Probing the Interaction between Individual Metal Nanocrystals and Two-Dimensional Metal Oxides via Electron Energy Loss Spectroscopy.

Metal nanoparticles can photosensitize two-dimensional metal oxides, facilitating their electrical connection to devices and enhancing their abilities in catalysis and sensing. In this study, we investigated how individual silver nanoparticles interact with two-dimensional tin oxide and antimony-doped indium oxide using electron energy loss spectroscopy (EELS). The measurement of the spectral line width of the longitudinal plasmon resonance of the nanoparticles in absence and presence of 2D materials allowed us to quantify the contribution of chemical interface damping to the line width. Our analysis reveals that a stronger interaction (damping) occurs with 2D antimony-doped indium oxide due to its highly homogeneous surface. The results of this study offer new insight into the interaction between metal nanoparticles and 2D materials.

Passivating Graphene and Suppressing Interfacial Phonon Scattering with Mechanically Transferred Large-Area Ga2O3.

We demonstrate a large-area passivation layer for graphene by mechanical transfer of ultrathin amorphous Ga2O3 synthesized on liquid Ga metal. A comparison of temperature-dependent electrical measurements of millimeter-scale passivated and bare graphene on SiO2/Si indicates that the passivated graphene maintains its high field effect mobility desirable for applications. Surprisingly, the temperature-dependent resistivity is reduced in passivated graphene over a range of temperatures below 220 K, due to the interplay of screening of the surface optical phonon modes of the SiO2 by high-dielectric-constant Ga2O3 and the relatively high characteristic phonon frequencies of Ga2O3. Raman spectroscopy and electrical measurements indicate that Ga2O3 passivation also protects graphene from further processing such as plasma-enhanced atomic layer deposition of Al2O3.

Wafer-Sized Ultrathin Gallium and Indium Nitride Nanosheets through the Ammonolysis of Liquid Metal Derived Oxides.

We report the synthesis of centimeter sized ultrathin GaN and InN. The synthesis relies on the ammonolysis of liquid metal derived two-dimensional (2D) oxide sheets that were squeeze-transferred onto desired substrates. Wurtzite GaN nanosheets featured typical thicknesses of 1.3 nm, an optical bandgap of 3.5 eV and a carrier mobility of 21.5 cm2 V-1 s-1, while the InN featured a thickness of 2.0 nm. The deposited nanosheets were highly crystalline, grew along the (001) direction and featured a thickness of only three unit cells. The method provides a scalable approach for the integration of 2D morphologies of industrially important semiconductors into emerging electronics and optical devices.

Surface chemistry altering electronic behaviour of liquid metal-derived tin oxide nanosheets.

Possessing excellent electronic properties and high chemical stability, semiconducting n-type two-dimensional (2D) tin dioxide (SnO2) nanosheets have been featured in sensing and electrocatalysis applications recently. Derived from non-layered crystal structures, 2D SnO2 has abundant unsaturated dangling bonds existing at the surface, providing interfacial activity. How the surface chemistry alters the electronic properties of 2D SnO2 nanomaterials remains unexplored. In this study, we synthesised ultra-thin 2D SnO2 nanosheets using a liquid metal (LM) touch printing technique and investigated experimentally and theoretically how the interactions of organic solvents composed of alkyl and hydroxyl groups with the surface of LM-derived 2D SnO2 modulate the electronic properties. It was found that alkane solvents can physically absorb onto the SnO2 surface with no impact on the material conductivity. Alcohol-based solvents on the other hand interact with the SnO2 surface via chemical absorptions primarily, in which oxygen atoms of hydroxyl groups in the alcohols form bonds with the surface atoms of SnO2. The binding stability is determined by the length and configuration of the hydrocarbon chain in alcohols. As representative long-chain alcohols, 1-octanol and 1-pentanol attach onto the SnO2 surface strongly, lowering the binding energy of Sn4+ and reducing the electron transfer ability of SnO2 nanosheets. Consequently, the electronic properties, i.e. conductivity and electronic mobility of SnO2 nanosheet-based electronic devices are decreased significantly.

Optically Tunable Electrical Oscillations in Oxide-Based Memristors for Neuromorphic Computing.

