Two-Step Conversion of Metal and Metal Oxide Precursor Films to 2D Transition Metal Dichalcogenides and Heterostructures.

The widely studied class of two-dimensional (2D) materials known as transition metal dichalcogenides (TMDs) are now well-poised to be employed in real-world applications ranging from electronic logic and memory devices to gas and biological sensors. Several scalable thin film synthesis techniques have demonstrated nanoscale control of TMD material thickness, morphology, structure, and chemistry and correlated these properties with high-performing, application-specific device metrics. In this review, the particularly versatile two-step conversion (2SC) method of TMD film synthesis is highlighted. The 2SC technique relies on deposition of a solid metal or metal oxide precursor material, followed by a reaction with a chalcogen vapor at an elevated temperature, converting the precursor film to a crystalline TMD. Herein, the variables at each step of the 2SC process including the impact of the precursor film material and deposition technique, the influence of gas composition and temperature during conversion, as well as other factors controlling high-quality 2D TMD synthesis are considered. The specific advantages of the 2SC approach including deposition on diverse substrates, low-temperature processing, orientation control, and heterostructure synthesis, among others, are featured. Finally, emergent opportunities that take advantage of the 2SC approach are discussed to include next-generation electronics, sensing, and optoelectronic devices, as well as catalysis for energy-related applications.

Orientation and morphology control in acid-catalyzed covalent organic framework thin films.

As thin films of semiconducting covalent organic frameworks (COFs) are demonstrating utility for ambipolar electronics, channel materials in organic electrochemical transistors (OECTs), and broadband photodetectors, control and modulation of their thin film properties is paramount. In this work, an interfacial growth technique is utilized to synthesize imine TAPB-PDA COF films at both the liquid-liquid interface as well as at the liquid-solid interface on a Si/SiO2 substrate. The concentration of acetic acid catalyst in the aqueous phase is shown to significantly influence the thin film morphology of the liquid-solid growth, with concentrations below 1 M resulting in no film nucleation, concentrations of 1-4 M enabling smooth film formation, and concentrations greater than 4 M resulting in films with a higher density of particulates on the surface. Importantly, while the films grown at the liquid-liquid interface are mixed-orientation, those grown directly at the liquid-solid interface on the Si/SiO2 surface have highly oriented COF layers aligned parallel to the substrate surface. Moreover, this liquid-solid growth process affords TAPB-PDA COF thin films with p-type charge transport having a transconductance of 10 µS at a gate voltage of -0.9 V in an OECT device structure.

Probing Interlayer Interactions and Commensurate-Incommensurate Transition in Twisted Bilayer Graphene through Raman Spectroscopy.

Twisted 2D layered materials have garnered much attention recently as a class of 2D materials whose interlayer interactions and electronic properties are dictated by the relative rotation/twist angle between the adjacent layers. In this work, we explore a prototype of such a twisted 2D system, artificially stacked twisted bilayer graphene (TBLG), where we probe, using Raman spectroscopy, the changes in the interlayer interactions and electron-phonon scattering pathways as the twist angle is varied from 0° to 30°. The long-range Moiré potential of the superlattice gives rise to additional intravalley and intervalley scattering of the electrons in TBLG, which has been investigated through their Raman signatures. Density functional theory (DFT) calculations of the electronic band structure of the TBLG superlattices were found to be in agreement with the resonant Raman excitations across the van Hove singularities in the valence and conduction bands predicted for TBLG due to hybridization of bands from the two layers. We also observe that the relative rotation between the graphene layers has a marked influence on the second order overtone and combination Raman modes signaling a commensurate-incommensurate transition in TBLG as the twist angle increases. This serves as a convenient and rapid characterization tool to determine the degree of commensurability in TBLG systems.

A Researcher's Perspective on Unconventional Lab-to-Fab for 2D Semiconductor Devices.

Current silicon technology is on the verge of reaching its performance limits. This aspect, coupled with the global chip shortage, makes a solid case for steering our attention toward the accelerated commercialization of other electronic materials. Among the available suite of emerging electronic materials, two-dimensional materials, including transition metal dichalcogenides (TMDs), exhibit improved short-channel effects, high electron mobility, and integration into CMOS-compatible processing. While these materials may not be able to replace silicon at the current stages of development, they can supplement Si in the form of Si-compatible CMOS processing and be manufactured for tailored applications. However, the major hurdle in the path of commercialization of such materials is the difficulty in producing their wafer-scale forms, which are not necessarily single crystalline but on a large scale. Recent but exploratory interest in 2D materials from industries, such as TSMC, necessitates an in-depth analysis of their commercialization potential based on trends and progress in entrenched electronic materials (Si) and ones with a short-term commercialization potential (GaN, GaAs). We also explore the possibility of unconventional fabrication techniques, such as printing, for 2D materials becoming more mainstream and being adopted by industries in the future. In this Perspective, we discuss aspects to optimize cost, time, thermal budget, and a general pathway for 2D materials to achieve similar milestones, with an emphasis on TMDs. Beyond synthesis, we propose a lab-to-fab workflow based on recent advances that can operate on a low budget with a mainstream full-scale Si fabrication unit.

