Distinct Contact Scaling Effects in MoS2 Transistors Revealed with Asymmetrical Contact Measurements.

2D semiconducting materials have immense potential for future electronics due to their atomically thin nature, which enables better scalability. While the channel scalability of 2D materials has been extensively studied, the current understanding of contact scaling in 2D devices is inconsistent and oversimplified. Here physically scaled contacts and asymmetrical contact measurements (ACMs) are combined to investigate the contact scaling behavior in 2D field-effect transistors. The ACMs directly compare electron injection at different contact lengths while using the exact same MoS2  channel, eliminating channel-to-channel variations. The results show that scaled source contacts can limit the drain current, whereas scaled drain contacts do not. Compared to devices with long contact lengths, devices with short contact lengths (scaled contacts) exhibit larger variations, 15% lower drain currents at high drain-source voltages, and a higher chance of early saturation and negative differential resistance. Quantum transport simulations reveal that the transfer length of Ni-MoS2  contacts can be as short as 5 nm. Furthermore, it is clearly identified that the actual transfer length depends on the quality of the metal-2D interface. The ACMs demonstrated here will enable further understanding of contact scaling behavior at various interfaces.

Are 2D Interfaces Really Flat?

Two-dimensional (2D) van der Waals materials are subject to mechanical deformation and thus forming bubbles and wrinkles during exfoliation and transfer. A lack of interfacial "flatness" has implications for interface properties, such as those formed by metal contacts or insulating layers. Therefore, an understanding of the detailed properties of 2D interfaces, especially their flatness under different conditions, is of high importance. Here we use cross-sectional scanning transmission electron microscopy (STEM) to investigate various 2D interfaces (2D-2D and 3D-2D) under the effects of stacking, atomic layer deposition (ALD), and metallization. We characterize and compare the flatness of the hBN-2D and metal-2D interfaces down to angstrom resolution. It is observed that the dry transfer of hexagonal boron nitride (hBN) can dramatically alter the interface structure. When characterizing 3D metal-2D interfaces, we find that Ni-MoS2 interfaces are more uneven and have larger nanocavities compared to other metal-2D interfaces. The electrical characteristics of a MoS2-based field-effect transistor are correlated to the interfacial transformation in the contact and channel regions. The device transconductance is improved by 40% after the hBN encapsulation, likely due to the interface interactions at both the channel and contacts. Overall, these observations reveal the intricacy of 2D interfaces and their dependence on the fabrication processes.

Optimal field-effect transistor operation for high-resolution biochemical measurements.

Field-effect transistors (FETs) are powerful tools for sensitive measurements of numerous biomarkers (e.g., proteins, nucleic acids, and antigen) and gaseous species. Most research studies in this field focused on building discrete devices with high performance. We show that instrumentation that is commonly used in multiple areas of physics and engineering can greatly improve the performance of measurement systems that embed FET-based transducers for biological applications. We review the state-of-the-art instrumentation in the field as applied to sensing with FETs. We show how high-performance dual-gate 2D FETs that we recently developed, when operated using closed-loop proportional-integral-derivative control, can drastically improve both the sensitivity and resolution. We further show that this closed-loop control approach can be extended to commonly used single-gate silicon FETs. The generalizability of the results will allow their application to virtually any previously developed FET-based sensor. Finally, we provide insight into further optimization and performance benefits that can be extracted by using the closed-loop feedback approach for applications in biosensing.

Substrate-mediated hyperbolic phonon polaritons in MoO3.

Hyperbolic phonon polaritons (HPhPs) are hybrid excitations of light and coherent lattice vibrations that exist in strongly optically anisotropic media, including two-dimensional materials (e.g., MoO3). These polaritons propagate through the material's volume with long lifetimes, enabling novel mid-infrared nanophotonic applications by compressing light to sub-diffractional dimensions. Here, the dispersion relations and HPhP lifetimes (up to ≈12 ps) in single-crystalline α-MoO3 are determined by Fourier analysis of real-space, nanoscale-resolution polariton images obtained with the photothermal induced resonance (PTIR) technique. Measurements of MoO3 crystals deposited on periodic gratings show longer HPhPs propagation lengths and lifetimes (≈2×), and lower optical compressions, in suspended regions compared with regions in direct contact with the substrate. Additionally, PTIR data reveal MoO3 subsurface defects, which have a negligible effect on HPhP propagation, as well as polymeric contaminants localized under parts of the MoO3 crystals, which are derived from sample preparation. This work highlights the ability to engineer substrate-defined nanophotonic structures from layered anisotropic materials.

