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Abstract Transition metal dichalcogenides (TMDs) have garnered attention as potential catalysts for water splitting owing to their unique structures, diverse electronic properties, and composition from earth‐abundant elements. While certain TMD catalysts, notably MoS2, have shown promising activity for hydrogen evolution reactions (HER), achieving performance comparable to traditional platinum catalysts remains a challenge. While significant effort has been invested into understanding the effect of TMD's structural properties, such as defectiveness and crystalline phases, recent work has emphasized the role of extrinsic factors on HER. This review summarizes the current understanding of the impact of commonly overlooked electrocatalytic effects that exhibit an enhanced importance in TMD‐based HER. By combining recent advances in theoretical modeling and experimental work, we review the dominating effects of extrinsic factors including electronic resistance, interfacial barriers, surface roughness, oxidation, and valence impurities. Our work aims to provide insights into optimizing TMDs as highly efficient catalysts for HER, facilitating future advancements in hydrogen generation technology.

The advancement of future electronic devices necessitates dielectric materials with enhanced compositional complexity and improved capabilities. We here demonstrate a gas-phase alloying approach that yields ultrathin and crystalline dielectrics with attractive properties for the integration into electronics. A surface-selective deposition process was shown to produce sulfur (S) and selenium (Se) alloys with large-scale uniformity. Through combination of experimental diffraction analysis and materials modeling, we establish the crystallinity of the alloy with a modified lattice structure compared to the host materials. The resulting lattice arrangement endows the alloy dielectric with high ionic mobility as validated by electrochemical impedance spectroscopy. Leveraging this innovative feature, we fabricate memristive devices exhibiting promising performance characteristics. Our findings demonstrate the feasibility of utilizing gas-phase alloying to engineer dielectrics with superior properties and functionality for future device integration.

Abstract 2D materials have shown great promise for novel electronic functionality. A common challenge for 2D materials‐based transistors is forming a high‐performance gate terminal due to the challenges of depositing a dielectric of sufficient quality and controllable thickness. Herein the van‐der‐Waals integration of a free‐standing Al2O3 dielectric membrane is demonstrated as a facile, scalable, and powerful gate dielectric. A process is developed that permits the wet transfer of an amorphous alumina layer with a finely adjustable equivalent oxide thickness (EOT) in the single nanometer range. Electrical characterization demonstrates the high breakdown field and low leakage of the dielectric and integration into 2D materials transistors reveals a high performance. The wafer‐scale uniformity of the dielectric membrane permits the formation of large‐scale flexible devices that exhibit good robustness and long‐term stability.

Two-dimensional (2D) materials promise advances in electronic devices beyond Moore’s scaling law through extended functionality, such as non-monotonic dependence of device parameters on input parameters. However, the robustness and performance of effects like negative differential resistance (NDR) and anti-ambipolar behavior have been limited in scale and robustness by relying on atomic defects and complex heterojunctions. In this paper, we introduce a novel device concept that utilizes the quantum capacitance of junctions between 2D materials and molecular layers. We realized a variable capacitance 2D molecular junction (vc2Dmj) diode through the scalable integration of graphene and single layers of stearic acid. The vc2Dmj exhibits NDR with a substantial peak-to-valley ratio even at room temperature and an active negative resistance region. The origin of this unique behavior was identified through thermoelectric measurements and ab initio calculations to be a hybridization effect between graphene and the molecular layer. The enhancement of device parameters through morphology optimization highlights the potential of our approach toward new functionalities that advance the landscape of future electronics.

Abstract The integration of 2D materials into future applications relies on advances in their quality and production. We here report a synthesis method that achieves ultrahigh optoelectronic performance at unprecedented fabrication scales. A mediator-assisted chemical vapor deposition process yields tungsten-disulfide (WS2) with near-unity photoluminescence quantum yield, superior photosensitivity and improved environmental stability. This enhancement is due to the decrease in the density of lattice defects and charge traps brought about by the self-regulating nature of the growth process. This robustness in the presence of precursor variability enables the high-throughput growth in atomically confined stacks and achieves uniform synthesis of single-layer WS2 on dozens of closely packed wafers. Our approach enhances the scientific and commercial potential of 2D materials as demonstrated in producing large-scale arrays of record-breaking optoelectronic devices.

