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The Boltzmann Tyranny, set by thermionic statistics, dictates the lower limit of switching slope (SS) of a MOSFET to be 60 mV/dec, the fundamental barrier for low-dissipative electronics. The large SS leads to nonscalable voltage, significant leakage, and power consumption, particularly at short channels, making transistor scaling an intimidating challenge. In recent decades, an array of steep-slope transistors has been proposed; none is close to an ideal switch with ultimately abrupt switching (SS ∼ 0 mV/dec) between the binary logic states. We demonstrated an all-2D-materials van-der-Waals-heterostructure (vdW)-based FET that exhibits ultrasteep switching (0.33 mV/dec), a large on/off current ratio (∼10 7 ), and an ultralow off current (∼0.1 pA). The "Subthreshold-Free" operation achieved by the collective behavior of functional materials enables FET switching directly from the OFF-state to the ON-state with entirely eliminated subthreshold region, behaving as the ideal logic switch. Two-inch wafer-scale device fabrication is demonstrated. Boosted by device innovation and emerging materials, the research presents an advancement in achieving the "beyond-Boltzmann" transistors, overcoming one of the CMOS electronics' most infamous technology barriers that have plagued the research community for decades.

van der Waals ferroic materials exhibit rich potential for implementing future generation functional devices. Among these, layered β'-In 2 Se 3 has fascinated researchers with its complex superlattice and domain structures. As opposed to ferroelectric α-In 2 Se 3 , the understanding of β'-In 2 Se 3 ferroic properties remains unclear because ferroelectric, antiferroelectric, and ferroelastic characteristics have been separately reported in this material. To develop useful applications, it is necessary to understand the microscopic structural properties and their correlation with macroscopic device characteristics. Herein, using scanning transmission electron microscopy (STEM), we observed that the arrangement of dipoles deviates from the ideal double antiparallel antiferroelectric character due to competition between antiferroelectric and ferroelectric structural ordering. By virtue of second-harmonic generation, four-dimensional STEM, and in-plane piezoresponse force microscopy, the long-range inversion-breaking symmetry, uncompensated local polarization, and net polarization domains are unambiguously verified, revealing β'-In 2 Se 3 as an in-plane ferrielectric layered material. Additionally, our device study reveals analogous resistive switching behaviors of different types owing to polarization switching, defect migration, and defect-induced charge trapping/detrapping processes.

2D materials with ferroelectric and piezoelectric properties are of interest for energy harvesting, memory storage and electromechanical systems. Here, we present a systematic study of the ferroelectric properties in NbOX 2 (X = Cl, I) across different spatial scales. The in-plane ferroelectricity in NbOX 2 was investigated using transport and piezoresponse force microscopy (PFM) measurements, where it was observed that NbOCl 2 has a stronger ferroelectric order than NbOI 2 . A high local field, exerted by both PFM and scanning tunneling microscopy (STM) tips, was found to induce 1D collinear ferroelectric strips in NbOCl 2 . STM imaging reveals the unreconstructed atomic structures of NbOX 2 surfaces, and scanning tunneling spectroscopy was used to probe the electronic states induced at defect (vacancy) sites.

To realize the practical application of lithium-sulfur (Li-S) batteries, there is a need to inhibit uncontrolled Li deposition by facilitating Li-ion migration, and suppress the irreversible consumption of cathodes by preventing polysulfide shuttling. However, a permselective artifical membrane or interlayer which features fast ion transport but low polysulfide crossover is elusive. Here, we report the design and synthesis of a fluorinated covalent organic framework (4F-COF)-based membrane with a high permselectivity and increased battery lifespan. Combining density functional theory calculation, molecular dynamic simulation, and in situ Raman analysis, we demonstrate that fluorinated COF eliminates polysulfides shutting and dendritic lithium formation. Consequently, Li symmetrical cells demonstrate Li plating/stripping behaviors for 2000 h under 1 mA cm -2 . More importantly, Li-S batteries based on the 4F-COF/PP separator achieve cycling retention of 82.3% over 1000 cycles at 2 C, rate performance of 568.0 mA h g -1 at 10 C, and an areal capacity of 7.60 mA h cm -2 with a high sulfur loading (∼9 mg cm -2 ). This work demonstrates that functionalizing nanochannels in COFs can impart permselectivity for energy storage applications.

The aqueous zinc (Zn) battery is a safe and eco-friendly energy-storage system. However, the use of Zn metal anodes is impeded by uncontrolled Zn deposition behavior. Herein, we regulate the Zn-ion deposition process for dendrite-free Zn metal anodes using an aminosilane molecular layer with high zincophilic sites and narrow molecule channels. The aminosilane molecular layer causes Zn ions to undergo consecutive processes including being captured by the amine functional groups of aminosilane and diffusing through narrow intermolecular channels before electroplating, which induces partial dehydration of hydrated Zn ions and uniform Zn ion flux, promoting reversible Zn stripping/plating. Through this molecule-induced capture-diffusion-deposition procedure of Zn ions, smooth and compact Zn electrodeposited layers are obtained. Hence, the aminosilane-modified Zn anode has high Coulombic efficiency (∼99.5%), long lifespan (∼3000 h), and high capacity retention in full cells (88.4% for 600 cycles). This strategy not only has great potential for achieving dendrite-free Zn anodes in practical Zn batteries but also suggests an interface-modification principle at the molecular level for other alternative metallic anodes.

