Tattoo-like epidermal sensors are an emerging class of truly wearable electronics, owing to their thinness and softness. While most of them are based on thin metal films, a silicon membrane, or nanoparticle-based printable inks, we report sub-micrometer thick, multimodal electronic tattoo sensors that are made of graphene. The graphene electronic tattoo (GET) is designed as filamentary serpentines and fabricated by a cost- and time-effective “wet transfer, dry patterning” method. It has a total thickness of 463 ± 30 nm, an optical transparency of ∼85%, and a stretchability of more than 40%. The GET can be directly laminated on human skin just like a temporary tattoo and can fully conform to the microscopic morphology of the surface of skin via just van der Waals forces. The open-mesh structure of the GET makes it breathable and its stiffness negligible. A bare GET is able to stay attached to skin for several hours without fracture or delamination. With liquid bandage coverage, a GET may stay functional on the skin for up to several days. As a dry electrode, GET–skin interface impedance is on par with medically used silver/silver-chloride (Ag/AgCl) gel electrodes, while offering superior comfort, mobility, and reliability. GET has been successfully applied to measure electrocardiogram (ECG), electromyogram (EMG), electroencephalogram (EEG), skin temperature, and skin hydration.Keywords: biosensor; electronic tattoo; epidermal electronics; graphene; wearable electronics;

Black phosphorus (BP) has attracted rapidly growing attention for high speed and low power nanoelectronics owing to its compelling combination of tunable bandgap (0.3 to 2 eV) and high carrier mobility (up to ∼1000 cm2/V·s) at room temperature. In this work, we report the first radio frequency (RF) flexible top-gated (TG) BP thin-film transistors on highly bendable polyimide substrate for GHz nanoelectronic applications. Enhanced p-type charge transport with low-field mobility ∼233 cm2/V·s and current density of ∼100 μA/μm at VDS = −2 V were obtained from flexible BP transistor at a channel length L = 0.5 μm. Importantly, with optimized dielectric coating for air-stability during microfabrication, flexible BP RF transistors afforded intrinsic maximum oscillation frequency fMAX ∼ 14.5 GHz and unity current gain cutoff frequency fT ∼ 17.5 GHz at a channel length of 0.5 μm. Notably, the experimental fT achieved here is at least 45% higher than prior results on rigid substrate, which is attributed to the improved air-stability of fabricated BP devices. In addition, the high-frequency performance was investigated through mechanical bending test up to ∼1.5% tensile strain, which is ultimately limited by the inorganic dielectric film rather than the 2D material. Comparison of BP RF devices to other 2D semiconductors clearly indicates that BP offers the highest saturation velocity, an important metric for high-speed and RF flexible nanosystems.

We report the first direct dry transfer of a single-crystalline thin film grown by molecular beam epitaxy. A double cantilever beam fracture technique was used to transfer epitaxial bismuth thin films grown on silicon (111) to silicon strips coated with epoxy. The transferred bismuth films retained electrical, optical, and structural properties comparable to the as-grown epitaxial films. Additionally, we isolated the bismuth thin films on freestanding flexible cured-epoxy post-transfer. The adhesion energy at the bismuth/silicon interface was measured to be ∼1 J/m2, comparable to that of exfoliated and wet transferred graphene. This low adhesion energy and ease of transfer is unexpected for an epitaxially grown film and may enable the study of bismuth’s unique electronic and spintronic properties on arbitrary substrates. Moreover, this method suggests a route to integrate other group-V epitaxial films (i.e., phosphorus) with arbitrary substrates, as well as potentially to isolate bismuthene, the atomic thin-film limit of bismuth.Keywords: 2D electronics; bismuth; Molecular beam epitaxy; thin films; transfer;

