOC[sub 11]SH, based on studies of several analogs with different alkoxy groups, are presented along with infrared spectra and band assignments for several isotopically labeled ferrocenyl esters (i.e., ethyl ferrocenecarboxylate, ethyl-d[sub 5] ferrocenecarboxylate, and 2-(dimethylamino)ethyl ferrocenecarboxylate). 55 refs., 7 figs., 2 tabs.

  17. Solidlike and liquidlike behavior in monolayers and multilayers of metal-bearing amphiphiles.

    PubMed

    Mukherjee, Smita; Datta, Alokmay; Giglia, Angelo; Mahne, Nicola; Nannarone, Stefano

    2011-08-01

    Atomic force microscopy (AFM) of cadmium stearate (CdSt) and cobalt stearate (CoSt) Langmuir-Blodgett films show differences in their in-plane morphologies. CdSt films, with a huge number of in-plane "pinhole" defects, follow self-affine behavior, whereas CoSt films, which are almost void of such in-plane defects, show deviation from self-affinity especially at small length scales, suggesting liquidlike behavior, imparting flexibility to the system, in plane. Phase images of CoSt obtained from tapping mode AFM show gentle undulations or hemispherelike features in contrast to its smooth topography, unlike the CdSt system where both height and phase images show self-affine domains. Near edge x-ray absorption fine structure spectroscopy indicates no preferred in-plane orientation of the head group in CoSt films. The undulating features in CoSt is explained by invoking a radially symmetric orientational distribution in the tilt of adjacent hydrocarbon tails, causing a small in-plane density variation which shows up in the phase image. These orientational disorders in adjacent tails probably allow "filling up" of in-plane defects thereby giving rise to its excellent in-plane coverage and hence a "liquidlike" behavior in CoSt. Brewster angle microscopy shows that parent Langmuir monolayers of stearic acid in the presence of Cd and Co ions in the aqueous subphase behave as two-dimensional "solids" and "liquids," respectively, suggesting the phenomena to be inherent in the amphiphiles and probably independent of their organization as monolayers and multilayers. PMID:21928998

  18. Carbon phosphide monolayers with superior carrier mobility.

    PubMed

    Wang, Gaoxue; Pandey, Ravindra; Karna, Shashi P

    2016-04-28

    Two dimensional (2D) materials with a finite band gap and high carrier mobility are sought after materials from both fundamental and technological perspectives. In this paper, we present the results based on the particle swarm optimization method and density functional theory which predict three geometrically different phases of the carbon phosphide (CP) monolayer consisting of sp2 hybridized C atoms and sp3 hybridized P atoms in hexagonal networks. Two of the phases, referred to as α-CP and β-CP with puckered or buckled surfaces are semiconducting with highly anisotropic electronic and mechanical properties. More remarkably, they have the lightest electrons and holes among the known 2D semiconductors, yielding superior carrier mobility. The γ-CP has a distorted hexagonal network and exhibits a semi-metallic behavior with Dirac cones. These theoretical findings suggest that the binary CP monolayer is a yet unexplored 2D material holding great promise for applications in high-performance electronics and optoelectronics. PMID:27067002

  19. Predicting Two-Dimensional Silicon Carbide Monolayers.

    PubMed

    Shi, Zhiming; Zhang, Zhuhua; Kutana, Alex; Yakobson, Boris I

    2015-10-27

    Intrinsic semimetallicity of graphene and silicene largely limits their applications in functional devices. Mixing carbon and silicon atoms to form two-dimensional (2D) silicon carbide (SixC1-x) sheets is promising to overcome this issue. Using first-principles calculations combined with the cluster expansion method, we perform a comprehensive study on the thermodynamic stability and electronic properties of 2D SixC1-x monolayers with 0 ≤ x ≤ 1. Upon varying the silicon concentration, the 2D SixC1-x presents two distinct structural phases, a homogeneous phase with well dispersed Si (or C) atoms and an in-plane hybrid phase rich in SiC domains. While the in-plane hybrid structure shows uniform semiconducting properties with widely tunable band gap from 0 to 2.87 eV due to quantum confinement effect imposed by the SiC domains, the homogeneous structures can be semiconducting or remain semimetallic depending on a superlattice vector which dictates whether the sublattice symmetry is topologically broken. Moreover, we reveal a universal rule for describing the electronic properties of the homogeneous SixC1-x structures. These findings suggest that the 2D SixC1-x monolayers may present a new "family" of 2D materials, with a rich variety of properties for applications in electronics and optoelectronics. PMID:26394207

