Understanding how junction resistances impact the conduction mechanism in nano-networks.

Networks of nanowires, nanotubes, and nanosheets are important for many applications in printed electronics. However, the network conductivity and mobility are usually limited by the resistance between the particles, often referred to as the junction resistance. Minimising the junction resistance has proven to be challenging, partly because it is difficult to measure. Here, we develop a simple model for electrical conduction in networks of 1D or 2D nanomaterials that allows us to extract junction and nanoparticle resistances from particle-size-dependent DC network resistivity data. We find junction resistances in porous networks to scale with nanoparticle resistivity and vary from 5 Ω for silver nanosheets to 24 GΩ for WS2 nanosheets. Moreover, our model allows junction and nanoparticle resistances to be obtained simultaneously from AC impedance spectra of semiconducting nanosheet networks. Through our model, we use the impedance data to directly link the high mobility of aligned networks of electrochemically exfoliated MoS2 nanosheets (≈ 7 cm2 V-1 s-1) to low junction resistances of ∼2.3 MΩ. Temperature-dependent impedance measurements also allow us to comprehensively investigate transport mechanisms within the network and quantitatively differentiate intra-nanosheet phonon-limited bandlike transport from inter-nanosheet hopping.

Long lived photogenerated charge carriers in few-layer transition metal dichalcogenides obtained from liquid phase exfoliation.

Semiconducting transition metal dichalcogenides are important optoelectronic materials thanks to their intense light-matter interaction and wide selection of fabrication techniques, with potential applications in light harvesting and sensing. Crucially, these applications depend on the lifetimes and recombination dynamics of photogenerated charge carriers, which have primarily been studied in monolayers obtained from labour-intensive mechanical exfoliation or costly chemical vapour deposition. On the other hand, liquid phase exfoliation presents a high throughput and cost-effective method to produce dispersions of mono- and few-layer nanosheets. This approach allows for easy scalability and enables the subsequent processing and formation of macroscopic films directly from the liquid phase. Here, we use transient absorption spectroscopy and spatiotemporally resolved pump-probe microscopy to study the charge carrier dynamics in tiled nanosheet films of MoS2 and WS2 deposited from the liquid phase using an adaptation of the Langmuir-Schaefer technique. We find an efficient photogeneration of charge carriers with lifetimes of several nanoseconds, which we ascribe to stabilisation at nanosheet edges. These findings provide scope for photocatalytic and photodetector applications, where long-lived charge carriers are crucial, and suggest design strategies for photovoltaic devices.

Quantitative analysis of printed nanostructured networks using high-resolution 3D FIB-SEM nanotomography.

Networks of solution-processed nanomaterials are becoming increasingly important across applications in electronics, sensing and energy storage/generation. Although the physical properties of these devices are often completely dominated by network morphology, the network structure itself remains difficult to interrogate. Here, we utilise focused ion beam - scanning electron microscopy nanotomography (FIB-SEM-NT) to quantitatively characterise the morphology of printed nanostructured networks and their devices using nanometre-resolution 3D images. The influence of nanosheet/nanowire size on network structure in printed films of graphene, WS2 and silver nanosheets (AgNSs), as well as networks of silver nanowires (AgNWs), is investigated. We present a comprehensive toolkit to extract morphological characteristics including network porosity, tortuosity, specific surface area, pore dimensions and nanosheet orientation, which we link to network resistivity. By extending this technique to interrogate the structure and interfaces within printed vertical heterostacks, we demonstrate the potential of this technique for device characterisation and optimisation.

Solution-Processed Heterojunction Photodiodes Based on WSe2 Nanosheet Networks.

Solution-processed photodetectors incorporating liquid-phase-exfoliated transition metal dichalcogenide nanosheets are widely reported. However, previous studies mainly focus on the fabrication of photoconductors, rather than photodiodes which tend to be based on heterojunctions and are harder to fabricate. Especially, there are rare reports on introducing commonly used transport layers into heterojunctions based on nanosheet networks. In this study, a reliable solution-processing method is reported to fabricate heterojunction diodes with tungsten selenide (WSe2 ) nanosheets as the optical absorbing material and PEDOT: PSS and ZnO as injection/transport-layer materials. By varying the transport layer combinations, the obtained heterojunctions show rectification ratios of up to ≈104 at ±1 V in the dark, without relying on heavily doped silicon substrates. Upon illumination, the heterojunction can be operated in both photoconductor and photodiode modes and displays self-powered behaviors at zero bias.

