Substrate-supported Monolayers Research Articles

Ab Initio Modeling of Mixed-Dimensional Heterostructures: A Path Forward.

Understanding the electronic structure of mixed-dimensional heterostructures is essential for maximizing their application potential. However, accurately modeling such interfaces is challenging due to the complex interplay between the subsystems. We employ a computational framework integrating first-principles methods, including GW, density functional theory (DFT), and the polarizable continuum model, to elucidate the electronic structure of mixed-dimensional heterojunctions formed by free-base phthalocyanines and monolayer molybdenum disulfide. We assess the impact of dielectric screening across various scenarios, from isolated molecules to organic films on a substrate-supported monolayer. Our findings show that while polarization effects cause significant renormalization of molecular energy levels, band energies and alignments in the most relevant setup can be accurately predicted through DFT simulations of the individual subsystems. Additionally, we analyze orbital hybridization, revealing potential pathways for interfacial charge transfer. This study offers new insights into hybrid inorganic/organic interfaces and provides a practical computational protocol suitable for scaled-up studies.

Optically controlled single-valley exciton doublet states with tunable internal spin structures and spin magnetization generation

Manipulating quantum states through light-matter interactions has been actively pursued in two-dimensional materials research. Significant progress has been made toward the optical control of the valley degrees of freedom in semiconducting monolayer transition-metal dichalcogenides, based on doubly degenerate excitons from their two distinct valleys in reciprocal space. Here, we introduce a type of optically controllable doubly degenerate exciton states that come from a single valley, dubbed as single-valley exciton doublet (SVXD) states. They are unique in that their constituent holes originate from the same valence band, making possible the direct optical control of the spin structure of the excited constituent electrons. Combining ab initio GW plus Bethe-Salpeter equation (GW-BSE) calculations and a theoretical analysis method, we demonstrate such SVXD in substrate-supported monolayer bismuthene-which has been successfully grown using molecular beam epitaxy. In each of the two distinct valleys in the Brillouin zone, strong spin-orbit coupling and [Formula: see text] symmetry lead to a pair of degenerate 1s exciton states (the SVXD states) with opposite spin configurations. Any coherent linear combinations of the SVXD in a single valley can be excited by light with a specific polarization, enabling full manipulation of their internal spin configurations. In particular, a controllable net spin magnetization can be generated through light excitation. Our findings open routes to control quantum degrees of freedom, paving the way for applications in spintronics and quantum information science.

Valley engineering electron-hole liquids in transition metal dichalcogenide monolayers

Electron-hole liquids (EHLs), a correlated state of matter and a thermodynamic liquid, have recently been found to exist at room temperature in suspended monolayers of ${\text{MoS}}_{2}$. Appreciably higher rates of radiative recombination inside the liquid as compared to free excitons hold promise for optoelectronic applications such as broadband lasing. In this paper, we show that leveraging the valley physics in ${\text{MoS}}_{2}$ may be a route towards achieving tunability of specific characteristics of an EHL, such as emission wavelength, linewidth, and, most importantly, the liquid density. The conditions under which EHLs form, in bulk semiconductors as well as transition metal dichalcogenide (TMDC) monolayers are quite stringent, requiring high crystal purity and cryogenic temperatures in bulk semiconductors, and suspension in monolayers. Using a simple yet powerful model for describing free excitons and show that a phase transition into the EHL state may be feasible in substrate-supported monolayer samples. More repeatable experimental realizations of EHLs may be essential to answer questions regarding the nature of electron-hole correlations and how they may be used to generate nontrivial states of light.

Facile, Electrochemical Chlorination of Graphene from an Aqueous NaCl Solution.

