Graphene via Microwave Expansion of Graphite Followed by Cryo-Quenching and its Application in Electrostatic Droplet Switching.

Monoelemental atomic sheets (Xenes) and other 2D materials offer record electronic mobility, high thermal conductivity, excellent Young's moduli, optical transparency, and flexural capability, revolutionizing ultrasensitive devices and enhancing performance. The ideal synthesis of these quantum materials should be facile, fast, scalable, reproducible, and green. Microwave expansion followed by cryoquenching (MECQ) leverages thermal stress in graphite to produce high-purity graphene within minutes. MECQ synthesis of graphene is reported at 640 and 800 W for 10 min, followed by liquid nitrogen quenching for 5 and 90 min of sonication. Microscopic and spectroscopic analyses confirmed the chemical identity and phase purity of monolayers and few-layered graphene sheets (200-12 µm). Higher microwave power yields thinner layers with enhanced purity. Molecular dynamics simulations and DFT calculations support the exfoliation under these conditions. Electrostatic droplet switching is demonstrated using MECQ-synthesized graphene, observing electrorolling of a mercury droplet on a BN/graphene interface at voltages above 20 V. This technique can inspire the synthesis of other 2D materials with high purity and enable new applications.

Microwave Doping of Sulfur and Iron in ß12 Borophene.

Borophene, a 2D material exhibiting unique crystallographic phases like the anisotropic atomic lattices of ß12 and X3 phases, has attracted considerable attention due to its intriguing Dirac nature and metallic attributes. Despite surpassing graphene in electronic mobility, borophene's potential in energy storage and catalysis remains untapped due to its inherent electrochemical and catalytic limitations. Elemental doping emerges as a promising strategy to introduce charge carriers, enabling localized electrochemical and catalytic functionalities. However, effective doping of borophene has been a complex and underexplored challenge. Here, an innovative, one-pot microwave-assisted doping method, tailored for the ß12 phase of borophene is introduced. By subjecting dispersed ß12 borophene in dimethylformamide to controlled microwave exposure with sulfur powder and FeCl3 as doping precursors, S- and Fe doping in borophene can be controlled. Employing advanced techniques including high-resolution transmission electron microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy, confirm successful sulfur and iron dopant incorporation onto ß12 borophene is confirmed, achieving doping levels of up to 11 % and 13 %, respectively. Remarkably, S- and Fe-doped borophene exhibit exceptional supercapacitive behavior, with specific capacitances of 202 and 120 F g-1 , respectively, at a moderate current density of 0.25 A g-1 .

Ag-Doped Free-Standing 2D TiO2 Sheets: Electronic, Optical, Magnetic, and Self-Healing Behaviour.

Beyond a critical doping level, Ag-2D TiO2 sheets (ATO) are deemed to be a flexible transparent conductor, useful for visible-range functional photonic/optoelectronic devices/sensors, sunlight-sensitive catalysis, and light-activated resistive switching. Due to the lack of control of surface energy which often leads to the formation of structural defects and even dimensionality crossover (2D to 0D) of materials during doping reaction, it is challenging to obtain ATO with a controlled doping level. Gauging the urgency, therefore we report the surface energy-controlled synthesis of ATO employing liquid phase exfoliation of TiO2 and subsequent hydrothermal Ag-doping in the presence of Hexamethylenetetramine (HMTA). Electron microscopy and atomic force microscopy reveal ATO sheets with large lateral dimensions. 6-fold, 4-fold, and strain-mediated crystallographic phases of 2D ATO have been revealed by high-resolution electron imaging. Successful tuning of the band gap down to ~2 eV with Ag doping up to ~10 % is obtained. Synthesized 2D ATO have been investigated for their electrical, optical, optoelectronic, photoluminescence, and ferromagnetic behaviour. Visible light-sensitive thermally/structurally robust semiconductor/conductor via tuneable doping will pave the way for their flexible as well as wearable device applications. Self-healing effect of AFM tip-generated mechanical stress has also been demonstrated.

