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.

Scalable Nanostructured Carbon Electrode Arrays for Enhanced Dopamine Detection.

Dopamine is a neurotransmitter that modulates arousal and motivation in humans and animals. It plays a central role in the brain "reward" system. Its dysregulation is involved in several debilitating disorders such as addiction, depression, Parkinson's disease, and schizophrenia. Dopamine neurotransmission and its reuptake in extracellular space takes place with millisecond temporal and nanometer spatial resolution. Novel nanoscale electrodes are needed with superior sensitivity and improved spatial resolution to gain an improved understanding of dopamine dysregulation. We report on a scalable fabrication of dopamine neurochemical probes of a nanostructured glassy carbon that is smaller than any existing dopamine sensor and arrays of more than 6000 nanorod probes. We also report on the electrochemical dopamine sensing of the glassy carbon nanorod electrode. Compared with a carbon fiber, the nanostructured glassy carbon nanorods provide about 2× higher sensitivity per unit area for dopamine sensing and more than 5× higher signal per unit area at low concentration of dopamine, with comparable LOD and time response. These glassy carbon nanorods were fabricated by pyrolysis of a lithographically defined polymeric nanostructure with an industry standard semiconductor fabrication infrastructure. The scalable fabrication strategy offers the potential to integrate these nanoscale carbon rods with an integrated circuit control system and with other complementary metal oxide semiconductor (CMOS) compatible sensors.

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.

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.

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.

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.

Fringing-field dielectrophoretic assembly of ultrahigh-density semiconducting nanotube arrays with a self-limited pitch.

One key challenge of realizing practical high-performance electronic devices based on single-walled carbon nanotubes is to produce electronically pure nanotube arrays with both a minuscule and uniform inter-tube pitch for sufficient device-packing density and homogeneity. Here we develop a method in which the alternating voltage-fringing electric field formed between surface microelectrodes and the substrate is utilized to assemble semiconducting nanotubes into well-aligned, ultrahigh-density and submonolayered arrays, with a consistent pitch as small as 21±6 nm determined by a self-limiting mechanism, based on the unique field focusing and screening effects of the fringing field. Field-effect transistors based on such nanotube arrays exhibit record high device transconductance (>50 µS µm(-1)) and decent on current per nanotube (~1 µA per tube) together with high on/off ratios at a drain bias of -1 V.

Toward high-performance digital logic technology with carbon nanotubes.

The slow-down in traditional silicon complementary metal-oxide-semiconductor (CMOS) scaling (Moore's law) has created an opportunity for a disruptive innovation to bring the semiconductor industry into a postsilicon era. Due to their ultrathin body and ballistic transport, carbon nanotubes (CNTs) have the intrinsic transport and scaling properties to usher in this new era. The remaining challenges are largely materials-related and include obtaining purity levels suitable for logic technology, placement of CNTs at very tight (∼5 nm) pitch to allow for density scaling and source/drain contact scaling. This review examines the potential performance advantages of a CNT-based computing technology, outlines the remaining challenges, and describes the recent progress on these fronts. Although overcoming these issues will be challenging and will require a large, sustained effort from both industry and academia, the recent progress in the field is a cause for optimism that these materials can have an impact on future technologies.

High-performance air-stable n-type carbon nanotube transistors with erbium contacts.

So far, realization of reproducible n-type carbon nanotube (CNT) transistors suitable for integrated digital applications has been a difficult task. In this work, hundreds of n-type CNT transistors from three different low work function metals-erbium, lanthanum, and yttrium-are studied and benchmarked against p-type devices with palladium contacts. The crucial role of metal type and deposition conditions is elucidated with respect to overall yield and performance of the n-type devices. It is found that high oxidation rates and sensitivity to deposition conditions are the major causes for the lower yield and large variation in performance of n-type CNT devices with low work function metal contacts. Considerable improvement in device yield is attained using erbium contacts evaporated at high deposition rates. Furthermore, the air-stability of our n-type transistors is studied in light of the extreme sensitivity of these metals to oxidation.

