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The commercial development of perovskite solar cells (PSCs) has been significantly delayed by the constraint of performing time-consuming degradation studies under real outdoor conditions. These are necessary steps to determine the device lifetime, an area where PSCs traditionally suffer. In this work, we demonstrate that the outdoor degradation behavior of PSCs can be predicted by employing accelerated indoor stability analyses. The prediction was possible using a swift and accurate pipeline of machine learning algorithms and mathematical decompositions. By training the algorithms with different indoor stability data sets, we can determine the most relevant stress factors, thereby shedding light on the outdoor degradation pathways. Our methodology is not specific to PSCs and can be extended to other PV technologies where degradation and its mechanisms are crucial elements of their widespread adoption.
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Perovskite photovoltaics offer a highly efficient and low-cost solar energy harvesting technology. However, the presence of lead (Pb) cations in photovoltaic halide perovskite (HaPs) materials is concerning, and quantifying the environmental hazard of accidental Pb2+ leaching into the soil is crucial for assessing the sustainability of this technology. Pb2+ from inorganic salts was previously found to remain in the upper soil layers due to adsorption. However, Pb-HaPs contain additional organic and inorganic cations, and competitive cation adsorption may affect Pb2+ retention in soils. Therefore, we measured, analyzed by simulations and report the depths to which Pb2+ from HaPs penetrates into 3 types of agricultural soil. Most of the HaP-leached Pb2+ is found to be retained already in the first cm of the soil columns, and subsequent rain events do not induce Pb2+ penetration below the first few cm of soil surface. Surprisingly, organic co-cations from the dissolved HaP are found to enhance the Pb2+ adsorption capacity in clay-rich soil, compared to non-HaP-based Pb2+ sources. Our results imply that installation over soil types with improved Pb2+ adsorption, and removal of only the contaminated topsoil, are sufficient means to prevent ground water contamination by HaP-leached Pb2+.
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Photo-switchable organic field-effect transistors (OFETs) represent an important platform for designing memory devices for a diverse array of products including security (brand-protection, copy-protection, keyless entry, etc.), credit cards, tickets, and multiple wearable organic electronics applications. Herein, we present a new concept by introducing self-assembled monolayers of donor-acceptor porphyrin-fullerene dyads as light-responsive triggers modulating the electrical characteristics of OFETs and thus pave the way to the development of advanced nonvolatile optical memory. The devices demonstrated wide memory windows, high programming speeds, and long retention times. Furthermore, we show a remarkable effect of the orientation of the fullerene-polymer dyads at the dielectric/semiconductor interface on the device behavior. In particular, the dyads anchored to the dielectric by the porphyrin part induced a reversible photoelectrical switching of OFETs, which is characteristic of flash memory elements. On the contrary, the devices utilizing the dyad anchored by the fullerene moiety demonstrated irreversible switching, thus operating as read-only memory (ROM). A mechanism explaining this behavior is proposed using theoretical DFT calculations. The results suggest the possibility of revisiting hundreds of known donor-acceptor dyads designed previously for artificial photosynthesis or other purposes as versatile optical triggers in advanced OFET-based multibit memory devices for emerging electronic applications.
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We report on utilizing free-standing hybrid perylenediimide/carbon nanotube (PDI/CNT) films fabricated in air as back contacts for fully inorganic perovskite solar cells (glass/FTO/dense TiO2/mesoporous TiO2/CsPbBr3/back electrode). The back contact electrode connection is performed by film transfer rather than by vacuum deposition or by wet processing, allowing the formation of highly homogeneous contacts under ambient conditions. The use of this novel electrode in solar cells based on CsPbBr3 resulted in efficiency of 5.8% without a hole transporting layer; it is significantly improved in comparison to the reference cells with standard gold electrodes. Overall device fabrication can be performed on air, using inexpensive processing methods. The hybrid film electrodes dramatically improve the cell photo-stability under ambient conditions and under real-life operating conditions outdoors. The champion unencapsulated device demonstrated less than 30% efficiency loss over 6 weeks of outdoor aging in Negev desert conditions. The CNT/PDI electrodes offer the combination of fabrication simplicity, unique contacting approach, high efficiency and good operational stability for perovskite photovoltaics.
