Ilaria Cardinaletti

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.

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.

Highly efficient perovskite solar cells with crosslinked PCBM interlayers

Commercially available phenyl-C61-butyric acid methyl ester (PCBM) is crosslinked with 1,6-diazidohexane (DAZH), resulting in films resistant to common solvents used in perovskite solar cell processing. By using crosslinked PCBM as an interlayer and (HC(NH2)2)0.66(CH3NH3)0.34PbI2.85Br0.15 as the active layer, we achieve small area devices and modules with a maximum steady-state power conversion efficiency of 18.1% and 14.9%, respectively.

A direct arylation approach towards efficient small molecule organic solar cells

Three extended molecular chromophores, differing in their central acceptor moiety and specifically designed as electron donor components for small molecule organic solar cells, are synthesized via a two-fold C–H arylation protocol. Upon removal of the side products inherent to the applied direct (hetero)arylation procedure, a record power conversion efficiency of 5.1% is achieved.

Impact of structure and homo-coupling of the central donor unit of small molecule organic semiconductors on solar cell performance

Currently, both low bandgap conjugated polymers and small molecule analogues are employed as electron donor components in state of the art bulk heterojunction organic photovoltaics, providing similar record efficiencies (∼10%). However, to evaluate molecular structure-device performance relations and (in particular) the effect of material purity, small molecule chromophores can be considered to be more versatile probes. In the present study, we have synthesized three small molecule donor materials with a varying central electron-rich building block, inspired by the well-known high-performance small molecule p-DTS(FBTTh2)2. The influence of this structural modification on the physicochemical material properties, electro-optical characteristics and solar cell performance is analysed. Most importantly, it is shown that the presence of homo-coupled side products generated during Stille cross-coupling reactions – which can be very hard to remove, even for small molecule semiconductors – is detrimental to solar cell performance, with a noticeable effect on the open-circuit voltage.

Structure–Property Relations of Methylamine Vapor Treated Hybrid Perovskite CH3NH3PbI3 Films and Solar Cells

The power conversion efficiency of halide perovskite solar cells is heavily dependent on the perovskite layer being sufficiently smooth and pinhole-free. It has been shown that these features can be obtained even when starting out from rough and discontinuous perovskite film by briefly exposing the film to methylamine (MA) vapor. The exact underlying physical mechanisms of this phenomenon are, however, still unclear. By investigating smooth, MA treated films based on very rough and discontinuous reference films of methylammonium triiode (MAPbI3) and considering their morphology, crystalline features, local conductive properties, and charge carrier lifetime, we unraveled the relation between their characteristic physical qualities and their performance in corresponding solar cells. We discovered that the extensive improvement in photovoltaic performance upon MA treatment is a consequence of the induced morphological enhancement of the perovskite layer together with improved electron injection into TiO2, which in fact compensates for an otherwise compromised bulk electronic quality simultaneously caused by the MA treatment.

Branched and linear A2–D–A1–D–A2 isoindigo-based solution-processable small molecules for organic field-effect transistors and solar cells

To establish a correlation between the molecular structure, physicochemical properties, thin film morphology, charge carrier mobility and photovoltaic performance of isoindigo-based electron donor type molecular semiconductors, a series of branched and linear A2–D–A1–D–A2 small molecules (A = acceptor, D = donor) are synthesized. The extended π-conjugated molecular chromophores have an electron-accepting isoindigo core, a bridging oligothiophene electron donor part and terminal octyl cyanoacrylate acceptor moieties. Their photophysical, thermal and electrochemical properties are analysed and the materials are applied in organic field-effect transistors and bulk heterojunction organic solar cells. Compared to an analogous benzothiadiazole-based small molecule, the isoindigo core deepens the HOMO energy level, enabling higher open-circuit voltages in organic solar cells. The linear isoindigo-based small molecule shows an enhanced hole mobility compared to the branched derivatives. The best power conversion efficiency of the investigated set is also obtained for the solar cell based on the linear (CA-3T-IID-3T-CA-l) donor molecule in combination with PC71BM.

Low bandgap copolymers based on monofluorinated isoindigo towards efficient polymer solar cells

To explore the effectiveness of monofluorinated isoindigo as an electron-deficient building block in push–pull conjugated polymers for organic solar cell applications, four low bandgap copolymers are effectively synthesized and characterized. The effects of fluorine introduction, thiophene spacer length and polymer molar mass on the general electro-optical polymer characteristics, thin film blend microstructure and electronic performance are investigated. Isoindigo monofluorination effectively improves the power conversion efficiency from 2.8 up to 5.0% upon molar mass optimization, without using any processing additives or post-treatments.