The electronic structures of boron nitride nanotubes (BNNTs) doped by organic molecules are investigated with density functional theory. Electrophilic molecule introduces acceptor states in the wide gap of BNNT close to the valence band edge, which makes the doped system a $p$-type semiconductor. However, with typical nucleophilic organic molecules encapsulation, only deep occupied molecular states but no shallow donor states are observed. There is a significant electron transfer from BNNT to electrophilic molecule, while the charge transfer between nucleophilic molecule and BNNT is neglectable. When both electrophilic and nucleophilic molecules are encapsulated in the same BNNT, large charge transfer between the two kinds of molecules occurs. The resulted small energy gap can strongly modify the transport and optical properties of the system.
Using density functional calculations, we investigate the structural and magnetic properties of ultrathin Gd and Gd-carbide nanowires (NWs) encapsulated in narrow carbon nanotubes (CNTs). The equilibrium geometry of an encapsulated (2 \times 2) Gd-NW is markedly different from that of bulk Gd crystals. The charge-density analysis shows pronounced spin-dependent electron transfer in the encapsulated Gd-NW in comparison with that of Gd-carbide NWs. We conclude that Gd-CNT hybridization is primarily responsible for both the structural difference and electron transfer in the encapsulated Gd-NW.
Tweaking the properties of carbon nanotubes is a prerequisite for their practical applications. Here we demonstrate fine-tuning the electronic properties of single-wall carbon nanotubes via filling with ferrocene molecules. The evolution of the bonding and charge transfer within the tube is demonstrated via chemical reaction of the ferrocene filler ending up as secondary inner tube. The charge transfer nature is interpreted well within density functional theory. This work gives the first direct observation of a fine-tuned continuous amphoteric doping of single-wall carbon nanotubes.
The electronic structures of boron nitride nanotubes (BNNTs) doped by different organic molecules under a transverse electric field were investigated via first-principles calculations. The external field reduces the energy gap of BNNT, thus makes the molecular bands closer to the BNNT band edges and enhances the charge transfers between BNNT and molecules. The effects of the electric field direction on the band structure are negligible. The electric field shielding effect of BNNT to the inside organic molecules is discussed. Organic molecule doping strongly modifies the optical property of BNN…
The structural, electronic and transport properties of metallocene molecules (MCp$_2$) and isolated or nanotube-encapsulated chains are studied by using a combination of density functional theory and non-equilibrium Green's functions. The analysis first discusses the whole series of isolated MCp$_2$ molecules, where M = V, Cr, Mn, Fe, Co, Ni, Ru, and Os. The series presents a rich range of electronic and magnetic behaviors due to the interplay between the crystal field interaction and Hund's rules, as the occupation of the $d$ shell increases. The article then shows how many of these interesti…
We analyze a new family of carbon nanotube-based molecular wires, formed by encapsulating metallocene molecules inside the nanotubes. Our simulations, that are based on a combination of non-equilibrium Green function techniques and density functional theory, indicate that these wires can be engineered to exhibit desirable magnetotransport effects for use in spintronics devices. The proposed structures should also be resilient to room-temperature fluctuations, and are expected to have a high yield.
In the present work, different synthesis procedures have been demonstrated to fill carbon nanotubes (CNTs) with $\mathrm{Fe}_{1-x}\mathrm{Ni}_x$ alloy nanoparticles (x = 0.33, 0.5). CNTs act as templates for the encapsulation of magnetic nanoparticles, and provide a protective shield against oxidation as well as prevent nanoparticles agglomeration. By variation of the reaction parameters, the purity of the samples, degree of filling, the composition and size of filling nanoparticles have been tailored and therefore the magnetic properties. The samples were analyzed by scanning electron microsc…
We present the first-principles study of effects of the charge dopants such as Cesium and Iodine encapsulated on the electronic structure of carbon nanotubes. An encapsulated cesium atom donates an electron to the nanotube and produces donor-like states below the conduction bands. In contrast, an iodine trimer (I$_{3}$) accepts an electron from the nanotube and produces an acceptor-like state above the valance band maximum. We find that a Cs atom inside a metallic armchair carbon nanotube gives rise to spatial oscillations of the density of states near the Fermi level.