Controlling the band gap by tuning the lattice structure through pressure engineering is a relatively new route for tailoring the optoelectronic properties of two-dimensional (2D) materials. Here, we investigate the electronic structure and lattice vibrational dynamics of the distorted monolayer 1T-MoS2 (1T′) and the monolayer 2H-MoS2 via a diamond anvil cell (DAC) and density functional theory (DFT) calculations. The direct optical band gap of the monolayer 2H-MoS2 increases by 11.7% from 1.85 to 2.08 eV, which is the highest reported for a 2D transition metal dichalcogenide (TMD) material. DFT calculations reveal a subsequent decrease in the band gap with eventual metallization of the monolayer 2H-MoS2, an overall complex structure–property relation due to the rich band structure of MoS2. Remarkably, the metastable 1T′-MoS2 metallic state remains invariant with pressure, with the J2, A1g, and E2g modes becoming dominant at high pressures. This substantial reversible tunability of the electronic and vibrational properties of the MoS2 family can be extended to other 2D TMDs. These results present an important advance toward controlling the band structure and optoelectronic properties of monolayer MoS2 via pressure, which has vital implications for enhanced device applications.

High-mobility two-dimensional (2D) semiconductors are desirable for high-performance mechanically flexible nanoelectronics. In this work, we report the first flexible black phosphorus (BP) field-effect transistors (FETs) with electron and hole mobilities superior to what has been previously achieved with other more studied flexible layered semiconducting transistors such as MoS2 and WSe2. Encapsulated bottom-gated BP ambipolar FETs on flexible polyimide afforded maximum carrier mobility of about 310 cm2/V·s with field-effect current modulation exceeding 3 orders of magnitude. The device ambipolar functionality and high-mobility were employed to realize essential circuits of electronic systems for flexible technology including ambipolar digital inverter, frequency doubler, and analog amplifiers featuring voltage gain higher than other reported layered semiconductor flexible amplifiers. In addition, we demonstrate the first flexible BP amplitude-modulated (AM) demodulator, an active stage useful for radio receivers, based on a single ambipolar BP transistor, which results in audible signals when connected to a loudspeaker or earphone. Moreover, the BP transistors feature mechanical robustness up to 2% uniaxial tensile strain and up to 5000 bending cycles.

Thin metal films can be used to catalyze the growth of nanomaterials in place of the bulk metal, while greatly reducing the amount of material used. A big drawback of copper thin films (0.5–1.5 μm thick) is that, under high temperature/vacuum synthesis, the mass loss of films severely reduces the process time due to discontinuities in the metal film, thereby limiting the time scale for controlling metal grain and film growth. In this work, we have developed a facile method, namely “covered growth” to extend the time copper thin films can be exposed to high temperature/vacuum environment for graphene synthesis. The key to preventing severe mass loss of copper film during the high temperature chemical vapor deposition (CVD) process is to have a cover piece on top of the growth substrate. This new “covered growth” method enables the high-temperature annealing of the copper film upward of 4 h with minimal mass loss, while increasing copper film grain and graphene domain size. Graphene was then successfully grown on the capped copper film with subsequent transfer for device fabrication. Device characterization indicated equivalent physical, chemical, and electrical properties to conventional CVD graphene. Our “covered growth” provides a convenient and effective solution to the mass loss issue of thin films that serve as catalysts for a variety of 2D material syntheses.Keywords: copper; CVD graphene; evaporation; grain growth; thin film

Tungsten disulfide (WS2) is a layered transition metal dichalcogenide (TMD) that differs from other two-dimensional (2D) compounds such as graphene due to its unique semiconducting, tunable-band-gap nature. Multilayered WS2 exhibits an indirect band gap Eg of ∼1.3 eV, along with a higher load-bearing ability that is promising for strain-tuning device applications, but the electronic properties of multilayered WS2 at higher strain conditions (i.e., static strain >12%) remain an open question. Here we have studied the structural, electronic, electrical, and vibrational properties of multilayered WS2 at hydrostatic pressures up to ∼35 GPa experimentally in a diamond anvil cell and theoretically using first-principles ab initio calculations. Our results show that WS2 undergoes an isostructural semiconductor-to-metallic (S–M) transition at approximately 22 GPa at 280 K, which arises from the overlap of the highest valence and lowest conduction bands. The S–M transition is caused by increased sulfur–sulfur interactions as the interlayer spacing decreases with applied hydrostatic pressure. The metalization in WS2 can be alternatively interpreted as a 2D to 3D (three-dimensional) phase transition that is associated with a substantial modulation of the charge carrier characteristics including a 6-order decrease in resistivity, a 2-order decrease in mobility, and a 4-order increase in carrier concentration. These distinct pressure-tunable characteristics of the dimensionalized WS2 differentiate it from other TMD compounds such as MoS2 and promise future developments in strain-modulated advanced devices.Keywords: 2D materials; diamond anvil cell; pressure engineering; strain; transition metal dichalcogenides;

