Backbone-driven host-dopant miscibility modulates molecular doping in NDI conjugated polymers

Molecular doping is the key to enabling organic electronic devices, however, the design strategies to maximize doping efficiency demands further clarity and comprehension. Previous reports focus on the effect of the side chains, but the role of the backbone is still not well understood. In this study, we synthesize a series of NDI-based copolymers with bithiophene, vinylene, and acetylenic moieties (P1G, P2G, and P3G, respectively), all containing branched triethylene glycol side chains. Using computational and experimental methods, we explore the impact of the conjugated backbone using three key parameters for doping in organic semiconductors: energy levels, microstructure, and miscibility. Our experimental results show that P1G undergoes the most efficient n-type doping owed primarily to its higher dipole moment, and better host–dopant miscibility with N-DMBI. In contrast, P2G and P3G possess more planar backbones than P1G, but the lack of long-range order, and poor host–dopant miscibility limit their doping efficiency. Our data suggest that backbone planarity alone is not enough to maximize the electrical conductivity (σ) of n-type doped organic semiconductors, and that backbone polarity also plays an important role in enhancing σ via host–dopant miscibility. Finally, the thermoelectric properties of doped P1G exhibit a power factor of 0.077 μW m−1 K−2, and ultra-low in-plane thermal conductivity of 0.13 W m−1K−1 at 5 mol% of N-DMBI, which is among the lowest thermal conductivity values reported for n-type doped conjugated polymers

Optimization of an Electron Transport Layer to Enhance the Power Conversion Efficiency of Flexible Inverted Organic Solar Cells

The photovoltaic (PV) performance of flexible inverted organic solar cells (IOSCs) with an active layer consisting of a blend of poly(3-hexylthiophene) and [6, 6]-phenyl C61-butlyric acid methyl ester was investigated by varying the thicknesses of ZnO seed layers and introducing ZnO nanorods (NRs). A ZnO seed layer or ZnO NRs grown on the seed layer were used as an electron transport layer and pathway to optimize PV performance. ZnO seed layers were deposited using spin coating at 3,000 rpm for 30 s onto indium tin oxide (ITO)-coated polyethersulphone (PES) substrates. The ZnO NRs were grown using an aqueous solution method at a low temperature (90°C). The optimized device with ZnO NRs exhibited a threefold increase in PV performance compared with that of a device consisting of a ZnO seed layer without ZnO NRs. Flexible IOSCs fabricated using ZnO NRs with improved PV performance may pave the way for the development of PV devices with larger interface areas for effective exciton dissociation and continuous carrier transport paths

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

Controlling the assembly of CdS nanorods via solvent and acidity.

We report control over the phase behavior of CdS nanorods via the solvent and acidity. CdS nanorods were synthesized using alkane phosphonic acid ligands, which were replaced after synthesis by a series of aromatic ligands. Change of ligand enabled us to cast films from different solvents. By replacing toluene with ethanol or water the rod-rod interactions dominate over rod-substrate interactions, thereby favoring simple hexagonal ordering (2D). When dispersed in water, a net electrostatic charge on the nanorods could be induced by deprotonating the ligands at high pH. This net charge favors 2D nematic ordering over homeotropic ordering of the nanorods on a substrate. A calculation of the van der Waals and electrostatic interactions is presented that explains the observed influence of solvent and pH.This work was supported by the Engineering and Physical Sciences Research Council, U.K

Modeling the photocurrent of poly-phenylene vinylene/fullerene-based solar cells

We have studied the photocurrent data of 20:80 wt% blends of poly(2-methoxy-5-(3',7'-dimethyloctyloxy)-p-phenylene vinylene) (MDMO-PPV) and [6,6]-phenyl C-61-butyric acid methyl ester (PCBM) bulk heterojunction solar cells. Two cases have been investigated: When only drift of charge carriers is taken into account, a voltage-independent photocurrent is expected, corresponding to the extraction of all generated charges. It is demonstrated that the experimental data are in disagreement with this prediction. However, when both drift and diffusion of charges are taken into account, the predicted photocurrent shows a different behavior: At low electric fields a linear behavior is predicted, which results from the diffusion of charges, followed by saturation at high fields. The agreement between the numerical result and the experimental data obtained from MDMO-PPV:PCBM cells is satisfactory when a charge carrier generation rate of G=1.6 x 10(27) m(-3)s(-1) is used showing the importance of diffusion at low fields, i.e., near the open-circuit voltage

Extraction of photo-generated charge carriers from polymer-fullerene bulk heterojunction solar cells

Two models describing charge extraction from insulators have been used to interpret the experimental photocurrent data of 20:80 wt% blends of poly(2-methoxy-5-(3',7'-dimethyloctyloxy)-p-phenylene vinylene) (MDMO-PPV) and [6,6]phenyl C-61,-butyric acid methyl ester (PCBM) bulk heterojunction solar cells. When only drift of charge carriers is taken into account, a square root dependence on voltage of the photocurrent is expected, governed by the difference between electron and hole mobility. It is demonstrated that both the magnitude and functional dependence of the predicted current are in disagreement with experimental data. However, when both drift and diffusion of charges are taken into account, the predicted photocurrent shows a different behaviour: At low electric fields a linear behaviour is predicted, which results from the diffusion of charges, folllowed by saturation at high fields. The agreement between the theoretical result and the experimental data obtained from MDMO-PPV:PCBM cells is satisfactory when a generation rate of G=1.46 x 10(27) electron-hole pairs/m(3)s is used, showing the importance of diffusion at low fields, i.e., near the open-circuit voltage

Scaling theory for percolative charge transport in disordered molecular semiconductors

We present a scaling theory for charge transport in disordered molecular semiconductors that extends percolation theory by including bonds with conductances close to the percolating one in the random-resistor network representing charge hopping. A general and compact expression is given for the charge mobility for Miller-Abrahams and Marcus hopping on different lattices with Gaussian energy disorder, with parameters determined from numerically exact results. The charge-concentration dependence is universal. The model-specific temperature dependence can be used to distinguish between the hopping models