Tuning Phonon Energies in Lanthanide-doped Potassium Lead Halide Nanocrystals for Enhanced Nonlinearity and Upconversion.

Optical applications of lanthanide-doped nanoparticles require materials with low phonon energies to minimize nonradiative relaxation and promote nonlinear processes like upconversion. Heavy halide hosts offer low phonon energies but are challenging to synthesize as nanocrystals. Here, we demonstrate the size-controlled synthesis of low-phonon-energy KPb2 X5 (X=Cl, Br) nanoparticles and the ability to tune nanocrystal phonon energies as low as 128 cm-1 . KPb2 Cl5 nanoparticles are moisture resistant and can be efficiently doped with lighter lanthanides. The low phonon energies of KPb2 X5 nanoparticles promote upconversion luminescence from higher lanthanide excited states and enable highly nonlinear, avalanche-like emission from KPb2 Cl5 : Nd3+ nanoparticles. The realization of nanoparticles with tunable, ultra-low phonon energies facilitates the discovery of nanomaterials with phonon-dependent properties, precisely engineered for applications in nanoscale imaging, sensing, luminescence thermometry and energy conversion.

Enhanced and stabilized hydrogen production from methanol by ultrasmall Ni nanoclusters immobilized on defect-rich h-BN nanosheets.

Employing liquid organic hydrogen carriers (LOHCs) to transport hydrogen to where it can be utilized relies on methods of efficient chemical dehydrogenation to access this fuel. Therefore, developing effective strategies to optimize the catalytic performance of cheap transition metal-based catalysts in terms of activity and stability for dehydrogenation of LOHCs is a critical challenge. Here, we report the design and synthesis of ultrasmall nickel nanoclusters (∼1.5 nm) deposited on defect-rich boron nitride (BN) nanosheet (Ni/BN) catalysts with higher methanol dehydrogenation activity and selectivity, and greater stability than that of some other transition-metal based catalysts. The interface of the two-dimensional (2D) BN with the metal nanoparticles plays a strong role both in guiding the nucleation and growth of the catalytically active ultrasmall Ni nanoclusters, and further in stabilizing these nanoscale Ni catalysts against poisoning by interactions with the BN substrate. We provide detailed spectroscopy characterizations and density functional theory (DFT) calculations to reveal the origin of the high productivity, high selectivity, and high durability exhibited with the Ni/BN nanocatalyst and elucidate its correlation with nanocluster size and support-nanocluster interactions. This study provides insight into the role that the support material can have both regarding the size control of nanoclusters through immobilization during the nanocluster formation and also during the active catalytic process; this twofold set of insights is significant in advancing the understanding the bottom-up design of high-performance, durable catalytic systems for various catalysis needs.

Supercompliant and Soft (CH_{3}NH_{3})_{3}Bi_{2}I_{9} Crystal with Ultralow Thermal Conductivity.

In this Letter, we show the phonon dispersion of (CH_{3}NH_{3})_{3}Bi_{2}I_{9} single crystals at 300 K measured by inelastic x-ray scattering. The frequencies of acoustic phonons are among the lowest of crystals. Nanoindentation measurements verified that these crystals are very compliant and considerably soft. The frequency overlap between acoustic and optical phonons results in strong acoustic-optical scattering. All these features lead to an ultralow thermal conductivity. The fundamental knowledge obtained from this study will accelerate the design of novel hybrid materials for energy applications.

Nanoparticle-Infused UHMWPE Layer as Multifunctional Coating for High-Performance PPTA Single Fibers.

High-performance fibers made of poly-(p-phenylene terephthalamide) (PPTA) with high stiffness and high strength are widely used in body armor for protection due to their high degree of molecular chain alignment along the fiber direction. However, their poor mechanical properties in the transverse direction and low surface friction are undesirable for applications requiring resistance to ballistic impact. Here we provide a simple yet effective surface engineering strategy to improve both the transverse mechanical properties and the tribological property by coating PPTA fibers with ultra-high molecular weight polyethylene (UHMWPE) embedded with silica nanoparticles. The coated-PPTA fiber shows remarkable enhancement in transverse mechanical properties including ~127% increase of Young's modulus, which is attributed to both the alignment of UHMWPE chains in the transverse direction and the embeded ceramic nanoparticles. Meanwhile, the surface friction of the coated fiber increases twofold as a result of the ceramic nanoparticles. In addition, the coated fibers exhibit an enhanced chemical resistance to external harsh environment. The improved transverse mechanical properties, surface frictional characteristics, and chemical resistance demonstrate that coating with UHMWPE and ceramic nanoparticles can be used as an effective approach to enhance the performance of PPTA and other high-performance polymer fibers for body armor applications.

