Polyfluorenes polymer heterojunctions

Several organics, e.g. pristine poly(3-octylthiophene), polyfluorene, bifunctional spiro compounds and polyphenyleneethynylene derivative, have been used for fabricating photOFETs. Responsivity as high as 0.5-1 A/W has been achieved in some of these transistors. We have already discussed the bulk heterojunction concept in Chapter 5. The bulk heterojunctions are fabricated using acceptor materials with high electron affinity (such as C<5o or soluble derivatives of C6o) mixed with conjugated polymers as electron donors. PhotOFETs based on conjugated polymer/fullerene blends are expected to show... 

The photophysics of jt-conjugated polymers are reviewed in detail in other chapters of this book. (See, for example, Chapter 3.) Here, we focus on the electronic and photophysical phenomena that occur at the heterojunction between two different semiconductor polymers. The heteroj unctions are formed by combining four different polyfluorene copolymers in blend or bilayer thin films and are investigated using time-resolved and steady-state, temperature- and elec-tric-field-dependent photoluminescence measurements as well as electroluminescence and time-resolved spectroscopy. We review a body of work carried out in our laboratories over the last few years, and published in numerous journal articles (see refs. [13-17]). 

The aim of this chapter is to elucidate the various electronic and optical processes that occur at heterojunctions between two semiconductor polymers. Most of the results presented are related to the presence of localized electronic states at heterojunctions between different polyfluorenes. These have an analog in solution systems of small molecules where they are called exciplex states. Here, we give an overview of the theories that have been developed for small-molecule solution systems (for more details see also [24] and [25]). In Section 2.1.3, we then discuss if and how these are applicable to solid-state films of blended conjugated polymers. 

In Section 2.1.4, the electronic and photophysical properties of donor-acceptor or type-II heterojunctions between two semiconductor polymers were investigated. Exciplex formation was found to be a general phenomenon for type-II heterojunctions between polyfluorene copolymers. These are among the most widely used materials in polymer optoelectronics, but the presence of exciplexes had not yet been fully appreciated. This is because the exciplex population is often depopulated via efficient endothermic transfer towards the exciton, which leads to bulk exciton instead of exciplex emission. However, via time- and temperature-depen-dent photoluminescence (PL) spectroscopy the exciplex states can be identified. Employing a relationship known from small-molecule solution systems that relates the relative HOMO and LUMO levels of the molecules to the exciplex emis-... 

M.-H. Chen, J. Hou, Z. Hong, G. Yang, S. Sista, L.-M. Chen, Y. Yang, Efficient Polymer Solar Cells with Thin Active Layers Based on Alternating Polyfluorene Copolymer/Fullerene Bulk Heterojunctions. Adv. Mater. 2009, 21,4238-4242. 

Andersson and coworkers have prepared solar cells based on blends of poly(2,7-(9-(2 -ethylhexyl)-9-hexyl-fluorene)-fl/t-5,5-(4, 7 -di-2-thienyl-2, l, 3 -benzothiadiazole) (223) and PCBM [416]. The polymer shows a Amax (545 nm) with a broad optical absorption in the visible spectrum and an efficiency of 2.2% has been measured under simulated solar light. The same group has also reported the synthesis of low bandgap polymers 200 (1 = 1.25 eV) and 224 (1 = 1.46 eV) which have been blended with a soluble pyrazolino[70]fiillerene and PCBM, respectively, to form bulk heterojunction solar cells of PCE of 0.7% [417] and 0.9% [418]. Incorporation of an electron-delident silole moiety in a polyfluorene chain affords an alternating conjugated copolymer (225) with an optical bandgap of 2.08 eV. A solar cell based on a mixture 1 4 of 225 and PCBM exhibits 2.01% of PCE [419]. 

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