Ultrafast 2D Nanosheet Assembly via Spontaneous Spreading Phenomenon.

In 2D materials, a key engineering challenge is the mass production of large-area thin films without sacrificing their uniform 2D nature and unique properties. Here, it is demonstrated that a simple fluid phenomenon of water/alcohol solvents can become a sophisticated tool for self-assembly and designing organized structures of 2D nanosheets on a water surface. In situ, surface characterizations show that water/alcohol droplets of 2D nanosheets with cationic surfactants exhibit spontaneous spreading of large uniform monolayers within 10 s. Facile transfer of the monolayers onto solid or flexible substrates results in high-quality mono- and multilayer films with high coverages (>95%) and homogeneous electronic/optical properties. This spontaneous spreading is quite general and can be applied to various 2D nanosheets, including metal oxides, graphene oxide, h-BN, MoS2, and transition metal carbides, enabling on-demand smart manufacture of large-size (>4 inchϕ) 2D nanofilms and free-standing membranes.

Understanding the role of solvents in bottom-up synthesis of multi-element hydroxides.

Here we report a comparative study on the bottom-up synthesis of multi-element hydroxides composed of Mg, Al, Fe and Zn cations to understand the role of solvents. Two common solvents, water and ethylene glycol, a typical polyol, are used. The polyol-derived MgAlFeZn-OH are nanosheets with homogeneous elemental distribution, while the hydrothermal-derived MgAlFeZn-OH are mixtures of plate-like hydroxide layers and rod-like spinel oxides. The coordinating properties and the high viscosity of the ethylene glycol provide the possibility to mediate the hydrolysis rates and to control the particle growth. The high specific surface area of the polyol-derived multi-element hydroxide nanosheets (352.4 m2 g-1) guarantees them as excellent adsorbents for adsorbing anionic dyes in aqueous solution.

Multiemission of Ce3+ from a Single Crystallographic Site Induced by Disordering of Ions.

White-light emission with a single activator is an attractive function of phosphors. In this work, we investigated the photoluminescence properties of Ca5.7Y1.3Si7O16.7N3.3, which is a compound denoted as Ca4+xY3-xSi7O15+xN5-x discovered by our group, with Ce-activation using optical measurements and density functional theory (DFT) calculation. Samples showed a tunable emission from purple to white under ultraviolet (UV) light. In this compound, Ca and Y as well as anions are distributed disorderly, and Ca/Y ions occupy two crystallographically distinct sites; those sites are possible sites for Ce substitution. DFT calculation and structural refinement revealed that the tunable emission was generated by Ce at the crystallographically equivalent site but with distinct local structures caused by the disordering of cations and anions. As far as we know, this is the first report about a white-light-emitting phosphor with only Ce activation.

Facile Synthesis of Pd Nanosheets and Implications for Superior Catalytic Activity.

As a member of the 2D materials family, 2D metal nanosheets (metallenes) have received increasing attention due to their intriguing properties distinct from those of graphene and other inorganic 2D nanosheets. However, the synthesis of metallenes is still challenging, owing to the lack of an efficient synthetic approach. Here we present a facile one-pot approach to the controlled synthesis of Pd nanosheets. A key feature of this process is a stepwise reaction using 2,4,6-trichlorophenyl formate (TCPF); TCPF emits carbon monoxide gas, which acts as both a reductant and a surface capping agent, promoting the anisotropic 2D growth of the Pd nanosheets. Photoemission spectroscopy revealed some peculiar features of the surface charge and valence band states due to suppressed electron transfer at the 2D surface. This surface state caused improved catalytic activity for the hydrogen evolution reaction compared to that of bulk Pd.

Engineering Interface Defects and Interdiffusion at the Degenerate Conductive In2O3/Al2O3 Interface for Stable Electrodes in a Saline Solution.