Ubiquitous energy conversion of two-dimensional molecular crystals.

Two-dimensional (2D) atomic crystals have triggered significant excitement due to their rich physics as well as potential industrial applications. The possibility of a molecular counterpart with scalable processability and superior performance is intriguing from both fundamental and applied perspectives. Here, we present the freestanding 2D molecular charge-transfer bis(ethylenedithio)tetrathiafulvalene-C60 crystals prepared by a modified Langmuir-Blodgett method, with precisely controlled few-layer thickness and centimeter-scale lateral dimension. The interconversion of intrinsic excited process, the long-range ordering and anisotropic stacking arrangement of the molecular layered crystals generate external stimuli responsive behaviors and anisotropic spin-charge conversion with magnetic energy conversion ability, as well as a superior UV photosensitivity. Moreover, the 2D freestanding crystals demonstrate superior magneto-electrical properties. These results suggest that a new class of 2D atomically thin molecular crystals with novel electronic, optical and magnetic properties have great potential for spintronic, energy and sensor applications.

Self-Assembled Metal Molecular Networks by Nanoconfinement.

Quasi-two-dimensional (2D) metal molecular networks (MMNs) often exhibit a nanoconfinement effect and high degree of anisotropy, which are highly diverse in their mechanical, electronic, and magnetic functionalities. Here we report an interfacial self-assembly of mechanically robust 2D MMNs, in which 3d transition metals are interconnected via molecular thiol bridges. The Langmuir-Schäfer assembled freestanding 2D nanosheets exhibit highly desired anisotropic charge transport and spin susceptibility, in which light and magnetic field induced charge transfer regulates the electronic interactions. Meanwhile, the mechanistic studies involving electronic structure reveal the molecular metal packing structure-controlled nanoconfinement and charge transfer. This study opens the door to 2D ultrathin metal coordination nanostructures for emerging functional materials and devices.

Freestanding Organic Charge-Transfer Conformal Electronics.

Wearable conformal electronics are essential components for next-generation humanlike sensing devices that can accurately respond to external stimuli in nonplanar and dynamic surfaces. However, to explore this potential, it is indispensable to achieve the desired level of deformability and charge-transport mobility in strain-accommodating soft semiconductors. Here, we show pseudo-two-dimensional freestanding conjugated polymer heterojunction nanosheets integrated into substrate-free conformal electronics owing to their exceptional crystalline controlled charge transport and high level of mechanical strength. These freestanding and mechanical robust polymer nanosheets can be adapted into a variety of artificial structured surfaces such as fibers, squares, circles, etc., which produce large-area stretchable conformal charge-transfer sensors for real-time static and dynamic monitoring.

Kirigami-Inspired Nanoconfined Polymer Conducting Nanosheets with 2000% Stretchability.

Stretchable conductors are essential components of wearable electronics. However, such materials typically sacrifice their electronic conductivity to achieve mechanical stretchability and elasticity. Here, the nanoconfinement and air/water interfacial assembly is explored to grow freestanding mechanical endurance conducting polymer nanosheets that can be stretched up to 2000% with simultaneously high electrical conductivity, inspired by kirigami. Such stretchable conductors show remarkable electronic and mechanical reversibility and reproducibility under more than 1000 cycle durability tests with 2000% deformability, which can be accurately predicted using finite element modeling. The conductivity of nanoconfined freestanding conductor nanosheets increases by three orders of magnitude from 2.2 × 10-3 to 4.002 S cm-1 is shown, due to the charge-transfer complex formation between polymer chain and halogen, while the electrical conductance of the stretchable kirigami nanosheets can be maintained over the entire strain regime. The nanoconfined polymer nanosheets can also act as a sensor capable of sensing the pressure with high durability and real-time monitoring.