We report a facile approach to directly chlorinate graphene from an aqueous sodium chloride solution under ambient conditions. By applying a moderate anodic voltage to substrate-supported monolayer graphene, the resultant chlorine radicals generated at the graphene surface enable efficient chlorination: X-ray photoelectron spectrum confirms the formation of C-Cl bonds, and reaction voltage-tunable Cl:C atomic ratios of up to 17% are achieved. In comparison, we find the corresponding electrochemical graphene bromination and iodination reactions much less viable. Electrical and Raman characterizations show substantial p-doping for the chlorinated graphene, yet good basal-plane integrity and electrical properties are maintained. Interference reflection microscopy and pH-dependent experiments next help elucidate the competition between the radical-mediated electrochemical chlorination and oxidation in the process, and rationalize acidic conditions for optimal chlorination. Reaction in a mixed NaCl-NaN3 solution shows the electrochemical chlorination to be fully suppressed by azidation, yet a sequential, two-step chlorination-azidation approach permits facile bifunctionalization.

Strain Relaxation in Misfitting Transition Metal Dichalcogenide Monolayer Superlattices: Wrinkling vs Misfit Dislocation Formation.

Two-dimensional (2D) superlattices composed of chemically heterogeneous transition-metal dichalcogenides (TMDs) have been proposed as key components in next-generation optoelectronic devices. For potential applications, coherent, defect-free compositional interfaces are usually required. In this paper, a combination of scaling theory and numerical analysis is employed to investigate strain relaxation mechanisms in misfitting, chemically heterogeneous TMDs. We demonstrate that, in free-standing superlattices, wrinkling of the monolayer is asymptotically preferred over misfit dislocation formation in both binary and ternary superlattices. For substrate-supported monolayers, however, misfit dislocation formation is thermodynamically favored above a critical superlattice width, implying the presence of an upper limit to the thermodynamic stability of coherent, misfitting 2D superlattices. Finally, it is shown numerically that the critical superlattice width is only weakly dependent on the misfit.

Probing built-in stress effect on the defect density of stretched monolayer graphene membranes

It is of great interest to link Raman scattering to the properties of disorders in graphene membranes, which provides an effective characterization method to probe atomic scale defects. The built-in stress effect on the defect densities of substrate-supported monolayer graphene membranes around wells is investigated. First, a modified phenomenological model is developed to depict the relationship between built-in stresses and defect-activated Raman intensities. To validate the rationality of the modified model, Raman spectroscopy is used to characterize stretched graphene membranes on different patterned substrates with micro-scale wells. The experimental data indicate that the intensity ratio of D mode to G mode ID/IG increases with the Raman test point approaching the well edge. According to the modified model, the increase of ID/IG means the rise of defect densities, which originates from the propagation of initial defects in graphene membranes under built-in tension. The underlying mechanism of defect density increasing phenomenon is that the built-in stresses provide the energy for defect propagations in stretched graphene membranes. Theoretical and experimental comparison well validates the rationality of the modified model. The work can provide a theoretical foundation for Raman characterization method of defect propagations in stretched graphene and applications of defective graphene-based nanodevices.

Characterization of Robust and Free-Standing 2D-Nanomembranes of UV-Polymerized Diacetylene Lipids.

Free-standing lipid membranes are promising as artificial functional membrane systems for application in separation, filtration, and nanopore sensing. To improve the mechanical properties of lipid membranes, UV-polymerized lipids have been introduced. We investigated free-standing as well as substrate-supported monolayers of 1-palmitoyl-2-(10,12-tricosadiynoyl)- sn-glycero-3-phosphoethanolamine (PTPE) and 1,2-bis(10,12-tricosadiynoyl)- sn-glycero-3-phosphocholine (DiynePC) and characterized them with respect to their structure, morphology, and stability. Using helium ion microscopy (HIM), we were able to visualize the integrity of the lipid 2D-nanomembranes spanning micrometer-sized voids under high-vacuum conditions. Atomic force microscopy (AFM) investigations under ambient conditions revealed formation of intact and robust pore-spanning 2D-nanomembranes up to 8 × 2 μm2 in size. Analysis by attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR) verified a distinct reduction of signal at 2143 cm-1 from diacetylene groups in the 2D-nanomembranes after UV-polymerization. Further high-resolution AFM investigations of unpolymerized lipid monolayers revealed a well-ordered two-dimensional network, when deposited on highly oriented pyrolytic graphite (HOPG). These structures were inhibited for polymerized adlayers. Structural models for the molecular arrangement of the adlayers are proposed and discussed.

