Direct Integration of Perovskite Solar Cells with Carbon Fiber Substrates.

Integrating photovoltaic devices onto the surface of carbon-fiber-reinforced polymer substrates should create materials with high mechanical strength that are also able to generate electrical power. Such devices are anticipated to find ready applications as structural, energy-harvesting systems in both the automotive and aeronautical sectors. Here, the fabrication of triple-cation perovskite n-i-p solar cells onto the surface of planarized carbon-fiber-reinforced polymer substrates is demonstrated, with devices utilizing a transparent top ITO contact. These devices also contain a "wrinkled" SiO2 interlayer placed between the device and substrate that alleviates thermally induced cracking of the bottom ITO layer. Devices are found to have a maximum stabilized power conversion efficiency of 14.5% and a specific power (power per weight) of 21.4 W g-1 (without encapsulation), making them highly suitable for mobile power applications.

Nonplanar Spray-Coated Perovskite Solar Cells.

Spray coating is an industrially mature technique used to deposit thin films that combines high throughput with the ability to coat nonplanar surfaces. Here, we explore the use of ultrasonic spray coating to fabricate perovskite solar cells (PSCs) over rigid, nonplanar surfaces without problems caused by solution dewetting and subsequent "run-off". Encouragingly, we find that PSCs can be spray-coated using our processes onto glass substrates held at angles of inclination up to 45° away from the horizontal, with such devices having comparable power conversion efficiencies (up to 18.3%) to those spray-cast onto horizontal substrates. Having established that our process can be used to create PSCs on surfaces that are not horizontal, we fabricate devices over a convex glass substrate, with devices having a maximum power conversion efficiency of 12.5%. To our best knowledge, this study represents the first demonstration of a rigid, curved perovskite solar cell. The integration of perovskite photovoltaics onto curved surfaces will likely find direct applications in the aerospace and automotive sectors.

Gas-Assisted Spray Coating of Perovskite Solar Cells Incorporating Sprayed Self-Assembled Monolayers.

Self-assembled monolayers (SAMs) are becoming widely utilized as hole-selective layers in high-performance p-i-n architecture perovskite solar cells. Ultrasonic spray coating and airbrush coating are demonstrated here as effective methods to deposit MeO-2PACz; a carbazole-based SAM. Potential dewetting of hybrid perovskite precursor solutions from this layer is overcome using optimized solvent rinsing protocols. The use of air-knife gas-quenching is then explored to rapidly remove the volatile solvent from an MAPbI3 precursor film spray-coated onto an MeO-2PACz SAM, allowing fabrication of p-i-n devices with power conversion efficiencies in excess of 20%, with all other layers thermally evaporated. This combination of deposition techniques is consistent with a rapid, roll-to-roll manufacturing process for the fabrication of large-area solar cells.

Perovskites on Ice: An Additive-Free Approach to Increase the Shelf-Life of Triple-Cation Perovskite Precursor Solutions.

Invited for this month's cover is the group of David Lidzey at the University of Sheffield. The image shows a futuristic view of large-scale perovskite solar cell (PSC) manufacture. This includes a high-volume roll-to-roll printing facility and cold-storage of PSC precursor solutions in large industrial fridges. The Full Paper itself is available at 10.1002/cssc.202100332.

Perovskites on Ice: An Additive-Free Approach to Increase the Shelf-Life of Triple-Cation Perovskite Precursor Solutions.

The development of stable perovskite precursor solutions is critical if solution-processable perovskite solar cells (PSCs) are to be practically manufacturable. Ideally, such precursors should combine high solution stability without using chemical additives that might compromise PSC performance. Here, it was shown that the shelf-life of high-performing perovskite precursors could be greatly improved by storing solutions at low-temperature without the need to alter chemical composition. Devices fabricated from solutions stored for 31 days at 4 °C achieved a champion power conversion efficiency (PCE) of 18.6 % (97 % of original PCE). The choice of precursor solvent also impacted solution shelf-life, with DMSO-based solutions having enhanced solution stability compared to those including DMF. The compositions of aged precursors were explored using NMR spectroscopy, and films made from these solutions were analysed using X-ray diffraction. It was concluded that the improvement in precursor solution stability is directly linked to the suppression of an addition-elimination reaction and the preservation of higher amounts of methylammonium within solution.

Rapid Scalable Processing of Tin Oxide Transport Layers for Perovskite Solar Cells.

