Precise pitch-scaling of carbon nanotube arrays within three-dimensional DNA nanotrenches.

Precise fabrication of semiconducting carbon nanotubes (CNTs) into densely aligned evenly spaced arrays is required for ultrascaled technology nodes. We report the precise scaling of inter-CNT pitch using a supramolecular assembly method called spatially hindered integration of nanotube electronics. Specifically, by using DNA brick crystal-based nanotrenches to align DNA-wrapped CNTs through DNA hybridization, we constructed parallel CNT arrays with a uniform pitch as small as 10.4 nanometers, at an angular deviation <2° and an assembly yield >95%.

Flat Monolayer Graphene Cathodes for Li-Oxygen Microbatteries.

Miniature batteries can accelerate the development of mobile electronics by providing sufficient energy to power small devices. Typical microbatteries commonly use thin-film inorganic electrodes based on Li-ion insertion reaction. However, they rely on the complicated thin-film synthesis method of inorganics containing many elements. Graphene, one atomic layer thick carbon sheet, has diverse physical and chemical properties and is compatible with conventional micron-scale device fabrication. Here, we study the use of chemical vapor deposition (CVD) grown monolayer graphene in a two-dimensional configuration, as a future Li-oxygen microbattery cathode. By maximizing the dissolution of discharge intermediates, we obtain 2610 Ah/ggraphene of capacity corresponding to 20% higher areal cathode energy density and 2.7 times higher cathode specific energy than that can be derived from the same volume or mass of conventional Li-ion battery cathode material. Furthermore, a clear observation on the discharge reaction on composite electrodes and their role in the charging reaction was made, thanks to the two-dimensional monolayer graphene Li-oxygen battery cathode. We demonstrate an easy integration of two-dimensional CVD graphene cathode into microscale devices by simply transferring or coating the target device substrate with flexible graphene layers. The ability to integrate and use monolayer graphene on arbitrary device substrates as well as precise control over a chemical derivation of the carbon interface can have a radical impact on future energy-storage devices.

Intrinsically ultrastrong plasmon-exciton interactions in crystallized films of carbon nanotubes.

In cavity quantum electrodynamics, optical emitters that are strongly coupled to cavities give rise to polaritons with characteristics of both the emitters and the cavity excitations. We show that carbon nanotubes can be crystallized into chip-scale, two-dimensionally ordered films and that this material enables intrinsically ultrastrong emitter-cavity interactions: Rather than interacting with external cavities, nanotube excitons couple to the near-infrared plasmon resonances of the nanotubes themselves. Our polycrystalline nanotube films have a hexagonal crystal structure, ∼25-nm domains, and a 1.74-nm lattice constant. With this extremely high nanotube density and nearly ideal plasmon-exciton spatial overlap, plasmon-exciton coupling strengths reach 0.5 eV, which is 75% of the bare exciton energy and a near record for room-temperature ultrastrong coupling. Crystallized nanotube films represent a milestone in nanomaterials assembly and provide a compelling foundation for high-ampacity conductors, low-power optical switches, and tunable optical antennas.

Large-Area High-Performance Flexible Pressure Sensor with Carbon Nanotube Active Matrix for Electronic Skin.

Artificial "electronic skin" is of great interest for mimicking the functionality of human skin, such as tactile pressure sensing. Several important performance metrics include mechanical flexibility, operation voltage, sensitivity, and accuracy, as well as response speed. In this Letter, we demonstrate a large-area high-performance flexible pressure sensor built on an active matrix of 16 × 16 carbon nanotube thin-film transistors (CNT TFTs). Made from highly purified solution tubes, the active matrix exhibits superior flexible TFT performance with high mobility and large current density, along with a high device yield of nearly 99% over 4 inch sample area. The fully integrated flexible pressure sensor operates within a small voltage range of 3 V and shows superb performance featuring high spatial resolution of 4 mm, faster response than human skin (<30 ms), and excellent accuracy in sensing complex objects on both flat and curved surfaces. This work may pave the road for future integration of high-performance electronic skin in smart robotics and prosthetic solutions.

Atomically Thin Femtojoule Memristive Device.

The morphology and dimension of the conductive filament formed in a memristive device are strongly influenced by the thickness of its switching medium layer. Aggressive scaling of this active layer thickness is critical toward reducing the operating current, voltage, and energy consumption in filamentary-type memristors. Previously, the thickness of this filament layer has been limited to above a few nanometers due to processing constraints, making it challenging to further suppress the on-state current and the switching voltage. Here, the formation of conductive filaments in a material medium with sub-nanometer thickness formed through the oxidation of atomically thin two-dimensional boron nitride is studied. The resulting memristive device exhibits sub-nanometer filamentary switching with sub-pA operation current and femtojoule per bit energy consumption. Furthermore, by confining the filament to the atomic scale, current switching characteristics are observed that are distinct from that in thicker medium due to the profoundly different atomic kinetics. The filament morphology in such an aggressively scaled memristive device is also theoretically explored. These ultralow energy devices are promising for realizing femtojoule and sub-femtojoule electronic computation, which can be attractive for applications in a wide range of electronics systems that desire ultralow power operation.

