Establishing Self-Dopant Design Principles from Structure-Function Relationships in Self-n-Doped Perylene Diimide Organic Semiconductors.

Self-doping is a particular doping method that has been applied to a wide range of organic semiconductors. However, there is a lack of understanding regarding the relationship between dopant structure and function. A structurally diverse series of self-n-doped perylene diimides (PDIs) is investigated to study the impact of steric encumbrance, counterion selection, and dopant/PDI tether distance on functional parameters such as doping, stability, morphology, and charge-carrier mobility. The studies show that self-n-doping is best enabled by the use of sterically encumbered ammoniums with short tethers and Lewis basic counterions. Additionally, water is found to inhibit doping, which concludes that thermal degradation is merely a phenomenological feature of certain dopants, and that residual solvent evaporation is the primary driver of thermally activated doping. In situ grazing-incidence wide-angle X-ray scattering studies show that sample annealing increases the π-π stacking distance and shrinks grain boundaries for improved long-range ordering. These features are then correlated to contactless carrier-mobility measurements with time-resolved microwave conductivity before and after thermal annealing. The collective relationships between structural features and functionality are finally used to establish explicit self-n-dopant design principles for the future design of materials with improved functionality.

Long-range charge carrier mobility in metal halide perovskite thin-films and single crystals via transient photo-conductivity.

Charge carrier mobility is a fundamental property of semiconductor materials that governs many electronic device characteristics. For metal halide perovskites, a wide range of charge carrier mobilities have been reported using different techniques. Mobilities are often estimated via transient methods assuming an initial charge carrier population after pulsed photoexcitation and measurement of photoconductivity via non-contact or contact techniques. For nanosecond to millisecond transient methods, early-time recombination and exciton-to-free-carrier ratio hinder accurate determination of free-carrier population after photoexcitation. By considering both effects, we estimate long-range charge carrier mobilities over a wide range of photoexcitation densities via transient photoconductivity measurements. We determine long-range mobilities for FA0.83Cs0.17Pb(I0.9Br0.1)3, (FA0.83MA0.17)0.95Cs0.05Pb(I0.9Br0.1)3 and CH3NH3PbI3-xClx polycrystalline films in the range of 0.3 to 6.7 cm2 V-1 s-1. We demonstrate how our data-processing technique can also reveal more precise mobility estimates from non-contact time-resolved microwave conductivity measurements. Importantly, our results indicate that the processing of polycrystalline films significantly affects their long-range mobility.

Time-Resolved Changes in Dielectric Constant of Metal Halide Perovskites under Illumination.

Despite their impressive performance as a solar absorber, much remains unknown on the fundamental properties of metal halide perovskites (MHPs). Their polar nature in particular is an intense area of study, and the relative permittivity (εr) is a parameter widely used to quantify polarization over a range of different time scales. In this report, we have exploited frequency-dependent time-resolved microwave conductivity (TRMC) to study how εr values of a range of MHPs change as a function of time, upon optical illumination. Further characterization of charge carriers and polarizability are conducted by femtosecond transient absorption and stimulated Raman spectroscopy. We find that changes in εr are roughly proportional to photogenerated carrier density but decay with a shorter time constant than conductance, suggesting that the presence of charge carriers alone does not determine polarization.

Long-range exciton diffusion in molecular non-fullerene acceptors.

The short exciton diffusion length associated with most classical organic semiconductors used in organic photovoltaics (5-20 nm) imposes severe limits on the maximum size of the donor and acceptor domains within the photoactive layer of the cell. Identifying materials that are able to transport excitons over longer distances can help advancing our understanding and lead to solar cells with higher efficiency. Here, we measure the exciton diffusion length in a wide range of nonfullerene acceptor molecules using two different experimental techniques based on photocurrent and ultrafast spectroscopy measurements. The acceptors exhibit balanced ambipolar charge transport and surprisingly long exciton diffusion lengths in the range of 20 to 47 nm. With the aid of quantum-chemical calculations, we are able to rationalize the exciton dynamics and draw basic chemical design rules, particularly on the importance of the end-group substituent on the crystal packing of nonfullerene acceptors.

A piperidinium salt stabilizes efficient metal-halide perovskite solar cells.

Longevity has been a long-standing concern for hybrid perovskite photovoltaics. We demonstrate high-resilience positive-intrinsic-negative perovskite solar cells by incorporating a piperidinium-based ionic compound into the formamidinium-cesium lead-trihalide perovskite absorber. With the bandgap tuned to be well suited for perovskite-on-silicon tandem cells, this piperidinium additive enhances the open-circuit voltage and cell efficiency. This additive also retards compositional segregation into impurity phases and pinhole formation in the perovskite absorber layer during aggressive aging. Under full-spectrum simulated sunlight in ambient atmosphere, our unencapsulated and encapsulated cells retain 80 and 95% of their peak and post-burn-in efficiencies for 1010 and 1200 hours at 60° and 85°C, respectively. Our analysis reveals detailed degradation routes that contribute to the failure of aged cells.

Publisher Correction: Deciphering photocarrier dynamics for tuneable high-performance perovskite-organic semiconductor heterojunction phototransistors.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Impact of Moisture on Mobility in Methylammonium Lead Iodide and Formamidinium Lead Iodide.