Vertical organic electrochemical transistors for complementary circuits.

Organic electrochemical transistors (OECTs) and OECT-based circuitry offer great potential in bioelectronics, wearable electronics and artificial neuromorphic electronics because of their exceptionally low driving voltages (<1 V), low power consumption (<1 µW), high transconductances (>10 mS) and biocompatibility1-5. However, the successful realization of critical complementary logic OECTs is currently limited by temporal and/or operational instability, slow redox processes and/or switching, incompatibility with high-density monolithic integration and inferior n-type OECT performance6-8. Here we demonstrate p- and n-type vertical OECTs with balanced and ultra-high performance by blending redox-active semiconducting polymers with a redox-inactive photocurable and/or photopatternable polymer to form an ion-permeable semiconducting channel, implemented in a simple, scalable vertical architecture that has a dense, impermeable top contact. Footprint current densities exceeding 1 kA cm-2 at less than ±0.7 V, transconductances of 0.2-0.4 S, short transient times of less than 1 ms and ultra-stable switching (>50,000 cycles) are achieved in, to our knowledge, the first vertically stacked complementary vertical OECT logic circuits. This architecture opens many possibilities for fundamental studies of organic semiconductor redox chemistry and physics in nanoscopically confined spaces, without macroscopic electrolyte contact, as well as wearable and implantable device applications.

Precision Modification of Monolayer Transition Metal Dichalcogenides via Environmental E-Beam Patterning.

Layered Transition Metal Dichalcogenides (TMDs) are an important class of materials that exhibit a wide variety of optoelectronic properties. The ability to spatially tailor their expansive property-space (e.g., conduction behavior, optical emission, surface interactions) is of special interest for applications including, but not limited to, sensing, bioelectronics, and spintronics/valleytronics. Current methods of property modulation focus on the modification of the basal surfaces and edge sites of the TMDs by the introduction of defects, functionalization with organic or inorganic moieties, alloying, heterostructure formation, and phase engineering. A majority of these methods lack the resolution for the development of next-generation nanoscale devices or are limited in the types of functionalities useful for efficient TMD property modification. In this study, we utilize electron-beam patterning on monolayer TMDs (MoSe2, WSe2 and MoS2) in the presence of a pressure-controlled atmosphere of water vapor within an environmental scanning electron microscope (ESEM). A series of parametric studies show local optical and electronic property modification depending on acceleration voltage, beam current, pressure, and electron dose. The ultimate pattern resolution achieved is 67 ± 9 nm. Raman and photoluminescence spectroscopies coupled with Kelvin Probe Force Microscopy reveal electron dose-dependent p-doping in the patterned regions, which we attribute to functionalization from the products of water vapor radiolysis (oxygen and hydroxyl groups). The modulation of the work function through patterning matches well with Density Functional Theory modeling. Finally, post-functionalization of the patterned areas with an organic fluorophore demonstrates a robust method to achieve nanoscale functionalization with high fidelity.

Quantum Materials Manufacturing.

The quantum age is just around the corner. As quantum systems become more stable, robust, and mainstream, tackling the challenge of high-throughput manufacturing will require further developments in materials synthesis, characterization, assembly, and diagnostics. As the building blocks of future technologies scale down to atomic and molecular scales, a paradigm shift in manufacturing will begin to take shape. Inspired by a quantum manufacturing world that elevates the Materials Genome Initiative to the next level, a "human-in-the-loop" framework for high-throughput manufacturing, which addresses key opportunities and challenges to be overcome, is outlined.

Exfoliation procedure-dependent optical properties of solution deposited MoS2 films.