The application of hardware-based neural networks can be enhanced by integrating sensory neurons and synapses that enable direct input from external stimuli. This work reports direct optical control of an oscillatory neuron based on volatile threshold switching in V3O5. The devices exhibit electroforming-free operation with switching parameters that can be tuned by optical illumination. Using temperature-dependent electrical measurements, conductive atomic force microscopy (C-AFM), in situ thermal imaging, and lumped element modelling, it is shown that the changes in switching parameters, including threshold and hold voltages, arise from overall conductivity increase of the oxide film due to the contribution of both photoconductive and bolometric characteristics of V3O5, which eventually affects the oscillation dynamics. Furthermore, V3O5 is identified as a new bolometric material with a temperature coefficient of resistance (TCR) as high as -4.6% K-1 at 423 K. The utility of these devices is illustrated by demonstrating in-sensor reservoir computing with reduced computational effort and an optical encoding layer for spiking neural network (SNN), respectively, using a simulated array of devices.

Gas sensors based on the oxide skin of liquid indium.

Various non-stratified two-dimensional (2D) materials can be obtained from liquid metal surfaces that are not naturally accessible. Homogenous nucleation on atomically flat interfaces of liquid metals with air produces unprecedented high-quality oxide layers that can be transferred onto desired substrates. The atomically flat and large areas provide large surface-to-volume ratios ideal for sensing applications. Versatile crucial applications of the liquid metal-derived 2D oxides have been realized; however, their gas-sensing properties remain largely underexplored. The cubic In2O3 structure, which is nonlayered, can be formed as an ultrathin layer on the surface of liquid indium during the self-limiting Cabrera-Mott oxidation process in the air. The morphology, crystal structure, and band structure of the harvested 2D In2O3 nanosheets from liquid indium are characterized. Sensing capability toward several gases, both inorganic and organic, entailing NO2, O2, NH3, H2, H2S, CO, and Methyl ethyl ketone (MEK) are explored. A high ohmic resistance change of 1974% at 10 ppm, fast response, and recovery times are observed for NO2 at an optimum temperature of 200 °C. The sensing fundamentals are investigated for NO2, and its performances and cross-selectivity to different gases are analyzed. The NO2 sensing response from room temperature to 300 °C has been measured and discussed, and stability after 24 hours of continuous operation is presented. The results demonstrate liquid metal-derived 2D oxides as promising materials for gas sensing applications.

Large Area Ultrathin InN and Tin Doped InN Nanosheets Featuring 2D Electron Gases.

Indium nitride (InN) has been of significant interest for creating and studying two-dimensional electron gases (2DEG). Herein we demonstrate the formation of 2DEGs in ultrathin doped and undoped 2D InN nanosheets featuring high carrier mobilities at room temperature. The synthesis is carried out via a two-step liquid metal-based printing method followed by a microwave plasma-enhanced nitridation reaction. Ultrathin InN nanosheets with a thickness of ∼2 ± 0.2 nm were isolated over large areas with lateral dimensions exceeding centimeter scale. Room temperature Hall effect measurements reveal carrier mobilities of ∼216 and ∼148 cm2 V-1 s-1 for undoped and doped InN, respectively. Further analysis suggests the presence of defined quantized states in these ultrathin nitride nanosheets that can be attributed to a 2D electron gas forming due to strong out-of-plane confinement. Overall, the combination of electronic and plasmonic features in undoped and doped ultrathin 2D InN holds promise for creating advanced optoelectronic devices and functional 2D heterostructures.

An exploration into two-dimensional metal oxides, and other 2D materials, synthesised via liquid metal printing and transfer techniques.

Two-dimensional (2D) metal oxides can be difficult to synthesise, and scaling up production using traditional methods is challenging. However, a new liquid metal-based technique, that utilises both "top-down" and "bottom-up" processes, has recently been introduced. These liquids oxidise to form an oxide surface "skin" which may be exfoliated as a 2D flake and subsequently used in various electronic devices and chemical reactions.

High-k 2D Sb2O3 Made Using a Substrate-Independent and Low-Temperature Liquid-Metal-Based Process.