Strong and Broadly Tunable Plasmon Resonances in Thick Films of Aligned Carbon Nanotubes.

Low-dimensional plasmonic materials can function as high quality terahertz and infrared antennas at deep subwavelength scales. Despite these antennas' strong coupling to electromagnetic fields, there is a pressing need to further strengthen their absorption. We address this problem by fabricating thick films of aligned, uniformly sized semiconducting carbon nanotubes and showing that their plasmon resonances are strong, narrow, and broadly tunable. With thicknesses ranging from 25 to 250 nm, our films exhibit peak attenuation reaching 70%, ensemble quality factors reaching 9, and electrostatically tunable peak frequencies by a factor of 2.3. Excellent nanotube alignment leads to the attenuation being 99% linearly polarized along the nanotube axis. Increasing the film thickness blueshifts the plasmon resonators down to peak wavelengths as low as 1.4 µm, a new near-infrared regime in which they can both overlap the S11 nanotube exciton energy and access the technologically important infrared telecom band.

Spatially Selective, High-Density Placement of Polyfluorene-Sorted Semiconducting Carbon Nanotubes in Organic Solvents.

High-performance logic based on carbon nanotubes (CNTs) requires high-density arrays of selectively placed semiconducting CNTs. Although polymer-wrapping methods can allow CNTs to be sorted to a >99.9% semiconducting purity, patterning these polymer-wrapped CNTs is an outstanding problem. We report the directed self-assembly of polymer-coated semiconducting CNTs using self-assembled monolayers that bind CNTs into arrays of patterned trenches. We demonstrate that CNTs can be placed into 100 nm wide HfO2 trenches with an electrical connection yield as high as 90% and into 50 nm wide trenches with a yield as high as 70%. Our directed self-assembly method is an important step forward in pitch scaling.

Coherent Plasmon and Phonon-Plasmon Resonances in Carbon Nanotubes.

Carbon nanotubes provide a rare access point into the plasmon physics of one-dimensional electronic systems. By assembling purified nanotubes into uniformly sized arrays, we show that they support coherent plasmon resonances, that these plasmons couple to nanotube and substrate phonons, and that the resulting phonon-plasmon resonances have quality factors as high as 10. Because nanotube plasmons intensely strengthen electromagnetic fields and light-matter interactions, they provide a compelling platform for surface-enhanced spectroscopy and tunable optical devices at deep-subwavelength scales.

Carbon nanotube transistors scaled to a 40-nanometer footprint.

The International Technology Roadmap for Semiconductors challenges the device research community to reduce the transistor footprint containing all components to 40 nanometers within the next decade. We report on a p-channel transistor scaled to such an extremely small dimension. Built on one semiconducting carbon nanotube, it occupies less than half the space of leading silicon technologies, while delivering a significantly higher pitch-normalized current density-above 0.9 milliampere per micrometer at a low supply voltage of 0.5 volts with a subthreshold swing of 85 millivolts per decade. Furthermore, we show transistors with the same small footprint built on actual high-density arrays of such nanotubes that deliver higher current than that of the best-competing silicon devices under the same overdrive, without any normalization. We achieve this using low-resistance end-bonded contacts, a high-purity semiconducting carbon nanotube source, and self-assembly to pack nanotubes into full surface-coverage aligned arrays.

High-speed logic integrated circuits with solution-processed self-assembled carbon nanotubes.

As conventional monolithic silicon technology struggles to meet the requirements for the 7-nm technology node, there has been tremendous progress in demonstrating the scalability of carbon nanotube field-effect transistors down to the size that satisfies the 3-nm node and beyond. However, to date, circuits built with carbon nanotubes have overlooked key aspects of a practical logic technology and have stalled at simple functionality demonstrations. Here, we report high-performance complementary carbon nanotube ring oscillators using fully manufacturable processes, with a stage switching frequency of 2.82 GHz. The circuit was built on solution-processed, self-assembled carbon nanotube arrays with over 99.9% semiconducting purity, and the complementary feature was achieved by employing two different work function electrodes.

Single Crystal Flexible Electronics Enabled by 3D Spalling.