Radiation-induced direct bandgap transition in few-layer MoS2

We report photoluminescence (PL) spectroscopy of air-suspended and substrate-supported molybdenum disulfide (MoS2) taken before and after exposure to proton radiation. For 2-, 3-, and 4-layer MoS2, the radiation causes a substantial (>10×) suppression of the indirect bandgap emission, likely due to a radiation-induced decoupling of the layers. For all samples measured (including the monolayer), we see the emergence of a defect-induced shoulder peak at around 1.7 eV, which is redshifted from the main direct bandgap emission at 1.85 eV. Here, defects induced by the radiation trap the excitons and cause them to be redshifted from the main direct band emission. After annealing, the defect-induced sideband disappears, but the indirect band emission remains suppressed, indicating a permanent transition into a direct bandgap material. While suspended 2-, 3-, and 4-layer MoS2 show no change in the intensity of the direct band emission after radiation exposure, substrate-supported MoS2 exhibits an approximately 2-fold increase in the direct bandgap emission after irradiation. Suspended monolayer MoS2 shows a 2–3× drop in PL intensity; however, substrate-supported monolayer MoS2 shows a 2-fold increase in the direct band emission.

Enhancing Multifunctionalities of Transition-Metal Dichalcogenide Monolayers via Cation Intercalation.

We have demonstrated that multiple functionalities of transition-metal dichalcogenide (TMDC) monolayers may be substantially improved by the intercalation of small cations (H+ or Li+) between the monolayers and underlying substrates. The functionalities include photoluminescence (PL) efficiency and catalytic activity. The improvement in PL efficiency may be up to orders of magnitude and can be mainly ascribed to two effects of the intercalated cations: p-doping to the monolayers and reducing the influence of substrates, but more studies are necessary to better understand the mechanism for the improvement in the catalytic functionality. The cation intercalation may be achieved by simply immersing substrate-supported monolayers into the solution of certain acids or salts. It is more difficult to intercalate under the monolayers interacting with substrates stronger, such as as-grown monolayers or the monolayers on 2D material substrates. This result presents a versatile strategy to simultaneously optimize multiple functionalities of TMDC monolayers.

Stabilizing the spin vortex crystal phase in two-dimensional iron-based superconductors

We present an investigation of the magnetic structure for iron-based superconductors (FeSCs) when inversion symmetry is broken, such as in substrate-supported monolayers or in the presence of a $c$-axis electric field. We perform group-, mean-field-, and density-functional-theoretic analyses on a model system of monolayer iron selenide (FeSe) on a strontium titanate $[{\mathrm{SrTiO}}_{3}$(001)] substrate. Our group- and mean-field-theoretic calculations are more generally applicable to thin films of the rest of the 11 (e.g., FeSe) family of iron-based superconductors, as well as to thin films of the 111 (e.g., LiFeAs) and 1111 (e.g., LaOFeAs) families, as these all belong to the same space group. We find that in systems with a collinear antiferromagnetic phase in bulk, when inversion symmetry is broken, the transition is instead into a ``spin vortex crystal'' phase and that a further phase transition can occur at a lower temperature in some circumstances. The spin vortex crystal is a ${C}_{4}$-symmetric magnetic phase which is related to this parent ${C}_{2}$-symmetric collinear antiferromagnetic (stripe) phase which is ubiquitous among the iron-based superconductors.

Monolayer WS2 Nanopores for DNA Translocation with Light-Adjustable Sizes.

