Jan C. Hummelen

Polymer photovoltaic cells : enhanced efficiencies via a network of internal donor-acceptor heterojunctions

The carrier collection efficiency (ηc) and energy conversion efficiency (ηe) of polymer photovoltaic cells were improved by blending of the semiconducting polymer with C60 or its functionalized derivatives. Composite films of poly(2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene) (MEH-PPV) and fullerenes exhibit ηc of about 29 percent of electrons per photon and ηe of about 2.9 percent, efficiencies that are better by more than two orders of magnitude than those that have been achieved with devices made with pure MEH-PPV. The efficient charge separation results from photoinduced electron transfer from the MEH-PPV (as donor) to C60 (as acceptor); the high collection efficiency results from a bicontinuous network of internal donor-acceptor heterojunctions.

Plastic solar cells

Recent developments in conjugated-polymer-based photovoltaic elements are reviewed. The photophysics of such photoactive devices is based on the photo-induced charge transfer from donor-type semiconducting conjugated polymers to acceptor-type conjugated polymers or acceptor molecules such as Buckminsterfullerene, C60. This photo-induced charge transfer is reversible, ultrafast (within 100 fs) with a quantum efficiency approaching unity, and the charge-separated state is metastable (up to milliseconds at 80 K). Being similar to the first steps in natural photosynthesis, this photo-induced electron transfer leads to a number of potentially interesting applications, which include sensitization of the photoconductivity and photovoltaic phenomena. Examples of photovoltaic architectures are presented and their potential in terrestrial solar energy conversion discussed. Recent progress in the realization of improved photovoltaic elements with 3 % power conversion efficiency is reported.

2.5% efficient organic plastic solar cells

We show that the power conversion efficiency of organic photovoltaic devices based on a conjugated polymer/methanofullerene blend is dramatically affected by molecular morphology. By structuring the blend to be a more intimate mixture that contains less phase segregation of methanofullerenes, and simultaneously increasing the degree of interactions between conjugated polymer chains, we have fabricated a device with a power conversion efficiency of 2.5% under AM1.5 illumination. This is a nearly threefold enhancement over previously reported values for such a device, and it approaches what is needed for the practical use of these devices for harvesting energy from sunlight.

Origin of the open circuit voltage of plastic solar cells

A series of highly soluble fullerene derivatives with varying acceptor strengths (i.e., first reduction potentials) was synthesized and used as electron acceptors in plastic solar cells. These fullerene derivatives, methanofullerene [6,6]-phenyl C61-butyric acid methyl ester (PCBM), a new azafulleroid, and a ketolactam quasifullerene, show a variation of almost 200 mV in their first reduction potential. The open circuit voltage of the corresponding devices was found to correlate directly with the acceptor strength of the fullerenes, whereas it was rather insensitive to variations of the work function of the negative electrode. These observations are discussed within the concept of Fermi level pinning between fullerenes and metals via surface charges.

Cathode dependence of the open-circuit voltage of polymer:fullerene bulk heterojunction solar cells

The open-circuit voltage (VOC) of bulk-heterojunction solar cells based on [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 has been investigated. In contrast to the present understanding, it is now demonstrated that for non-ohmic contacts the experimental VOC is determined by the work function difference of the electrodes. A total variation of more than 0.5 V of the VOC was observed by variation of the negative electrode (cathode) work function. For ohmic contacts the VOC is governed by the LUMO and HOMO levels of the acceptor and donor, respectively, which pin the Fermi levels of the cathode and anode. The band bending created by accumulated charges at an ohmic contact produce a considerable loss in VOC of 0.2 V at room temperature. The experimentally observed voltage loss in VOC of 0.38 V due to the presence of ohmic contacts at both interfaces strongly limits the maximum open-circ...

