In Situ Probing Molecular Intercalation in Two-Dimensional Layered Semiconductors.

The electrochemical molecular intercalation of two-dimensional layered materials (2DLMs) produces stable and highly tunable superlattices between monolayer 2DLMs and self-assembled molecular layers. This process allows unprecedented flexibility in integrating highly distinct materials with atomic/molecular precision to produce a new generation of organic/inorganic superlattices with tunable chemical, electronic, and optical properties. To better understand the intercalation process, we developed an on-chip platform based on MoS2 model devices and used optical, electrochemical, and in situ electronic characterizations to resolve the intermediate stages during the intercalation process and monitor the evolution of the molecular superlattices. With sufficient charge injection, the organic cetyltrimethylammonium bromide (CTAB) intercalation induces the phase transition of MoS2 from semiconducting 2H phase to semimetallic 1T phase, resulting in a dramatic increase of electrical conductivity. Therefore, in situ monitoring the evolution of the device conductance reveals the electrochemical intercalation dynamics with an abrupt conductivity change, signifying the onset of the molecule intercalation. In contrast, the intercalation of tetraheptylammonium bromide (THAB), a branched molecule in a larger size, resulting in a much smaller number of charges injected to avoid the 2H to 1T phase transition. Our study demonstrates a powerful platform for in situ monitoring the molecular intercalation of many 2DLMs (MoS2, WSe2, ReS2, PdSe2, TiS2, and graphene) and systematically probing electronic, optical, and optoelectronic properties at the single-nanosheet level.

A field-effect approach to directly profiling the localized states in monolayer MoS2.

A fundamental understanding of the charge transport mechanism in two-dimensional semiconductors (e.g., MoS2) is crucial for fully exploring their potential in electronic and optoelectronic devices. By using monolayer graphene as the barrier-free contact to MoS2, we show that the field-modulated conductivity can be used to probe the electronic structure of the localized states. A series of regularly distributed plateaus were observed in the gate-dependent transfer curves. Calculations based on the variable-range hopping theory indicate that such plateaus can be attributed to the discrete localized states near mobility edge. This method provides an effective approach to directly profiling the localized states in conduction channel with an ultrahigh resolution up to 1 meV.

Monolayer atomic crystal molecular superlattices.

Artificial superlattices, based on van der Waals heterostructures of two-dimensional atomic crystals such as graphene or molybdenum disulfide, offer technological opportunities beyond the reach of existing materials. Typical strategies for creating such artificial superlattices rely on arduous layer-by-layer exfoliation and restacking, with limited yield and reproducibility. The bottom-up approach of using chemical-vapour deposition produces high-quality heterostructures but becomes increasingly difficult for high-order superlattices. The intercalation of selected two-dimensional atomic crystals with alkali metal ions offers an alternative way to superlattice structures, but these usually have poor stability and seriously altered electronic properties. Here we report an electrochemical molecular intercalation approach to a new class of stable superlattices in which monolayer atomic crystals alternate with molecular layers. Using black phosphorus as a model system, we show that intercalation with cetyl-trimethylammonium bromide produces monolayer phosphorene molecular superlattices in which the interlayer distance is more than double that in black phosphorus, effectively isolating the phosphorene monolayers. Electrical transport studies of transistors fabricated from the monolayer phosphorene molecular superlattice show an on/off current ratio exceeding 107, along with excellent mobility and superior stability. We further show that several different two-dimensional atomic crystals, such as molybdenum disulfide and tungsten diselenide, can be intercalated with quaternary ammonium molecules of varying sizes and symmetries to produce a broad class of superlattices with tailored molecular structures, interlayer distances, phase compositions, electronic and optical properties. These studies define a versatile material platform for fundamental studies and potential technological applications.

Vertical Charge Transport and Negative Transconductance in Multilayer Molybdenum Disulfides.

