Miniaturized spectrometers with a tunable van der Waals junction.

Miniaturized computational spectrometers, which can obtain incident spectra using a combination of device spectral responses and reconstruction algorithms, are essential for on-chip and implantable applications. Highly sensitive spectral measurement using a single detector allows the footprints of such spectrometers to be scaled down while achieving spectral resolution approaching that of benchtop systems. We report a high-performance computational spectrometer based on a single van der Waals junction with an electrically tunable transport-mediated spectral response. We achieve high peak wavelength accuracy (∼0.36 nanometers), high spectral resolution (∼3 nanometers), broad operation bandwidth (from ∼405 to 845 nanometers), and proof-of-concept spectral imaging. Our approach provides a route toward ultraminiaturization and offers unprecedented performance in accuracy, resolution, and operation bandwidth for single-detector computational spectrometers.

Dielectric Engineering Boosts the Efficiency of Carbon Nanotube Photodiodes.

Carbon nanotube (CNT) photodiodes are a promising system for high-efficiency photocurrent generation due to the strong Coulomb interactions that can drive carrier multiplication. If the Coulomb interactions are too strong, however, exciton formation can hamper photocurrent generation. Here, we explore, experimentally and theoretically, the effect of the environmental dielectric constant (εenv) on the photocurrent generation process in CNTs. We study individual ultraclean CNTs of known chiral index in a vacuum or dry nitrogen gas (εenv = 1) and oil (εenv = 2.15). The efficiency of photocurrent generation improves by more than an order of magnitude in oil. Two mechanisms explain this improvement. First, the refractive index of the environment optimizes the interference between incident and reflected light. Second, exciton binding energies are reduced in oil, changing the relaxation pathways of photoexcited carriers. We varied the axial electric field in the pn junction from 4 to 14 V/µm. Our measurements at high field indicate that autoionization of second-subband excitons can coexist with carrier multiplication. Dielectric screening makes this coexistence regime more accessible and allows us to reach photocurrent quantum yields greater than 100%.

Quantum Interferences in Ultraclean Carbon Nanotubes.

Electronic analogs of optical interferences are powerful tools to investigate quantum phenomena in condensed matter. In carbon nanotubes (CNTs), it is well established that an electronic Fabry-Perot interferometer can be realized. Other types of quantum interferences should also arise in CNTs, but have proven challenging to realize. In particular, CNTs have been identified as a system to realize the electronic analog of a Sagnac interferometer-the most sensitive optical interferometer. To realize this Sagnac effect, interference between nonidentical transmission channels in a single CNT must be observed. Here, we use suspended, ultraclean CNTs of known chiral index to study both Fabry-Perot and Sagnac electron interferences. We verify theoretical predictions for the behavior of Sagnac oscillations and the persistence of the Sagnac oscillations at high temperatures. As suggested by existing theoretical studies, our results show that these quantum interferences may be used for electronic structure characterization of carbon nanotubes and the study of many-body effects in these model one-dimensional systems.

Frequency-Division Multiplexing with Graphene Active Electrodes for Neurosensor Applications.

Multielectrode arrays are used broadly for neural recording, both in vivo and for ex vivo cultured neurons. In most cases, recording sites are passive electrodes wired to external read-out circuitry, and the number of wires is at least equal to the number of recording sites. We present an approach to break the conventional N-wire, N-electrode array architecture using graphene active electrodes, which allow signal upconversion at the recording site and sharing of each interface wire among multiple active electrodes using frequency-division multiplexing (FDM). The presented work includes the design and implementation of a frequency modulation and readout architecture using graphene FET electrodes, a custom integrated circuit (IC) analog front-end (AFE), and digital demodulation. The AFE was fabricated in 0.18 µm CMOS; electrical characterization and multi-channel FDM results are provided, including GFET-based signal modulation and IC/DSP demodulation. Long-term, this approach can simultaneously enable high signal count, high spatial resolution, and high temporal precision to infer functional interactions between neurons while markedly decreasing access wires.

Extremely Efficient Photocurrent Generation in Carbon Nanotube Photodiodes Enabled by a Strong Axial Electric Field.

