Bimolecular recombination in methylammonium lead triiodide perovskite is an inverse absorption process.

Nature communications 9 (2018) 293-

CL Davies, MR Filip, JB Patel, TW Crothers, C Verdi, AD Wright, RL Milot, F Giustino, MB Johnston, LM Herz

Photovoltaic devices based on metal halide perovskites are rapidly improving in efficiency. Once the Shockley-Queisser limit is reached, charge-carrier extraction will be limited only by radiative bimolecular recombination of electrons with holes. Yet, this fundamental process, and its link with material stoichiometry, is still poorly understood. Here we show that bimolecular charge-carrier recombination in methylammonium lead triiodide perovskite can be fully explained as the inverse process of absorption. By correctly accounting for contributions to the absorption from excitons and electron-hole continuum states, we are able to utilise the van Roosbroeck-Shockley relation to determine bimolecular recombination rate constants from absorption spectra. We show that the sharpening of photon, electron and hole distribution functions significantly enhances bimolecular charge recombination as the temperature is lowered, mirroring trends in transient spectroscopy. Our findings provide vital understanding of band-to-band recombination processes in this hybrid perovskite, which comprise direct, fully radiative transitions between thermalized electrons and holes.

Hybrid Perovskites: Prospects for Concentrator Solar Cells

Advanced Science (2018)

Q Lin, Z Wang, HJ Snaith, MB Johnston, LM Herz

© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Perovskite solar cells have shown a meteoric rise of power conversion efficiency and a steady pace of improvements in their stability of operation. Such rapid progress has triggered research into approaches that can boost efficiencies beyond the Shockley-Queisser limit stipulated for a single-junction cell under normal solar illumination conditions. The tandem solar cell architecture is one concept here that has recently been successfully implemented. However, the approach of solar concentration has not been sufficiently explored so far for perovskite photovoltaics, despite its frequent use in the area of inorganic semiconductor solar cells. Here, the prospects of hybrid perovskites are assessed for use in concentrator solar cells. Solar cell performance parameters are theoretically predicted as a function of solar concentration levels, based on representative assumptions of charge-carrier recombination and extraction rates in the device. It is demonstrated that perovskite solar cells can fundamentally exhibit appreciably higher energy-conversion efficiencies under solar concentration, where they are able to exceed the Shockley-Queisser limit and exhibit strongly elevated open-circuit voltages. It is therefore concluded that sufficient material and device stability under increased illumination levels will be the only significant challenge to perovskite concentrator solar cell applications.

Photocurrent Spectroscopy of Perovskite Solar Cells Over a Wide Temperature Range from 15 to 350 K.

The journal of physical chemistry letters 9 (2018) 263-268

JB Patel, Q Lin, O Zadvorna, CL Davies, LM Herz, MB Johnston

Solar cells based on metal halide perovskite thin films show great promise for energy generation in a range of environments from terrestrial installations to space applications. Here we assess the device characteristics of the prototypical perovskite solar cells based on methylammonium lead triiodide (CH3NH3PbI3) over a broad temperature range from 15 to 350 K (-258 to 77 °C). For these devices, we observe a peak in the short-circuit current density and open-circuit voltage at 200 K (-73 °C) with decent operation maintained up to 350 K. We identify the clear signature of crystalline PbI2 contributing directly to the low-temperature photocurrent spectra, showing that PbI2 plays an active role (beyond passivation) in CH3NH3PbI3 solar cells. Finally we observe a blue-shift in the photocurrent spectrum with respect to the absorption spectrum at low temperature (15 K), allowing us to extract a lower limit on the exciton binding energy of 9.1 meV for CH3NH3PbI3.

Exciton Diffusion Length and Charge Extraction Yield in Organic Bilayer Solar Cells.

Advanced materials (Deerfield Beach, Fla.) 29 (2017)

B Siegmund, MT Sajjad, J Widmer, D Ray, C Koerner, M Riede, K Leo, IDW Samuel, K Vandewal

A method for resolving the diffusion length of excitons and the extraction yield of charge carriers is presented based on the performance of organic bilayer solar cells and careful modeling. The technique uses a simultaneous variation of the absorber thickness and the excitation wavelength. Rigorously differing solar cell structures as well as independent photoluminescence quenching measurements give consistent results.

A generic interface to reduce the efficiency-stability-cost gap of perovskite solar cells.

