Advanced Functional Materials and Devices (AFMD) Group

Abstract:

Electronic doping of organic semiconductors is essential for their usage in highly efficient optoelectronic devices. Although molecular and metal complex-based dopants have already enabled significant progress of devices based on organic semiconductors, there remains a need for clean, efficient and low-cost dopants if a widespread transition towards larger-area organic electronic devices is to occur. Here we report dimethyl sulfoxide adducts as p-dopants that fulfil these conditions for a range of organic semiconductors. These adduct-based dopants are compatible with both solution and vapour-phase processing. We explore the doping mechanism and use the knowledge we gain to 'decouple' the dopants from the choice of counterion. We demonstrate that asymmetric p-doping is possible using solution processing routes, and demonstrate its use in metal halide perovskite solar cells, organic thin-film transistors and organic light-emitting diodes, which showcases the versatility of this doping approach.

Abstract:

Organic solar cells (OSCs), also known as organic photovoltaics (OPVs), are an emerging solar cell technology composed of carbon-based, organic molecules, which convert energy from the sun into electricity. Key for their performance is the microstructure of the light-absorbing organic bulk heterojunction. To study this, organic solar films composed of both fullerene C60 as electron acceptor and different mole percentages of di-[4-(N,N-di-p-tolyl-amino)-phenyl]-cyclohexane (TAPC) as electron donor were evaporated in vacuum in different mixing ratios (5, 50 and 95 mol%) on an ITO-coated glass substrate held at room temperature and at 110 °C. The microstructure of the C60: TAPC heterojunction was studied by grazing incidence wide angle X-ray scattering to understand the effect of substrate heating. By increasing the substrate temperature from ambient to 110 °C, it was found that no significant change was observed in the crystal size for the C60: TAPC concentrations investigated in this study. In addition to the variation done in the substrate temperature, the variation of the mole percent of the donor (TAPC) was studied to conclude the effect of both the substrate temperature and the donor concentration on the microstructure of the OSC films. Bragg peaks were attributed to C60 in the pure C60 sample and in the blend with low donor mole percentage (5%), but the C60 peaks became nondiscernible when the donor mole percentage was increased to 50% and above, showing that TAPC interrupted the formation of C60 crystals.

Abstract:

We use the electron spin as a probe to gain insight into the mechanism of molecular doping in a p-doped zinc phthalocyanine host across a broad range of temperatures (80–280 K) and doping concentrations (0–5 wt% of F6-TCNNQ). Electron paramagnetic resonance (EPR) spectroscopy discloses the presence of two main paramagnetic species distinguished by two different g-tensors, which are assigned based on density functional theory calculations to the formation of a positive polaron on the host and a radical anion on the dopant. Close inspection of the EPR spectra shows that radical anions on the dopants couple in an antiferromagnetic manner at device-relevant doping concentrations, thereby suggesting the presence of dopant clustering, and that positive polarons on the molecular host move by polaron hopping with an activation energy of 5 meV. This activation energy is substantially smaller than that inferred from electrical conductivity measurements (∼233 meV), as the latter also includes a (major) contribution from charge-transfer state dissociation. It emerges from this study that probing the electron spin can provide rich information on the nature and dynamics of charge carriers generated upon doping molecular semiconductors, which could serve as a basis for the design of the next generation of dopant and host materials.

Abstract:

<p>We use the electron spin as a probe to gain insight into the mechanism of molecular doping in a p-doped zinc phthalocyanine host across a broad range of temperatures (80–280 K) and doping concentrations (0–5 wt% of F6-TCNNQ).</p>