2+δ-Dimensional Materials via Atomistic Z-Welding.

Pivotal to functional van der Waals stacked flexible electronic/excitonic/spintronic/thermoelectric chips is the synergy amongst constituent layers. However; the current techniques viz. sequential chemical vapor deposition, micromechanical/wet-chemical transfer are mostly limited due to diffused interfaces, and metallic remnants/bubbles at the interface. Inter-layer-coupled 2+δ-dimensional materials, as a new class of materials can be significantly suitable for out-of-plane carrier transport and hence prompt response in prospective devices. Here, the discovery of the use of exotic electric field ≈106  V cm- 1 (at microwave hot-spot) and 2 thermomechanical conditions i.e. pressure ≈1 MPa, T ≈ 200 °C (during solvothermal reaction) to realize 2+δ-dimensional materials is reported. It is found that Pz Pz chemical bonds form between the component layers, e.g., CB and CN in G-BN, MoN and MoB in MoS2 -BN hybrid systems as revealed by X-ray photoelectron spectroscopy. New vibrational peaks in Raman spectra (BC ≈1320 cm-1 for the G-BN system and MoB ≈365 cm-1 for the MoS2 -BN system) are recorded. Tunable mid-gap formation, along with diodic behavior (knee voltage ≈0.7 V, breakdown voltage ≈1.8 V) in the reduced graphene oxide-reduced BN oxide (RGO-RBNO) hybrid system is also observed. Band-gap tuning in MoS2 -BN system is observed. Simulations reveal stacking-dependent interfacial charge/potential drops, hinting at the feasibility of next-generation functional devices/sensors.

Role of External Stimuli in Engineering Magnetic Phases and Real-Time Spin Dynamics of Co/Mn Oxides.

Magnetism in atomically thin two-dimensional (2D) materials can be easily manipulated by alloying, functionalization, external ultrafast laser pulse, strain, electric field, etc. In this work, we have performed a series of spin-resolved density functional theory calculations on 2D magnetic hexagonal transition-metal oxide alloys, CoMnO4. We have explored different alloy patterns and found the most stable magnetic phases in each pattern, resulting in a stable ferromagnetic (FM) ground state depending upon the pattern. We have used Janus functionalization in these materials to tune the magnetic nature of the system from FM to antiferromagnetic (AFM) states. To further control the spin dynamics, we have applied an ultrafast laser pulse to the Janus systems to explore an AFM-to-FM transition process. Finally, applying strain and electric field to the Janus alloys allows us to tune the structure-property relationship in the 2D layers to obtain desirable spin arrangements.

Microwave Synthesized 2D Gold and Its 2D-2D Hybrids.

Xenes, i.e., monoelemental two-dimensional atomic sheets, are promising for sensitive and ultrafast sensor applications owing to exceptional carrier mobility; however, most of them oxidize below 500 °C and therefore cannot be employed for high-temperature applications. 2D gold, an oxidation-resistant plasmonic Xene, is extremely promising. 2D gold was experimentally realized by both atomic layer deposition and chemical synthesis using sodium citrate. However, it is imperative to develop a new facile single-step method to synthesize 2D gold. Here, liquid-phase synthesis of 2D gold is demonstrated by microwave exposure to auric chloride dispersed in dimethylformamide. Microscopies (AFM and high-resolution TEM), spectroscopies (Raman, UV-vis, and X-ray photoelectron), and X-ray diffraction establish the formation of a hexagonal crystallographic phase for 2D gold. 2D-2D hybrids of 2D gold have also been synthesized and investigated for electronic/optoelectronic behaviors and SERS-based molecular sensing. DFT band structure calculation for 2D gold and its hybrids corroborates the experimental findings.

Tuning Magnetic Anisotropy in Two-Dimensional Metal-Semiconductor Janus van der Waals Heterostructures.