Two-dimensional materials are promising for a range of applications, as well as testbeds for probing the physics of low-dimensional systems. Tungsten disulfide (WS2) monolayers exhibit a direct band gap and strong photoluminescence (PL) in the visible range, opening possibilities for advanced optoelectronic applications. Here, we report the realization of two-dimensional nanometer-size pores in suspended monolayer WS2 membranes, allowing for electrical and optical response in ionic current measurements. A focused electron beam was used to fabricate nanopores in WS2 membranes suspended on silicon-based chips and characterized using PL spectroscopy and aberration-corrected high-resolution scanning transmission electron microscopy. It was observed that the PL intensity of suspended WS2 monolayers is ∼10-15 times stronger when compared to that of substrate-supported monolayers, and low-dose scanning transmission electron microscope viewing and drilling preserves the PL signal of WS2 around the pore. We establish that such nanopores allow ionic conductance and DNA translocations. We also demonstrate that under low-power laser illumination in solution, WS2 nanopores grow slowly in size at an effective rate of ∼0.2-0.4 nm/s, thus allowing for atomically controlled nanopore size using short light pulses.

Thermal Conductivity of Monolayer Molybdenum Disulfide Obtained from Temperature-Dependent Raman Spectroscopy

Atomically thin molybdenum disulfide (MoS2) offers potential for advanced devices and an alternative to graphene due to its unique electronic and optical properties. The temperature-dependent Raman spectra of exfoliated, monolayer MoS2 in the range of 100-320 K are reported and analyzed. The linear temperature coefficients of the in-plane E2g 1 and the out-of-plane A1g modes for both suspended and substrate-supported monolayer MoS2 are measured. These data, when combined with the first-order coefficients from laser power-dependent studies, enable the thermal conductivity to be extracted. The resulting thermal conductivity κ = (34.5(4) W/mK at room temperature agrees well with the first principles lattice dynamics simulations. However, this value is significantly lower than that of graphene. The results from this work provide important input for the design of MoS2-based devices where thermal management is critical.

Exciton Dynamics in Suspended Monolayer and Few-Layer MoS2 2D Crystals

Femtosecond transient absorption spectroscopy and microscopy were employed to study exciton dynamics in suspended and Si₃N₄ substrate-supported monolayer and few-layer MoS₂ 2D crystals. Exciton dynamics for the monolayer and few-layer structures were found to be remarkably different from those of thick crystals when probed at energies near that of the lowest energy direct exciton (A exciton). The intraband relaxation rate was enhanced by more than 40 fold in the monolayer in comparison to that observed in the thick crystals, which we attributed to defect assisted scattering. Faster electron-hole recombination was found in monolayer and few-layer structures due to quantum confinement effects that lead to an indirect-direct band gap crossover. Nonradiative rather than radiative relaxation pathways dominate the dynamics in the monolayer and few-layer MoS₂. Fast trapping of excitons by surface trap states was observed in monolayer and few-layer structures, pointing to the importance of controlling surface properties in atomically thin crystals such as MoS₂ along with controlling their dimensions.

Controlling the Position of Functional Groups at the Liquid/Solid Interface: Impact of Molecular Symmetry and Chirality

With the aim of controlling the position of functional groups in a substrate-supported monolayer, a new family of functionalized linear alkyl chains was designed and synthesized, aided by molecular mechanics and dynamics simulations of its two-dimensional self-assembly on graphite. The self-assembly of these amino functionalized diamides at the liquid/solid interface was investigated with scanning tunneling microscopy. Intermolecular hydrogen-bonding interactions involving amides, combined with the effect of molecular symmetry and chirality, were found to guide the self-assembly. Control of the relative position and orientation of the amine groups was achieved, in the case of enantiopure compounds. Interestingly, racemates led to both racemic conglomerate and solid solution formation, with a concomitant loss of positional and orientational control of the amino groups as a result.