Mechanically Strong Polymer Sheets from Aligned Ultrahigh-Molecular-Weight Polyethylene Nanocomposites.

Ultrahigh-molecular-weight polyethylene (UHMWPE) is of great interest as a next-generation body armor material because of its superior mechanical properties. However, such unique properties depend critically on its microscopic structure characteristics, including the degree of crystallinity, chain alignment, and morphology. Here, we present a highly aligned UHMWPE and its composite sheets containing uniformly dispersed boron nitride (BN) nanosheets. The dispersion of BN nanosheets into the UHMWPE matrix increases its mechanical properties over a broad temperature range. Experiments and simulation confirm that the alignment of chain segments in the composite matrix increases with temperature, leading to an improvement in mechanical properties at high temperature. Together with the large thermal conductivity of UHMWPE and BN, our findings serve to expand the application spectrum of highly aligned polymer nanocomposite materials for ballistic panels and body armor over a broad range of temperatures.

Light-induced dilation in nanosheets of charge-transfer complexes.

We report the observation of a sizable photostrictive effect of 5.7% with fast, submillisecond response times, arising from a light-induced lattice dilation of a molecular nanosheet, composed of the molecular charge-transfer compound dibenzotetrathiafulvalene (DBTTF) and C60 An interfacial self-assembly approach is introduced for the thickness-controlled growth of the thin films. From photoabsorption measurements, molecular simulations, and electronic structure calculations, we suggest that photostriction within these films arises from a transformation in the molecular structure of constituent molecules upon photoinduced charge transfer, as well as the accommodation of free charge carriers within the material. Additionally, we find that the photostrictive properties of the nanosheets are thickness-dependent, a phenomenon that we suggest arises from surface-induced conformational disorder in the molecular components of the film. Moreover, because of the molecular structure in the films, which results largely from interactions between the constituent π-systems and the sulfur atoms of DBTTF, the optoelectronic properties are found to be anisotropic. This work enables the fabrication of 2D molecular charge-transfer nanosheets with tunable thicknesses and properties, suitable for a wide range of applications in flexible electronic technologies.

Author Correction: Tunable two-dimensional interfacial coupling in molecular heterostructures.

We regretfully omitted to give credit to a previous figure upon which the surface-tension scheme in Fig. 1b is based. The caption to Fig. 1 should have included the following: "The surface-tension scheme in Fig. 1b is adapted from Fig. 1a in Noh, J., Jeong, S. & Lee, J.-Y. Ultrafast formation of air-processable and high-quality polymer films on an aqueous substrate. Nat. Commun. 7, 12374 (2016)."

Chiral Molecular Ferroelectrics with Polarized Optical Effect and Electroresistive Switching.

Multifunctional properties of chiral molecules arise from the coexistence of mirror-symmetry-induced stereoisomers and optical rotation characteristics in one material. One of these complex phenomena in these molecules is chiral ferroelectricity, providing the coupling between polarized light and the spatial asymmetry induced dipole moment. Herein we describe the chiral polarization and electroresistance in molecular ferroelectric (R)-(-)-3-hydroxyquinuclidinium chloride thin films with a Curie temperature of 340 K. The high transmittance of chiral ferroelectrics is coupled with polarized light for a linear electro-optic effect, which exhibits angle-dependent optical behaviors. The polarization-controlled conductance imposes a large on/off ratio (∼26.6) of electroresistive switching in molecular ferroelectrics with superior antifatigue endurance.

Tunable electroresistance and electro-optic effects of transparent molecular ferroelectrics.

Recent progress in molecular ferroelectrics (MOFEs) has been overshadowed by the lack of high-quality thin films for device integration. We report a water-based air-processable technique to prepare large-area MOFE thin films, controlled by supersaturation growth at the liquid-air interface under a temperature gradient and external water partial pressure. We used this technique to fabricate ImClO4 thin films and found a large, tunable room temperature electroresistance: a 20-fold resistance variation upon polarization switching. The as-grown films are transparent and consist of a bamboo-like structure of (2,[Formula: see text],0) and (1,0,[Formula: see text]) structural variants of R3m symmetry with a reversible polarization of 6.7 µC/cm2. The resulting ferroelectric domain structure leads to a reversible electromechanical response of d33 = 38.8 pm/V. Polarization switching results in a change of the refractive index, n, of single domains, [Formula: see text]. The remarkable combination of these characteristics renders MOFEs a prime candidate material for new nanoelectronic devices. The information that we present in this work will open a new area of MOFE thin-film technologies.