In the family of 2D materials, atomically thin magnetic systems are relatively new and highly exploitable. Understanding the spin symmetry in such materials has opened a new path toward controlling the magnetic texture. In this study, we have shown that the plethora of different interface formations in the Janus or pure metal-semiconductor-based van der Waals heterostructures 1T-VXY (X, Y = S, Se, Te)-Cr2A3B3 (A, B = I, Cl, Br) allows us to explore and modify the spin-orbit and ligand-metal interactions to fine-tune magnetic anisotropy and different spin symmetries in these systems. We have utilized the interlayer interactions to modulate spin-orbit coupling (SOC) in heterolayers to regulate the magnetic anisotropy in such systems. We have compared systems with the same compositions and different interfaces, for example, Janus VSTe-Janus Cr2I3Br3 and Janus VTeS-Janus Cr2I3Br3, to show that the first one is an Ising ferromagnet, whereas the second one is an XY ferromagnet because of the SOC effect of the heavy ligand atoms.

Unravelling Photoinduced Interlayer Spin Transfer Dynamics in Two-Dimensional Nonmagnetic-Ferromagnetic van der Waals Heterostructures.

Although light is the fastest means to manipulate the interfacial spin injection and magnetic proximity related quantum properties of two-dimensional (2D) magnetic van der Waals (vdW) heterostructures, its potential remains mostly untapped. Here, inspired by the recent discovery of 2D ferromagnets Fe3GeTe2 (FGT), we applied the real-time density functional theory (rt-TDDFT) to study photoinduced interlayer spin transfer dynamics in 2D nonmagnetic-ferromagnetic (NM-FM) vdW heterostructures, including graphene-FGT, silicene-FGT, germanene-FGT, antimonene-FGT and h-BN-FGT interfaces. We observed that laser pulses induce significant large spin injection from FGT to nonmagnetic (NM) layers within a few femtoseconds. In addition, we identified an interfacial atom-mediated spin transfer pathway in heterostructures in which the photoexcited spin of Fe first transfers to intralayered Te atoms and then hops to interlayered NM layers. Interlayer hopping is approximately two times slower than intralayer spin transfer. Our results provide the microscopic understanding for optically control interlayer spin dynamics in 2D magnetic heterostructures.

Direct Optoelectronic Imaging of 2D Semiconductor-3D Metal Buried Interfaces.

The semiconductor-metal junction is one of the most critical factors for high-performance electronic devices. In two-dimensional (2D) semiconductor devices, minimizing the voltage drop at this junction is particularly challenging and important. Despite numerous studies concerning contact resistance in 2D semiconductors, the exact nature of the buried interface under a three-dimensional (3D) metal remains unclear. Herein, we report the direct measurement of electrical and optical responses of 2D semiconductor-metal buried interfaces using a recently developed metal-assisted transfer technique to expose the buried interface, which is then directly investigated using scanning probe techniques. We characterize the spatially varying electronic and optical properties of this buried interface with <20 nm resolution. To be specific, potential, conductance, and photoluminescence at the buried metal/MoS2 interface are correlated as a function of a variety of metal deposition conditions as well as the type of metal contacts. We observe that direct evaporation of Au on MoS2 induces a large strain of ∼5% in the MoS2 which, coupled with charge transfer, leads to degenerate doping of the MoS2 underneath the contact. These factors lead to improvement of contact resistance to record values of 138 kΩ µm, as measured using local conductance probes. This approach was adopted to characterize MoS2-In/Au alloy interfaces, demonstrating contact resistance as low as 63 kΩ µm. Our results highlight that the MoS2/metal interface is sensitive to device fabrication methods and provide a universal strategy to characterize buried contact interfaces involving 2D semiconductors.

Biomolecular sensing by surface-enhanced Raman scattering of monolayer Janus transition metal dichalcogenide.