Ferroelectric materials play an important role in a wide spectrum of semiconductor technologies and device applications. Two-dimensional (2D) van der Waals (vdW) ferroelectrics with surface-insensitive ferroelectricity that is significantly different from their traditional bulk counterparts have further inspired intensive interest. Integration of ferroelectrics into 2D-layered-material-based devices is expected to offer intriguing working principles and add desired functionalities for next-generation electronics. Herein, fundamental properties of ferroelectric materials that are compatible with 2D devices are introduced, followed by a critical review of recent advances on the integration of ferroelectrics into 2D devices. Representative device architectures and corresponding working mechanisms are discussed, such as ferroelectrics/2D semiconductor heterostructures, 2D ferroelectric tunnel junctions, and 2D ferroelectric diodes. By leveraging the favorable properties of ferroelectrics, a variety of functional 2D devices including ferroelectric-gated negative capacitance field-effect transistors, programmable devices, nonvolatile memories, and neuromorphic devices are highlighted, where the application of 2D vdW ferroelectrics is particularly emphasized. This review provides a comprehensive understanding of ferroelectrics-integrated 2D devices and discusses the challenges of applying them into commercial electronic circuits.

In artificial van der Waals (vdW) layered devices, twisting the stacking angle has emerged as an effective strategy to regulate the electronic phases and optical properties of these systems. Along with the twist registry, the lattice reconstruction arising from vdW interlayer interaction has also inspired significant research interests. The control of twist angles is significantly important because the moiré periodicity determines the electron propagation length on the lattice and the interlayer electron-electron interactions. However, the moiré periodicity is hard to be modified after the device has been fabricated. In this work, we have demonstrated that the moiré periodicity can be precisely modulated with a localized laser annealing technique. This is achieved with regulating the interlayer lattice mismatch by the mismatched lattice constant, which originates from the variable density of sulfur vacancy generated during laser modification. The existence of sulfur vacancy is further verified by excitonic emission energy and lifetime in photoluminescence measurements. Furthermore, we also discover that the mismatched lattice constant has the equivalent contribution as the twist angle for determining the lattice mismatch. Theoretical modeling elaborates the moiré-wavelength-dependent energy variations at the interface and mimics the evolution of moiré morphology.

Synthesizing urea from nitrate and carbon dioxide through an electrocatalysis approach under ambient conditions is extraordinarily sustainable. However, this approach still lacks electrocatalysts developed with high catalytic efficiencies, which is a key challenge. Here, we report the high-efficiency electrocatalytic synthesis of urea using indium oxyhydroxide with oxygen vacancy defects, which enables selective C-N coupling toward standout electrocatalytic urea synthesis activity. Analysis by operando synchrotron radiation-Fourier transform infrared spectroscopy showcases that *CO 2 NH 2 protonation is the potential-determining step for the overall urea formation process. As such, defect engineering is employed to lower the energy barrier for the protonation of the *CO 2 NH 2 intermediate to accelerate urea synthesis. Consequently, the defect-engineered catalyst delivers a high Faradaic efficiency of 51.0%. In conjunction with an in-depth study on the catalytic mechanism, this design strategy may facilitate the exploration of advanced catalysts for electrochemical urea synthesis and other sustainable applications.

Liquid-phase exfoliation can be developed for the large-scale production of two-dimensional materials for photonic applications. Although atomically thin 2D transition metal dichalcogenides (TMDs) show enhanced nonlinear optical properties or photoluminescence quantum yield relative to the bulk phase, these properties are weak in the absolute sense due to the ultrashort optical path, and they are also sensitive to layer-dependent symmetry properties. Another practical issue is that the chemical stability of some TMDs (e.g., Weyl semimetals) decreases dramatically as the thickness scales down to monolayer, precluding application as optical components in air. To address these issues, a way of exfoliating TMDs that ensures instantaneous passivation needs to be developed. Here, we employed a polymer-assisted electrochemical exfoliation strategy to synthesize PVP-passivated TMDs monolayers that could be spin coated and restacked into organic-inorganic superlattices with well-defined X-ray diffraction patterns. The segregation of restacked TMDs (e.g., MoS 2 ) by PVP allows the inversion asymmetry of individual layers to be maintained in these superlattices, which allows second harmonic generation and photoluminescence to be linearly scaled with thickness. PVP-passivated monolayer 1T'-MoTe 2 saturable absorber fabricated from these flakes exhibits fast response and recovery time (<150 fs) and pulse stability. Continuous-wave mode-locking based on 1T'-MoTe 2 saturable absorber in a fiber ring laser cavity has been realized, attaining a fundamental repetition rate of 3.15 MHz and pulse duration as short as 867 fs at 1563 nm.