Flexible and stretchable electronics are becoming increasingly important in many emerging applications. Due to the outstanding electrical properties of single crystal semiconductors, there is great interest in releasing single crystal thin films and fabricating flexible electronics with these conventionally rigid materials. In this study the authors report a universal single crystal layer release process, called "3D spalling," extending beyond prior art. In contrast to the conventional way of removing blanket layers from their substrates, the new process reported here enables 3D control over the shape and thickness of the removed regions, allowing direct formation of arbitrarily shaped structures of released film and locally specified thickness for each region. As an exemplary demonstration, silicon flexible tactile sensors are fabricated with sensitivities comparable to those of high performance sensors on rigid substrates. Finite element modeling indicates that the size and thickness of the selectively released features can be tuned over a wide range.

Coupling-Enhanced Broadband Mid-infrared Light Absorption in Graphene Plasmonic Nanostructures.

Plasmons in graphene nanostructures show great promise for mid-infrared applications ranging from a few to tens of microns. However, mid-infrared plasmonic resonances in graphene nanostructures are usually weak and narrow-banded, limiting their potential in light manipulation and detection. Here, we investigate the coupling among graphene plasmonic nanostructures and further show that, by engineering the coupling, enhancement of light-graphene interaction strength and broadening of spectral width can be achieved simultaneously. Leveraging the concept of coupling, we demonstrate a hybrid two-layer graphene nanoribbon array which shows 5-7% extinction within the entire 8-14 µm (∼700-1250 cm-1) wavelength range, covering one of the important atmosphere "infrared transmission windows". Such coupled hybrid graphene plasmonic nanostructures may find applications in infrared sensing and free-space communications.

A Dynamically Reconfigurable Ambipolar Black Phosphorus Memory Device.

Nonvolatile charge-trap memory plays an important role in many modern electronics technologies, from portable electronic systems to large-scale data centers. Conventional charge-trap memory devices typically work with fixed channel carrier polarity and device characteristics. However, many emerging applications in reconfigurable electronics and neuromorphic computing require dynamically tunable properties in their electronic device components that can lead to enhanced circuit versatility and system functionalities. Here, we demonstrate an ambipolar black phosphorus (BP) charge-trap memory device with dynamically reconfigurable and polarity-reversible memory behavior. This BP memory device shows versatile memory properties subject to electrostatic bias. Not only the programmed/erased state current ratio can be continuously tuned by the back-gate bias, but also the polarity of the carriers in the BP channel can be reversibly switched between electron- and hole-dominated conductions, resulting in the erased and programmed states exhibiting interchangeable high and low current levels. The BP memory also shows four different memory states and, hence, 2-bit per cell data storage for both n-type and p-type channel conductions, demonstrating the multilevel cell storage capability in a layered material based memory device. The BP memory device with a high mobility and tunable programmed/erased state current ratio and highly reconfigurable device characteristics can offer adaptable memory device properties for many emerging applications in electronics technology, such as neuromorphic computing, data-adaptive energy efficient memory, and dynamically reconfigurable digital circuits.

Black Phosphorus Mid-Infrared Photodetectors with High Gain.

Recently, black phosphorus (BP) has joined the two-dimensional material family as a promising candidate for photonic applications due to its moderate bandgap, high carrier mobility, and compatibility with a diverse range of substrates. Photodetectors are probably the most explored BP photonic devices, however, their unique potential compared with other layered materials in the mid-infrared wavelength range has not been revealed. Here, we demonstrate BP mid-infrared detectors at 3.39 µm with high internal gain, resulting in an external responsivity of 82 A/W. Noise measurements show that such BP photodetectors are capable of sensing mid-infrared light in the picowatt range. Moreover, the high photoresponse remains effective at kilohertz modulation frequencies, because of the fast carrier dynamics arising from BP's moderate bandgap. The high photoresponse at mid-infrared wavelengths and the large dynamic bandwidth, together with its unique polarization dependent response induced by low crystalline symmetry, can be coalesced to promise photonic applications such as chip-scale mid-infrared sensing and imaging at low light levels.

High-Performance p-Type Black Phosphorus Transistor with Scandium Contact.

A record high current density of 580 µA/µm is achieved for long-channel, few-layer black phosphorus transistors with scandium contacts after 400 K vacuum annealing. The annealing effectively improves the on-state current and Ion/Ioff ratio by 1 order of magnitude and the subthreshold swing by ∼2.5×, whereas Al2O3 capping significantly degrades transistor performances, resulting in 5× lower on-state current and 3× lower Ion/Ioff ratio. The influences of moisture on black phosphorus metal contacts are elucidated by analyzing the hysteresis of 3-20 nm thick black phosphorus transistors with scandium and gold contacts under different conditions: as-fabricated, after vacuum annealing, and after Al2O3 capping. The optimal black phosphorus film thickness for transistors with scandium contacts is found to be ∼10 nm. Moreover, p-type performance is shown in all transistors with scandium contacts, suggesting that the Fermi level is pinned closer to the valence band regardless of the flake thickness.

Physically unclonable cryptographic primitives using self-assembled carbon nanotubes.