Efficient and bright organic light-emitting diodes on single-layer graphene electrodes.

Organic light-emitting diodes are emerging as leading technologies for both high quality display and lighting. However, the transparent conductive electrode used in the current organic light-emitting diode technologies increases the overall cost and has limited bendability for future flexible applications. Here we use single-layer graphene as an alternative flexible transparent conductor, yielding white organic light-emitting diodes with brightness and efficiency sufficient for general lighting. The performance improvement is attributed to the device structure, which allows direct hole injection from the single-layer graphene anode into the light-emitting layers, reducing carrier trapping induced efficiency roll-off. By employing a light out-coupling structure, phosphorescent green organic light-emitting diodes exhibit external quantum efficiency >60%, while phosphorescent white organic light-emitting diodes exhibit external quantum efficiency >45% at 10,000 cd m(-2) with colour rendering index of 85. The power efficiency of white organic light-emitting diodes reaches 80 lm W(-1) at 3,000 cd m(-2), comparable to the most efficient lighting technologies.

Carbon nanotube complementary wrap-gate transistors.

Among the challenges hindering the integration of carbon nanotube (CNT) transistors in digital technology are the lack of a scalable self-aligned gate and complementary n- and p-type devices. We report CNT transistors with self-aligned gates scaled down to 20 nm in the ideal gate-all-around geometry. Uniformity of the gate wrapping the nanotube channels is confirmed, and the process is shown not to damage the CNTs. Further, both n- and p-type transistors were realized by using the appropriate gate dielectric-HfO2 yielded n-type and Al2O3 yielded p-type-with quantum simulations used to explore the impact of important device parameters on performance. These discoveries not only provide a promising platform for further research into gate-all-around CNT devices but also demonstrate that scalable digital switches with realistic technological potential can be achieved with carbon nanotubes.

High purity isolation and quantification of semiconducting carbon nanotubes via column chromatography.

The isolation of semiconducting carbon nanotubes (CNTs) to ultrahigh (ppb) purity is a prerequisite for their integration into high-performance electronic devices. Here, a method employing column chromatography is used to isolate semiconducting nanotubes to 99.9% purity. The study finds that by modifying the solution preparation step, both the metallic and semiconducting fraction are resolved and elute using a single surfactant system, allowing for multiple iterations. Iterative processing enables a far more rapid path to achieving the level of purities needed for high performance computing. After a single iteration, the metallic peak in the absorption spectra is completely attenuated. Although absorption spectroscopy is typically used to characterize CNT purity, it is found to be insufficient in quantifying solutions of high purity (>98 to 99%) due to low signal-to-noise in the metallic region of ultrahigh purity solutions. Therefore, a high throughput electrical testing method was developed to quantify the degree of separation by characterizing ∼4000 field-effect transistors fabricated from the separated nanotubes after multiple iterations of the process. The separation and characterization methods described here provide a path to produce the ultrahigh purity semiconducting CNT solutions needed for high performance electronics.

Arrays of single-walled carbon nanotubes with full surface coverage for high-performance electronics.

Single-walled carbon nanotubes have exceptional electronic properties and have been proposed as a replacement for silicon in applications such as low-cost thin-film transistors and high-performance logic devices. However, practical devices will require dense, aligned arrays of electronically pure nanotubes to optimize performance, maximize device packing density and provide sufficient drive current (or power output) for each transistor. Here, we show that aligned arrays of semiconducting carbon nanotubes can be assembled using the Langmuir-Schaefer method. The arrays have a semiconducting nanotube purity of 99% and can fully cover a surface with a nanotube density of more than 500 tubes/µm. The nanotube pitch is self-limited by the diameter of the nanotube plus the van der Waals separation, and the intrinsic mobility of the nanotubes is preserved after array assembly. Transistors fabricated using this approach exhibit significant device performance characteristics with a drive current density of more than 120 µA µm(-1), transconductance greater than 40 µS µm(-1) and on/off ratios of ∼1 × 10(3).