Monolayer transition metal dichalcogenide (TMD) alloys have emerged as a unique material system for promising applications in electronics, optoelectronics, and spintronics due to their tunable electronic structures, effective masses of carriers, and valley polarization with various alloy compositions. Although spin-orbit engineering has been extensively studied in monolayer TMD alloys, the valley Zeeman effect in these alloys still remains largely unexplored. Here we demonstrate the enhanced valley magnetic response in Mo 0.5 W 0.5 Se 2 alloy monolayers and Mo 0.5 W 0.5 Se 2 /WS 2 heterostructures probed by magneto-photoluminescence spectroscopy. The large g factors of negatively charged excitons (trions) of Mo 0.5 W 0.5 Se 2 have been extracted for both pure Mo 0.5 W 0.5 Se 2 monolayers and Mo 0.5 W 0.5 Se 2 /WS 2 heterostructures, which are attributed to the significant impact of doping-induced strong many-body Coulomb interactions on trion emissions under an out-of-plane magnetic field. Moreover, compared with the monolayer Mo 0.5 W 0.5 Se 2 , the slightly reduced valley Zeeman splitting in Mo 0.5 W 0.5 Se 2 /WS 2 is a consequence of the weakened exchange interaction arising from p -doping in Mo 0.5 W 0.5 Se 2 via interlayer charge transfer between Mo 0.5 W 0.5 Se 2 and WS 2 . Such interlayer charge transfer further evidences the formation of type-II band alignment, in agreement with the density functional theory calculations. Our findings give insights into the spin-valley and interlayer coupling effects in monolayer TMD alloys and their heterostructures, which are essential to develop valleytronic applications based on the emerging family of TMD alloys.

While direct bandgap monolayer 2D transition metal dichalcogenides (TMDs) have emerged as an important optoelectronic material due to strong light-matter interactions, their multilayer counterparts exhibit an indirect bandgap resulting in poor photon emission quantum yield. We report strong direct bandgap-like photoluminescence at ∼1.9 eV from multilayer MoS 2 grown on SrTiO 3 , whose intensity is significantly higher than that observed in multilayer MoS 2 /SiO 2 . Using high-resolution electron microscopy we observe interlayer twist and >8% increase in the van der Waals gap, which leads to weaker interlayer coupling. This affects the evolution of the band structure in multilayer MoS 2 as probed by transient absorption spectroscopy, causing higher photo carrier recombination at the direct gap. Our results provide a platform that could enable multilayer TMDs for robust optical device applications.

Heteroatom-doped carbon-based materials are of significance for clean energy conversion and storage because of their fascinating electronic properties, low cost, high durability, and environmental friendliness. Atomically precise fabrication of carbon-based materials with well-defined heteroatom-dopant positions and atomic-scale understanding of their atomic-level electronic properties is a challenge. Herein, we demonstrate the bottom-up on-surface synthesis of 1D and 2D monolayer carbon nitride nanostructures with precise control of the nitrogen-atom doping sites and pore sizes. We also observe an electronic band offset at the C-N heterojunction. Using high-resolution scanning tunneling microscopy, the atomic structure of the as-prepared carbon nitride nanoporous monolayers are revealed, indicating successful and precise control of the structures and N atom doping sites. Furthermore, corroborated by theoretical calculations, scanning tunneling spectroscopy measurements reveal a valence band shift of 140 meV that results in an electric field of 2.9 × 10 8 V m -1 at the C-N heterojunction, indicating efficient separation of the electron-hole pair at the N doping site. Our finding offers direct atomic-level insights into the local electronic structure of the heteroatom-doped carbon-based materials.

Two-dimensional ferroelectrics is attractive for synaptic device applications because of its low power consumption and amenability to high-density device integration. Here, we demonstrate that tin monosulfide (SnS) films less than 6 nm thick show optimum performance as a semiconductor channel in an in-plane ferroelectric analogue synaptic device, whereas thicker films have a much poorer ferroelectric response due to screening effects by a higher concentration of charge carriers. The SnS ferroelectric device exhibits synaptic behaviors with highly stable room-temperature operation, high linearity in potentiation/depression, long retention, and low cycle-to-cycle/device-to-device variations. The simulated device based on ferroelectric SnS achieves ∼92.1% pattern recognition accuracy in an artificial neural network simulation. By switching the ferroelectric domains partially, multilevel conductance states and the conductance ratio can be obtained, achieving high pattern recognition accuracy.

The "Zeeman effect" offers unique opportunities for magnetic manipulation of the spin degree of freedom (DOF). Recently, valley Zeeman splitting, referring to the lifting of valley degeneracy, has been demonstrated in two-dimensional transition metal dichalcogenides (TMDs) at liquid helium temperature. However, to realize the practical applications of valley pseudospins, the valley DOF must be controllable by a magnetic field at room temperature, which remains a significant challenge. Magnetic doping in TMDs can enhance the Zeeman splitting; however, to achieve this experimentally is not easy. Here, we report unambiguous magnetic manipulation of valley Zeeman splitting at 300 K ( g eff = -6.4) and 10 K ( g eff = -11) in a CVD-grown Fe-doped MoS 2 monolayer; the effective Landé g eff factor can be tuned to -20.7 by increasing the Fe dopant concentration, which represents an approximately 5-fold enhancement as compared to undoped MoS 2 . Our measurements and calculations reveal that the enhanced splitting and g eff factors are due to the Heisenberg exchange interaction of the localized magnetic moments (Fe 3d electrons) with MoS 2 through the d-orbital hybridization.