  20. Predicting Two-Dimensional Silicon Carbide Monolayers.

    PubMed

    Shi, Zhiming; Zhang, Zhuhua; Kutana, Alex; Yakobson, Boris I

    2015-10-27

    Intrinsic semimetallicity of graphene and silicene largely limits their applications in functional devices. Mixing carbon and silicon atoms to form two-dimensional (2D) silicon carbide (SixC1-x) sheets is promising to overcome this issue. Using first-principles calculations combined with the cluster expansion method, we perform a comprehensive study on the thermodynamic stability and electronic properties of 2D SixC1-x monolayers with 0 ≤ x ≤ 1. Upon varying the silicon concentration, the 2D SixC1-x presents two distinct structural phases, a homogeneous phase with well dispersed Si (or C) atoms and an in-plane hybrid phase rich in SiC domains. While the in-plane hybrid structure shows uniform semiconducting properties with widely tunable band gap from 0 to 2.87 eV due to quantum confinement effect imposed by the SiC domains, the homogeneous structures can be semiconducting or remain semimetallic depending on a superlattice vector which dictates whether the sublattice symmetry is topologically broken. Moreover, we reveal a universal rule for describing the electronic properties of the homogeneous SixC1-x structures. These findings suggest that the 2D SixC1-x monolayers may present a new "family" of 2D materials, with a rich variety of properties for applications in electronics and optoelectronics.

  1. Phase transformations in binary colloidal monolayers.

    PubMed

    Yang, Ye; Fu, Lin; Marcoux, Catherine; Socolar, Joshua E S; Charbonneau, Patrick; Yellen, Benjamin B

    2015-03-28

    Phase transformations can be difficult to characterize at the microscopic level due to the inability to directly observe individual atomic motions. Model colloidal systems, by contrast, permit the direct observation of individual particle dynamics and of collective rearrangements, which allows for real-space characterization of phase transitions. Here, we study a quasi-two-dimensional, binary colloidal alloy that exhibits liquid-solid and solid-solid phase transitions, focusing on the kinetics of a diffusionless transformation between two crystal phases. Experiments are conducted on a monolayer of magnetic and nonmagnetic spheres suspended in a thin layer of ferrofluid and exposed to a tunable magnetic field. A theoretical model of hard spheres with point dipoles at their centers is used to guide the choice of experimental parameters and characterize the underlying materials physics. When the applied field is normal to the fluid layer, a checkerboard crystal forms; when the angle between the field and the normal is sufficiently large, a striped crystal assembles. As the field is slowly tilted away from the normal, we find that the transformation pathway between the two phases depends strongly on crystal orientation, field strength, and degree of confinement of the monolayer. In some cases, the pathway occurs by smooth magnetostrictive shear, while in others it involves the sudden formation of martensitic plates. PMID:25677504

