Tin Sulfide (SnS) Films Deposited by an Electric Field-Assisted Continuous Spray Pyrolysis Technique with Application as Counter Electrodes in Dye-Sensitized Solar Cells

The deposition of tin sulfide (SnS) nanostructured films using a continuous spray pyrolysis technique is reported with an electric field present at the nozzle for influencing the atomization and the subsequent film deposition. In the absence of the electric field, the X-ray diffraction pattern shows the orthorhombic phase of SnS with a crystallographic preferred orientation along the (040) plane. The application of the electric field results in significant improvement in the morphology and a reduction in surface roughness (28 nm from 37 nm). The direct optical band gap of the films deposited with and without the electric field is estimated to be 1.5 and 1.7 eV, respectively. The photothermal deflection spectroscopy studies show a lower energetic disorder (no Urbach tail), which indicates an annealing effect in the SnS films deposited under the electric field. The improvement in the film properties is reflected in the expected improvement in the power conversion efficiency (PCE) of dye-sensitized solar cells fabricated using the SnS film as a counter electrode. An enhancement of PCE from 2.07% for the film deposited without the electric field to 2.89% for the film deposited with the electric field shows the role of the electric field in the fabrication of improved SnS film

Slow Carrier Cooling in Hybrid Pb-Sn Halide Perovskites

Low bandgap perovskites, such as mixed Pb-Sn systems, are essential to make bottom cells in all perovskite tandem photovoltaics. However, currently the fundamental dynamics of carriers in these materials are not well explored. Here we use ultrafast broadband pump-probe spectroscopy to probe the two-stage carrier cooling dynamics in CH3NH3Pb1-xSnxI3 perovskites and show that the cooling is slower than in pure Pb systems. The first stage of cooling is associated with Fröhlich interactions between carriers and metal-iodide bonds that slows down monotonically with increasing Sn content. The second stage of cooling involves the decay of optical phonon into acoustic phonons and is slowest for 60% Sn content, due to an increasing gap between the optical and acoustic phonon branches. Our results provide first insights into carrier cooling dynamics in hybrid Pb-Sn halide perovskites and pave the way for further understanding of the fundamental nature of Fröhlich interactions and the decay of optical phonons in perovskite systems.EPSR

Fabrication of ZnO/Cu<inf>2</inf>O heterojunctions in atmospheric conditions: Improved interface quality and solar cell performance

Zn_1-xMg_xO/Cu_2O heterojunctions were successfully fabricated in open-air at low temperatures via atmospheric atomic layer deposition of Zn_1-xMg_xO on thermally oxidized cuprous oxide. Solar cells employing these heterojunctions demonstrated a power conversion efficiency exceeding 2.2% and an open-circuit voltage of 0.65 V. Surface oxidation of Cu_2O to CuO prior to and during Zn_1-xMg_xO deposition was identified as the limiting factor to obtaining a high quality heterojunction interface. Optimization of deposition conditions to minimize Cu_2O surface oxidation led to improved device performance, tripling the open-circuit voltage and doubling the short-circuit current density. These values are the highest reported for a ZnO/Cu_2O interface formed in air, and highlight atmospheric ALD as a promising technique for inexpensive and scalable fabrication of ZnO/Cu_2O heterojunctions.This is the final published version. It is also available from Elsevier at http://www.sciencedirect.com/science/article/pii/S0927024814005005#

Charge Generation and Electron-Trapping Dynamics in Hybrid Nanocrystal-Polymer Solar Cells

We investigate the charge-trapping dynamics in hybrid nanocrystal-polymer systems and their effect on performance in photovoltaic devices. Employing various steady-state spectroscopy techniques and ultrafast, three-pulse transient absorption methods, we identify the depth of electron trap states in the nanocrystal band gap and measure their population dynamics. Our findings show that photogenerated electrons are trapped at midgap states on the nanocrystal within hundreds of picoseconds. The trapping of the majority of charge carriers before charge extraction results in a lowering of the quasi-Fermi level of the electrons which limits the device open-circuit voltage, thereby underlining the significance of these processes in conjugated polymer/nanocrystal hybrid photovoltaics.Engineering and Physical Sciences Research Council (Grant IDs: EP/M005143/1, EP/G060738/1, EP/G037221/1), Worshipful Company of Armourers and Brasiers (Gauntlet Trust award), German National Academic Foundation (Studienstiftung)This is the final version of the article. It first appeared from the American Chemical Society via http://dx.doi.org/10.1021/acs.jpcc.6b0759

Electroluminescence from Organometallic Lead Halide Perovskite-Conjugated Polymer Diodes

Organometallic lead perovskite-based solar cells can be converted to light-emitting diodes by engineering the current density. Diodes are fabricated with adjacent perovskite and conjugated polymer layers using orthogonal solvents. Under forward bias, these devices show simultaneous emission from both the luminescent conjugated polymer and the perovskite, providing direct information on electron and hole recombination as a function of device architecture and bias voltage.We gratefully acknowledge funding from the Engineering and Physical Sciences Research Council (EPSRC). A.K. acknowledges NRF-Singapore for a scholarship.This is the final version of the article. It first appeared from Wiley via http://dx.doi.org/10.1002/aelm.20150000

Real-Time Observation of Exciton-Phonon Coupling Dynamics in Self-Assembled Hybrid Perovskite Quantum Wells

