Alexander B. Sieval

Photovoltaic performance of an ultrasmall band gap polymer

A conjugated polymer (PBTTQ) that consists of alternating electron-rich bithiophene and electron-deficient thiadiazoloquinoxaline units was synthesized via Yamamoto polymerization with Ni(cod)(2) and provides a band gap of 0.94 eV. This represents one of the smallest band gaps obtained for a soluble conjugated polymer. When applied in a bulk heterojunction solar cell together with [84]PCBM as the electron acceptor, the polymer affords a response up to 1.3 microm.

Temperature Dependence of Exciton Diffusion in Conjugated Polymers

The temperature dependence of the exciton dynamics in a conjugated polymer is studied using time-resolved spectroscopy. Photoluminescence decays were measured in heterostructured samples containing a sharp polymer-fullerene interface, which acts as an exciton quenching wall. Using a 1D diffusion model, the exciton diffusion length and diffusion coefficient were extracted in the temperature range of 4-293 K. The exciton dynamics reveal two temperature regimes: in the range of 4-150 K, the exciton diffusion length (coefficient) of approximately 3 nm (approximately 1.5 x 10 (-4) cm2/s) is nearly temperature independent. Increasing the temperature up to 293 K leads to a gradual growth up to 4.5 nm (approximately 3.2 x 10 (-4) cm2/ s). This demonstrates that exciton diffusion in conjugated polymers is governed by two processes: an initial downhill migration toward lower energy states in the inhomogenously broadened density of states, followed by temperature activated hopping. The latter process is switched off below 150 K.

Thienyl analog of 1-"3-methoxycarbonyl…propyl-1-phenyl-†6,6‡- methanofullerene for bulk heterojunction photovoltaic devices in combination with polythiophenes

An analog of 1-(3-methoxycarbonyl)propyl-1-phenyl-[6,6]-methanofullerene (PCBM) was designed with the aim of improving miscibility with polythiophene donors, especially poly(3-hexyl thiophene) (P3HT). In the title compound the phenyl group from PCBM is replaced by a thienyl group, it is named 1-(3-methoxycarbonyl)propyl-1-thienyl-[6,6]-methanofullerene (ThCBM). In this letter, experimental studies of the morphology, charge transport, and solar cell performance in blends of P3HT:ThCBM are reported. This may open a route for the design of more specific fullerene based acceptor materials, which may optimize the morphology of bulk heterojunction photovoltaic devices with respect to their transport.

Origin of fullerene-induced vitrification of fullerene:donor polymer photovoltaic blends and its impact on solar cell performance

Organic solar cell blends comprised of an electron donating polymer and electron accepting fullerene typically form upon solution casting a thin-film structure made up of a complex mixture of phases. These phases can vary greatly in: composition, order and thermodynamic stability; and they are dramatically influenced by the processing history. Understanding the processes that govern the formation of these phases and their subsequent effect on the efficiency of photo-generating and extracting charge carriers is of utmost importance to enable rational design and processing of these blends. Here we show that the vitrifying effect of three fullerene derivatives ([60]PCBM, bis[60]PCBM, and [60]ICBA) on the prototypical donor polymer (rr-P3HT) can dominate microstructure formation of fullerene/donor polymer blends cast from solution. Using a dynamic crystallization model based on an amalgamation of Flory–Huggins and Lauritzen–Hoffman theory coupled to solvent evaporation we demonstrate that this vitrification, which can result in a large fraction of highly intermixed amorphous solid solution of the fullerene and the polymer, is due to kinetic and thermodynamic reasons. The former is partly determined by the glass transition temperature of the individual components while donor polymer:fullerene miscibility, strongly influenced by the chemical nature of the donor and the fullerene and leading to thermodynamic mixing, dictates the second phenomena. We show that our approximate dynamic crystallization model assists understanding the different solid-state structure formation of rr-P3HT:fullerene blends. Due to the generality of the assumptions used, our model should be widely applicable and assist to capture the influence of the different vitrification mechanisms also of other photovoltaic blends, including the high-efficiency systems based on the strongly aggregating PCE11 (PffBT4T-2OD), which also feature clear signs of vitirfication upon blending with, e.g., [60]PCBM. Hence, our model will provide essential materials design criteria and enable identification of suitable processing guidelines for existing and new high-performing blends from the outset.

