We investigate the electronic structure of carbon nanotubes functionalized by adsorbates anchored with single C-C covalent bonds. We find that, despite the particular adsorbate, a spin moment with a universal value of 1.0 $μ_B$ per molecule is induced at low coverage. Therefore, we propose a mechanism of bonding-induced magnetism at the carbon surface. The adsorption of a single molecule creates a dispersionless defect state at the Fermi energy, which is mainly localized in the carbon wall and presents a small contribution from the adsorbate. This universal spin moment is fairly independent of the coverage as long as all the molecules occupy the same graphenic sublattice. The magnetic coupling between adsorbates is also studied and reveals a key dependence on the graphenic sublattice adsorption site.
Carbon nanotubes are of central importance for applications in nano-electronics thanks to their exceptional transport properties. They can be used as sensors, for example in biological applications, provided that they are functionalized to detect specific molecules. Due to their one-dimensional geometry the carbon nanotubes are very sensitive to the phenomenon of Anderson localization and it is therefore essential to know how the functionalization modifies their conduction properties and if they remain good conductors. Here we present a study of the quantum localization induced by functionaliz…
Scanning tunneling microscopy (STM) gives us the opportunity to map the surface of functionalized carbon nanotubes in an energy resolved manner and with atomic precision. But this potential is largely untapped, mainly due to sample stability issues which inhibit reliable measurements. Here we present a simple and straightforward solution that makes away with this difficulty, by incorporating the functionalized multiwalled carbon nanotubes (MWCNT) into a few layer graphene - nanotube composite. This enabled us to measure energy resolved tunneling conductance maps on the nanotubes, which shed li…
In terms of lattice dynamics theory, we study the vibrational properties of the oxygen-functionalized single wall carbon nanotubes (O-SWCNs). Due to the C-O and O-O interactions, many degenerate phonon modes are split and even some new phonon modes are obtained, different from the bare SWCNs. A distinct Raman shift is found in both the radial breathing mode and G modes, depending not only on the tube diameter and chirality but also on oxygen coverage and adsorption configurations. With the oxygen coverage increasing, interesting, a nonmonotonic up- and down-shift is observed in G modes, which …
We report optically induced aggregation and subsequent separation of selective single-walled carbon nanotubes (SWNT) functionalized with bacteriorhodopsin in the aqueous solution. Well-dispersed, aqueous solutions of hydrophobic pristine SWNT were prepared using a biocompatible surfactant. Dispersed SWNTs were then functionalized with biologically synthesized, optically active purple membrane from Halobacterium salinarium S9. Bacteriorhodopsin is the optically active protein of the purple membrane. Charge transfer and interactions between an optically active purple membrane (PM) and nanotubes …
We report the first observation of an optical transition from a ground trion state T to excited trion state T* in (6,5) single-wall carbon nanotubes non-covalently doped with hydrochloric acid. The position of such an excited trion level T* is estimated as 2,12 eV, while the ground trion level T has an energy of 1,08 eV. Besides, pump-probe transient absorption spectroscopy indicates that the ground trion level T cannot be excited directly. Instead, we propose that trions form after nonradioactive relaxation from excitons, dressed by interaction with doping induced hole-polarons. We also repor…
Using density-functional calculations, we study the effect of sp$^3$-type defects created by different covalent functionalizations on the electronic and magnetic properties of graphene. We find that the induced magnetic properties are {\it universal}, in the sense that they are largely independent on the particular adsorbates considered. When a weakly-polar single covalent bond is established with the layer, a local spin-moment of 1.0 $μ_B$ always appears in graphene. This effect is similar to that of H adsorption, which saturates one $p_z$ orbital in the carbon layer. The magnetic couplings b…