The breaking of multiple symmetries by periodic lattice distortion at a commensurate charge density wave (CDW) state is expected to give rise to intriguing interesting properties. However, accessing the commensurate CDW state on bulk TaS 2 crystals typically requires cryogenic temperatures (77 K), which precludes practical applications. Here, we found that heteroepitaxial growth of a 2H-tantalum disulfide bilayer on a hexagonal-boron nitride ( h -BN) substrate produces a robust commensurate CDW order at room temperature, characterized by a Moiré superlattice of 3 × 3 TaS 2 on a 4 × 4 h -BN unit cell. The CDW order is confirmed by scanning transmission electron microscopy and Raman measurements. Theoretical calculations reveal that the stabilizing energy for the CDW phase of the monolayer and bilayer 2H-TaS 2 -on- h -BN substrates arises primarily from interfacial electrostatic interactions and, to a lesser extent, interfacial strain. Our work shows that engineering interfacial electrostatic interactions in an ultrathin van der Waals heterostructure constitutes an effective way to enhance CDW order in two-dimensional materials.

Two-dimensional (2D) hybrid organic-inorganic Ruddlesden-Popper perovskites (RPPs) have been recently shown to exhibit large nonlinear optical properties due to the strong excitonic effects present in their multiple quantum wells. In this work, we use nondegenerate pump-probe spectroscopy in the 600-1000 nm wavelength range to study the influence of nonlinear effects on the ultrafast dynamics of 2D RPP thin flakes. We find that, under sub-bandgap excitation, ∼100 nm thick perovskite sheets allow up to ∼2% reflectivity modulation within a 20 fs period, due to the nonlinear optical Kerr effect and two-photon absorption, surpassing by a factor of ∼5 the reported nonlinear performance of photonic metasurfaces and single nanoantennas. When the excitation is resonant with the excitonic absorption, the ultrafast nature of the nonlinear response is lost due to the presence of linear absorption creating long-lived free carriers. Our results suggest that 2D RPPs are potential nanoscale all-optical modulators in the visible/near-infrared waveband for applications such as ultrafast information processing, optical data transmission, and high-performance computing.

Phase-controlled synthesis of two-dimensional transition-metal dichalcogenides (TMDCs) is of great interest due to the distinct properties of the different phases. However, it is challenging to prepare metallic phase of group-VI TMDCs due to their metastability. At the monolayer level, interface engineering can be used to stabilize the metastable phase. Here, we demonstrate the selective growth of either single-layer 1H- or 1T'-MoSe 2 on Au(111) by molecular-beam epitaxy; the two phases can be unambiguously distinguished using scanning tunnelling microscopy and spectroscopy. While the growth of 1H-MoSe 2 is favorable on pristine Au(111), the growth of 1T'-MoSe 2 is promoted by the predeposition of Se on Au(111). The selective growth of the 1T'-MoSe 2 on Se-pretreated Au(111) is attributed to the Mo intercalation induced stabilization of the 1T' phase, which is supported by density functional theory calculations. In addition, 1T' twin boundaries and 1H-1T' heterojunctions were observed and found to exhibit enhanced tunnelling conductivity. The substrate pretreatment approach for phase-controlled epitaxy could be applicable to other group-VI TMDCs grown on Au (111).

Controlling superconducting phase transition on a two-dimensional (2D) material is of great fundamental and technological interest from the viewpoint of making 2D resistance-free electronic circuits. Here, we demonstrate that a 1 T-to-2 H phase transition can be induced on the topmost monolayer of bulk (<100 nm thick) 1 T-TaS 2 by thermal annealing. The monolayer 2 H-TaS 2 on bulk 1 T-TaS 2 exhibits a superconducting transition temperature ( T c ) of 2.1 K, which is significantly enhanced compared to that of bulk 2 H-TaS 2 . Scanning tunneling microscopy measurements reveal a 3 × 3 charge density wave (CDW) in the phase-switched monolayer at 4.5 K. The enhanced T c is explained by the suppressed 3 × 3 CDW and a charge-transfer doping from the 1 T substrate. We further show that the monolayer 2 H-TaS 2 could be switched back to 1 T phase by applying a voltage pulse. The observed surface-limited superconducting phase transition offers a convenient way to prepare robust 2D superconductivity on bulk 1 T-TaS 2 crystal, thereby bypassing the need to exfoliate monolayer samples.

Molybdenum diselenide (MoSe 2 ) is a promising two-dimensional material for next-generation electronics and optoelectronics. However, its application has been hindered by a lack of large-scale synthesis. Although chemical vapor deposition (CVD) using laboratory furnaces has been applied to grow two-dimensional (2D) MoSe 2 cystals, no continuous film over macroscopically large area has been produced due to the lack of uniform control in these systems. Here, we investigate the molecular beam epitaxy (MBE) of 2D MoSe 2 on hexagonal boron nitride (hBN) substrate, where highly crystalline MoSe 2 film can be grown with electron mobility ∼15 cm 2 /(V s). Scanning transmission electron microscopy (STEM) shows that MoSe 2 grains grown at an optimum temperature of 500 °C are highly oriented and coalesced to form continuous film with predominantly mirror twin boundaries. Our work suggests that van der Waals epitaxy of 2D materials is tolerant of lattice mismatch but is facilitated by substrates with similar symmetry.

Polymorph engineering of 2H-MoS 2 , which can be achieved by alkali metal intercalation to obtain either the mixed 2H/1T' phases or a homogeneous 1T' phase, has received wide interest recently, since this serves as an effective route to tune the electrical and catalytic properties of MoS 2 . As opposed to an idealized single crystal-to-single crystal phase conversion, the 2H to 1T' phase conversion results in crystal domain size reduction as well as strained lattices, although how these develop with composition is not well understood. Herein, the evolution of the phonon modes in Li-intercalated 1T'-MoS 2 (Li x MoS 2 ) are investigated as a function of different 1T'-2H compositions. We observed that the strain evolution in the mixed phases is revealed by the softening of four Raman modes, B g ( J 1 ), A g ( J 3 ), E 1 2g , and A 1g , with increasing 1T' phase composition. Additionally, the first-order temperature coefficients of the 1T' phonon mode vary linearly with increasing 1T' composition, which is explained by increased electron-phonon and strain-phonon coupling.