High dielectric constant (high-k) ultrathin films are required as insulating gate materials. The well-known high-k dielectrics, including HfO2, ZrO2, and SrTiO3, feature three-dimensional lattice structures and are thus not easily obtained in the form of distinct ultrathin sheets. Therefore, their deposition as ultrathin layers still imposes challenges for electronic industries. Consequently, new high-k nanomaterials with k in the range of 40 to 100 and a band gap exceeding 4 eV are highly sought after. Antimony oxide nanosheets appear as a potential candidate that could fulfill these characteristics. Here, we report on the stoichiometric cubic polymorph of 2D antimony oxide (Sb2O3) as an ideal high-k dielectric sheet that can be synthesized via a low-temperature, substrate-independent, and silicon-industry-compatible liquid metal synthesis technique. A bismuth-antimony alloy was produced during the growth process. Preferential oxidation caused the surface of the melt to be dominated by α-Sb2O3. This ultrathin α-Sb2O3 was then deposited onto desired surfaces via a liquid metal print transfer. A tunable sheet thickness between ∼1.5 and ∼3 nm was achieved, while the lateral dimensions were within the millimeter range. The obtained α-Sb2O3 exhibited high crystallinity and a wide band gap of ∼4.4 eV. The relative permittivity assessment revealed a maximum k of 84, while a breakdown electric field of ∼10 MV/cm was observed. The isolated 2D α-Sb2O3 nanosheets were utilized in top-gated field-effect transistors that featured low leakage currents, highlighting that the obtained material is a promising gate oxide for conventional and van der Waals heterostructure-based electronics.

Printable Single-Unit-Cell-Thick Transparent Zinc-Doped Indium Oxides with Efficient Electron Transport Properties.

Ultrathin transparent conductive oxides (TCOs) are emerging candidates for next-generation transparent electronics. Indium oxide (In2O3) incorporated with post-transition-metal ions (e.g., Sn) has been widely studied due to their excellent optical transparency and electrical conductivity. However, their electron transport properties are deteriorated at the ultrathin two-dimensional (2D) morphology compared to that of intrinsic In2O3. Here, we explore the domain of transition-metal dopants in ultrathin In2O3 with the thicknesses down to the single-unit-cell limit, which is realized in a large area using a low-temperature liquid metal printing technique. Zn dopant is selected as a representative to incorporate into the In2O3 rhombohedral crystal framework, which results in the gradual transition of the host to quasimetallic. While the optical transmittance is maintained above 98%, an electron field-effect mobility of up to 87 cm2 V-1 s-1 and a considerable sub-kΩ-1 cm-1 ranged electrical conductivity are achieved when the Zn doping level is optimized, which are in a combination significantly improved compared to those of reported ultrathin TCOs. This work presents various opportunities for developing high-performance flexible transparent electronics based on emerging ultrathin TCO candidates.

Ultrathin Ga2 O3 Glass: A Large-Scale Passivation and Protection Material for Monolayer WS2.

Atomically thin transition metal dichalcogenide crystals (TMDCs) have extraordinary optical properties that make them attractive for future optoelectronic applications. Integration of TMDCs into practical all-dielectric heterostructures hinges on the ability to passivate and protect them against necessary fabrication steps on large scales. Despite its limited scalability, encapsulation of TMDCs in hexagonal boron nitride (hBN) currently has no viable alternative for achieving high performance of the final device. Here, it is shown that the novel, ultrathin Ga2 O3 glass is an ideal centimeter-scale coating material that enhances optical performance of the monolayers and protects them against further material deposition. In particular, Ga2 O3 capping of monolayer WS2 outperforms commercial-grade hBN in both scalability and optical performance at room temperature. These properties make Ga2 O3 highly suitable for large-scale passivation and protection of monolayer TMDCs in functional heterostructures.

Antibacterial Liquid Metals: Biofilm Treatment via Magnetic Activation.

