Wibren D. Oosterbaan

Efficient formation, isolation and characterization of poly(3-alkylthiophene) nanofibres: probing order as a function of side-chain length

Efficient fibre formation for all regioregular poly(3-alkylthiophene)s (P3ATs) with alkyl chain lengths (A) between 3 and 9 carbon atoms has been accomplished in several solvents. It was observed that for the aliphatic and (chlorinated) aromatic hydrocarbon solvents used, the solvent refractive index offers some rationale to predict the feasibility of a solvent for fibre formation. The fibres were separated from remaining non-organised polymer by centrifugation. This enabled the characterisation of the isolated fibres in function of alkyl chain length (A) with TEM, AFM, XRD and UV-Vis spectroscopy. The fibres are 20 ± 5 nm wide and 0.5 to >4 µm long and mainly crystallize in the common type I crystal phase. The order within the fibres was probed with XRD, SAED, and UV-Vis and was found to strongly improve with increasing alkyl chain length in going from P33T to P35T, resulting in a longer conjugation length. For P35T to P39T the improvement in order is only marginal. Fibres from P37T were found to mainly crystallize in a crystal phase slightly different from type I that we refer to as type I′. This new crystal structure has a lattice constant a that is marginally shorter than that of phase I and a slightly longer lattice constant b of 4.0 A and thus in XRD can hardly be distinguished from phase I. It is furthermore characterized by a blue-shifted absorption band in UV-Vis spectroscopy. The type I′ fibres were converted into normal type I fibres in the solid state at 70 °C and in solution around 50 °C.

Varying polymer crystallinity in nanofiber poly(3-alkylthiophene): PCBM solar cells: Influence on charge-transfer state energy and open-circuit voltage

The effect of poly(3-alkylthiophene) (P3AT) crystallinity in (nanofiber P3AT):PCBM photovoltaic devices on the energy of the charge-transfer state (ECT) and on the open-circuit voltage (Voc) is investigated for poly(3-butythiophene), poly(3-pentylthiophene) and poly(3-hexylhiophene). P3AT crystallinity, expressed as the crystalline nanofiber mass fraction f to the total P3AT mass in the spin-coating dispersion, is varied between ∼0.1 and ∼0.9 by temperature control. ECT, as obtained by Fourier-transform photocurrent spectroscopy decreased with f as ECT=ECT0−0.2f eV. Alkyl side-chain length only influences ECT0. Voc relates to ECT as Voc=ECT/q−0.6 V.

Light-emitting organic field-effect transistor using an organic heterostructure within the transistor channel

The authors have realized a light-emitting organic field-effect transistor. Excitons are generated at the interface between a n-type and a p-type organic semiconductor heterostructure inside the transistor channel. The dimensions and the position of the p-n heterostructure are defined by photolithography. The p-n heterostructure is at a distance of several microns from the metal electrodes. Therefore, the exciton and photon quenching in this device is reduced. Numerical simulations fit well with the experimental data and show that the light-emitting zone can move within the transistor channel.

Ground-state charge-transfer complex formation in hybrid poly(3-hexyl thiophene):titanium dioxide solar cells

The existence of a ground-state charge-transfer (CT) complex in a conjugated polymer:metal oxide nanoparticle bulk heterojunction photovoltaic cell is demonstrated by Fourier-transform photocurrent spectroscopy (FTPS). The CT complex between poly(3-hexylthiophene) (P3HT) and titanium dioxide (TiO2) is characterized by a weak additional photocurrent band (onset 1eV) in the FTPS spectra, situated below the conjugated polymer bandgap of 2eV. The presence of CT interaction between P3HT and TiO2 in relation to frontier orbital alignment is discussed, as well as the contribution of a sub-bandgap interfacial CT state to the electron transfer process in P3HT:TiO2 solar cells.

Poly(3-alkylthiophene) nanofibers for optoelectronic devices

Semiconducting poly(3-alkylthiophene) nanofibers show remarkable optical and electrical properties, and because of their high aspect ratios they are perfectly suited to serve as organic quasi one-dimensional charge carriers. Hence, they offer interesting perspectives for next generation printable optoelectronic applications. This feature article provides an overview of the current state of the art regarding the preparation and characterization of poly(3-alkylthiophene) nanofibers, and a discussion on nanofiber-based optoelectronic applications, i.e. organic field-effect transistors and bulk heterojunction organic solar cells. In addition, current shortcomings and points of attention for future development are identified.

