Elucidating the Mechanism of Large Phosphate Molecule Intercalation Through Graphene-Substrate Heterointerfaces.

Intercalation is the process of inserting chemical species into the heterointerfaces of two-dimensional (2D) layered materials. While much research has focused on the intercalation of metals and small gas molecules into graphene, the intercalation of larger molecules through the basal plane of graphene remains challenging. In this work, we present a new mechanism for intercalating large molecules through monolayer graphene to form confined oxide materials at the graphene-substrate heterointerface. We investigate the intercalation of phosphorus pentoxide (P2O5) molecules directly from the vapor phase and confirm the formation of confined P2O5 at the graphene-substrate heterointerface using various techniques. Density functional theory (DFT) corroborates the experimental results and reveals the intercalation mechanism, whereby P2O5 dissociates into small fragments catalyzed by defects in the graphene that then permeates through lattice defects and reacts at the heterointerface to form P2O5. This process can also be used to form new confined metal phosphates (e.g., 2D InPO4). While the focus of this study is on P2O5 intercalation, the possibility of intercalation from predissociated molecules catalyzed by defects in graphene may exist for other types of molecules as well. This in-depth study advances our understanding of intercalation routes of large molecules via the basal plane of graphene as well as heterointerface chemical reactions leading to the formation of distinctive confined complex oxide compounds.

Recent Advances in 2D Material Theory, Synthesis, Properties, and Applications.

Two-dimensional (2D) material research is rapidly evolving to broaden the spectrum of emergent 2D systems. Here, we review recent advances in the theory, synthesis, characterization, device, and quantum physics of 2D materials and their heterostructures. First, we shed insight into modeling of defects and intercalants, focusing on their formation pathways and strategic functionalities. We also review machine learning for synthesis and sensing applications of 2D materials. In addition, we highlight important development in the synthesis, processing, and characterization of various 2D materials (e.g., MXnenes, magnetic compounds, epitaxial layers, low-symmetry crystals, etc.) and discuss oxidation and strain gradient engineering in 2D materials. Next, we discuss the optical and phonon properties of 2D materials controlled by material inhomogeneity and give examples of multidimensional imaging and biosensing equipped with machine learning analysis based on 2D platforms. We then provide updates on mix-dimensional heterostructures using 2D building blocks for next-generation logic/memory devices and the quantum anomalous Hall devices of high-quality magnetic topological insulators, followed by advances in small twist-angle homojunctions and their exciting quantum transport. Finally, we provide the perspectives and future work on several topics mentioned in this review.

Cost-effective carbon fiber precursor selections of polyacrylonitrile-derived blend polymers: carbonization chemistry and structural characterizations.

Blending polyacrylonitrile (PAN) with plastic wastes and bio-based polymers provides a convenient and inexpensive method to realize cost-effective carbon fiber (CF) precursors. In this work, PAN-based blend precursors are investigated using ReaxFF reactive molecular dynamics simulations with respect to the formation of all-carbon rings, the evolutions of oxygen-containing and nitrogen-containing species, and the migration of carbon atoms to form turbostratic graphene. From these simulations, we identify that PAN/cellulose (CL) blend manifests the highest carbon yield and the most substantial all-carbon ring formation. This ReaxFF-based finding is confirmed by Raman and TEM experiments indicating high crystallinity for PAN/CL-derived blend CFs. We trace the pathway of gasification and carbonization of PAN/CL to elaborate the mechanism of the formation of all-carbon ring networks. We discover that the acetals of CL can catalyze the cyclization of the blend precursor, allowing for the search for CL derivatives or the other kinds of bio-based polymers with similar functionalities as alternative blends. In addition, we examine the structural characteristics using the carbon-carbon (C-C) radial distribution functions, C-C bond length distributions, and sp2 C atom ratios for the four representative precursors, i.e., PAN, oxidized PAN, PAN/nylon 6,6, and PAN/CL. Our simulation results show the most extensive all-carbon ring cluster and graphitic structure growths for PAN/CL. Therefore, we propose PAN/CL as a cost-effective alternative CF precursor, since (a) CL is naturally abundant and eco-friendly for production, (b) the blend precursor PAN/CL does not require oxidation treatment, (c) PAN/CL has a high carbon yield with substantial all-carbon ring formation, and (d) PAN/CL based CFs potentially provide a mechanical property enhancement.

Scalable Characterization of 2D Gallium-Intercalated Epitaxial Graphene.

Scalable synthesis of two-dimensional gallium (2D-Ga) covered by graphene layers was recently realized through confinement heteroepitaxy using silicon carbide substrates. However, the thickness, uniformity, and area coverage of the 2D-Ga heterostructures have not previously been studied with high-spatial resolution techniques. In this work, we resolve and measure the 2D-Ga heterostructure thicknesses using scanning electron microscopy (SEM). Utilizing multiple correlative methods, we find that SEM image contrast is directly related to the presence of uniform bilayer Ga at the interface and a variation of the number of graphene layers. We also investigate the origin of SEM contrast using both experimental measurements and theoretical calculations of the surface potentials. We find that a carbon buffer layer is detached due to the gallium intercalation, which increases the surface potential as an indication of the 2D-Ga presence. We then scale up the heterostructure characterization over a few-square millimeter area by segmenting SEM images, each acquired with nanometer-scale in-plane resolution. This work leverages the spectroscopic imaging capabilities of SEM that allows high-spatial resolution imaging for tracking intercalants, identifying relative surface potentials, determining the number of 2D layers, and further characterizing scalability and uniformity of low-dimensional materials.

