Ultraviolet (UV/Vis) and Electroabsorption (EA) spectroscopy is used to examine and differentiate between intermolecular and intra molecular excited state species in fullerene films. Charge Transfer (CT) states are identified at 2.4 eV and 2.7 eV and dipole moments are calculated. Thermal annealing of C60 films is monitored in situ using absorption spectroscopy and electroabsorption spectroscopy. Recorded spectra display both some temperature dependent and partially irreversible effects, indicating the occurrence of an annealing process. EA shows that the CT states associated with the transferring an electron from the HOMO of one molecule located at the (0,0,0) position to the LUMO of its nearest neighbour in the (1/2,1/2,0) have been modified as a result of the annealing process. Confirmation of this structural change due to the annealing process is provided by previously reported X-Ray crystallographic work.
Samples of raw nanotubes are compared to those deposited from solutions to examine separation of nanotube bundles. Single wall nanotubes bundles produced by the arc-discharge and HiPco methods were solubilised in toluene, DMF and 1,2 dichloroethane. Resonant Raman spectroscopy was used to determine if debundling of the tubes sample occurred. The results showed some degree of debundling, best for the 1,2 dichloroethane solvent, which also shows long term solubility.
Photoluminescence intensity PL measurements were taken for a range of PmPV concentrations, in which HiPco single walled carbon nanotubes (SWNTs) at 100%, 10%, 1%, 0.1%, 0.01% and 0% mass fractions were added. The PL intensity of the composite was shown to decrease for all mass fractions, relative to the polymer up to 1.56x10-3g/l of PmPV, above which there is an initial increase in the composite emission yield with respect to the polymer. This increase is associated with an interaction within the composite, which results in a decrease in polymer aggregate formation, which has been shown to quench intensity yields. Within the concentration range studied 5.9x10-8g/l to 2g/l the photoluminescence intensity yield for each system is highly non linear. Previously the ratio of the maximum PL intensity of the composite, which includes both, bound and unbound polymer chains, and the maximum PL intensity of the polymer, which includes only unbound polymer chains was plotted as a function of polymer concentration. From this the authors calculated the amount of free polymer within each composite and derived a model, which showed that as the polymer concentration is lowered the bundles break up until isolated SWNTs are stable at low concentrations. In particular for their 100% mass fraction polymer/HiPco SWNT it was shown that individual nanotubes are stable in solutions ~3x10-5kg/m3. Here we utilize this approach and results indicate that as the mass fraction of nanotubes in reduced, individual nanotubes are stable at higher polymer concentrations. In particular for our 100% mass fraction results indicate that below ~1.5x10-4g/l individual nanotubes are stable. This result indicates that the choice of polymer and or solvent has a significant effect on the debundling and aggregation within these systems.
This paper shows the solublisation and de-bundling of SWNT with an aim to obtaining individual SWNT. By achieving this goal their theoretically proposed properties can be verified and their industrial potential realised. It is well documented that Single Wall Carbon Nanotubes (SWNTs) show varying degrees of solubility in a number of organic solvents. Solubility of SWNTs in toluene was found to be negligible. With toluene having such a poor affinity for SWNT it is clear that the solvent interaction with the SWNT is negligible. Therefore toluene is an ideal candidate for monitoring the improvements in the solubility of the SWNTs as a result of interaction with dye molecules such as terphenyl and anthracene. The suspensions formed are stable for periods greater than thirty-six months. Spectroscopic analysis clearly shows interaction and de-bundling of SWNT on addition of the dye molecules. The fluorescence of the dye molecules is quenched on interaction with SWNTs and in the case of terphenyl, the spectrum is red shifted which gives further support to the notion of interaction. With the quenching in fluorescence of the dye molecules signifying interaction, a large range of concentrations were studied in order to quantify the degree of interaction between the SWNT and dye molecules. It was found at high concentrations such as 1 x 10-3 M, that both the dye molecules and SWNT formed aggregates. At lower concentrations such as 1 x 10-9 M for terphenyl and 1 x 10-6 M for anthracene, it was found that free dye and individual SWNT were interacting. Raman spectroscopy of the composites formed on interaction show vibrational modes that are not present in either the SWNTs or dye powders. It was found that both the dye and SWNTs had Infra Red (IR) active vibrational modes at the positions at which these new or unique Raman modes occur in the composite spectra. It is therefore thought that the new Raman modes in the composite samples are related to the IR modes. The Raman Radial Breathing Modes (RBMs) give detail as to how diameter selective the dye samples are when compared to the pristine SWNT modes. Red shifting of the RBMs for both composite spectra was observed. It is believed that such a result is due to the de-bundling of the SWNT on interaction with the dye molecules.