A low-temperature Al2O3 deposition process provides a simplified method to form a conductive two-dimensional electron gas (2DEG) at the metal oxide/Al2O3 heterointerface. However, the impact of key factors of the interface defects and cation interdiffusion on the interface is still not well understood. Furthermore, there is still a blank space in terms of applications that go beyond the understanding of the interface's electrical conductivity. In this work, we carried out a systematic experimental study by oxygen plasma pretreatment and thermal annealing post-treatment to study the impact of interface defects and cation interdiffusion at the In2O3/Al2O3 interface on the electrical conductance, respectively. Combining the trends in electrical conductance with the structural characteristics, we found that building a sharp interface with a high concentration of interface defects provides a reliable approach to producing such a conductive interface. After applying this conductive interface as electrodes for fabricating a field-effect transistor (FET) device, we found that this interface electrode exhibited ultrastability in phosphate-buffered saline (PBS), a commonly used biological saline solution. This study provides new insights into the formation of conductive 2DEGs at metal oxide/Al2O3 interfaces and lays the foundation for further applications as electrodes in bioelectronic devices.

Thermal and Chemical Phase Engineering of Two-Dimensional Ruthenate.

Monolayer ruthenate nanosheets obtained by exfoliating layered ruthenium oxide exhibit excellent electrical conductivity, redox activity, and catalytic activity, which render them suitable for advanced electronic and energy devices. However, to fully exploit the benefits, we require further structural insights into a complex polymorphic nature and diversity in relevant electronic states of two-dimensional (2D) ruthenate systems. In this study, the 2D structures, stability, and electronic states of 2D ruthenate are investigated on the basis of thermal and chemical phase engineering approaches. We reveal that contrary to a previous report, exfoliation of an oblique 1T phase precursor leads to nanosheets having an identical phase without exfoliation-induced phase transition to a 1H phase. The oblique 1T phase in the nanosheets is found to be metastable and, thus, transforms successively to a rectangular 1T phase upon heating. A phase-controllable synthesis via Co doping affords nanosheets with metastable rectangular and thermally stable hexagonal 1T phases at a Co content of 5-10 and 20 at%, respectively. The 1T phases show metallic electronic states, where the d-d optical transitions between the Ru 4d (t2g) orbital depend on the symmetry of the Ru framework. The Co doping in ruthenate nanosheets unexpectedly suppresses the redox and catalytic activities under acidic conditions. In contrast, the Co2+/3+ redox pair is activated and produces conductive nanosheets with high electrochemical capacitance in an alkaline condition.

Layer-dependent stability of 2D mica nanosheets.

We report on the layer-dependent stability of muscovite-type two-dimensional (2D) mica nanosheets (KAl3Si3O10(OH)2). First-principles calculations on mica nanosheets with different layer thicknesses (n = 1, 2, and 3) reveal their layer-dependent stability; odd-numbered 2D mica nanosheets are more stable than even-numbered ones, and the preferable stability of odd-numbered layers originates from electronic effects. A core-shielding model is proposed with a reasonable assumption, successfully proving the instability of the even-numbered mica nanosheets. Raman imaging supports that the population of odd-numbered mica nanosheets is predominant in exfoliated mica products. The alternating charge states with odd/even layers were evidenced by Kelvin probe force microscopy. We also demonstrate a unique photocatalytic degradation, opening new doors for environmental applications of mica nanosheets.

Gigantic Thermal Shielding in 2D Oxide Nanosheets.

Thermal shielding materials that can block near-infrared (NIR) light from the sunlight while maintaining visible transparency have become increasingly important from an energy-saving perspective. Here, we demonstrate a gigantic NIR shielding by an engineered plasmonic material based on a two-dimensional (2D) polytungstate (Cs4-xW11O35-d). Starting from a charge-neutral polytungstate (Cs4W11O35), we synthesize charge-imbalanced 2D nanosheets (Cs4-xW11O35-d) that undergo an unusual structural change with the semiconductor-to-metal transition in a reduced atmosphere. Layer-by-layer engineering of the 2D nanosheets enables a plasmon-induced enhancement of the NIR reflectance (>53%) with a high visible transparency (>71%), realizing high-performance thermal shielding. Our approach offers a solution for future thermal management technology.

Ultrahigh Energy Storage in 2D High-κ Perovskites.

Dielectric capacitors have greater power densities than batteries, and, unlike batteries, they do not utilize chemical reactions during cycling. Thus, they can become ideal, safe energy storage devices. However, dielectric capacitors yield rather low energy densities compared with other energy storage devices such as batteries and supercapacitors. Here, we present a rational approach for designing ultrahigh energy storage capacitors using two-dimensional (2D) high-κ dielectric perovskites (Ca2Nam-3NbmO3m+1; m = 3-6). Individual Ca2Nam-3NbmO3m+1 nanosheets exhibit an ultrahigh dielectric strength (638-1195 MV m-1) even in the monolayer form, which exceeds those of conventional dielectric materials. Multilayer stacked nanosheet capacitors exhibit ultrahigh energy densities (174-272 J cm-3), high efficiencies (>90%), excellent reliability (>107 cycles), and temperature stability (-50-300 °C); the maximum energy density is much higher than those of conventional dielectric materials and even comparable to those of lithium-ion batteries. Enhancing the energy density may make dielectric capacitors more competitive with batteries.

