Prediction of a Novel Electromechanical Response in Polar Polymers with Rigid Backbones: Contrasting Furan-Derived Nanothreads to Poly(Vinylidene Fluoride).

Syn furan nanothreads have all oxygen atoms arranged on one side of the thread backbone; these polar threads present intriguing opportunities in electromechanical response owing to their rigid ladder-like backbone. We retrained a C/H/O reactive force field to simulate their response to external electric field for both end-anchored individual threads and bulk nanothread crystals, contrasting the results to those for poly(vinylidene fluoride) (PVDF) polymer. Whereas the field induces a length-independent torque in PVDF through backbone rotation about σ bonds, furan-derived nanothreads generate a length-dependent torque by progressively twisting their rigid backbone. This mode of response couples the rotational history of the electric field to axial tension in the anchored thread. In simulations of densely packed syn furan nanothread crystals without anchors, the crystals pole in a field (∼3 GV/m at 300 K) similar to that seen in simulations of PVDF, suggesting that crystals of polar nanothreads can be ferroelectric.

Confined Monolayer Ag As a Large Gap 2D Semiconductor and Its Momentum Resolved Excited States.

2D materials have intriguing quantum phenomena that are distinctively different from their bulk counterparts. Recently, epitaxially synthesized wafer-scale 2D metals, composed of elemental atoms, are attracting attention not only for their potential applications but also for exotic quantum effects such as superconductivity. By mapping momentum-resolved electronic states using time-resolved and angle-resolved photoemission spectroscopy (ARPES), we reveal that monolayer Ag confined between bilayer graphene and SiC is a large gap (>1 eV) 2D semiconductor, consistent with ab initio GW calculations. The measured valence band dispersion matches the GW quasiparticle band structure. However, the conduction band dispersion shows an anomalously large effective mass of 2.4 m0. Possible mechanisms for this large enhancement in the "apparent mass" are discussed.

Theoretical Studies of Furan and Thiophene Nanothreads: Structures, Cycloaddition Barriers, and Activation Volumes.

This theoretical study examines the formation, structure, and stability of two of the most ordered nanothreads produced yet, those derived from furan and thiophene. The energetic consequences and activation barriers of the first two steps of oligomerization via a Diels-Alder mechanism were examined. The ca. 20 GPa difference in the synthetic pressures (lower for furan) is explainable in terms of the greater loss of aromaticity by the thiophene. The effects of pressure on the reaction profiles, operating through a volume decrease along the reaction coordinate, are illustrated. The interesting option of polymerization proceeding in one or two directions opens up the possibility of polymers with opposing, cumulative dipole moments. The computed activation volumes are consistently more negative for furan, in accordance with the lower onset pressure of furan polymerization. The energetics of three ordered polymer structures were examined. The syn polymer, with all O/S atoms on the same side, if not allowed to distort, is at a high energy relative to the other two due to the O/S lone pair repulsion, understandably greater for S than for O at the 2.8/2.6 Å separation. Set free, the syn isomers curve or arch in two- or three-dimensional (helical) ways, whose energetics are traced in detail. The syn polymer can also stabilize itself by twisting into zig-zag or helical energy minima. The release of strain in a linear thread as the pressure is relaxed to 1 atm, with consequent thread curving, is a likely mechanism for the observed loss of the crystalline order in the polymer as it is returned to ambient pressure.

Photochemically Mediated Polymerization of Molecular Furan and Pyridine: Synthesis of Nanothreads at Reduced Pressures.

Nanothreads are emerging one-dimensional sp3-hybridized materials with high predicted tensile strength and a tunable band gap. They can be synthesized by compressing aromatic or nonaromatic small molecules to pressures ranging from 15-30 GPa. Recently, new avenues are being sought that reduce the pressure required to afford nanothreads; the focus has been placed on the polymerization of molecules with reduced aromaticity, favorable stacking, and/or the use of higher reaction temperatures. Herein, we report the photochemically mediated polymerization of pyridine and furan aromatic precursors, which achieves nanothread formation at reduced pressures. In the case of pyridine, it was found that a combination of slow compression/decompression with broadband UV light exposure yielded a crystalline product featuring a six-fold diffraction pattern with similar interplanar spacings to previously synthesized pyridine-derived nanothreads at a reduced pressure. When furan is compressed to 8 GPa and exposed to broadband UV light, a crystalline solid is recovered that similarly demonstrates X-ray diffraction with an interplanar spacing akin to that of the high-pressure synthesized furan-derived nanothreads. Our method realizes a 1.9-fold reduction in the maximum pressure required to afford furan-derived nanothreads and a 1.4-fold reduction in pressure required for pyridine-derived nanothreads. Density functional theory and multiconfigurational wavefunction-based computations were used to understand the photochemical activation of furan and subsequent cascade thermal cycloadditions. The reduction of the onset pressure is caused by an initial [4+4] cycloaddition followed by increasingly facile thermal [4+2]-cycloadditions during polymerization.

