Nonreciprocal Giant Magneto-Optic Effects in Transition-Metal Dichalcogenides without Magnetic Field
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Magnetic exchange field has been demonstrated to be effective in enhancing the valley splitting of monolayer transition-metal dichalcogenides experimentally. However, how magnetic exchange coupling affects the magnetooptical behaviors in massive Dirac systems remains elusive. Using k⃗·p⃗ model and Kubo formula, we theoretically report that optical Hall conductivity and giant magnetooptical effects can be induced in monolayer transition-metal dichalcogenides even if there is no any magnetic field involved when considering magnetic exchange interaction. Such an unusual result originates from the fact that the existence of magnetic exchange coupling effectively enables the breaking of time reversal symmetry, which grants the removal of valley degeneracy and unveils the possibility of generation and manipulation of magnetooptical effects in monolayer transition-metal dichalcogenides with no need for magnetic field. Our results suggest that the presence of magnetic exchange coupling of transition-metal dichalcogenides represents an alternative strategy capable of inducing magnetoopitcal effects, which can be extended to other monolayer massive Dirac systems.Template
Brewster's angle
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Photoinitiated thiol-yne chemistry is utilized as a click reaction for grafting of acid-terminated alkynes to thiol-terminated monolayers on a gold substrate to create stable, low-density monolayers. The resulting monolayers are compared with a well-packed 11-mercaptoundecanoic acid monolayer and the analogous low-density monolayers prepared through a solution phase synthetic approach. The overall structuring of the monolayer prepared by solid-phase grafting is characterized by contact angle goniometry and Fourier transform infrared spectroscopy. The results show that the product monolayer has an intermediate surface energy and a more disordered chemical structuring compared to a traditional well-packed self-assembled monolayer, showing a low-packing density of the chains at the monolayer surface. The monolayer's structure and electrochemical stability were studied by reductive desorption of the thiolates. The prepared low-density monolayers have a higher electrochemical stability than traditional well-packed monolayers, which results from the crystalline structure at the gold interface. This technique allows for simple, fast preparation of low-density monolayers of higher stability than well-packed monolayers. The use of a photomask to restrict light access to the substrate yielded these low-density monolayers in patterned regions defined by light exposure. This general thiol-yne approach is adaptable to a variety of analogous low-density monolayers with diverse chemical functionalities.
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Mixed monolayers consisting of 4-fluorobenzenethiolate and 1-octadecanethiolate on Au surfaces were formed by immersing in an ethanol solution of 4-fluorobenzenethiol (FBT), and subsequently by immersing in that of 1-octadecanethiol (ODT). To obtain systematically a mixed monolayer, the formation of FBT- and ODT-monolayers was investigated with respect to the reaction time and concentration of the solution. The monolayer formed on a Au surface was evaluated based on the work function, the water contact angle, and the X-ray photoelectron spectroscopy (XPS) spectra measured. The XPS measurement of substrates prepared for formation of a mixed monolayer exhibited F 1s and C 1s spectra supporting the presence of a mixed monolayer consisting of 4-fluorobenezenethiolate and 1-octadecanethiolate.
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The electrostatic binding and metal coordination between metal ions and Langmuir monolayers or LB films are discussed, and their effects on the monolayer 2D structure and related phase behavior are analyzed. The interfacial recognition and sensing for metal ions by Langmuir monolayers are also shown. Langmuir monolayers and LB films as 2D template to induce the 2D-oriented crystal growth via metal/monolayer binding is especially demonstrated. The abnormal catalytic characteristics, the functions and devices of metal-incorporated Langmuir monolayers and LB films are displayed by some examples. The review also shows the application of metal-chelating lipid monolayers on the interfacial study of bio-macromolecules. The review suggests the great roles of metal/monolayer binding in alternating monolayer structures and the assembly of functional metal complexes.
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The molecular interactions of monolayers composed of cyclic and linear forms of surfactins (SFs) were evaluated through atomic force microscopy (AFM) together with a Langmuir monolayer technique. The surface pressure (π)-area per molecule (A) isotherm of a pure cyclic surfactin (CSF) monolayer exhibited a liquid expanded (Le) monolayer, while that of a pure linear surfactin (LSF) monolayer exhibited a liquid condensed (Lc) monolayer, demonstrating that the CSFs are in a rather loose molecular packing state owing to its bulky heptapeptide ring. The plots of the mean area per molecule of the CSF/LSF monolayers were well fitted to the ideal curves, suggesting that ideal mixing occurs, or that the two components are immiscible in a monolayer. The AFM images of the CSF/LSF monolayers transferred at 25 mN/m gave phase-separated microdomain structures, indicating that the CSFs and LSFs are almost immiscible and separated into a CSF-rich and LSF-rich phases, as suggested from the analysis of the mean area per molecule of the monolayers. Our results clearly demonstrated that the cleavage of the cyclic heptapeptide headgroup of CSF drastically changes its molecular packing state in a monolayer and that AFM observation combined with the Langmuir monolayer technique is quite useful to explore the manner of self-assembly of a binary system of microbial products such as CSFs and LSFs.
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Direct evidence has been presented for condensed phase formation in adsorbed monolayers at surfactant solution surfaces, which is quite the same as phase transitions from expanded to condensed phases in spread monolayers by compression. It thus follows that there is no clear boundary between adsorbed and spread monolayers. However, there are many different modes of relaxation in spread monolayers ouing to the greater non-equilibrium nature of spread monolayers during compression compared to adsorbed monolayers.
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