Automated One-Drop Assembly for Facile 2D Film Deposition.

The effective application of 2D materials is strongly dependent on the mass production of high-quality large-area 2D thin films. Here, we demonstrate a strategy for the automated manufacturing of high-quality 2D thin films using a modified drop-casting approach. Our approach is simple; by using an automated pipette, a dilute aqueous suspension is dropped onto a substrate heated on a hotplate, and controlled convection by Marangoni flow and liquid removal causes the nanosheets to come together to form a tile-like monolayer film in 1-2 min. Ti0.87O2 nanosheets are utilized as a model system for investigating the control parameters such as concentrations, suction speeds, and substrate temperatures. We perform the automated one-drop assembly of a range of 2D nanosheets (metal oxides, graphene oxide, and hexagonal boron nitride) and successfully fabricate various functional thin films in multilayered, heterostructured, and sub-micrometer-thick forms. Our deposition method enables on-demand large-size (>2 inchϕ) manufacturing of high-quality 2D thin films while reducing the time and sample consumption.

Free-Standing Molecularly Thin Amorphous Silica Nanosheets.

Recent progress in 2D materials has initiated new fields of molecularly thin amorphous materials with mysterious properties and structures. However, designed synthesis of molecularly thin amorphous silica still remains a challenge; whether free-standing molecularly thin amorphous silica nanosheets can exist is unclear. Here, this issue is addressed by using a new chemical protocol; solid-state surfactant lamellae with ordered alkyl-chain arrangements can serve as superior templates guiding free-standing amorphous silica nanosheets. Simple sonication of the lamellar hybrids allows exfoliation into monolayer amorphous silica nanosheets with 0.9 nm thickness. In addition, the nanosheets show the distinctive feature of high colloidal stability that enables atomic layer engineering of silica nanocoatings and dielectric nanofilms. The approach may shed new light on the properties and applications of old silica.

Damage-free LED lithography for atomically thin 2D material devices.

Desired electrode patterning on two-dimensional (2D) materials is a foremost step for realizing the full potentials of 2D materials in electronic devices. Here, we introduce an approach for damage-free, on-demand manufacturing of 2D material devices using light-emitting diode (LED) lithography. The advantage of this method lies in mild photolithography by simply combining an ordinary optical microscope with a commercially available LED projector; the low-energy red component is utilized for optical characterization and alignment of devices, whereas the high-energy blue component is utilized for photoresist exposure and development of personal computer designed electrode patterns. This method offers maskless, damage-free photolithography, which is particularly suitable for 2D materials that are sensitive to conventional lithography. We applied this LED lithography to device fabrication of selected nanosheets (MoS2, graphene oxides and RuO2), and achieved damage-free lithography of various patterned electrodes with feature sizes as small as 1-2 µm. The LED lithography offers a useful approach for cost-effective mild lithography without any costly instruments, high vacuum, or complex operation.

Tailored synthesis of molecularly thin platinum nanosheets using designed 2D surfactant solids.

The assembly of the surfactants has been utilized as unique templates for the controlled synthesis of metal nanosheets. However, current strategies for metal nanosheets have mainly focused on the liquid-phase surfactant assembly. Herein, we found the solid-state surfactants as designable crystals suitable for nanostructural control and proposed a novel synthetic route for molecularly thin Pt metal nanosheets using solid surfactant crystals as a precursor. The 2D surfactant crystals containing planarly arranged Pt complexes were prepared, and the subsequent UV-ozone treatment and reduction process allowed us to obtain Pt metal nanosheets. Pt metal nanosheets had a distinct morphology with various thicknesses (from 1.5 nm to 3.0 nm), characteristic of 2D surfactant crystals.

Construction of Multilayer Films and Superlattice- and Mosaic-like Heterostructures of 2D Metal Oxide Nanosheets via a Facile Spin-Coating Process.