  2. Recombinant albumin monolayers on latex particles.

    PubMed

    Sofińska, Kamila; Adamczyk, Zbigniew; Kujda, Marta; Nattich-Rak, Małgorzata

    2014-01-14

    The adsorption of recombinant human serum albumin (rHSA) on negatively charged polystyrene latex micro-particles was studied at pH 3.5 and the NaCl concentration range of 10(-3) to 0.15 M. The electrophoretic mobility of latex monotonically increased with the albumin concentration in the suspension. The coverage of adsorbed albumin was quantitatively determined using the depletion method, where the residual protein concentration was determined by electrokinetic measurements and AFM imaging. It was shown that albumin adsorption was irreversible. Its maximum coverage on latex varied between 0.7 mg m(-2) for 10(-3) M NaCl to 1.3 mg m(-2) for 0.15 M NaCl. The latter value matches the maximum coverage previously determined for human serum albumin on mica using the streaming potential method. The increase in the maximum coverage was interpreted in terms of reduced electrostatic repulsion among adsorbed molecules. These facts confirm that albumin adsorption at pH 3.5 is governed by electrostatic interactions and proceeds analogously to colloid particle deposition. The stability of albumin monolayers was measured in additional experiments where changes in the latex electrophoretic mobility and the concentration of free albumin in solutions were monitored over prolonged time periods. Based on these experimental data, a robust procedure of preparing albumin monolayers on latex particles of well-controlled coverage and molecule distribution was proposed. PMID:24354916

  3. Atomic force microscopy reveals two phases in single stranded DNA self-assembled monolayers.

    PubMed

    Kosaka, Priscila M; González, Sheila; Domínguez, Carmen M; Cebollada, Alfonso; San Paulo, Alvaro; Calleja, Montserrat; Tamayo, Javier

    2013-08-21

    We have investigated the structure of single-stranded (ss) DNA self-assembled monolayers (SAMs) on gold by combining peak force tapping, Kelvin probe and phase contrast atomic force microscopy (AFM) techniques. The adhesion, surface potential and phase shift signals show heterogeneities in the DNA film structure at two levels: microscale and nanoscale; which cannot be clearly discerned in the topography. Firstly, there is multilayer aggregation covering less than 5% of the surface. The DNA multilayers seem to be ordered phases and their existence suggests that DNA end-to-end interaction can play a role in the self-assembly process. Secondly, we find the formation of two phases in the DNA monolayer, which differ both in surface energy and surface potential. We relate the two domains to differences in the packing density and in the ssDNA conformation. The discovered heterogeneities in ssDNA SAMs provide a new scenario in our vision of these relevant films that have direct consequences on their biological, chemical and physical properties. PMID:23832284

  4. Structure and Order of Phosphonic Acid-Based Self-Assembled Monolayers on Si(100)

    PubMed Central

    Dubey, Manish; Weidner, Tobias; Gamble, Lara J.; Castner, David G.

    2010-01-01

    Organophosphonic acid self-assembled monolayers (SAMs) on oxide surfaces have recently seen increased use in electrical and biological sensor applications. The reliability and reproducibility of these sensors require good molecular organization in these SAMs. In this regard, packing, order and alignment in the SAMs is important, as it influences the electron transport measurements. In this study, we examine the order of hydroxyl- and methyl- terminated phosphonate films deposited onto silicon oxide surfaces by the tethering by aggregation and growth method using complementary, state-of-art surface characterization tools. Near edge x-ray absorption fine structure (NEXAFS) spectroscopy and in situ sum frequency generation (SFG) spectroscopy are used to study the order of the phosphonate SAMs in vacuum and under aqueous conditions, respectively. X-ray photoelectron spectroscopy and time of flight secondary ion mass spectrometry results show that these samples form chemically intact monolayer phosphonate films. NEXAFS and SFG spectroscopy showed that molecular order exists in the octadecylphosphonic acid and 11-hydroxyundecylphosphonic acid SAMs. The chain tilt angles in these SAMs were approximately 37° and 45°, respectively. PMID:20735054

  5. Atomic force microscopy reveals two phases in single stranded DNA self-assembled monolayers.

    PubMed

    Kosaka, Priscila M; González, Sheila; Domínguez, Carmen M; Cebollada, Alfonso; San Paulo, Alvaro; Calleja, Montserrat; Tamayo, Javier

    2013-08-21

    We have investigated the structure of single-stranded (ss) DNA self-assembled monolayers (SAMs) on gold by combining peak force tapping, Kelvin probe and phase contrast atomic force microscopy (AFM) techniques. The adhesion, surface potential and phase shift signals show heterogeneities in the DNA film structure at two levels: microscale and nanoscale; which cannot be clearly discerned in the topography. Firstly, there is multilayer aggregation covering less than 5% of the surface. The DNA multilayers seem to be ordered phases and their existence suggests that DNA end-to-end interaction can play a role in the self-assembly process. Secondly, we find the formation of two phases in the DNA monolayer, which differ both in surface energy and surface potential. We relate the two domains to differences in the packing density and in the ssDNA conformation. The discovered heterogeneities in ssDNA SAMs provide a new scenario in our vision of these relevant films that have direct consequences on their biological, chemical and physical properties.