Atomic-Level Structure Determines Electron-Phonon Scattering Rates in 2-D Polar Metal Heterostructures.

The electron dynamics of atomically thin 2-D polar metal heterostructures, which consisted of a few crystalline metal atomic layers intercalated between hexagonal silicon carbide and graphene grown from the silicon carbide, were studied using nearly degenerate transient absorption spectroscopy. Optical pumping created charge carriers in both the 2-D metals and graphene components. Wavelength-dependent probing suggests that graphene-to-metal carrier transfer occurred on a sub-picosecond time scale. Following rapid (<300 fs) carrier-carrier scattering, charge carriers monitored through the metal interband transition relaxed through several consecutive cooling mechanisms that included sub-picosecond carrier-phonon scattering and dissipation to the silicon carbide substrate over tens of picoseconds. By studying 2-D In, 2-D Ga, and a Ga/In alloy, we resolved accelerated electron-phonon scattering rates upon alloy formation as well as structural influences on the excitation of in-plane phonon shear modes. More rapid cooling in alloys is attributed to increased lattice disorder, which was observed through correlative polarization-resolved second harmonic generation and electron microscopy. This connection between the electronic relaxation rates, far-field optical responses, and metal lattice disorder is made possible by the intimate relation between nonlinear optical properties and atomic-level structure in these materials. These studies provided insights into electronic carrier dynamics in 2-D crystalline elemental metals, including resolving contributions from specific components of a 2-D metal-containing heterojunction. The correlative ultrafast spectroscopy and nonlinear microscopy results suggest that the energy dissipation rates can be tuned through atomic-level structures.

Tunable 2D Group-III Metal Alloys.

Chemically stable quantum-confined 2D metals are of interest in next-generation nanoscale quantum devices. Bottom-up design and synthesis of such metals could enable the creation of materials with tailored, on-demand, electronic and optical properties for applications that utilize tunable plasmonic coupling, optical nonlinearity, epsilon-near-zero behavior, or wavelength-specific light trapping. In this work, it is demonstrated that the electronic, superconducting, and optical properties of air-stable 2D metals can be controllably tuned by the formation of alloys. Environmentally robust large-area 2D-Inx Ga1- x alloys are synthesized byConfinement Heteroepitaxy (CHet). Near-complete solid solubility is achieved with no evidence of phase segregation, and the composition is tunable over the full range of x by changing the relative elemental composition of the precursor. The optical and electronic properties directly correlate with alloy composition, wherein the dielectric function, band structure, superconductivity, and charge transfer from the metal to graphene are all controlled by the indium/gallium ratio in the 2D metal layer.

Graphene reinforced carbon fibers.

The superlative strength-to-weight ratio of carbon fibers (CFs) can substantially reduce vehicle weight and improve energy efficiency. However, most CFs are derived from costly polyacrylonitrile (PAN), which limits their widespread adoption in the automotive industry. Extensive efforts to produce CFs from low cost, alternative precursor materials have failed to yield a commercially viable product. Here, we revisit PAN to study its conversion chemistry and microstructure evolution, which might provide clues for the design of low-cost CFs. We demonstrate that a small amount of graphene can minimize porosity/defects and reinforce PAN-based CFs. Our experimental results show that 0.075 weight % graphene-reinforced PAN/graphene composite CFs exhibits 225% increase in strength and 184% enhancement in Young's modulus compared to PAN CFs. Atomistic ReaxFF and large-scale molecular dynamics simulations jointly elucidate the ability of graphene to modify the microstructure by promoting favorable edge chemistry and polymer chain alignment.

Atomistic Scale Analysis of the Carbonization Process for C/H/O/N-Based Polymers with the ReaxFF Reactive Force Field.

During the carbonization process of raw polymer precursors, graphitic structures can evolve. The presence of these graphitic structures affects mechanical properties of the carbonized carbon fibers. To gain a better understanding of the chemistry behind the evolution of these structures, we performed atomistic-scale simulations using the ReaxFF reactive force field. Three different polymers were considered as a precursor: idealized ladder PAN (polyacrylonitrile), a proposed oxidized PAN, and poly( p-phenylene-2,6-benzobisoxazole). We determined the underlying molecular details of polymer conversion into a carbon fiber structure. Because these are C/H/O/N-based polymers, we first developed an improved force field for C/H/O/N chemistry based on the density functional theory data with a particular focus on N2 formation kinetics and its interactions with polymer-associated radicals formed during the carbonization process. Then, using this improved force field, we performed atomistic-scale simulations of the initial stage of the carbonization process for the considered polymers. On the basis of our simulation data, the molecular pathways for the formation of low-molecular-weight gas species and all-carbon ring formation were determined. We also examined the possible alignment of the developed all-carbon 6-membered ring clusters, which is crucial for the further graphitic structure evolution.