Spectroscopic photodetection is a powerful tool in disciplines such as medical diagnosis, industrial process monitoring, or agriculture. However, its application in novel fields, including wearable and bio-integrated electronics is hampered by the use of bulky dispersive optics. Here, we employ solution-processed organic donor-acceptor blends in a resonant optical cavity device architecture for wavelength-tunable photodetection. While conventional photodetectors respond to above-gap excitation, the cavity device exploits weak subgap absorption of intermolecular charge-transfer states of the intercalating Poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT):[6,6]-Phenyl-C61-butyric acid methyl ester (PCBM) bimolecular crystal. This enables a highly wavelength selective, nearinfrared photoresponse with a spectral resolution down to 14 nm, as well as dark currents and detectivities comparable with commercial inorganic photodetectors. A miniaturized spectrophotometer, comprising an array of narrowband photo-detectors is fabricated using blade-coated PBTTT:PCBM thin films with a thickness gradient. As application example, we demonstrate water transmittance spectral measured by this device.
A series of heteroleptic ruthenium(II) polypyridyl complexes containing phenanthroline ligands have been designed, synthesized, and characterized. The spectroscopic and electrochemical properties of the complexes have been studied in solution and adsorbed onto semiconductor nanocrystalline metal oxide particles. The results show that for two of the ruthenium complexes, bearing electron-donating (-NH2) or electron-withdrawing (-NO2) groups, the presence of the redox-active I(-)/I3(-) electrolyte produces important changes in the interfacial charge transfer processes that limit the device performance. For example, those dyes enhanced the electron recombination reaction between the photoinjected electrons at TiO2 and the oxidized redox electrolyte. In an effort to understand the details of such striking observations, we have monitored the charge transfer reactions taking place at the different interfaces of the devices using time-resolved single photon counting, laser transient spectroscopy, and light-induced photovoltage measurements.
Ferroelectric perovskite oxides are emerging as a promising photoactive layer for photovoltaic applications because of their very high stability and their alternative ferroelectricity-related mechanism for solar energy conversion that could lead to extraordinarily high efficiencies. One of the biggest challenges so far is to reduce their band gap toward the visible region while simultaneously retaining ferroelectricity. To address these two issues, herein an elemental composition engineering of BiFeO 3 is performed by substituting Fe by Co cations, as a means to tune the characteristics of the transition metal–oxygen bond. We demonstrate by solution processing the formation of epitaxial, pure phase, and stable BiFe 1– x Co x O 3 thin films for x ≤ 0.3 and film thickness up to 100 nm. Importantly, the band gap can be tuned from 2.7 to 2.3 eV upon cobalt substitution while simultaneously enhancing ferroelectricity. As a proof of concept, nonoptimized vertical devices have been fabricated and, reassuringly, the electrical photoresponse in the visible region of the Co-substituted phase is improved with respect to the unsubstituted oxide.
(MDMO-PPV) or poly(3-hexylthiophene) (P3HT) combined with soluble fullerenes, [6,7] up to current PCE values exceeding 10% for several systems. [9][10][11][12][13] There is no specific fundamental limitation to organic materials that indicates that much higher values are not possible, and the number of potential candidates is nearly infinite. Indeed, the organic nature of the photoactive materials offers a myriad of possibilities to modify their chemical structure; for the case of conjugated polymers, there exists a vast assortment of combinations depending on the choice of moieties, the bridging atoms, the length and branching points of the alkyl side chains, and the molecular weight, to name but a few. Using search engines to inspect the literature, we estimate that in the last ten years ≈5000 organic conjugated materials have been tested in BHJ solar cells, albeit only a few tenths have been studied and optimized in depth. While applied quantum theory can help to select promising candidates, [14][15][16] the final performance often depends on a number of issues difficult to predict a priori, such as solubility, miscibility of compounds, tendency to crystallize, exact energy levels in the blend, etc. In practice, this means that for a given promising backbone, a family of systems need to be tested, including different side chains, molecular weights, donor:acceptor combinations, etc. [17] Within this large and uncharted spectrum of materials and processing variables, combinatorial screening methodologies are highly on demand to speed up their exploration while helping the technology to approach the theoretical Shockley-Queisser limit of >20% PCE. [18,19] From the engineering point of view, three main aspects must be addressed for the evaluation of a material system for BHJ solar cells, namely the active layer thickness, the donor-acceptor (D:A) blending ratio and the nanoscale morphology (typically controlled by deposition conditions, thermal annealing, and use of additives). Ideally, those three variables can be optimized separately and to some extent it is usually an acceptable approximation; however, the full potential of a novel active layer material requires for fine tuning of the preparation conditions that take into consideration the subtle interplay between them. [20] For instance, the optimum thickness is often found close to the first interference maximum, which is governed by the refractive index of the active layer; this, on the other hand, will be a function of the D:A ratio (fullerenes typically have higher refractive index than polymers) and the degree of crystallinity One of the major bottlenecks in the development of organic photovoltaics is the time needed to evaluate each material system. This time ranges from weeks to months if different variables such as blend composition, thickness, annealing, and additives are to be explored. In this study, the use of lateral gradients is proposed in order to evaluate the photovoltaic potential of a material system up to 50 times faster. A platform that c...
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