High-density integration of carbon nanotubes via chemical self-assembly.

Carbon nanotubes have potential in the development of high-speed and power-efficient logic applications. However, for such technologies to be viable, a high density of semiconducting nanotubes must be placed at precise locations on a substrate. Here, we show that ion-exchange chemistry can be used to fabricate arrays of individually positioned carbon nanotubes with a density as high as 1 × 10(9) cm(-2)-two orders of magnitude higher than previous reports. With this approach, we assembled a high density of carbon-nanotube transistors in a conventional semiconductor fabrication line and then electrically tested more than 10,000 devices in a single chip. The ability to characterize such large distributions of nanotube devices is crucial for analysing transistor performance, yield and semiconducting nanotube purity.

Evaluation of field-effect mobility and contact resistance of transistors that use solution-processed single-walled carbon nanotubes.

Solution-processed single-walled carbon nanotubes (SWNTs) offer many unique processing advantages over nanotubes grown by the chemical vapor deposition (CVD) method, including capabilities of separating the nanotubes by electronic type and depositing them onto various substrates in the form of ultradensely aligned arrays at low temperature. However, long-channel transistors that use solution-processed SWNTs generally demonstrate inferior device performance, which poses concerns over the feasibility of using these nanotubes in high-performance logic applications. This paper presents the first systematic study of contact resistance, intrinsic field-effect mobility (µ(FE)), and conductivity (σ(m)) of solution-processed SWNTs based on both the transmission line method and the Y function method. The results indicate that, compared to CVD nanotubes, although solution-processed SWNTs have much lower µ(FE) for semiconducting nanotubes and lower σ(m) for metallic nanotubes due to the presence of a higher level of structural defects, such defects do not affect the quality of electric contacts between the nanotube and metal source/drain electrodes. Therefore, solution-processed SWNTs are expected to offer performance comparable to that of CVD nanotubes in ultimately scaled field-effect transistors, where contacts will dominate electron transport instead of electron scattering in the channel region. These results show promise for using solution-processed SWNTs for high-performance nanoelectronic devices.

Tunable infrared plasmonic devices using graphene/insulator stacks.

The collective oscillation of carriers--the plasmon--in graphene has many desirable properties, including tunability and low loss. However, in single-layer graphene, the dependence on carrier concentration of both the plasmonic resonance frequency and magnitude is relatively weak, limiting its applications in photonics. Here, we demonstrate transparent photonic devices based on graphene/insulator stacks, which are formed by depositing alternating wafer-scale graphene sheets and thin insulating layers, then patterning them together into photonic-crystal-like structures. We show experimentally that the plasmon in such stacks is unambiguously non-classical. Compared with doping in single-layer graphene, distributing carriers into multiple graphene layers effectively enhances the plasmonic resonance frequency and magnitude, which is different from the effect in a conventional semiconductor superlattice and is a direct consequence of the unique carrier density scaling law of the plasmonic resonance of Dirac fermions. Using patterned graphene/insulator stacks, we demonstrate widely tunable far-infrared notch filters with 8.2 dB rejection ratios and terahertz linear polarizers with 9.5 dB extinction ratios. An unpatterned stack consisting of five graphene layers shields 97.5% of electromagnetic radiation at frequencies below 1.2 THz. This work could lead to the development of transparent mid- and far-infrared photonic devices such as detectors, modulators and three-dimensional metamaterial systems.

Engineering of contact resistance between transparent single-walled carbon nanotube films and a-Si:H single junction solar cells by gold nanodots.

The viability of single-walled carbon nanotubes (SWCNTs) as a transparent conducting electrode on a-Si:H based single junction solar cells was explored. A Schottky barrier formed at a SWCNT/a-Si:H interface was removed by introducing high work function gold nanodots at the SWCNT/a-Si:H interface. This allows comparable device performance from SWCNT-electrode-based a-Si:H solar cells to that obtained by using conventional transparent conducting oxides.