Conjugated polymer chains have many degrees of conformational freedom and interact weakly with each other, resulting in complex microstructures in the solid state. Understanding charge transport in such systems, which have amorphous and ordered phases exhibiting varying degrees of order, has proved difficult owing to the contribution of electronic processes at various length scales. The growing technological appeal of these semiconductors makes such fundamental knowledge extremely important for materials and process design. We propose a unified model of how charge carriers travel in conjugated polymer films. We show that in high-molecular-weight semiconducting polymers the limiting charge transport step is trapping caused by lattice disorder, and that short-range intermolecular aggregation is sufficient for efficient long-range charge transport. This generalization explains the seemingly contradicting high performance of recently reported, poorly ordered polymers and suggests molecular design strategies to further improve the performance of future generations of organic electronic materials.

http://absimage.aps.org/image/MAR14/MWS_MAR14-2013-020288.pdf

A general relationship between disorder, aggregation and charge transport in conjugated polymers

State-of-the-art, high-performance perovskite solar cells (PSCs) contain a large amount of iodine to realize smaller bandgaps. However, the presence of numerous iodine vacancies at the surface of the film formed by their evaporation during the thermal annealing process has been broadly shown to induce deep-level defects, incur nonradiative charge recombination, and induce photocurrent hysteresis, all of which limit the efficiency and stability of PSCs. In this work, modifying the defective surface of perovskite films with cadmium iodide (CdI2) effectively reduces the degree of surface iodine deficiency and stabilizes iodine ions via the formation of strong Cd-I ionic bonds. This largely reduces the interfacial charge recombination loss, yielding a high efficiency of 21.9% for blade-coated PSCs with an open-circuit voltage of 1.20 V, corresponding to a record small voltage deficit of 0.31 V. The CdI2 surface treatment also improves the operational stability of the PSCs, retaining 92% efficiency after constant illumination at 1 sun intensity for 1000 h. This work provides a promising strategy to optimize the surface/interface optoelectronic properties of perovskites for more efficient and stable solar cells and other optoelectronic devices.

Reducing Surface Halide Deficiency for Efficient and Stable Iodide-Based Perovskite Solar Cells.

Organic semiconductors have become essential parts of thin-film electronic devices, particularly as hole transport layers (HTLs) in perovskite solar cells (PSCs) where they represent one of the major bottlenecks to further enhancements in both device stability and efficiency. Small molecule 2,2′,7,7′-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9′-spirobifluorene (spiro-OMeTAD) and polymer poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) are two of the first successful HTLs used in PSCs, and have remained at the forefront of developing high efficiency devices for almost a decade. Since their first application, many investigations into the properties of spiro-OMeTAD and PTAA have contributed to a growing understanding of the mechanisms that enable their success as HTLs. This review summarizes and discusses the key electronic and morphological properties, doping strategies and mechanisms, and degradation pathways of both spiro-OMeTAD and PTAA. A critical comparison between the two materials is provided, highlighting both the similarities which explain their enduring popularity as well as key differences in electrical and morphological properties. From this analysis emerges an improved understanding of the fundamental properties that enable the persistent success of HTL materials, which are found to include not only hole conductivity, band gap, and morphology, but also interactions with dopants, the perovskite, and environmental stressors. The knowledge about these properties, which are critically summarized in this review, is also applicable to the many other types of organic electronic devices now employing spiro-OMeTAD and PTAA. A detailed examination of the properties of materials reveals a clear set of guiding principles for the development of future generation HTLs. Applying these design strategies to produce more advanced HTLs will be essential to further improve the stability, efficiency, and commercialization of PSCs.

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Lessons learned from spiro-OMeTAD and PTAA in perovskite solar cells

Tin perovskites have emerged as promising alternatives to toxic lead perovskites in next-generation photovoltaics, but their poor environmental stability remains an obstacle towards more competitive performances. Therefore, a full understanding of their decomposition processes is needed to address these stability issues. Herein, we elucidate the degradation mechanism of 2D/3D tin perovskite films based on (PEA)0.2(FA)0.8SnI3 (where PEA is phenylethylammonium and FA is formamidinium). We show that SnI4, a product of the oxygen-induced degradation of tin perovskite, quickly evolves into iodine via the combined action of moisture and oxygen. We identify iodine as a highly aggressive species that can further oxidise the perovskite to more SnI4, establishing a cyclic degradation mechanism. Perovskite stability is then observed to strongly depend on the hole transport layer chosen as the substrate, which is exploited to tackle film degradation. These key insights will enable the future design and optimisation of stable tin-based perovskite optoelectronics.

