Robust Electron Transport Layers via In Situ Cross-Linking of Perylene Diimide and Fullerene for Perovskite Solar Cells

While employing charge transport layers (CTLs) in optoelectronic devices including hybrid perovskite solar cells is essential for high performance, using solution-processed organic semiconductor-based CTLs poses challenges for device fabrication. Cross-linking the organic semiconductor is a viable approach, but cross-linked CTLs require additional development for practical application. Here a facile in situ strategy to prepare a cross-linked electron transport layer (ETL) is demonstrated by employing a semiconducting cross-linker composed of perylenediimidediazide, together with the fullerene (C-60) derivative coded as PCBM. Varying the PCBM ratio the cross-linking conditions affords a tunable ETL that exhibits solvent tolerance, suitable electron mobility (>10(-4) cm(2) V-1 s(-1)), and hydrophobicity at cross-linking temperatures as low as 120 degrees C. In both the n-i-p structure and the p-i-n perovskite solar cells employing our ETL, stable power generation and hysteresis-free performance are achieved. Optimized p-i-n devices with our cross-linked ETL gave power conversion efficiency of over 12% (active area of 1.07 cm(2)). These results suggest that robust n-type semiconducting films obtained with our cross-linking method are promising as ETLs in practical optoelectronic applications.

Dynamics of Electronic and Ionic Charges in Cyanine Organic Semiconductor Devices

Sandra Christina Jenatsch

Organic semiconductor materials have been widely applied in optoelectronic devices to replace their inorganic counterparts and explore new fields of applications. Due to their high extinction coefficients, chemical tunability and solubility, cyanine dyes are an interesting class of molecules to be employed in organic semiconductor devices. Their beneficial properties have been demonstrated in organic solar cells (OSC), photodetectors and recently in organic light-emitting electrochemical cells (OLEC). The focus of this thesis is to analyse different aspects regarding the dynamics of electronic and ionic charges in cyanine based devices. Models and conclusions are not restricted to cyanine based devices but can potentially be applied in various systems where combined ionic and electronic charges are present. In order to focus on electronic processes in OSCs, a combination of steady-state, transient and impedance analysis is used. It is resolved that trapped charges can be introduced at the dye/hole extracting layer interface by using specific solvents for the cyanine layer fabrication. These measurements also reveal the low hole mobility of cyanine films which in turn limits the possible upper layer thickness in OSCs. A frequently used way to enhance the conductivity of organic semiconductors is the addition of extra charges by chemical doping. This concept is employed for a near-infrared absorbing dye which is used as donor in a bilayer solar cell. The dependence of all figures of merit versus doping concentration and layer thickness is studied in detail. It is found that the performance of the optimised cell is not further improved by doping, but that it presents a good option if thicker layers are required, e.g. on rough substrates. Furthermore, the stability and degradation pathway of the p-doped species is analysed. This information is of general relevance as they also occur after charge transfer at the heterojunction interface of an OSC and during operation of OLECs. The dynamics of ionic charge carriers is separated into two contributions. In a first step, the steady-state diffusion profile of the counter ion within a cyanine/fullerene bilayer structure is scrutinised using different profiling techniques. An unexpected constant ion profile is found throughout the C60 layer. Simultaneously, the potential within the acceptor is measured by the Kelvin probe technique. A mechanism of combined electron and ion transfer from the C60 to the dye and vice versa is proposed which is in agreement with the experimental results. A prerequisite for OLEC operation is the mobility of ionic charge carriers. Their dynamics in cyanine salts under the effect of an external field is therefore studied in such devices. Several methods are developed and applied to characterise the dynamic p-i-n structure in detail, i.e. the position and width of the intrinsic region as well as the doping concentrations in p- and n-doped regions. The combination of all these methods helps to understand the transient behaviour of these cyanine devices but can also be adapted to other OLEC systems. A major drawback of cyanine dyes as emissive material is their low fluorescence quantum yield in solid films. To overcome this restriction and improve the OLEC efficiency, host-guest systems with various visibly emitting dyes are studied. The gain in fluorescence quantum yield in the film can directly be transferred to an increase in external quantum efficiency of the device.

EPFL2017

Dynamics of Electronic and Ionic Charges in Cyanine Organic Semiconductor Devices

Sandra Christina Jenatsch

EPFL2017