This study reports a design of a variety of nanostructured films of 2D oxide nanosheets. We systematically examined the deposition of perovskite-type Ca2Nb3O10- nanosheets by spin-coating their dimethyl sulfoxide dispersion. Neat and homogeneous monolayer tiling was attained on various substrates by selecting an optimum rotation speed, which was dependent on the nanosheet concentration. Repeating the optimized spin-coating process allowed for layer-by-layer deposition of the nanosheets into multilayer films with a designed layer number. Vertical superlattice heterostructures could also be assembled by alternately spin-coating the suspensions of Ca2Nb3O10- and Ti0.87O20.52- nanosheets. Furthermore, spin-coating of a mixed suspension of Ca2Nb3O10- and Ti0.87O20.52- nanosheets led to a mixed mosaic-like monolayer of these two nanosheets. The present study thus demonstrated spin-coating as a facile and powerful route to construct various nanostructures based on 2D oxide nanosheets.

Solution-Processed Two-Dimensional Metal Oxide Anticorrosion Nanocoating.

Molecularly thin two-dimensional (2D) nanomaterials are attractive building blocks for constructing anticorrosion nanocoatings as an ultimate pursuit in the metal-related industry. However, the nanocoating of prefocused graphene is far from industrial demands due to its high cost, low scalability, and insufficient quality. We propose all requirements to realize rational anticorrosion nanocoating of metal oxide nanosheets. The proof-of-concept study with Ti0.87O2 and Ca2Nb3O10 nanosheets demonstrates that the 10 and 20 nm thick coatings fabricated by a facile layer-by-layer (LbL) self-assembly on stainless steel (SUS) give perfect inhibition efficiency (IE) values of 99.92% and 99.89%, respectively. A driving test with a nanosheet-coated car-baffle demonstrated suitable corrosion resistance and mechanical and thermal robustness for industrial applications. The revealed and controlled thermal oxidation mechanisms are critical toward high-temperature application of the 2D oxide anticorrosion nanocoating. The advantages of nanosheet coating and extensible materials design will open a solid but exciting route to anticorrosion nanotechnology.

Rational Assembly of Two-Dimensional Perovskite Nanosheets as Building Blocks for New Ferroelectrics.

Artificial materials in the form of superlattices have been studied actively in quest of new engineering methods or design rules for the development of desired functionalities, in particular high-k ferroelectricity, ferromagnetism, and high mobility electron gas. This work presents a controlled assembly strategy for fabricating atomically precise interfaces of two-dimensional (2D) homologous perovskite nanosheets (Ca2Nam-3NbmO3m+1-; m = 3-6) to construct artificial superlattices. The distinctive thickness of each 2D homologous perovskite nanosheets attributed to the presence of different number of NbO6 octahedra provides an exquisite control to engineer interfacial properties for tailored design of superior high-k properties and emergence of ferroelectricity. The higher dielectric constant (εr = 427) and development of ferroelectricity for (Ca2Nb3O10-/Ca2Na2Nb5O16-)6 superlattice indicate that superlattice films with both odd number of NbO6 octahedra possess extended polarization due to the potential effect of heterointerface and ferroelectric instabilities. Furthermore, the increased discontinuities/offsets in Ca2Nb3O10- and Ca2Na3Nb6O19- nanosheets band alignment results in superior insulating properties (∼1 × 10-11 A cm-2 at 1 V) for (Ca2Nb3O10-/Ca2Na3Nb6O19-)6 superlattice. These findings exhibit new research opportunities for the development of novel artificial high-k dielectric/ferroelectric via precise control of interfaces at the atomic level and can be extended to the large family of 2D perovskite compounds.

Single Droplet Assembly for Two-Dimensional Nanosheet Tiling.

Recent advances in two-dimensional (2D) materials offer an opportunity for atomic layer engineering of functional thin films and superlattices. For future applications of 2D materials, there is an urgent need to develop convenient deposition processes that enable precise control of thin-film architectures while reducing the time, cost, and energy/sample consumption. Here, we demonstrate a strategy for nanosheet assembly using a simple drop casting with a pipet and a hot plate. By controlled thermal convection of a single droplet on a hot plate, a range of 2D nanosheets, such as Ti0.87O20.52-, Ca2Nb3O10-, Ru0.95O20.2-, and graphene oxide, can be neatly tiled to form an ideal monolayer on various substrates in ∼30 s over a wide area (i.e., a 50 mmϕ substrate). The mechanism and control strategies are discussed. We also demonstrate the production of various functional coatings such as conducting, semiconducting, insulating, magnetic, and photochromic coatings in multilayer, superlattice, and submicrometer-thick forms, offering the potential for a convenient way to produce high-quality 2D nanosheet films.

