Poly polymer heterojunctions

Nowadays the best performing organic photovoltaic cell is represented by a bulk heterojunction (BHJ) solar cell based on the polymer poly(3-hexylthiophene) (P3HT) and the fullerene derivative [6, 6]-phenyl-C61-butyric acid methyl ester (PCBM), with reproducible efficiencies approaching 5% [262,263], However, a serious drawback for the preparation of efficient organic photovoltaic cells is represented by the low optical absorbance in the red/near-infrared region of the lightharvesting component(s), as well as their low extinction coefflcient(s). 

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 first realizations of polymer-polymer bulk heterojunction solar cells were independently reported in the mid-1990s by Yu and Heeger as well as by Halls et al. [28,30]. These solar cells were prepared from blends of two poly(para-phenylenevinylene) (PPV) derivatives the well-known MEH-PPV (poly[2-methoxy-5-(2 -ethylhexyloxy)-l,4-phenylenevinylene]) was used as donor component, while cyano-PPV (CN-PPV) served as acceptor component (identical to MEH-PPV with an additional cyano (- CN) substitution at the vinylene group). The blends showed increased photocurrent and power conversion efficiency (20-100 times) when compared to the respective single component solar cells. 

Similar bulk heterojunctions with CN-PPV as acceptor polymer were realized with poly(3-hexylthiophene) (P3HT or denoted as PAT6 here) and PDPATPSi as donors, leading to a comparable behavior [31]. 

Currently, much work is devoted to the synthesis of conducting polymers for use in a variety of applications. Polyacetylene, the prototype conducting polymer, has been successfully demonstrated to be useful in constructing p-n heterojunctions, (1) Schottky barrier diodes, (2,3) liquid junction photoelectro-chemical solar cells, (4) and more recently as the active electrode in polymeric batteries. (5) Research on poly (p-phenylene) has demonstrated that this polymer can also be utilized in polymeric batteries. (6)... 

M. M. Alam and S. A. Jenekhe. Nanolayered heterojunctions of donor and acceptor conjugated polymers of interest in light emitting and photovoltaic devices Photoinduced electron transfer at poly-thiophene/polyquinoline interfaces. J. 

Finally, conjugated materials 40 based on poly(phenylene thiophene) and poly (fluorene thiophene) main chain polymers functionalized with pendant trithiocyanato ruthenium terpyridine complexes were synthesized by the Suzuki coupling reaction. Heterojunction photovoltaic cells with the simple structure ITO/polymer/C-60/Al were fabricated. Under simulated AM1.5 solar light illumination, the short circuit currents, open circuit voltages, and power conversion efficiencies of the photovoltaic cells were measured to be 1.53-2.58 mAcm 2, 0.12-0.24 V, and 0.084-0.12%, respectively [77]. 

At the early development of polymer solar cells, a planar p-n junction structure represented the mainstream in mimicking conventional silicon-based solar cells. However, the obtained devices demonstrated poor photovoltaic performances due to the long distance between the exciton and junction interface and insufficient light absorption due to the thin light absorber. It was not until 1995 that the dilemma was overcome with the discovery of a novel bulk heterojunction in which donor and acceptor form interpenetrated phases. Poly[2-methoxy-5-(2 -ethylhexyloxy)-p-phenylene vinylene] was blended with Ceo or its derivatives to form the bulk heterojunction. A much improved power conversion efficiency of 2.9% was thus achieved under the illumination of 20 mW/cm. (Yu et al., 1995). The emergence of the donor/acceptor bulk-heterojunction structure had boosted the photovoltaic performances of polymer solar cells. Currently, a maximal power conversion efficiency of 10.6% had been reported on the basis of synthesizing appropriate polymer materials and designing a tandem structure (You et al., 2013). The detailed discussions are provided in Chapter 5. 

Alkyl was introduced into insoluble PTh as side chain, producing the soluble and most successful P3HT polymer (Li et al., 2005). However, this alkyl side chain also decreases the crystallinity of polymer in the heterojunction blend, which is negative for high carrier mobility. It has been reported that with lower side chain density, the performance can be greatly improved. The latest report shows that the performance and stability can be both enhanced by reducing the side chain density on fluorinated poly(4-(2 -ethylhexyl)-4-octyl-4H-cyclopenta[2, l-h 3,4-h ]-dithiophene-2,6-diyl-a/f-6,7-difluoro-2,3-bis... 

Rathgeber S, Perlich J, KAhnlenz F, TArk S, Egbe DA, Hoppe H, et al. Correlation between polymer architecture, mesoscale structure and photovoltaic performance in side-chain-modified poly(p-arylene-ethynyl-ene)-alt-poly(p-arylene-vinylene) PCBM bulk-heterojunction solar cells. Polymer 2011 52(17) 3819-26. 

Greenwald, Y, et al. 1998. Polymer-polymer rectifying heterojunction based on poly(dicyanothio-phene) and MEH-PPV. J Polym Sci A Polym Chem 36 3115. 

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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