Reduced interface effect of proton beam irradiation on the electrical properties of WSe2/hBN field effect transistors.

Two-dimensional transition metal dichalcogenide (TMDC) semiconductors are emerging as strong contenders for electronic devices that can be used in highly radioactive environments such as outer space where conventional silicon-based devices exhibit nonideal characteristics for such applications. To address the radiation-induced interface effects of TMDC-based electronic devices, we studied high-energy proton beam irradiation effects on the electrical properties of field-effect transistors (FETs) made with tungsten diselenide (WSe2) channels and hexagonal boron-nitride (hBN)/SiO2gate dielectrics. The electrical characteristics of WSe2FETs were measured before and after the irradiation at various proton beam doses of 1013, 1014, and 1015cm-2. In particular, we demonstrated the dependence of proton irradiation-induced effects on hBN layer thickness in WSe2FETs. We observed that the hBN layer reduces the WSe2/dielectric interface effect which would shift the transfer curve of the FET toward the positive direction of the gate voltage. Also, this interface effect was significantly suppressed when a thicker hBN layer was used. This phenomenon can be explained by the fact that the physical separation of the WSe2channel and SiO2dielectric by the hBN interlayer prevents the interface effects originating from the irradiation-induced positive trapped charges in SiO2reaching the interface. This work will help improve our understanding of the interface effect of high-energy irradiation on TMDC-based nanoelectronic devices.

Key research development by Prof Mark Reed in molecular electronic devices.

In memory of Professor Mark Reed, who passed away on May 5, 2021, this article summarizes a series of his past groundbreaking developments in molecular electronic devices. Specifically, three key reports are summarized; measurement of the electrical conductance of molecular junctions using the mechanically controlled break junction technique and demonstration of negative differential resistance and orbital gating effect observed in molecular junctions. Also, a brief outlook on molecular electronics research field is addressed.

Nonlinear Luttinger liquid plasmons in semiconducting single-walled carbon nanotubes.

Interacting electrons confined in one dimension are generally described by the Luttinger liquid formalism, where the low-energy electronic dispersion is assumed to be linear and the resulting plasmonic excitations are non-interacting. Instead, a Luttinger liquid in one-dimensional materials with nonlinear electronic bands is expected to show strong plasmon-plasmon interactions, but an experimental demonstration of this behaviour has been lacking. Here, we combine infrared nano-imaging and electronic transport to investigate the behaviour of plasmonic excitations in semiconducting single-walled carbon nanotubes with carrier density controlled by electrostatic gating. We show that both the propagation velocity and the dynamic damping of plasmons can be tuned continuously, which is well captured by the nonlinear Luttinger liquid theory. These results contrast with the gate-independent plasmons observed in metallic nanotubes, as expected for a linear Luttinger liquid. Our findings provide an experimental demonstration of one-dimensional electron dynamics beyond the conventional linear Luttinger liquid paradigm and are important for understanding excited-state properties in one dimension.

Metallic Carbon Nanotube Nanocavities as Ultracompact and Low-loss Fabry-Perot Plasmonic Resonators.

Plasmonic resonators enable deep subwavelength manipulation of light matter interactions and have been intensively studied both in fundamental physics as well as for potential technological applications. While various metallic nanostructures have been proposed as plasmonic resonators, their performances are rather limited at mid- and far-infrared wavelengths. Recently, highly confined and low-loss Luttinger liquid plasmons in metallic single-walled carbon nanotubes (SWNTs) have been observed at infrared wavelengths. Here, we tailor metallic SWNTs into ultraclean nanocavities by advanced scanning probe lithography and investigate plasmon modes in these individual nanocavities by infrared nanoimaging. The dependence of mode evolutions on cavity length and excitation wavelength can be captured by a Fabry-Perot resonator model of a plasmon nanowaveguide terminated by highly reflective ends. Plasmonic resonators based on SWNT nanocavities approach the ultimate plasmon confinement limit and open the door to the strong light-matter coupling regime, which may enable various nanophotonic applications.

Tunneling Spectroscopy in Carbon Nanotube-Hexagonal Boron Nitride-Carbon Nanotube Heterojunctions.