We present exemplary results of extensive studies of mechanical, electronic and transport properties of covalent functionalization of graphene monolayers (GML) with -NH2. We report new results of ab initio studies of covalent functionalization of GML with -NH2 groups up to 12.5% concentration. Our studies are performed in the framework of the density functional theory (DFT) and non-equilibrium Green's function (NEGF). We discuss the stability (adsorption energy), elastic moduli, electronic structure, band gaps, and effective electron masses as a function of the density of the adsorbed molecule…
Annotation A carbon nanotubes (CNT) filled polymer nanocomposites with their unique physical, mechanical and electro-optical properties has repeatedly discussed in the literature. The main part of this problem is to obtain high quality dispersion of CNTs. If for water-soluble polymers this problem can be considered as solved, it is not so for hydrophobic polymers, and PVC is an important example of this kind. This paper describes the methods of dispersion of SWNTs bundles in PVC, both by the use of specially synthesized surfactants, and by means of chemical surface modification of CNTs. The ma…
We investigate the time-dependent electronic transport in single-walled carbon nanotubes (SWCNTs) functionalized with Au clusters on CO gas exposure. Using a tight-binding Hamiltonian and the nonequilibrium Green's function (NEGF) formalism the time-dependent zeroth and first order contributions to the current are calculated. The zeroth order contribution is identified as the time-dependent Landauer formula in terms of the slow time variable, whereas the first order contribution is found to be small. The Green's function for the SWCNT is derived using the equation of motion and Dyson equation …
We study the effects of covalent functionalization of single wall carbon nanotubes (CNT) on their elastic properties. We consider simple organic molecules -NH, -NH2, -CH2, -CH3, -OH attached to CNTs' surface at various densities. The studies are based on the first principles calculations in the framework of density functional theory. We have determined the changes in the geometry and the elastic moduli of the functionalized CNTs as a function of the density of adsorbed molecules. It turns out that elastic moduli diminish with increasing concentration of adsorbands, however, the functionalized …
The controlled introduction of covalent sp$^{3}$ defects into semiconducting single-walled carbon nanotubes (SWCNTs) gives rise to exciton localization and red-shifted near-infrared luminescence. The single-photon emission characteristics of these functionalized SWCNTs make them interesting candidates for electrically driven quantum light sources. However, the impact of sp$^{3}$ defects on the carrier dynamics and charge transport in carbon nanotubes remains an open question. Here, we use ultrafast, time-resolved optical-pump terahertz-probe spectroscopy as a direct and quantitative technique …
We use DFT to study the effect of molecular adsorbates on the conductance of metallic carbon nanotubes. The five molecules considered (NO2, NH2, H, COOH, OH) lead to similar scattering of the electrons. The adsorption of a single molecule suppresses one of the two available channels of the CNT at low bias conductance. If more molecules are adsorbed on the same sublattice, the remaining open channel can be blocked or not, depending on the relative position of the adsorbates. If a simple geometric condition is fulfilled this channel is still open, even after adsorbing an arbitrary number of mole…
We present a first-principles study of the electronic transport properties of micrometer long semiconducting CNTs randomly covered with carbene functional groups. Whereas prior studies suggested that metallic tubes are hardly affected by such addends, we show here that the conductance of semiconducting tubes with standard diameter is on the contrary severely damaged. The configurational averaged conductance as a function of tube diameter and with a coverage of up to one hundred functional groups is extracted. Our results indicate that the search for a conductance-preserving covalent functional…
High spin polarization materials or spin filters are key components in spintronics, a niche subfield of electronics where carrier spins play a functional role. Carrier transmission through these materials is "spin selective" i.e. these materials are able to discriminate between "up" and "down" spins. Common spin filters include transition metal ferromagnets and their alloys, with typical spin selectivity (or, polarization) ~50% or less. Here we consider carrier transport in an archetypical one-dimensional molecular hybrid in which a single wall carbon nanotube (SWCNT) is wrapped around by sing…