Tunable two-dimensional interfacial coupling in molecular heterostructures.

Two-dimensional van der Waals heterostructures are of considerable interest for the next generation nanoelectronics because of their unique interlayer coupling and optoelectronic properties. Here, we report a modified Langmuir-Blodgett method to organize two-dimensional molecular charge transfer crystals into arbitrarily and vertically stacked heterostructures, consisting of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF)/C60 and poly(3-dodecylthiophene-2,5-diyl) (P3DDT)/C60 nanosheets. A strong and anisotropic interfacial coupling between the charge transfer pairs is demonstrated. The van der Waals heterostructures exhibit pressure dependent sensitivity with a high piezoresistance coefficient of -4.4 × 10-6 Pa-1, and conductance and capacitance tunable by external stimuli (ferroelectric field and magnetic field). Density functional theory calculations confirm charge transfer between the n-orbitals of the S atoms in BEDT-TTF of the BEDT-TTF/C60 layer and the π* orbitals of C atoms in C60 of the P3DDT/C60 layer contribute to the inter-complex CT. The two-dimensional molecular van der Waals heterostructures with tunable optical-electronic-magnetic coupling properties are promising for flexible electronic applications.Two-dimensional van der Waals heterostructures are of interest due to their unique interlayer coupling and optoelectronic properties. Here authors develop a Langmuir-Blodgett method to organize charge transfer molecular heterostructures with externally tunable conductance and capacitance and broadband photoresponse.

Metal-Cluster-Based Colloidal Excimer Superstructures.

Luminescent network: Colloidal excimer superstructures with unique optical and electronic properties have recently been described. Ground-state gold cluster cores were held together by the hydrogen-bonding network formed by their capping ligands, which enabled excimer formation.

Colloidal preparation and electrocatalytic hydrogen production of MoS2 and WS2 nanosheets with controllable lateral sizes and layer numbers.

Although layered transition metal dichalcogenide (TMD) nanosheets have attracted great attention due to their unique properties, it still remains challenge to develop a facile strategy for the precise control of the lateral sizes and layer numbers of TMD nanosheets. In this study, we demonstrate a solution-phase synthetic protocol to prepare colloidal MS2 (M = Mo, W) nanosheets which possess extremely small lateral dimensions from 15 to 40 nm and well-controlled odd numbers of layers, such as 1, 3, and 5 layers, as characterized by transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. The size- and layer-dependence of the optical properties of colloidal MS2 (M = Mo, W) nanosheets are revealed by Raman and absorption spectra for the first time. These colloidal nanosheets, especially the single-layer ones, possess a large number of edge sites that serve as active sites for the hydrogen evolution reaction (HER). The catalysts exhibit a small HER overpotential and low Tafel slope of approximately 100 mV and 52 mV per decade for MoS2, and 80 mV and 46 mV per decade for WS2, respectively. Importantly, these products show enhanced stability after 500 potential cycles, and the current density remains almost unchanged during the test.

Plasmonic nanohalo optical probes for highly sensitive imaging of survivin mRNA in living cells.

A strategy is designed for sensitive detection of tumor biomarker survivin mRNA based on resonance Rayleigh scattering of a single AuNP nanohalo probe that couples large gold nanoparticles (L-AuNPs, 52 nm) with small AuNPs (S-AuNPs, 18 nm) through the affinity interaction between streptavidin and biotin. This core-satellite plasmon ruler is further applied to imaging survivin mRNA in living cells.

Hybrid Chalcopyrite-Polymer Magnetoconducting Materials.