Electron tunneling spectroscopy is a powerful technique to probe the unique physical properties of one-dimensional (1D) single-walled carbon nanotubes (SWNTs), such as the van Hove singularities in the density of states or the power-law tunneling probability of a Luttinger liquid. However, little is known about the tunneling behavior between two 1D SWNTs over a large energy spectrum. Here, we investigate the electron tunneling behavior between two crossed SWNTs across a wide spectral window up to 2 eV in the unique carbon nanotube-hexagonal boron nitride-carbon nanotube heterojunctions. We observe many sharp resonances in the differential tunneling conductance at different bias voltages applied between the SWNTs. These resonances can be attributed to elastic tunneling into the van Hove singularities of different 1D subbands in both SWNTs, and they allow us to determine the quasi-particle bandgaps and higher-lying 1D subbands in SWNTs on the insulating substrate.

Logarithm Diameter Scaling and Carrier Density Independence of One-Dimensional Luttinger Liquid Plasmon.

Quantum-confined electrons in one-dimensional (1D) metals are described by a Luttinger liquid. The collective charge excitations (i.e., plasmons) in a Luttinger liquid can behave qualitatively different from their conventional counterparts. For example, the Luttinger liquid plasmon velocity is uniquely determined by the electron-electron interaction, which scales logarithmly with the diameter of the 1D material. In addition, the Luttinger liquid plasmon is predicted to be independent of the carrier concentration. Here, we report the observation of such unusual Luttinger liquid plasmon behaviors in metallic single-walled carbon nanotubes, a model system featuring strong electron quantum confinement. We systematically investigate the plasmon propagation in over 30 metallic carbon nanotubes of different diameters using infrared nanoscopy. We establish that the plasmon velocity has a weak logarithm dependence on the nanotube diameter, as predicted by the Luttinger liquid theory. We further study the plasmon excitation as a function of the carrier density in electrostatically gated metallic carbon nanotubes and demonstrate that the plasmon velocity is completely independent of the carrier density. These behaviors are in striking contrast to conventional plasmons in 1D metallic shells, where the plasmon dispersion changes dramatically with the metal electron density and the 1D diameter. The unusual behaviors of Luttinger liquid plasmon may enable novel nanophotonic applications based on carbon nanotubes.

Air-Stable Room-Temperature Mid-Infrared Photodetectors Based on hBN/Black Arsenic Phosphorus/hBN Heterostructures.

Layered black phosphorus (BP) has attracted wide attention for mid-infrared photonics and high-speed electronics, due to its moderate band gap and high carrier mobility. However, its intrinsic band gap of around 0.33 electronvolt limits the operational wavelength range of BP photonic devices based on direct interband transitions to around 3.7 µm. In this work, we demonstrate that black arsenic phosphorus alloy (b-As xP1- x) formed by introducing arsenic into BP can significantly extend the operational wavelength range of photonic devices. The as-fabricated b-As0.83P0.17 photodetector sandwiched within hexagonal boron nitride (hBN) shows peak extrinsic responsivity of 190, 16, and 1.2 mA/W at 3.4, 5.0, and 7.7 µm at room temperature, respectively. Moreover, the intrinsic photoconductive effect dominates the photocurrent generation mechanism due to the preservation of pristine properties of b-As0.83P0.17 by complete hBN encapsulation, and these b-As0.83P0.17 photodetectors exhibit negligible transport hysteresis. The broad and large photoresponsivity within mid-infrared resulting from the intrinsic photoconduction, together with the excellent long-term air stability, makes b-As0.83P0.17 alloy a promising alternative material for mid-infrared applications, such as free-space communication, infrared imaging, and biomedical sensing.

Correlation of Electron Tunneling and Plasmon Propagation in a Luttinger Liquid.

Quantum-confined electrons in one dimension behave as a Luttinger liquid. However, unambiguous demonstration of Luttinger liquid phenomena in single-walled carbon nanotubes (SWNTs) has been challenging. Here we investigate well-defined SWNT cross junctions with a point contact between two Luttinger liquids and combine electrical transport and optical nanoscopy measurements to correlate completely different physical properties (i.e., the electron tunneling and the plasmon propagation) in the same Luttinger liquid system. The suppressed electron tunneling at SWNT junctions exhibits a power-law scaling, which yields a Luttinger liquid interaction parameter that agrees quantitatively with that independently determined from the plasmon velocity based on the near-field optical nanoscopy.

Synthesis of Graphene Nanoribbons by Ambient-Pressure Chemical Vapor Deposition and Device Integration.