The development of high-precision large-area optical coatings and devices comprising low-dimensional materials hinges on scalable solution-based manufacturability with control over exfoliation procedure-dependent effects. As such, it is critical to understand the influence of technique-induced transition metal dichalcogenide (TMDC) optical properties that impact the design, performance, and integration of advanced optical coatings and devices. Here, we examine the optical properties of semiconducting MoS2 films from the exfoliation formulations of four prominent approaches: solvent-mediated exfoliation, chemical exfoliation with phase reconversion, redox exfoliation, and native redox exfoliation. The resulting MoS2 films exhibit distinct refractive indices (n), extinction coefficients (k), dielectric functions (ε1 and ε2), and absorption coefficients (α). For example, a large index contrast of Δn ≈ 2.3 is observed. These exfoliation procedures and related chemistries produce different exfoliated flake dimensions, chemical impurities, carrier doping, and lattice strain that influence the resulting optical properties. First-principles calculations further confirm the impact of lattice defects and doping characteristics on MoS2 optical properties. Overall, incomplete phase reconfiguration (from 1T to mixed crystalline 2H and amorphous phases), lattice vacancies, intraflake strain, and Mo oxidation largely contribute to the observed differences in the reported MoS2 optical properties. These findings highlight the need for controlled technique-induced effects as well as the opportunity for continued development of, and improvement to, liquid phase exfoliation methodologies. Such chemical and processing-induced effects present compelling routes to engineer exfoliated TMDC optical properties toward the development of next-generation high-performance mirrors, narrow bandpass filters, and wavelength-tailored absorbers.

Graphene and Beyond: Recent Advances in Two-Dimensional Materials Synthesis, Properties, and Devices.

Since the isolation of graphene in 2004, two-dimensional (2D) materials research has rapidly evolved into an entire subdiscipline in the physical sciences with a wide range of emergent applications. The unique 2D structure offers an open canvas to tailor and functionalize 2D materials through layer number, defects, morphology, moiré pattern, strain, and other control knobs. Through this review, we aim to highlight the most recent discoveries in the following topics: theory-guided synthesis for enhanced control of 2D morphologies, quality, yield, as well as insights toward novel 2D materials; defect engineering to control and understand the role of various defects, including in situ and ex situ methods; and properties and applications that are related to moiré engineering, strain engineering, and artificial intelligence. Finally, we also provide our perspective on the challenges and opportunities in this fascinating field.

Microwave Facilitated Covalent Organic Framework/Transition Metal Dichalcogenide Heterostructures.

Organic/inorganic heterostructures present a versatile platform for creating materials with new functionalities and hybrid properties. In particular, junctions between two dimensional materials have demonstrated utility in next generation electronic, optical, and optoelectronic devices. This work pioneers a microwave facilitated synthesis process to readily incorporate few-layer covalent organic framework (COF) films onto monolayer transition metal dichalcogenides (TMDC). Preferential microwave excitation of the monolayer TMDC flakes result in selective attachment of COFs onto the van der Waals surface with film thicknesses between 1 and 4 nm. The flexible process is extended to multiple TMDCs (MoS2, MoSe2, MoSSe) and several well-known COFs (TAPA-PDA COF, TPT-TFA-COF, and COF-5). Photoluminescence studies reveal a power-dependent defect formation in the TMDC layer, which facilitates electronic coupling between the materials at higher TMDC defect densities. This coupling results in a shift in the A-exciton peak location of MoSe2, with a red or blue shift of 50 or 19 meV, respectively, depending upon the electron donating character of the few-layer COF films. Moreover, optoelectronic devices fabricated from the COF-5/TMDC heterostructure present an opportunity to tune the PL intensity and control the interaction dynamics within inorganic/organic heterostructures.

Piezoelectricity across 2D Phase Boundaries.

Piezoelectricity in low-dimensional materials and metal-semiconductor junctions has attracted recent attention. Herein, a 2D in-plane metal-semiconductor junction made of multilayer 2H and 1T' phases of molybdenum(IV) telluride (MoTe2 ) is investigated. Strong piezoelectric response is observed using piezoresponse force microscopy at the 2H-1T' junction, despite that the multilayers of each individual phase are weakly piezoelectric. The experimental results and density functional theory calculations suggest that the amplified piezoelectric response observed at the junction is due to the charge transfer across the semiconducting and metallic junctions resulting in the formation of dipoles and excess charge density, allowing the engineering of piezoelectric response in atomically thin materials.

Effective Optical Properties of Laterally Coalescing Monolayer MoS2.

Two-dimensional (2D) transition metal dichalcogenides (TMDCs) exhibit compelling dimension-dependent exciton-dominated optical behavior influenced by thickness and lateral quantum confinement effects. Thickness quantum confinement effects have been observed; however, experimental optical property assessment of nanoscale lateral dimension monolayer TMDCs is lacking. Here, we employ ex situ spectroscopic ellipsometry to evaluate laterally coalescing monolayer metalorganic chemical vapor deposited MoS2. A multisample analysis is used to constrain Bruggeman and Maxwell-Garnett effective medium approximations and the effective dielectric functions are derived for laterally coalesced and uncoalesced MoS2 films (∼10-94% surface coverage for ∼10-140 nm lateral grain sizes). This analysis demonstrates the ability to probe MoS2 optical exciton behavior at growth-relevant grain sizes in relation to chemical vapor nucleation density, ripening, and lateral growth conditions. Our analysis is pertinent toward expected in situ epitaxial 2D TMDC film growth metrology to enable the facile development of monolayer films with targeted process-dependent optical properties.