Ferroelectric ordering of water has been at the heart of intense debates due to its importance in enhancing our understanding of the condensed matter. Here, the authors observe ferroelectric properties of water ice in a two dimensional phase under confinement between two graphene layers.

Abstract We here present a planarized solid-state chemical reaction that can produce transition metal monochalcogenide (TMMC) 2D crystals with large lateral extent and finely controllable thickness down to individual layers. The enhanced lateral diffusion of a gaseous reactant at the interface between a solid precursor and graphene was found to provide a universal route towards layered TMMCs of different compositions. A unique layer-by-layer growth mechanism yields atomically abrupt crystal interfaces and kinetically controllable thickness down to a single TMMC layer. Our approach stabilizes 2D crystals with commonly unattainable thermodynamic phases, such as β-Cu2S and γ-CuSe, and spectroscopic characterization reveals ultra-large phase transition depression and interesting electronic properties. The presented ability to produce large-scale 2D crystals with high environmental stability was applied to highly sensitive and fast optoelectronic sensors. Our approach extends the morphological, compositional, and thermodynamic complexity of 2D materials.

Abstract Despite significant progress in the fabrication and application of semiconductor materials for optical emitters and sensors, few materials can cover the cyan-gap between 450 and 500 nm. We here introduce a robust and facile method to deposit amorphous Sb2S3 films with a bandgap of 2.8 eV. By exploiting the tunable functionality of graphene, a two-dimensional material, efficient deposition from a chemical was achieved. Ozone-generated defects in the graphene were shown to be required to enhance the morphology and quality of the material and comprehensive characterization of the seed layer and the Sb2S3 film were applied to design an optimal deposition process. The resulting material exhibits efficient carrier transport and high photodetector performance as evidenced by unprecedented responsivity and detectivity in semiconductor/graphene/glass vertical heterostructures. (112 A/W, 2.01 × 1012 Jones, respectively).

Pyrochlore titanate (Y2Ti2O7) is a promising material for a wide range of applications in optoelectronics and photocatalysis due to its advantageous chemical, mechanical, and optical properties. To enhance its potential for such uses, however, a high-quality and scalable synthesis method is required. We here investigate the crystallization of sol–gel produced Y2Ti2O7 layers. We observe a transition of the amorphous pyrochlore phase at annealing temperatures below 700 °C. The transmittances of the Y2Ti2O7 thin layers annealed at 400 to 700 °C are approximately 92.3%. The refractive indices and packing densities of Y2Ti2O7 thin layers annealed at 400–700 °C/1 h vary from 1.931 to 1.954 and 0.835 to 0.846, respectively. The optical bandgap energies of Y2Ti2O7 thin layers annealed at 400–700 °C/1 h reduce from 4.356 to 4.319 eV because of the Moss–Burstein effect. These good electronic and optical properties make Y2Ti2O7 thin layers a promising host material for many potential applications.

Abstract Graphene’s attractiveness in many applications is limited by its high resistance. Extrinsic doping has shown promise to overcome this challenge but graphene’s performance remains below industry requirements. This issue is caused by a limited charge transfer efficiency (CTE) between dopant and graphene. Using AuCl3 as a model system, we measure CTE as low as 5% of the expected values due to the geometrical capacitance of small adsorbate clusters. We here demonstrate a strategy for enhancing the CTE by a two-step optimization of graphene’s surface energy prior to AuCl3 doping. First, exposure to UV ozone modified the hydrophilicity of graphene and was found to decrease the cluster’s geometric capacitance, which had a direct effect on the CTE. Occurrence of lattice defects at high UV exposure, however, deteriorated graphene’s transport characteristics and limited the effectiveness of this pretreatment step. Thus, prior to UV exposure, a functionalized polymer layer was introduced that could further enhance graphene’s surface energy while protecting it from damage. Combination of these treatment steps were found to increase the AuCl3 charge transfer efficiency to 70% and lower the sheet resistance to 106 Ω/γ at 97% transmittance which represents the highest reported performance for doped single layer graphene and is on par with commercially available transparent conductors.