Rapid, quantitative therapeutic screening for Alzheimer's enzymes enabled by optimal signal transduction with transistors.

We show that commercially sourced n-channel silicon field-effect transistors (nFETs) operating above their threshold voltage with closed loop feedback to maintain a constant channel current allow a pH readout resolution of (7.2 ± 0.3) × 10-3 at a bandwidth of 10 Hz, or ≈3-fold better than the open loop operation commonly employed by integrated ion-sensitive field-effect transistors (ISFETs). We leveraged the improved nFET performance to measure the change in solution pH arising from the activity of a pathological form of the kinase Cdk5, an enzyme implicated in Alzheimer's disease, and showed quantitative agreement with previous measurements. The improved pH resolution was realized while the devices were operated in a remote sensing configuration with the pH sensing element off-chip and connected electrically to the FET gate terminal. We compared these results with those measured by using a custom-built dual-gate 2D field-effect transistor (dg2DFET) fabricated with 2D semi-conducting MoS2 channels and a signal amplification of 8. Under identical solution conditions the nFET performance approached the dg2DFETs pH resolution of (3.9 ± 0.7) × 10-3. Finally, using the nFETs, we demonstrated the effectiveness of a custom polypeptide, p5, as a therapeutic agent in restoring the function of Cdk5. We expect that the straight-forward modifications to commercially sourced nFETs demonstrated here will lower the barrier to widespread adoption of these remote-gate devices and enable sensitive bioanalytical measurements for high throughput screening in drug discovery and precision medicine applications.

Quantum capacitance-limited MoS2 biosensors enable remote label-free enzyme measurements.

We have demonstrated atomically thin, quantum capacitance-limited, field-effect transistors (FETs) that enable the detection of pH changes with 75-fold higher sensitivity (≈4.4 V per pH) over the Nernst value of 59 mV per pH at room temperature when used as a biosensor. The transistors, which are fabricated from monolayer films of MoS2, use a room temperature ionic liquid (RTIL) in place of a conventional oxide gate dielectric and exhibit very low intrinsic noise resulting in a pH resolution of 92 × 10-6 at 10 Hz. This high device performance, which is a function of the structure of our device, is achieved by remotely connecting the gate to a pH sensing element allowing the FETs to be reused. Because pH measurements are fundamentally important in biotechnology, the increased resolution demonstrated here will benefit numerous applications ranging from pharmaceutical manufacturing to clinical diagnostics. As an example, we experimentally quantified the function of the kinase Cdk5, an enzyme implicated in Alzheimer's disease, at concentrations that are 5-fold lower than physiological values, and with sufficient time-resolution to allow the estimation of both steady-state and kinetic parameters in a single experiment. The high sensitivity, increased resolution, and fast turnaround time of the measurements will allow the development of early diagnostic tools and novel therapeutics to detect and treat neurological conditions years before currently possible.

Reproducible Performance Improvements to Monolayer MoS2 Transistors through Exposed Material Forming Gas Annealing.

Metal-mediated exfoliation has been demonstrated as a promising approach for obtaining large-area flakes of two-dimensional (2D) materials to fabricate prototypical nanoelectronics. However, several processing challenges related to organic contamination at the interface of a 2D material and gate oxide must be overcome to realize robust devices with high yields. Here, we demonstrate an optimized process to realize high-performance field-effect transistor (FET) arrays from large-area (∼5000 µm2), monolayer MoS2 with a yield of 85%. A central element of this process is an exposed material forming gas anneal (EM-FGA) that results in uniform FET performance metrics (i.e., field-effect mobilities, threshold voltages, and contact performance). Complementary analytical measurements show that the EM-FGA process reduces deleterious channel doping effects by decreasing organic contamination while also reducing the prevalence of insulating molybdenum oxide, effectively improving the MoS2-gate oxide interface. The uniform FET performance metrics and high device yield achieved by applying the EM-FGA technique on large-area 2D material flakes will help advance the fabrication of complex 2D nanoelectronic devices and demonstrate the need for improved engineering of the 2D material-gate oxide interface.

Electrical Detection of Singlet Fission in Single Crystal Tetracene Transistors.

