Alexander A Green

Northwestern University, Evanston, Illinois, United States

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Publications (46)389.76 Total impact

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    ABSTRACT: Arc discharge single-walled carbon nanotubes (SWCNTs) possess superlative optical and electronic properties that are of high interest for technologically important applications including fiber optic communications, biomedical imaging, and field-effect transistors. However, as-grown arc discharge SWCNTs possess a mixture of metallic and semiconducting species in addition to a wide diameter distribution (1.2 to 1.7 nm) that limit their performance in devices. While previous postsynthetic sorting efforts have achieved separation by electronic type and diameter refinement for metallic arc discharge SWCNTs, tight diameter distributions of semiconducting arc discharge SWCNTs have not yet been realized. Herein, we present two advances in density gradient ultracentrifugation that enable the isolation of high purity (>99%) semiconducting arc discharge SWCNTs with narrow diameter distributions centered at 1.6 and 1.4 nm. The resulting diameter-refined populations of semiconducting arc discharge SWCNTs possess monodisperse characteristics that are well-suited for high-performance optical and electronic technologies.
    Journal of Physical Chemistry Letters 08/2013; 4(17):2805–2810. · 6.59 Impact Factor
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    ABSTRACT: Atom-thick materials such as single-walled carbon nanotubes (SWCNTs) and graphene exhibit ultrahigh sensitivity to chemical perturbation partly because all of the constituent atoms are surface atoms. However, low selectivity due to non-specific binding on the graphitic surface is a challenging issue to many applications including chemical sensing. Here, we demonstrated simultaneous attainment of high sensitivity and selectivity in thin-film field effect transistors (TFTs) based on outer-wall selectively functionalized double-walled carbon nanotubes (DWCNTs). With carboxylic acid functionalized DWCNT TFTs, we obtained excellent gate modulation (on/off ratio as high as 4000) with relatively high ON currents at a CNT areal density as low as 35 ng/cm2. The devices displayed an NH3 sensitivity of 60 nM (or ~1 ppb), which is comparable to small molecule aqueous solution detection using state-of-the-art SWCNT TFT sensors while concomitantly achieving 6,000 times higher chemical selectivity towards a variety of amine-containing analyte molecules over other small molecules. These results highlight the potential of using covalently functionalized double-walled carbon nanotubes for simultaneous ultrahigh selective and sensitive detection of chemicals and illustrate some of the structural advantages of this double-wall materials strategy to nanoelectronics.
    Journal of the American Chemical Society 01/2013; · 10.68 Impact Factor
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    ABSTRACT: The method by which surfactants selectively interact with particular electronic types of single-walled carbon nanotubes (SWCNTs) and thereby enable the isolation of metallic and semiconducting species is not well understood. While density gradient ultracentrifugation (DGU) has demonstrated its potential as a powerful nanomaterial separation technique, this study utilizes DGU as an analytic tool to probe the interactions between amphiphilic block copolymers, surfactants capable of electronic type extraction, and the SWCNT surface. By modulating the pH during DGU, we find that the linear shaped Pluronic copolymers can extract either metallic or semiconducting SWCNTs at purities in excess of 99%. Furthermore, the first electronic type sorting mechanism is given by which oxygen absorption and subsequent protonation of the SWCNT surface acts to template copolymer adhesion. Detailed characterization reveals the underlying mechanism for pH-shifted DGU and is thus likely to enable future development of more efficient and facile SWCNT electronic type sorting methods.
    The Journal of Physical Chemistry C. 09/2012; 116(37):20103–20108.
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    ABSTRACT: We report the radio-frequency performance of carbon nanotube array transistors that have been realized through the aligned assembly of highly separated, semiconducting carbon nanotubes on a fully scalable device platform. At a gate length of 100 nm, we observe output current saturation and obtain as-measured, extrinsic current gain and power gain cut-off frequencies, respectively, of 7 GHz and 15 GHz. While the extrinsic current gain is comparable to the state-of-the-art the extrinsic power gain is improved. The de-embedded, intrinsic current gain and power gain cut-off frequencies of 153 GHz and 30 GHz are the highest values experimentally achieved to date. We analyze the consistency of DC and AC performance parameters and discuss the requirements for future applications of carbon nanotube array transistors in high-frequency electronics.
    Applied Physics Letters 08/2012; 101(5). · 3.79 Impact Factor