  6. Polymerization of a diacetylenic phospholipid monolayer at the air-water interface

    NASA Astrophysics Data System (ADS)

    Bourdieu, L.; Chatenay, D.; Daillant, J.; Luzet, D.

    1994-01-01

    Monolayers of a polymerizable phospholipid on water have been studied both before and after polymerization. Before polymerization, the phase diagram is established by isotherm measurements and optical microscopy (epifluorescence and direct observation between crossed polarizer and analyzer). This allows us to bring into evidence a coexistence region between a condensed and an expanded phase, above a triple point temperature T_t = 20 ^{circ}C. The dramatic influence of impurities on the size of coexistence domains between the condensed phase and the expanded one is clearly demonstrated, even at a very low concentration of impurities. Structural and morphological modifications during the polymerization where investigated using X-ray surface scattering together with atomic force microscopy. Whatever the polymerization conditions (constant area or constant pressure), X-ray reflectivity clearly shows the reorientation of the diacetylenic links. Only constant area polymerization leads to a viscoelastic behavior of the film, as shown by talcum decoration. The topochemical nature of the polymerization of diacetylenic groups induces strong constraints on the monolayers and, when the polymerization is achieved at constant area, leads to the collapse of the films evidenced by both techniques.

  7. Comparison between cucurbiturils and β-cyclodextrin interactions with cholesterol molecules present in Langmuir monolayers used as a biomembrane model.

    PubMed

    Tovani, Camila Bussola; de Souza, João Francisco Ventrici; Cavallini, Thiago de Souza; Demets, Grégoire Jean-François; Ito, Amando; Barioni, Marina Berardi; Pazin, Wallance Moreira; Zaniquelli, Maria Elisabete Darbello

    2013-11-01

    Specific surface techniques can probe the interaction of cholesterol (Chol) with substances that are able to host and/or sequester this biomolecule, provided that the additives are properly assembled at the interface. Reports on inclusion complexes of Chol with β-cyclodextrins exist in the literature. Here we compare the interaction of β-cyclodextrin and cucurbiturils with Chol present in Langmuir phospholipid (dipalmitoylphosphatidylcholine, DPPC) monolayers, used as a biomembrane model. Cucurbiturils, CB[n], comprise macrocyclic host molecules consisting of n glycoluril units. Classic surface pressure curves, dilatational surface viscoelasticity measurements, and fluorescence emission spectra and images obtained by time-resolved fluorescence of the corresponding Langmuir-Blodgett films have shown that homologues with 5 and 6 glycoluril units, CB[5] and CB[6], do not form inclusion complexes. Higher-order homologues, such as CB[7], are likely to complex with Chol with changes in the minimum molecular areas recorded for DPPC/Chol monolayers, the fluorescence decay lifetimes, and the dilatational surface viscosities of the monolayers generated in the presence of these molecules. Moreover, we proof the removal of cholesterol from the biomimetic interface in the presence of CB[7] by means of fluorescence spectra from the subphase support of monolayers containing fluorescent-labeled Chol.