The development of scalable deposition methods for perovskite solar cell materials is critical to enable the commercialization of this nascent technology. Herein, we investigate the use and processing of nanoparticle SnO2 films as electron transport layers in perovskite solar cells and develop deposition methods for ultrasonic spray coating and slot-die coating, leading to photovoltaic device efficiencies over 19%. The effects of postprocessing treatments (thermal annealing, UV ozone, and O2 plasma) are then probed using structural and spectroscopic techniques to characterize the nature of the np-SnO2/perovskite interface. We show that a brief "hot air flow" method can be used to replace extended thermal annealing, confirming that this approach is compatible with high-throughput processing. Our results highlight the importance of interface management to minimize nonradiative losses and provide a deeper understanding of the processing requirements for large-area deposition of nanoparticle metal oxides.

Potassium iodide reduces the stability of triple-cation perovskite solar cells.

The addition of alkali metal halides to hybrid perovskite materials can significantly impact their crystallisation and hence their performance when used in solar cell devices. Previous work on the use of potassium iodide (KI) in active layers to passivate defects in triple-cation mixed-halide perovskites has been shown to enhance their luminescence efficiency and reduce current-voltage hysteresis. However, the operational stability of KI passivated perovskite solar cells under ambient conditions remains largely unexplored. By investigating perovskite solar cell performance with SnO2 or TiO2 electron transport layers (ETL), we propose that defect passivation using KI is highly sensitive to the composition of the perovskite-ETL interface. We reconfirm findings from previous reports that KI preferentially interacts with bromide ions in mixed-halide perovskites, and - at concentrations >5 mol% in the precursor solution - modifies the primary absorber composition as well as leading to the phase segregation of an undesirable secondary non-perovskite phase (KBr) at high KI concentration. Importantly, by studying both material and device stability under continuous illumination and bias under ambient/high-humidity conditions, we show that this secondary phase becomes a favourable degradation product, and that devices incorporating KI have reduced stability.

High-Efficiency Spray-Coated Perovskite Solar Cells Utilizing Vacuum-Assisted Solution Processing.

We use ultrasonic spray-coating to fabricate cesium-containing triple-cation perovskite solar cells with a power-conversion efficiency of up to 17.8%. Our fabrication route involves a brief exposure of the partially wet spray-cast films to a low vacuum, a process that is used to control film crystallization. We show that films that are not vacuum-exposed are relatively rough and inhomogeneous, while vacuum-exposed films are smooth and consist of small and densely packed perovskite crystals. The process techniques developed here represent a step toward a scalable and industrially compatible manufacturing process capable of creating stable and high-performance perovskite solar cells.

Manipulating Crystallization of Organolead Mixed-Halide Thin Films in Antisolvent Baths for Wide-Bandgap Perovskite Solar Cells.

Wide-bandgap perovskite solar cells (PSCs) based on organolead (I, Br)-mixed halide perovskites (e.g., MAPbI2Br and MAPbIBr2 perovskite with bandgaps of 1.77 and 2.05 eV, respectively) are considered as promising low-cost alternatives for application in tandem or multijunction photovoltaics (PVs). Here, we demonstrate that manipulating the crystallization behavior of (I, Br)-mixed halide perovskites in antisolvent bath is critical for the formation of smooth, dense thin films of these perovskites. Since the growth of perovskite grains from a precursor solution tends to be more rapid with increasing Br content, further enhancement in the nucleation rate becomes necessary for the effective decoupling of the nucleation and the crystal-growth stages in Br-rich perovskites. This is enabled by introducing simple stirring during antisolvent-bathing, which induces enhanced advection transport of the extracted precursor-solvent into the bath environment. Consequently, wide-bandgap planar PSCs fabricated using these high quality mixed-halide perovskite thin films, Br-rich MAPbIBr2, in particular, show enhanced PV performance.

Pt- and TCO-Free Flexible Cathode for DSSC from Highly Conducting and Flexible PEDOT Paper Prepared via in Situ Interfacial Polymerization.

