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Photochromic molecules are part of a large class of materials in which light stimulus not only induces a color variation but also affects other physicochemical properties. However, the change of bulk electrical properties (e.g., electrical conductivity) via light excitation remains difficult to control because the intrinsically switchable molecules may lose their functionality when wired with conductive electrodes. In contrast with previous work based on single molecules, here we demonstrate a facile and accessible “wet-chemical” method to produce light-induced electrical switching. The electrical conductivity of a photochromic blend composed of diarylethene polymer and single-walled carbon nanotubes (SWNTs) is reversibly tuned according with UV–vis excitation. The devices present good thermal stability and remarkable fatigue resistance under ambient conditions. Supported by electrical and spectroscopic evidence, we show that the intertube electrical coupling, mediated by the light-induced electrocyclizat...

Density gradient ultracentrifugation (DGU) has emerged as a promising tool to prepare chirality enriched nanotube samples. Here, we assess the performance of different surfactants for DGU. Bile salts (e.g., sodium cholate (SC), sodium deoxycholate (SDC), and sodium taurodeoxycholate (TDC)) are more effective in individualizing Single Wall Carbon Nanotubes (SWNTs) compared to linear chain surfactants (e.g., sodium dodecylbenzene sulfonate (SDBS) and sodium dodecylsulfate (SDS)) and better suited for DGU. Using SC, a narrower diameter distribution (0.69-0.81 nm) is achieved through a single DGU step on CoMoCAT tubes, when compared to SDC and TDC (0.69-0.89 nm). No selectivity is obtained using SDBS. due to its ineffectiveness in debundling. We assign the reduce selectivity of dihydroxy bile salts (S DC and TDC) in comparison with trihydroxy SC to the formation of secondary micelles. This is determined by the number and position of hydroxyl ( OH) groups on the a-side of the steroid backbone. We also enrich CoMoCAT SWNT in the 0.84-0.92 nm range using the Pluronic F98 triblock copolymer. Mixtures of bile salts (SC) and linear chain surfactants (SOS) are used to enrich metallic and semiconducting laser-ablation grown SWNTs. We demonstrate enrichment of a single chirality, (6,5), combining diameter and metallic versus semiconductillg separation on CoMoCAT samples.

We report on light emission from biased metallic single-wall carbon nanotube (SWNT), multiwall carbon nanotube (MWNT) and few-layer graphene (FLG) devices. SWNT devices were assembled from tubes with different diameters in the range 0.7-1.5 nm. They emit light in the visible spectrum with peaks at 1.4 and 1.8 eV. Similar peaks are observed for MWNT and FLG devices. We propose that this light emission is due to phonon-assisted radiative decay from populated pi* band states at the M point to the Fermi level at the K point. Since for most carbon nanotubes as well as for graphene the energy of unoccupied states at the M point is close to 1.6 eV, the observation of two emission peaks at approximately 1.6 +/- approximately 0.2 eV could indicate radiative decay under emission or absorption of optical phonons, respectively.

We study the photo-induced transmission change (ΔT/T) upon quasi-continuum laser excitation, for different modulation frequency and excitation intensity in films of (6, 5) enriched CoMoCat single wall nanotubes (SWNTs) embedded in a polymeric matrix. This technique probes long-lived excited species, with lifetime in the 1 ms–1 s domain. The observed line-shape of ΔT/T spectra that can be assigned to a superposition of ground state bleaching and absorption modulation. We speculate that photo-excitation creates charges which get trapped in the sample, acquiring ms lifetime. This causes bleaching of the ground state absorption due to state filling and possibly a tube diameter expansion, with consequent blue shift of the optical transition.

Space resolved Stark spectroscopy is introduced as a non invasive optical technique for imaging electric field distribution in organic semiconductors. Stark spectroscopy relies on the electric field induced change in the absorption/reflection. It is shown that local monitoring of Stark shift with confocal spatial resolution provides quantitative information on the strength of the local field as well as charge distribution within the transport channel.

Structure-property relationships are of fundamental importance to develop quantitative models describing charge transport in organic semiconductor based electronic devices, which are among the best candidates for future portable and lightweight electronic applications. While microstructural investigations, such as those based on X-rays, electron microscopy, or polarized optical probes, provide necessary information for the rationalization of transport in macromolecular solids, a general model predicting how charge accommodates within structural maps is not yet available. Therefore, techniques capable of directly monitoring how charge is distributed when injected into a polymer film and how it correlates to structural domains can help fill this gap. Supported by density functional theory calculations, here we show that polarized charge modulation microscopy (p-CMM) can unambiguously and selectively map the orientational order of the only conjugated segments that are probed by mobile charge in the few nanometer thick accumulation layer of a high-mobility polymer-based field-effect transistor . Depending on the specific solvent-induced microstructure within the accumulation layer, we show that p-CMM can image charge-probed domains that extend from submicrometer to tens of micrometers size, with markedly different degrees of alignment. Wider and more ordered p-CMM domains are associated with improved carrier mobility, as extracted from device characteristics. This observation evidences the unprecedented opportunity to correlate, directly in a working device, electronic properties with structural information on those conjugated segments involved in charge transport at the buried semiconductor-dielectric interface of a field-effect device.