Negative transconductance (NTC) devices have been heavily investigated for their potential in low power logical circuit, memory, oscillating, and high-speed switching applications. Previous NTC devices are largely attributed to two working mechanisms: quantum mechanical tunneling, and mobility degradation at high electrical field. Herein we report a systematic investigation of charge transport in multilayer two-dimensional semiconductors (2DSCs) with optimized van der Waals contact and for the first time demonstrate NTC and antibipolar characteristics in multilayer 2DSCs (such as MoS2, WSe2). By varying the measurement temperature, bias voltage, and body thickness, we found the NTC behavior can be attributed to a vertical potential barrier in the multilayer 2DSCs and the competing mechanisms between intralayer lateral transport and interlayer vertical transport, thus representing a new working mechanism for NTC operation. Importantly, this vertical potential barrier arises from inhomogeneous carrier distribution in 2DSC from the near-substrate region to the bulk region, which is in contrast to conventional semiconductors with homogeneous doping defined by bulk dopants. We further show that the unique NTC behavior can be explored for creating frequency doublers and phase shift keying circuits with only one transistor, greatly simplifying the circuit design compared to conventional technology.

Synthesis of 2D Layered BiI3 Nanoplates, BiI3 /WSe2 van der Waals Heterostructures and Their Electronic, Optoelectronic Properties.

Two-dimensional layered materials (2DLMs) have attracted considerable recent interest as a new material platform for fundamental materials science and potential new technologies. Here we report the growth of layered metal halide materials and their optoelectronic properties. BiI3 nanoplates can be readily grown on SiO2 /Si substrates with a hexagonal geometry, with a thickness in the range of 10-120 nm and a lateral dimension of 3-10 µm. Transmission electron microscopy and electron diffraction studies demonstrate that the individual nanoplates are high quality single crystals. Micro-Raman studies show characteristic Ag band at ≈115 cm-1 with slight red-shift with decreasing thickness, and micro-photoluminescence studies show uniform emission around 690 nm with blue-shift with decreasing thickness. Electrical transport studies of individual nanoplates show n-type semiconductor characteristics with clear photoresponse. Further, the BiI3 can be readily grown on other 2DLMs (e.g., WSe2 ) to form van der Waals heterostructures. Electrical transport measurements of BiI3 /WSe2 vertical heterojunctions demonstrate p-n diode characteristics with gate-tunable rectification behavior and distinct photovoltaic effect. The synthesis of the BiI3 nanoplates can expand the library of 2DLMs and enable a wider range of van der Waals heterostructures.

Gate-Induced Insulator to Band-Like Transport Transition in Organolead Halide Perovskite.

Understanding the intrinsic charge transport in organolead halide perovskites is essential for the development of high-efficiency photovoltaics and other optoelectronic devices. Despite the rapid advancement of the organolead halide perovskite in photovoltaic and optoelectronic applications, the intrinsic charge-carrier transport in these materials remains elusive partly due to the difficulty of fabricating electrical devices and obtaining good electrical contact. Here we report the fabrication of organolead halide perovskite microplates with mono- or bilayer graphene as low barrier electrical contact. Systematic charge-transport studies reveal an insulator to band-like transport transition. Our studies indicate that the insulator to band-like transport transition depends on the orthorhombic-to-tetragonal phase-transition temperature and defect densities of the organolead halide perovskite microplates. Our findings not only are important for the fundamental understanding of charge-transport behavior but also offer valuable practical implications for photovoltaics and optoelectronic applications based on the organolead halide perovskite.

The Effect of Thermal Annealing on Charge Transport in Organolead Halide Perovskite Microplate Field-Effect Transistors.

Transformation of unipolar n-type semiconductor behavior to ambipolar and finally to unipolar p-type behavior in CH3 NH3 PbI3 microplate field-effect transistors by thermal annealing is reported. The photoluminescence spectra essentially maintain the same features before and after the thermal annealing process, demonstrating that the charge transport measurement provides a sensitive way to probe low-concentration defects in perovskite materials.

Pushing the Performance Limit of Sub-100 nm Molybdenum Disulfide Transistors.

Two-dimensional semiconductors (2DSCs) such as molybdenum disulfide (MoS2) have attracted intense interest as an alternative electronic material in the postsilicon era. However, the ON-current density achieved in 2DSC transistors to date is considerably lower than that of silicon devices, and it remains an open question whether 2DSC transistors can offer competitive performance. A high current device requires simultaneous minimization of the contact resistance and channel length, which is a nontrivial challenge for atomically thin 2DSCs, since the typical low contact resistance approaches for 2DSCs either degrade the electronic properties of the channel or are incompatible with the fabrication process for short channel devices. Here, we report a new approach toward high-performance MoS2 transistors by using a physically assembled nanowire as a lift-off mask to create ultrashort channel devices with pristine MoS2 channel and self-aligned low resistance metal/graphene hybrid contact. With the optimized contact in short channel devices, we demonstrate sub-100 nm MoS2 transistor delivering a record high ON-current of 0.83 mA/µm at 300 K and 1.48 mA/µm at 20 K, which compares well with that of silicon devices. Our study, for the first time, demonstrates that the 2DSC transistors can offer comparable performance to the 2017 target for silicon transistors in International Technology Roadmap for Semiconductors (ITRS), marking an important milestone in 2DSC electronics.

