Bulk heterojunction layers

One of the most promising uses of C60 involves its potential application, when mixed with 7r-conjligated polymers, in polymer solar cells. Most often the so-called bulk heterojunction configuration is used, in which the active layer consists of a blend of electron-donating materials, for example, p-type conjugated polymers, and an electron-accepting material (n-type), such as (6,6)-phenyl-Cgi -butyric acid methyl ester (PCBM, Scheme 9.6).38... 

In a bulk-heterojunction photovoltaic cell with methanofullerene [6,6]-phenyl C61-butyric acid methyl ester (PCBM) as an electron acceptor, alternating copolymer 19 (Fig. 9), derived from 2,7-fluorene and 2,5-dithienylsilole, can show impressive performance as the electron donor.31 In a device configuration of ITO/PEDOT/active layer/Ba/Al, the dark current density—bias curve shows a small leakage current, suggesting a continuous, pinhole-free active layer in the device. Under illumination of an AM 1.5 solar simulator at 100 mW/cm2, a high short-circuit current of 5.4 mA/cm2, an open-circuit voltage of 0.7 V, and a fill factor of 31.5% are achieved. The calculated energy conversion efficiency is 2.01%. 

FIGURE 15. A platinum(II) polyyne-based photocell in (a) single-layer and (b) bulk heterojunction structures. 

Scheme 5.9 Scheme of a hybrid photovoltaic cell with an active layer consisting of a composite of a conjugated polymer and semiconductor nanocrystals (so-called bulk heterojunction). 

Fig. 5.3. Formation of a bulk heterojunction and subsequent photoinduced electron transfer inside such a composite formed from the interpenetrating donor/acceptor network, plotted with the device structure for such a junction (a). The diagrams showing energy levels of an MDMO-PPV/PCBM system for flat band conditions (b) and under short-circuit conditions (c) do not take into account possible interfacial layers at the metal/semiconductor interface...

In general, a large serial resistance and an over-small parallel resistance (shunt) tend to reduce the FF. Strategies for reducing the serial resistivity by improving the quality of the Ohmic contact will be discussed. The insertion of very thin polar layers like LiF have been shown to reduce the interface barrier at the cathode in bulk heterojunction solar cells, if they are evaporated between the photoactive material and an A1 electrode [93,94]. 

The use of low bandgap polymers (ER < 1.8 eV) to extend the spectral sensitivity of bulk heterojunction solar cells is a real solution to this problem. These polymers can either substitute one of the two components in the bulk hetero junction (if their transport properties match) or they can be mixed into the blend. Such a three-component layer, comprising semiconductors with different bandgaps in a single layer, can be visualized as a variation of a tandem cell in which only the current and not the voltage can be added up. 

First, the drift current is calculated in the case of a constant electrical field, as one would expect for very thin bulk heterojunction solar cells. If the width W of the active layer is similar to the drift length of the carrier, the device will behave as a MIM junction, where the intrinsic semiconductor is fully depleted. The current is then determined by integrating the generation rate G = —dP/dx over the active layer, where P is the photon flux ... 

A significant increase in the forward current and in the FF is observed for conjugated polymer/fullerene bulk heterojunction solar cells upon insertion of a thin layer of LiF between the organic layer and the Al electrode (negative electrode of the solar cell), as shown in Fig. 5.37a and b. 

Table 5.3. Solar cell characteristics (PF and Voc) of MDMO-PPV/PCBM bulk heterojunction devices for various interfacial layers (LiF, SiO ) with different thicknesses compared to a solar cell with a pristine A1 electrode, and also calculated diode characteristics Rs and Rp found using (5.39) for the various interfacial layers...

The observed experimental result that Voc decreases linearly for bulk heterojunction solar cells allows us to conclude that, at least in the high temperature range (T > 200 K), these solar cells may be described by a diode model with Ip exp(E/kT). Here E is a parameter analogous to Eg for conventional semiconductors. For conjugated polymer/fullerene bulk heterojunction solar cells, E should correspond to the energy difference between the HOMO level of the donor and the LUMO level of the acceptor components of the active layer [as also suggested by the extrapolated value of V oc(0 K)]. 

This view of Voc generation is additionally supported by the fact that the values of the temperature coefficient dUoc/dT = -(1.40-1.65) mVK-1 for the cells under the present study (with bilayer LiF/Al and ITO/PEDOT contacts) coincide with those for polymer/fullerene bulk heterojunction solar cells of the previous generation (with the same components of the active layer but without LiF and PEDOT contact layers) [156]. In this picture, the temperature dependence of Voc is directly correlated with the temperature dependence of the quasi-Fermi levels of the components of the active layer under illumination, i.e., of the polymer and the fullerene. Therefore, the temperature dependence of Voc over a wide range, and in particular V),c(0 K), are essential parameters for understanding bulk hetero junction solar cells. 

Mihailetchi [134] investigated the open circuit voltage of the bulk heterojunction organic solar cells based on methanol-fullerene [6,6]-phenyl C61-butyric acid methyl ester (PCBM) as electron acceptor and poly[2-methoxy-5(3 ,7 -dimethyloctyloxy)-p-phenylene vinylene] (OC1C10-PPV) as an electron donor. It is known that a single layer device follows the MIM model [166] and the open circuit voltage V0c is equal to the difference in the work functions of the metal electrodes [134], If charges accumulate in the... 

Figure 7.10 Tandem solar cell structure for polymer blend solar cells, based on the design demonstrated by Hadipour et al. (2006). In this all-solution-processed device, the top cell consists of a polymer PCBM bulk heterojunction with an absorption maximum of 550 nm and preferentially absorbs short-wavelength light, while the bottom cell is made from a bulk heterojunction of PCBM with a red-absortring polymer and absorbs longer-wavelength light. The composite gold-PEDOT PSS internal layer connects the two cells in...

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