High carrier mobility along the [111] orientation in Cu2O photoelectrodes.

Solar fuels offer a promising approach to provide sustainable fuels by harnessing sunlight1,2. Following a decade of advancement, Cu2O photocathodes are capable of delivering a performance comparable to that of photoelectrodes with established photovoltaic materials3-5. However, considerable bulk charge carrier recombination that is poorly understood still limits further advances in performance6. Here we demonstrate performance of Cu2O photocathodes beyond the state-of-the-art by exploiting a new conceptual understanding of carrier recombination and transport in single-crystal Cu2O thin films. Using ambient liquid-phase epitaxy, we present a new method to grow single-crystal Cu2O samples with three crystal orientations. Broadband femtosecond transient reflection spectroscopy measurements were used to quantify anisotropic optoelectronic properties, through which the carrier mobility along the [111] direction was found to be an order of magnitude higher than those along other orientations. Driven by these findings, we developed a polycrystalline Cu2O photocathode with an extraordinarily pure (111) orientation and (111) terminating facets using a simple and low-cost method, which delivers 7 mA cm-2 current density (more than 70% improvement compared to that of state-of-the-art electrodeposited devices) at 0.5 V versus a reversible hydrogen electrode under air mass 1.5 G illumination, and stable operation over at least 120 h.

Electrochemically-gated graphene broadband microwave waveguides for ultrasensitive biosensing.

Identification of non-amplified DNA sequences and single-base mutations is essential for molecular biology and genetic diagnostics. This paper reports a novel sensor consisting of electrochemically-gated graphene coplanar waveguides coupled with a microfluidic channel. Upon exposure to analytes, propagation of electromagnetic waves in the waveguides is modified as a result of interactions with the fringing field and modulation of graphene dynamic conductivity resulting from electrostatic gating. Probe DNA sequences are immobilised on the graphene surface, and the sensor is exposed to DNA sequences which either perfectly match the probe, contain a single-base mismatch or are unrelated. By monitoring the scattering parameters at frequencies between 50 MHz and 50 GHz, unambiguous and reproducible discrimination of the different strands is achieved at concentrations as low as one attomole per litre (1 aM). By controlling and synchronising frequency sweeps, electrochemical gating, and liquid flow in the microfluidic channel, the sensor generates multidimensional datasets. Advanced data analysis techniques are utilised to take full advantage of the richness of the dataset. A classification accuracy >97% between all three sequences is achieved using different Machine Learning models, even in the presence of simulated noise and low signal-to-noise ratios. The sensor exceeds state-of-the-art sensitivity of field-effect transistors and microwave sensors for the identification of single-base mismatches.

Putting High-Index Cu on the Map for High-Yield, Dry-Transferred CVD Graphene.

Reliable, clean transfer and interfacing of 2D material layers are technologically as important as their growth. Bringing both together remains a challenge due to the vast, interconnected parameter space. We introduce a fast-screening descriptor approach to demonstrate holistic data-driven optimization across the entirety of process steps for the graphene-Cu model system. We map the crystallographic dependences of graphene chemical vapor deposition, interfacial Cu oxidation to decouple graphene, and its dry delamination across inverse pole figures. Their overlay enables us to identify hitherto unexplored (168) higher index Cu orientations as overall optimal orientations. We show the effective preparation of such Cu orientations via epitaxial close-space sublimation and achieve mechanical transfer with a very high yield (>95%) and quality of graphene domains, with room-temperature electron mobilities in the range of 40000 cm2/(V s). Our approach is readily adaptable to other descriptors and 2D material systems, and we discuss the opportunities of such a holistic optimization.

Automated Computer Vision-Enabled Manufacturing of Nanowire Devices.

We present a high-throughput method for identifying and characterizing individual nanowires and for automatically designing electrode patterns with high alignment accuracy. Central to our method is an optimized machine-readable, lithographically processable, and multi-scale fiducial marker system─dubbed LithoTag─which provides nanostructure position determination at the nanometer scale. A grid of uniquely defined LithoTag markers patterned across a substrate enables image alignment and mapping in 100% of a set of >9000 scanning electron microscopy (SEM) images (>7 gigapixels). Combining this automated SEM imaging with a computer vision algorithm yields location and property data for individual nanowires. Starting with a random arrangement of individual InAs nanowires with diameters of 30 ± 5 nm on a single chip, we automatically design and fabricate >200 single-nanowire devices. For >75% of devices, the positioning accuracy of the fabricated electrodes is within 2 pixels of the original microscopy image resolution. The presented LithoTag method enables automation of nanodevice processing and is agnostic to microscopy modality and nanostructure type. Such high-throughput experimental methodology coupled with data-extensive science can help overcome the characterization bottleneck and improve the yield of nanodevice fabrication, driving the development and applications of nanostructured materials.