  8. Monolayer Single-Crystal 1T'-MoTe2 Grown by Chemical Vapor Deposition Exhibits Weak Antilocalization Effect.

    PubMed

    Naylor, Carl H; Parkin, William M; Ping, Jinglei; Gao, Zhaoli; Zhou, Yu Ren; Kim, Youngkuk; Streller, Frank; Carpick, Robert W; Rappe, Andrew M; Drndić, Marija; Kikkawa, James M; Johnson, A T Charlie

    2016-07-13

    Growth of transition metal dichalcogenide (TMD) monolayers is of interest due to their unique electrical and optical properties. Films in the 2H and 1T phases have been widely studied but monolayers of some 1T'-TMDs are predicted to be large-gap quantum spin Hall insulators, suitable for innovative transistor structures that can be switched via a topological phase transition rather than conventional carrier depletion [ Qian et al. Science 2014 , 346 , 1344 - 1347 ]. Here we detail a reproducible method for chemical vapor deposition of monolayer, single-crystal flakes of 1T'-MoTe2. Atomic force microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy confirm the composition and structure of MoTe2 flakes. Variable temperature magnetotransport shows weak antilocalization at low temperatures, an effect seen in topological insulators and evidence of strong spin-orbit coupling. Our approach provides a pathway to systematic investigation of monolayer, single-crystal 1T'-MoTe2 and implementation in next-generation nanoelectronic devices. PMID:27223343

  9. Monolayer Single-Crystal 1T'-MoTe2 Grown by Chemical Vapor Deposition Exhibits Weak Antilocalization Effect.

    PubMed

    Naylor, Carl H; Parkin, William M; Ping, Jinglei; Gao, Zhaoli; Zhou, Yu Ren; Kim, Youngkuk; Streller, Frank; Carpick, Robert W; Rappe, Andrew M; Drndić, Marija; Kikkawa, James M; Johnson, A T Charlie

    2016-07-13

    Growth of transition metal dichalcogenide (TMD) monolayers is of interest due to their unique electrical and optical properties. Films in the 2H and 1T phases have been widely studied but monolayers of some 1T'-TMDs are predicted to be large-gap quantum spin Hall insulators, suitable for innovative transistor structures that can be switched via a topological phase transition rather than conventional carrier depletion [ Qian et al. Science 2014 , 346 , 1344 - 1347 ]. Here we detail a reproducible method for chemical vapor deposition of monolayer, single-crystal flakes of 1T'-MoTe2. Atomic force microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy confirm the composition and structure of MoTe2 flakes. Variable temperature magnetotransport shows weak antilocalization at low temperatures, an effect seen in topological insulators and evidence of strong spin-orbit coupling. Our approach provides a pathway to systematic investigation of monolayer, single-crystal 1T'-MoTe2 and implementation in next-generation nanoelectronic devices.

  10. Gold nanoparticles modified electrode via a mercapto-diazoaminobenzene monolayer and its development in DNA electrochemical biosensor.

    PubMed

    Li, Feng; Feng, Yan; Dong, Pingjun; Tang, Bo

    2010-05-15

    A novel protocol for the gold nanoparticles (AuNPs) modification on the electrode surface was proposed, which was based on the self-assembly of AuNPs on the mercapto-diazoaminobenzene monolayer modified electrode. The mercapto-diazoaminobenzene monolayer was obtained by covalent immobilization of 4-aminothiophenol (4-ATP) molecules onto another 4-ATP monolayer functionalized gold electrode by diazotization-coupling reaction. The DNA immobilization and hybridization on the AuNPs modified electrode was further investigated. The prepared AuNPs-ATP-diazo-ATP film demonstrated efficient electron transfer ability for the electroactive species toward the electrode surface due to a large conjugated structure of the mercapto-diazoaminobenzene monolayer. The recognition of fabricated electrochemical DNA biosensor toward complementary single-stranded DNA was determined by differential pulse voltammetry with the use of Co(phen)(3)3+ as an electrochemical indicator. A linear detection range for the complementary target DNA was obtained from 3.01 x 10(-10) to 1.32 x 10(-8) M with a detection limit of 9.10 x 10(-11) M. The fabricated biosensor also possessed good selectivity and could be regenerated easily. PMID:20207131

  11. Hydrogen exchange mass spectrometry of proteins at Langmuir monolayers

    PubMed Central

    Pirrone, Gregory F.; Vernon, Briana C.; Kent, Michael S.; Engen, John R.

