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.

/pdf/polymer-photovoltaic-cells-enhanced-efficiencies-via-a-2lwj3yarfe.pdf

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

The energy costs associated with separating tightly bound excitons (photoinduced electron-hole pairs) and extracting free charges from highly disordered low-mobility networks represent fundamental losses for many low-cost photovoltaic technologies. We report a low-cost, solution-processable solar cell, based on a highly crystalline perovskite absorber with intense visible to near-infrared absorptivity, that has a power conversion efficiency of 10.9% in a single-junction device under simulated full sunlight. This "meso-superstructured solar cell" exhibits exceptionally few fundamental energy losses; it can generate open-circuit photovoltages of more than 1.1 volts, despite the relatively narrow absorber band gap of 1.55 electron volts. The functionality arises from the use of mesoporous alumina as an inert scaffold that structures the absorber and forces electrons to reside in and be transported through the perovskite.

https://science.sciencemag.org/content/sci/early/2012/10/03/science.1228604.full.pdf

Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites

Organic-inorganic perovskites have shown promise as high-performance absorbers in solar cells, first as a coating on a mesoporous metal oxide scaffold and more recently as a solid layer in planar heterojunction architectures. Here, we report transient absorption and photoluminescence-quenching measurements to determine the electron-hole diffusion lengths, diffusion constants, and lifetimes in mixed halide (CH3NH3PbI(3-x)Cl(x)) and triiodide (CH3NH3PbI3) perovskite absorbers. We found that the diffusion lengths are greater than 1 micrometer in the mixed halide perovskite, which is an order of magnitude greater than the absorption depth. In contrast, the triiodide absorber has electron-hole diffusion lengths of ~100 nanometers. These results justify the high efficiency of planar heterojunction perovskite solar cells and identify a critical parameter to optimize for future perovskite absorber development.

/pdf/electron-hole-diffusion-lengths-exceeding-1-micrometer-in-an-3rhimkkmrj.pdf

Electron-hole diffusion lengths exceeding 1 micrometer in an organometal trihalide perovskite absorber.

Many different photovoltaic technologies are being developed for large-scale solar energy conversion. The wafer-based first-generation photovoltaic devices have been followed by thin-film solid semiconductor absorber layers sandwiched between two charge-selective contacts and nanostructured (or mesostructured) solar cells that rely on a distributed heterojunction to generate charge and to transport positive and negative charges in spatially separated phases. Although many materials have been used in nanostructured devices, the goal of attaining high-efficiency thin-film solar cells in such a way has yet to be achieved. Organometal halide perovskites have recently emerged as a promising material for high-efficiency nanostructured devices. Here we show that nanostructuring is not necessary to achieve high efficiencies with this material: a simple planar heterojunction solar cell incorporating vapour-deposited perovskite as the absorbing layer can have solar-to-electrical power conversion efficiencies of over 15 per cent (as measured under simulated full sunlight). This demonstrates that perovskite absorbers can function at the highest efficiencies in simplified device architectures, without the need for complex nanostructures.

Efficient planar heterojunction perovskite solar cells by vapour deposition

https://absimage.aps.org/image/MAR14/MWS_MAR14-2013-000770.pdf

Electron-Hole Diffusion Lengths Exceeding 1 Micrometer in an Organometal Trihalide Perovskite Absorber

THE photovoltaic effect involves the production of electrons and holes in a semiconductor device under illumination, and their subsequent collection at opposite electrodes. In many inorganic semiconductors, photon absorption produces free electrons and holes directly1. But in molecular semiconductors, absorption creates electrona¤-hole pairs (excitons) which are bound at room temperature2, so that charge collection requires their dissociation. Exciton dissociation is known to be efficient at interfaces between materials with different electron affinities and ionization potentials, where the electron is accepted by the material with larger electron affinity and the hole by the material with lower ionization potential3. A two-layer diode structure can thus be used, in which excitons generated in either layer diffuse towards the interface between the layers. However, the exciton diffusion range is typically at least a factor of 10 smaller than the optical absorption depth, thus limiting the efficiency of charge collection3. Here we show that the interpenetrating network formed from a phase-segregated mixture of two semiconducting polymers provides both the spatially distributed interfaces necessary for efficient charge photo-generation, and the means for separately collecting the electrons and holes. Devices using thin films of these polymer mixtures show promise for large-area photodetectors.

Efficient photodiodes from interpenetrating polymer networks

We report measurements of the photovoltaic effect in diode structures formed with thin films (100 nm) of the conjugated polymer poly(p-phenylene vinylene), PPV, sandwiched between electrodes of indium/tin oxide, ITO, and either aluminium, magnesium or calcium. Under illumination incident through the ITO contact, large open-circuit voltages were measured, which saturated at approximately 1.2 V for Al and Mg devices, and approximately 1.7 V for Ca devices. Quantum efficiencies (short-circuit current/incident photon flux) of order 1% were measured at low intensities (0.1 mW cm-2). The spectral response of the photocurrent demonstrates that photon absorption near the electron-collecting electrode optimizes the photocurrent, indicating that device performance is limited by low electron mobilities in the bulk PPV. The photocurrent exhibits a weak temperature dependence, with an activation energy that is a function of the electric field in the polymer. We have used these measurements to estimate an exciton binding energy in PPV of approximately 0.4 eV.

https://iopscience.iop.org/article/10.1088/0953-8984/6/7/009/pdf

The photovoltaic response in poly(p-phenylene vinylene) thin-film devices

When an exciton approaches the interface between two conjugated polymers, either energy or charge transfer can take place. We present a detailed experimental investigation of these processes in various binary polymer systems. The results are interpreted in the context of quantum-chemical calculations that provide estimates of the relative energies of intrachain versus interchain excited states in pairs of various PPV-related chains. In particular, we show that charge-transfer occurs at the interface between MEH-PPV and a cyanosubstituted PPV derivative, whereas energy transfer takes place at the interface of PPV with the same cyanosubstituted polymer. @S0163-1829~99!08031-5#

/pdf/charge-and-energy-transfer-processes-at-polymer-polymer-59d86lrt1l.pdf

J. J. M. Halls

Papers

Efficient photodiodes from interpenetrating polymer networks

The photovoltaic response in poly(p-phenylene vinylene) thin-film devices

Charge- and energy-transfer processes at polymer/polymer interfaces : a joint experimental and theoretical study

Novel luminescent polymers