Efficient, stable and scalable perovskite solar cells using poly(3-hexylthiophene).

Perovskite solar cells typically comprise electron- and hole-transport materials deposited on each side of a perovskite active layer. So far, only two organic hole-transport materials have led to state-of-the-art performance in these solar cells1: poly(triarylamine) (PTAA)2-5 and 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene (spiro-OMeTAD)6,7. However, these materials have several drawbacks in terms of commercialization, including high cost8, the need for hygroscopic dopants that trigger degradation of the perovskite layer9 and limitations in their deposition processes10. Poly(3-hexylthiophene) (P3HT) is an alternative hole-transport material with excellent optoelectronic properties11-13, low cost8,14 and ease of fabrication15-18, but so far the efficiencies of perovskite solar cells using P3HT have reached only around 16 per cent19. Here we propose a device architecture for highly efficient perovskite solar cells that use P3HT as a hole-transport material without any dopants. A thin layer of wide-bandgap halide perovskite is formed on top of the narrow-bandgap light-absorbing layer by an in situ reaction of n-hexyl trimethyl ammonium bromide on the perovskite surface. Our device has a certified power conversion efficiency of 22.7 per cent with hysteresis of ±0.51 per cent; exhibits good stability at 85 per cent relative humidity without encapsulation; and upon encapsulation demonstrates long-term operational stability for 1,370 hours under 1-Sun illumination at room temperature, maintaining 95 per cent of the initial efficiency. We extend our platform to large-area modules (24.97 square centimetres)-which are fabricated using a scalable bar-coating method for the deposition of P3HT-and achieve a power conversion efficiency of 16.0 per cent. Realizing the potential of P3HT as a hole-transport material by using a wide-bandgap halide could be a valuable direction for perovskite solar-cell research.

Large tunable photoeffect on ion conduction in halide perovskites and implications for photodecomposition.

In the same way as electron transport is crucial for information technology, ion transport is a key phenomenon in the context of energy research. To be able to tune ion conduction by light would open up opportunities for a wide realm of new applications, but it has been challenging to provide clear evidence for such an effect. Here we show through various techniques, such as transference-number measurements, permeation studies, stoichiometric variations, Hall effect experiments and the use of blocking electrodes, that light excitation enhances by several orders of magnitude the ionic conductivity of methylammonium lead iodide, the archetypal metal halide photovoltaic material. We provide a rationale for this unexpected phenomenon and show that it straightforwardly leads to a hitherto unconsidered photodecomposition path of the perovskite.

The Nature of Ion Conduction in Methylammonium Lead Iodide: A Multimethod Approach.

By applying a multitude of experimental techniques including 1 H, 14 N, 207 Pb NMR and 127 I NMR/NQR, tracer diffusion, reaction cell and doping experiments, as well as stoichiometric variation, conductivity, and polarization experiments, iodine ions are unambiguously shown to be the mobile species in CH3 NH3 PbI3 , with iodine vacancies shown to represent the mechanistic centers under equilibrium conditions. Pb2+ and CH3 NH3+ ions do not significantly contribute to the long range transport (upper limits for their contributions are given), whereby the latter exhibit substantial local motion. The decisive electronic contribution to the mixed conductivity in the experimental window stems from electron holes. As holes can be associated with iodine orbitals, local variations of the iodine stoichiometry may be fast and enable light effects on ion transport.

The Significance of Ion Conduction in a Hybrid Organic-Inorganic Lead-Iodide-Based Perovskite Photosensitizer.

The success of perovskite solar cells has sparked enormous excitement in the photovoltaic community not only because of unexpectedly high efficiencies but also because of the future potential ascribed to such crystalline absorber materials. Far from being exhaustively studied in terms of solid-state properties, these materials surprised by anomalies such as a huge apparent low-frequency dielectric constant and pronounced hysteretic current-voltage behavior. Here we show that methylammonium (but also formamidinium) iodoplumbates are mixed conductors with a large fraction of ion conduction because of iodine ions. In particular, we measure and model the stoichiometric polarization caused by the mixed conduction and demonstrate that the above anomalies can be explained by the build-up of stoichiometric gradients as a consequence of ion blocking interfaces. These findings provide insight into electrical charge transport in the hybrid organic-inorganic lead halide solar cells as well as into new possibilities of improving the photovoltaic performance by controlling the ionic disorder.