The electrical conductivity of metallic carbon nanotubes (CNTs) quickly saturates with respect to bias voltage due to scattering from a large population of optical phonons. Decay of these dominant scatterers in pristine CNTs is too slow to offset an increased generation rate at high voltage bias. We demonstrate from first principles that encapsulation of 1D atomic chains within a single-walled CNT can enhance decay of "hot" phonons by providing additional channels for thermalisation. Pacification of the phonon population growth reduces electrical resistivity of metallic CNTs by 51% for an exam…
We report a comprehensive study on the electrochemical performance of four different Transition Metal Oxides encapsulated inside carbon nanotubes (CNT). Irrespective of the type of oxide-encapsulate, all these samples exhibit superior cyclic stability as compared to the bare-oxide. Innovative use of camphor during sample synthesis enables precise control over the morphology of these self-organized carbon nanotube structures, which in turn appears to play a crucial role in the magnitude of the specific capacity. A comparative evaluation of the electrochemical data on different samples bring for…
We studied the temperature stability of the endohedral fullerene molecule, N@C60, inside single-wall carbon nanotubes using electron spin resonance spectroscopy. We found that the nitrogen escapes at higher temperatures in the encapsulated material as compared to its pristine, crystalline form. The temperature dependent spin-lattice relaxation time, T_1, of the encapsulated molecule is significantly shorter than that of the crystalline material, which is explained by the interaction of the nitrogen spin with the conduction electrons of the nanotubes.
Toroidal carbon nanotubes can serve as hosts for encapsulated loops of atomic metal wires. Such composite structures have been analyzed using density functional theory for a semiconducting C$_{120}$ torus encapsulating chains of Fe, Au and Cu atoms. The sheathed metal necklaces form a zigzag structure and drops the HOMO/LUMO bandgap to less than 0.1 eV. The iron composite is ferromagnetic with a magnetic moment essentially the same as that of bcc iron. The azimuthal symmetry of these toroidal composites suggests that they may offer novel elecromagnetic properties not associated with straight, …
The weak-chemisorption/charge-transfer picture for adsorption of aromatic molecules over carbon nanotubes, proposed in the commented paper, is criticized.
Near-field spectroscopy has been extensively applied recently to analyze collective optical properties of materials at the nanoscale. However, vibrations of small molecules were only recognizable in close proximity to a metallic resonator. We show that encapsulation in boron nitride nanotubes (BNNT) enhances the near-field vibrational spectra of C$_{60}$ fullerene, reaching a sensitivity limit of a few hundred molecules. Furthermore, products of chemical reactions inside the tubes can be identified, so long as their vibrational signatures lie in the polariton gap of the BNNT.
Molecular dynamics simulations have been used to investigate the structures of Lennard-Jones (LJ) nanowires (NWs) encapsulated by carbon nanotubes (CNTs). We found that, when the radius of CNTs is small, the structures of NWs are quite simple, {\it i.e,} only multishell NWs are formed. For CNTs with larger radius, the structure of NWs becomes much richer. In addition to crystal and multishell NWs, three new kinds of NWs are found, {\it i.e,} a hybrid NW with a crystal core coated by a few shells, a crystal NW with droplet-like pits on the side of NW, and a multishell NW with droplet-like pits …
We investigate the geometry, stability, electronic structure and optical properties of C24H12 coronenes encapsulated in a single-wall (19,0) carbon nanotube. By an adequate combination of advanced electronic-structure techniques, involving weak and van derWaals interaction, as well as many-body effects for establishing electronic properties and excitations, we have accurately characterized this hybrid carbon nanostructure, which arises as a promising candidate for opto-electronic nanodevices. In particular, we show that the structure of the stacked coronenes inside the nanotube is characterize…
A series of solid organic acids were used to p-dope carbon nanotubes. The extent of doping is shown to be dependent on the pKa value of the acids. Highly fluorinated carboxylic acids and sulfonic acids are very effective in shifting the threshold voltage and making carbon nanotube field effect transistors to be more p-type devices. Weaker acids like phosphonic or hydroxamic acids had less effect. The doping of the devices was accompanied by a reduction of the hysteresis in the transfer characteristics. In-solution doping survives standard fabrication processes and renders p-doped carbon nanotu…
As the dimensions of electronic devices approach those of molecules, the size, geometry and chemical composition of the contact electrodes play increasingly dominant roles in device functions. It is shown here that single-walled carbon nanotubes (SWNT) can be used as quasi one-dimensional (1D) electrodes to construct organic field effect transistors (FET) with molecular scale width (~2 nm) and channel length (1-3 nm). An important feature owing to the quasi 1D electrode geometry is the favorable gate electrostatics that allows for efficient switching of ultra-short organic channels. This affor…