Graphene nanoribbons (GNRs), quasi-one-dimensional graphene strips, have shown great potential for nanoscale electronics, optoelectronics, and photonics. Atomically precise GNRs can be "bottom-up" synthesized by surface-assisted assembly of molecular building blocks under ultra-high-vacuum conditions. However, large-scale and efficient synthesis of such GNRs at low cost remains a significant challenge. Here we report an efficient "bottom-up" chemical vapor deposition (CVD) process for inexpensive and high-throughput growth of structurally defined GNRs with varying structures under ambient-pressure conditions. The high quality of our CVD-grown GNRs is validated by a combination of different spectroscopic and microscopic characterizations. Facile, large-area transfer of GNRs onto insulating substrates and subsequent device fabrication demonstrate their promising potential as semiconducting materials, exhibiting high current on/off ratios up to 6000 in field-effect transistor devices. This value is 3 orders of magnitude higher than values reported so far for other thin-film transistors of structurally defined GNRs. Notably, on-surface mass spectrometry analyses of polymer precursors provide unprecedented evidence for the chemical structures of the resulting GNRs, especially the heteroatom doping and heterojunctions. These results pave the way toward the scalable and controllable growth of GNRs for future applications.

Redox sorting of carbon nanotubes.

This work expands the redox chemistry of single-wall carbon nanotubes (SWCNTs) by investigating its role in a number of SWCNT sorting processes. Using a polyethylene glycol (PEG)/dextran (DX) aqueous two-phase system, we show that electron-transfer between redox molecules and SWCNTs triggers reorganization of the surfactant coating layer, leading to strong modulation of nanotube partition in the two phases. While the DX phase is thermodynamically more favored by an oxidized SWCNT mixture, the mildly reducing PEG phase is able to recover SWCNTs from oxidation and extract them successively from the DX phase. Remarkably, the extraction order follows SWCNT bandgap: semiconducting nanotubes of larger bandgap first, followed by semiconducting nanotubes of smaller bandgap, then nonarmchair metallic tubes of small but nonvanishing bandgap, and finally armchair metallic nanotubes of zero bandgap. Furthermore, we show that redox-induced surfactant reorganization is a common phenomenon, affecting nanotube buoyancy in a density gradient field, affinity to polymer matrices, and solubility in organic solvents. These findings establish redox modulation of surfactant coating structures as a general mechanism for tuning a diverse range of SWCNT sorting processes and demonstrate for the first time that armchair and nonarmchair metallic SWCNTs can be separated by their differential response to redox.

Tandem Solar Cells Using GaAs Nanowires on Si: Design, Fabrication, and Observation of Voltage Addition.

Multijunction solar cells provide us a viable approach to achieve efficiencies higher than the Shockley-Queisser limit. Due to their unique optical, electrical, and crystallographic features, semiconductor nanowires are good candidates to achieve monolithic integration of solar cell materials that are not lattice-matched. Here, we report the first realization of nanowire-on-Si tandem cells with the observation of voltage addition of the GaAs nanowire top cell and the Si bottom cell with an open circuit voltage of 0.956 V and an efficiency of 11.4%. Our simulation showed that the current-matching condition plays an important role in the overall efficiency. Furthermore, we characterized GaAs nanowire arrays grown on lattice-mismatched Si substrates and estimated the carrier density using photoluminescence. A low-resistance connecting junction was obtained using n(+)-GaAs/p(+)-Si heterojunction. Finally, we demonstrated tandem solar cells based on top GaAs nanowire array solar cells grown on bottom planar Si solar cells. The reported nanowire-on-Si tandem cell opens up great opportunities for high-efficiency, low-cost multijunction solar cells.

Nearly exclusive growth of small diameter semiconducting single-wall carbon nanotubes from organic chemistry synthetic end-cap molecules.

The inability to synthesize single-wall carbon nanotubes (SWCNTs) possessing uniform electronic properties and chirality represents the major impediment to their widespread applications. Recently, there is growing interest to explore and synthesize well-defined carbon nanostructures, including fullerenes, short nanotubes, and sidewalls of nanotubes, aiming for controlled synthesis of SWCNTs. One noticeable advantage of such processes is that no metal catalysts are used, and the produced nanotubes will be free of metal contamination. Many of these methods, however, suffer shortcomings of either low yield or poor controllability of nanotube uniformity. Here, we report a brand new approach to achieve high-efficiency metal-free growth of nearly pure SWCNT semiconductors, as supported by extensive spectroscopic characterization, electrical transport measurements, and density functional theory calculations. Our strategy combines bottom-up organic chemistry synthesis with vapor phase epitaxy elongation. We identify a strong correlation between the electronic properties of SWCNTs and their diameters in nanotube growth. This study not only provides material platforms for electronic applications of semiconducting SWCNTs but also contributes to fundamental understanding of the growth mechanism and controlled synthesis of SWCNTs.