Sonication-assisted liquid phase exfoliation of two-dimensional CrTe3 under inert conditions.

Liquid phase exfoliation (LPE) has been used for the successful fabrication of nanosheets from a large number of van der Waals materials. While this allows to study fundamental changes of material properties' associated with reduced dimensions, it also changes the chemistry of many materials due to a significant increase of the effective surface area, often accompanied with enhanced reactivity and accelerated oxidation. To prevent material decomposition, LPE and processing in inert atmosphere have been developed, which enables the preparation of pristine nanomaterials, and to systematically study compositional changes over time for different storage conditions. Here, we demonstrate the inert exfoliation of the oxidation-sensitive van der Waals crystal, CrTe3. The pristine nanomaterial was purified and size-selected by centrifugation, nanosheet dimensions in the fractions quantified by atomic force microscopy and studied by Raman, X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDX) and photo spectroscopic measurements. We find a dependence of the relative intensities of the CrTe3 Raman modes on the propagation direction of the incident light, which prevents a correlation of the Raman spectral profile to the nanosheet dimensions. XPS and EDX reveal that the contribution of surface oxides to the spectra is reduced after exfoliation compared to the bulk material. Further, the decomposition mechanism of the nanosheets was studied by time-dependent extinction measurements after water titration experiments to initially dry solvents, which suggest that water plays a significant role in the material decomposition.

Solution-Processed NiPS3 Thin Films from Liquid Exfoliated Inks with Long-Lived Spin-Entangled Excitons.

Antiferromagnets are promising materials for future opto-spintronic applications since they show spin dynamics in the THz range and no net magnetization. Recently, layered van der Waals (vdW) antiferromagnets have been reported, which combine low-dimensional excitonic properties with complex spin-structure. While various methods for the fabrication of vdW 2D crystals exist, formation of large area and continuous thin films is challenging because of either limited scalability, synthetic complexity, or low opto-spintronic quality of the final material. Here, we fabricate centimeter-scale thin films of the van der Waals 2D antiferromagnetic material NiPS3, which we prepare using a crystal ink made from liquid phase exfoliation (LPE). We perform statistical atomic force microscopy (AFM) and scanning electron microscopy (SEM) to characterize and control the lateral size and number of layers through this ink-based fabrication. Using ultrafast optical spectroscopy at cryogenic temperatures, we resolve the dynamics of photoexcited excitons. We find antiferromagnetic spin arrangement and spin-entangled Zhang-Rice multiplet excitons with lifetimes in the nanosecond range, as well as ultranarrow emission line widths, despite the disordered nature of our films. Thus, our findings demonstrate scalable thin-film fabrication of high-quality NiPS3, which is crucial for translating this 2D antiferromagnetic material into spintronic and nanoscale memory devices and further exploring its complex spin-light coupled states.

High-Mobility Flexible Transistors with Low-Temperature Solution-Processed Tungsten Dichalcogenides.

The investigation of high-mobility two-dimensional (2D) flakes beyond molybdenum disulfide (MoS2) will be necessary to create a library of high-mobility solution-processed networks that conform to substrates and remain functional over thousands of bending cycles. Here we report electrochemical exfoliation of large-aspect-ratio (>100) semiconducting flakes of tungsten diselenide (WSe2) and tungsten disulfide (WS2) as well as MoS2 as a comparison. We use Langmuir-Schaefer coating to achieve highly aligned and conformal flake networks, with minimal mesoporosity (∼2-5%), at low processing temperatures (120 °C) and without acid treatments. This allows us to fabricate electrochemical transistors in ambient air, achieving average mobilities of µMoS2 ≈ 11 cm2 V-1 s-1, µWS2 ≈ 9 cm2 V-1 s-1, and µWSe2 ≈ 2 cm2 V-1 s-1 with a current on/off ratios of Ion/Ioff ≈ 2.6 × 103, 3.4 × 103, and 4.2 × 104 for MoS2, WS2, and WSe2, respectively. Moreover, our transistors display threshold voltages near ∼0.4 V with subthreshold slopes as low as 182 mV/dec, which are essential factors in maintaining power efficiency and represent a 1 order of magnitude improvement in the state of the art. Furthermore, the performance of our WSe2 transistors is maintained on polyethylene terephthalate (PET) even after 1000 bending cycles at 1% strain.