Influence of nanomorphology on the photovoltaic action of polymer–fullerene composites

Composites of conjugated poly(3-hexylthiophene) (P3HT) and the fullerene derivative [6,6]-phenyl-C61 butyric acid methyl ester (PCBM) demonstrate an efficient photogeneration of mobile charge carriers. Thermal annealing of P3HT:PCBM based devices gives rise to a significant increase of the photovoltaic efficiency, as follows from measurements of the external quantum efficiency and the current-voltage characteristics. Upon annealing, the absorption spectrum of the P3HT:PCBM composite undergoes a strong modification, whereas in the pure components it remains unchanged. The absorption of the annealed blends becomes stronger and red shifted in the wavelength region ascribed to P3HT, while the absorption due to the PCBM contribution does not change. Atomic force microscope measurements on P3HT:PCBM disclose some variation in morphology due to the crystallization of PCBM. The concentration of the PCBM clusters and their size (up to 500 nm) were found to be correlated with the amount of PCBM in the blend. We have studied the performance of photovoltaic devices with different weight ratios of P3HT:PCBM, namely, 1:3, 1:2, 1:1.5, 1:1, 1:0.9, 1:0.8, and 1:0.7. The photocurrent and the power conversion efficiency showed a maximum between 1:1 and 1:0.9. We conclude the variation in the absorption spectrum and the red shift to result from molecular diffusion of PCBM out of the polymer matrix upon annealing. The growth of the PCBM clusters leads to formation of percolation paths and, therefore, improves the photocurrent. Above a certain concentration, the PCBM crystals provide mechanical stress on the metal electrode, therefore possibly damaging the interface. Optimization of the composite weight ratio reveals the important role played by morphology for the transport properties of bulk heterojunction P3HT:PCBM based solar cells.

Small Bandgap Polymers for Organic Solar Cells (Polymer Material Development in the Last 5 Years)

During the last decade the field of polymer photovoltaics has seen a tremendous improvement in both device efficiency and understanding of the underlying physical processes. One has come to a point in which the prototypical large bandgap material system P3HT:PCBM is nearing optimal device performance. In order to enhance efficiencies even further, research activities for new materials are needed with better aligned energy levels. One interesting approach is by narrowing the donor bandgap to enhance light absorption. Recent developments on small band gap (<2.0 eV) materials for photovoltaic applications are reviewed. First, an introduction is given regarding the processes governing the exciton dissociation, charge transport requirements, energy level engineering of both donor and acceptor materials, and other parameters determining the photovoltaic performance. The focus is on polymeric donor materials, which are subdivided by the type of monomeric units that constitute the backbone. Finally, the synthetic methods and conditions, processing of the devices, and the device performances are summarized.

Tracing photoinduced electron transfer process in conjugated polymer/fullerene bulk heterojunctions in real time

Abstract Ultrafast spectroscopic studies using an optical excitation of a conjugated polymer by sub-10-fs pulses are reported. Phonon modes which are strongly coupled to the electronic excitation of the conjugated polymer are directly observed as coherent oscillations during the pump–probe experiment, mirroring the resonant/nonresonant Raman spectrum of the conjugated polymer. In composites of a conjugated polymer with a fullerene the primary photoexcitation is found to be an ultrafast photoinduced electron transfer. We are able to time resolve for the first time the kinetics of this charge transfer process with a forward transfer time of around τ ct ∼45 fs.

Isolation of the heterofullerene C59N as its dimer (C59N)(2)

The heterofullerene ion C59N+ is formed efficiently in the gas phase during fast atom bombardment mass spectroscopy of a cluster-opened N-MEM (N-methoxyethoxy methyl) ketolactam. This transformation is shown to occur also in solution in the presence of strong acid, affording biazafullerenyl (C59N)2 in good yield. It is proposed that the azafullerene dimer is formed upon in situ reduction of the highly reactive azafulleronium ion. The isolation and characterization of biazafullerenyl opens a viable route for the preparation of other heterofullerenes in solution.

Influence of the solvent on the crystal structure of PCBM and the efficiency of MDMO-PPV:PCBM ‘plastic’ solar cells

Two crystal structures of PCBM, obtained from different crystallisation solvents, are presented; a proposed link with solvent dependence of the efficiency of MDMO-PPV:PCBM solar cells is described.