We present the electrical detection of singlet fission in tetracene by using a field-effect transistor (FET). Singlet fission is a photoinduced spin-dependent process, yielding two triplet excitons from the absorption of a single photon. In this study, we engineered a more deterministic platform composed of an organic single crystal FET rather than amorphous or polycrystalline FETs to elucidate spin-dependent processes under magnetic fields. Despite the unipolar operation and relatively high mobility of single crystal tetracene FETs, we were able to manipulate spin dependent processes to detect magnetoconductance (MC) at room temperature by illuminating the FETs and tuning the bias voltage to adjust majority charge carrier density and trap occupancy. In considering the crystalline direction and magnetic field interactions in tetracene, we show the MC response observed in tetracene FETs to be the result of the singlet fission process.

Improved contacts to p-type MoS2 transistors by charge-transfer doping and contact engineering.

MoS2 is known to show stubborn n-type behavior due to its intrinsic band structure and Fermi level pinning. Here, we investigate the combined effects of molecular doping and contact engineering on the transport and contact properties of monolayer (ML) MoS2 devices. Significant p-type (hole-transport) behavior was only observed for chemically doped MoS2 devices with high work function palladium (Pd) contacts, while MoS2 devices with low work function metal contacts made from titanium showed ambipolar behavior with electron transport favored even after prolonged p-doping treatment. ML MoS2 transistors with Pd contacts exhibit effective hole mobilities of (2.3 ± 0.7) cm2 V-1 S-1 and an on/off ratio exceeding 106. We also show that p-doping can help to improve electrical contacts in p-type field-effect transistors: relatively low contact resistances of (482 ± 40) kΩ µm and a Schottky barrier height of ≈156 meV were obtained for ML MoS2 transistors. To demonstrate the potential application of 2D-based complementary electronic devices, a MoS2 inverter based on pristine (n-type) and p-doped monolayer MoS2 was fabricated. This work presents a simple and effective route for contact engineering, which enables the exploration and development of high-efficiency 2D-based semiconductor devices.

Contact and Noncontact Measurement of Electronic Transport in Individual 2D SnS Colloidal Semiconductor Nanocrystals.

Colloidal-based solution syntheses offer a scalable and cost-efficient means of producing 2D nanomaterials in high yield. While much progress has been made toward the controlled and tailorable synthesis of semiconductor nanocrystals in solution, it remains a substantial challenge to fully characterize the products' inherent electronic transport properties. This is often due to their irregular morphology or small dimensions, which demand the formation of colloidal assemblies or films as a prerequisite to performing electrical measurements. Here, we report the synthesis of nearly monodisperse 2D colloidal nanocrystals of semiconductor SnS and a thorough investigation of the intrinsic electronic transport properties of single crystals. We utilize a combination of multipoint contact probe measurements and ultrafast terahertz spectroscopy to determine the carrier concentration, carrier mobility, conductivity/resistivity, and majority carrier type of individual colloidal semiconductor nanocrystals. Employing this metrological approach, we compare the electronic properties extracted for distinct morphologies of 2D SnS and relate them to literature values. Our results indicate that the electronic transport of colloidal semiconductors may be tuned through prudent selection of the synthetic conditions. We find that these properties compare favorably to SnS grown using vapor deposition techniques, illustrating that colloidal solution synthesis is a promising route to scalable production of nanoscale 2D materials.

Controllable, Wide-Ranging n-Doping and p-Doping of Monolayer Group 6 Transition-Metal Disulfides and Diselenides.

Developing processes to controllably dope transition-metal dichalcogenides (TMDs) is critical for optical and electrical applications. Here, molecular reductants and oxidants are introduced onto monolayer TMDs, specifically MoS2 , WS2 , MoSe2 , and WSe2 . Doping is achieved by exposing the TMD surface to solutions of pentamethylrhodocene dimer as the reductant (n-dopant) and "Magic Blue," [N(C6 H4 -p-Br)3 ]SbCl6 , as the oxidant (p-dopant). Current-voltage characteristics of field-effect transistors show that, regardless of their initial transport behavior, all four TMDs can be used in either p- or n-channel devices when appropriately doped. The extent of doping can be controlled by varying the concentration of dopant solutions and treatment time, and, in some cases, both nondegenerate and degenerate regimes are accessible. For all four TMD materials, the photoluminescence intensity; for all four materials the PL intensity is enhanced with p-doping but reduced with n-doping. Raman and X-ray photoelectron spectroscopy (XPS) also provide insight into the underlying physical mechanism by which the molecular dopants react with the monolayer. Estimates of changes of carrier density from electrical, PL, and XPS results are compared. Overall a simple and effective route to tailor the electrical and optical properties of TMDs is demonstrated.