Defect seeded remote epitaxy of GaAs films on graphene.

Remote epitaxy is an emerging materials synthesis technique which employs a 2D interface layer, often graphene, to enable the epitaxial deposition of low defect single crystal films while restricting bonding between the growth layer and the underlying substrate. This allows for the subsequent release of the epitaxial film for integration with other systems and reuse of growth substrates. This approach is applicable to material systems with an ionic component to their bonding, making it notably appealing for III-V alloys, which are a technologically important family of materials. Chemical vapour deposition growth of graphene and wet transfer to a III-V substrate with a polymer handle is a potentially scalable and low cost approach to producing the required growth surface for remote epitaxy of these materials, however, the presence of water promotes the formation of a III-V oxide layer, which degrades the quality of subsequently grown epitaxial films. This work demonstrates the use of an argon ion beam for the controlled introduction of defects in a monolayer graphene interface layer to enable the growth of a single crystal GaAs film by molecular beam epitaxy, despite the presence of a native oxide at the substrate/graphene interface. A hybrid mechanism of defect seeded lateral overgrowth with remote epitaxy contributing the coalescence of the film is indicated. The exfoliation of the GaAs films reveals the presence of defect seeded nucleation sites, highlighting the need to balance the benefits of defect seeding on crystal quality against the requirement for subsequent exfoliation of the film, for future large area development of this approach.

Giant Magnetoresistance in a Chemical Vapor Deposition Graphene Constriction.

Magnetic field-driven insulating states in graphene are associated with samples of very high quality. Here, this state is shown to exist in monolayer graphene grown by chemical vapor deposition (CVD) and wet transferred on Al2O3 without encapsulation with hexagonal boron nitride (h-BN) or other specialized fabrication techniques associated with superior devices. Two-terminal measurements are performed at low temperature using a GaAs-based multiplexer. During high-throughput testing, insulating properties are found in a 10 µm long graphene device which is 10 µm wide at one contact with an ≈440 nm wide constriction at the other. The low magnetic field mobility is ≈6000 cm2 V-1 s-1. An energy gap induced by the magnetic field opens at charge neutrality, leading to diverging resistance and current switching on the order of 104 with DC bias voltage at an approximate electric field strength of ≈0.04 V µm-1 at high magnetic field. DC source-drain bias measurements show behavior associated with tunneling through a potential barrier and a transition between direct tunneling at low bias to Fowler-Nordheim tunneling at high bias from which the tunneling region is estimated to be on the order of ≈100 nm. Transport becomes activated with temperature from which the gap size is estimated to be 2.4 to 2.8 meV at B = 10 T. Results suggest that a local electronically high quality region exists within the constriction, which dominates transport at high B, causing the device to become insulating and act as a tunnel junction. The use of wet transfer fabrication techniques of CVD material without encapsulation with h-BN and the combination with multiplexing illustrates the convenience of these scalable and reasonably simple methods to find high quality devices for fundamental physics research and with functional properties.

Quantum Emitter Localization in Layer-Engineered Hexagonal Boron Nitride.

Hexagonal boron nitride (hBN) is a promising host material for room-temperature, tunable solid-state quantum emitters. A key technological challenge is deterministic and scalable spatial emitter localization, both laterally and vertically, while maintaining the full advantages of the 2D nature of the material. Here, we demonstrate emitter localization in hBN in all three dimensions via a monolayer (ML) engineering approach. We establish pretreatment processes for hBN MLs to either fully suppress or activate emission, thereby enabling such differently treated MLs to be used as select building blocks to achieve vertical (z) emitter localization at the atomic layer level. We show that emitter bleaching of ML hBN can be suppressed by sandwiching between two protecting hBN MLs, and that such thin stacks retain opportunities for external control of emission. We exploit this to achieve lateral (x-y) emitter localization via the addition of a patterned graphene mask that quenches fluorescence. Such complete emitter site localization is highly versatile, compatible with planar, scalable processing, allowing tailored approaches to addressable emitter array designs for advanced characterization, monolithic device integration, and photonic circuits.