    2015-01-01

    Hydrogen exchange (HX) mass spectrometry (MS) is valuable for providing conformational information for proteins/peptides that are very difficult to analyze with other methods such as peripheral membrane proteins and peptides that interact with membranes. We developed a new type of HX MS measurement that integrates Langmuir monolayers. A lipid monolayer was generated, a peptide or protein associated with it, and then the monolayer-associated peptide or protein was exposed to deuterium. The deuterated species was recovered from the monolayer, digested, and deuterium incorporation monitored by MS. Test peptides showed that deuterium recovery in an optimized protocol was equivalent to deuterium recovery in conventional solution HX MS. The reproducibility of the measurements was high despite the requirement of generating a new monolayer for each deuterium labeling time. We validated that known conformational changes in the presence of a monolayer/membrane could be observed with the peptide melittin and the myristoylated protein Arf-1. Results in an accompanying paper show that the method can reveal details of conformational changes in a protein (HIV-1 Nef) which adopts a different conformation depending on if it can insert into the lipid layer. Overall, the HX MS Langmuir monolayer method provided new and meaningful conformational information for proteins that associate with lipid layers. The combination of HX MS results with neutron or X-ray reflection of the same proteins in Langmuir monolayers can be more informative than isolated use of either method. PMID:26134943

  12. Hydrogen Exchange Mass Spectrometry of Proteins at Langmuir Monolayers.

    PubMed

    Pirrone, Gregory F; Vernon, Briana C; Kent, Michael S; Engen, John R

    2015-07-21

    Hydrogen exchange (HX) mass spectrometry (MS) is valuable for providing conformational information for proteins/peptides that are very difficult to analyze with other methods such as peripheral membrane proteins and peptides that interact with membranes. We developed a new type of HX MS measurement that integrates Langmuir monolayers. A lipid monolayer was generated, a peptide or protein associated with it, and then the monolayer-associated peptide or protein was exposed to deuterium. The deuterated species was recovered from the monolayer, digested, and deuterium incorporation monitored by MS. Test peptides showed that deuterium recovery in an optimized protocol was equivalent to deuterium recovery in conventional solution HX MS. The reproducibility of the measurements was high, despite the requirement of generating a new monolayer for each deuterium labeling time. We validated that known conformational changes in the presence of a monolayer/membrane could be observed with the peptide melittin and the myristoylated protein Arf-1. Results in an accompanying paper show that the method can reveal details of conformational changes in a protein (HIV-1 Nef), which adopts a different conformation, depending on whether or not it is able to insert into the lipid layer. Overall, the HX MS Langmuir monolayer method provided new and meaningful conformational information for proteins that associate with lipid layers. The combination of HX MS results with neutron or X-ray reflection of the same proteins in Langmuir monolayers can be more informative than the isolated use of either method.

  13. Incommensurate and commensurate modulations of Ba{sub 5}RTi{sub 3}Nb{sub 7}O{sub 30} (R = La, Nd) tungsten bronzes and the ferroelectric domain structures

    SciTech Connect

    Mao, Min Min; Li, Kun; Zhu, Xiao Li; Chen, Xiang Ming

    2015-04-07

    Incommensurate and commensurate structural modulations of Ba{sub 5}RTi{sub 3}Nb{sub 7}O{sub 30} (R = La, Nd) tungsten bronze ceramics were investigated by using a cooling holder equipped transmission electron microscopy in the temperature range from 100 K to 363 K. The incommensurate modulation was observed in both Ba{sub 5}LaTi{sub 3}Nb{sub 7}O{sub 30} and Ba{sub 5}NdTi{sub 3}Nb{sub 7}O{sub 30} at room temperature, while there was a transition from incommensurate tilted structure to commensurate superstructure for Ba{sub 5}NdTi{sub 3}Nb{sub 7}O{sub 30} with decreasing temperature. The incommensurate and commensurate modulations were determined by the A-site occupancy of Ba and R cations. The A-site disorder resulted in larger incommensurability parameter δ and the diffusion of the satellite reflection spots. The effect of A-site disorder on the coupling between long-range dipolar order and the commensurate modulation was also discussed. The obvious ferroelectric 180° domains with spike-like shape parallel to c axis were observed for Ba{sub 5}NdTi{sub 3}Nb{sub 7}O{sub 30}, while no macro ferroelectric domain was determined for Ba{sub 5}LaTi{sub 3}Nb{sub 7}O{sub 30}.