Shape Entropy of a Reconfigurable Ising Surface.

Disclinations in a 2D sheet create regions of Gaussian curvature whose inversion produces a reconfigurable surface with many distinct metastable shapes, as shown by molecular dynamics of a disclinated graphene monolayer. This material has a near-Gaussian "density of shapes" and an effectively antiferromagnetic interaction between adjacent cones. A∼10 nm patch has hundreds of distinct metastable shapes with tunable stability and topography on the size scale of biomolecules. As every conical disclination provides an Ising-like degree of freedom, we call this technique "Isigami."

Nonstoichiometric Salt Intercalation as a Means to Stabilize Alkali Doping of 2D Materials.

Although doping with alkali atoms is a powerful technique for introducing charge carriers into physical systems, the resulting charge-transfer systems are generally not air stable. Here we describe computationally a strategy towards increasing the stability of alkali-doped materials that employs stoichiometrically unbalanced salt crystals with excess cations (which could be deposited during, e.g., in situ gating) to achieve doping levels similar to those attained by pure alkali metal doping. The crystalline interior of the salt crystal acts as a template to stabilize the excess dopant atoms against oxidation and deintercalation, which otherwise would be highly favorable. We characterize this doping method for graphene, NbSe_{2}, and Bi_{2}Se_{3} and its effect on direct-to-indirect band gap transitions, 2D superconductivity, and thermoelectric performance. Salt intercalation should be generally applicable to systems which can accommodate this "ionic crystal" doping (and particularly favorable when geometrical packing constraints favor nonstoichiometry).

Illuminating Invisible Grain Boundaries in Coalesced Single-Orientation WS2 Monolayer Films.

Engineering atomic-scale defects is crucial for realizing wafer-scale, single-crystalline transition metal dichalcogenide monolayers for electronic devices. However, connecting atomic-scale defects to larger morphologies poses a significant challenge. Using electron microscopy and ReaxFF reactive force field-based molecular dynamics simulations, we provide insights into WS2 crystal growth mechanisms, providing a direct link between synthetic conditions and microstructure. Dark-field TEM imaging of coalesced monolayer WS2 films illuminates defect arrays that atomic-resolution STEM imaging identifies as translational grain boundaries. Electron diffraction and high-resolution imaging reveal that the films have nearly a single orientation with imperfectly stitched domains that tilt out-of-plane when released from the substrate. Imaging and ReaxFF simulations uncover two types of translational mismatch, and we discuss their origin related to relatively fast growth rates. Statistical analysis of >1300 facets demonstrates that microstructural features are constructed from nanometer-scale building blocks, describing the system across sub-Ångstrom to multimicrometer length scales.

Perfect and Defective 13C-Furan-Derived Nanothreads from Modest-Pressure Synthesis Analyzed by 13C NMR.

The molecular structure of nanothreads produced by the slow compression of 13C4-furan was studied by advanced solid-state NMR. Spectral editing showed that >95% of carbon atoms were bonded to one hydrogen (C-H) and that there were 2-4% CH2, 0.6% C═O, and <0.3% CH3 groups. Alkenes accounted for 18% of the CH moieties, while trapped, unreacted furan made up 7%. Two-dimensional (2D) 13C-13C and 1H-13C NMR identified 12% of all carbon in asymmetric O-CH═CH-CH-CH- and 24% in symmetric O-CH-CH═CH-CH- rings. While the former represented defects or chain ends, some of the latter appeared to form repeating thread segments. Around 10% of carbon atoms were found in highly ordered, fully saturated nanothread segments. Unusually slow 13C spin-exchange with sites outside the perfect thread segments documented a length of at least 14 bonds; the small width of the perfect-thread signals also implied a fairly long, regular structure. Carbons in the perfect threads underwent relatively slow spin-lattice relaxation, indicating slow spin exchange with other threads and smaller amplitude motions. Through partial inversion recovery, the signals of the perfect threads were observed and analyzed selectively. Previously considered syn-threads with four different C-H bond orientations were ruled out by centerband-only detection of exchange NMR, which was, on the contrary, consistent with anti-threads. The observed 13C chemical shifts were matched well by quantum-chemical calculations for anti-threads but not for more complex structures like syn/anti-threads. These observations represent the first direct determination of the atomic-level structure of fully saturated nanothreads.