The search for emerging materials combining magnetic and semiconducting properties has attracted widespread interest in contemporary materials science. Chalcopyrite (CuFeS2), as an earth abundant and nontoxic chalcogenide compound in the I-III-VI2 family, is a promising class of such materials that exhibit unusual electrical, optical, and magnetic properties. However, its successful implementation largely depends on our ability to understand, control and manipulate their structural, transport and spin behavior. Here we show that solution processing monodispersed CuFeS2 quantum dots exhibit a strong coupling among optical, electronic, and magnetic degrees of freedom. The photoresponse and magnetoconductance of CuFeS2 quantum dots are realized under external stimuli. We further exploit a fast and efficient way to achieve an exceptionally large performance in a magneto-optoelectronic hybrid system consisting of magnetic semiconducting CuFeS2 and conducting polymer matrix. The results demonstrate a promising potential of magnetic semiconductor CuFeS2 in the field of spin electronics.

Bandgap- and Radial-Position-Dependent Mn-Doped Zn-Cu-In-S/ZnS Core/Shell Nanocrystals.

This paper presents a mechanistic study on the doping of Zn-Cu-In-S/ZnS core/shell quantum dots (QDs) with Mn by changing the Zn-Cu-In-S QD bandgap and dopant position inside the samples (Zn-Cu-In-S core and ZnS shell). Results show that for the Mn:Zn-Cu-In-S/ZnS system, a Mn-doped emission can be obtained when the bandgap value of the QDs is larger than the energy of Mn-doped emission. Conversely, a bandgap emission is only observed for the doped system when the bandgap value of QDs is smaller than the energy gap of the Mn-doped emission. In the Zn-Cu-In-S/Mn:ZnS systems, doped QDs show dual emissions, consisting of bandgap and Mn dopant emissions, instead of one emission band when the value of the host bandgap is larger than the energy of the Mn-doped emission. These findings indicate that the emission from Mn-doped Zn-Cu-In-S/ZnS core/shell QDs depends on the bandgap of the QDs and the dopant position inside the core/shell material. The critical bandgap of the host materials is estimated to have the same value as the energy of the Mn d-d transition. Subsequently, the mechanism of photoluminescence properties of the Mn:Zn-Cu-In-S/ZnS and Zn-Cu-In-S/Mn:ZnS core/shell QD systems is proposed. Control experiments are then carried out by preparing Mn-doped Zn(Cu)-In-S QDs with various bandgaps, and the results confirm the reliability of the suggested mechanism. Therefore, the proposed mechanism can aid the design and synthesis of novel host materials in fabricating doped QDs.

Dual-Wavelength Electrochemiluminescence Ratiometry Based on Resonance Energy Transfer between Au Nanoparticles Functionalized g-C3N4 Nanosheet and Ru(bpy)3(2+) for microRNA Detection.

Here, a dual-wavelength ratiometric electrochemiluminescence (ECL) approach is reported based on resonance energy transfer (RET) from graphite-like carbon nitride nanosheet (g-C3N4 NS) to Ru(bpy)3(2+) for sensitive detection of microRNA (miRNA). In this approach, Au nanoparticles (Au NPs) functionalized g-C3N4 NS nanohybrid (Au-g-C3N4 NH) coated on glassy carbon electrode (GCE) could exhibit strong and stable ECL emissions with emission peak centered at 460 nm. The ECL emission at such wavelength matched well with the absorption peak of Ru(bpy)3(2+) as well as impeccably stimulating the emission of Ru(bpy)3(2+) at the wavelength of 620 nm, producing ECL-RET with high efficiency. Thus, based on the ECL signals quenching at 460 nm and increasing at 620 nm, a dual-wavelength ratiometric ECL-RET system was achieved. This system was then utilized for determination of target miRNA. With the attachment of thiol-modified molecular beacon on Au-g-C3N4 NH, target miRNA hybridized with the molecular beacon to form a DNA-RNA duplex. The obtained DNA-RNA duplex could be cleaved by duplex-specific nuclease to release target miRNA which would take part in the next cycle for further hybridization. Finally, the introducing of Ru(bpy)3(2+) was through the probe DNA-Ru(bpy)3(2+) complementary with the rest single-strand DNA on electrode. By measuring the ratio of ECL(460 nm)/ECL(620 nm), we could accurately quantify the concentration of miRNA-21 in a wide range from 1.0 fM to 1.0 nM. This work provides an important reference for the study of dual-wavelength ECL ratiometry and also exhibits potential capability in the detection of nucleic acids.