  14. Methylene blue adsorption on a DMPA lipid langmuir monolayer.

    PubMed

    Giner Casares, Juan José; Camacho, Luis; Martín-Romero, Maria Teresa; López Cascales, José Javier

    2010-07-12

    Adsorption of methylene blue (MB) onto a dimyristoylphosphatidic acid (DMPA) Langmuir air/water monolayer is studied by molecular dynamics (MD) simulations, UV reflection spectroscopy and surface potential measurements. The free-energy profile associated with MB transfer from water to the lipid monolayer shows two minima of -66 and -60 kJ mol(-1) for its solid and gas phase, respectively, corresponding to a spontaneous thermodynamic process. From the position of the free-energy minima, it is possible to predict the precise location of MB in the interior of the DMPA monolayer. Thus, MB is accommodated in the phosphoryl or carbonyl region of the DMPA Langmuir air/water interface, depending on the isomorphic state (solid or gas phase, respectively). Reorientation of MB, measured from the bulk solution to the interior of the lipid monolayer, passes from a random orientation in bulk solution to an orientation parallel to the surface of the lipid monolayer when MB is absorbed. PMID:20544777

  15. Methylene blue adsorption on a DMPA lipid langmuir monolayer.

    PubMed

    Giner Casares, Juan José; Camacho, Luis; Martín-Romero, Maria Teresa; López Cascales, José Javier

    2010-07-12

    Adsorption of methylene blue (MB) onto a dimyristoylphosphatidic acid (DMPA) Langmuir air/water monolayer is studied by molecular dynamics (MD) simulations, UV reflection spectroscopy and surface potential measurements. The free-energy profile associated with MB transfer from water to the lipid monolayer shows two minima of -66 and -60 kJ mol(-1) for its solid and gas phase, respectively, corresponding to a spontaneous thermodynamic process. From the position of the free-energy minima, it is possible to predict the precise location of MB in the interior of the DMPA monolayer. Thus, MB is accommodated in the phosphoryl or carbonyl region of the DMPA Langmuir air/water interface, depending on the isomorphic state (solid or gas phase, respectively). Reorientation of MB, measured from the bulk solution to the interior of the lipid monolayer, passes from a random orientation in bulk solution to an orientation parallel to the surface of the lipid monolayer when MB is absorbed.

  16. Monolayer-by-monolayer stacked pyramid-like MoS2 nanodots on monolayered MoS2 flakes with enhanced photoluminescence.

    PubMed

    Yuan, Cailei; Cao, Yingjie; Luo, Xingfang; Yu, Ting; Huang, Zhenping; Xu, Bo; Yang, Yong; Li, Qinliang; Gu, Gang; Lei, Wen

    2015-11-01

    The precise control of the morphology and crystal shape of MoS2 nanostructures is of particular importance for their application in nanoelectronic and optoelectronic devices. Here, we describe a single step route for the synthesis of monolayer-by-monolayer stacked pyramid-like MoS2 nanodots on monolayered MoS2 flakes using a chemical vapor deposition method. First-principles calculations demonstrated that the bandgap of the pyramid-like MoS2 nanodot is a direct bandgap. Enhanced local photoluminescence emission was observed in the pyramid-like MoS2 nanodot, in comparison with monolayered MoS2 flakes. The findings presented here provide new opportunities to tailor the physical properties of MoS2via morphology-controlled synthesis.

  17. Improved mechanical stability of acetoxypropyl cellulose upon blending with ultranarrow PbS nanowires in Langmuir monolayer matrix.