Growth and Characterisation Studies of Eu3O4 Thin Films Grown on Si/SiO2 and Graphene.

We report the growth, structural and magnetic properties of the less studied Eu-oxide phase, Eu3O4, thin films grown on a Si/SiO2 substrate and Si/SiO2/graphene using molecular beam epitaxy. The X-ray diffraction scans show that highly textured crystalline Eu3O4(001) films are grown on both substrates, whereas the film deposited on graphene has a better crystallinity than that grown on the Si/SiO2 substrate. The SQUID measurements show that both films have a Curie temperature of ∼5.5±0.1 K, with a magnetic moment of ∼320 emu/cm3 at 2 K. The mixed valence of the Eu cations has been confirmed by the qualitative analysis of the depth-profile X-ray photoelectron spectroscopy measurements with the Eu2+:Eu3+ ratio of 28:72. However, surprisingly, our films show no metamagnetic behaviour as reported for the bulk and powder form. Furthermore, the microscopic optical images and Raman measurements show that the graphene underlayer remains largely intact after the growth of the Eu3O4 thin films.

Understanding metal organic chemical vapour deposition of monolayer WS2: the enhancing role of Au substrate for simple organosulfur precursors.

We find that the use of Au substrate allows fast, self-limited WS2 monolayer growth using a simple sequential exposure pattern of low cost, low toxicity precursors, namely tungsten hexacarbonyl and dimethylsulfide (DMS). We use this model reaction system to fingerprint the technologically important metal organic chemical vapour deposition process by operando X-ray photoelectron spectroscopy (XPS) to address the current lack of understanding of the underlying fundamental growth mechanisms for WS2 and related transition metal dichalcogenides. Au effectively promotes the sulfidation of W with simple organosulfides, enabling WS2 growth with low DMS pressure (<1 mbar) and a suppression of carbon contamination of as-grown WS2, which to date has been a major challenge with this precursor chemistry. Full WS2 coverage can be achieved by one exposure cycle of 10 minutes at 700 °C. We discuss our findings in the wider context of previous literature on heterogeneous catalysis, 2D crystal growth, and overlapping process technologies such as atomic layer deposition (ALD) and direct metal conversion, linking to future integrated manufacturing processes for transition metal dichalcogenide layers.

Integrated Wafer Scale Growth of Single Crystal Metal Films and High Quality Graphene.

We report on an approach to bring together single crystal metal catalyst preparation and graphene growth in a combined process flow using a standard cold-wall chemical vapor deposition (CVD) reactor. We employ a sandwich arrangement between a commercial polycrystalline Cu foil and c-plane sapphire wafer and show that close-spaced vacuum sublimation across the confined gap can result in an epitaxial, single-crystal Cu(111) film at high growth rate. The arrangement is scalable (we demonstrate 2″ wafer scale) and suppresses reactor contamination with Cu. While starting with an impure Cu foil, the freshly prepared Cu film is of high purity as measured by time-of-flight secondary ion mass spectrometry. We seamlessly connect the initial metallization with subsequent graphene growth via the introduction of hydrogen and gaseous carbon precursors, thereby eliminating contamination due to substrate transfer and common lengthy catalyst pretreatments. We show that the sandwich approach also enables for a Cu surface with nanometer scale roughness during graphene growth and thus results in high quality graphene similar to previously demonstrated Cu enclosure approaches. We systematically explore the parameter space and discuss the opportunities, including subsequent dry transfer, generality, and versatility of our approach particularly regarding the cost-efficient preparation of different single crystal film orientations and expansion to other material systems.

High-Throughput Electrical Characterization of Nanomaterials from Room to Cryogenic Temperatures.

