Near Room Temperature Production of Segregated Network Composites of Carbon Nanotubes and Regolith as Multifunctional, Extra-Terrestrial Building Materials.

Constructing a semi-permanent base on the moon or Mars will require maximal use of materials found in situ and minimization of materials and equipment transported from Earth. This will mean a heavy reliance on regolith (Lunar or Marian soil) and water, supplemented by small quantities of additives fabricated on Earth. Here it is shown that SiO2-based powders, as well as Lunar and Martian regolith simulants, can be fabricated into building materials at near-ambient temperatures using only a few weight-percent of carbon nanotubes as a binder. These composites have compressive strength and toughness up to 100 MPa and 3 MPa respectively, higher than the best terrestrial concretes. They are electrically conductive (>20 S m-1) and display an extremely large piezoresistive response (gauge factor >600), allowing these composites to be used as internal sensors to monitor the structural health of extra-terrestrial buildings.

Highly Conductive Networks of Silver Nanosheets.

Although printed networks of semiconducting nanosheets have found success in a range of applications, conductive nanosheet networks are limited by low conductivities (<106 S m-1 ). Here, dispersions of silver nanosheets (AgNS) that can be printed into highly conductive networks are described. Using a commercial thermal inkjet printer, AgNS patterns with unannealed conductivities of up to (6.0 ± 1.1) × 106  S m-1 are printed. These networks can form electromagnetic interference shields with record shielding effectiveness of >60 dB in the microwave region at thicknesses <200 nm. High resolution patterns with line widths down to 10 µm are also printed using an aerosol-jet printer which, when annealed at 200 °C, display conductivity >107  S m-1 . Unlike conventional Ag-nanoparticle inks, the 2D geometry of AgNS yields smooth, short-free interfaces between electrode and active layer when used as the top electrode in vertical nanosheet heterostructures. This shows that all-printed vertical heterostructures of AgNS/WS2 /AgNS, where the top electrode is a mesh grid, function as photodetectors demonstrating that such structures can be used in optoelectronic applications that usually require transparent conductors.

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.

Printable G-Putty for Frequency- and Rate-Independent, High-Performance Strain Sensors.

While nanocomposite electromechanical sensors are expected to display reasonable conductivity and high sensitivity, little consideration is given to eliminating hysteresis and strain rate/frequency dependence from their response. For example, while G-putty, a composite of graphene and polysiloxane, has very high electromechanical sensitivity, its extreme viscoelasticity renders it completely unsuitable for real sensors due to hysteretic and rate-/frequency-dependent effects. Here it is shown that G-putty can be converted to an ink and printed into patterned thin films on elastic substrates. A partial graphene-polymer phase segregation during printing increases the thin-film conductivity by ×106 compared to bulk, while the mechanical effects of the substrate largely suppress hysteresis and completely remove strain rate and frequency dependence. This allows the fabrication of practical, high-gauge-factor, wearable sensors for pulse measurements as well as patterned sensors for low-signal vibration sensing.

Mechanical Properties of Conducting Printed Nanosheet Network Thin Films Under Uniaxial Compression.

Thin film networks of solution processed nanosheets show remarkable promise for use in a broad range of applications including strain sensors, energy storage, printed devices, textile electronics, and more. While it is known that their electronic properties rely heavily on their morphology, little is known of their mechanical nature, a glaring omission given the effect mechanical deformation has on the morphology of porous systems and the promise of mechanical post processing for tailored properties. Here, this work employs a recent advance in thin film mechanical testing called the Layer Compression Test to perform the first in situ analysis of printed nanosheet network compression. Due to the well-defined deformation geometry of this unique test, this work is able to explore the out-of-plane elastic, plastic, and creep deformation in these systems, extracting properties of elastic modulus, plastic yield, viscoelasticity, tensile failure and sheet bending vs. slippage under both out of plane uniaxial compression and tension. This work characterizes these for a range of networks of differing porosities and sheet sizes, for low and high compression, as well as the effect of chemical cross linking. This work explores graphene and MoS2 networks, from which the results can be extended to printed nanosheet networks as a whole.

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.

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.

Transparent Conductors Printed from Grids of Highly Conductive Silver Nanosheets.

Transparent conductors (TCs) represent key components in many applications from optoelectronic devices to electromagnetic shielding. While commercial applications typically use thin films of indium tin oxide, this material is brittle and increasingly scarce, meaning higher performing and cheaper alternatives are sought after. Solution-processible metals would be ideal owing to their high conductivities and printability. However, due to their opacity to visible light, such films need to be very thin to achieve transparency, thus limiting the minimum resistance achievable. One solution is to print metallic particles in a grid structure, which has the advantages of high tunable transparency and resistance at the cost of uniformity. Here, we report silver nanosheets that have been aerosol jet printed into grids as high-performance transparent conductors. We first investigate the effect of annealing on the silver nanosheets where we observe the onset of junction sintering at 160 °C after which the silver network becomes continuous. We then investigate the effect of line width and thickness on the electrical performance and the effect of varying the aperture dimensions on the optical performance. Using these data, we develop simple models, which allow us to optimize the grid and demonstrate a printed transparent conductor with a transmittance of 91% at a sheet resistance of 4.6 Ω/sq.

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.