Antibiotic resistance has made the treatment of biofilm-related infections challenging. As such, the quest for next-generation antimicrobial technologies must focus on targeted therapies to which pathogenic bacteria cannot develop resistance. Stimuli-responsive therapies represent an alternative technological focus due to their capability of delivering targeted treatment. This study provides a proof-of-concept investigation into the use of magneto-responsive gallium-based liquid metal (LM) droplets as antibacterial materials, which can physically damage, disintegrate, and kill pathogens within a mature biofilm. Once exposed to a low-intensity rotating magnetic field, the LM droplets become physically actuated and transform their shape, developing sharp edges. When placed in contact with a bacterial biofilm, the movement of the particles resulting from the magnetic field, coupled with the presence of nanosharp edges, physically ruptures the bacterial cells and the dense biofilm matrix is broken down. The antibacterial efficacy of the magnetically activated LM particles was assessed against both Gram-positive and Gram-negative bacterial biofilms. After 90 min over 99% of both bacterial species became nonviable, and the destruction of the biofilms was observed. These results will impact the design of next-generation, LM-based biofilm treatments.

Broad-spectrum treatment of bacterial biofilms using magneto-responsive liquid metal particles.

The formation and proliferation of bacterial biofilms on surfaces, particularly those on biomedical devices, is a significant issue that results in substantial economic losses, presenting severe health risks to patients. Furthermore, heterogeneous biofilms consisting of different bacterial species can induce the increase in pathogenicity, and the resistance to antimicrobial agents due to the synergistic interactions between the different species. Heterogeneous bacterial biofilms are notoriously difficult to treat due to the presence of extracellular polymeric substances (EPS) and, in conjunction with the rapid rise of multi-drug resistant pathogens, this means that new solutions for anti-biofilm treatment are required. In this study, we investigate the application of magneto-responsive gallium-based liquid metal (GLM-Fe) nanomaterials against a broad range of Gram-positive and Gram-negative bacterial mono-species and multi-species biofilms. The GLM-Fe particles exhibit a magneto-responsive characteristic, causing spherical particles to undergo a shape transformation to high-aspect-ratio nanoparticles with sharp asperities in the presence of a rotating magnetic field. These shape-transformed particles are capable of physically removing bacterial biofilms and rupturing individual cells. Following treatment, both mono-species and multi-species biofilms demonstrated significant reductions in their biomass and overall cell viability, demonstrating the broad-spectrum application of this antibacterial technology. Furthermore, the loss of integrity of the bacterial cell wall and membranes was visualized using a range of microscopy techniques, and the leakage of intracellular components (such as nucleic acids and protein) was observed. Insights gained from this study will impact the design of future liquid metal-based biofilm treatments, particularly those that rely on magneto-responsive properties.

Atomically thin TiO2 nanosheets synthesized using liquid metal chemistry.

The library of true two-dimensional materials is limited since many transition metal compounds are not stratified and can thus not be easily isolated as nanosheets. Here, micron-sized ultrathin rutile TiO2 nanosheets featuring uniform thickness (2 ± 0.5 nm) with dielectric constant (ε⊥ = 24) have been synthesized via a liquid metal synthesis strategy.

Exciton-Driven Chemical Sensors Based on Excitation-Dependent Photoluminescent Two-Dimensional SnS.

Excitation wavelength-dependent photoluminescence (PL) in two-dimensional (2D) transition-metal chalcogenides enables a strong excitonic interaction for high-performance chemical and biological sensing applications. In this work, we explore the possible candidates in the domain of post-transition-metal chalcogenides. Few-layered 2D p-type tin monosulfide (SnS) nanoflakes with submicrometer lateral dimensions are synthesized from the liquid phase exfoliation of bulk crystals. Excitation wavelength-dependent PL is found, and the excitonic radiative lifetime is more than one order enhanced compared to that of the bulk counterpart because of the quantum confinement effect. Paramagnetic NO2 gas is selected as a representative to investigate the exciton-driven chemical-sensing properties of 2D SnS. Physisorption of NO2 results in the formation of dipoles on the surface of 2D SnS, causing the redistribution of photoexcited charges in the body and therefore modifying PL properties. For practical sensing applications, 2D SnS is integrated into a resistive transducing platform. Under light irradiation, the sensor exhibits excellent sensitivity and selectivity to NO2 at a relatively low operating temperature of 60 °C. The limit of detection is 17 parts per billion (ppb), which is significantly improved over other previously reported 2D p-type semiconductor-based NO2 sensors.