Manipulation of lattice strain is emerging as a powerful means to modify the properties of low-dimensional materials. Most approaches rely on external forces to induce strain, and the role of interlayer van der Waals (vdW) coupling in generating strain profiles in homobilayer transition metal dichalcogenide (TMDC) films is rarely considered. Here, by applying atomic-resolution electron microscopy and density functional theory calculations, we observed that a mirror twin boundary (MTB) modifies the interlayer vdW coupling in bilayer TMDC films, leading to the development of local strain for a few nanometers in the vicinity of the MTB. Interestingly, when a single MTB in one layer is "paired" with another MTB in an adjacent layer, interlayer-induced strain is reduced when the MTBs approach each other. Therefore, MTBs are not just 1D discontinuities; they can exert localized 2D strain on the adjacent lattices.

Two-dimensional hybrid organic-inorganic Ruddlesden-Popper perovskites (RPPs) have attracted considerable attention due to their rich photonic and optoelectronic properties. The natural multi-quantum-well structure of 2D RPPs has been predicted to exhibit a large third-order nonlinearity. However, nonlinear optical studies on 2D RPPs have previously been conducted only on bulk polycrystalline samples, in which only weak third-harmonic generation (THG) has been observed. Here, we perform parametric nonlinear optical characterization of 2D perovskite nanosheets mechanically exfoliated from four different lead halide RPP single crystals, from which we observe ultrastrong THG with a maximum effective third-order susceptibility (χ (3) ) of 1.12 × 10 -17 m 2 V -2 . A maximum conversion efficiency of 0.006% is attained, which is more than 5 orders of magnitude higher than previously reported values for 2D materials. The THG emission is resonantly enhanced at the excitonic band gap energy of the 2D RPP crystals and can be tuned from violet to red by selecting the RPP homologue with the requisite resonance. Due to signal depletion effects and phase-matching conditions, the strongest nonlinear response is achieved for thicknesses less than 100 nm.

Two-dimensional (2-D) polymer has properties that are attractive for energy storage applications because of its combination of heteroatoms, porosities and layered structure, which provides redox chemistry and ion diffusion routes through the 2-D planes and 1-D channels. Here, conjugated aromatic polymers (CAPs) were synthesized in quantitative yield via solid-state polymerization of phenazine-based precursor crystals. By choosing flat molecules (2-TBTBP and 3-TBQP) with different positions of bromine substituents on a phenazine-derived scaffold, C-C cross coupling was induced following thermal debromination. CAP-2 is polymerized from monomers that have been prepacked into layered structure (3-TBQP). It can be mechanically exfoliated into micrometer-sized ultrathin sheets that show sharp Raman peaks which reflect conformational ordering. CAP-2 has a dominant pore size of ∼0.8 nm; when applied as an asymmetric supercapacitor, it delivers a specific capacitance of 233 F g -1 at a current density of 1.0 A g -1 , and shows outstanding cycle performance.

Manipulation of spin degree of freedom (DOF) of electrons is the fundamental aspect of spintronic and valleytronic devices. Two-dimensional transition metal dichalcogenides (2D TMDCs) exhibit an emerging valley pseudospin, in which spin-up (-down) electrons are distributed in a +K (-K) valley. This valley polarization gives a DOF for spintronic and valleytronic devices. Recently, magnetic exchange interactions between graphene and magnetic insulator yttrium iron garnet (YIG) have been exploited. However, the physics of 2D TMDCs with YIG have not been shown before. Here we demonstrate strong many-body effects in a heterostructure geometry comprising a MoS 2 monolayer and YIG. High-order trions are directly identified by mapping absorption and photoluminescence at 12 K. The electron doping density is up to ∼10 13 cm -2 , resulting in a large splitting of ∼40 meV between trions and excitons. The trions exhibit a high circular polarization of ∼80% under optical pumping by circularly polarized light at ∼1.96 eV; it is confirmed experimentally that both phonon scattering and electron-hole exchange interaction contribute to the valley depolarization with temperature; importantly, a magnetoresistance (MR) behavior in the MoS 2 monolayer was observed, and a giant MR ratio of ∼30% is achieved, which is 1 order of magnitude larger than the reported ratio in MoS 2 /CoFe 2 O 4 heterostructures. Our experimental results confirm that the giant MR behaviors are attributed to the interfacial spin accumulation due to YIG substrates. Our work provides an insight into spin manipulation in a heterostructure of monolayer materials and magnetic substrates.

Achieving homogeneous phase transition and uniform charge distribution is essential for good cycle stability and high capacity when phase conversion materials are used as electrodes. Herein, we show that chemical lithiation of bulk 2H-MoS 2 distorts its crystalline domains in three primary directions to produce mosaic-like 1T' nanocrystalline domains, which improve phase and charge uniformity during subsequent electrochemical phase conversion. 1T'-Li x MoS 2 , a macroscopic dense material with interconnected nanoscale grains, shows excellent cycle stability and rate capability in a lithium rechargeable battery compared to bulk or exfoliated-restacked MoS 2 . Transmission electron microscopy studies reveal that the interconnected MoS 2 nanocrystals created during the phase change process are reformable even after multiple cycles of galvanostatic charging/discharging, which allows them to play important roles in the long term cycling performance of the chemically intercalated TMD materials. These studies shed light on how bulk TMDs can be processed into quasi-2D nanophase material for stable energy storage.