The greatest remaining barrier to the commercialization of perovskite solar cells is their instability to ambient environmental conditions. While most studies of the electronic stability of perovskites employ finished devices, we here exploit the contactless characterization technique time-resolved microwave conductivity to probe electronic properties in the absence of encapsulation and interface effects. By tracking the mobility of charge carriers in two archetypal perovskite compounds, methylammonium lead iodide (MAPbI3) and formamidinium lead iodide (FAPbI3) under various conditions, we are able to make decisive statements about the role of water in the electronic performance of perovskites. Overall, we observe a strong negative correlation between hydration and mobility in MAPbI3, but not in FAPbI3. We anticipate that the data presented herein will serve as a valuable resource in future stability studies in perovskite solar cells and, ultimately, lead to more stable devices.

Deciphering photocarrier dynamics for tuneable high-performance perovskite-organic semiconductor heterojunction phototransistors.

Looking beyond energy harvesting, metal-halide perovskites offer great opportunities to revolutionise large-area photodetection technologies due to their high absorption coefficients, long diffusion lengths, low trap densities and simple processability. However, successful extraction of photocarriers from perovskites and their conversion to electrical signals remain challenging due to the interdependency of photogain and dark current density. Here we report hybrid hetero-phototransistors by integrating perovskites with organic semiconductor transistor channels to form either "straddling-gap" type-I or "staggered-gap" type-II heterojunctions. Our results show that gradual transforming from type-II to type-I heterojunctions leads to increasing and tuneable photoresponsivity with high photogain. Importantly, with a preferential edge-on molecular orientation, the type-I heterostructure results in efficient photocarrier cycling through the channel. Additionally, we propose the use of a photo-inverter circuitry to assess the phototransistors' functionality and amplification. Our study provides important insights into photocarrier dynamics and can help realise advanced device designs with "on-demand" optoelectronic properties.

Main-Group Halide Semiconductors Derived from Perovskite: Distinguishing Chemical, Structural, and Electronic Aspects.

Main-group halide perovskites have generated much excitement of late because of their remarkable optoelectronic properties, ease of preparation, and abundant constituent elements, but these curious and promising materials differ in important respects from traditional semiconductors. The distinguishing chemical, structural, and electronic features of these materials present the key to understanding the origins of the optoelectronic performance of the well-studied hybrid organic-inorganic lead halides and provide a starting point for the design and preparation of new functional materials. Here we review and discuss these distinguishing features, among them a defect-tolerant electronic structure, proximal lattice instabilities, labile defect migration, and, in the case of hybrid perovskites, disordered molecular cations. Additionally, we discuss the preparation and characterization of some alternatives to the lead halide perovskites, including lead-free bismuth halides and hybrid materials with optically and electronically active organic constituents.

Mono- and Mixed-Valence Tetrathiafulvalene Semiconductors (TTF)BiI4 and (TTF)4BiI6 with 1D and 0D Bismuth-Iodide Networks.

Two new compounds containing tetrathiafulvalene (TTF) cations with extended and discrete anions based on Bi and I are reported. The compound (TTF)BiI4 comprises [BiI2I4/2]- chains of edge-shared octahedra that are interspersed with stacks of TTF+•. The compound (TTF)4BiI6 has mixed-valence stacks of TTF and TTF+• and discrete molecules of TTF+• separated by discrete [BiI6]-3 anions. The optical and electrical transport properties of these compounds are reported. Due to the mixed-valence stacks of TTF, (TTF)4BiI6 is the significantly better electrical conductor than (TTF)BiI4, despite the discrete nature of the inorganic moiety.

Infinite Polyiodide Chains in the Pyrroloperylene-Iodine Complex: Insights into the Starch-Iodine and Perylene-Iodine Complexes.

We report the preparation and X-ray crystallographic characterization of the first crystalline homoatomic polymer chain, which is part of a semiconducting pyrroloperylene-iodine complex. The crystal structure contains infinite polyiodide I∞ (δ-) . Interestingly, the structure of iodine within the insoluble, blue starch-iodine complex has long remained elusive, but has been speculated as having infinite chains of iodine. Close similarities in the low-wavenumber Raman spectra of the title compound and starch-iodine point to such infinite polyiodide chains in the latter as well.

Flexible Organic Transistors with Controlled Nanomorphology.

We report the controlled nanomorphology of semiconducting polymers on chemically and mechanically stable nanogrooved polymer substrates. By employing silicon dioxide thin films with finely adjusted thicknesses on nanogrooved polymer substrates, semiconducting polymer thin films oriented and aligned along the nanogrooves were obtained. Organic field-effect transistors (OFETs) fabricated from the oriented semiconducting polymer, poly[4-(4,4-dihexadecyl-4H-cyclopenta[1,2-b:5,4-b']dithiophen-2-yl)-alt-[1,2,5]thiadiazolo-[3,4-c]pyridine] (PCDTPT), yielded saturation hole mobilities as high as 19.3 cm(2) V(-1 )s(-1), and the flexible "plastic" transistors demonstrated excellent mechanical stability under various bending conditions. These results represent important progress for solution-processed flexible OFETs and demonstrate that directed self-assembly of semiconducting polymers can be achieved by soft nanostructures.