Electronic and Ionic Transport Dynamics in Organolead Halide Perovskites.

Ion migration has been postulated as the underlying mechanism responsible for the hysteresis in organolead halide perovskite devices. However, the electronic and ionic transport dynamics and how they impact each other in organolead halide perovskites remain elusive to date. Here we report a systematic investigation of the electronic and ionic transport dynamics in organolead halide perovskite microplate crystals and thin films using temperature-dependent transient response measurements. Our study reveals that thermally activated ionic and electronic conduction coexist in perovskite devices. The extracted activation energies suggest that the electronic transport is easier, but ions migrate harder in microplates than in thin films, demonstrating that the crystalline quality and grain boundaries can fundamentally modify electronic and ionic transport in perovskites. These findings offer valuable insight on the electronic and ionic transport dynamics in organolead halide perovskites, which is critical for optimizing perovskite devices with reduced hysteresis and improved stability and efficiency.

High-Current-Density Vertical-Tunneling Transistors from Graphene/Highly Doped Silicon Heterostructures.

Scalable fabrication of vertical-tunneling transistors is presented based on heterostructures formed between graphene, highly doped silicon, and its native oxide. Benefiting from the large density of states of highly doped silicon, the tunneling transistors can deliver a current density over 20 A cm(-2) . This study demonstrates that the interfacial native oxide plays a crucial role in governing the carrier transport in graphene-silicon heterostructures.

Size-dependent phase transition in methylammonium lead iodide perovskite microplate crystals.

Methylammonium lead iodide perovskite has attracted considerable recent interest for solution processable solar cells and other optoelectronic applications. The orthorhombic-to-tetragonal phase transition in perovskite can significantly alter its optical, electrical properties and impact the corresponding applications. Here, we report a systematic investigation of the size-dependent orthorhombic-to-tetragonal phase transition using a combined temperature-dependent optical, electrical transport and transmission electron microscopy study. Our studies of individual perovskite microplates with variable thicknesses demonstrate that the phase transition temperature decreases with reducing microplate thickness. The sudden decrease of mobility around phase transition temperature and the presence of hysteresis loops in the temperature-dependent mobility confirm that the orthorhombic-to-tetragonal phase transition is a first-order phase transition. Our findings offer significant fundamental insight on the temperature- and size-dependent structural, optical and charge transport properties of perovskite materials, and can greatly impact future exploration of novel electronic and optoelectronic devices from these materials.

van der Waals Heterojunction Devices Based on Organohalide Perovskites and Two-Dimensional Materials.

The recently emerged organohalide perovskites (e.g., CH3NH3PbI3) have drawn intense attention for high efficiency solar cells. However, with a considerable solubility in many solvents, these perovskites are not typically compatible with conventional lithography processes for more complicated device fabrications that are important for both fundamental studies and technological applications. Here, we report the creation of novel heterojunction devices based on perovskites and two-dimensional (2D) crystals by taking advantage of the layered characteristic of lead iodide (PbI2) and vapor-phase intercalation. We show that a graphene/perovskite/graphene vertical stack can deliver a highest photoresponsivity of ∼950 A/W and photoconductive gain of ∼2200, and a graphene/WSe2/perovskite/graphene heterojunction can display a high on/off ratio (∼10(6)) transistor behavior with distinct gate-tunable diode characteristics and open-circuit voltages. Such unique perovskite-2D heterostructures have significant potential for future optoelectronic research and can enable broad possibilities with compositional tunability of organohalide perovskites and the versatility offered by diverse 2D materials.

Wafer-scale growth of large arrays of perovskite microplate crystals for functional electronics and optoelectronics.