/pdf/degradation-mechanism-of-hybrid-tin-based-perovskite-solar-1scwre7v17.pdf

Degradation mechanism of hybrid tin-based perovskite solar cells and the critical role of tin (IV) iodide.

Perovskites with bandgaps between 1.7 and 1.8 eV are optimal for tandem configurations with crystalline silicon (c-Si) because they facilitate efficient harvest of solar energy. In that respect, achieving a high open-circuit voltage (VOC) in such wide-bandgap perovskite solar cells is crucial for a high overall power conversion efficiency (PCE). Here, we provide key insights into the factors affecting the VOC in wide-bandgap perovskite solar cells. We show that the influence of the hole transport layer (HTL) on VOC is not simply through its ionization potential but mainly through the quality of the perovskite–HTL interface. With effective interface passivation, we demonstrate perovskite solar cells with a bandgap of 1.72 eV that exhibit a VOC of 1.22 V. Furthermore, by combining the high-VOC perovskite solar cell with a c-Si solar cell, we demonstrate a perovskite–Si four-terminal tandem solar cell with a PCE of 27.1%, exceeding the record PCE of single-junction Si solar cells.

/pdf/minimizing-voltage-loss-in-wide-bandgap-perovskites-for-38xw3rxy3y.pdf

Minimizing voltage loss in wide-bandgap perovskites for tandem solar cells

Lead halide perovskites have rapidly emerged as candidate materials for high-performing solar cells, but show serious issues related to long-term stability. Methylammonium (MA) lead perovskites wit...

/pdf/understanding-the-enhanced-stability-of-bromide-substitution-3rt30dz79v.pdf

Understanding the Enhanced Stability of Bromide Substitution in Lead Iodide Perovskites

The control and optimization of interfacial charge transfer processes is crucial to the design of efficient perovskite solar cells. Herein, we measure the yield and kinetics of hole transfer across the methylammonium lead triiodide perovskite|polymeric hole transport material heterojunction, as a function of the interfacial energy offset, ΔE, between the highest occupied molecular orbital of the hole transport material and the valence band edge of the perovskite. A combination of steady-state and time-resolved photoluminescence, along with transient absorption spectroscopy, revealed that only a small driving energy (ΔE ∼ 0.07 eV) is required to induce highly efficient hole transfer. The findings of this paper suggest that further improvements in the open-circuit voltage, and so the power conversion efficiency, of perovskite solar cells could be achieved by incorporating hole transport materials that provide an interfacial energy offset in the range 0 < ΔE < 0.18 eV.

Effect of Interfacial Energetics on Charge Transfer from Lead Halide Perovskite to Organic Hole Conductors

/pdf/surface-passivation-of-perovskite-films-via-iodide-salt-33wbxrca6u.pdf

Surface Passivation of Perovskite Films via Iodide Salt Coatings for Enhanced Stability of Organic Lead Halide Perovskite Solar Cells

Understanding interfacial charge transfer processes such as trap-mediated recombination and injection into charge transport layers (CTLs) is crucial for the improvement of perovskite solar cells. Herein, we reveal that the chemical binding of charge transport layers to CH3NH3PbI3 defect sites is an integral part of the interfacial charge injection mechanism in both n-i-p and p-i-n architectures. Specifically, we use a mixture of optical and X-ray photoelectron spectroscopy to show that binding interactions occur via Lewis base interactions between electron-donating moieties on hole transport layers and the CH3NH3PbI3 surface. We then correlate the extent of binding with an improvement in the yield and longer lifetime of injected holes with transient absorption spectroscopy. Our results show that passivation-mediated charge transfer has been occurring undetected in some of the most common perovskite configurations and elucidate a key design rule for the chemical structure of next-generation CTLs.

Robert J. E. Westbrook

Papers

Degradation mechanism of hybrid tin-based perovskite solar cells and the critical role of tin (IV) iodide.

Understanding the Enhanced Stability of Bromide Substitution in Lead Iodide Perovskites

Effect of Interfacial Energetics on Charge Transfer from Lead Halide Perovskite to Organic Hole Conductors

Surface Passivation of Perovskite Films via Iodide Salt Coatings for Enhanced Stability of Organic Lead Halide Perovskite Solar Cells

Lewis Base Passivation Mediates Charge Transfer at Perovskite Heterojunctions.