Functionalized Poly(3-hexylthiophene)s via Lithium–Bromine Exchange

Poly(3-hexylthiophene) (P3HT) is one of the most extensively investigated conjugated polymers and has been employed as the active material in many devices including field-effect transistors, organic photovoltaics and sensors. As a result, methods to further tune the properties of P3HT are desirable for specific applications. Herein, we report a facile postpolymerization modification strategy to functionalize the 4-position of commercially available P3HT in two simple steps–bromination of the 4-position of P3HT (Br–P3HT) followed by lithium−bromine exchange and quenching with an electrophile. We achieved near quantitative lithium–bromine exchange with Br–P3HT, which requires over 100 thienyl lithiates to be present on a single polymer chain. The lithiated-P3HT is readily combined with functional electrophiles, resulting in P3HT derivatives with ketones, secondary alcohols, trimethylsilyl (TMS) group, fluorine, or an azide at the 4-position. We demonstrated that the azide-modified P3HT could undergo Cu-catalyzed or Cu-free click chemistry, significantly expanding the complexity of the structures that can be appended to P3HT using this method.National Science Foundation (U.S.) (ECCS-0939514

Comparative study: the effect of annealing conditions on the properties of P3HT:PCBM blends

This paper presents a detailed study on the role of various annealing treatments on organic poly(3-hexylthiophene) and [6]-phenyl-C61-butyric acid methyl ester blends under different experimental conditions. A combination of analytical tools is used to study the alteration of the phase separation, structure and photovoltaic properties of the P3HT:PCBM blend during the annealing process. Results showed that the thermal annealing yields PCBM ‘‘needle-like’’ crystals and that prolonged heat treatment leads to extensive phase separation, as demonstrated by the growth in the size and quantity of PCBM crystals. The substrate annealing method demonstrated an optimal morphology by eradicating and suppressing the formation of fullerene clusters across the film, resulting in longer P3HT fibrils with smaller diameter. Improved optical constants, PL quenching and a decrease in the P3HT optical bad-gap were demonstrated for the substrate annealed films due to the limited diffusion of the PCBM molecules. An effective strategy for determining an optimized morphology through substrate annealing treatment is therefore revealed for improved device efficiency.Web of Scienc

Photochemical Charge Separation in Poly(3-hexylthiophene) (P3HT) Films Observed with Surface Photovoltage Spectroscopy

Surface photovoltage spectroscopy (SPS) was used to probe photon induced charge separation in thin films of regioregular and regiorandom poly(3-hexylthiophene) (P3HT) as a function of excitation energy. Both positive and negative photovoltage signals were observed under sub-band-gap (<2.0 eV) and super-band-gap (>2.0 eV) excitation of the polymer. The dependence of the spectra on substrate work function, thermal annealing, film thickness, and illumination intensity was investigated, allowing the identification of interface, charge transfer (CT), and band-gap states in the amorphous and crystalline regions of the polymer films. The ability to probe these states in polymer films will aid the development and optimization of organic electronic devices such as photovoltaics (OPVs), light-emitting diodes (OLEDs), and field effect transistors (OFETs). The direction and size of the observed photovoltage features can be explained using the depleted semiconductor model. © 2013 American Chemical Society

P3HT-Based Solar Cells: Structural Properties and Photovoltaic Performance

Each year we are bombarded with B.Sc. and Ph.D. applications from students that want to improve the world. They have learned that their future depends on changing the type of fuel we use and that solar energy is our future. The hope and energy of these young people will transform future energy technologies, but it will not happen quickly. Organic photovoltaic devices are easy to sketch, but the materials, processing steps, and ways of measuring the properties of the materials are very complicated. It is not trivial to make a systematic measurement that will change the way other research groups think or practice. In approaching this chapter, we thought about what a new researcher would need to know about organic photovoltaic devices and materials in order to have a good start in the subject. Then, we simplified that to focus on what a new researcher would need to know about poly-3-hexylthiophene:phenyl-C61-butyric acid methyl ester blends (P3HT: PCBM) to make research progress with these materials. This chapter is by no means authoritative or a compendium of all things on P3HT:PCBM. We have selected to explain how the sample fabrication techniques lead to control of morphology and structural features and how these morphological features have specific optical and electronic consequences for organic photovoltaic device applications

Design, synthesis and photovoltaic properties of [60]fullerene based molecular materials

The possibility to use new organic semiconductor materials, in place of silicon wafers, in the fabrication of photovoltaic devices on substrates offer the prospect of lower manufacturing costs, particularly for large area applications. Thus, one of the most promising areas in fullerene research involves its potential application, mixed with conjugated polymers, in mimicking photosynthesis and in the related solar energy conversion. The tendency to phase segregation in blends of C60 derivatives and conjugated polymers has to be optimized to improve both charge photogeneration and transport in photovoltaic devices. In order to optimize device performances, a great deal of work has been devoted to the development of new device architectures and to elucidating the photophysical processes underlying the photovoltaic response. However, optimization of cells has been carried out with just a few materials and recent findings show that new developments can be very successful if a broader scope of materials in the composite layers becomes accessible. Thus, in this communication we present new approaches toward the synthesis of [60]fullerene derivatives specifically designed to be used in the fabrication of photovoltaic devices. (i) the first approach involves the synthesis of functionalized C60 and C70 derivatives with enhanced solubility; (ii) the second approach is directed to the synthesis of systems containing a conjugated moiety antenna covalently linked to the C60 unit. Together with the synthesis of these new materials, electrochemical and photophysical investigations have been also carried out. Photovoltaic devices have been fabricated with selected materials