The interaction of carbon nanotubes with soft organic molecules such as cyclodextrins and other saccharides has recently been shown to produce water-soluble composites. Such systems offer considerable advantages over polymer based composites due to their biocompatibility and non-covalent coupling which can potentially preserve the unique properties of the tubes. The mechanism of interaction of such systems has been proposed to be dominated by hydrophobic and hydrophilic interactions along the surface of the tube. In this study a number of composite systems have been formed with HiPco carbon nanotubes using starch.
The electrical properties of C60 have been extensively studied in both the solid and solution phases. The vibrational spectroscopy of C60 is predominantly molecular in character. However electronic spectroscopy reveals features, which are specific to the solid. These features have been attributed to intermolecular charge transfer states. The relative importance of these inter- and intramolecular processes in terms of their contribution to the electronic transport is discussed. Cyclic voltammetry is employed to generate charged molecular species, which also contribute to the conduction process and comparisons to optical excited states species are drawn. The cyclic voltammetry was monitored in situ with vibrational spectroscopy so as to observe any shifts in the C60 spectrum due to charging. The current voltage characteristics of thin film sandwich structures fabricated by vacuum are then presented and discussed. A strongly non-linear behaviour is observed, a sharp increase in the device conductance being observed at relatively low voltages at both room temperature and at 20K. The room temperature IV curves confirm a lattice collapse upon charging. The high conductivity state is however observed to be stable at low temperature.
The excited state properties of C60 thin films have been probed in the temperature range 77-273K using Raman spectroscopy. The change in the Raman pentagonal pinch mode of C60 (whose position is largely independent of temperature) was monitored as a function of the excitation intensity at 514.5nm. This mode, normally positioned at 1469cm-1, was seen to shift reversibly to a lower Raman frequency with increasing laser intensity. Two excited state species have been identified. The first, at 1466cm-1 has been associated with the molecular triplet of C60 as determined from measurements preformed in solution. The second species at 1463cm-1, has been speculated to be an excited state co-operative involving two or more excited states in the solid and is seen to be intrinsic to solid state C60 below the phase transition, as similar measurements in solution show no Raman evolution beyond 1466cm-1. This species observed at 1463cm-1 has previously been reported in the depolymerisation of solid state C60, as well as in reversible processes in C60 crystals and has been characterised by a nonlinear photo-luminescence and photoconductivity. It is further proposed in this study that this excited state is analogous to a number of highly conducting states recently reported for C60. The data presented highlights the existence of a highly non-linear delocalised excited state species at low temperatures which is intrinsic to solid state C60.
Interactions between Arc Discharge single walled carbon nanotubes within polymer composites have been well documented. Here hybrid systems of the conjugated organic polymer poly (p-phenylene vinylene-co-2,5-dioctyloxy -m-phenylene vinylene) (PmPV) and carbon nanotubes produced by Gas-Phase Decomposition of CO (HiPco) process are explored using Raman spectroscopy. Laser excitation wavelengths of 514.5nm and 633nm are employed to determine the specific nature of interaction. Also presented at laser energies 1.96eV and 2.4eV, are hybrid systems of Arc Discharge SWNTs at similar mass fractions to enable a direct comparison of solubility of each nanotube type within the polymer composite to be made. Comparisons are also made between the two hybrid systems in relation to range of nanotube diameters selected at 514.5 and 633nm.
Single wall carbon nanotubes are insoluble in most organic solvents such as toluene. Improvements in the solubility of the single wall carbon nanotubes are however seen as a result of specific interactions with molecules such as terphenyl and anthracene. Suspensions formed in toluene with these molecules and the single wall carbon nanotubes are seen to be stable over prolonged periods. Spectroscopic analysis clearly shows an interaction between the carbon nanotubes and the molecules. It is proposed in this study that the use of these more simple molecular systems may help elucidate the nature and extent of the interaction in more complex composite based systems.
