The semiconductor industry has seen a remarkable miniaturization trend, driven by many scientific and technological innovations. But if this trend is to continue, and provide ever faster and cheaper computers, the size of microelectronic circuit components will soon need to reach the scale of atoms or molecules—a goal that will require conceptually new device structures. The idea that a few molecules, or even a single molecule, could be embedded between electrodes and perform the basic functions of digital electronics—rectification, amplification and storage—was first put forward in the mid-1970s. The concept is now realized for individual components, but the economic fabrication of complete circuits at the molecular level remains challenging because of the difficulty of connecting molecules to one another. A possible solution to this problem is ‘mono-molecular’ electronics, in which a single molecule will integrate the elementary functions and interconnections required for computation.

Electronics using hybrid-molecular and mono-molecular devices

We demonstrate logic circuits with field-effect transistors based on single carbon nanotubes. Our device layout features local gates that provide excellent capacitive coupling between the gate and nanotube, enabling strong electrostatic doping of the nanotube from p-doping to n-doping and the study of the nonconventional long-range screening of charge along the one-dimensional nanotubes. The transistors show favorable device characteristics such as high gain (>10), a large on-off ratio (>10(5)), and room-temperature operation. Importantly, the local-gate layout allows for integration of multiple devices on a single chip. Indeed, we demonstrate one-, two-, and three-transistor circuits that exhibit a range of digital logic operations, such as an inverter, a logic NOR, a static random-access memory cell, and an ac ring oscillator.

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Logic circuits with carbon nanotube transistors

Carbon nanotubes exhibit many unique intrinsic physical and chemical properties and have been intensively explored for biological and biomedical applications in the past few years. In this comprehensive review, we summarize the main results from our and other groups in this field and clarify that surface functionalization is critical to the behavior of carbon nanotubes in biological systems. Ultrasensitive detection of biological species with carbon nanotubes can be realized after surface passivation to inhibit the non-specific binding of biomolecules on the hydrophobic nanotube surface. Electrical nanosensors based on nanotubes provide a label-free approach to biological detection. Surface-enhanced Raman spectroscopy of carbon nanotubes opens up a method of protein microarray with detection sensitivity down to 1 fmol/L. In vitro and in vivo toxicity studies reveal that highly water soluble and serum stable nanotubes are biocompatible, nontoxic, and potentially useful for biomedical applications. In vivo biodistributions vary with the functionalization and possibly also size of nanotubes, with a tendency to accumulate in the reticuloendothelial system (RES), including the liver and spleen, after intravenous administration. If well functionalized, nanotubes may be excreted mainly through the biliary pathway in feces. Carbon nanotube-based drug delivery has shown promise in various In vitro and in vivo experiments including delivery of small interfering RNA (siRNA), paclitaxel and doxorubicin. Moreover, single-walled carbon nanotubes with various interesting intrinsic optical properties have been used as novel photoluminescence, Raman, and photoacoustic contrast agents for imaging of cells and animals. Further multidisciplinary explorations in this field may bring new opportunities in the realm of biomedicine.

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Carbon Nanotubes in Biology and Medicine: In vitro and in vivo Detection, Imaging and Drug Delivery

As a consequence of degeneracies arising from crystal symmetries, it is possible for electron states at band-edges ('valleys') to have additional spin-like quantum numbers. An important question is whether coherent manipulation can be performed on such valley pseudospins, analogous to that implemented using true spin, in the quest for quantum technologies. Here, we show that valley coherence can be generated and detected. Because excitons in a single valley emit circularly polarized photons, linear polarization can only be generated through recombination of an exciton in a coherent superposition of the two valley states. Using monolayer semiconductor WSe2 devices, we first establish the circularly polarized optical selection rules for addressing individual valley excitons and trions. We then demonstrate coherence between valley excitons through the observation of linearly polarized luminescence, whose orientation coincides with that of the linearly polarized excitation, for any given polarization angle. In contrast, the corresponding photoluminescence from trions is not observed to be linearly polarized, consistent with the expectation that the emitted photon polarization is entangled with valley pseudospin. The ability to address coherence, in addition to valley polarization, is a step forward towards achieving quantum manipulation of the valley index necessary for coherent valleytronics.

http://depts.washington.edu/xulab/wordpress/wp-content/uploads/2012/03/nnano.2013.151.pdf

Optical generation of excitonic valley coherence in monolayer WSe2

Carbon nanotubes: opportunities and challenges

Unprocessed single-walled carbon nanotubes suspended in air at room temperature emit bright, sharply peaked band gap photoluminescence. This is in contrast with measurements taken from nanotubes lying on the flat surface for which no luminescence was detected. Each individual nanotube has a luminescence peak of similar linewidth ( approximately 13 meV), with different species emitting at various different wavelengths spanning at least 1.0 to 1.6 microm. A strong enhancement of photoluminescence intensity is observed when the excitation wavelength is resonant with the second Van Hove singularity, unambiguously confirming the origin of the photoluminescence.

Bright band gap photoluminescence from unprocessed single-walled carbon nanotubes.