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H2O2 is a sacrificial reductant that is often used as a hole scavenger to gain insight into photoanode properties. Here we show a distinct mechanism of H2O2 photo-oxidation on haematite (α-Fe2O3) photoanodes. We found that the photocurrent voltammograms display non-monotonous behaviour upon varying the H2O2 concentration, which is not in accord with a linear surface reaction mechanism that involves a single reaction site as in Eley-Rideal reactions. We postulate a nonlinear kinetic mechanism that involves concerted interaction between adions induced by H2O2 deprotonation in the alkaline solution with adjacent intermediate species of the water photo-oxidation reaction, thereby involving two reaction sites as in Langmuir-Hinshelwood reactions. The devised kinetic model reproduces our main observations and predicts coexistence of two surface reaction paths (bi-stability) in a certain range of potentials and H2O2 concentrations. This prediction is confirmed experimentally by observing a hysteresis loop in the photocurrent voltammogram measured in the predicted coexistence range.
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High-performance photovoltaic polymers bearing cross-linkable function together with a photorobust conjugated backbone are highly desirable for organic solar cells to achieve both high device efficiency and long-term stability. In this study, a family of such polymers is reported based on poly[(2,5-bis(2-hexyldecyloxy)phenylene)- alt-(5,6-difluoro-4,7-di(thiophen-2-yl)benzo[ c]-[1,2,5]thiadiazole)] (PPDT2FBT), a high-performance photovoltaic donor-acceptor polymer, with different contents of terminal vinyl-appended side chains for cross-linking. The polymers were named PPDT2FBT-V x and prepared by varying the feeding ratio ( x mol %, x = 0, 5, 10, and 15) of the vinyl-appended monomer in polymerization. It was found that the vinyl integration did not sacrifice the original high photovoltaic performance of the polymers, as evidenced by comparable average power conversion efficiencies (PCEs) (6.95, 7.02, and 7.63%) observed for optimized devices based on PPDT2FBT-V0, PPDT2FBT-V5, and PPDT2FBT-V10, respectively, in blending with [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM). Unlike thermal cross-linking that greatly reduced device efficiency, UV cross-linking has proven to be an effective way to achieve both high device efficiency and thermostability for PPDT2FBT-V10 solar cells. UV-cross-linked PPDT2FBT-V10 solar cells displayed an initial average PCE of 5.28% and almost no decrease upon heat treatment at 120 °C for 40 h. Morphology studies revealed that UV-cross-linking did not only alter initial nanophase separation but also suppressed morphology evolution by aggregation in bulk heterojunction blend films. Photo-cross-linking requires material photostability. It is therefore worthwhile to note that these polymers and their blends with PC71BM were found to be extremely photostable, even upon continuous exposure to concentrated sunlight (up to 200 suns), and UV-cross-linking does not hamper this photostability. Further studies found that the devices fabricated with the UV-cross-linked PPDT2FBT-V10/PC71BM active layer can endure continuous light exposure to a solar simulator without deteriorating their performance.
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Herein, the use of highly concentrated sunlight for materials science research is reviewed. Specific research directions include: (1) the generation of inorganic nanostructures, some of which had eluded experimental realization with conventional synthetic processes, and (2) elucidating the processes governing the degradation of organic and perovskite-based photovoltaic materials and devices, along with accelerated assessment of their stability. Both approaches employ solar concentrators capable of producing flux densities exceeding those of terrestrial solar radiation by up to three orders of magnitude, and are geared toward either creating extensive ultrahot reactor conditions conducive to the rapid, safe synthesis of unusual nanomaterials or judiciously interrogating photovoltaic devices.
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Functionalized and fully characterized graphene-based lubricant additives are potential 2D materials for energy-efficient tribological applications in machine elements, especially at macroscopic contacts. Two different reduced graphene oxide (rGO) derivatives, terminated by hydroxyl and epoxy-hydroxyl groups, were prepared and blended with two different molecular weights of polyethylene glycol (PEG) for tribological investigation. Epoxy-hydroxyl-terminated rGO dispersed in PEG showed significantly smaller values of the friction coefficient. In this condition, PEG chains intercalate between the functionalized graphene sheets, and shear can take place between the PEG and rGO sheets. However, the friction coefficient was unaffected when hydroxyl-terminated rGO was coupled with PEG. This can be explained by the strong coupling between graphene sheets through hydroxyl units, causing the interaction of PEG with the rGO to be non- effective for lubrication. On the other hand, antiwear properties of hydroxyl-terminated rGO were significantly enhanced compared to epoxy-hydroxyl functionalized rGO due to the integrity of graphene sheet clusters.