Atomically thin half-van der Waals metals enabled by confinement heteroepitaxy.

Atomically thin two-dimensional (2D) metals may be key ingredients in next-generation quantum and optoelectronic devices. However, 2D metals must be stabilized against environmental degradation and integrated into heterostructure devices at the wafer scale. The high-energy interface between silicon carbide and epitaxial graphene provides an intriguing framework for stabilizing a diverse range of 2D metals. Here we demonstrate large-area, environmentally stable, single-crystal 2D gallium, indium and tin that are stabilized at the interface of epitaxial graphene and silicon carbide. The 2D metals are covalently bonded to SiC below but present a non-bonded interface to the graphene overlayer; that is, they are 'half van der Waals' metals with strong internal gradients in bonding character. These non-centrosymmetric 2D metals offer compelling opportunities for superconducting devices, topological phenomena and advanced optoelectronic properties. For example, the reported 2D Ga is a superconductor that combines six strongly coupled Ga-derived electron pockets with a large nearly free-electron Fermi surface that closely approaches the Dirac points of the graphene overlayer.

Field-Tunable Interactions and Frustration in Underlayer-Mediated Artificial Spin Ice.

Artificial spin ice systems have opened experimental windows into a range of model magnetic systems through the control of interactions among nanomagnet moments. This control has previously been enabled by altering the nanomagnet size and the geometry of their placement. Here we demonstrate that the interactions in artificial spin ice can be further controlled by including a soft ferromagnetic underlayer below the moments. Such a substrate also breaks the symmetry in the array when magnetized, introducing a directional component to the correlations. Using spatially resolved magneto-optical Kerr effect microscopy to image the demagnetized ground states, we show that the correlation of the demagnetized states depends on the direction of the underlayer magnetization. Further, the relative interaction strength of nearest and next-nearest neighbors varies significantly with the array geometry. We exploit this feature to induce frustration in an inherently unfrustrated square lattice geometry, demonstrating new possibilities for effective geometries in two-dimensional nanomagnetic systems.

Nonlinear Dark-Field Imaging of One-Dimensional Defects in Monolayer Dichalcogenides.

One-dimensional defects in two-dimensional (2D) materials can be particularly damaging because they directly impede the transport of charge, spin, or heat and can introduce a metallic character into otherwise semiconducting systems. Current characterization techniques suffer from low throughput and a destructive nature or limitations in their unambiguous sensitivity at the nanoscale. Here we demonstrate that dark-field second harmonic generation (SHG) microscopy can rapidly, efficiently, and nondestructively probe grain boundaries and edges in monolayer dichalcogenides (i.e., MoSe2, MoS2, and WS2). Dark-field SHG efficiently separates the spatial components of the emitted light and exploits interference effects from crystal domains of different orientations to localize grain boundaries and edges as very bright 1D patterns through a Cerenkov-type SHG emission. The frequency dependence of this emission in MoSe2 monolayers is explained in terms of plasmon-enhanced SHG related to the defect's metallic character. This new technique for nanometer-scale imaging of the grain structure, domain orientation and localized 1D plasmons in 2D different semiconductors, thus enables more rapid progress toward both applications and fundamental materials discoveries.

Unexpected Near-Infrared to Visible Nonlinear Optical Properties from 2-D Polar Metals.

Near-infrared-to-visible second harmonic generation from air-stable two-dimensional polar gallium and indium metals is described. The photonic properties of 2D metals, including the largest second-order susceptibilities reported for metals (approaching 10 nm/V), are determined by the atomic-level structure and bonding of two-to-three-atom-thick crystalline films. The bond character evolved from covalent to metallic over a few atomic layers, changing the out-of-plane metal-metal bond distances by approximately ten percent (0.2 Å), resulting in symmetry breaking and an axial electrostatic dipole that mediated the large nonlinear response. Two different orientations of the crystalline metal atoms, corresponding to lateral displacements <2 Å, persisted in separate micrometer-scale terraces to generate distinct harmonic polarizations. This strong atomic-level structure-property interplay suggests metal photonic properties can be controlled with atomic precision.

Nondestructive Measurements of the Mechanical and Structural Properties of Nanostructured Metalattices.