We investigate through non-equilibrium Molecular Dynamics simulations the structure and flow of fluids in functionalized nanopores. The nanopores are modeled as cylindrical structures with solvophilic and solvophobic sites. Two fluids are modeled. The first is a standard Lennard Jones fluid. The second one is modeled with a isotropic two-length scale potential, which exhibits in bulk water-like anomalies. Our results indicates distinct dependence of the overall mass flux for each species of fluid with the number of solvophilic sites for different nanotubes radii. Also, the density and fluid st…
The photoconductance properties of photosystem I (PSI) covalently bound to carbon nanotubes (CNTs) are measured. We demonstrate that the PSI forms active electronic junctions with the CNTs enabling control of the CNTs photoconductance by the PSI. In order to electrically contact the photoactive proteins, a cysteine mutant is generated at one end of the PSI by genetic engineering. The CNTs are covalently bound to this reactive group using carbodiimide chemistry. We detect an enhanced photoconductance signal of the hybrid material at photon wavelengths resonant to the absorption maxima of the PS…
We developed a scalable, label-free all-electronic sensor for D-glucose based on a carbon nanotube transistor functionalized with pyrene-1-boronic acid. This sensor responds to glucose in the range 1 uM - 100 mM, which includes typical glucose concentrations in human blood and saliva. Control experiments establish that functionalization with the boronic acid provides high sensitivity and selectivity for glucose. The devices show better sensitivity than commercial blood glucose meters and could represent a general strategy to bloodless glucose monitoring by detecting low concentrations of gluco…
In the last decade, solid state nanopores nanogaps have attracted significant interest in the rapid detection of DNA nucleotides. However, reducing the noise through the controlled translocating of the DNA nucleobases is a central issue for the developing nanogap nanopore based DNA sequencing to achieve single nucleobase resolution. Furthermore, the high reactivity of the graphene pores gaps exhibits clogging of the pore gap, leading to the blockage of the pores gaps, yielding sticking, and irreversible pore closure. To address the prospective of functionalization of carbon nanostructure and f…
We report the production of covalently bonded selenium double-helices within the narrow cavity inside double-wall carbon nanotubes. The double-helix structure, characterized by high-resolution transmission electron microscopy and X-ray diffraction, is completely different from the bulk atomic arrangement and may be considered a new structural phase of Se. Supporting ab initio calculations indicate that the observed encapsulated Se double-helices are radially compressed and have formed from free Se atoms or short chains contained inside carbon nanotubes. The calculated electronic structure of S…
Covalent functionalization of semiconducting single-wall carbon nanotubes (CNT) introduces new photoluminescent emitting states. Theses states are spatially localized at around functionalization sites and strongly red-shifted relative to the emission commonly observed from the nanotube band-edge exciton state. A particularly important feature of these localized exciton states is that, because the exciton is no longer free to diffusively sample photoluminescent quenching sites along the CNT length, its lifetime is significantly extended. We have recently demonstrated that an important relaxatio…
Diazonium reactions with carbon nanotubes form optical $sp^3$ defects that can be used in optical and electrical circuits. We investigate a direct on-device reaction supported by confined laser irradiation and present a technique where an arbitrary carbon nanotube can be preferentially functionalized within a device by matching the light frequency with its transition energy. An exemplary reaction was carried out between (9,7) nanotube and 4-bromobenzenediazonium tetrafluoroborate. The substrate supported nanotubes of multiple semiconducting chiralities were locally exposed to laser light while…
The normal paper used in any printer is among the cheapest flexible organic materials that exist. We demonstrate that we can print on paper high-frequency circuits tunable with an applied dc voltage. This is possible with the help of an ink containing functionalized carbon nanotubes and water. After the water is evaporated from the paper, the nanotubes remain steadily imprinted on paper, showing a semiconducting behaviour and tunable electrical properties.