Highly scalable, uniform, and sensitive biosensors based on top-down indium oxide nanoribbons and electronic enzyme-linked immunosorbent assay.

Nanostructure field-effect transistor (FET) biosensors have shown great promise for ultra sensitive biomolecular detection. Top-down assembly of these sensors increases scalability and device uniformity but faces fabrication challenges in achieving the small dimensions needed for sensitivity. We report top-down fabricated indium oxide (In2O3) nanoribbon FET biosensors using highly scalable radio frequency (RF) sputtering to create uniform channel thicknesses ranging from 50 to 10 nm. We combine this scalable sensing platform with amplification from electronic enzyme-linked immunosorbent assay (ELISA) to achieve high sensitivity to target analytes such as streptavidin and human immunodeficiency virus type 1 (HIV-1) p24 proteins. Our approach circumvents Debye screening in ionic solutions and detects p24 protein at 20 fg/mL (about 250 viruses/mL or about 3 orders of magnitude lower than commercial ELISA) with a 35% conduction change in human serum. The In2O3 nanoribbon biosensors have 100% device yield and use a simple 2 mask photolithography process. The electrical properties of 50 In2O3 nanoribbon FETs showed good uniformity in on-state current, on/off current ratio, mobility, and threshold voltage. In addition, the sensors show excellent pH sensitivity over a broad range (pH 4 to 9) as well as over the physiological-related pH range (pH 6.8 to 8.2). With the demonstrated sensitivity, scalability, and uniformity, the In2O3 nanoribbon sensor platform makes great progress toward clinical testing, such as for early diagnosis of acquired immunodeficiency syndrome (AIDS).

Vapor-phase transport deposition, characterization, and applications of large nanographenes.

Recently, chemical synthesis of a range of large nanographene molecules with various shapes and sizes opened a new path to utilize them in various applications and devices. However, due to their extended aromatic cores and high molecular weight, film formation of large nanographene molecules, bearing more than 90 sp(2) carbon atoms in aromatic cores, is very challenging, which has prevented their applications such as in thin-film transistors. Here, we developed an effective approach to prepare films of such large nanographene molecules using a vapor-phase transport (VPT) technique based on molecule sublimation. The VPT of these molecules was made possible by combining the molecules and the target substrate in a small confinement of vacuum-sealed glass tube, so that a small amount of sublimation can be utilized to create films. Surprisingly, such heavy and large molecules can be deposited on any substrate by this method to create films of assembled large nanographene molecules while maintaining their aromatic cores intact, which was confirmed using mass spectrometry measurements. Moreover, field-effect transistors based on these films are depleted and show significantly improved current on/off ratio compared to previous large nanographene-based transistors fabricated using liquid-phase-based process. Our work shows that VPT deposition can be a viable technique to prepare films based on large nanographene molecules and potentially other high molecular weight compounds, which may find exciting applications in electronics and optoelectronics.

Capacity retention behavior and morphology evolution of SixGe1-x nanoparticles as lithium-ion battery anode.

Engineering silicon into nanostructures has been a well-adopted strategy to improve the cyclic performance of silicon as a lithium-ion battery anode. Here, we show that the electrode performance can be further improved by alloying silicon with germanium. We have evaluated the electrode performance of SixGe1-x nanoparticles (NPs) with different compositions. Experimentally, SixGe1-x NPs with compositions approaching Si50Ge50 are found to have better cyclic retention than both Si-rich and Ge-rich NPs. During the charge/discharge process, NP merging and Si-Ge homogenization are observed. In addition, a distinct morphology difference is observed after 100 cycles, which is believed to be responsible for the different capacity retention behavior. The present study on SixGe1-x alloy NPs sheds light on the development of Si-based electrode materials for stable operation in lithium-ion batteries (e.g., through a comprehensive design of material structure and chemical composition). The investigation of composition-dependent morphology evolution in the delithiated Li-SiGe ternary alloy also significantly broadens our understanding of dealloying in complex systems, and it is complementary to the well-established understanding of dealloying behavior in binary systems (e.g., Au-Ag alloys).

Solution ionic strength engineering as a generic strategy to coat graphene oxide (GO) on various functional particles and its application in high-performance lithium-sulfur (Li-S) batteries.