In this work, we demonstrate that monolayer Janus MoSSe is an effective and universal platform for enhancing Raman signal and detecting biomolecules for the first time. The out-of-plane dipoles in monolayer Janus MoSSe redistribute charges of adsorbed biomolecules, polarize biomolecules and enhance their Raman vibrational intensity. The estimated Raman enhancement factor is higher than 105, which is comparable with the highest reported enhancement factor for 2D substrates. The C-C stretching Raman peak around 1360 cm-1 is used to indicate the glucose concentration, and its peak-integrated intensity increases linearly with the glucose concentration in the range of 1-10 mM. DFT calculations also confirm that charge redistribution in glucose induced by dipole interactions can enhance Raman intensity significantly when glucose molecules are adsorbed onto monolayer Janus MoSSe.

Engineering Magnetic Phases in Two-Dimensional Non-van der Waals Transition-Metal Oxides.

The family of 2D magnetic materials is continuously expanding because of the rapid discovery of exfoliable van der Waals magnetic systems. Recently, the synthesis of non-van der Waals magnetic "hematene" from common iron ore has opened an unconventional route to 2D material discovery. These non-van der Waals 2D systems are chemically stable and easily available and may have different or enhanced properties compared to their van der Waals counterparts. In this work, we have investigated and explained the nature of magnetic ordering in non-van der Waals 2D metal oxides. Two-dimensional hematene is found to be fully oxygen-passivated and stable under ambient conditions. It exhibits a striped ferrimagnetic ground state with a small net magnetic moment. Superexchange interactions are predicted to control the magnetic ground state of hematene, where pressure-induced spin crossover results in an observable net magnetic moment. Modulating the superexchange by alloying hematenes alters the magnetic ordering, tuning the system to a ferromagnetic ground state. Extending this strategy to the design of a new 2D material, we propose 2D chromia (α-Cr2O3) or "chromene", which, because of larger inter-transition metal distances and suppressed AFM superexchange, has a ferromagnetic ground state. We also show that tuning the magnetic ordering in these materials controls the transport properties by modulating the band gap, which may be of use in spintronic or catalytic applications.

Long-range ferromagnetism in nickel-based hybrid structure with semiconductor behavior.

Here we report a new three-dimensional nickel-based hybrid structure [Ni3(BTB)2(BPE)4(H2O)2]·2DMF·2H2O, 1 [where BTB = 1,3,5-tris(4-carboxyphenyl)benzene and BPE = 1,2-bis((4-pyridyl)ethane)], which exhibits long-range ferromagnetism and semiconductor behavior. The dipolar interaction between the magnetic spins is suggested to explain the development of long-range ferromagnetic ordering, where the superexchange interaction can be unwanted due to the large distance between the magnetic spins. Optical band gap and resistance vs. temperature measurements reveal the semiconductor nature of this compound. The density of states calculations shed light towards the origin of the low band gap value.

Surface-Engineered MXenes: Electric Field Control of Magnetism and Enhanced Magnetic Anisotropy.

Controlling magnetism in two-dimensional (2D) materials via electric fields and doping enables robust long-range order by providing an external mechanism to modulate magnetic exchange interactions and anisotropy. In this report, we predict that transition metal carbide and nitride MXenes are promising candidates for controllable magnetic 2D materials. The surface terminations introduced during synthesis act as chemical dopants that influence the electronic structure, enabling controllable magnetic order. We show ground-state magnetic ordering in Janus M2XO xF2- x (M is an early transition metal, X is carbon or nitrogen, and x = 0.5, 1, or 1.5) with asymmetric surface functionalization, where local structural and chemical disorder induces magnetic ordering in some systems that are nonmagnetic or weakly magnetic in their pristine form. The resulting magnetic states of these noncentrosymmetric structures can be robustly switched and stabilized by tuning the interlayer exchange couplings with small applied electric fields. Furthermore, bond directionality is enhanced by Janus functionalization, resulting in improved magnetic anisotropy, which is essential to stable 2D magnetic ordering. The mixed termination-induced anisotropy leads to robust Ising ferromagnetism with an out-of-plane easy axis over the full range of relevant termination compositions for Janus Mn2N. Janus Cr2C, V2C, and Ti2C were found to be robustly antiferromagnetic. Our results provide a strategy for exploiting asymmetric surface functionalization to achieve room-temperature nanoscale magnetism under ambient conditions in MXenes with currently available synthesis techniques.