Scalable Design of Two-Dimensional Oxide Nanosheets for Construction of Ultrathin Multilayer Nanocapacitor.

Large size of capacitors is the main hurdle in miniaturization of current electronic devices. Herein, a scalable solution-based layer-by-layer engineering of metallic and high-κ dielectric nanosheets into multilayer nanosheet capacitors (MNCs) with overall thickness of ≈20 nm is presented. The MNCs are built through neat tiling of 2D metallic Ru0.95 O2 0.2- and high-κ dielectric Ca2 NaNb4 O13 - nanosheets via the Langmuir-Blodgett (LB) approach at room temperature which is verified by cross-sectional high-resolution transmission electron microscopy (HRTEM). The resultant MNCs demonstrate a high capacitance of 40-52 µF cm-2 and low leakage currents down to 10-5 -10-6 A cm-2 . Such MNCs also possess complimentary in situ robust dielectric properties under high-temperature measurements up to 250 °C. Based on capacitance normalized by the thickness, the developed MNC outperforms state-of-the-art multilayer ceramic capacitors (MLCC, ≈22 µF cm-2 /5 × 104  nm) present in the market. The strategy is effective due to the advantages of facile, economical, and ambient temperature solution assembly.

Synthesis of NaMoO3F and Na5W3O9F5 with Morphological Controllability in Non-Aqueous Solvents.

NaMoO3F and Na5W3O9F5 were synthesized by solvothermal reaction of MoO3 and WO3, respectively, with NaF in nonaqueous solvents. These reactions were realized at low temperatures (150-200 °C) without the use of HF. This synthesis method is much more facile and safe procedure compared with general synthesis methods for oxyfluorides which includes hydrothermal reaction under a presence of HF or solid-state reaction at high temperatures in vacuum sealed tube or under high pressure. In the case of the reaction of MoO3 with NaF, the kind of solvent largely affected the obtained morphologies of NaMoO3F. The morphology in the case of acetonitrile as a solvent was rodlike with a micrometer-scale size, while that in the case of ethanol was polyhedral with a size of several hundred nanometers. In addition, the solvothermal reaction of WO3 with NaF led to the formation of Na5W3O9F5. Also, the difference of solvents for the solvothermal reaction affected the obtained particle sizes. The effect of the solvents on the morphologies of the obtained oxyfluorides probably resulted from the difference of the solubility of NaF and the subsequent dissolution ratio of MoO3 or WO3 in the used solvents. Our synthesis method can expand the applicability of oxyfluorides by providing a new phase and/or unique morphology.

On/Off Boundary of Photocatalytic Activity between Single- and Bilayer MoS2.

Molecularly thin two-dimensional (2D) semiconductors are emerging as photocatalysts owing to their layer-number-dependent quantum effects and high charge separation efficiency. However, the correlation among the dimensionality, crystallinity, and photocatalytic activity of such 2D nanomaterials remains unclear. Herein, a Ag photoreduction technique coupled with microscopic analyses is employed to spatially resolve the photocatalytic activity of MoS2 as a model catalyst. Interestingly, we find that only monolayer (1L)-MoS2 is active for a Ag photoreduction reaction. The photocatalytic activity of 1L-MoS2 is enhanced by a built-in electrical field originated from the MoS2/SiO2 interface, instead of by the specific surface structure and quantum electronic state of 1L-MoS2. Furthermore, we observe photocatalytic active sites to be geometrically distributed on triangular 1L-MoS2 crystals, wherein the Ag particles are preferentially deposited on the outermost zigzag edges and defective inner parts of the triangular grains. The degradation of photocatalytic activity and electron mobility with the formation of Mo(VI) species indicates that the species inhibit the in-plane diffusion of the photogenerated electrons to the reductive sites. The monolayer-selectivity, activation, and inactivation mechanisms, unveiled in this work, will offer future directions in designing 2D nanophotocatalysts.