Exploring the synthesis of novel molecular nanostructures has been in the forefront of material research in the last decade. One of the most interesting nanostructures are single wall carbon nanotubes (SWCNTs). Their catalyst free growth, however, remains an elusive goal. Here, we present the growth of single wall carbon nanotubes from organic solvents such as benzene and toluene in a confined environment, inside a host SWCNT. The solvents encapsulated in SWCNTs are transformed to an inner tube when subject to a heat treatment under dynamic vacuum at 1270 $^{\circ}$C. We used isotope labeling …
We report high luminance organic light-emitting diodes by use of acid functionalized multi-walled carbon nanotube (o-MWCNTs) as efficient hole injector electrodes with a simple and solution processable device structure. At only 10 V, the luminance can reach nearly 50,000 cd/m2 with an external quantum efficiency over 2% and a current efficiency greater than 21 cd/A. The investigation of hole-only devices shows that the mechanism for hole injection is changed from injection limited to bulk limited because of the higher effective work function of the anode modified by the o-MWCNTs. We expect the…
Extreme nanowires (ENs) represent the ultimate class of crystals: They are the smallest possible periodic materials. With atom-wide motifs repeated in one dimension (1D), they offer a privileged perspective into the Physics and Chemistry of low-dimensional systems. Single-walled carbon nanotubes (SWCNTs) provide ideal environments for the creation of such materials. Here we present a comprehensive study of Te ENs encapsulated inside ultra- narrow SWCNTs with diameters between 0.7 nm and 1.1 nm. We combine state-of-the-art imaging techniques and 1D-adapted ab initio structure prediction to trea…
A printing process for high-resolution transfer of all components for organic electronic devices on plastic substrates has been developed and demonstrated for pentacene (Pn), poly (3-hexylthiophene) and carbon nanotube (CNT) thin-film transistors (TFTs). The nanotransfer printing process allows fabrication of an entire device without exposing any component to incompatible processes and with reduced need for special chemical preparation of transfer or device substrates. Devices on plastic substrates include a Pn TFT with a saturation, field-effect mobility of 0.09 cm^2 (Vs)^-1 and on/off ratio …
The inability to synthesize single-wall carbon nanotubes (SWCNTs) possessing uniform electronic properties and chirality represents the major impediment to their widespread applications. Recently, there is growing interest to explore and synthesize well-defined carbon nanostructures, including fullerenes, short nanotubes, and sidewalls of nanotubes, aiming for controlled synthesis of SWCNTs. One noticeable advantage of such processes is that no metal catalysts are used, and the produced nanotubes will be free of metal contamination. Many of these methods, however, suffer shortcomings of either…
By sequential feeding of catalyst materials, it is revealed that the active growth sites are at the bottom of the carbon nanotubes (CNTs), and that catalyst particles are constantly encapsulated into nanotubes from the bottom. This gives a better insight into the mechanism of CNT formation and on ways to control the growth process. CNTs encapsulated with different materials should enable the study of their electronic or magnetic properties, with potential applications as building blocks for nanoelectronics and as fillers in composites for electromagenetic shielding.
Organic color centers in single-walled carbon nanotubes have demonstrated exceptional ability to generate single photons at room temperature in the telecom range. Combining the color centers with pristine air-suspended tubes would be desirable for improved performance, but all current synthetic methods occur in solution which makes them incompatible. Here we demonstrate formation of color centers in air-suspended nanotubes using vapor-phase reaction. Functionalization is directly verified on the same nanotubes by photoluminescence spectroscopy, with unambiguous statistics from more than a few …
The functionalization of single-walled carbon nanotubes (SWCNTs) with luminescent sp$^{3}$ defects has greatly improved their performance in applications such as quantum light sources and bioimaging. Here, we report the covalent functionalization of purified semiconducting SWCNTs with stable organic radicals (perchlorotriphenylmethyl, PTM) carrying a net spin. This model system allows us to use the near-infrared photoluminescence arising from the defect-localized exciton as a highly sensitive probe for the short-range interaction between the PTM radical and the SWCNT. Our results point toward …
We calculate the van der Waals energy of a C60 molecule when it is encapsulated in a single-walled carbon nanotube with discrete atomistic structure. orientational degrees of freedom and longitudinal displacements of the molecule are taken into account, and several achiral and chiral carbon nanotubes are considered. A comparison with earlier work where the tube was approximated by a continuous cylindrical distribution of carbon atoms is made. We find that such an approximation is valid for high and intermediate tube radii; for low tube radii, minor chirality effects come into play. Three molec…