Here, we report the preparation of a flexible, free-standing, Pt- and TCO-free counter electrode in dye-sensitized solar cell (DSSC)-derived from polyethylenedioxythiophene (PEDOT)-impregnated cellulose paper. The synthetic strategy of making the thin flexible PEDOT paper is simple and scalable, which can be achieved via in situ polymerization all through a roll coating technique. The very low sheet resistance (4 Ω/□) obtained from a film of 40 µm thick PEDOT paper (PEDOT-p-5) is found to be superior to the conventional fluorine-doped tin oxide (FTO) substrate. The high conductivity (357 S/cm) displayed by PEDOT-p-5 is observed to be stable under ambient conditions as well as flexible and bending conditions. With all of these features in place, we could develop an efficient Pt- and TCO-free flexible counter electrode from PEDOT-p-5 for DSSC applications. The catalytic activity toward the tri-iodide reduction of the flexible electrode is analyzed by adopting various electrochemical methodologies. PEDOT-p-5 is found to display higher exchange current density (7.12 mA/cm(2)) and low charge transfer resistance (4.6 Ω) compared to the benchmark Pt-coated FTO glass (2.40 mA/cm(2) and 9.4 Ω, respectively). Further, a DSSC fabricated using PEDOT-p-5 as the counter electrode displays a comparable efficiency of 6.1% relative to 6.9% delivered by a system based on Pt/FTO as the counter electrode.

Intercalation crystallization of phase-pure α-HC(NH2)2PbI3 upon microstructurally engineered PbI2 thin films for planar perovskite solar cells.

The microstructure of the solid-PbI2 precursor thin film plays an important role in the intercalation crystallization of the formamidinium lead triiodide perovskite (α-HC(NH2)2PbI3). It is shown that microstructurally engineered PbI2 thin films with porosity and low crystallinity are the most favorable for conversion into uniform-coverage, phase-pure α-HC(NH2)2PbI3 perovskite thin films. Planar perovskite solar cells fabricated using these thin films deliver power conversion efficiency (PCE) up to 13.8%.

Microstructures of Organometal Trihalide Perovskites for Solar Cells: Their Evolution from Solutions and Characterization.

The use of organometal trihalide perovskites (OTPs) in perovskite solar cells (PSCs) is revolutionizing the field of photovoltaics, which is being led by advances in solution processing of OTP thin films. First, we look at fundamental phenomena pertaining to nucleation/growth, coarsening, and microstructural evolution involved in the solution-processing of OTP thin films for PSCs from a materials-science perspective. Established scientific principles that govern some of these phenomena are invoked in the context of specific literature examples of solution-processed OTP thin films. Second, the nature and the unique characteristics of OTP thin-film microstructures themselves are discussed from a materials-science perspective. Finally, we discuss the challenges and opportunities in the characterization of OTP thin films for not only gaining a deep understanding of defects and microstructures but also elucidating classical and nonclassical phenomena pertaining to nucleation/growth, coarsening, and microstructural evolution in these films. The overall goal is to have deterministic control over the solution-processing of tailored OTP thin films with desired morphologies and microstructures.

Dramatic Enhancement in Photoresponse of ß-In2S3 through Suppression of Dark Conductivity by Synthetic Control of Defect-Induced Carrier Compensation.

We report on the synthesis of dense and faceted indium sulfide (ß-In2S3) nano-octahedron films on fluorine-doped tin oxide-coated glass by the hydrothermal method and their photoresponse properties in a flip chip device configuration. We have examined the temporal evolution of the phase constitution, morphology, and optoelectronic properties for films obtained after growth interruption at specific intervals. It is noted that, initially, an In(OH)3 film forms, which is gradually transformed to the ß-In2S3 phase over time. In the case of the film wherein most, but not all, of In(OH)3 is consumed, an exceptionally large photoresponse (light to dark current ratio) of ∼10(4) and response time(s) (rise/fall) of ∼88/280 ms are realized. This superior performance is attributed to nearly complete carrier compensation achievable in the system under high pressure growth leading to dramatic reduction of dark conductivity. It is argued that the temporally growth-controlled equilibrium between quasi-In interstitials and cation vacancies dictates the optoelectronic properties.

CH3NH3PbI(3-x)(BF4)x: molecular ion substituted hybrid perovskite.

A molecular ion (BF4(-)) substituted hybrid perovskite CH3NH3PbI(3-x)(BF4)x is synthesized. The substituted perovskite shows significant enhancement in electrical conductivity at low frequencies and improved photoresponse under AM1.5 illumination as compared to the perovskite (CH3NH3PbI3).