Science (New York, N.Y.) 358 (2017) 1192-1197

Y Hou, X Du, S Scheiner, DP McMeekin, Z Wang, N Li, MS Killian, H Chen, M Richter, I Levchuk, N Schrenker, E Spiecker, T Stubhan, NA Luechinger, A Hirsch, P Schmuki, H-P Steinrück, RH Fink, M Halik, HJ Snaith, CJ Brabec

A major bottleneck delaying the further commercialization of thin-film solar cells based on hybrid organohalide lead perovskites is interface loss in state-of-the-art devices. We present a generic interface architecture that combines solution-processed, reliable, and cost-efficient hole-transporting materials without compromising efficiency, stability, or scalability of perovskite solar cells. Tantalum-doped tungsten oxide (Ta-WO x )/conjugated polymer multilayers offer a surprisingly small interface barrier and form quasi-ohmic contacts universally with various scalable conjugated polymers. In a simple device with regular planar architecture and a self-assembled monolayer, Ta-WO x -doped interface-based perovskite solar cells achieve maximum efficiencies of 21.2% and offer more than 1000 hours of light stability. By eliminating additional ionic dopants, these findings open up the entire class of organics as scalable hole-transporting materials for perovskite solar cells.

Impact of microstructure on the electron-hole interaction in lead halide perovskites


AM Soufiani, Z Yang, T Young, A Miyata, A Surrente, A Pascoe, K Galkowski, M Abdi-Jalebi, R Brenes, J Urban, N Zhang, V Bulovic, O Portugall, Y-B Cheng, RJ Nicholas, A Ho-Baillie, MA Green, P Plochocka, SD Stranks

Photon Reabsorption Masks Intrinsic Bimolecular Charge-Carrier Recombination in CH3NH3PbI3 Perovskite.

Nano letters 17 (2017) 5782-5789

TW Crothers, RL Milot, JB Patel, ES Parrott, J Schlipf, P Müller-Buschbaum, MB Johnston, LM Herz

An understanding of charge-carrier recombination processes is essential for the development of hybrid metal halide perovskites for photovoltaic applications. We show that typical measurements of the radiative bimolecular recombination constant in CH3NH3PbI3 are strongly affected by photon reabsorption that masks a much larger intrinsic bimolecular recombination rate constant. By investigating a set of films whose thickness varies between 50 and 533 nm, we find that the bimolecular charge recombination rate appears to slow by an order of magnitude as the film thickness increases. However, by using a dynamical model that accounts for photon reabsorption and charge-carrier diffusion we determine that a single intrinsic bimolecular recombination coefficient of value 6.8 × 10-10 cm3s-1 is common to all samples irrespective of film thickness. Hence, we postulate that the wide range of literature values reported for such coefficients is partly to blame on differences in photon out-coupling between samples with crystal grains or mesoporous scaffolds of different sizes influencing light scattering, whereas thinner films or index-matched surrounding layers can reduce the possibility for photon reabsorption. We discuss the critical role of photon confinement on free charge-carrier retention in thin photovoltaic layers and highlight an approach to assess the success of such schemes from transient spectroscopic measurement.

Ultrahigh magnetic field spectroscopy reveals the band structure of the three-dimensional topological insulator Bi2Se3

PHYSICAL REVIEW B 96 (2017) ARTN 121111

A Miyata, Z Yang, A Surrente, O Drachenko, DK Maude, O Portugall, LB Duffy, T Hesjedal, P Plochocka, RJ Nicholas

Charge-Carrier Mobilities in Metal Halide Perovskites: Fundamental Mechanisms and Limits

ACS ENERGY LETTERS 2 (2017) 1539-1548

LM Herz

Quasi-one-dimensional density of states in a single quantum ring.

Scientific reports 7 (2017) 40026-

H Kim, W Lee, S Park, K Kyhm, K Je, RA Taylor, G Nogues, LS Dang, JD Song

Generally confinement size is considered to determine the dimensionality of nanostructures. While the exciton Bohr radius is used as a criterion to define either weak or strong confinement in optical experiments, the binding energy of confined excitons is difficult to measure experimentally. One alternative is to use the temperature dependence of the radiative recombination time, which has been employed previously in quantum wells and quantum wires. A one-dimensional loop structure is often assumed to model quantum rings, but this approximation ceases to be valid when the rim width becomes comparable to the ring radius. We have evaluated the density of states in a single quantum ring by measuring the temperature dependence of the radiative recombination of excitons, where the photoluminescence decay time as a function of temperature was calibrated by using the low temperature integrated intensity and linewidth. We conclude that the quasi-continuous finely-spaced levels arising from the rotation energy give rise to a quasi-one-dimensional density of states, as long as the confined exciton is allowed to rotate around the opening of the anisotropic ring structure, which has a finite rim width.