Methylammonium lead iodide perovskite has attracted intensive interest for its diverse optoelectronic applications. However, most studies to date have been limited to bulk thin films that are difficult to implement for integrated device arrays because of their incompatibility with typical lithography processes. We report the first patterned growth of regular arrays of perovskite microplate crystals for functional electronics and optoelectronics. We show that large arrays of lead iodide microplates can be grown from an aqueous solution through a seeded growth process and can be further intercalated with methylammonium iodide to produce perovskite crystals. Structural and optical characterizations demonstrate that the resulting materials display excellent crystalline quality and optical properties. We further show that perovskite crystals can be selectively grown on prepatterned electrode arrays to create independently addressable photodetector arrays and functional field effect transistors. The ability to grow perovskite microplates and to precisely place them at specific locations offers a new material platform for the fundamental investigation of the electronic and optical properties of perovskite materials and opens a pathway for integrated electronic and optoelectronic systems.

An on-chip electrical transport spectroscopy approach for in situ monitoring electrochemical interfaces.

In situ monitoring electrochemical interfaces is crucial for fundamental understanding and continued optimization of electrocatalysts. Conventional spectroscopic techniques are generally difficult to implement for in situ electrochemical studies. Here we report an on-chip electrical transport spectroscopy approach for directly probing the electrochemical surfaces of metallic nanocatalysts in action. With a four-electrode device configuration, we demonstrate that the electrical properties of ultrafine platinum nanowires are highly sensitive and selective to the electrochemical surface states, enabling a nanoelectronic signalling pathway that reveals electrochemical interface information during in-device cyclic voltammetry. Our results not only show a high degree of consistency with generally accepted conclusions in platinum electrochemistry but also offer important insights on various practically important electrochemical reactions. This study defines a nanoelectronic strategy for in situ electrochemical surface studies with high surface sensitivity and surface specificity.

Toward barrier free contact to molybdenum disulfide using graphene electrodes.

Two-dimensional layered semiconductors such as molybdenum disulfide (MoS2) have attracted tremendous interest as a new class of electronic materials. However, there are considerable challenges in making reliable contacts to these atomically thin materials. Here we present a new strategy by using graphene as the back electrodes to achieve ohmic contact to MoS2. With a finite density of states, the Fermi level of graphene can be readily tuned by a gate potential to enable a nearly perfect band alignment with MoS2. We demonstrate for the first time a transparent contact to MoS2 with zero contact barrier and linear output behavior at cryogenic temperatures (down to 1.9 K) for both monolayer and multilayer MoS2. Benefiting from the barrier-free transparent contacts, we show that a metal-insulator transition can be observed in a two-terminal MoS2 device, a phenomenon that could be easily masked by Schottky barriers found in conventional metal-contacted MoS2 devices. With further passivation by boron nitride (BN) encapsulation, we demonstrate a record-high extrinsic (two-terminal) field effect mobility up to 1300 cm(2)/(V s) in MoS2 at low temperature.

Cosolvent approach for solution-processable electronic thin films.

Low-temperature solution-processable electronic materials are of considerable interest for large-area, low-cost electronics, thermoelectrics, and photovoltaics. Using a soluble precursor and suitable solvent to formulate a semiconductor ink is essential for large-area fabrication of semiconductor thin films. To date, it has been shown that hydrazine can be used as a versatile solvent to process a wide range of inorganic semiconductors. However, hydrazine is highly toxic and not suitable for large-scale manufacturing. Here we report a binary mixed solvent of amine and thiol for effective dispersion and dissolution of a large number of inorganic semiconductors including Cu2S, Cu2Se, In2S3, In2Se3, CdS, SnSe, and others. The mixed solvent is significantly less toxic and safer than hydrazine, while at the same time offering the comparable capability of formulating diverse semiconductor ink with a concentration as high as >200 mg/mL. We further show that such ink material can be readily processed into high-performance semiconducting thin films (Cu2S and Cu2Se) with the highest room-temperature conductivity among solution-based materials. Furthermore, we show that complex semiconductor alloys with tunable band gaps, such as CuIn(S(x)Se(1-x))2 (0 ≤ x ≤ 1), can also be readily prepared by simply mixing Cu2S, Cu2Se, In2S3, and In2Se3 ink solutions in a proper ratio. Our study outlines a general strategy for the formulation of inorganic semiconductor ink for low-temperature processing of large-area electronic thin films on diverse substrates and can greatly impact diverse areas including flexible electronics, thermoelectrics, and photovoltaics.

Few-layer molybdenum disulfide transistors and circuits for high-speed flexible electronics.