Metalattices are artificial 3D solids, periodic on sub-100 nm length scales, that enable the functional properties of materials to be tuned. However, because of their complex structure, predicting and characterizing their properties is challenging. Here we demonstrate the first nondestructive measurements of the mechanical and structural properties of metalattices with feature sizes down to 14 nm. By monitoring the time-dependent diffraction of short wavelength light from laser-excited acoustic waves in the metalattices, we extract their acoustic dispersion, Young's modulus, filling fraction, and thicknesses. Our measurements are in excellent agreement with macroscopic predictions and potentially destructive techniques such as nanoindentation and scanning electron microscopy, with increased accuracy over larger areas. This is interesting because the transport properties of these metalattices do not obey bulk predictions. Finally, this approach is the only way to validate the filling fraction of metalattices over macroscopic areas. These combined capabilities can enable accurate synthesis of nanoenhanced materials.

Nanoarchitecture through Strained Molecules: Cubane-Derived Scaffolds and the Smallest Carbon Nanothreads.

Relative to the rich library of small-molecule organics, few examples of ordered extended (i.e., nonmolecular) hydrocarbon networks are known. In particular, sp3 bonded, diamond-like materials represent appealing targets because of their desirable mechanical, thermal, and optical properties. While many covalent organic frameworks (COFs)-extended, covalently bonded, and porous structures-have been realized through molecular architecture with exceptional control, the design and synthesis of dense, covalent extended solids has been a longstanding challenge. Here we report the preparation of a sp3-bonded, low-dimensional hydrocarbon synthesized via high-pressure, solid-state diradical polymerization of cubane (C8H8), which is a saturated, but immensely strained, cage-like molecule. Experimental measurements show that the obtained product is crystalline with three-dimensional order that appears to largely preserve the basic structural topology of the cubane molecular precursor and exhibits high hardness (comparable to fused quartz) and thermal stability up to 300 °C. Among the plausible theoretical candidate structures, one-dimensional carbon scaffolds comprising six- and four-membered rings that pack within a pseudosquare lattice provide the best agreement with experimental data. These diamond-like molecular rods with extraordinarily small thickness are among the smallest members in the carbon nanothread family, and calculations indicate one of the stiffest one-dimensional systems known. These results present opportunities for the synthesis of purely sp3-bonded extended solids formed through the strain release of saturated molecules, as opposed to only unsaturated precursors.

Local Structure and Bonding of Carbon Nanothreads Probed by High-Resolution Transmission Electron Microscopy.

Carbon nanothreads are a new one-dimensional sp3-bonded nanomaterial of CH stoichiometry synthesized from benzene at high pressure and room temperature by slow solid-state polymerization. The resulting threads assume crystalline packing hundreds of micrometers across. We show high-resolution electron microscopy (HREM) images of hexagonal arrays of well-aligned thread columns that traverse the 80-100 nm thickness of the prepared sample. Diffuse scattering in electron diffraction reveals that nanothreads are packed with axial and/or azimuthal disregistry between them. Layer lines in diffraction from annealed nanothreads provide the first evidence of translational order along their length, indicating that this solid-state reaction proceeds with some regularity. HREM also reveals bends and defects in nanothread crystals that can contribute to the broadening of their diffraction spots, and electron energy-loss spectroscopy confirms them to be primarily sp3-hybridized, with less than 27% sp2 carbon, most likely associated with partially saturated "degree-4" threads.

Crystallites of magnetic charges in artificial spin ice.

Artificial spin ice is a class of lithographically created arrays of interacting ferromagnetic nanometre-scale islands. It was introduced to investigate many-body phenomena related to frustration and disorder in a material that could be tailored to precise specifications and imaged directly. Because of the large magnetic energy scales of these nanoscale islands, it has so far been impossible to thermally anneal artificial spin ice into desired thermodynamic ensembles; nearly all studies of artificial spin ice have either treated it as a granular material activated by alternating fields or focused on the as-grown state of the arrays. This limitation has prevented experimental investigation of novel phases that can emerge from the nominal ground states of frustrated lattices. For example, artificial kagome spin ice, in which the islands are arranged on the edges of a hexagonal net, is predicted to support states with monopolar charge order at entropies below that of the previously observed pseudo-ice manifold. Here we demonstrate a method for thermalizing artificial spin ices with square and kagome lattices by heating above the Curie temperature of the constituent material. In this manner, artificial square spin ice achieves unprecedented thermal ordering of the moments. In artificial kagome spin ice, we observe incipient crystallization of the magnetic charges embedded in pseudo-ice, with crystallites of magnetic charges whose size can be controlled by tuning the lattice constant. We find excellent agreement between experimental data and Monte Carlo simulations of emergent charge-charge interactions.

Constraining Carbon Nanothread Structures by Experimental and Calculated Nuclear Magnetic Resonance Spectra.