Reproducible planar heterojunction solar cells based on one-step solution-processed methylammonium lead halide perovskites

Chemistry of Materials 29 (2017) 462-473

S Bai, N Sakai, W Zhang, Z Wang, JTW Wang, F Gao, HJ Snaith

© 2016 American Chemical Society. Metal halide perovskites have been demonstrated as one of the most promising materials for low-cost and high-performance photovoltaic applications. However, due to the susceptible crystallization process of perovskite films on planar substrates and the high sensitivity of the physical and optoelectronic nature of the internal interfaces within the devices, researchers in different laboratories still experience poor reproducibility in fabricating efficient perovskite solar cells with planar heterojunction device structures. In this methods paper, we present detailed information on the reagents, equipment, and procedures for the fabrication of planar perovskite solar cells in both “regular” n-i-p and “inverted” p-i-n architectures based on one-step solution-processed methylammonium lead triiodide (MAPbI 3 ) perovskite films. We discuss key parameters affecting the crystallization of perovskite and the device interfaces. This methods paper will provide a guideline for the reproducible fabrication of planar heterojunction solar cells based on MAPbI 3 perovskite films. We believe that the shared experience on MA-based perovskite films and planar solar cells will be also useful for the optimization process of perovskites with varied compositions and other emerging perovskite-based optoelectronic devices.

V-Shaped Hole-Transporting TPD Dimers Containing Troger's Base Core

JOURNAL OF PHYSICAL CHEMISTRY C 121 (2017) 10267-10274

T Braukyla, N Sakai, M Daskeviciene, V Jankauskas, E Kamarauskas, R Komskis, T Malinauskas, S Jursenas, HJ Snaith, V Getautis

Temperature-dependent fine structure splitting in InGaN quantum dots


T Wang, TJ Puchtler, T Zhu, JC Jarman, CC Kocher, RA Oliver, RA Taylor

Impact of the Halide Cage on the Electronic Properties of Fully Inorganic Cesium Lead Halide Perovskites

ACS Energy Letters 2 (2017) 1621-1627

Z Yang, A Surrente, K Galkowski, A Miyata, O Portugall, RJ Sutton, AA Haghighirad, HJ Snaith, DK Maude, P Plochocka, RJ Nicholas

© 2017 American Chemical Society. Perovskite solar cells with record power conversion efficiency are fabricated by alloying both hybrid and fully inorganic compounds. While the basic electronic properties of the hybrid perovskites are now well understood, key electronic parameters for solar cell performance, such as the exciton binding energy of fully inorganic perovskites, are still unknown. By performing magneto-transmission measurements, we determine with high accuracy the exciton binding energy and reduced mass of fully inorganic CsPbX 3 perovskites (X = I, Br, and an alloy of these). The well-behaved (continuous) evolution of the band gap with temperature in the range of 4-270 K suggests that fully inorganic perovskites do not undergo structural phase transitions like their hybrid counterparts. The experimentally determined dielectric constants indicate that at low temperature, when the motion of the organic cation is frozen, the dielectric screening mechanism is essentially the same for both hybrid and inorganic perovskites and is dominated by the relative motion of atoms within the lead halide cage.

A Nanophotonic Structure Containing Living Photosynthetic Bacteria.

Small (Weinheim an der Bergstrasse, Germany) 13 (2017)

D Coles, LC Flatten, T Sydney, E Hounslow, SK Saikin, A Aspuru-Guzik, V Vedral, JK-H Tang, RA Taylor, JM Smith, DG Lidzey

Photosynthetic organisms rely on a series of self-assembled nanostructures with tuned electronic energy levels in order to transport energy from where it is collected by photon absorption, to reaction centers where the energy is used to drive chemical reactions. In the photosynthetic bacteria Chlorobaculum tepidum, a member of the green sulfur bacteria family, light is absorbed by large antenna complexes called chlorosomes to create an exciton. The exciton is transferred to a protein baseplate attached to the chlorosome, before migrating through the Fenna-Matthews-Olson complex to the reaction center. Here, it is shown that by placing living Chlorobaculum tepidum bacteria within a photonic microcavity, the strong exciton-photon coupling regime between a confined cavity mode and exciton states of the chlorosome can be accessed, whereby a coherent exchange of energy between the bacteria and cavity mode results in the formation of polariton states. The polaritons have energy distinct from that of the exciton which can be tuned by modifying the energy of the optical modes of the microcavity. It is believed that this is the first demonstration of the modification of energy levels within living biological systems using a photonic structure.