Here we show how Stark spectroscopy, coupled with confocal microscopy, is able to directly map the electric field in an n-type Copper-Fluorinated Phthalocyanine Thin-Film Transistor (TFT) under different operating conditions. To this extent, we locally probe Electro-Reflectance, with a nominal spatial resolution better than 500 nm, exploiting the fact that the detected signal is directly proportional to the square of the local field on the probe volume. This electric field imaging technique has unique advantages because it is non-invasive, since it exploits low incident power and because it probes the existing field in the bulk rather than the surface. Combining the experimental data with numerical modeling, it is possible not only to reconstruct the space charge profile in the few-nanometer thick accumulation layer, but also to extract the AC electron mobility.

We demonstrate an easy and scalable way to get devices in which the electrical resistance can be tuned by UV/visible light exposure. In particular, such a feature is based on photochromic diarylethene polymer - carbon nanotubes blend where reversible light controlled switching of the photochromic component induces a change in the electrical conductivity of the material. Differently from the single molecule approach, we use a simple ‘wet-chemistry method’ to obtain a net of carbon nanotubes embedded in a photochromic polymer. When the device is illuminated with UV light, a decreasing in the electric resistance of the active layer occurs. A resistance modulation up to 300% of the initial value is achieved, which is completely reversible with visible light illumination. The process is repeatable many times with a good fatigue resistance at room conditions. Supported by electrical and spectroscopic evidences, we show that the light-triggered electrocyclization of the polymer affects the inter-tube charge mobility, resulting in large overall change in the resistance of the device.

Photochromic materials reversibly change their colour due to a photochemical reaction that takes place when the material is irradiated with photons of suitable energy. This peculiar feature has been extensively exploited to develop smart sunglasses, filters and inks. With a proper molecular design it is possible to enable modulation not only of colour but also of other properties such as refractive index, dipole moment, nonlinear optical properties or conductivity by a photoswitching of the molecular structure. The approach herein developed consists in modifying, upon irradiation, the properties of a molecular component coupled with the photochromic molecule. In particular, the switching features of photochromic systems are matched with the intriguing peculiar properties of carbon nanotubes (CNTs). A photochromic polyester has been properly synthesised to be used as switching polymer matrix coupled with a network of CNTs. Irradiation of the polymer/CNTs blend results into a light-triggered conductance switching. The reversible electrocyclization of the polymer under UV-vis illumination results into a modification of the inter-tube charge mobility, and accordingly, of the overall resistance of the blend. Solution techniques allow us to obtain blended films with sheet resistance modulation larger than 150%, good thermal stability and fatigue resistance at room conditions, in an easier, faster and scalable way as respect to the single-molecule approach.y

A technique to measure scattering-free absorption of small amounts of powder nanostructured materials, based on time-resolved diffuse optical spectroscopy, has been demonstrated and experimentally validated on two carbon materials.

We establish the use of dielectrophoresis for the directed parallel assembly of individual flakes and nanoribbons of few-layer graphene into electronic devices. This is a bottom-up approach where source and drain electrodes are prefabricated and the flakes are deposited from a solution using an alternating electric field applied between the electrodes. These devices are characterized by scanning electron microscopy, atomic force microscopy, Raman spectroscopy and electron transport measurements. They are shown to be electrically active and their current carrying capacity and subsequent failure mechanism is revealed. Akin to carbon nanotubes, we show that the dielectrophoretic deposition is self-limiting to one flake per device and is scalable to ultra-large-scale integration densities, thereby enabling the rapid screening of a large number of devices., Comment: ACS Nano, (2009) In Press

By combining confocal microscopy with electroreflectance spectroscopy we directly map electric field amplitude distribution between electrodes in a prototypical organic semiconductor device. We demonstrate this approach on a copper phthalocyanine photodetector.

We report on the triplet spectra and dynamics in two types of oligomeric films deposited by two different techniques: thermal evaporation and spin coating. The different molecular arrangement in both films is manifested in a red shift of the absorption, PL, and T-1-T-n absorption spectra of the sublimated film relative to the spin-coated one. Triplet recombination dynamics studied with steady-state photoinduced absorption (PA) spectroscopy follow a dispersive bimolecular recombination model away from the trap filling regime. We obtained values for the triplet bimolecular recombination ratio (beta) of 3.4 x 10(-14) and 1.1 x 10(-15) cm(3) s(-1) for evaporated and spin-coated film, respectively, the difference being attributed to diverse molecular arrangement in both films.