Single-walled carbon nanotubes (SWNTs) suspended in air over trenches are imaged using their intrinsic near-infrared (NIR) photoluminescence (1.0−1.6 μm). Far-field emission from extended suspended lengths (∼50 μm) is both spatially and spectrally resolved, and SWNTs are classified based on the spatial uniformity of their emission intensity and emission wavelength. In a few cases, emission assigned to different (n,m) species is observed along the same suspended segment. Most SWNTs imaged on millisecond time scales show steady emission, but a few fluctuate and suffer a reduction of intensity. The quantum efficiency is dramatically higher than that in previous reports and is estimated at 7%, a value that is precise but subject to corrections because of assumptions about absorption and coherence.

Photoluminescence imaging of suspended single-walled carbon nanotubes.

Photoluminescence (PL) and photoluminescence excitation (PLE) spectra are obtained from individual single-walled carbon nanotubes (SWNTs). Individual SWNT spectra are compared with spectra from ensembles. The PL spectrum of an individual SWNT in air at room temperature has a single asymmetric peak of width typically 10 to 15 meV, with no detected background. Both absorption and emission are strongly polarized along the tube axis. Photoluminescence excitation spectroscopy on single SWNTs clearly confirms the unique, one-to-one association of optical absorption resonances with individual emission peaks. Resonances in the PLE spectra are typically $\ensuremath{\approx}30\mathrm{meV}$ wide, with the PL intensity enhanced tenfold over nonresonant excitation. Whether for emission or absorption, the peak shape and peak width are almost the same for a single nanotube as they are for the corresponding species in a large ensemble. That is, there is no significant inhomogeneous broadening. While ensemble measurements are complicated by the superposition of many PL peaks from many different species, single nanotube spectra clearly isolate a single peak and are thus simpler to interpret.

Photoluminescence from an individual single-walled carbon nanotube

Single-walled carbon nanotubes (SWNTs) are luminescent. Up to now, two preparation methods, both of which isolate individual SWNTs, have enabled the detection of nanotube bandgap photoluminescence (PL): encapsulation of individual SWNTs into surfactant micelles and direct growth of individual SWNTs suspended in air between pillars. This paper compares the PL obtained from suspended SWNTs to published PL data obtained from encapsulated SWNTs. We find that emission peaks are blueshifted by 28 meV on average for the suspended nanotubes as compared to the encapsulated nanotubes. Similarly, the resonant absorption peaks at the second set of van Hove singularities are blueshifted on average by 16 meV. Both shifts depend weakly on the particular chirality and diameter of the SWNT.

Photoluminescence from single-walled carbon nanotubes: a comparison between suspended and micelle-encapsulated nanotubes

A systematic study on the use of 9,9-dialkylfluorene homopolymers (PFs) for large-diameter semiconducting (sc-) single-walled carbon nanotube (SWCNT) enrichment is the focus of this report. The enrichment is based on a simple three-step extraction process: (1) dispersion of as-produced SWCNTs in a PF solution; (2) centrifugation at a low speed to separate the enriched sc-tubes; (3) filtration to collect the enriched sc-SWCNTs and remove excess polymer. The effect of the extraction conditions on the purity and yield including molecular weight and alkyl side-chain length of the polymers, SWCNT concentration, and polymer/SWCNT ratio have been examined. It was observed that PFs with alkyl chain lengths of C10, C12, C14, and C18, all have an excellent capability to enrich laser-ablation sc-SWCNTs when their molecular weight is larger than ∼10000 Da. More detailed studies were therefore carried out with the C12 polymer, poly(9,9-di-n-dodecylfluorene), PFDD. It was found that a high polymer/SWCNT ratio leads to an enhanced yield but a reduced sc-purity. A ratio of 0.5–1.0 gives an excellent sc-purity and a yield of 5–10% in a single extraction as assessed by UV-vis-NIR absorption spectra. The yield can also be promoted by multiple extractions while maintaining high sc-purity. Mechanistic experiments involving time-lapse dispersion studies reveal that m-SWCNTs have a lower propensity to be dispersed, yielding a sc-SWCNT enriched material in the supernatant. Dispersion stability studies with partially enriched sc-SWCNT material further reveal that m-SWCNTs:PFDD complexes will re-aggregate faster than sc-SWCNTs:PFDD complexes, providing further sc-SWCNT enrichment. This result confirms that the enrichment was due to the much tighter bundles in raw materials and the more rapid bundling in dispersion of the m-SWCNTs. The sc-purity is also confirmed by Raman spectroscopy and photoluminescence excitation (PLE) mapping. The latter shows that the enriched sc-SWCNT sample has a narrow chirality and diameter distribution dominated by the (10,9) species with d = 1.29 nm. The enriched sc-SWCNTs allow a simple drop-casting method to form a dense nanotube network on SiO2/Si substrates, leading to thin film transistors (TFTs) with an average mobility of 27 cm2 V−1 s−1 and an average on/off current ratio of 1.8 × 106 when considering all 25 devices having 25 μm channel length prepared on a single chip. The results presented herein demonstrate how an easily scalable technique provides large-diameter sc-SWCNTs with high purity, further enabling the best TFT performance reported to date for conjugated polymer enriched sc-SWCNTs.

Jacques Lefebvre

Papers

Bright band gap photoluminescence from unprocessed single-walled carbon nanotubes.

Photoluminescence imaging of suspended single-walled carbon nanotubes.

Photoluminescence from an individual single-walled carbon nanotube

Photoluminescence from single-walled carbon nanotubes: a comparison between suspended and micelle-encapsulated nanotubes

Enrichment of large-diameter semiconducting SWCNTs by polyfluorene extraction for high network density thin film transistors