Mixed-organic-cation perovskite photovoltaics for enhanced solar-light harvesting.

Hybrid organic-inorganic lead halide perovskite APbX3 pigments, such as methylammonium lead iodide, have recently emerged as excellent light harvesters in solid-state mesoscopic solar cells. An important target for the further improvement of the performance of perovskite-based photovoltaics is to extend their optical-absorption onset further into the red to enhance solar-light harvesting. Herein, we show that this goal can be reached by using a mixture of formamidinium (HN=CHNH3 (+), FA) and methylammonium (CH3 NH3 (+), MA) cations in the A position of the APbI3 perovskite structure. This combination leads to an enhanced short-circuit current and thus superior devices to those based on only CH3 NH3 (+). This concept has not been applied previously in perovskite-based solar cells. It shows great potential as a versatile tool to tune the structural, electrical, and optoelectronic properties of the light-harvesting materials.

A new hematite photoanode doping strategy for solar water splitting: oxygen vacancy generation.

The enhancement of the electrical conductivity by doping is important in hematite (α-Fe(2)O(3)) photoanodes for efficient solar water oxidation. However, in spite of many successful demonstrations using extrinsic dopants, such as Sn, Ti, and Si, the achieved photocurrent is still lower than the practical requirement. There is still lack of our understanding of how intrinsic oxygen defects can change the photocurrent and interact with the extrinsic dopants. In this study, we systematically investigate the interplay of oxygen vacancies and extrinsic Sn dopants in the context of photoanodic properties. As a result, we demonstrate that the controlled generation of oxygen vacancies can activate the photoactivity of pure hematite remarkably and further enhance the Sn doping effects synergistically. Furthermore, the correlated behavior of oxygen vacancies and Sn dopants is closely linked to the variation of electrical conductance and results in the optimum concentration region to show the high photocurrent and low onset voltage.

Adjusted Bulk and Interfacial Properties in Highly Stable Semitransparent Perovskite Solar Cells Fabricated by Thermocompression Bonding between Perovskite Layers.

In order to shield perovskite solar cells (PSCs) from extrinsic degradation factors and ensure long-term stability, effective encapsulation technology is indispensable. Here, a facile process is developed to create a glass-glass encapsulated semitransparent PSC using thermocompression bonding. From quantifying the interfacial adhesion energy and considering the power conversion efficiency of devices, it is confirmed that bonding between perovskite layers formed on a hole transport layer (HTL)/indium-doped tin oxide (ITO) glass and an electron transport layer (ETL)/ITO glass can offer an excellent lamination method. The PSCs fabricated through this process have only buried interfaces between the perovskite layer and both charge transport layers as the perovskite surface is transformed into bulk. The thermocompression process leads the perovskite to have larger grains and smoother, denser interfaces, thereby not only reducing defect and trap density but also suppressing ion migration and phase segregation under illumination. In addition, the laminated perovskite demonstrates enhanced stability against water. The self-encapsulated semitransparent PSCs with a wide-band-gap perovskite (Eg ∼ 1.67 eV) demonstrate a power conversion efficiency of 17.24% and maintain long-term stability with PCE > ∼90% in the 85 °C shelf test for over 3000 h and with PCE > ∼95% under AM 1.5 G, 1-sun illumination in an ambient atmosphere for over 600 h.

Effective Visible-Light-Driven Photocatalytic Degradation of Harmful Antibiotics Using Reduced Graphene Oxide-Zinc Sulfide-Copper Sulfide Nanocomposites as a Catalyst.

In recent decades, antibiotics have been found in aquatic environments, raising severe concerns. In this study, a unique reduced graphene oxide-zinc sulfide-copper sulfide (rGO-ZnS-CuS) nanocomposite (NC) prepared by using a straightforward surfactant-free in situ microwave method was used for antibiotic degradation via photocatalysis. The structural and morphological characteristics of the produced catalysts were characterized using various techniques, confirming the successful development of nanocomposite structures of better quality than that of the pure samples. The photocatalytic degradation of antibiotics containing ofloxacin was also investigated. The results suggest that the rGO-ZCS NC outperformed the other composites in terms of photocatalytic activity toward ofloxacin degradation. Superoxide and hydroxyl radicals were the main active species during the degradation process. According to our results, the catalytic activity of rGO-ZCS NC is much better than that of the other composites.