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The photochemical stability of encapsulated films of mixed halide perovskites with a range of MAPb(I1-x Brx )3 (MA=methylammonium) compositions (solid solutions) was investigated under accelerated stressing using concentrated sunlight. The relevance of accelerated testing to standard operational conditions of solar cells was confirmed by comparison to degradation experiments under outdoor sunlight exposure. We found that MAPbBr3 films exhibited no degradation, while MAPbI3 and mixed halide MAPb(I1-x Brx )3 films decomposed yielding crystallization of inorganic PbI2 accompanied by degradation of the perovskite solar light absorption, with faster absorption degradation in mixed halide films. The crystal coherence length was found to correlate with the stability of the films. We postulate that the introduction of Br into the mixed halide solid solution stressed its structure and induced more structural defects and/or grain boundaries compared to pure halide perovskites, which might be responsible for the accelerated degradation. Hence, the cause for accelerated degradation may be the increased defect density rather than the chemical composition of the perovskite materials.
Assuntos
Compostos de Cálcio/química , Fontes de Energia Elétrica , Halogênios/química , Óxidos/química , Luz Solar , Titânio/química , Estabilidade de MedicamentosRESUMO
We report on accelerated degradation testing of MAPbX3 films (X = I or Br) by exposure to concentrated sunlight of 100 suns and show that the evolution of light absorption and the corresponding structural modifications are dependent on the type of halide ion and the exposure temperature. One hour of such exposure provides a photon dose equivalent to that of one sun exposure for 100 hours. The degradation in absorption of MAPbI3 films after exposure to 100 suns for 60 min at elevated sample temperature (â¼45-55 °C), due to decomposition of the hybrid perovskite material, is documented. No degradation was observed after exposure to the same sunlight concentration but at a lower sample temperature (â¼25 °C). No photobleaching or decomposition of MAPbBr3 films was observed after exposure to similar stress conditions (light intensity, dose, and temperatures). Our results indicate that the degradation is highly dependent on the hybrid perovskite composition and can be light- and thermally enhanced.
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Photosynthesis is used by plants, algae and bacteria to convert solar energy into stable chemical energy. The initial stages of this process--where light is absorbed and energy and electrons are transferred--are mediated by reaction centres composed of chlorophyll and carotenoid complexes. It has been previously shown that single small molecules can be used as functional components in electric and optoelectronic circuits, but it has proved difficult to control and probe individual molecules for photovoltaic and photoelectrochemical applications. Here, we show that the photocurrent generated by a single photosynthetic protein-photosystem I-can be measured using a scanning near-field optical microscope set-up. One side of the protein is anchored to a gold surface that acts as an electrode, and the other is contacted by a gold-covered glass tip. The tip functions as both counter electrode and light source. A photocurrent of â¼10 pA is recorded from the covalently bound single-protein junctions, which is in agreement with the internal electron transfer times of photosystem I.
Assuntos
Carotenoides/química , Clorofila/química , Luz , Complexo de Proteína do Fotossistema I/química , Transporte de ElétronsRESUMO
Carotenoids (Car) act as "wires" that discharge unwanted electrons in the reaction center of higher plants. One step in this "side-path" electron conduction is thought to be mediated by Car oxidation. We have carried out direct measurements of the conductance of single-Car molecules under potential control in a membrane-mimicking environment, and we found that when Car are oxidized conductance is enhanced and the electronic decay constant (beta) is decreased. However, the neutral molecule may already be conductive enough to account for observed electron transfer rates.
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Carotenoides/metabolismo , Condutividade Elétrica , Carotenoides/química , Transporte de Elétrons , ElétronsRESUMO
The effect of surface treatments on p-CdTe/n-CdS solar cell performance was examined. Adsorption of organic molecules with various magnitudes and directions of the dipole moment on p-CdTe resulted in controlled changes in electron affinity and surface bond bending. Similar adsorption on CdTe in state-of-the-art p-CdTe/n-CdS solar cells changes the cell performance, and we explain this by a combination of increased series resistance and changes in light absorption and in cell photovoltage. While at this stage no improvement in performance has been found with these cell structures, which are the result of years of empirical optimization, the molecular effect on the photovoltage shows that it is possible in this way to control the photovoltaic effect at this junction. Separate optimization may well lead to improvement by inserting a dipole layer near the photovoltaic interface. Our results also show that this is even possible when dipole adsorption is performed on the complete polycrystalline thin-film cell.