Self-assembled hybrid perovskite quantum wells have attracted attention due to their tunable emission properties, ease of fabrication and device integration. However, the dynamics of excitons in these materials, especially how they couple to phonons remains an open question. Here, we investigate two widely used materials, namely butylammonium lead iodide (CH3(CH2)3NH3)2PbI4 and hexylammonium lead iodide (CH3(CH2)5NH3)2PbI4, both of which exhibit broad photoluminescence tails at room temperature. We performed femtosecond vibrational spectroscopy to obtain a real-time picture of the exciton phonon interaction and directly identified the vibrational modes that couple to excitons. We show that the choice of the organic cation controls which vibrational modes the exciton couples to. In butylammonium lead iodide, excitons dominantly couple to a 100 cm-1 phonon mode, whereas in hexylammonium lead iodide, excitons interact with phonons with frequencies of 88 cm-1 and 137 cm-1. Using the determined optical phonon energies, we analyzed PL broadening mechanisms. At low temperatures (<100 K), the broadening is due to acoustic phonon scattering, whereas at high temperatures, LO phonon-exciton coupling is the dominant mechanism. Our results help explain the broad photoluminescence lineshapes observed in hybrid perovskite quantum wells and provide insights into the mechanism of exciton-phonon coupling in these materials

Excitonic Properties of Low-Band-Gap Lead-Tin Halide Perovskites

The MAPb1–xSnxI3 (x = 0–1) (MA = methylammonium) perovskite family comprises a range of ideal absorber band gaps for single- and multijunction perovskite solar cells. Here, we use spectroscopic measurements to reveal a range of hitherto unknown fundamental properties of this materials family. Temperature-dependent transmission results show that the temperature of the tetragonal to orthorhombic structural transition decreases with increasing tin content. Through low-temperature magnetospectroscopy, we show that the exciton binding energy is lower than 16 meV, revealing that the dominant photogenerated species at typical operational conditions of optoelectronic devices are free charges rather than excitons. The reduced mass increases approximately proportionally to the band gap, and the mass values (0.075–0.090me) can be described with a two-band k·p perturbation model extended across the broad band gap range of 1.2–2.4 eV. Our findings can be generalized to predict values for the effective mass and binding energy for other members of this family of materials

What Controls the Rate of Ultrafast Charge Transfer and Charge Separation Efficiency in Organic Photovoltaic Blends.

In solar energy harvesting devices based on molecular semiconductors, such as organic photovoltaics (OPVs) and artificial photosynthetic systems, Frenkel excitons must be dissociated via charge transfer at heterojunctions to yield free charges. What controls the rate and efficiency of charge transfer and charge separation is an important question, as it determines the overall power conversion efficiency (PCE) of these systems. In bulk heterojunctions between polymer donor and fullerene acceptors, which provide a model system to understand the fundamental dynamics of electron transfer in molecular systems, it has been established that the first step of photoinduced electron transfer can be fast, of order 100 fs. But here we report the first study which correlates differences in the electron transfer rate with electronic structure and morphology, achieved with sub-20 fs time resolution pump-probe spectroscopy. We vary both the fullerene substitution and donor/fullerene ratio which allow us to control both aggregate size and the energetic driving force for charge transfer. We observe a range of electron transfer times from polymer to fullerene, from 240 fs to as short as 37 fs. Using ultrafast electro-optical pump-push-photocurrent spectroscopy, we find the yield of free versus bound charges to be weakly dependent on the energetic driving force, but to be very strongly dependent on fullerene aggregate size and packing. Our results point toward the importance of state accessibility and charge delocalization and suggest that energetic offsets between donor and acceptor levels are not an important criterion for efficient charge generation. This provides design rules for next-generation materials to minimize losses related to driving energy and boost PCE.Engineering and Physical Sciences Research Council, Winton Programme for the Physics of Sustainability, University of Cambridge, China Scholarship Council, SoltechThis is the final version of the article. It first appeared from the American Chemical Society via http://dx.doi.org/10.1021/jacs.6b0513

A Novel Mitigation Mechanism for Photo-Induced Trapping in an Anthradithiophene Derivative Using Additives

© 2020 Wiley-VCH GmbH A novel trap mitigation mechanism using molecular additives, which relieves a characteristic early turn-on voltage in a high-mobility p-type acene-based small-molecule organic semiconductor, when processed from hydrous solvents, is reported. The early turn-on voltage is attributed to photo-induced trapping, and additive incorporation is found to be very effective in suppressing this effect. Remarkably, the molecular additive does not disturb the charge transport properties of the small-molecule semiconductor, but rather intercalates in the crystal structure. This novel technique allows for the solution-processing of small molecular semiconductors from hydrous solvents, greatly simplifying manufacturing processes for large-area electronics. Along with various electric and spectroscopic characterization techniques, simulations have given a deeper insight into the trap mitigation effect induced by the additive

Visualizing excitations at buried heterojunctions in organic semiconductor blends

Interfaces play a crucial role in semiconductor devices, but in many device architectures they are nanostructured, disordered and buried away from the surface of the sample. Conventional optical, X-ray and photoelectron probes often fail to provide interface-specific information in such systems. Here we develop an all-optical time-resolved method to probe the local energetic landscape and electronic dynamics at such interfaces, based on the Stark effect caused by electron–hole pairs photo-generated across the interface. Using this method, we found that the electronically active sites at the polymer/fullerene interfaces in model bulk-heterojunction blends fall within the low-energy tail of the absorption spectrum. This suggests that these sites are highly ordered compared with the bulk of the polymer film, leading to large wavefunction delocalization and low site energies. We also detected a 100 fs migration of holes from higher- to lower-energy sites, consistent with these charges moving ballistically into more ordered polymer regions. This ultrafast charge motion may be key to separating electron–hole pairs into free charges against the Coulomb interaction.This work was supported by the Engineering and Physical Sciences Research Council (EPSRC) and the Winton Programme for the Physics of Sustainability. A.C.J. thanks the University of Cambridge for funding (CHESS). Synchrotron measurements were undertaken on the SAXS beamline at the Australian Synchrotron, Victoria, Australia and we acknowledge the help of N. Lal with the measurements. S.H. thanks the framework project Soltech for funding