Efficient and Air-Stable Mixed-Cation Lead Mixed-Halide Perovskite Solar Cells with n-Doped Organic Electron Extraction Layers.

Advanced materials (Deerfield Beach, Fla.) 29 (2017)

Z Wang, DP McMeekin, N Sakai, S van Reenen, K Wojciechowski, JB Patel, MB Johnston, HJ Snaith

Air-stable doping of the n-type fullerene layer in an n-i-p planar heterojunction perovskite device is capable of enhancing device efficiency and improving device stability. Employing a (HC(NH2 )2 )0.83 Cs0.17 Pb(I0.6 Br0.4 )3 perovskite as the photoactive layer, glass-glass laminated devices are reported, which sustain 80% of their "post burn-in" efficiency over 3400 h under full sun illumination in ambient conditions.

Dicyanovinylene-substituted oligothiophenes for organic solar cells

in Advances in Polymer Science, 272 (2017) 51-75

C Koerner, H Ziehlke, R Fitzner, M Riede, A Mishra, P Bäuerle, K Leo

© Springer International Publishing Switzerland 2017. We investigate dicyanovinyl-substituted oligothiophene derivatives as absorber materials in organic solar cells. We determine structure–property relationships, which are important for materials design. We demonstrate the influence of those structural changes on the processing ability, energy levels, optical properties, thin-film morphology, and charge transport. Furthermore, we give a detailed picture of the microscopic processes between photon absorption and charge carrier generation, in particular, the importance of triplet exciton losses and a relationship between the yield of charge carrier generation and macroscopic charge-transport properties.

Structure-Activity Correlations for Bronsted Acid, Lewis Acid, and Photocatalyzed Reactions of Exfoliated Crystalline Niobium Oxides

CHEMCATCHEM 9 (2017) 144-154

Y Koito, GJ Rees, JV Hanna, MMJ Li, Y-K Peng, T Puchtler, R Taylor, T Wang, H Kobayashi, IF Teixeira, MA Khan, HT Kreissl, SCE Tsang

The 2017 terahertz science and technology roadmap


SS Dhillon, MS Vitiello, EH Linfield, AG Davies, MC Hoffmann, J Booske, C Paoloni, M Gensch, P Weightman, GP Williams, E Castro-Camus, DRS Cumming, F Simoens, I Escorcia-Carranza, J Grant, S Lucyszyn, M Kuwata-Gonokami, K Konishi, M Koch, CA Schmuttenmaer, TL Cocker, R Huber, AG Markelz, ZD Taylor, VP Wallace, JA Zeitler, J Sibik, TM Korter, B Ellison, S Rea, P Goldsmith, KB Cooper, R Appleby, D Pardo, PG Huggard, V Krozer, H Shams, M Fice, C Renaud, A Seeds, A Stoehr, M Naftaly, N Ridler, R Clarke, JE Cunningham, MB Johnston

Organic molecule fluorescence as an experimental test-bed for quantum jumps in thermodynamics.

Proceedings. Mathematical, physical, and engineering sciences 473 (2017) 20170099-

C Browne, T Farrow, OCO Dahlsten, RA Taylor, V Vlatko

We demonstrate with an experiment how molecules are a natural test bed for probing fundamental quantum thermodynamics. Single-molecule spectroscopy has undergone transformative change in the past decade with the advent of techniques permitting individual molecules to be distinguished and probed. We demonstrate that the quantum Jarzynski equality for heat is satisfied in this set-up by considering the time-resolved emission spectrum of organic molecules as arising from quantum jumps between states. This relates the heat dissipated into the environment to the free energy difference between the initial and final state. We demonstrate also how utilizing the quantum Jarzynski equality allows for the detection of energy shifts within a molecule, beyond the relative shift.