We present multiplexer methodology and hardware for nanoelectronic device characterization. This high-throughput and scalable approach to testing large arrays of nanodevices operates from room temperature to milli-Kelvin temperatures and is universally compatible with different materials and integration techniques. We demonstrate the applicability of our approach on two archetypal nanomaterials-graphene and semiconductor nanowires-integrated with a GaAs-based multiplexer using wet or dry transfer methods. A graphene film grown by chemical vapor deposition is transferred and patterned into an array of individual devices, achieving 94% yield. Device performance is evaluated using data fitting methods to obtain electrical transport metrics, showing mobilities comparable to nonmultiplexed devices fabricated on oxide substrates using wet transfer techniques. Separate arrays of indium-arsenide nanowires and micromechanically exfoliated monolayer graphene flakes are transferred using pick-and-place techniques. For the nanowire array mean values for mobility µFE = 880/3180 cm2 V-1 s-1 (lower/upper bound), subthreshold swing 430 mV dec-1, and on/off ratio 3.1 decades are extracted, similar to nonmultiplexed devices. In another array, eight mechanically exfoliated graphene flakes are transferred using techniques compatible with fabrication of two-dimensional superlattices, with 75% yield. Our results are a proof-of-concept demonstration of a versatile platform for scalable fabrication and cryogenic characterization of nanomaterial device arrays, which is compatible with a broad range of nanomaterials, transfer techniques, and device integration strategies from the forefront of quantum technology research.

Crystal Orientation Dependent Oxidation Modes at the Buried Graphene-Cu Interface.

We combine spatially resolved scanning photoelectron spectroscopy with confocal Raman and optical microscopy to reveal how the oxidation of the buried graphene-Cu interface relates to the Cu crystallographic orientation. We analyze over 100 different graphene covered Cu (high and low index) orientations exposed to air for 2 years. Four general oxidation modes are observed that can be mapped as regions onto the polar plot of Cu surface orientations. These modes are (1) complete, (2) irregular, (3) inhibited, and (4) enhanced wrinkle interface oxidation. We present a comprehensive characterization of these modes, consider the underlying mechanisms, compare air and water mediated oxidation, and discuss this in the context of the diverse prior literature in this area. This understanding incorporates effects from across the wide parameter space of 2D material interface engineering, relevant to key challenges in their emerging applications, ranging from scalable transfer to electronic contacts, encapsulation, and corrosion protection.

Tunable Anion-Selective Transport through Monolayer Graphene and Hexagonal Boron Nitride.

Membranes that selectively filter for both anions and cations are central to technological applications from clean energy generation to desalination devices. 2D materials have immense potential as these ion-selective membranes due to their thinness, mechanical strength, and tunable surface chemistry; however, currently, only cation-selective membranes have been reported. Here we demonstrate the controllable cation and anion selectivity of both monolayer graphene and hexagonal boron nitride. In particular, we measure the ionic current through membranes grown by chemical vapor deposition containing well-known defects inherent to scalably produced and wet-transferred 2D materials. We observe a striking change from cation selectivity with monovalent ions to anion selectivity by controlling the concentration of multivalent ions and inducing charge inversion on the 2D membrane. Furthermore, we find good agreement between our experimental data and theoretical predictions from the Goldman-Hodgkin-Katz equation and use this model to extract selectivity ratios. These tunable selective membranes conduct up to 500 anions for each cation and thus show potential for osmotic power generation.

A Peeling Approach for Integrated Manufacturing of Large Monolayer h-BN Crystals.

Hexagonal boron nitride (h-BN) is the only known material aside from graphite with a structure composed of simple, stable, noncorrugated atomically thin layers. While historically used as a lubricant in powder form, h-BN layers have become particularly attractive as an ultimately thin insulator, barrier, or encapsulant. Practically all emerging electronic and photonic device concepts currently rely on h-BN exfoliated from small bulk crystallites, which limits device dimensions and process scalability. We here focus on a systematic understanding of Pt-catalyzed h-BN crystal formation, in order to address this integration challenge for monolayer h-BN via an integrated chemical vapor deposition (CVD) process that enables h-BN crystal domain sizes exceeding 0.5 mm and a merged, continuous layer in a growth time of less than 45 min. The process makes use of commercial, reusable Pt foils and allows a delamination process for easy and clean h-BN layer transfer. We demonstrate sequential pick-up for the assembly of graphene/h-BN heterostructures with atomic layer precision, while minimizing interfacial contamination. The approach can be readily combined with other layered materials and enables the integration of CVD h-BN into high-quality, reliable 2D material device layer stacks.