We demonstrate wafer-scale integration of single electron memories based on carbon nanotube field effect transistors (cnfets) by a complete self assembly process. First, a dry self assembly based on a Hot Filament assisted Chemical Vapor Deposition technique allows both localized growth and in situ electrical connection of carbon nanotubes on predefined catalytic electrodes. The semiconducting carbon nanotubes integration yield can exceed 50% for a batch. Secondly, a wet self-assembly attaches single 30 nm-diameter gold bead in the nanotube vicinity via chemical functionalization. The bead act…
Applications based on Single Walled Carbon Nanotube (SWNT) are good example of the great need to continuously develop metrology methods in the field of nanotechnology. Contact and interface properties are key parameters that determine the efficiency of SWNT functionalized nanomaterials and nanodevices. In this work we have taken advantage of a good control of the SWNT growth processes at an atomic force microscope (AFM) tip apex and the use of a low noise (1E-13 m/rtHz) AFM to investigate the mechanical behavior of a SWNT touching a surface. By simultaneously recording static and dynamic prope…
Vapor sensors based on functionalized carbon nanotubes (NTs) have shown great promise, with high sensitivity conferred by the reduced dimensionality and exceptional electronic properties of the NT. Critical challenges in the development of NT-based sensor arrays for chemical detection include the demonstration of reproducible fabrication methods and functionalization schemes that provide high chemical diversity to the resulting sensors. Here, we outline a scalable approach to fabricating arrays of vapor sensors consisting of NT field effect transistors functionalized with single-stranded DNA (…
We report the functionalization of carbon nanotubes with two azobenzene-based chromophores with large internal dipole moments and opposite dipole orientations. The molecules are attached to the nanotubes non-covalently via a pyrene tether. A combination of characterization techniques shows uniform molecular coverage on the nanotubes, with minimal aggregation of excess chromophores on the substrate. The large on/off ratios and the sub-threshold swings of the nanotube-based field-effect transistors (FETs) are preserved after functionalization, and different shifts in threshold voltage are observ…
By employing the first-principles calculations, we investigate electronic properties of a novel carbon nanostructure called a carbon nanobud, in which a $C_{60}$ molecule covalently attaches or embeds in an armchair carbon nanotube. We find that the carbon nanobud exhibits either semiconducting or metallic behavior, depending on the size of the nanotube, as well as the combination mode. Moreover, with respect to the case of the corresponding pristine nanotubes, some new electronic states appear at 0.3-0.8 eV above the Fermi level for the carbon nanobuds with the attaching mode, which agrees we…
We present results of extensive theoretical studies concerning stability, morphology, and band structure of single wall carbon nanotubes (CNTs) covalently functionalized by -CHn(for n=2,3,4),-NHn(for n=1,2,3,4),-COOH and -OH groups. Our studies are based on ab initio calculations in the framework of the density functional theory. We determine the dependence of the binding energies on the concentration of the adsorbed molecules, critical densities of adsorbed molecules, global and local changes in the morphology, and electronic structure paying particular attention to the functionalization indu…
Electrical resistivity and magnetoresistance(MR) in polyaniline(PANI) with carbon nanotube(CNT) and functionalized carbon nanotube(fCNT) composites have been studied for different weight percentage down to the temperature 4.2K and up to magnetic field 5T. Resistivity increases significantly in composite at low temperature due to functionalization of CNT compare to only CNT. Interestingly transition from negative to positive magnetoresistance has been observed for 10wt% of composite as the effect of disorder is more in fCNT/PANI. This result depicts that the MR has strong dependency on disorder…
The conductivity of carbon nanotube (CNT) networks can be improved markedly by doping with nitric acid. In the present work, CNTs and junctions of CNTs functionalized with NO$_3$ molecules are investigated to understand the microscopic mechanism of nitric acid doping. According to our density functional theory band structure calculations, there is charge transfer from the CNT to adsorbed molecules indicating p-type doping. The average doping efficiency of the NO$_3$ molecules is higher if the NO$_3$ molecules form complexes with water molecules. In addition to electron transport along individu…
Singlet fission (SF) process, where a singlet exciton decays into a pair of spin one exciton states which are in the total spin singlet state, is one of the possible channels for multiple exciton generation (MEG). In chiral single-wall carbon nanotubes (SWCNTs) efficient SF is present within the solar spectrum energy range which is shown by the many-body perturbation theory (MBPT) calculations based on the density functional theory (DFT) simulations. We calculate SF exciton-to-biexction decay rates ${\rm R}_{1\to 2}$ and biexciton-to-exction rates ${\rm R}_{2\to1}$ in the (6,2), (6,5), (10,5) …
We show that charge doping can induce transitions between three distinct adsorbate phases in hydrogenated and fluorinated graphene. By combining ab initio, approximate density functional theory and tight binding calculations we identify a transition from islands of C$_8$H$_2$ and C$_8$F$_2$ to random adsorbate distributions around a doping level of $\pm 0.05$ e/C-atom. Furthermore, in situations with random adsorbate coverage, charge doping is shown to trigger an ordering transition where the sublattice symmetry is spontaneously broken when the doping level exceeds the adsorbate concentration.…