A one-dimensional (1D) sp3 carbon nanomaterial with high lateral packing order, known as carbon nanothreads, has recently been synthesized by slowly compressing and decompressing crystalline solid benzene at high pressure. The atomic structure of an individual nanothread has not yet been determined experimentally. We have calculated the 13C nuclear magnetic resonance (NMR) chemical shifts, chemical shielding tensors, and anisotropies of several axially ordered and disordered partially saturated and fully saturated nanothreads within density functional theory and systematically compared the results with experimental solid-state NMR data to assist in identifying the structures of the synthesized nanothreads. In the fully saturated threads, every carbon atom in each progenitor benzene molecule has bonded to a neighboring molecule (i.e., 6 bonds per molecule, a so-called "degree-6" nanothread), while the partially saturated threads examined retain a single double bond per benzene ring ("degree-4"). The most-parsimonious theoretical fit to the experimental 1D solid-state NMR spectrum, constrained by the measured chemical shift anisotropies and key features of two-dimensional NMR spectra, suggests a certain combination of degree-4 and degree-6 nanothreads as plausible components of this 1D sp3 carbon nanomaterial, with intriguing hints of a [4 + 2] cycloaddition pathway toward nanothread formation from benzene columns in the progenitor molecular crystal, based on the presence of nanothreads IV-7, IV-8, and square polymer in the minimal fit.

The Chemical Structure of Carbon Nanothreads Analyzed by Advanced Solid-State NMR.

Carbon nanothreads are a new type of one-dimensional sp3-carbon nanomaterial formed by slow compression and decompression of benzene. We report characterization of the chemical structure of 13C-enriched nanothreads by advanced quantitative, selective, and two-dimensional solid-state nuclear magnetic resonance (NMR) experiments complemented by infrared (IR) spectroscopy. The width of the NMR spectral peaks suggests that the nanothread reaction products are much more organized than amorphous carbon. In addition, there is no evidence from NMR of a second phase such as amorphous mixed sp2/sp3-carbon. Spectral editing reveals that almost all carbon atoms are bonded to one hydrogen atom, unlike in amorphous carbon but as is expected for enumerated nanothread structures. Characterization of the local bonding structure confirms the presence of pure fully saturated "degree-6" carbon nanothreads previously deduced on the basis of crystal packing considerations from diffraction and transmission electron microscopy. These fully saturated threads comprise between 20% and 45% of the sample. Furthermore, 13C-13C spin exchange experiments indicate that the length of the fully saturated regions of the threads exceeds 2.5 nm. Two-dimensional 13C-13C NMR spectra showing bonding between chemically nonequivalent sites rule out enumerated single-site thread structures such as polytwistane or tube (3,0) but are consistent with multisite degree-6 nanothreads. Approximately a third of the carbon is in "degree-4" nanothreads with isolated double bonds. The presence of doubly unsaturated degree-2 benzene polymers can be ruled out on the basis of 13C-13C NMR with spin exchange rate constants tuned by rotational resonance and 1H decoupling. A small fraction of the sample consists of aromatic rings within the threads that link sections with mostly saturated bonding. NMR provides the detailed bonding information necessary to refine solid-state organic synthesis techniques to produce pure degree-6 or degree-4 carbon nanothreads.

Carbon Nitride Nanothread Crystals Derived from Pyridine.

Carbon nanothreads are a new one-dimensional sp3 carbon nanomaterial. They assemble into hexagonal crystals in a room temperature, nontopochemical solid-state reaction induced by slow compression of benzene to 23 GPa. Here we show that pyridine also reacts under compression to form a well-ordered sp3 product: C5NH5 carbon nitride nanothreads. Solid pyridine has a different crystal structure from solid benzene, so the nontopochemical formation of low-dimensional crystalline solids by slow compression of small aromatics may be a general phenomenon that enables chemical design of properties. The nitrogen in the carbon nitride nanothreads may improve processability, alters photoluminescence, and is predicted to reduce the bandgap.

Dual-Sided Adsorption: Devil's Staircase of Coverage Fractions.

By adsorbing the same species onto both sides of a suspended, atomically thin membrane, it is possible to couple two distinct surface adsorption systems. This new system, with reflection symmetry about the membrane, is described by a phase diagram with two axes, both representing the chemical potential of the same element, but in distinct half-spaces. For the case of potassium adsorption onto a graphene membrane, the result is a devil's staircase of fractions for the proportion of adsorbates adhered to one side. Fractions with simpler denominators are favored across wider regions of chemical potential, a pattern reminiscent of other fractional systems across a wide range of physics. Since the system can support multiple devil's staircases each at a distinct overall adsorbate areal density, points along the boundary between adjacent staircases can come arbitrarily close to violating the Gibbs phase rule. This dual-sided adsorbate geometry provides a means to explore surface science for pairs of weakly coupled surfaces.