Quantifying the Piezoresistive Mechanism in High-Performance Printed Graphene Strain Sensors.

Printed strain sensors will be important in applications such as wearable devices, which monitor breathing and heart function. Such sensors need to combine high sensitivity and low resistance with other factors such as cyclability, low hysteresis, and minimal frequency/strain-rate dependence. Although nanocomposite sensors can display a high gauge factor (G), they often perform poorly in the other areas. Recently, evidence has been growing that printed, polymer-free networks of nanoparticles, such as graphene nanosheets, display very good all-round sensing performance, although the details of the sensing mechanism are poorly understood. Here, we perform a detailed characterization of the thickness dependence of piezoresistive sensors based on printed networks of graphene nanosheets. We find both conductivity and gauge factor to display percolative behavior at low network thickness but bulk-like behavior for networks above ∼100 nm thick. We use percolation theory to derive an equation for gauge factor as a function of network thickness, which well-describes the observed thickness dependence, including the divergence in gauge factor as the percolation threshold is approached. Our analysis shows that the dominant contributor to the sensor performance is not the effect of strain on internanosheet junctions but the strain-induced modification of the network structure. Finally, we find these networks display excellent cyclability, hysteresis, and frequency/strain-rate dependence as well as gauge factors as high as 350.

Solution processed, vertically stacked hetero-structured diodes based on liquid-exfoliated WS2 nanosheets: from electrode-limited to bulk-limited behavior.

Vertically stacked metal-semiconductor-metal heterostructures, based on liquid-processed nanomaterials, hold great potential for various printed electronic applications. Here we describe the fabrication of such devices by spray-coating semiconducting tungsten disulfide (WS2) nanosheets onto indium tin oxide (ITO) bottom electrodes, followed by spraying single-walled carbon nanotubes (SWNTs) as the top electrode. Depending on the formulation of the SWNTs ink, we could fabricate either Ohmic or Schottky contacts at the WS2/SWNTs interface. Using isopropanol-dispersed SWNTs led to Ohmic contacts and bulk-limited devices, characterized by out-of-plane conductivities of ∼10-4 S m-1. However, when aqueous SWNTs inks were used, rectification was observed, due to the formation of a doping-induced Schottky barrier at the WS2/SWNTs interface. For thin WS2 layers, such devices were characterized by a barrier height of ∼0.56 eV. However, increasing the WS2 film thickness led to increased series resistance, leading to a change-over from electrode-limited to bulk-limited behavior at a transition thickness of ∼2.6 µm. This work demonstrates that Ohmic/Schottky behavior is tunable and lays the foundation for fabricating large-area 2D nanosheet-based solution-deposited devices and stacks.

Negative Gauge Factor Piezoresistive Composites Based on Polymers Filled with MoS2 Nanosheets.

Nanocomposite strain sensors, particularly those consisting of polymer-graphene composites, are increasingly common and are of great interest in the area of wearable sensors. In such sensors, application of strain yields an increase in resistance due to the effect of deformation on interparticle junctions. Typically, widening of interparticle separation is thought to increase the junction resistance by reducing the probability of tunnelling between conducting particles. However, an alternative approach would be to use piezoresistive fillers, where an applied strain modifies the intrinsic filler resistance and so the overall composite resistance. Such an approach would broaden sensing capabilities, as using negative piezoresistive fillers could yield strain-induced resistance reductions rather than the usual resistance increases. Here, we introduce nanocomposites based on polyethylene oxide (PEO) filled with MoS2 nanosheets. Doping of the MoS2 by the PEO yields nanocomposites which are conductive enough to act as sensors, while efficient stress transfer leads to nanosheet deformation in response to an external strain. The intrinsic negative piezoresistance of the MoS2 leads to a reduction of the composite resistance on the application of small tensile strains. However, at higher strain the resistance grows due to increases in junction resistance. MoS2-PEO composite gauge factors are approximately -25 but fall to -12 for WS2-PEO composites and roughly -2 for PEO filled with MoSe2 or WSe2. We develop a simple model, which describes all these observations. Finally, we show that these composites can be used as dynamic strain sensors.

Non-resonant light scattering in dispersions of 2D nanosheets.

Extinction spectra of nanomaterial suspensions can be dominated by light scattering, hampering quantitative spectral analysis. No simple models exist for the wavelength-dependence of the scattering coefficients in suspensions of arbitrary-sized, high-aspect-ratio nanoparticles. Here, suspensions of BN, talc, GaS, Ni(OH)2, Mg(OH)2 and Cu(OH)2 nanosheets are used to explore non-resonant scattering in wide-bandgap 2D nanomaterials. Using an integrating sphere, scattering coefficient (σ) spectra were measured for a number of size-selected fractions for each nanosheet type. Generally, σ scales as a power-law with wavelength in the non-resonant regime: σ(λ)∝[λ/〈L〉]-m, where 〈L〉 is the mean nanosheet length. For all materials, the scattering exponent, m, forms a master-curve, transitioning from m = 4 to m = 2, as the characteristic nanosheet area increases, indicating a transition from Rayleigh to van der Hulst scattering. In addition, once material density and refractive index are factored out, the proportionality constant relating σ to [λ/〈L〉]-m, also forms a master-curve when plotted versus 〈L〉.