    PubMed

    Maji, Subrata; Kundu, Sudarshan; Pinto, L F V; Godinho, M H; Khan, Ali Hossain; Acharya, Somobrata

    2013-12-10

    Cellulose and cellulose derivatives have long been used as membrane fabrication. Langmuir monolayer behavior, which naturally mimics membranes, of acetoxypropyl cellulose (APC) and lead sulfide (PbS) nanowire mixtures at different volume ratios is reported. Surface pressure (π)-area (A) isotherms of APC and PbS nanowires mixtures at different volume ratios show a gradual decrease in the monolayer area with increasing volume fraction of PbS nanowires. Change of surface potential with monolayer area at different volume ratios also reveals a gradual increase in the surface potential indicating incorporation of PbS nanowires within APC matrix. The compressibility and elastic constants measurements reveal an enhancement of the elasticity upon incorporation of PbS nanowires up to certain volume fractions. An enhancement in stability of the blend is observed upon PbS nanowire incorporation to the APC matrix. Rheological measurements also support the robustness of the mixture of APC and PbS nanowires in 3D bulk phase. Such robust ultrathin films of cellulose based-nanowire blend obtained by means of the Langmuir technique may lead to novel routes for designing cellulosic-based thin films and membranes.

  18. Film Reviews.

    ERIC Educational Resources Information Center

    Lance, Larry M.; Atwater, Lynn

    1987-01-01

    Reviews four Human Sexuality films and videos. These are: "Personal Decisions" (Planned Parenthood Federation of America, 1985); "The Touch Film" (Sterling Production, 1986); "Rethinking Rape" (Film Distribution Center, 1985); "Not A Love Story" (National Film Board of Canada, 1981). (AEM)

  19. Diels-Alder Reaction of Anthranilic Acids: A Versatile Route to Dense Monolayers on Flat Edge and Basal Plane Graphitic Carbon Substrates.

    PubMed

    Farquhar, Anna K; Fitchett, Christopher M; Dykstra, Haidee M; Waterland, Mark R; Brooksby, Paula A; Downard, Alison J

    2016-09-01

    Methods that reliably yield monolayers of covalently anchored modifiers on graphene and other planar graphitic materials are in demand. Covalently bonded groups can add functionality to graphitic carbon for applications ranging from sensing to supercapacitors and can tune the electronic and optical properties of graphene. Limiting modification to a monolayer gives a layer with well-defined concentration and thickness providing a minimum barrier to charge transfer. Here we investigate the use of anthranilic acid derivatives for grafting aryl groups to few layer graphene and pyrolyzed photoresist film (PPF). Under mild conditions, anthranilic acids generate arynes, which undergo Diels-Alder cycloadditions. Using spectroscopy, electrochemistry, and atomic force microscopy, we demonstrate that the reaction yields monolayers of aryl groups on graphene and PPF with maximum surface coverages consistent with densely packed layers. Our study confirms that anthranilic acids offer a convenient route to covalent modification of planar graphitic carbons (both basal and edge plane materials). PMID:27529723

  20. A photoemission study of Pd ultrathin films on Pt(111)

    SciTech Connect

    Mun, Bongjin Simon; Lee, Choongman; Stamenkovic, Vojislav; Markovic, Nenad M.; Ross Jr., Philip N.

    2005-05-11

    The origin of surface core-level shift (SCLS) of Pd thin films on Pt(111) substrate is investigated. At sub-monolayer coverage of Pd thin films, the splitting of Pd 3d core level peaks indicate the contribution of both initial and final-state of photo-ionization processes while there is almost no change on valence band (VB) spectra. When the coverage of Pd reaches to single monolayer, the final-state relaxation effect on the Pd 3d vanishes and only the initial-state effect, a negative SCLS, is present. Also, the VB spectrum at Pd monolayer films shows a clear band narrowing, that is the origin of the negative SCLS at monolayer coverage. As the Pd coverage is increased to more than monolayer thickness, the Pd 3d peaks start to show the surface layer contribution from second and third layers, positive SCLS, and the VB spectrum shows even narrower band width, possibly due to the formation of surface states and strained effect of Pd adlayers on top of the first pseudomorphic layer.