Self-Organization of an Amphiphilic Rod−Coil−Rod Block Copolymer into Liquid Crystalline, Substrate-Supported Monolayers and Bilayers

We report that the amphiphilic rod−coil−rod triblock copolymer with a coil attractive to the substrate surface self-organize into liquid crystalline monolayers or bilayers of a few nanometers thickness on the substrate surface. The copolymer investigated is a triblock copolymer, poly(n-hexyl isocyanate-b-2-vinylpyridine-b-n-hexyl isocyanate) (PHIC-b-P2VP-b-PHIC). Key processes of self-organization in the thin films, such as adsorption, desorption, diffusion, nematic and smectic ordering, and microphase separation, are tuned by exposing dip- or immersion-coated nanoscale films to the vapor of solvents which are rod (PHIC)-selective, coil (P2VP)-selective, or good to both blocks. Reorganization of the rod−coils in the nanofilms yielded various morphologies in the monolayer or bilayer, including unique long-range-ordered, smectic-on-nematic biphasic sheets. The results offer understanding on the complex morphological evolution in amphiphilic rod−coil block copolymers on the substrate surface.

Fusion Peptide of Influenza Hemagglutinin Requires a Fixed Angle Boomerang Structure for Activity

The fusion peptide of influenza hemagglutinin is crucial for cell entry of this virus. Previous studies showed that this peptide adopts a boomerang-shaped structure in lipid model membranes at the pH of membrane fusion. To examine the role of the boomerang in fusion, we changed several residues proposed to stabilize the kink in this structure and measured fusion. Among these, mutants E11A and W14A expressed hemagglutinins with hemifusion and no fusion activities, and F9A and N12A had no effect on fusion, respectively. Binding enthalpies and free energies of mutant peptides to model membranes and their ability to perturb lipid bilayer structures correlated well with the fusion activities of the parent full-length molecules. The structure of W14A determined by NMR and site-directed spin labeling features a flexible kink that points out of the membrane, in sharp contrast to the more ordered boomerang of the wild-type, which points into the membrane. A specific fixed angle boomerang structure is thus required to support membrane fusion.

Slow rotational mobilities of antibodies and lipids associated with substrate-supported phospholipid monolayers as measured by polarized fluorescence photobleaching recovery

Polarized fluorescence photobleaching recovery has been used to monitor slow rotational motions of a fluorescently-labeled anti-dinitrophenyl mouse IgGl monoclonal antibody (ANO2) specifically bound to substrate-supported monolayers composed of a mixture of distearoylphosphatidylcholine (DSPC) and dinitrophenyldioleoylphosphatidylethanolamine (DNP-DOPE). ANO2 antibodies were labeled with a new bifunctional carbocyanine fluorophore that has two amino-reactive groups; steady-state fluorescence anisotropy data confirmed the expected result that the ANO2-conjugated bifunctional probe had less independent flexibility than ANO2-conjugated unifunctional fluorescence labels. Rotational mobilities were also measured for the fluorescent lipid 1,1'-dioctadecyl 3,3,3',3'-tetramethylindocarbocyanine (dil) in DSPC and in mixed DSPC/DNP-DOPE monolayers in the presence and absence of unlabeled ANO2 antibodies. The apparent rotational correlation time and fractional mobility of ANO2 on supported monolayers were approximately 70 and approximately 0.3 s, respectively. These measured parameters of rotational mobility did not depend on the ANO2 surface density or on kinetic factors, but addition of unlabeled polyclonal anti-(mouse IgG) antibodies significantly decreased the apparent mobile fraction. The measured fluorescence recovery curves for dil were consistent with two fluorophore populations with rotational correlation times of approximately 4 and approximately 100 s and a population of immobile fluorescent lipid. No difference in fluorescence recovery and decay curves was measured for dil in DSPC monolayers, DSPC/DNP-DOPE monolayers, and DSPC/DNP-DOPE monolayers treated with unlabeled ANO2 antibodies.

Collective tilt behavior in dense, substrate-supported monolayers of long-chain molecules: a molecular dynamics study

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCollective tilt behavior in dense, substrate-supported monolayers of long-chain molecules: a molecular dynamics studyJames P. Bareman and Michael L. KleinCite this: J. Phys. Chem. 1990, 94, 13, 5202–5205Publication Date (Print):June 1, 1990Publication History Published online1 May 2002Published inissue 1 June 1990https://doi.org/10.1021/j100376a003RIGHTS & PERMISSIONSArticle Views280Altmetric-Citations101LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (547 KB) Get e-Alerts