The hydrogen-methane compound (H_2)_4CH_4---or for short H4M---is one of the most promising hydrogen-storage materials. This van der Waals compound is extremely rich in molecular hydrogen: 33.3 mass%, not including the hydrogen bound in CH_4; including it, we reach even 50.2 mass%. Unfortunately, H4M is not stable under ambient pressure and temperature, requiring either low temperature or high pressure. In this paper, we investigate the properties and structure of the molecular and crystalline forms of H4M, using ab initio methods based on van der Waals DFT (vdW-DF). We further investigate the…
We develop two new amphiphilic molecules that are shown to act as efficient surfactants for carbon nanotubes in non-polar organic solvents. The active conjugated groups, which are highly attracted to graphene nanotube surface, are based on pyrene and porphyrin. We show that relatively short (C18) carbon tails are insufficient to provide stabilization. As our ultimate aim is to disperse and stabilize nanotubes in siloxane matrix (polymer and crosslinked elastomer), both surfactant molecules were made with long siloxane tails to facilitate solubility and steric stabilization. We show that pyrene…
We show that the performance of pentacene transistors can be significantly improved by maximizing the interfacial area at single walled carbon nanotube (SWCNT)/pentacene. The interfacial areas are varied by anchoring short SWCNTs of different densities (0-30/μm) to the Pd electrodes. The average mobility is increased three, six and nine times for low, medium and high SWCNT densities, respectively, compared to the devices with zero SWCNT. The current on-off ratio and on-current are increased up to 40 times and 20 times with increasing the SWCNT density. We explain the improved device performanc…
Growing graphene nanoribbons from small organic molecules encapsulated in carbon nanotubes can result in products with uniform width and chirality. We propose a method based on encapsulation of 1,2,4-trichlorobenzene from the liquid phase and subsequent annealing. This procedure results in graphene nanoribbons several tens of nanometers long. The presence of nanoribbons was proven by Raman spectra both on macroscopic samples and on the nanoscale by tip-enhanced Raman scattering and high-resolution transmission electron microscopic images.
Recently (PRL 96, 106804 (2006)) it was suggested that cobaltocene(CC) molecules encapsulated into (7,7) carbon nanotubes (CNT@(7,7)) could be the basis for new spintronic devices. We show here based on impact molecular dynamics and DFT calculations that when dynamical aspects are explicitly considered the CC encapsulation into CNT@(7,7) does not occur, it is prevented by a dynamic barrier mainly due to van der Waals interactions. Our results show that CNT@(13,0) having enough axial space for encapsulation but no enough one to allow freely rotation of the cobaltocene molecule would be a feasib…
Metallocenes can be encapsulated inside the carbon nanotubes. The structural, energetic and electronic properties of organometallic MCp2@SWCNT are obtained from DFT method. We verify that such encapsulation is noncovalent functionalization, and examined binding energies and charge transfers of MCp2@(16,0)SWCNT systems. Consistent with recent experimental findings, the optimal distance between FeCp2 center and near tube-wall is 4.7 (5.1) Å for the configuration where MCp2's five-fold axis is parallel (vertical) to nanotube axis, while the minimal diameter is 9.4 (10.2) Å to exothermically encap…
Luminescent metal-organic frameworks (MOFs) offer a multifunctional platform for creating non-invasive sensors and tuneable optoelectronics. However, fluorochromic materials that are photophysically resilient and show high sensitivity towards different physical and chemical stimuli are scarce. We report a facile host-guest nanoconfinement strategy to construct a fluorescent hybrid material with multiple sensing capabilities. We design and fabricate a new Guest@MOF material: comprising a zeolitic MOF (ZIF-71) as a nanoporous host for encapsulating rhodamine B (RhB dye) guest molecules, resultin…
We report the synthesis of the quasi-one-dimensional transition metal trichalcogenide NbSe3 in the few chain limit, including the realization of isolated single chains. The chains are encapsulated in protective boron nitride or carbon nanotube sheaths to prevent oxidation and to facilitate characterization. Transmission electron microscopy reveals static and dynamic structural torsional waves not found in bulk NbSe3 crystals. Electronic structure calculations indicate that charge transfer drives the torsional wave instability. Very little covalent bonding is found between the chains and the na…
Synergistic Effect of Multi-Walled Carbon Nanotubes and Ladder-Type Conjugated Polymers on the Performance of N-Type Organic Electrochemical Transistors