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    ABSTRACT: We have used laser-excited photocurrent microscopy to map the internal electrostatic potential profile of semiconducting single-walled carbon nanotube (S-SWCNT) array devices with a spatial resolution of 250 nm. The measurements of S-SWCNTs on optically transparent samples provide new insights into the physical principles of device operation and reveal performance-limiting local heterogeneities in the electrostatic potential profile not observable with other imaging techniques. The experiments deliver photocurrent images from the underside of the S-SWCNT-metal contacts and thus enable the direct measurement of the charge carrier transfer lengths at the palladium-S-SWCNT and aluminum-S-SWCNT interfaces. We use the experimental results to formulate design rules for optimized layouts of S-SWCNT-based photovoltaic devices. Furthermore, we demonstrate the external control of the electrostatic potential profile in S-SWCNT array devices equipped with local metal gates.
    ACS Nano 07/2012; 6(8):7303-10. · 12.06 Impact Factor
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    ABSTRACT: Electronic two-dimensional Fourier transform (2D-FT) spectroscopy is applied to semiconducting single-walled carbon nanotubes and provides a spectral and time-domain map of exciton-phonon assisted excitations. Using 12 fs long pulses, we resolve side-bands above the E(22) transition that correspond with the RBM, G, G', 2G and other multiphonon modes. The appearance of 2D-FT spectral cross-peaks explicitly resolves discrete phonon assisted population transfer that scatters excitations to the E(22) (Γ-pt) state, often through a second-order exciton-phonon coupling process. All 2D-FT peaks exhibit a strong peak amplitude modulation at the G-band period (21 fs) which we show originates from an impulsive stimulated Raman process that populates a ground-state G-band vibrational coherence over a 1.3 ps phonon lifetime.
    Nano Letters 01/2012; 12(2):813-9. · 13.03 Impact Factor
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    ABSTRACT: The exciton dynamics for an ensemble of individual, suspended (6,5), single-walled carbon nanotubes revealed by single color E(22) resonant pump-probe spectroscopy for a wide range of pump fluences are reported. The optically excited initial exciton population ranges from approximately 5 to 120 excitons per ∼725 nm nanotube. At the higher fluences of this range, the pump-probe signals are no longer linearly dependent on the pump intensity. A single, predictive model is described that fits all data for two decades of pump fluences and three decades of delay times. The model introduces population loss from the optically active zero momentum E(22) state to the rest of the E(22) subband, which is dark due to momentum selection rules. In the single exciton limit, the E(11) dynamics are well described by a stretched exponential, which is a direct consequence of diffusion quenching from an ensemble of nanotubes of different lengths. The observed change in population relaxation dynamics as a function of increasing pump intensity is attributed to exciton-exciton Auger de-excitation in the E(11) subband and, to a lesser extent, in the E(22) subband. From the fit to the model, an average defect density 1/ρ = 150 nm and diffusion constants D(11) = 4 cm(2)/s and D(22) = 0.2 cm(2)/s are determined.
    ACS Nano 11/2011; 5(12):9898-906. · 12.06 Impact Factor
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    ABSTRACT: Double-walled carbon nanotubes (DWCNTs) with outer metallic (M) or semiconducting (S) shells were sorted by density-gradient ultracentrifugation and examined by Raman spectroscopy and in situ Raman spectroelectrochemistry. The combination of sorting and the selection of appropriate laser excitation energies allowed the disentanglement of the effects of different variations of the electronic type (M or S) of the inner and outer tubes in DWCNTs on the doping behavior and charge transfer between the inner and outer walls. Charge transfer from the outer tube to the inner tube occurs only if the electronic states of the outer tube are filled with electrons or holes, and if these filled states are higher in energy than those of the inner tube. Therefore, each combination of inner and outer tube (i.e., inner@outer: M@M, M@S, S@M, and S@S) exhibits a distinct behavior. The potential needed to observe the effects of charge transfer between the inner and outer tubes is found to increase in the following order: M@M < S@M < M@S < S@S.
    Chemistry 08/2011; 17(35):9806-15. · 5.93 Impact Factor
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    ABSTRACT: Atom-thick materials such as single-wall carbon nanotubes (SWNTs) and graphene are prone to chemical attacks because all constituent atoms are exposed. Here we report the retention of optical and electrical properties of inner tubes in heavily functionalized double-wall carbon nanotubes (DWNTs). Correlated optical absorption spectroscopy, Raman scattering, and thin film electrical conductivity all suggest that an inner tube behaves strikingly similar to a pristine SWNT; however, because of the protection of the outer wall, the inner tube can survive aggressive chemical attacks (e.g., by diazonium chemistry) without compromising physical properties. At the saturation limit of the diazonium functionalization, an SWNT network becomes electrically insulating; in stark contrast, the double-walled structure retains 50% of the initial conductivity, owing to the intact inner tube pathway. These results suggest the possibility of high-performance DWNT electronic devices with important capabilities for tailored surface chemistry on the outer walls, whereas the inner tubes are chemically protected.Keywords: double-walled carbon nanotubes; electronic nanomaterials; semiconducting nanotubes; chemical selectivity; spectroscopy; electrical percolation; electrode network