Metal-Free Phthalocyanine as a Hole Transporting Material and a Surface Passivator for Efficient and Stable Perovskite Solar Cells.

Perovskite solar cells in an n-i-p structure record high power conversion efficiency, but issues of insufficient thermal stability and the high cost of p-type hole transporting materials have been raised as drawbacks. H2 -phthalocyanine (Pc) is introduced as a hole transport material to ensure the thermal stability and simultaneously have served surface passivation effects on hybrid halide perovskites as a Lewis base. Pyrrolic nitrogen in the Pc reacts with uncoordinated Pb2+ ions on the perovskite surface. Upon enhancing the interfacial interaction between phthalocyanine and the perovskite, the open circuit voltage in devices increases as compared to that of devices using a metal-phthalocyanine complex. While the phthalocyanine-applied device maintains superior thermal long-term stability, the power conversion efficiency also exceeds 20%.

High-Performance Flexible Ultraviolet Photodetectors Based on Facilely Synthesized Ecofriendly ZnAl:LDH Nanosheets.

Recent studies have focused on the development of efficient, flexible, and highly sensitive ultraviolet photodetectors (UV PDs) with various wide band-gap materials. In the present study, the application of environmentally friendly zinc-aluminum layered double hydroxide (ZnAl-CO3:LDH) is demonstrated for a high-performance, flexible UV PD. The vertically oriented ZnAl:LDH nanosheets (ZnAl:LDH Ns) are facilely synthesized by dipping the sputtered 10 wt % aluminum-doped zinc oxide thin films in deionized water at room temperature. Without passivation, the UV PDs exhibit an exceptional light-to-dark current ratio of 104 and a responsivity of ∼34.7 mA/W at a bias of 1 V. Moreover, the spectral responsivity and detectivity are enhanced to ∼148.3 mA/W and 2.5 × 1012 Jones, respectively, by passivating the ZnAl:LDH Ns with polydimethylsiloxane (PDMS), thus making the device suitable for application in UV detectors. In addition, the ambient atmosphere effect on PD performance, which elucidates the clear understanding of the PD working mechanism, is also investigated. The passivation of the Ns by PDMS also helps to enhance the mechanical robustness and long-term stability of the PD. The methodology demonstrated herein highlights the potential of the ZnAl:LDH material in realizing the next generation of flexible UV PDs.

Roll-to-roll gravure-printed flexible perovskite solar cells using eco-friendly antisolvent bathing with wide processing window.

Driven by recent improvements in efficiency and stability of perovskite solar cells (PSCs), upscaling of PSCs has come to be regarded as the next step. Specifically, a high-throughput, low-cost roll-to-roll (R2R) processes would be a breakthrough to realize the commercialization of PSCs, with uniform formation of precursor wet film and complete conversion to perovskite phase via R2R-compatible processes necessary to accomplish this goal. Herein, we demonstrate the pilot-scale, fully R2R manufacturing of all the layers except for electrodes in PSCs. Tert-butyl alcohol (tBuOH) is introduced as an eco-friendly antisolvent with a wide processing window. Highly crystalline, uniform formamidinium (FA)-based perovskite formation via tBuOH:EA bathing was confirmed by achieving high power conversion efficiencies (PCEs) of 23.5% for glass-based spin-coated PSCs, and 19.1% for gravure-printed flexible PSCs. As an extended work, R2R gravure-printing and tBuOH:EA bathing resulted in the highest PCE reported for R2R-processed PSCs, 16.7% for PSCs with R2R-processed SnO2/FA-perovskite, and 13.8% for fully R2R-produced PSCs.

Gravure-Printed Flexible Perovskite Solar Cells: Toward Roll-to-Roll Manufacturing.

