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.

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

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

There has been an intensive search for cost-effective photovoltaics since the development of the first solar cells in the 1950s. [1–3] Among all alternative technologies to silicon-based pn-junction solar cells, organic solar cells could lead the most significant cost reduction. [4] The field of organic photovoltaics (OPVs) comprises organic/inorganic nanostructures like dyesensitized solar cells, multilayers of small organic molecules, and phase-separated mixtures of organic materials (the bulkheterojunction solar cell). A review of several OPV technologies has been presented recently. [5] Light absorption in organic solar cells leads to the generation of excited, bound electron– hole pairs (often called excitons). To achieve substantial energy-conversion efficiencies, these excited electron–hole pairs need to be dissociated into free charge carriers with a high yield. Excitons can be dissociated at interfaces of materials with different electron affinities or by electric fields, or the dissociation can be trap or impurity assisted. Blending conjugated polymers with high-electron-affinity molecules like C60 (as in the bulk-heterojunction solar cell) has proven to be an efficient way for rapid exciton dissociation. Conjugated polymer–C60 interpenetrating networks exhibit ultrafast charge transfer (∼40 fs). [6,7] As there is no competing decay process of the optically excited electron–hole pair located on the polymer in this time regime, an optimized mixture with C60 converts absorbed photons to electrons with an efficiency close to 100%. [8] The associated bicontinuous interpenetrating network enables efficient collection of the separated charges at the electrodes. The bulk-heterojunction solar cell has attracted a lot of attention because of its potential to be a true low-cost photovoltaic technology. A simple coating or printing process would enable roll-to-roll manufacturing of flexible, low-weight PV modules, which should permit cost-efficient production and the development of products for new markets, e.g., in the field of portable electronics. One major obstacle for the commercialization of bulk-heterojunction solar cells is the relatively small device efficiencies that have been demonstrated up to now. [5] The best energy-conversion efficiencies published for small-area devices approach 5%. [9–11] A detailed analysis of state-of-the-art bulk-heterojunction solar cells [8] reveals that the efficiency is limited by the low opencircuit voltage (Voc) delivered by these devices under illumination. Typically, organic semiconductors with a bandgap of about 2 eV are applied as photoactive materials, but the observed open-circuit voltages are only in the range of 0.5–1 V. There has long been a controversy about the origin of the Voc in conjugated polymer–fullerene solar cells. Following the classical thin-film solar-cell concept, the metal–insulator–metal (MIM) model was applied to bulk-heterojunction devices. In the MIM picture, Voc is simply equal to the work-function difference of the two metal electrodes. The model had to be modified after the observation of the strong influence of the reduction potential of the fullerene on the open-circuit volt

Design Rules for Donors in Bulk‐Heterojunction Solar Cells—Towards 10 % Energy‐Conversion Efficiency

A polymer solar-cell based on a bulk hetereojunction design with an internal quantum efficiency of over 90% across the visible spectrum (425 nm to 575 nm) is reported. The device exhibits a power-conversion efficiency of 6% under standard air-mass 1.5 global illumination tests.

Bulk heterojunction solar cells with internal quantum efficiency approaching 100

Fossil fuel alternatives, such as solar energy, are moving to the forefront in a variety of research fields. Polymer-based organic photovoltaic systems hold the promise for a cost-effective, lightweight solar energy conversion platform, which could benefit from simple solution processing of the active layer. The function of such excitonic solar cells is based on photoinduced electron transfer from a donor to an acceptor. Fullerenes have become the ubiquitous acceptors because of their high electron affinity and ability to transport charge effectively. The most effective solar cells have been made from bicontinuous polymer–fullerene composites, or so-called bulk heterojunctions. The best solar cells currently achieve an efficiency of about 5 %, thus significant advances in the fundamental understanding of the complex interplay between the active layer morphology and electronic properties are required if this technology is to find viable application.

Polymer–Fullerene Composite Solar Cells

https://onlinelibrary.wiley.com/doi/pdf/10.1002/adma.200690091

High Photovoltaic Performance of a Low‐Bandgap Polymer

High Photovoltaic Performance of a Low-Bandgap Polymer. Adv Mater 18:2884

The challenge to reversing the layer sequence of organic photovoltaics (OPVs) is to prepare a selective contact bottom cathode and to achieve a suitable morphology for carrier collection in the inverted structure. The authors report the creation of an efficient electron selective bottom contact based on a solution-processed titanium oxide interfacial layer on the top of indium tin oxide. The use of o-xylene as a solvent creates an efficient carrier collection network with little vertical phase segregation, providing sufficient performance for both regular and inverted solar cells. The authors demonstrate inverted layer sequence OPVs with AM 1.5 calibrated power conversion efficiencies of over 3%.

Highly efficient inverted organic photovoltaics using solution based titanium oxide as electron selective contact

We designed and synthesized a series of conjugated polymers containing alternating electron-donating and electron-accepting units based on (4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b‘]dithiophene), 4,7-(2,1,3)-benzothiadiazole, and 5,5‘-[2,2‘]bithiophene. These polymers possess an optical band gap as low as 1.4 eV (i.e., in the case of poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b‘]dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)]), and their absorption characteristics can be tuned by adjusting the ratio of the two electron-donating units:  (4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b‘]dithiophene) and 5,5‘-[2,2‘]bithiophene. The desirable absorption attributes of these materials qualify them as excellent candidates for light-harvesting materials in organic photovoltaic applications allowing for high short-circuit current. Electrochemical studies indicate sufficiently deep HOMO/LUMO levels that enable a high photovoltaic device open-circuit voltage when fullerene derivatives are used as ...

Panchromatic Conjugated Polymers Containing Alternating Donor/Acceptor Units for Photovoltaic Applications

[*] Prof. J. R. Durrant, Mr. A. Maurano, Dr. R. Hamilton, Dr. C. G. Shuttle, Dr. B. O’Regan, Dr. W. Zhang, Prof. I. McCulloch Departments of Chemistry, Imperial College London South Kensington SW7 2AZ (United Kingdom) E-mail: j.durrant@imperial.ac.uk Dr. A. M. Ballantyne, Prof. J. Nelson Departments of Physics, Imperial College London South Kensington SW7 2AZ (United Kingdom) Dr. H. Azimi, Dr. M. Morana, Prof. C. J. Brabec Konarka Austria, Altenbergerstrasse 69 A-4040 Linz (Austria) Dr. H. Azimi Christian Doppler Laboratory for Surface Optics Johannes Kepler University Linz (Austria)

/pdf/recombination-dynamics-as-a-key-determinant-of-open-circuit-owmdjaihvi.pdf

Recombination Dynamics as a Key Determinant of Open Circuit Voltage in Organic Bulk Heterojunction Solar Cells: A Comparison of Four Different Donor Polymers

Mauro Morana

Papers

High Photovoltaic Performance of a Low‐Bandgap Polymer

High Photovoltaic Performance of a Low-Bandgap Polymer. Adv Mater 18:2884

Highly efficient inverted organic photovoltaics using solution based titanium oxide as electron selective contact

Panchromatic Conjugated Polymers Containing Alternating Donor/Acceptor Units for Photovoltaic Applications

Recombination Dynamics as a Key Determinant of Open Circuit Voltage in Organic Bulk Heterojunction Solar Cells: A Comparison of Four Different Donor Polymers