Solvent-Modulated Emission Properties in a Superhydrophobic Oligo( p-phenyleneethynylene)-Based 3D Porous Supramolecular Framework.

A chromophoric oligo( p-phenyleneethynylene) (OPE) bola-amphiphile with dioxyoctyl side chains (H2OPE-C8) has been self-assembled with CdII to form a 1D coordination polymer, {Cd(OPE-C8)(DMF)2(H2O)} (1), which is further interdigitated to form a 2D network. Such 2D networks are further interwoven to form a 3D supramolecular framework with surface-projected alkyl chains. The desolvated framework showed permanent porosity, as realized from the CO2 adsorption profile. 1 showed high water contact angles, portraying its superhydrophobic nature. 1 also showed a linker-based cyan luminescence. Solvent removal led to a bathochromic shift in emission into the green region. Resolvation with N, N-dimethylformamide brought back the original cyan emission, whereas for tetrahydrofuran, ethanol, and methanol, it persisted at an intermediate state. Density functional theory calculations unraveled that, twisting of the OPE phenyl rings generated the red shift in emission.

Shining Light on New-Generation Two-Dimensional Materials from a Computational Viewpoint.

Energy- and sensing-related applications using two-dimensional (2D) materials with tunable optoelectronic properties have been a hot topic of research. The genres of 2D materials grow every day, leading to new possibilities in optoelectronic devices. In this Perspective, we have discussed in a nutshell several impacts of light-matter interactions in new-generation 2D materials. Using reliable computational approaches, in-depth understanding about the fundamental optical absorption and emission character as well as further prediction of the potential applications for these materials in the field of photovoltaics and sensing have been explored. Various modifications of the parent 2D materials by computational designing with enhanced performance have been investigated to guide the experimental efforts. The major computational challenges and their probable solutions for 2D-material-based optoelectronic research have also been briefly outlined.

Effects of point defects on the magnetoelectronic structures of MXenes from first principles.

"MXene", a new class of two dimensional materials, has attracted considerable research interest due to its unusual chemical bonding pattern as well as promising technological applications. Like other 2D materials, very recently, these classes of materials were also found to be prone to structural defects, thus altering the electronic and transport properties of the host. Using extensive first-principles based simulations, we investigated the structural and magnetoelectronic (i.e., magnetic and electronic) behaviour of the most probable point defects in these MXene systems, such as single vacancies and Schottky type double vacancies. Defect formation energies appeared to be strongly dependent upon local chemical bonding and the nature of reconstruction. Moreover, this layered material exhibited prominent metal to semiconductor or semiconductor to metal transition depending upon the type of the system or the defect. Moreover, a few of the defective MXenes become magnetic in nature due to the presence of unpaired electrons in the spin split d-orbitals. Thus, it is evident that intrinsic point defects in MXene can emerge as a potential tool to modulate the properties of 2D layered MXenes towards promising device applications.

Doping Phosphorene with Holes and Electrons through Molecular Charge Transfer.

An important aspect of phosphorene, the novel two-dimensional semiconductor, is whether holes and electrons can both be doped in this material. Some reports found that only electrons can be preferentially doped into phosphorene. There are some theoretical calculations showing charge-transfer interaction with both tetrathiafulvalene (TTF) and tetracyanoethylene (TCNE). We have carried out an investigation of chemical doping of phosphorene by a variety of electron donor and acceptor molecules, employing both experiment and theory, Raman scattering being a crucial aspect of the study. We find that both electron acceptors and donors interact with phosphorene by charge-transfer, with the acceptors having more marked effects. All the three Raman bands of phosphorene soften and exhibit band broadening on interaction with both donor and acceptor molecules. First-principles calculations establish the occurrence of charge-transfer between phosphorene with donors as well as acceptors. The absence of electron-hole asymmetry is noteworthy.