Two-dimensional layered materials, such as molybdenum disulfide, are emerging as an exciting material system for future electronics due to their unique electronic properties and atomically thin geometry. Here we report a systematic investigation of MoS2 transistors with optimized contact and device geometry, to achieve self-aligned devices with performance including an intrinsic gain over 30, an intrinsic cut-off frequency fT up to 42 GHz and a maximum oscillation frequency fMAX up to 50 GHz, exceeding the reported values for MoS2 transistors to date (fT~0.9 GHz, fMAX~1 GHz). Our results show that logic inverters or radio frequency amplifiers can be formed by integrating multiple MoS2 transistors on quartz or flexible substrates with voltage gain in the gigahertz regime. This study demonstrates the potential of two-dimensional layered semiconductors for high-speed flexible electronics.

Kinetic manipulation of silicide phase formation in Si nanowire templates.

The phase formation sequence of silicides in two-dimensional (2-D) structures has been well-investigated due to their significance in microelectronics. Applying high-quality silicides as contacts in nanoscale silicon (Si) devices has caught considerable attention recently for their potential in improving and introducing new functions in nanodevices. However, nucleation and diffusion mechanisms are found to be very different in one-dimensional (1-D) nanostructures, and thus the phase manipulation of silicides is yet to be achieved there. In this work, we report kinetic phase modulations to selectively enhance or hinder the growth rates of targeted nickel (Ni) silicides in a Si nanowire (NW) and demonstrate that Ni31Si12, δ-Ni2Si, θ-Ni2Si, NiSi, and NiSi2 can emerge as the first contacting phase at the silicide/Si interface through these modulations. First, the growth rates of silicides are selectively tuned through template structure modifications. It is demonstrated that the growth rate of diffusion limited phases can be enhanced in a porous Si NW due to a short diffusion path, which suppresses the formation of interface limited NiSi2. In addition, we show that a confining thick shell can be applied around the Si NW to hinder the growth of the silicides with large volume expansion during silicidation, including Ni31Si12, δ-Ni2Si, and θ-Ni2Si. Second, a platinum (Pt) interlayer between the Ni source and the Si NW is shown to effectively suppress the formation of the phases with low Pt solubility, including the dominating NiSi2. Lastly, we show that with the combined applications of the above-mentioned approaches, the lowest resistive NiSi phase can form as the first phase in a solid NW with a Pt interlayer to suppress NiSi2 and a thick shell to hinder Ni31Si12, δ-Ni2Si, and θ-Ni2Si simultaneously. The resistivity and maximum current density of NiSi agree reasonably to reported values.

Chemical vapor deposition synthesis and Raman spectroscopic characterization of large-area graphene sheets.

We present a chemical vapor deposition (CVD) method to catalytically synthesize large-area, transferless, single- to few-layer graphene sheets using hexamethyldisilazane (HMDS) on a SiO2/Si substrate as a carbon source and thermally evaporated alternating Ni/Cu/Ni layers as a catalyst. The as-synthesized graphene films were characterized by Raman spectroscopic imaging to identify single- to few-layer sheets. This HMDS-derived graphene layer is continuous over the entire growth substrate, and single- to trilayer mixed sheets can be up to 30 µm in the lateral dimension. With the synthetic CVD method proposed here, graphene can be grown into tailored shapes directly on a SiO2/Si surface through vapor priming of HMDS onto predefined photolithographic patterns. The transparent and conductive HMDS-derived graphene exhibits its potential for widespread electronic and opto-electronic applications.

High-quality graphene p-n junctions via resist-free fabrication and solution-based noncovalent functionalization.

An essential issue in graphene nanoelectronics is to engineer the carrier type and density and still preserve the unique band structure of graphene. We report the realization of high-quality graphene p-n junctions by noncovalent chemical functionalization. A generic scheme for the graphene p-n junction fabrication is established by combining the resist-free approach and spatially selective chemical modification process. The effectiveness of the chemical functionalization is systematically confirmed by surface topography and potential measurements, spatially resolved Raman spectroscopic imaging, and transport/magnetotransport measurements. The transport characteristics of graphene p-n junctions are presented with observations of high carrier mobilities, Fermi energy difference, and distinct quantum Hall plateaus. The chemical functionalization of graphene p-n junctions demonstrated in this study is believed to be a feasible scheme for modulating the doping level in graphene for future graphene-based nanoelectronics.