High-Density, Localized Quantum Emitters in Strained 2D Semiconductors.

Two-dimensional chalcogenide semiconductors have recently emerged as a host material for quantum emitters of single photons. While several reports on defect- and strain-induced single-photon emission from 2D chalcogenides exist, a bottom-up, lithography-free approach to producing a high density of emitters remains elusive. Further, the physical properties of quantum emission in the case of strained 2D semiconductors are far from being understood. Here, we demonstrate a bottom-up, scalable, and lithography-free approach for creating large areas of localized emitters with high density (∼150 emitters/um2) in a WSe2 monolayer. We induce strain inside the WSe2 monolayer with high spatial density by conformally placing the WSe2 monolayer over a uniform array of Pt nanoparticles with a size of 10 nm. Cryogenic, time-resolved, and gate-tunable luminescence measurements combined with near-field luminescence spectroscopy suggest the formation of localized states in strained regions that emit single photons with a high spatial density. Our approach of using a metal nanoparticle array to generate a high density of strained quantum emitters will be applied to scalable, tunable, and versatile quantum light sources.

Laser-Fabricated 2D Molybdenum Disulfide Electronic Sensor Arrays for Rapid, Low-Cost, Ultrasensitive Detection of Influenza A and SARS-Cov-2.

Multiplex electronic antigen sensors for detection of SARS-Cov-2 spike glycoproteins and hemagglutinin from influenza A are fabricated using scalable processes for straightforward transition to economical mass-production. The sensors utilize the sensitivity and surface chemistry of a 2D MoS2 transducer for attachment of antibody fragments in a conformation favorable for antigen binding with no need for additional linker molecules. To make the devices, ultra-thin layers (3 nm) of amorphous MoS2 are sputtered over pre-patterned metal electrical contacts on a glass chip at room temperature. The amorphous MoS2 is then laser annealed to create an array of semiconducting 2H-MoS2 transducer regions between metal contacts. The semiconducting crystalline MoS2 region is functionalized with monoclonal antibody fragments complementary to either SARS-CoV-2 S1 spike protein or influenza A hemagglutinin. Quartz crystal microbalance experiments indicate strong binding and maintenance of antigen avidity for antibody fragments bound to MoS2. Electrical resistance measurements of sensors exposed to antigen concentrations ranging from 2-20 000 pg mL-1 reveal selective responses. Sensor architecture is adjusted to produce an array of sensors on a single chip suited for detection of analyte concentrations spanning six orders of magnitude from pg mL-1 to µg mL-1.

Optical microscopy and confocal data of aerosol jet printed lines over a 16-hour print duration.

Optical microscopy images and confocal data for Aerosol Jet Printed (AJP) lines over a 16 hour print duration is provide in this dataset ("Mapping Drift in Morphology and Electrical Performance in Aerosol Jet Printing" [1]). Lines were uninterruptedly printed by AJP on a glass substrate using silver nanoparticle ink over a 16-hour time frame. The ink used for this experiment was a 0.6:0.3:0.2 mL mixture of Clariant Prelect TPS 50 G2 silver nanoparticle ink, ethylene glycol, and deionized water, respectively. Deposition was achieved with an Optomec AJ 300-UP Aerosol JetTM Deposition System using a Sprint Series Ultrasonic Atomizer MAX, aerodynamic filtering, and a nozzle having an orifice diameter of 150 µm. The typical focus ratio of 1.75 within standard range was used. The optical microscopic images of 350 µm AJP printed lines at 80 different time points were then selectively collected. Keyence VK-X200 with 150x magnification was used, which provided 50 µm to 267 pixel resolution image with more than 1000 cross-sections at each time point. Filtering of the pixels with outlying heights was performed with a multi-file analyzer. The dataset was primarily collected to understand system-level, temporal drifts in print morphology, which would further allow to predict electrical performance in time domain. Additional purposes for the dataset include: 1) benchmark dataset for morphology and print performance between AJP systems and print settings, 2) test data for new image filtering, segmentation, and classification algorithms and 3) baseline training data for real-time, in situ classification of operational time windows for AJP feedback control.

Light-matter coupling in large-area van der Waals superlattices.