Enhanced catalytic activity of polyethylenedioxythiophene towards tri-iodide reduction in DSSCs via 1-dimensional alignment using hollow carbon nanofibers.

Here, we report a highly conducting 1-dimensionally (1-D) aligned polyethylenedioxythiophene (PEDOT) along the inner and outer surfaces of a hollow carbon nanofiber (CNF) and its application as a counter electrode in a dye sensitized solar cell (DSSC). The hybrid material (CP-25) displays a conversion efficiency of 7.16% compared to 7.30% for the standard Pt counter electrode, 4.48% for bulk PEDOT and 5.56% for CNF. The enhanced conversion efficiency of CP-25 is attributed to the accomplishment of high conductivity and surface area of PEDOT through the 1-D alignment compared to its bulk counterpart. Reduced charge transfer resistance and high conductivity of CP-25 could be proven by cyclic voltammetry, impedance analysis and Tafel experiments. Further, through a long-term stability test involving efficiency profiling for 20 days, it is observed that CP-25 possesses excellent durability compared to the bulk PEDOT.

ZnO(N)-Spiro-MeOTAD hybrid photodiode: an efficient self-powered fast-response UV (visible) photosensor.

Organic-inorganic hybrid photo-detectors with a self-sufficient mode of operation represent a research area of great current interest. In most efficient photodetectors and optoelectronic devices compound semiconductors containing toxic elements such as Cd, As, Te, S, Se etc. are used and these are also expensive. Hence there is also a rapidly growing interest in replacing these with environmentally friendly and earth-abundant materials. Herein, we report a facile solution-processed fabrication of a self-powered organic-inorganic hybrid photodetector using n-type oriented ZnO nanorods and p-type Spiro-MeOTAD semiconductor. ZnO is eco-friendly and earth-abundant, and Spiro-MeOTAD is non-hazardous. We show that the latter has far less toxicity than the toxic elements stated above. This visible blind UV photodetector shows high sensitivity (10(2)) and a UV/visible rejection ratio of 300. It also exhibits fast response times of τ(rise) ~ 200 µs and τ(fall) ~ 950 µs. Importantly, with a small modification of nitrogen incorporation in ZnO one can also realize a highly-sensitive self-powered visible light photodetector with at least 1000% (or higher) improvements in quality factors (photocurrent/sensitivity/response time) as compared to previously reported organic-inorganic hybrid photo-detectors based on metal-chalcogenides (CdS-PANI or CuInSe2-P3HT). Interestingly, the broadband sensitivity of such N:ZnO-Spiro-MeOTAD photodiode enables sensing of low intensity (~28 µW cm(-2)) ambient white light with a high photocurrent density of 120 nA cm(-2) making it an efficient ambient white light detector.

Citrate milling of oxides: from poly-dispersed micron scale to nearly mono-dispersed nanoscale.

Complex (multivalent/mixed valent) oxides involving two or more cations (e.g. ABO3, AB2O4 and A2B2O7) exhibit the most fascinating range of physical and chemical properties amongst the family of materials systems. There is growing interest in nanoscale forms of such oxides which emanates from the novel changes in their properties with size. To obtain nanomaterials with a high degree of crystallinity it is desirable to first make crystalline oxide powders by high temperature processing and then mill them down to nanometer size. In this paper we show that simple citric acid treatment of BiFeO3 and Bi2O3 powders leads to the desired micron-scale to nanoscale transformation, yielding nearly monodispersed nanoparticles. Importantly, these are highly dispersible and stable in water. By performing similar experiments on Fe3O4 and Fe2O3 we have elucidated the possible mechanism, which hinges on valence-controlled dissolution and ripening phenomena.

Strong photo-response in a flip-chip nanowire p-Cu2O/n-ZnO junction.

Cu(2)O nanoneedles are synthesized on a copper substrate by a simple anodization and reducing ambient annealing protocol. ZnO nanorods are grown on ITO coated glass by a low temperature chemical route. The electronic and photo-response properties of the p-Cu(2)O/n-ZnO flip-chip heterojunction are then studied and analyzed. We show that the I-V characteristic is rectifying and the junction exhibits a good photoresponse (∼120% under 1 V reverse bias) under AM 1.5 (1 Sun) illumination. This nano-heterojunction photo-response is far stronger as compared to that of a pulsed laser deposited thin film p-Cu(2)O/n-ZnO heterojunction, which can be attributed to higher junction area in the former case.