Ferroelectric materials exhibit a phase transition to a paraelectric state driven by temperature - called the Curie transition. In conventional ferroelectrics, the Curie transition is caused by a change in crystal symmetry, while the material itself remains a continuous three-dimensional solid crystal. However, ferroelectric polymers behave differently. Polymeric materials are typically of semi-crystalline nature, meaning that they are an intermixture of crystalline and amorphous regions. Here, we demonstrate that the semi-crystalline morphology of the ferroelectric copolymer of vinylidene fluoride and trifluoroethylene (P(VDF-TrFE)) strongly affects its Curie transition, as not only a change in crystal symmetry but also in morphology occurs. We demonstrate, by high-resolution nanomechanical measurements, that the semi-crystalline microstructure in the paraelectric state is formed by crystalline domains embedded into a softer amorphous phase. Using in situ X-ray diffraction measurements, we show that the local electromechanical response of the crystalline domains is counterbalanced by the amorphous phase, effectively masking its macroscopic effect. Our quantitative multi-scale characterisations unite the nano- and macroscopic material properties of the ferroelectric polymer P(VDF-TrFE) through its semi-crystalline nature.
Nanoscale investigations by scanning probe microscopy have provided major contributions to the rapid development of organic–inorganic halide perovskites (OIHP) as optoelectronic devices. Further improvement of device level properties requires a deeper understanding of the performance-limiting mechanisms such as ion migration, phase segregation, and their effects on charge extraction both at the nano- and macroscale. Here, we have studied the dynamic electrical response of Cs 0.05 (FA 0.83 MA 0.17 ) 0.95 PbI 3– x Br x perovskite structures by employing conventional and microsecond time-resolved open-loop Kelvin probe force microscopy (KPFM). Our results indicate strong negative charge carrier trapping upon illumination and very slow (>1 s) relaxation of charges at the grain boundaries. The fast electronic recombination and transport dynamics on the microsecond scale probed by time-resolved open-loop KPFM show diffusion of charge carriers toward grain boundaries and indicate locally higher recombination rates because of intrinsic compositional heterogeneity. The nanoscale electrostatic effects revealed are summarized in a collective model for mixed-halide CsFAMA. Results on multilayer solar cell structures draw direct relations between nanoscale ionic transport, charge accumulation, recombination properties, and the final device performance. Our findings extend the current understanding of complex charge carrier dynamics in stable multication OIHP structures.
Organic‐inorganic hybrid semiconductors are an emerging class of materials for direct conversion X‐ray detection due to attractive characteristics such as high sensitivity and the potential to form conformal detectors. However, existing hybrid semiconductor X‐ray detectors display dark currents that are 1000–10 000× higher than industrially relevant values of 1–10 pA mm−2. Herein, ultra‐low dark currents of <10 pA mm−2, under electric fields as high as ≈4 V µm−1, for hybrid X‐ray detectors consisting of bismuth oxide nanoparticles (for enhanced X‐ray attenuation) incorporated into an organic bulk heterojunction consisting of p‐type Poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) and n‐type [6,6]‐Phenyl C71 butyric acid methyl ester (PC70BM) are reported. Such ultra‐low dark currents are realized through the enrichment of the hole selective p‐type organic semiconductor near the anode contact. The resulting detectors demonstrate broadband X‐ray response including an exceptionally high sensitivity of ≈1.5 mC Gy−1 cm−2 and <6% variation in angular dependence response under 6 MV hard X‐rays. The above characteristics in combination with excellent dose linearity, dose rate linearity, and reproducibility over a broad energy range enable these detectors to be developed for medical and industrial applications.
Curved X‐ray detectors have the potential to revolutionize diverse sectors due to benefits such as reduced image distortion and vignetting compared to their planar counterparts. While the use of inorganic semiconductors for curved detectors are restricted by their brittle nature, organic–inorganic hybrid semiconductors which incorporated bismuth oxide nanoparticles in an organic bulk heterojunction consisting of poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) and [6,6]‐phenyl C71 butyric acid methyl ester (PC70BM) are considered to be more promising in this regard. However, the influence of the P3HT molecular weight on the mechanical stability of curved, thick X‐ray detectors remains less well understood. Herein, high P3HT molecular weights (>40 kDa) are identified to allow increased intermolecular bonding and chain entanglements, resulting in X‐ray detectors that can be curved to a radius as low as 1.3 mm with low deviation in X‐ray response under 100 repeated bending cycles while maintaining an industry‐standard dark current of <1 pA mm−2 and a sensitivity of ≈ 0.17 μC Gy−1 cm−2. This study identifies a crucial missing link in the development of curved detectors, namely the importance of the molecular weight of the polymer semiconductors used.
Antisolvent-assisted spin coating has been widely used for fabricating metal halide perovskite films with smooth and compact morphology. However, localized nanoscale inhomogeneities exist in these films owing to rapid crystallization, undermining their overall optoelectronic performance. Here, we show that by relaxing the requirement for film smoothness, outstanding film quality can be obtained simply through a post-annealing grain growth process without passivation agents. The morphological changes, driven by a vaporized methylammonium chloride (MACl)–dimethylformamide (DMF) solution, lead to comprehensive defect elimination. Our nanoscale characterization visualizes the local defective clusters in the as-deposited film and their elimination following treatment, which couples with the observation of emissive grain boundaries and excellent inter- and intragrain optoelectronic uniformity in the polycrystalline film. Overcoming these performance-limiting inhomogeneities results in the enhancement of the photoresponse to low-light (<0.1 mW cm –2 ) illumination by up to 40-fold, yielding high-performance photodiodes with superior low-light detection.
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