The performance of a photovoltaic device is strongly dependent on the light harvesting properties of the absorber layer as well as the charge separation at the donor/acceptor interfaces. Atomically thin two-dimensional transition metal dichalcogenides (2-D TMDCs) exhibit strong light-matter interaction, large optical conductivity, and high electron mobility; thus they can be highly promising materials for next-generation ultrathin solar cells and optoelectronics. However, the short optical absorption path inherent in such atomically thin layers limits practical applications. A heterostructure geometry comprising 2-D TMDCs (e.g., MoS2) and a strongly absorbing material with long electron-hole diffusion lengths such as methylammonium lead halide perovskites (CH3NH3PbI3) may overcome this constraint to some extent, provided the charge transfer at the heterostructure interface is not hampered by their band offsets. Herein, we demonstrate that the intrinsic band offset at the CH3NH3PbI3/MoS2 interface can be overcome by creating sulfur vacancies in MoS2 using a mild plasma treatment; ultrafast hole transfer from CH3NH3PbI3 to MoS2 occurs within 320 fs with 83% efficiency following photoexcitation. Importantly, our work highlights the feasibility of applying defect-engineered 2-D TMDCs as charge-extraction layers in perovskite-based optoelectronic devices.

Graphene nanomaterials have been actively investigated for biomedical and biological applications, including that of cancer. Despite progress made, most of such studies are conducted on dispersed graphene nanosheets in solution. Consequently, the use of planar graphene films, especially in cancer research, has not been fully explored. Here, we investigate the cellular interactions between the graphene material films and breast cancer cell lines, specifically the effects these films have on cellular proliferation, spreading area, and cytotoxicity. We demonstrate that the graphene oxide (GO) film selectively accelerates the proliferation of both metastatic (MDA-MB-231) and nonmetastatic (MCF-7) breast cancer cells, but not that of noncancer breast epithelial cells (MCF-10A). Contrastingly, this accelerated proliferation is not observed with the use of graphene (G) film. Moreover, GO induces negligible cytotoxicity on these cells. We suggest that the observed phenomena originate from the synergistic effect resulted from the high loading capacity and conformational change of cellular attachment proteins on the GO film, and the high amount of oxygenated groups present in the material. We anticipate that our findings can further shed light on the graphene-cancer cellular interactions and provide better understanding for the future design and application of graphene-based nanomaterials in cancer research.

Chemical vapor deposition (CVD) is one of the most promising growth techniques to scale up the production of monolayer graphene. At present, there are intense efforts to control the orientation of graphene grains during CVD, motivated by the fact that there is a higher probability for oriented grains to achieve seamless merging, forming a large single crystal. However, it is still challenging to produce single-crystal graphene with no grain boundaries over macroscopic length scales, especially when the nucleation density of graphene nuclei is high. Nonetheless, nanocrystalline graphene with highly oriented grains may exhibit single-crystal-like properties. Herein, we investigate the spectroscopic signatures of graphene film containing highly oriented, nanosized grains (20-150 nm) using angle-resolved photoemission spectroscopy (ARPES) and high-resolution electron energy loss spectroscopy (HREELS). The robustness of the Dirac cone, as well as dispersion of its phonons, as a function of graphene's grain size and before and after film coalescence, was investigated. In view of the sensitivity of atomically thin graphene to atmospheric adsorbates and intercalants, ARPES and HREELS were also used to monitor the changes in spectroscopic signatures of the graphene film following exposure to the ambient atmosphere.

Direct patterning of ultrathin MoS2 films with well-defined structures and controllable thickness is appealing since the properties of MoS2 sheets are sensitive to the number of layer and surface properties. In this work, we employed a facile, effective, and well-controlled technique to achieve micropatterning of MoS2 films with a focused laser beam. We demonstrated that a direct focused laser beam irradiation was able to achieve localized modification and thinning of as-synthesized MoS2 films. With a scanning laser beam, microdomains with well-defined structures and controllable thickness were created on the same film. We found that laser modification altered the photoelectrical property of the MoS2 films, and subsequently, photodetectors with improved performance have been fabricated and demonstrated using laser modified films.

Strain and defect engineering of graphene can modify the topological features of electronic states, leading to novel properties such as pseudomagnetism in bubbles and metallicity in extended topological defects. A consequence of graphene being a soft membrane is that it can be strain-engineered to become highly corrugated by modifying its adhesion to the substrate. Extended grain boundaries in graphene can be constructed from periodic combinations of nonhexagonal rings (5-7 pairs). However, a controlled method of producing these defects is not currently available. In this Perspective, we discuss some of the recent advances in studying the properties and formation mechanisms of strained structures and defects in graphene, extending across both physics and chemistry.

Graphene has been hailed as a wonderful material in electronics, and recently, it is the rising star in photonics, as well. The wonderful optical properties of graphene afford multiple functions of signal emitting, transmitting, modulating, and detection to be realized in one material. In this paper, the latest progress in graphene photonics, plasmonics, and broadband optoelectronic devices is reviewed. Particular emphasis is placed on the ability to integrate graphene photonics onto the silicon platform to afford broadband operation in light routing and amplification, which involves components like polarizer, modulator, and photodetector. Other functions like saturable absorber and optical limiter are also reviewed.