    Journal of Physical Chemistry Letters. 06/2011; 2.
  • Alexander A. Green, Mark C. Hersam
    Advanced Materials 05/2011; 23(19):2127 - 2127. · 14.83 Impact Factor
  • Advanced Materials 04/2011; 23(15):1734-8. · 14.83 Impact Factor
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    ABSTRACT: The ability to disperse pristine graphene at high concentrations in aqueous solutions is an enabling step for large-scale processing and emerging biomedical applications. Herein we demonstrate that nonionic, biocompatible block copolymers are able to produce graphene dispersions with concentrations exceeding 0.07 mg mL–1 via sonication and centrifugation, resulting in optical densities above 4 OD cm–1 in the visible and near-infrared regions of the electromagnetic spectrum. The dispersion efficiency of graphene using Pluronic and Tetronic block copolymers varies substantially depending on the lengths of their hydrophilic and hydrophobic domains, with the best of these copolymers sharing similar domain molecular weight ratios and comparable overall molecular weights. This study presents a new class of biocompatible dispersing agents for graphene in aqueous solution, thus suggesting a facile route to employ graphene in biomedical sensing, imaging, and therapeutic applications.Keywords: graphene; block copolymer; pluronic; tetronic; dispersion; suspension
    The Journal of Physical Chemistry Letters. 04/2011; 2(9).
  • Alexander A Green, Mark C Hersam
    Advanced Materials 04/2011; 23(19):2185-90. · 14.83 Impact Factor
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    ABSTRACT: Theoretical calculations predict that the collapse pressure for double-walled carbon nanotubes (DWCNTs) is proportional to 1/R 3 , where R is the effective or average radius of a DWCNT. In order to address the problem of CNT stability at high pressure and stress, we performed a resonance Raman study of DWCNTs dispersed in sodium cholate using 532 and 633 nm laser excitation. Raman spectra of the recovered samples show minor versus irreversible changes with increasing I D /I G ratio after exposure to high non-hydrostatic pressure of 23 and 35 GPa, respectively. The system exhibits nearly 70% pressure hysteresis in radial breathing vibrational mode signals recovery on pressure release which is twice that predicted by theory.
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    ABSTRACT: Theoretical calculations predict that the collapse pressure for double-walled carbon nanotubes (DWCNTs) is proportional to 1/R 3 , where R is the effective or average radius of a DWCNT. In order to address the problem of CNT stability at high pressure and stress, we performed a resonance Raman study of DWCNTs dispersed in sodium cholate using 532 and 633 nm laser excitation. Raman spectra of the recovered samples show minor versus irreversible changes with increasing I D /I G ratio after exposure to high non-hydrostatic pressure of 23 and 35 GPa, respectively. The system exhibits nearly 70% pressure hysteresis in radial breathing vibrational mode signals recovery on pressure release which is twice that predicted by theory.
  • Alexander A Green, Mark C Hersam
    [Show abstract] [Hide abstract]
    ABSTRACT: Double-walled carbon nanotubes (DWNTs) can adopt four distinct permutations arising from the electronic type (metallic or semiconducting) of their inner and outer walls. This polydispersity limits the utility of DWNTs in applications such as thin film electronics. We demonstrate that density gradient ultracentrifugation can be employed to address this source of heterogeneity by producing DWNTs with well-defined outer-wall electronic types. Optical absorption measurements of sorted DWNTs reveal outer-wall purities of 96% and 98% for sorted semiconducting and metallic samples, respectively. Electrical characterization of semiconducting and metallic outer-wall DWNTs in thin film transistors directly confirms the efficacy of these separations, with semiconducting DWNT devices yielding on/off ratios 2 orders of magnitude higher than comparable metallic DWNT devices.
    ACS Nano 02/2011; 5(2):1459-67. · 12.06 Impact Factor
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    ABSTRACT: The work function of palladium is known to be sensitive to hydrogen by the formation of a surface dipole layer or Pd hydride. One approach to detect such a change in the work function can be based on the formation of a Schottky barrier between the palladium metal and a semiconductor. Here, we study the hydrogen sensitivity of Schottky barrier field-effect transistors made for the first time from diameter- and chirality-sorted semiconducting single-walled carbon nanotubes (s-SWNTs) in contact with Pd electrodes. We observe an unrivaled 100-fold change in the on-state conductance at 100 ppm H2 compared to air for devices with s-SWNT and diameters between 1 and 1.6 nm. Hydrogen sensing is not observed for devices of Pd-contacted few-layer graphene (FLG), as expected due to the absence of a significant Schottky barrier. Unexpectedly, we observe also a vanishing sensitivity for small-diameter SWNTs. We explain this observation by changes in the nanotube work function caused by spillover and chemisorption of atomic hydrogen onto small-diameter nanotubes. We also observe that long-term sensing stability is only achieved if the gate voltage is inverted periodically. Under constant gate bias, the sensitivity reduces with time, which we relate to gate screening by accumulated charges in the substrate.