Two-dimensional (2D) crystals have renewed opportunities in design and assembly of artificial lattices without the constraints of epitaxy. However, the lack of thickness control in exfoliated van der Waals (vdW) layers prevents realization of repeat units with high fidelity. Recent availability of uniform, wafer-scale samples permits engineering of both electronic and optical dispersions in stacks of disparate 2D layers with multiple repeating units. Here we present optical dispersion engineering in a superlattice structure comprising alternating layers of 2D excitonic chalcogenides and dielectric insulators. By carefully designing the unit cell parameters, we demonstrate greater than 90% narrow band absorption in less than 4 nm of active layer excitonic absorber medium at room temperature, concurrently with enhanced photoluminescence in square-centimetre samples. These superlattices show evidence of strong light-matter coupling and exciton-polariton formation with geometry-tuneable coupling constants. Our results demonstrate proof of concept structures with engineered optical properties and pave the way for a broad class of scalable, designer optical metamaterials from atomically thin layers.

Spalling-Induced Liftoff and Transfer of Electronic Films Using a van der Waals Release Layer.

Heterogeneous integration strategies are increasingly being employed to achieve more compact and capable electronics systems for multiple applications including space, electric vehicles, and wearable and medical devices. To enable new integration strategies, the growth and transfer of thin electronic films and devices, including III-nitrides, metal oxides, and 2D materials, using 2D boron nitride (BN)-on-sapphire templates are demonstrated. The van der Waals (vdW) BN layer, in this case, acts as a preferred mechanical release layer for precise separation at the substrate-film interface and leaves a smooth surface suitable for vdW bonding. A tensilely stressed Ni layer sputtered on top of the film induces controlled spalling fracture that propagates at the BN/sapphire interface. By incorporating controlled spalling, the process yield and sensitivity are greatly improved, owed to the greater fracture energy provided by the stressed metal layer relative to a soft tape or rubber stamp. With stress playing a critical role in this process, the influence of residual stress on detrimental cracking and bowing is investigated. Additionally, a back-end selected area lift-off technique is developed which allows for isolation and transfer of individual devices or arbitrary shapes.

Turn of the decade: versatility of 2D hexagonal boron nitride.

The era of two-dimensional (2D) materials, in its current form, truly began at the time that graphene was first isolated just over 15 years ago. Shortly thereafter, the use of 2D hexagonal boron nitride (h-BN) had expanded in popularity, with use of the thin isolator permeating a significant number of fields in condensed matter and beyond. Due to the impractical nature of cataloguing every use or research pursuit, this review will cover ground in the following three subtopics relevant to this versatile material: growth, electrical measurements, and applications in optics and photonics. Through understanding how the material has been utilized, one may anticipate some of the exciting directions made possible by the research conducted up through the turn of this decade.

Facile Post-deposition Annealing of Graphene Ink Enables Ultrasensitive Electrochemical Detection of Dopamine.

A growing body of research focuses on engineering materials for electrochemical detection of dopamine (DA), a critical neurotransmitter involved in motor function, reward processes, and blood pressure regulation. Among various sensing materials, graphene is highly attractive due to its excellent electrical conductivity and, in particular, the π-π interaction between the aromatic rings of DA and graphene. However, the lowest detection limits reported solely using graphene are nominally 1 nM. To improve the sensor sensitivity, various strategies are being explored, including chemical functionalization, heterostructure/composite formation, elemental doping, and modification with biomolecules (aptamers, enzymes, etc.). In this work, we demonstrate that commercially available graphene ink can exhibit selective and highly sensitive detection of DA by tuning the surface chemistry utilizing a simple, one-step annealing process. The annealing condition directly impacts the sensor response to DA, with the optimal conditions (30 min at 300 °C under 3% H2 + Ar) yielding a distinguishable and selective response to DA down to 5 pM. X-ray photoelectron spectroscopy (XPS) confirms that the improved selectivity is due to the increased fraction of oxygen functionalities (in particular, C-OH), while Raman spectroscopy shows a higher degree of defectiveness for this condition compared to others. Evaluation of the interaction of three molecular components of DA (i.e., aromatic ring, hydroxyl groups, and amine group) with graphene confirms that the π-π interaction and -OH groups play a prominent role in the improved adsorption of DA on the graphene surface. Furthermore, we demonstrate a proof-of-concept, all-solution processable sensor on polyimide substrates using graphene ink. Tuning the sensor response by varying the annealing condition offers a simple avenue for developing sensitive, selective, and low-cost point-of-care biosensors, while low-temperature annealing ensures compatibility with flexible substrates, such as polyimide.