Exploring Two-Dimensional Transport Phenomena in Metal Oxide Heterointerfaces for Next-Generation, High-Performance, Thin-Film Transistor Technologies.

In the last decade, metal oxides have emerged as a fascinating class of electronic material, exhibiting a wide range of unique and technologically relevant characteristics. For example, thin-film transistors formed from amorphous or polycrystalline metal oxide semiconductors offer the promise of low-cost, large-area, and flexible electronics, exhibiting performances comparable to or in excess of incumbent silicon-based technologies. Atomically flat interfaces between otherwise insulating or semiconducting complex oxides, are also found to be highly conducting, displaying 2-dimensional (2D) charge transport properties, strong correlations, and even superconductivity. Field-effect devices employing such carefully engineered interfaces are hoped to one day compete with traditional group IV or III-V semiconductors for use in the next-generation of high-performance electronics. In this Concept article we provide an overview of the different metal oxide transistor technologies and potential future research directions. In particular, we look at the recent reports of multilayer oxide thin-film transistors and the possibility of 2D electron transport in these disordered/polycrystalline systems and discuss the potential of the technology for applications in large-area electronics.

Temperature-Dependent Polarization in Field-Effect Transport and Photovoltaic Measurements of Methylammonium Lead Iodide.

While recent improvements in the reported peak power conversion efficiency (PCE) of hybrid organic-inorganic perovskite solar cells have been truly astonishing, there are many fundamental questions about the electronic behavior of these materials. Here we have studied a set of electronic devices employing methylammonium lead iodide ((MA)PbI3) as the active material and conducted a series of temperature-dependent measurements. Field-effect transistor, capacitor, and photovoltaic cell measurements all reveal behavior consistent with substantial and strongly temperature-dependent polarization susceptibility in (MA)PbI3 at temporal and spatial scales that significantly impact functional behavior. The relative PCE of (MA)PbI3 photovoltaic cells is observed to reduce drastically with decreasing temperature, suggesting that such polarization effects could be a prerequisite for high-performance device operation.

High Electron Mobility Thin-Film Transistors Based on Solution-Processed Semiconducting Metal Oxide Heterojunctions and Quasi-Superlattices.

High mobility thin-film transistor technologies that can be implemented using simple and inexpensive fabrication methods are in great demand because of their applicability in a wide range of emerging optoelectronics. Here, a novel concept of thin-film transistors is reported that exploits the enhanced electron transport properties of low-dimensional polycrystalline heterojunctions and quasi-superlattices (QSLs) consisting of alternating layers of In2O3, Ga2O3, and ZnO grown by sequential spin casting of different precursors in air at low temperatures (180-200 °C). Optimized prototype QSL transistors exhibit band-like transport with electron mobilities approximately a tenfold greater (25-45 cm2 V-1 s-1) than single oxide devices (typically 2-5 cm2 V-1 s-1). Based on temperature-dependent electron transport and capacitance-voltage measurements, it is argued that the enhanced performance arises from the presence of quasi 2D electron gas-like systems formed at the carefully engineered oxide heterointerfaces. The QSL transistor concept proposed here can in principle extend to a range of other oxide material systems and deposition methods (sputtering, atomic layer deposition, spray pyrolysis, roll-to-roll, etc.) and can be seen as an extremely promising technology for application in next-generation large area optoelectronics such as ultrahigh definition optical displays and large-area microelectronics where high performance is a key requirement.

Correlating Non-Geminate Recombination with Film Structure: A Comparison of Polythiophene: Fullerene Bilayer and Blend Films.

The morphology of the active layer in polymer:fullerene solar cells is a key parameter in determining their performance. In this study we monitor the charge carrier dynamics in bilayers of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) (fabricated by sequential spin coating and vacuum deposition) before and after thermal annealing, and compare these against conventional solution processed bulk heterojunction (BHJ) blend films. Transmission electron microscopy images, supported by field effect mobility data show that while not-annealed P3HT/PC61BM bilayers possess a sharp interface, intermixing proceeds upon annealing. Transient absorption studies indicate that the not-annealed bilayer yields fewer, but longer lived, charge carriers compared to the BHJ. Monte Carlo (MC) simulations further suggest that the difference in non-geminate recombination dynamics observed for the BHJ and bilayer films could be related to the confinement of charge carriers to the interface, with the lower dimensionality for the flat interface bilayer films relative to the intercalated donor-acceptor network BHJ films leading to lower recombination.

Synthesis and characterization of fused pyrrolo[3,2-d:4,5-d']bisthiazole-containing polymers.

The synthesis of a novel electron-deficient fused pyrrolo[3,2-d:4,5-d']bisthiazole is reported from 2-bromothiazole. This was copolymerized with thiophene, selenophene, thienothiophene, and bithiophene by microwave-assisted Stille polycondensation. The resulting polymers exhibited small optical band gaps combined with low-lying HOMO energy levels and demonstrated semiconducting behavior in organic field effect transistors.