Quantifying atom-scale dopant movement and electrical activation in Si:P monolayers.

Advanced hydrogen lithography techniques and low-temperature epitaxial overgrowth enable the patterning of highly phosphorus-doped silicon (Si:P) monolayers (ML) with atomic precision. This approach to device fabrication has made Si:P monolayer systems a testbed for multiqubit quantum computing architectures and atomically precise 2-D superlattice designs whose behaviors are directly tied to the deterministic placement of single dopants. However, dopant segregation, diffusion, surface roughening, and defect formation during the encapsulation overgrowth introduce large uncertainties to the exact dopant placement and activation ratio. In this study, we develop a unique method by combining dopant segregation/diffusion models with sputter profiling simulation to monitor and control, at the atomic scale, dopant movement using room-temperature grown locking layers (LLs). We explore the impact of LL growth rate, thickness, rapid thermal annealing, surface accumulation, and growth front roughness on dopant confinement, local crystalline quality, and electrical activation within Si:P 2-D systems. We demonstrate that dopant movement can be more efficiently suppressed by increasing the LL growth rate than by increasing the LL thickness. We find that the dopant segregation length can be suppressed below a single Si lattice constant by increasing the LL growth rates at room temperature while maintaining epitaxy. Although dopant diffusivity within the LL is found to remain high (on the order of 10-17 cm2 s-1) even below the hydrogen desorption temperature, we demonstrate that exceptionally sharp dopant confinement with high electrical quality within Si:P monolayers can be achieved by combining a high LL growth rate with low-temperature LL rapid thermal annealing. The method developed in this study provides a key tool for 2-D fabrication techniques that require precise dopant placement to suppress, quantify, and predict a single dopant's movement at the atomic scale.

Contacts to solution-synthesized SnS nanoribbons: dependence of barrier height on metal work function.

Tin(ii) monosulfide (SnS) is a layered, anisotropic material that is of interest as a two-dimensional semiconductor for opto-electronic, thermoelectric, and piezoelectric applications. In this study, the effect of work function on contact behavior was investigated. Ni/Au, Pd/Au, Cr/Au, and Ti/Au contacts were fabricated onto individual, solution-synthesized, p-type SnS nanoribbons. The lower work function metals (Cr and Ti) formed Schottky contacts, whereas the higher work function metals (Ni and Pd) formed ohmic or semi-ohmic contacts. Of the ohmic contacts, Ni was found to have a lower contact resistance (∼10-4 Ω cm2 or lower) than Pd (∼10-3 Ω cm2 or lower). Both the calculated Schottky barriers (0.39 and 0.50 eV) for Cr and Ti, respectively, and the ohmic behavior for Ni and Pd agree with behavior predicted by Schottky-Mott theory. The results indicate that high work function metals should be considered to form low resistance contacts to SnS multilayers.

The influence of isomer purity on trap states and performance of organic thin-film transistors.

Organic field-effect transistor (OFET) performance is dictated by its composition and geometry, as well as the quality of the organic semiconductor (OSC) film, which strongly depends on purity and microstructure. When present, impurities and defects give rise to trap states in the bandgap of the OSC, lowering device performance. Here, 2,8-difluoro-5,11-bis(triethylsilylethynyl)-anthradithiophene is used as a model system to study the mechanism responsible for performance degradation in OFETs due to isomer coexistence. The density of trapping states is evaluated through temperature dependent current-voltage measurements, and it is discovered that OFETs containing a mixture of syn- and anti-isomers exhibit a discrete trapping state detected as a peak located at ~ 0.4 eV above the valence-band edge, which is absent in the samples fabricated on single-isomer films. Ultraviolet photoelectron spectroscopy measurements and density functional theory calculations do not point to a significant difference in electronic band structure between individual isomers. Instead, it is proposed that the dipole moment of the syn-isomer present in the host crystal of the anti-isomer locally polarizes the neighboring molecules, inducing energetic disorder. The isomers can be separated by applying gentle mechanical vibrations during film crystallization, as confirmed by the suppression of the peak and improvement in device performance.

Electrical Stabilization of Surface Resistivity in Epitaxial Graphene Systems by Amorphous Boron Nitride Encapsulation.