Carbon nanotube (CNT) photodiodes have the potential to convert light into electrical current with high efficiency. However, previous experiments have revealed the photocurrent quantum yield (PCQY) to be well below 100%. In this work, we show that the axial electric field increases the PCQY of CNT photodiodes. Under optimal conditions, our data suggest PCQY > 100%. We studied, both experimentally and theoretically, CNT photodiodes at room temperature using optical excitation corresponding to the S22, S33, and S44 exciton resonances. The axial electric field inside the pn junction was controlled using split gates that are capacitively coupled to the suspended CNT. Our results give new insight into the photocurrent generation pathways in CNTs and the field dependence and diameter dependence of PCQY.

Band-Gap-Dependent Electronic Compressibility of Carbon Nanotubes in the Wigner Crystal Regime.

Electronic compressibility, the second derivative of ground-state energy with respect to total electron number, is a measurable quantity that reveals the interaction strength of a system and can be used to characterize the orderly crystalline lattice of electrons known as the Wigner crystal. Here, we measure the electronic compressibility of individual suspended ultraclean carbon nanotubes in the low-density Wigner crystal regime. Using low-temperature quantum transport measurements, we determine the compressibility as a function of carrier number in nanotubes with varying band gaps. We observe two qualitatively different trends in compressibility versus carrier number, both of which can be explained using a theoretical model of a Wigner crystal that accounts for both the band gap and the confining potential experienced by charge carriers. We extract the interaction strength as a function of carrier number for individual nanotubes and show that the compressibility can be used to distinguish between strongly and weakly interacting regimes.

Interaction-Driven Giant Orbital Magnetic Moments in Carbon Nanotubes.

Carbon nanotubes continue to be model systems for studies of confinement and interactions. This is particularly true in the case of so-called "ultraclean" carbon nanotube devices offering the study of quantum dots with extremely low disorder. The quality of such systems, however, has increasingly revealed glaring discrepancies between experiment and theory. Here, we address the outstanding anomaly of exceptionally large orbital magnetic moments in carbon nanotube quantum dots. We perform low temperature magnetotransport measurements of the orbital magnetic moment and find it is up to 7 times larger than expected from the conventional semiclassical model. Moreover, the magnitude of the magnetic moment monotonically drops with the addition of each electron to the quantum dot directly contradicting the widely accepted shell filling picture of single-particle levels. We carry out quasiparticle calculations, both from first principles and within the effective-mass approximation, and find the giant magnetic moments can only be captured by considering a self-energy correction to the electronic band structure due to electron-electron interactions.

Deciphering Design Principles of Förster Resonance Energy Transfer-Based Protease Substrates: Thermolysin-Like Protease from Geobacillus stearothermophilus as a Test Case.

Protease activity is frequently assayed using short peptides that are equipped with a Förster resonance energy transfer (FRET) reporter system. Many frequently used donor-acceptor pairs are excited in the ultraviolet range and suffer from low extinction coefficients and quantum yields, limiting their usefulness in applications where a high sensitivity is required. A large number of alternative chromophores are available that are excited in the visible range, for example, based on xanthene or cyanine core structures. These alternatives are not only larger in size but also more hydrophobic. Here, we show that the hydrophobicity of these chromophores not only affects the solubility of the resulting FRET-labeled peptides but also their kinetic parameters in a model enzymatic reaction. In detail, we have compared two series of 4-8 amino acid long peptides, designed to serve as substrates for the thermolysin-like protease (TLP-ste) from Geobacillus stearothermophilus. These peptides were equipped with a carboxyfluorescein donor and either Cy5 or its sulfonated derivative Alexa Fluor 647 as the acceptor. We show that the turnover rate k cat is largely unaffected by the choice of the acceptor fluorophore, whereas the K M value is significantly lower for the Cy5- than for the Alexa Fluor 647-labeled substrates. TLP-ste is a rather nonspecific protease with a large number of hydrophobic amino acids surrounding the catalytic site, so that the fluorophore itself may form additional interactions with the enzyme. This hypothesis is supported by the result that the difference between Cy5- and Alexa Fluor 647-labeled substrates becomes less pronounced with increasing peptide length, that is, when the fluorophore is positioned at a larger distance from the catalytic site. These results suggest that fluorophores may become an integral part of FRET-labeled peptide substrates and that K M and k cat values are generally only valid for a specific combination of the peptide sequence and FRET pair.