Organic phototransistors using poly(3-hexylthiophene) nanofibres

Here we report the fabrication of nanofibre-based organic phototransistors (OPTs) using preformed poly(3-hexylthiophene) (P3HT) nanofibres. OPT performance is analysed based on two important parameters: photoresponsivity R and photosensitivity P. Before testing the devices as OPTs, the normal organic field-effect transistor (OFET) operation is characterized, revealing a surface-coverage-dependent performance. With R reaching 250 A W(-1) in the on-state (V(GS) = -40 V) and P reaching 6.8 × 10(3) in the off-state (V(GS) = 10 V) under white light illumination (I(inc) = 0.91 mW cm(-2)), the best nanofibre-based OPTs outperform the OPTs fabricated from a solution of P3HT in chlorobenzene, in which no preformed fibres are present. The better performance is attributed to an increase in active layer crystallinity, a better layer connectivity and an improved edge-on orientation of the thiophene rings along the polymer backbone, resulting in a longer exciton diffusion length and enhanced charge carrier mobility, linked to a decreased interchain coupling energy. In addition, the increased order in the active layer crystallinity induces a better spectral overlap between the white light emission spectrum and the active layer absorption spectrum, and the absorption of incident light is maximised by the favourable parallel orientation of the polymer chains with respect to the OPT substrate. Combining both leads to an increase in the overall light absorption. In comparison with previously reported solution-processed organic OPTs, it is shown here that no special dielectric surface treatment or post-deposition treatment of the active device layer is needed to obtain high OPT performance. Finally, it is also shown that, inherent to an intrinsic gate-tuneable gain mechanism, changing the gate potential results in a variation of R over at least five orders of magnitude. As such, it is shown that R can be adjusted according to the incident light intensity.

Poly(3-alkylthiophene) Nanofibers for Photovoltaic Energy Conversion

The use of nanostructured non-conventional semiconductors such as conjugated polymers and metal oxides (e.g. TiO2), opens promising perspectives towards a new generation of solar cells based on the concept of donor:acceptor bulk heterojunctions. In this concept donor material and acceptor material form interpenetrating networks allowing light absorption, charge transfer and charge transport throughout the entire bulk of the thin film. Since nanomorphology is of crucial importance for this type of solar cells, in this contribution the use of nanofibers in bulk heterojunction solar cells is explored in order to obtain highways for charge transport. We investigate in particular the use of P3AT (poly(3-alkylthiophene)) nanofibers and show that the polymer fraction aggregated into fibers can be easily controlled by temperature. We find an optimal efficiency at intermediate fiber fraction and show that it can be linked to the morphology of the active layer.

Light-emitting organic field-effect transistors using an organic heterostructure inside the transistor channel

We have realized a light-emitting organic field-effect transistor (LEOFET). Excitons are generated at the interface of an n-type and a p-type organic semiconductor heterostructure inside the transistor channel. The dimensions and the position of the p-n heterostructure are defined by photolithography. The recombination region is several microns from the metal electrodes. Therefore, the exciton quenching probability in this device is reduced. Numerical simulations show that the recombination region can move within the transistor channel by changing the biasing conditions.

The use of nanofibers of P3HT in bulk heterojunction solar cells: the effect of order and morphology on the performance of P3HT:PCBM blends

Poly-3-AlkylThiophenes (P3ATs) with an n-alkyl chain length varying from C3 till C9 were synthesized by using the Rieke method. Subsequently, these materials were used to make P3AT/PCBM blends which were investigated in bulk heterojunction (BHJ) solar cells. The phase diagram of a P3H(exyl)T:PCBM blend was measured by means of standard and modulated temperature differential scanning calorimetry (DSC and MTDSC). A single glass transition is observed for all compositions. The glass transition temperature (Tg) increases with increasing PCBM concentration: from 12 °C for pure P3HT to 131 °C for pure PCBM. The observed range of Tgs defines the operating window for thermal annealing and explains the long-term instability of both morphology and photovoltaic performance of P3HT:PCBM solar cells. All regioregular P3ATs allow for efficient fiber formation in several solvents. The fibers formed are typically 15 to 25 nm wide and 0.5 to >4 μm long and mainly crystalline. By means of temperature control the fiber content in the casting solution for P3AT:PCBM BHJ solar cells is controlled while keeping the overall molecular weight of the polymer in the blend constant. In this way, fiber isolation and the use of solvent mixtures are avoided and with P3HT nanofibers, a power conversion efficiency of 3.2 % was achieved. P3AT:PCBM BHJ solar cells were also prepared from P3B(utyl)T, P3P(entyl)T and P3HT using the good solvent o-dichlorobenzene and a combination of slow drying and thermal annealing. In this way, power conversion efficiencies of 3.2, 4.3, and 4.6 % were obtained, respectively. P3PT is proved to be a potentially competitive material compared to P3HT.