Information security underpins many aspects of modern society. However, silicon chips are vulnerable to hazards such as counterfeiting, tampering and information leakage through side-channel attacks (for example, by measuring power consumption, timing or electromagnetic radiation). Single-walled carbon nanotubes are a potential replacement for silicon as the channel material of transistors due to their superb electrical properties and intrinsic ultrathin body, but problems such as limited semiconducting purity and non-ideal assembly still need to be addressed before they can deliver high-performance electronics. Here, we show that by using these inherent imperfections, an unclonable electronic random structure can be constructed at low cost from carbon nanotubes. The nanotubes are self-assembled into patterned HfO2 trenches using ion-exchange chemistry, and the width of the trench is optimized to maximize the randomness of the nanotube placement. With this approach, two-dimensional (2D) random bit arrays are created that can offer ternary-bit architecture by determining the connection yield and switching type of the nanotube devices. As a result, our cryptographic keys provide a significantly higher level of security than conventional binary-bit architecture with the same key size.

End-bonded contacts for carbon nanotube transistors with low, size-independent resistance.

Moving beyond the limits of silicon transistors requires both a high-performance channel and high-quality electrical contacts. Carbon nanotubes provide high-performance channels below 10 nanometers, but as with silicon, the increase in contact resistance with decreasing size becomes a major performance roadblock. We report a single-walled carbon nanotube (SWNT) transistor technology with an end-bonded contact scheme that leads to size-independent contact resistance to overcome the scaling limits of conventional side-bonded or planar contact schemes. A high-performance SWNT transistor was fabricated with a sub-10-nanometer contact length, showing a device resistance below 36 kilohms and on-current above 15 microampere per tube. The p-type end-bonded contact, formed through the reaction of molybdenum with the SWNT to form carbide, also exhibited no Schottky barrier. This strategy promises high-performance SWNT transistors, enabling future ultimately scaled device technologies.

Power Dissipation and Electrical Breakdown in Black Phosphorus.

We report operating temperatures and heating coefficients measured in a multilayer black phosphorus device as a function of injected electrical power. By combining micro-Raman spectroscopy and electrical transport measurements, we have observed a linear temperature increase up to 600 K at a power dissipation rate of 0.896 K µm(3)/mW. By further increasing the bias voltage, we determined the threshold power and temperature for electrical breakdown and analyzed the fracture in the black phosphorus layer that caused the device failure by means of scanning electron microscopy and atomic force microscopy. The results will benefit the research and development of electronics and optoelectronics based on novel two-dimensional materials.

Origins and characteristics of the threshold voltage variability of quasiballistic single-walled carbon nanotube field-effect transistors.

Ultrascaled transistors based on single-walled carbon nanotubes are identified as one of the top candidates for future microprocessor chips as they provide significantly better device performance and scaling properties than conventional silicon technologies. From the perspective of the chip performance, the device variability is as important as the device performance for practical applications. This paper presents a systematic investigation on the origins and characteristics of the threshold voltage (VT) variability of scaled quasiballistic nanotube transistors. Analysis of experimental results from variable-temperature measurement as well as gate oxide thickness scaling studies shows that the random variation from fixed charges present on the oxide surface close to nanotubes dominates the VT variability of nanotube transistors. The VT variability of single-tube transistors has a figure of merit that is quantitatively comparable with that of current silicon devices; and it could be reduced with the adoption of improved device passivation schemes, which might be necessary for practical devices incorporating multiple nanotubes, whose area normalized VT variability becomes worse due to the synergic effects from the limited surface coverage of nanotubes and the nonlinearity of the device off-state leakage current, as predicted by the Monte Carlo simulation.

Black phosphorus radio-frequency transistors.

Few-layer and thin film forms of layered black phosphorus (BP) have recently emerged as a promising material for applications in high performance nanoelectronics and infrared optoelectronics. Layered BP thin films offer a moderate bandgap of around 0.3 eV and high carrier mobility, which lead to transistors with decent on-off ratios and high on-state current densities. Here, we demonstrate the gigahertz frequency operation of BP field-effect transistors for the first time. The BP transistors demonstrated here show respectable current saturation with an on-off ratio that exceeds 2 × 10(3). We achieved a current density in excess of 270 mA/mm and DC transconductance above 180 mS/mm for hole conduction. Using standard high frequency characterization techniques, we measured a short-circuit current-gain cutoff frequency fT of 12 GHz and a maximum oscillation frequency fmax of 20 GHz in 300 nm channel length devices. BP devices may offer advantages over graphene transistors for high frequency electronics in terms of voltage and power gain due to the good current saturation properties arising from their finite bandgap, thus can be considered as a promising candidate for the future high performance thin film electronics technology for operation in the multi-GHz frequency range and beyond.