Comparative study of sonication-assisted liquid phase exfoliation of six layered coordination polymers.

Sonication-assisted liquid phase exfoliation was applied to six different layered coordination polymers (CPs) in aqueous surfactant solution. The resulting nanosheets were investigated for structural and compositional integrity and microscopic analysis gives insights into the relationship between the crystal structure of the materials and their exfoliability. Larger open pores seem to favour the production of nanosheets with higher aspect ratio of lateral size to thickness.

Liquid Processing of Interfacially Grown Iron-Oxide Flowers into 2D-Platelets Yields Lithium-Ion Battery Anodes with Capacities of Twice the Theoretical Value.

Iron oxide (Fe2 O3 ) is an abundant and potentially low-cost material for fabricating lithium-ion battery anodes. Here, the growth of α-Fe2 O3 nano-flowers at an electrified liquid-liquid interface is demonstrated. Sonication is used to convert these flowers into quasi-2D platelets with lateral sizes in the range of hundreds of nanometers and thicknesses in the range of tens of nanometers. These nanoplatelets can be combined with carbon nanotubes to form porous, conductive composites which can be used as electrodes in lithium-ion batteries. Using a standard activation process, these anodes display good cycling stability, reasonable rate performance and low-rate capacities approaching 1500 mAh g-1 , consistent with the current state-of-the-art for Fe2 O3 . However, by using an extended activation process, it is found that the morphology of these composites can be significantly changed, rendering the iron oxide amorphous and significantly increasing the porosity and internal surface area. These morphological changes yield anodes with very good cycling stability and low-rate capacity exceeding 2000 mAh g-1 , which is competitive with the best anode materials in the literature. However, the data implies that, after activation, the iron oxide displays a reduced solid-state lithium-ion diffusion coefficient resulting in somewhat degraded rate performance.

The Role of Additives in Suppressing the Degradation of Liquid-Exfoliated WS2 Monolayers.

Group VI transition metal dichalcogenides (TMDs) are considered to be chemically widely inert, but recent reports point toward an oxidation of monolayered sheets in ambient conditions, due to defects. To date, the degradation of monolayered TMDs is only studied on individual, substrate-supported nanosheets with varying defect type and concentration, strain, and in an inhomogeneous environment. Here, degradation kinetics of WS2 nanosheet ensembles in the liquid phase are investigated through photoluminescence measurements, which selectively probe the monolayers. Monolayer-enriched WS2 dispersions are produced with varying lateral sizes in the two common surfactant stabilizers sodium cholate (SC) and sodium dodecyl sulfate (SDS). Well-defined degradation kinetics are observed, which enable the determination of activation energies of the degradation and decouple photoinduced and thermal degradation. The thermal degradation is slower than the photoinduced degradation and requires higher activation energy. Using SC as surfactant, it is sufficiently suppressed. The photoinduced degradation can be widely prevented through chemical passivation achieved through the addition of cysteine which, on the one hand, coordinates to defects on the nanosheets and, on the other hand, stabilizes oxides on the surface, which shield the nanosheets from further degradation.

Synthesis and Exfoliation of a New Layered Mesoporous Zr-MOF Comprising Hexa- and Dodecanuclear Clusters as Well as a Small Organic Linker Molecule.

A new layered mesoporous Zr-MOF of composition [Zr30O20(OH)26(OAc)18L18] was synthesized by employing 5-acetamidoisophthalic acid (H2L) using acetic acid as the solvent. The new MOF, denoted as CAU-45, exhibits a honeycomb structure of stacked layers which comprise both hexa- and dodecanucelar zirconium clusters. Its structure was solved from submicrometer-sized crystals by continuous rotation electron diffraction (cRED). Liquid phase exfoliation and size selection were successfully performed on the material.

Luminogens for Aggregation-Induced Emission via Titanium-Mediated Double Nucleophilic Addition to 2,5-Dialkynylpyridines: Formation and Transformation of the Emitting Aggregates.