The oxygen reduction (ORR) and oxygen evolution reactions (OER) in Zn-air batteries (ZABs) require highly efficient, cost-effective and stable electrocatalysts as replacements to traditionally high cost, inconsistently stable and low poison resistant Platinum group metals (PGM) catalysts. Although, nitrogen-doped carbon nanotube (NCNT) arrays have been developed over recent decades through various advanced technologies are now capable of catalyzing ORR efficiently, their underdeveloped bifunctional property, hydrophobic surface, and detrimental preparation strategy are found to limit practical…
One-dimensional crystals have long range translational invariance which manifests as long exciton diffusion lengths, but such intrinsic properties are often obscured by environmental perturbations. We use a first-passage approach to model single-walled carbon nanotube (SWCNT) exciton dynamics (including exciton-exciton annihilation and end effects) and compare it to results from both continuous-wave and multi-pulse ultrafast excitation experiments to extract intrinsic SWCNT properties. Excitons in suspended SWCNTs experience macroscopic diffusion lengths, on the order of the SWCNT length, (1.3…
We report the stability and electronic structures of the boron nitride nanotubes (BNNTs) with diameters below 4 A by semi-empirical quantum mechanical molecular dynamics simulations and ab initio calculations. Among them (3,0), (3,1), (2,2), (4,0), (4,1) and (3,2) BNNTs can be stable well over room temperature. These small BNNTs become globally stable when encapsulated in a larger BNNT. It is found that the energy gaps and work functions of these small BNNTs are strongly dependent on their chirality and diameters. The small zigzag BNNTs become desirable semiconductors and have peculiar distrib…
This work proposes new chemical and mechanical materials and techniques for III-V semiconductor NW/silicone membrane formation and optoelectronic device fabrication. Molecular beam epitaxy (MBE)-synthesized n-, p- and i-GaP NWs were encapsulated by introduced G-coating method into synthesized polydimethylsiloxane-graft-polystyrene and released from the Si growth substrate. The fabricated membranes were contacted with different materials including single-walled carbon nanotubes or ferrocenyl-containing polymethylhydrosiloxane with and without multi-walled carbon nanotubes doping. The electrical…
The conductance of {\em cis/trans} isomers of stilbene molecules connected to armchair single wall carbon nanotubes is studied in the Landauer formalism combined with a density-functional based approach. For a given arrangement of the electrodes, dramatic differences in the transmission between both isomers are found. For a given isomer, the conductance can be varied by orders of magnitude by changing the molecule-electrode relative orientation. Both effects can be explained by a simple, physically transparent interference rule, which suggests a straightforward conductance control in such mole…
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 …
We report the results of \textit{ab initio} simulations of the electronic properties of a chain of C$_{60}$ molecules encapsulated in a boron nitride nanotube - so called BN-nanopeapod. It is demonstrated that this structure can be effectively doped by depositing potassium atoms on the external wall of the BN-nanotube. The resulting material becomes a true metallic one-dimensional crystal, where the conduction states are formed solely by the fullerene chain. At the doping rate of one K atom per C$_{60}$ molecule, the system shows the density of states at the Fermi level considerably higher tha…
Our ability to understand and tailor metal-organic interfaces is mandatory to functionalize organic complexes for next generation electronic and spintronic devices. For magnetic data storage applications, metal-carrying organic molecules, so called single molecular magnets (SMM) are of particular interest as they yield the possibility to store information on the molecular scale. In this work, we focus on the adsorption properties of the prototypical SMM Sc3N@C80 grown in a monolayer film on the Ag(111) substrate. We provide clear evidence of a pyramidal distortion of the otherwise planar Sc3N …
Solution-processed, large-area, and flexible electronics largely relies on the excellent electronic properties of sp$^2$-hybridized carbon molecules, either in the form of $π$-conjugated small molecules and polymers or graphene and carbon nanotubes. Carbon with sp-hybridization, the foundation of the elusive allotrope carbyne, offers vast opportunities for functionalized molecules in the form of linear carbon atomic wires (CAWs), with intriguing and even superior predicted electronic properties. While CAWs represent a vibrant field of research, to date, they have only been applied sparingly to…
There is increasing attention to chemical applications of transmission electron microscopy, which is often plagued by radiation damage. The damage in organic matter predominantly occurs via ionization (radiolysis). Although radiolysis is highly important, previous studies on radiolysis have largely been descriptive and qualitative, lacking in such fundamental information as the product structure, the influence of the energy of the electrons, and the reaction kinetics. We need a chemically well-defined system to obtain such data, and have chosen as a model a variable-temperature and variable-vo…