The largest applications of high-performance graphene will likely be realized when combined with ubiquitous Si very large scale integrated (VLSI) technology, affording a new portfolio of “back end of the line” devices including graphene radio frequency transistors, heat and transparent conductors, interconnects, mechanical actuators, sensors, and optical devices. To this end, we investigate the scalable growth of polycrystalline graphene through chemical vapor deposition (CVD) and its integration with Si VLSI technology. The large-area Raman mapping on CVD polycrystalline graphene on 150 and 300 mm wafers reveals >95% monolayer uniformity with negligible defects. About 26 000 graphene field-effect transistors were realized, and statistical evaluation indicates a device yield of ∼74% is achieved, 20% higher than previous reports. About 18% of devices show mobility of >3000 cm2/(V s), more than 3 times higher than prior results obtained over the same range from CVD polycrystalline graphene. The peak mobility observed here is ∼40% higher than the peak mobility values reported for single-crystalline graphene, a major advancement for polycrystalline graphene that can be readily manufactured. Intrinsic graphene features such as soft current saturation and three-region output characteristics at high field have also been observed on wafer-scale CVD graphene on which frequency doubler and amplifiers are demonstrated as well. Our growth and transport results on scalable CVD graphene have enabled 300 mm synthesis instrumentation that is now commercially available.Keywords: analog applications; CVD; device performance statistics; field-effect transistors; mobility; polycrystalline graphene; wafer-scale integration;

While there has been increasing studies of MoS2 and other two-dimensional (2D) semiconducting dichalcogenides on hard conventional substrates, experimental or analytical studies on flexible substrates has been very limited so far, even though these 2D crystals are understood to have greater prospects for flexible smart systems. In this article, we report detailed studies of MoS2 transistors on industrial plastic sheets. Transistor characteristics afford more than 100x improvement in the ON/OFF current ratio and 4x enhancement in mobility compared to previous flexible MoS2 devices. Mechanical studies reveal robust electronic properties down to a bending radius of 1 mm which is comparable to previous reports for flexible graphene transistors. Experimental investigation identifies that crack formation in the dielectric is the responsible failure mechanism demonstrating that the mechanical properties of the dielectric layer is critical for realizing flexible electronics that can accommodate high strain. Our uniaxial tensile tests have revealed that atomic-layer-deposited HfO2 and Al2O3 films have very similar crack onset strain. However, crack propagation is slower in HfO2 dielectric compared to Al2O3 dielectric, suggesting a subcritical fracture mechanism in the thin oxide films. Rigorous mechanics modeling provides guidance for achieving flexible MoS2 transistors that are reliable at sub-mm bending radius.Keywords: bending radius; crack formation; critical strain; field-effect transistor; flexible transistor; graphene; mobility; MoS2; polyimide; transition metal dichalcogenides

Despite the widespread interest in graphene electronics over the past decade, high-performance graphene field-effect transistors (GFETs) on flexible substrates have been rarely achieved, even though this atomic sheet is widely understood to have greater prospects for flexible electronic systems. In this article, we report detailed studies on the electrical and mechanical properties of vapor synthesized high-quality monolayer graphene integrated onto flexible polyimide substrates. Flexible graphene transistors with high-k dielectric afforded intrinsic gain, maximum carrier mobilities of 3900 cm2/V·s, and importantly, 25 GHz cutoff frequency, which is more than a factor of 2.5 times higher than prior results. Mechanical studies reveal robust transistor performance under repeated bending, down to 0.7 mm bending radius, whose tensile strain is a factor of 2–5 times higher than in prior studies. In addition, integration of functional coatings such as highly hydrophobic fluoropolymers combined with the self-passivation properties of the polyimide substrate provides water-resistant protection without compromising flexibility, which is an important advancement for the realization of future robust flexible systems based on graphene.Keywords: CVD graphene; field effect transistors; flexible electronics; mobility; RF and analog device; transit frequency; water-resistant