In this study we examine the interaction of both cis and trans poly(m-phenylenevinylene-co-2,5-dioctyloxy-p-phenylenevinylene (PmPV-co-DOctOPV) with C60 in solution From the presented data it is clear that there is an interaction between the HE PmPV and C60. Just what this interaction is however is not as clear. A possible explanation that fits the available data involves the HE PmPV wrapping around the C60 molecules, similar to the effect observed by Dalton et al with Carbon Nanotubes. In theory the close proximately of the coils to the C60 molecules may allow for charge transfer or energy transfer between to the two molecules. If this theory is correct it would explain the why the absorption spectra of HE-PmPV at the different loaded fraction displays a negative deviation for the expected values. It may be speculated that due to the coiling the C60 molecules are prevented from absorbing photons of light, consequently resulting in a reduction in it's contribution to the overall intensity. This theory would also explain the increased quenching effect observed in the luminescence spectra at the same percentage weights, since the close proximity of the coils to the C60 molecules allows for charge or energy transfer between the two.
An analysis of the Raman spectra of single-walled HiPco carbon nanotube powder using laser energies of 1.92 eV, 2.4 eV, 2.5 eV, and 2.7 eV, including a comparison of the Stokes and anti-Stokes contributions is presented. The diameter distribution was determined to be 0.8-1.2nm from the spectral positioning of the Radial Breathing Modes. The diameter distribution is consistent with that determined by NIR absorption spectroscopy. At all excitation energies the profile of the G-line indicates a predominance of semiconducting tubes although at 2.4 eV there is some indication of some contribution from metallic tubes. In all cases the anti Stokes line was weak and the Stokes/anti Stokes ratio was at least an order of magnitude indicating at most weak resonance enhancement in either.
Organic materials have, in recent decades, been shown to be insulators, semiconductors, or even metallic when doped and the prospect of cheap, easily fabricated devices has attracted much interest. Primitive devices have been demonstrated and yet potentially competitive performance has been limited to polymer light emitting diodes. The recent report that lattice expanded C60 single crystals can be made superconducting, with a transition temperature of 117K, by the injection of charge via a FET type geometry has once again highlighted the potential of C60 in the development of molecular electronic devices. In light of the aforementioned report it is essential that a true understanding of the inter- and intramolecular processes in terms of their contribution to the electronic transport be obtained. In this study the current voltage characteristics of C60 thin film sandwich structures fabricated by vacuum deposition on indium tin oxide (ITO) with an aluminium top electrode are presented and discussed. A strongly non-linear behavior and a sharp increase in the device conductivity was observed at relatively low voltages (~2V), at both room and low temperatures (20K). At room temperature the system is seen to collapse, and in situ Raman measurements indicate a solid state reduction of the fullerene thin film to form a polymeric state. The high conductivity state was seen to be stable at elevated voltages and low temperatures. This state is seen to be reversible with the application of high voltages. At these high voltages the C60 film was seen to sporadically emit white light at randomly localized points analogous to the much documented electroluminescence in single crystals. Moreover the evidence suggests that this highly conducting species maybe similar in nature to a high intensity optically excited species. It is further speculated that the species recently reported in the superconducting lattice expanded C60 single crystals may also be analogous to the highly conducting species observed here.
The production of small diameter (0.7-1.2nm) and high purity single walled carbon nanotubes using a gas-phase catalytic approach has aroused considerable interest in the chemistry of this unique material. Most recently it has been proposed that tubes produced in this manner can be cut by simply grinding them in a soft organic material such as g-cyclodextrin. The results reported on such cutting techniques however concentrated upon microscopy thereby limiting the degree of information, which could be deduced about the type of interaction between the two materials. In this study electronic and vibrational spectroscopy as well as Differential Scanning Calorimetry has been performed upon a ground mixture of the aforementioned single walled carbon nanotubes and γ-Cyclodextrin. The mixture was prepared by grinding in a 30:1 ratio γ-cyclodextrin and single walled carbon nanotubes for approximately two hours with the drop-wise addition of ethanol (1ml) in the first 10 minutes. A similar ground mixture of g-Cyclodextrin and multi walled carbon nanotubes was also prepared to help asses the type and degree of interaction between the single walled carbon nanotubes and the γ-Cyclodextrin. Absorption spectroscopy showed changes to the electronic structure of both the single walled carbon nanotubes and the γ-Cyclodextrin, while evidence from Raman spectroscopy indicates that the cyclodextrins are absorbed via van der Waals forces along the length of the tube inducing a compressive strain. No such evidence for an interaction with multi walled carbon nanotubes was observed suggesting the possibility of a diameter selective interaction. Finally as a comparison a sample containing 5mg of tubes was refluxed in an aqueous solution of γ cyclodextrin (0.3M) for ~72 hour similar to early studies preformed on C60 and γ cyclodextrin