Lateral tunnel junctions are fundamental building blocks for molecular electronics and novel sensors, but current fabrication approaches achieve device yields below 10%, which limits their appeal for circuit integration and large-scale application. We here demonstrate a new approach to reliably form nanometer-sized gaps between electrodes with high precision and unprecedented control. This advance in nanogap production is enabled by the unique properties of 2D materials-based contacts. The large difference in reactivity of 2D materials’ edges compared to their basal plane results in a sequential removal of atoms from the contact perimeter. The resulting trimming of exposed graphene edges in a remote hydrogen plasma proceeds at speeds of less than 1 nm per minute, permitting accurate control of the nanogap dimension through the etching process. Carrier transport measurements reveal the high quality of the nanogap, thus-produced tunnel junctions with a 97% yield rate, which represents a tenfold increase in productivity compared to previous reports. Moreover, 70% of tunnel junctions fall within a nanogap range of only 0.5 nm, representing an unprecedented uniformity in dimension. The presented edge-trimming approach enables the conformal narrowing of gaps and produces novel one-dimensional nano-trench geometries that can sustain larger tunneling currents than conventional 0D nano-junctions. Finally, the potential of our approach for future electronics was demonstrated by the realization of an atom-based memory.

The development of graphene structures with controlled edges is greatly desired for understanding heterogeneous electrochemical (EC) transfer and boosting EC applications of graphene-based electrodes. We herein report a facile, scalable, and robust method to produce graphene mesh (GM) electrodes with tailorable edge lengths. Specifically, the GMs were fabricated at 850 °C under a vacuum level of 0.6 Pa using catalytic nickel templates obtained based on a crack lithography. As the edge lengths of the GM electrodes increased from 5.48 to 24.04 m, their electron transfer rates linearly increased from 0.08 to 0.16 cm∙s−1, which are considerably greater than that (0.056 ± 0.007 cm∙s−1) of basal graphene structures (defined as zero edge length electrodes). To illustrate the EC sensing potentiality of the GM, a high-sensitivity glucose detection was conducted on the graphene/Ni hybrid mesh with the longest edge length. At a detection potential of 0.6 V, the edge-rich graphene/Ni hybrid mesh sensor exhibited a wide linear response range from 10.0 μM to 2.5 mM with a limit of detection of 1.8 μM and a high sensitivity of 1118.9 μA∙mM−1∙cm−2. Our findings suggest that edge-rich GMs can be valuable platforms in various graphene applications such as graphene-based EC sensors with controlled and improved performance.

The success of van-der-Waals electronics, which combine large-scale-deposition capabilities with high device performance, relies on the efficient production of suitable 2D materials. Shear exfoliation of 2D materials’ flakes from bulk sources can generate 2D materials with low amounts of defects, but the production yield has been limited below industry requirements. Here, we introduce additive-assisted exfoliation (AAE) as an approach to significantly increase the efficiency of shear exfoliation and produce an exfoliation yield of 30%. By introducing micrometer-sized particles that do not exfoliate, the gap between rotor and stator was dynamically reduced to increase the achievable shear rate. This enhancement was applied to WS2 and MoS2 production, which represent two of the most promising 2D transition-metal dichalcogenides. Spectroscopic characterization and cascade centrifugation reveal a consistent and significant increase in 2D material concentrations across all thickness ranges. Thus, the produced WS2 films exhibit high thickness uniformity in the nanometer-scale and can open up new routes for 2D materials production towards future applications.

Characterizations of photoresponse of a graphene oxide (GO) thin film to a near infrared laser light were studied. Results showed the photocurrent in the GO thin film was cathodic, always flowing in an opposite direction to the initial current generated by the preset bias voltage that shows a fundamental discrepancy from the photocurrent in the reduced graphene oxide thin film. Light illumination on the GO thin film thus results in more free electrons that offset the initial current. By examining GO thin films reduced at different temperatures, the critical temperature for reversing the photocurrent from cathodic to anodic was found around 187°C. The dynamic photoresponse for the GO thin film was further characterized through the response time constants within the laser on and off durations, denoted as τon and τoff, respectively. τon for the GO thin film was comparable to the other carbon-based thin films such as carbon nanotubes and graphenes. τoff was, however, much larger than that of the other's. This discrepancy was attributable to the retardation of exciton recombination rate thanks to the existing oxygen functional groups and defects in the GO thin films.