Giant modulation of the electronic band gap of carbon nanotubes by dielectric screening.

Carbon nanotubes (CNTs) are a promising material for high-performance electronics beyond silicon. But unlike silicon, the nature of the transport band gap in CNTs is not fully understood. The transport gap in CNTs is predicted to be strongly driven by electron-electron (e-e) interactions and correlations, even at room temperature. Here, we use dielectric liquids to screen e-e interactions in individual suspended ultra-clean CNTs. Using multiple techniques, the transport gap is measured as dielectric screening is increased. Changing the dielectric environment from air to isopropanol, we observe a 25% reduction in the transport gap of semiconducting CNTs, and a 32% reduction in the band gap of narrow-gap CNTs. Additional measurements are reported in dielectric oils. Our results elucidate the nature of the transport gap in CNTs, and show that dielectric environment offers a mechanism for significant control over the transport band gap.

Photocurrent Quantum Yield in Suspended Carbon Nanotube p-n Junctions.

We study photocurrent generation in individual suspended carbon nanotube p-n junctions using spectrally resolved scanning photocurrent microscopy. Spatial maps of the photocurrent allow us to determine the length of the p-n junction intrinsic region, as well as the role of the n-type Schottky barrier. We show that reverse-bias operation eliminates complications caused by the n-type Schottky barrier and increases the length of the intrinsic region. The absorption cross-section of the CNT is calculated using an empirically verified model, and the effect of substrate reflection is determined using FDTD simulations. We find that the room temperature photocurrent quantum yield is approximately 30% when exciting the carbon nanotube at the S44 and S55 excitonic transitions. The quantum yield value is an order of magnitude larger than previous estimates.

Determination of the Thermal Noise Limit of Graphene Biotransistors.

To determine the thermal noise limit of graphene biotransistors, we have measured the complex impedance between the basal plane of single-layer graphene and an aqueous electrolyte. The impedance is dominated by an imaginary component but has a finite real component. Invoking the fluctuation-dissipation theorem, we determine the power spectral density of thermally driven voltage fluctuations at the graphene/electrolyte interface. The fluctuations have 1/f(p) dependence, with p = 0.75-0.85, and the magnitude of fluctuations scales inversely with area. Our results explain noise spectra previously measured in liquid-gated suspended graphene devices and provide realistic targets for future device performance.

Single electron charge sensitivity of liquid-gated carbon nanotube transistors.

Random telegraph signals corresponding to activated charge traps were observed with liquid-gated CNT FETs. The high signal-to-noise ratio that we observe demonstrates that single electron charge sensing is possible with CNT FETs in liquids at room temperature. We have characterized the gate-voltage dependence of the random telegraph signals and compared to theoretical predictions. The gate-voltage dependence clearly identifies the sign of the activated trapped charge.

Photothermoelectric effect in suspended semiconducting carbon nanotubes.

We have performed scanning photocurrent microscopy measurements of field-effect transistors (FETs) made from individual ultraclean suspended carbon nanotubes (CNTs). We investigate the spatial-dependence, polarization-dependence, and gate-dependence of photocurrent and photovoltage in this system. While previous studies of surface-bound CNT FET devices have identified the photovoltaic effect as the primary mechanism of photocurrent generation, our measurements show that photothermoelectric phenomena play a critical role in the optoelectronic properties of suspended CNT FETs. We have quantified the photothermoelectric mechanisms and identified regimes where they overwhelm the photovoltaic mechanism.

Scalable graphene field-effect sensors for specific protein detection.

We demonstrate that micron-scale graphene field-effect transistor biosensors can be fabricated in a scalable fashion from large-area chemical vapor deposition derived graphene. We electrically detect the real-time binding and unbinding of a protein biomarker, thrombin, to and from aptamer-coated graphene surfaces. Our sensors have low background noise and high transconductance, comparable to exfoliated graphene devices. The devices are reusable and have a shelf-life greater than one week.

Origins of charge noise in carbon nanotube field-effect transistor biosensors.