Trapping and sensing of hazardous insecticides by chemically modified single walled carbon nanotubes.

The use of insecticides in agriculture is a common practice all over the world, but they are often known to be harmful towards the human body. This requires attention by experimentalists and theorists alike. In this work, using Born-Oppenheimer molecular dynamics (BOMD) and density functional theory (DFT) calculations, we have demonstrated the efficient trapping of several hazardous insecticide molecules on a carbon nanotube (CNT) surface. Our BOMD simulations suggest that under ambient conditions, though pristine CNTs are quite inefficient, transition metal atom (TM) incorporated nitrogen doped CNTs can trap the hazardous molecules at room temperature efficiently. Thorough investigations exhibit the presence of strong η6 bonding between the aromatic group of the pesticide and the TM adatom of the defective CNT, leading to the trapping of the molecules on the CNT surface. These CNTs are efficient trapping agents even in the presence of water and quite robust for any pesticides with aromatic group(s) in them. Furthermore, interestingly, the charge transfer interactions between the molecules and the defective CNTs lead to molecule specific optical absorption spectra of the composites, effectively developing defective CNTs as a detective optical sensor for pesticide molecules.

Reversible Polymorphism, Liquid Crystallinity, and Stimuli-Responsive Luminescence in a Bola-amphiphilic π-System: Structure-Property Correlations Through Nanoindentation and DFT Calculations.

We report the design, synthesis, detailed characterization, and analysis of a new multifunctional π-conjugated bola-amphiphilic chromophore: oligo-(p-phenyleneethynylene)dicarboxylic acid with dialkoxyoctadecyl side chains (OPE-C18-1). OPE-C18-1 shows two polymorphs at 123 K (OPE-C18-1') and 373 K (OPE-C18-1″), whose crystal structures were characterized via single crystal X-ray diffraction. OPE-C18-1 also exhibits thermotropic liquid crystalline property revealing a columnar phase. The inherent π-conjugation of OPE-C18-1 imparts luminescence to the system. Photoluminescence measurements on the mesophase also reveal similar luminescence as in the crystalline state. Additionally, OPE-C18-1 shows mechano-hypsochromic luminescence behavior. Density functional theory (DFT)-based calculations unravel the origins behind the simultaneous existence of all these properties. Nanoindentation experiments on the single crystal reveal its mechanical strength and accurately correlate the molecular arrangement with the liquid crystalline and mechanochromic luminescence behavior.

Role of donor-acceptor macrocycles in sequence specific peptide recognition and their optoelectronic properties: a detailed computational insight.

In this study, we have considered an experimentally synthesized organic donor-acceptor (D-A) macrocycle (CPP-TCAQ) and have modified it by incorporating different acceptor groups. We have performed density functional theory and classical molecular dynamics studies on these D-A macrocycles. We have clearly shown that cyclo[10]paraphenylene-2,6-tetracyanoanthraquinodimethanylene (CPP-TCAQ) isomers interact specifically with one particular peptide sequence tyr-leu-ala, over its structural isomer, tyr-ala-leu. However, other functionalized macrocycles bind to the tyr-ala-leu peptide sequence over tyr-leu-ala. Our calculations show that the presence of hydrogen bonds as well as π-π interactions responsible for this specific selection. Interestingly, it is the additional charge transfer induced dipolar interactions that favour binding of the tripeptide with the bulky C-terminal leucine amino acid, tyr-ala-leu. We confirmed that these host-guest complexes are stable in water medium as well as at room temperature. Thus, these hosts can bind effectively to any protein fragment bearing a particular tripeptide. Interestingly, the macrocycle, which recognizes the peptide sequence with a bulky C-terminal amino acid, also shows photophysical properties. The reasons for this happen to be the same (dipolar interactions introduce dipole allowed states for optical absorption as well as attracting the oppositely oriented dipolar groups). Recognition of the peptide sequence with a bulky C-terminal group is carried out for the first time with this functionalised macrocycle, which in addition shows photophysical properties.