Structure/Property/Processing Relationships for Organic Solar Cells

Rapid developments in the field of organic solar cells have been driven by this technologys potentially advantageous traits: the environmentally friendly, low-cost generation of energy with the possibility of large area manufacturing of flexible, lightweight, semi-transparent devices, with predicted low energy payback times. Major step changes leading to vastly improved devices with ever-increasing performance have been achieved through new insights into materials design and an improved understanding of the often complex microstructure and phase morphology of organic solar cell systems. This chapter summarises the advances in synthesis, concentrating on the relevant structure/property relations and how the chemical structure affects processing and the microstructure. This is followed by a detailed discussion of classical materials science approaches that assist in gaining insights into complex materials systems, such as organic solar cell blends from the molecular to the micrometre scale, with a focus on polymer-based systems and how to apply this knowledge to future larger area processing of organic photovoltaic architectures.

CHAPTER 6:Structure/Property/Processing Relationships for Organic Solar Cells

Rapid developments in the field of organic solar cells have been driven by this technologys potentially advantageous traits: the environmentally friendly, low-cost generation of energy with the possibility of large area manufacturing of flexible, lightweight, semi-transparent devices, with predicted low energy payback times. Major step changes leading to vastly improved devices with ever-increasing performance have been achieved through new insights into materials design and an improved understanding of the often complex microstructure and phase morphology of organic solar cell systems. This chapter summarises the advances in synthesis, concentrating on the relevant structure/property relations and how the chemical structure affects processing and the microstructure. This is followed by a detailed discussion of classical materials science approaches that assist in gaining insights into complex materials systems, such as organic solar cell blends from the molecular to the micrometre scale, with a focus on polymer-based systems and how to apply this knowledge to future larger area processing of organic photovoltaic architectures.

Structure/property/processing relationships for organic solar cells

Rapid developments in the field of organic solar cells have been driven by this technologys potentially advantageous traits: the environmentally friendly, low-cost generation of energy with the possibility of large area manufacturing of flexible, lightweight, semi-transparent devices, with predicted low energy payback times. Major step changes leading to vastly improved devices with ever-increasing performance have been achieved through new insights into materials design and an improved understanding of the often complex microstructure and phase morphology of organic solar cell systems. This chapter summarises the advances in synthesis, concentrating on the relevant structure/property relations and how the chemical structure affects processing and the microstructure. This is followed by a detailed discussion of classical materials science approaches that assist in gaining insights into complex materials systems, such as organic solar cell blends from the molecular to the micrometre scale, with a focus on polymer-based systems and how to apply this knowledge to future larger area processing of organic photovoltaic architectures.

Diels-Alders adducts of C60 and esters of 3-(1-indenyl)-propionic acid

A series of new, easily synthesized C60-fullerene derivatives is introduced that allow for optimization of the interactions between rr-P3HT and the fullerene by systematic variation of the size of the ester group. Two compounds gave overall cell efficiencies of 4.8%, clearly outperforming [60]PCBM which gives 4.3% under identical conditions.

Exciton diffusion and dissociation in conjugated polymer/fullerene heterostructures

Time-resolved luminescence spectroscopy has been used to investigate exciton diffusion in thin films of poly(p-phenylene vinylene) (PPV) based derivatives. Exciton density distribution upon photoexcitation in polymer/fullerene heterostructures has been modeled and exciton diffusion length values of 5 nm and 6 nm are estimated for two different PPV derivatives, which differ by three orders of magnitude in charge carrier mobility due to reduced energetic disorder. Hence, the exciton diffusion length is not correlated to the charge carrier mobility in this class of materials.