Sabine Bertho

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.

Modeling the temperature induced degradation kinetics of the short circuit current in organic bulk heterojunction solar cells

We acknowledge the institute for the promotion of science and technology in Flanders (IWT Vlaanderen) for funding via the IWT-SBO project Polyspec, the Fund for Scientific Research, Flanders (Belgium) (F.W.O.) in the framework of project G.0252.04 and the Special Research Fund (B.O.F.).

Toward bulk heterojunction polymer solar cells with thermally stable active layer morphology

Abstract. When state-of-the-art bulk heterojunction organic solar cells with ideal morphology are exposed to prolonged storage or operation at elevated temperatures, a thermally induced disruption of the active layer blend can occur, in the form of a separation of donor and acceptor domains, leading to diminished photovoltaic performance. Toward the long-term use of organic solar cells in real-life conditions, an important challenge is, therefore, the development of devices with a thermally stable active layer morphology. Several routes are being explored, ranging from the use of high glass transition temperature, cross-linkable and/or side-chain functionalized donor and acceptor materials, to light-induced dimerization of the fullerene acceptor. A better fundamental understanding of the nature and underlying mechanisms of the phase separation and stabilization effects has been obtained through a variety of analytical, thermal analysis, and electro-optical techniques. Accelerated aging systems have been used to study the degradation kinetics of bulk heterojunction solar cells in situ at various temperatures to obtain aging models predicting solar cell lifetime. The following contribution gives an overview of the current insights regarding the intrinsic thermally induced aging effects and the proposed solutions, illustrated by examples of our own research groups.

Description of the nanostructured morphology of [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) by XRD, DSC and solid‐state NMR

PCBM or [6,6]‐phenyl‐C61‐butyric acid methyl ester is nowadays still one of the most successful electron acceptors for plastic bulk heterojunction (BHJ) photovoltaic devices. In this study, a set of complementary techniques, i.e. solid‐state NMR, XRD and DSC, is proposed as a fast and sensitive tool to screen the morphology of PCBM specimens with different preparation histories. Based on proton NMR relaxation decay time values, an interval can be derived that situates the average crystal dimensions and which can further be refined on the basis of XRD patterns and DSC thermograms. Copyright

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.

How stable are polymer : PCBM bulk heterojunction solar cells?

This paper investigates the thermal stability of organic bulk heterojunction solar cells, with a special focus on the thermal ageing of both photovoltaic parameters and morphology of the active layer. The photovoltaic parameters of a set of bulk heterojunction solar cells were determined by IV-characterization and their bulk morphology was investigated with transmission electron microscopy (TEM). A link could be made between the degradation of the short circuit current under a thermal treatment and the corresponding change in bulk morphology. A possible improvement of the thermal stability of bulk heterojunction solar cells is presented through the use of a polymer with higher glass transition temperature.

Crystallization kinetics and morphology relations on thermally annealed bulk heterojunction solar cell blends studied by rapid heat cool calorimetry (RHC)

Optimizing the post-production annealing conditions of polymer:fullerene bulk heterojunction solar cells is vitally important, not only for fine-tuning the morphology - thus increasing the efficiency - but also for retaining the desired morphology during long-term operation. However, optimal conditions for annealing temperatures and times can only be chosen, once thermal transition temperatures and annealing kinetics of the blends are well-known. For instance, for systems with glass transition temperatures (Tg) lower than the maximum device operation temperature of 80°C, the mobility needed for morphology coarsening is present, leading to efficiencies decreasing in the course of time. Using advanced fast-scanning thermal analysis techniques, the formation of nuclei and growth of crystals during heating or cooling can be reduced or avoided, and thus, the fast crystallization processes occurring during annealing of the polymer:fullerene blends can be followed. In this study, non-isothermal and isothermal crystallization kinetics of the P3HT:PCBM (poly(3-hexyl thiophene: [6,6] -phenyl C61 - butyric acid methyl ester) and P3HT:bis-PCBM blends are investigated and compared by using Rapid Heating Cooling Calorimetry (RHC).

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.

Thermal stability of organic solar cells: the decay in photocurrent linked with changes in active layer morphology

Nowadays bulk heterojunction polymer:fullerene (PCBM) solar cells reach efficiencies of 5% through the use of high mobility donor polymers (e.g. P3HT) and through a continued nanoscale control of the morphology of the donor-acceptor interpenetrating networks [1]. One of the general bottlenecks of organic solar cells is their poor stability. Organic solar cells have a low resistance towards oxygen, UV-light, high temperatures etc. This work focuses on the thermal stability of organic solar cells.