We report new findings on the chemical vapor deposition (CVD) of monolayer graphene with negligible defects (≥95% negligible defect-peak over 200 μm × 200 μm areas) on evaporated copper films. Compared to copper foils used in the CVD of graphene, several new unexpected results have been observed including high-quality monolayer synthesis at temperatures <900 °C, a new growth window using a hydrogen-free methane precursor for low-defects, and electron microscope evidence of commensurate growth of graphene grains on underlying copper grains. These thermal, chemical, and physical growth characteristics of graphene on copper films can be attributed to the distinct differences in the dominant crystal orientation of copper films (111) versus foils (100), and consequent dissimilar interplay with the precursor gas. This study suggests that reduced temperature, hydrogen-free synthesis of defect-negligible monolayer graphene is feasible, with the potential to shape and scale graphene grains by controlling the size and crystal orientation of the underlying copper grains.Keywords: chemical vapor deposition; crystal orientation; Cu (111); graphene; hydrogen; methane

This article demonstrated monolayer graphene grown on annealed Cu (111) films on standard oxidized 100-mm Si wafers with higher quality than existing reports. Large area Raman mapping indicated high uniformity (>97% coverage) of monolayer graphene with immeasurable defects (>95% defect-negligible) across the entire wafer. Key to these results is the phase transition of evaporated copper films from amorphous to (111) preferred crystalline, which resulted in subsequent growth of high quality graphene, as corroborated by X-ray diffraction and electron backscatter diffraction. Noticeably, such phase transition of the copper film was observed on a technologically ubiquitous Si wafer with a standard amorphous thermal oxide. A modified two-step etching transfer process was introduced to preserve the clean surface and electrical property of transferred monolayer graphene. The fabricated graphene field effect transistor on a flexible polyimide film achieved peak mobility over 4900 cm2/(V s) at ambient condition.

We report on the gigahertz radio frequency (RF) performance of chemical vapor deposited (CVD) monolayer MoS2 field-effect transistors (FETs). Initial DC characterizations of fabricated MoS2 FETs yielded current densities exceeding 200 μA/μm and maximum transconductance of 38 μS/μm. A contact resistance corrected low-field mobility of 55 cm2/(V s) was achieved. Radio frequency FETs were fabricated in the ground–signal–ground (GSG) layout, and standard de-embedding techniques were applied. Operating at the peak transconductance, we obtain short-circuit current-gain intrinsic cutoff frequency, fT, of 6.7 GHz and maximum intrinsic oscillation frequency, fmax, of 5.3 GHz for a device with a gate length of 250 nm. The MoS2 device afforded an extrinsic voltage gain Av of 6 dB at 100 MHz with voltage amplification until 3 GHz. With the as-measured frequency performance of CVD MoS2, we provide the first demonstration of a common-source (CS) amplifier with voltage gain of 14 dB and an active frequency mixer with conversion gain of −15 dB. Our results of gigahertz frequency performance as well as analog circuit operation show that large area CVD MoS2 may be suitable for industrial-scale electronic applications.

Because of the drastically different intralayer versus interlayer bonding strengths, the mechanical, thermal, and electrical properties of two-dimensional (2D) materials are highly anisotropic between the in-plane and out-of-plane directions. The structural anisotropy may also play a role in chemical reactions, such as oxidation, reduction, and etching. Here, the composition, structure, and electrical properties of mechanically exfoliated WSe2 nanosheets on SiO2/Si substrates were studied as a function of the extent of thermal oxidation. A major component of the oxidation, as indicated from optical and Raman data, starts from the nanosheet edges and propagates laterally toward the center. Partial oxidation also occurs in certain areas at the surface of the flakes, which are shown to be highly conductive by microwave impedance microscopy. Using secondary ion mass spectroscopy, we also observed extensive oxidation at the WSe2–SiO2 interface. The combination of multiple microcopy methods can thus provide vital information on the spatial evolution of chemical reactions on 2D materials and the nanoscale electrical properties of the reaction products.