The electronic properties of graphene sheets decorated with nanodiamond (ND) particles have been investigated. The chemical fusion of ND to the graphene lattice creates pockets of local defects with robust interfacial bonding. At the ND-bonded regions, the atoms of graphene lattice follow sp(3)-like bonding, and such regions play the role of conduction bottlenecks for the percolating sp(2) graphene network. The low-temperature charge transport reveals an insulating behavior for the disordered system associated with Anderson localization for the charge carriers in graphene. A large negative magnetoresistance is observed in this insulating regime, and its origin is discussed in the context of magnetic correlations of the localized charge carriers with local magnetic domains and extrinsic metal impurities associated with the ND.

The graphene Moiré superstructure offers a complex landscape of humps and valleys to molecules adsorbing and diffusing on it. Using C(60) molecules as the classic hard sphere analogue, we examine its assembly and layered growth on this corrugated landscape. At the monolayer level, the cohesive interactions of C(60) molecules adsorbing on the Moiré lattice freeze the molecular rotation of C(60) trapped in the valley sites, resulting in molecular alignment of all similarly trapped C(60) molecules at room temperature. The hierarchy of adsorption potential well on the Moiré lattice causes diffusion-limited dendritic growth of C(60) films, as opposed to isotropic growth observed on a smooth surface like graphite. Due to the strong binding energy of the C(60) film, part of the dentritic C(60) films polymerize at 850 K and act as solid carbon sources for graphene homoepitaxy. Our findings point to the possibility of using periodically corrugated graphene in molecular spintronics due to its ability to trap and align organic molecules at room temperature., (© 2011 American Chemical Society)

The separation of chemical vapor deposited (CVD) graphene from the metallic catalyst it is grown on, followed by a subsequent transfer to a dielectric substrate, is currently the adopted method for device fabrication. Most transfer techniques use a chemical etching method to dissolve the metal catalysts, thus imposing high material cost in large-scale fabrication. Here, we demonstrate a highly efficient, nondestructive electrochemical route for the delamination of CVD graphene film from metal surfaces. The electrochemically delaminated graphene films are continuous over 95% of the surface and exhibit increasingly better electronic quality after several growth cycles on the reused copper catalyst, due to the suppression of quasi-periodical nanoripples induced by copper step edges. The electrochemical delamination process affords the advantages of high efficiency, low-cost recyclability, and minimal use of etching chemicals.

The culture of bone marrow derived mesenchymal stem cells (MSCs), as well as the control of its differentiation toward different tissue lineage, is a very important part of tissue engineering, where cells are combined with artificial scaffold to regenerate tissues. Graphene (G) and graphene oxide (GO) sheets are soft membranes with high in-plane stiffness and can potentially serve as a biocompatible, transferable, and implantable platform for stem cell culture. While the healthy proliferation of stem cells on various carbon platforms has been demonstrated, the chemical role of G and GO, if any, in guiding uncommitted stem cells toward differentiated cells is not known. Herein, we report that the strong noncovalent binding abilities of G allow it to act as a preconcentration platform for osteogenic inducers, which accelerate MSCs growing on it toward the osteogenic lineage. The molecular origin of accelerated differentation is investigated by studying the binding abilities of G and GO toward different growth agents. Interestingly, differentiation to adipocytes is greatly suppressed on G because insulin, which is a key regulator for the synthesis of fatty acids, is denatured upon π-π adsorption on G; in contrast, GO does not interfere with adipogenesis due to electrostatic binding with insulin. The different binding interactions and their subsequent influence on stem cell growth and differentiation are ascribed to different degrees of π-π stacking and electrostatic and hydrogen bonding mediated by G and GO., (© 2011 American Chemical Society)

The electronic properties of graphene sheets and nanoribbons with different degrees of hydrogenation have been investigated using a combination of charge transport and Raman spectroscopy experiments. The field-effect transistor mobility of graphene is shown to be highly sensitive to the treatment time during atomic hydrogen dose and follows an exponential decrease with time. Raman spectroscopy demonstrates linearly increasing defect-band intensity, and when considered together with transport data, the relationship between graphene mobility and the crystalline size of intact sp(2) carbon regions can be derived. Further, the increase in width of the voltage plateau for monolayer and bilayer graphene points to the formation of midgap states. For partially hydrogenated graphene, the temperature-dependent transport in these states shows a weak insulating behavior. A comparison of Raman spectrum and conductivity data of partially hydrogenated monolayer and bilayer graphene suggests that the latter is also quite susceptible to adsorption of hydrogen atoms, despite a stiffer lattice structure.

The electronic properties of graphene can be modulated by charged lipid bilayer adsorbing on the surface. Biorecognition events which lead to changes in membrane integrity can be monitored electrically using an electrolyte-gated biomimetic membrane-graphene transistor. Here, we demonstrate that the bactericidal activity of antimicrobial peptides can be sensed electrically by graphene based on a complex interplay of biomolecular doping and ionic screening effect.