Exfoliation Behavior of van der Waals Strings: Case Study of Bi2S3.

The family of crystals constituting covalently bound strings, held together by van der Waals forces, can be exfoliated into smaller entities, similar to crystals made of van der Waals sheets. Depending on the anisotropy of such crystals, as well as the spacing between their strings in each direction, van der Waals sheets or ribbons can be obtained after the exfoliation process. In this work, we demonstrate that ultrathin nanoribbons of bismuth sulfide (Bi2S3) can be synthesized via a high-power sonication process. The thickness and width of these ribbons are governed by the van der Waals spacings around the strings within the parent crystal. The lengths of the nanoribbons are initially limited by the dimensions of the starting bulk particles. Interestingly, these nanoribbons change stoichiometry and composition and are elongated when the duration of agitation increases because of Ostwald ripening. An application of the exfoliated van der Waals strings is presented for optical biosensing using photoluminescence of Bi2S3 nanoribbons, reaching detection limits of less than 10 nM L-1 in response to bovine serum albumin. The concept of exfoliating van der Waals strings could be extended to a large class of crystals for creating bodies ranging from sheets to strings, with optoelectronic properties different from that of their bulk counterparts.

Bi2O3 monolayers from elemental liquid bismuth.

Atomically thin, semiconducting transition and post transition metal oxides are emerging as a promising category of materials for high-performance oxide optoelectronic applications. However, the wafer-scale synthesis of crystalline atomically thin samples has been a challenge, particularly for oxides that do not present layered crystal structures. Herein we use a facile, scalable method to synthesise ultrathin bismuth oxide nanosheets using a liquid metal facilitated synthesis approach. Monolayers of α-Bi2O3 featuring sub-nanometre thickness, high crystallinity and large lateral dimensions could be isolated from the liquid bismuth surface. The nanosheets were found to be n-type semiconductors with a direct band gap of ∼3.5 eV and were suited for developing ultra violet (UV) photodetectors. The developed devices featured a high responsivity of ∼400 AW-1 when illuminated with 365 nm UV light and fast response times of ∼70 µs. The developed methods and obtained nanosheets can likely be developed further towards the synthesis of other bismuth based atomically thin chalcogenides that hold promise for electronic, optical and catalytic applications.

Printing two-dimensional gallium phosphate out of liquid metal.

Two-dimensional piezotronics will benefit from the emergence of new crystals featuring high piezoelectric coefficients. Gallium phosphate (GaPO4) is an archetypal piezoelectric material, which does not naturally crystallise in a stratified structure and hence cannot be exfoliated using conventional methods. Here, we report a low-temperature liquid metal-based two-dimensional printing and synthesis strategy to achieve this goal. We exfoliate and surface print the interfacial oxide layer of liquid gallium, followed by a vapour phase reaction. The method offers access to large-area, wide bandgap two-dimensional (2D) GaPO4 nanosheets of unit cell thickness, while featuring lateral dimensions reaching centimetres. The unit cell thick nanosheets present a large effective out-of-plane piezoelectric coefficient of 7.5 ± 0.8 pm V-1. The developed printing process is also suitable for the synthesis of free standing GaPO4 nanosheets. The low temperature synthesis method is compatible with a variety of electronic device fabrication procedures, providing a route for the development of future 2D piezoelectric materials.

A liquid metal reaction environment for the room-temperature synthesis of atomically thin metal oxides.

Two-dimensional (2D) oxides have a wide variety of applications in electronics and other technologies. However, many oxides are not easy to synthesize as 2D materials through conventional methods. We used nontoxic eutectic gallium-based alloys as a reaction solvent and co-alloyed desired metals into the melt. On the basis of thermodynamic considerations, we predicted the composition of the self-limiting interfacial oxide. We isolated the surface oxide as a 2D layer, either on substrates or in suspension. This enabled us to produce extremely thin subnanometer layers of HfO2, Al2O3, and Gd2O3 The liquid metal-based reaction route can be used to create 2D materials that were previously inaccessible with preexisting methods. The work introduces room-temperature liquid metals as a reaction environment for the synthesis of oxide nanomaterials with low dimensionality.