Determining the major noise sources in nanoscale field-effect transistor (nanoFET) biosensors is critical for improving bioelectronic interfaces. We use the carbon nanotube (CNT) FET biosensor platform to examine the noise generated by substrate interactions and surface adsorbates, both of which are present in current nanoFET biosensors. The charge noise model is used as a quantitative framework to show that insulating substrates and surface adsorbates are both significant contributors to the noise floor of CNT FET biosensors. Removing substrate interactions and surface adsorbates reduces the power spectral density of background voltage fluctuations by 19-fold.

Transfer-printing of as-fabricated carbon nanotube devices onto various substrates.

Exact replicas of carbon nanotube devices as fabricated on SiO(2) /Si substrates are prepared on various non-conventional substrates such as nonplanar or soft substrates by a simple, yet versatile, transfer-printing "cut-and-paste" method. In this way, harsh growth and fabrication processes can be minimized on the target substrates. The electrical characteristics of transfer-printed devices are compared to those of original devices.

Increasing the detection speed of an all-electronic real-time biosensor.

Biosensor response time, which depends sensitively on the transport of biomolecules to the sensor surface, is a critical concern for future biosensor applications. We have fabricated carbon nanotube field-effect transistor biosensors and quantified protein binding rates onto these nanoelectronic sensors. Using this experimental platform we test the effectiveness of a protein repellent coating designed to enhance protein flux to the all-electronic real-time biosensor. We observe a 2.5-fold increase in the initial protein flux to the sensor when upstream binding sites are blocked. Mass transport modelling is used to calculate the maximal flux enhancement that is possible with this strategy. Our results demonstrate a new methodology for characterizing nanoelectronic biosensor performance, and demonstrate a mass transport optimization strategy that is applicable to a wide range of microfluidic based biosensors.

Variable-force microscopy for advanced characterization of horizontally aligned carbon nanotubes.

Atomic force microscopy (AFM) performed with variable-force imaging was recently demonstrated to be an accurate method of determining the diameter and number of sidewalls of a carbon nanotube (CNT). This AFM technique provides an alternative to transmission electron microscopy (TEM) when TEM imaging is not possible due to substrate thickness. We have used variable-force AFM to characterize horizontally aligned CNTs grown on ST-cut quartz. Our measurements reveal new aspects of horizontally aligned growth that are essential for enhancing the performance of CNT-based devices as well as understanding the growth mechanism. First, previously reported optimal growth conditions produce a large spread in CNT diameters and a significant fraction of double-walled CNTs. Second, monodispersity is significantly improved when growth temperature is reduced. Third, CNTs with diameters up to 5 nm align to the substrate, suggesting the interaction between CNTs and the quartz lattice is more robust than previously reported.

Identifying individual single-walled and double-walled carbon nanotubes by atomic force microscopy.

We show that the number of concentric graphene cylinders forming a carbon nanotube can be found by squeezing the tube between an atomic force microscope tip and a silicon substrate. The compressed height of a single-walled nanotube (double-walled nanotube) is approximately two (four) times the interlayer spacing of graphite. Measured compression forces are consistent with the predicted bending modulus of graphene and provide a mechanical signature for identifying individual single-walled and double-walled nanotubes.

Identifying the mechanism of biosensing with carbon nanotube transistors.

Carbon nanotube transistors have outstanding potential for electronic detection of biomolecules in solution. The physical mechanism underlying sensing however remains controversial, which hampers full exploitation of these promising nanosensors. Previously suggested mechanisms are electrostatic gating, changes in gate coupling, carrier mobility changes, and Schottky barrier effects. We argue that each mechanism has its characteristic effect on the liquid gate potential dependence of the device conductance. By studying both the electron and hole conduction, the sensing mechanisms can be unambiguously identified. From extensive protein-adsorption experiments on such devices, we find that electrostatic gating and Schottky barrier effects are the two relevant mechanisms, with electrostatic gating being most reproducible. If the contact region is passivated, sensing is shown to be dominated by electrostatic gating, which demonstrates that the sensitive part of a nanotube transistor is not limited to the contact region, as previously suggested. Such a layout provides a reliable platform for biosensing with nanotubes.