A generic and facile method of coating graphene oxide (GO) on particles is reported, with sulfur/GO core-shell particles demonstrated as an example for lithium-sulfur (Li-S) battery application with superior performance. Particles of different diameters (ranging from 100 nm to 10 µm), geometries, and compositions (sulfur, silicon, and carbon) are successfully wrapped up by GO, by engineering the ionic strength in solutions. Importantly, our method does not involve any chemical reaction between GO and the wrapped particles, and therefore, it can be extended to vast kinds of functional particles. The applications of sulfur/GO core-shell particles as Li-S battery cathode materials are further investigated, and the results show that sulfur/GO exhibit significant improvements over bare sulfur particles without coating. Galvanic charge-discharge test using GO/sulfur particles shows a specific capacity of 800 mAh/g is retained after 1000 cycles at 1 A/g current rate if only the mass of sulfur is taken into calculation, and 400 mAh/g if the total mass of sulfur/GO is considered. Most importantly, the capacity decay over 1000 cycles is less than 0.02% per cycle. The coating method developed in this study is facile, robust, and versatile and is expected to have wide range of applications in improving the properties of particle materials.

Large-scale fabrication, 3D tomography, and lithium-ion battery application of porous silicon.

Recently, silicon-based lithium-ion battery anodes have shown encouraging results, as they can offer high capacities and long cyclic lifetimes. The applications of this technology are largely impeded by the complicated and expensive approaches in producing Si with desired nanostructures. We report a cost-efficient method to produce nanoporous Si particles from metallurgical Si through ball-milling and inexpensive stain-etching. The porosity of porous Si is derived from particle's three-dimensional reconstructions by scanning transmission electron microscopy (STEM) tomography, which shows the particles' highly porous structure when etched under proper conditions. Nanoporous Si anodes with a reversible capacity of 2900 mAh/g was attained at a charging rate of 400 mA/g, and a stable capacity above 1100 mAh/g was retained for extended 600 cycles tested at 2000 mA/g. The synthetic route is low-cost and scalable for mass production, promising Si as a potential anode material for the next-generation lithium-ion batteries with enhanced capacity and energy density.

Aligned epitaxial SnO2 nanowires on sapphire: growth and device applications.

Semiconducting SnO2 nanowires have been used to demonstrate high-quality field-effect transistors, optically transparent devices, photodetectors, and gas sensors. However, controllable assembly of rutile SnO2 nanowires is necessary for scalable and practical device applications. Here, we demonstrate aligned, planar SnO2 nanowires grown on A-plane, M-plane, and R-plane sapphire substrates. These parallel nanowires can reach 100 µm in length with sufficient density to be patterned photolithographically for field-effect transistors and sensor devices. As proof-of-concept, we show that transistors made this way can achieve on/off current ratios on the order of 10(6), mobilities around 71.68 cm(2)/V·s, and sufficiently high currents to drive external organic light-emitting diode displays. Furthermore, the aligned SnO2 nanowire devices are shown to be photosensitive to UV light with the capability to distinguish between 254 and 365 nm wavelengths. Their alignment is advantageous for polarized UV light detection; we have measured a polarization ratio of photoconductance (σ) of 0.3. Lastly, we show that the nanowires can detect NO2 at a concentration of 0.2 ppb, making them a scalable, ultrasensitive gas sensing technology. Aligned SnO2 nanowires offer a straightforward method to fabricate scalable SnO2 nanodevices for a variety of future electronic applications.

GaAs nanowire array solar cells with axial p-i-n junctions.

Because of unique structural, optical, and electrical properties, solar cells based on semiconductor nanowires are a rapidly evolving scientific enterprise. Various approaches employing III-V nanowires have emerged, among which GaAs, especially, is under intense research and development. Most reported GaAs nanowire solar cells form p-n junctions in the radial direction; however, nanowires using axial junction may enable the attainment of high open circuit voltage (Voc) and integration into multijunction solar cells. Here, we report GaAs nanowire solar cells with axial p-i-n junctions that achieve 7.58% efficiency. Simulations show that axial junctions are more tolerant to doping variation than radial junctions and lead to higher Voc under certain conditions. We further study the effect of wire diameter and junction depth using electrical characterization and cathodoluminescence. The results show that large diameter and shallow junctions are essential for a high extraction efficiency. Our approach opens up great opportunity for future low-cost, high-efficiency photovoltaics.