Invited for the cover of this issue are Lutz H. Gade, Claudia Backes, and co-workers at Heidelberg University. The image depicts 2-(1,2,2-triarylvinyl)-pyridines, which are luminogens for aggregation-induced emission which "light up" upon irradiation. Read the full text of the article at 10.1002/chem.201905611.

Luminogens for Aggregation-Induced Emission via Titanium-Mediated Double Nucleophilic Addition to 2,5-Dialkynylpyridines: Formation and Transformation of the Emitting Aggregates.

New luminogens for aggregation-induced emission (AIE), which are characterized by a branched cross-conjugated 2,6-bis(1,2,2-triarylvinyl)pyridine motif, have been synthesized exploiting the one-pot Ti-mediated tetraarylation of 2,6-bis(arylethynyl)pyridines. Thin layer solid-state emitters were prepared by spin-coating of the luminogens, while AIE-colloidal dispersions were investigated in terms of optical density and scattering behaviour. This has given insight into particle size distributions, time evolution of the aggregation and the influence of different functionalization patterns on the luminescence of molecular aggregates. In particular, a combination of extinction spectroscopy and dynamic light scattering is being proposed as a powerful method for investigating the dynamic aggregation process in AIE-type colloids.

Enriching and Quantifying Porous Single Layer 2D Polymers by Exfoliation of Chemically Modified van der Waals Crystals.

2D polymer sheets with six positively charged pyrylium groups at each pore edge in a stacked single crystal can be transformed into a 2D polymer with six pyridines per pore by exposure to gaseous ammonia. This reaction furnishes still a crystalline material with tunable protonation degree at regular nano-sized pores promising as separation membrane. The exfoliation is compared for both 2D polymers with the latter being superior. Its liquid phase exfoliation yields nanosheet dispersions, which can be size-selected using centrifugation cascades. Monolayer contents of ≈30 % are achieved with ≈130 nm sized sheets in mg quantities, corresponding to tens of trillions of monolayers. Quantification of nanosheet sizes, layer number and mass shows that this exfoliation is comparable to graphite. Thus, we expect that recent advances in exfoliation of graphite or inorganic crystals (e.g. scale-up, printing etc.) can be directly applied to this 2D polymer as well as to covalent organic frameworks.

Equipartition of Energy Defines the Size-Thickness Relationship in Liquid-Exfoliated Nanosheets.

Liquid phase exfoliation is a commonly used method to produce 2D nanosheets from a range of layered crystals. However, such nanosheets display broad size and thickness distributions and correlations between area and thickness, issues that limit nanosheet application potential. To understand the factors controlling the exfoliation process, we have liquid-exfoliated 11 different layered materials, size-selecting each into fractions before using AFM to measure the nanosheet length, width, and thickness distributions for each fraction. The resultant data show a clear power-law scaling of nanosheet area with thickness for each material. We have developed a simple nonequilibrium thermodynamics-based model predicting that the power-law prefactor is proportional to both the ratios of in-plane-tearing/out-of-plane-peeling energies and in-plane/out-of-plane moduli. By comparing the experimental data with the modulus ratio calculated from first-principles, we find close agreement between experiment and theory. This supports our hypothesis that energy equipartition holds between nanosheet tearing and peeling during sonication-assisted exfoliation.

Enhancement of antibiotic-activity through complexation with metal ions - Combined ITC, NMR, enzymatic and biological studies.

Alternative solutions need to be developed to overcome the growing problem of multi-drug resistant bacteria. This study explored the possibility of creating complexes of antibiotics with metal ions, thereby increasing their activity. Analytical techniques such as isothermal titration calorimetry and nuclear magnetic resonance were used to examine the structure and interactions between Cu(II), Ag(I) or Zn(II) and ß-lactam antibiotics. The metal-ß-lactam complexes were also tested for antimicrobial activity, by micro-broth dilution and disk diffusion methods, showing a synergistic increase in the activity of the drugs, and enzymatic inhibition assays confirming inhibition of ß-lactamases responsible for resistance. The metal-antibiotic complex concept was proven to be successful with the activity of the drugs enhanced against ß-lactamase-producing bacteria. The highest synergistic effects were observed for complexes formed with Ag(I).