The dual role of graphene (or reduced graphene oxide) as atomic template and structural scaffold in the nucleation and assembly of organic nanostructures is demonstrated. The π-π stacking interactions between graphene and aromatic organic molecules affords synergistic binding interactions, with the host and guest assuming the interchangeable roles of atomic template and structural scaffold. Beginning with the seeding of organic wires on graphene template, the outgrown organic wires in turn act as one-dimensional scaffolds where graphene sheets coat around to form a unique graphene-organic hybrid structure. Using this π-assembly approach, we have synthesized one-dimensional hybrid structures consisting of graphene-N,N'-dioctyl-3,4,9,10-perylenedicarboximide (PDI) organic wires. This hybrid structure shows enhanced performance over its individual components in donor-acceptor type (PDI-Graphene/polythiophene) solar cells.

We report a new route to prepare high quality, monolayer graphene by the dehydrogenation of graphane-like film grown by plasma-enhanced chemical vapor deposition. Large-area monolayer graphane-like film is first produced by remote-discharged radio frequency plasma beam deposition at 650 °C on Cu/Ti-coated SiO(2)-Si. The advantages of the plasma deposition include very short deposition time (<5 min) and a lower growth temperature of 650 °C compared to the current thermal chemical vapor deposition approach (1000 °C). Near edge X-ray adsorption, Raman spectroscopy, and transmission electron microscopy as well as scanning tunneling microscopy have been applied to characterize the graphane-to-graphene transition for the as-deposited films. The fingerprint quantum hall effect of monolayer graphene can be obtained on the fully dehydrogenated graphane-like film; four fully quantized half-integer plateaus are observed. The interconvertibility between graphane-like and graphene here opens up a possible route for the fabrication of regions with varying conductivity in a single deposition system using maskless, laser writing.

The present study reports room-temperature ferromagnetic behaviors in three-dimensional (3D)-aligned thiol-capped single-crystalline ZnO nanowire (NW) and nanotube (NT) arrays as well as polycrystalline ZnO NT arrays. Besides the observation of height-dependent saturation magnetization, a much higher M(s) of 166 microemu cm(-2) has been found in NTs compared to NWs (36 microemu cm(-2)) due to larger surface area in ZnO NTs, indicating morphology-dependent magnetic properties in ZnO NW/NT systems. Density functional calculations have revealed that the origin of ferromagnetism is mainly attributed to spin-polarized 3p electrons in S sites and, therefore, has a strong correlation with Zn-S bond anisotropy. The preferential magnetization direction of both single-crystalline NTs and NWs lies perpendicular to the tube/wire axis due to the aligned high anisotropy orientation of the Zn-S bonds on the lateral (100) face of ZnO NWs and NTs. Polycrystalline ZnO NTs, however, exhibit a preferential magnetization direction parallel to the tube axis which is ascribed to shape anisotropy dominating the magnetic response. Our results demonstrate the interplay of morphology, dimensions, and crystallinity on spin alignment and magnetic anisotropy in a 3D semiconductor nanosystem with interfacial magnetism.

We report a high-throughput method of generating graphene monolayer (>90% yield) from weakly oxidized, poorly dispersed graphite oxide (GO) aggregates. These large-sized GO aggregates consist of multilayer graphite flakes which are oxidized on the outer layers, while the inner layers consist of pristine or mildly oxidized graphene sheets. Intercalation-exfoliation of these GO aggregates by tetrabutylammonium cations yields large-sized conductive graphene sheets (mean sheet area of 330 +/- 10 microm(2)) with high monolayer yield. Thin-film field-effect transistors made from these graphene sheets exhibit high mobility upon nullifying Coulomb scattering by ionic screening. Ionic screening versus chemical doping effects of different ions such as chloride and fluoride on these graphene films were investigated with a combination of in situ Raman spectroscopy and transport measurement.

Organometallic wires are interesting alternatives to conventional molecular wires based on a pure organic system because of the presence of d orbitals in the transition metal complex. However, synthetic problems, such as decreased stability of the compounds when labile metal complexes are present, often impede their isolation in a pure state and preclude a rapid development of such hybrid molecular wires. In this work, we show that preassembled self-assembled monolayers (SAM) based on pyridine-terminated 1-((4-acetylthiophenyl)ethynyl)-4-((4-pyridyl)ethynyl)benzene can act as a template for the architectural build up of a second layer of transition metal complexes to form an array of organometallic molecular wires on gold. Ru(II)(terpy)(bipy)(2+) (terpy = 2,2':6',2''-terpyridine and bipy = 2,2'-bipyridine) or cyclometalated Pt(II)(pbipy) (pbipy = 6-phenyl-2,2'-bipyridine) were axially coordinated onto the organic SAM via its terminal pyridinium moieties. Current-voltage studies show that the electronic coupling between the transition metal and organic wire produces a molecular wire that exhibits higher conductance than the original organic chain. The presence of the transition metal complexes in the hybrid molecular wire introduces distinctive negative differential resistance (NDR) effects.

In this work we demonstrate a facile means to generate fluorescent carbon nanoribbons, nanoparticles, and graphene from graphite electrode using ionic liquid-assisted electrochemical exfoliation. A time-dependence study of products exfoliated from the graphite anode allows the reconstruction of the exfoliation mechanism based on the interplay of anodic oxidation and anion intercalation. We have developed strategies to control the distribution of the exfoliated products. In addition, the fluorescence of these carbon nanomaterials can be tuned from the visible to ultraviolet region by controlling the water content in the ionic liquid electrolyte.