Homogeneous monolayer epitaxial graphene (EG) is an ideal candidate for the development of millimeter-sized devices with single-crystal domains. A clean fabrication process was used to produce EG-based devices, with n-type doping level of the order of 1012 cm-2. Generally, electrical properties of EG, such as longitudinal resistivity, remain unstable when devices are exposed to air due to adsorption of molecular dopants, whose presence shifts the carrier density close to the Dirac point (<1010 cm-2) or into the p-type regime. Here, we report experimental results on the use of amorphous boron nitride (a-BN) as an encapsulation layer, whereby EG can maintain its longitudinal resistivity and have its carrier density modulated. Furthermore, we exposed 12 devices to controlled temperatures of up to 85 °C and relative humidity of up to 85% and reported that an approximately 20 nm a-BN encapsulation thickness is sufficient to preserve their longitudinal resistivity to within 10% of the previously measured value. We monitored the electronic properties of our encapsulated and nonencapsulated EG samples by magnetotransport measurements, using a neodymium iron boron magnet. Our results have essential importance in the mass production of millimeter-scale graphene devices, with stable electrical properties.

Interacting nanoscale magnetic superatom cluster arrays in molybdenum oxide bronzes.

In this study, we examine several reduced ternary molybdates in the family of yellow rare earth molybdenum bronzes produced by electrochemical synthesis with composition LnMo16O44. These compounds contain an array of electrically isolated but magnetically interacting multi-atom clusters with composition Mo8O36. These arrayed superatom clusters support a single hole shared among the eight molybdenum atoms in the unit, corresponding to a net spin moment of 1µB, and exhibit magnetic exchange between the units via the MoO4 tetrahedra (containing Mo6+ ions) and the LnO8 cubes (containing Ln3+ ions). The findings presented here expand on the physics of the unusual collective properties of multi-atom clusters and extend the discussion of such assemblages to the rich structural chemistry of molybdenum bronzes.

Preservation of Surface Conductivity and Dielectric Loss Tangent in Large-Scale, Encapsulated Epitaxial Graphene Measured by Noncontact Microwave Cavity Perturbations.

Regarding the improvement of current quantized Hall resistance (QHR) standards, one promising avenue is the growth of homogeneous monolayer epitaxial graphene (EG). A clean and simple process is used to produce large, precise areas of EG. Properties like the surface conductivity and dielectric loss tangent remain unstable when EG is exposed to air due to doping from molecular adsorption. Experimental results are reported on the extraction of the surface conductivity and dielectric loss tangent from data taken with a noncontact resonance microwave cavity, assembled with an air-filled, standard R100 rectangular waveguide configuration. By using amorphous boron nitride (a-BN) as an encapsulation layer, stability of EG's electrical properties under ambient laboratory conditions is greatly improved. Moreover, samples are exposed to a variety of environmental and chemical conditions. Both thicknesses of a-BN encapsulation are sufficient to preserve surface conductivity and dielectric loss tangent to within 10% of its previously measured value, a result which has essential importance in the mass production of millimeter-scale graphene devices demonstrating electrical stability.

Organic Spin-Valves and Beyond: Spin Injection and Transport in Organic Semiconductors and the Effect of Interfacial Engineering.

Since the first observation of the spin-valve effect through organic semiconductors, efforts to realize novel spintronic technologies based on organic semiconductors have been rapidly growing. However, a complete understanding of spin-polarized carrier injection and transport in organic semiconductors is still lacking and under debate. For example, there is still no clear understanding of major spin-flip mechanisms in organic semiconductors and the role of hybrid metal-organic interfaces in spin injection. Recent findings suggest that organic single crystals can provide spin-transport media with much less structural disorder relative to organic thin films, thus reducing momentum scattering. Additionally, modification of the band energetics, morphology, and even spin magnetic moment at the metal-organic interface by interface engineering can greatly impact the efficiency of spin-polarized carrier injection. Here, progress on efficient spin-polarized carrier injection into organic semiconductors from ferromagnetic metals by using various interface engineering techniques is presented, such as inserting a metallic interlayer, a molecular self-assembled monolayer (SAM), and a ballistic carrier emitter. In addition, efforts to realize long spin transport in single-crystalline organic semiconductors are discussed. The focus here is on understanding and maximizing spin-polarized carrier injection and transport in organic semiconductors and insight is provided for the realization of emerging organic spintronics technologies.