William R. Mateker

Progress in Understanding Degradation Mechanisms and Improving Stability in Organic Photovoltaics.

Understanding the degradation mechanisms of organic photovoltaics is particularly important, as they tend to degrade faster than their inorganic counterparts, such as silicon and cadmium telluride. An overview is provided here of the main degradation mechanisms that researchers have identified so far that cause extrinsic degradation from oxygen and water, intrinsic degradation in the dark, and photo-induced burn-in. In addition, it provides methods for researchers to identify these mechanisms in new materials and device structures to screen them more quickly for promising long-term performance. These general strategies will likely be helpful in other photovoltaic technologies that suffer from insufficient stability, such as perovskite solar cells. Finally, the most promising lifetime results are highlighted and recommendations to improve long-term performance are made. To prevent degradation from oxygen and water for sufficiently long time periods, OPVs will likely need to be encapsulated by barrier materials with lower permeation rates of oxygen and water than typical flexible substrate materials. To improve stability at operating temperatures, materials will likely require glass transition temperatures above 100 °C. Methods to prevent photo-induced burn-in are least understood, but recent research indicates that using pure materials with dense and ordered film morphologies can reduce the burn-in effect.

Efficient charge generation by relaxed charge-transfer states at organic interfaces

Interfaces between organic electron-donating (D) and electron-accepting (A) materials have the ability to generate charge carriers on illumination. Efficient organic solar cells require a high yield for this process, combined with a minimum of energy losses. Here, we investigate the role of the lowest energy emissive interfacial charge-transfer state (CT1) in the charge generation process. We measure the quantum yield and the electric field dependence of charge generation on excitation of the charge-transfer (CT) state manifold via weakly allowed, low-energy optical transitions. For a wide range of photovoltaic devices based on polymer:fullerene, small-molecule:C60 and polymer:polymer blends, our study reveals that the internal quantum efficiency (IQE) is essentially independent of whether or not D, A or CT states with an energy higher than that of CT1 are excited. The best materials systems show an IQE higher than 90% without the need for excess electronic or vibrational energy.

The mechanism of burn-in loss in a high efficiency polymer solar cell.

Degradation in a high efficiency polymer solar cell is caused by the formation of states in the bandgap. These states increase the energetic disorder in the system. The power conversion efficiency loss does not occur when current is run through the device in the dark but occurs when the active layer is photo-excited.

Reducing burn-in voltage loss in polymer solar cells by increasing the polymer crystallinity

In order to commercialize polymer solar cells, the fast initial performance losses present in many high efficiency materials will have to be managed. This burn-in degradation is caused by light-induced traps and its characteristics depend on which polymer is used. We show that the light-induced traps are in the bulk of the active layer and we find a direct correlation between their presence and the open-circuit voltage loss in devices made with amorphous polymers. Solar cells made with crystalline polymers do not show characteristic open circuit voltage losses, even though light-induced traps are also present in these devices. This indicates that crystalline materials are more resistant against the influence of traps on device performance. Recent work on crystalline materials has shown there is an energetic driving force for charge carriers to leave amorphous, mixed regions of bulk heterojunctions, and charges are dominantly transported in pure, ordered phases. This energetic landscape allows efficient charge generation as well as extraction and also may benefit the stability against light-induced traps.

Morphological and electrical control of fullerene dimerization determines organic photovoltaic stability

Fullerene dimerization has been linked to short circuit current (Jsc) losses in organic solar cells comprised of certain polymer–fullerene systems. We investigate several polymer–fullerene systems, which present Jsc loss to varying degrees, in order to determine under which conditions dimerization occurs. By reintroducing dimers into fresh devices, we confirm that the photo-induced dimers are indeed the origin of the Jsc loss. We find that both film morphology and electrical bias affect the photodimerization process and thus the associated loss of Jsc. In plain fullerene films, a higher degree of crystallinity can inhibit the dimerization reaction, as observed by high performance liquid chromatography (HPLC) measurements. In blend films, the amount of dimerization depends on the degree of mixing between polymer and fullerene. For highly mixed systems with very amorphous polymers, no dimerization is observed. In solar cells with pure polymer and fullerene domains, we tune the fullerene morphology from amorphous to crystalline by thermal annealing. Similar to neat fullerene films, we observe improved light stability for devices with crystalline fullerene domains. Changing the operating conditions of the investigated solar cells from Voc to Jsc also significantly reduces the amount of dimerization-related Jsc loss; HPLC analysis of the active layer shows that more dimers are formed if the cell is held at Voc instead of Jsc. The effect of bias on dimerization, as well as a clear correlation between PL quenching and reduced dimerization upon addition of small amounts of an amorphous polymer into PC60BM films, suggests a reaction mechanism via excitons.

Improving the long-term stability of PBDTTPD polymer solar cells through material purification aimed at removing organic impurities

While bulk heterojunction (BHJ) solar cells fabricated from high Mn PBDTTPD achieve power conversion efficiencies (PCE) as high as 7.3%, the short-circuit current density (JSC) of these devices can drop by 20% after seven days of storage in the dark and under inert conditions. This degradation is characterized by the appearance of S-shape features in the reverse bias region of current–voltage (J–V) curves that increase in amplitude over time. Conversely, BHJ solar cells fabricated from low Mn PBDTTPD do not develop S-shaped J–V curves. However, S-shapes identical to those observed in high Mn PBDTTPD solar cells can be induced in low Mn devices through intentional contamination with the TPD monomer. Furthermore, when high Mn PBDTTPD is purified via size exclusion chromatography (SEC) to reduce the content of low molecular weight species, the JSC of polymer devices is significantly more stable over time. After 111 days of storage in the dark under inert conditions, the J–V curves do not develop S-shapes and the JSC degrades by only 6%. The S-shape degradation feature, symptomatic of low device lifetimes, appears to be linked to the presence of low molecular weight contaminants, which may be trapped within samples of high Mn polymer that have not been purified by SEC. Although these impurities do not affect initial device PCE, they significantly reduce device lifetime, and solar cell stability is improved by increasing the purity of the polymer materials.