    ACS Nano 02/2011; 5(3):1670-6. · 12.06 Impact Factor
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    ABSTRACT: We report a detailed study of ultrafast exciton dephasing processes in semiconducting single-walled carbon nanotubes employing a sample highly enriched in a single tube species, the (6,5) tube. Systematic measurements of femtosecond pump-probe, two-pulse photon echo, and three-pulse photon echo peak shift over a broad range of excitation intensities and lattice temperature (from 4.4 to 292 K) enable us to quantify the timescales of pure optical dephasing (T(2)(*)), along with exciton-exciton and exciton-phonon scattering, environmental effects as well as spectral diffusion. While the exciton dephasing time (T(2)) increases from 205 fs at room temperature to 320 fs at 70 K, we found that further decrease of the lattice temperature leads to a shortening of the T(2) times. This complex temperature dependence was found to arise from an enhanced relaxation of exciton population at lattice temperatures below 80 K. By quantitatively accounting the contribution from the population relaxation, the corresponding pure optical dephasing times increase monotonically from 225 fs at room temperature to 508 fs at 4.4 K. We further found that below 180 K, the pure dephasing rate (1/T(2)(*)) scales linearly with temperature with a slope of 6.7 ± 0.6 μeV/K, which suggests dephasing arising from one-phonon scattering (i.e., acoustic phonons). In view of the large dynamic disorder of the surrounding environment, the origin of the long room temperature pure dephasing time is proposed to result from reduced strength of exciton-phonon coupling by motional narrowing over nuclear fluctuations. This consideration further suggests the occurrence of remarkable initial exciton delocalization and makes nanotubes ideal to study many-body effects in spatially confined systems.
    The Journal of Chemical Physics 01/2011; 134(3):034504. · 3.16 Impact Factor
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    ABSTRACT: Theoretical calculations predict that the collapse pressure for double-walled carbon nanotubes (DWCNTs) is proportional to 1/R , where R is the effective or average radius of a DWCNT. In order to address the problem of CNT stability at high pressure and stress, we performed a resonance Raman study of DWCNTs dispersed in sodium cholate using 532 and 633 nm laser excitation. Raman spectra of the recovered samples show minor versus irreversible changes with increasing ID/IG ratio after exposure to high non-hydrostatic pressure of 23 and 35 GPa, respectively. The system exhibits nearly 70% pressure hysteresis in radial breathing vibrational mode signals recovery on pressure release which is twice that predicted by theory.
    High Pressure Research 01/2011; 31(1):186-190. · 0.90 Impact Factor
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    ABSTRACT: We demonstrate a light emitting p-i-n diode made of a highly aligned film of separated (99%) semiconducting carbon nanotubes, self-assembled from solution. By using a split gate technique, we create p- and n-doped regions in the nanotube film that are separated by a micron-wide gap. We inject p- and n-type charge carriers into the device channel from opposite contacts and investigate the radiative recombination using optical micro-spectroscopy. We find that the threshold-less light generation efficiency in the intrinsic carbon nanotube film segment can be enhanced by increasing the potential drop across the junction, demonstrating the LED-principle in a carbon nanotube film for the first time. The device emits infrared light that is polarized along the long axes of the carbon nanotubes that form the aligned film.
    Optics Express 12/2010; 18(25):25738-45. · 3.55 Impact Factor

Publication Stats

1k Citations
389.76 Total Impact Points

Institutions

  • 2006–2013
    • Northwestern University
      • • Department of Materials Science and Engineering
      • • Division of Hospital Medicine
      Evanston, Illinois, United States
  • 2012
    • Karlsruhe Institute of Technology
      • Institut für Nanotechnologie
      Eggenstein-Leopoldshafen, Baden-Wuerttemberg, Germany
  • 2008–2012
    • University of California, Berkeley
      • Department of Chemistry
      Berkeley, MO, United States
  • 2011
    • Lawrence Berkeley National Laboratory
      Berkeley, California, United States
  • 2008–2010
    • Ludwig-Maximilian-University of Munich
      • Department of Biochemistry
      München, Bavaria, Germany
  • 2009
    • Università di Pisa
      • Department of Physics "E.Fermi"
      Pisa, Tuscany, Italy