Recent advances in perovskite solar cells (PSCs) have resulted in greater than 23% efficiency with superior advantages such as flexibility and solution-processability, allowing PSCs to be fabricated by a high-throughput and low-cost roll-to-roll (R2R) process. The development of scalable deposition processes is crucial to realize R2R production of flexible PSCs. Gravure printing is a promising candidate with the benefit of direct printing of the desired layer with arbitrary shape and size by using the R2R process. Here, flexible PSCs are fabricated by gravure printing. Printing inks and processing parameters are optimized to obtain smooth and uniform films. SnO2 nanoparticles are uniformly printed by reducing surface tension. Perovskite layers are successfully formed by optimizing the printing parameters and subsequent antisolvent bathing. 2,2',7,7'-Tetrakis-(N,N-di-4-methoxyphenylamino)-9,9'-spirobifluorene is also successfully printed. The all-gravure-printed device exhibits 17.2% champion efficiency, with 15.5% maximum power point tracking efficiency for 1000 s. Gravure-printed flexible PSCs based on a two-step deposition of perovskite layer are also demonstrated. Furthermore, a R2R process based on the gravure printing is demonstrated. The champion efficiency of 9.7% is achieved for partly R2R-processed PSCs based on a two-step fabrication of the perovskite layer.

Achieving Long-Term Operational Stability of Perovskite Solar Cells with a Stabilized Efficiency Exceeding 20% after 1000 h.

Perovskite solar cells (PSCs) with mesoporous TiO2 (mp-TiO2) as the electron transport material attain power conversion efficiencies (PCEs) above 22%; however, their poor long-term stability is a critical issue that must be resolved for commercialization. Herein, it is demonstrated that the long-term operational stability of mp-TiO2 based PSCs with PCE over 20% is achieved by isolating devices from oxygen and humidity. This achievement attributes to systematic understanding of the critical role of oxygen in the degradation of PSCs. PSCs exhibit fast degradation under controlled oxygen atmosphere and illumination, which is accompanied by iodine migration into the hole transport material (HTM). A diffusion barrier at the HTM/perovskite interface or encapsulation on top of the devices improves the stability against oxygen under light soaking. Notably, a mp-TiO2 based PSC with a solid encapsulation retains 20% efficiency after 1000 h of 1 sun (AM1.5G including UV) illumination in ambient air.

Biofunctionalized ceramic with self-assembled networks of nanochannels.

Nature designs circulatory systems with hierarchically organized networks of gradually tapered channels ranging from micrometer to nanometer in diameter. In most hard tissues in biological systems, fluid, gases, nutrients and wastes are constantly exchanged through such networks. Here, we developed a biologically inspired, hierarchically organized structure in ceramic to achieve effective permeation with minimum void region, using fabrication methods that create a long-range, highly interconnected nanochannel system in a ceramic biomaterial. This design of a synthetic model-material was implemented through a novel pressurized sintering process formulated to induce a gradual tapering in channel diameter based on pressure-dependent polymer agglomeration. The resulting system allows long-range, efficient transport of fluid and nutrients into sites and interfaces that conventional fluid conduction cannot reach without external force. We demonstrate the ability of mammalian bone-forming cells placed at the distal transport termination of the nanochannel system to proliferate in a manner dependent solely upon the supply of media by the self-powering nanochannels. This approach mimics the significant contribution that nanochannel transport plays in maintaining living hard tissues by providing nutrient supply that facilitates cell growth and differentiation, and thereby makes the ceramic composite "alive".

Tyrosine-mediated two-dimensional peptide assembly and its role as a bio-inspired catalytic scaffold.

In two-dimensional interfacial assemblies, there is an interplay between molecular ordering and interface geometry, which determines the final morphology and order of entire systems. Here we present the interfacial phenomenon of spontaneous facet formation in a water droplet driven by designed peptide assembly. The identified peptides can flatten the rounded top of a hemispherical droplet into a plane by forming a macroscopic two-dimensional crystal structure. Such ordering is driven by the folding geometry of the peptide, interactions of tyrosine and crosslinked stabilization by cysteine. We discover the key sequence motifs and folding structures and study their sequence-specific assembly. The well-ordered, densely packed, redox-active tyrosine units in the YYACAYY (H-Tyr-Tyr-Ala-Cys-Ala-Tyr-Tyr-OH) film can trigger or enhance chemical/electrochemical reactions, and can potentially serve as a platform to fabricate a molecularly tunable, self-repairable, flat peptide or hybrid film.