Negative Capacitance and Inverted Hysteresis: Matching Features in Perovskite Solar Cells.

Negative capacitance in the low-frequency domain and inverted hysteresis are familiar features in perovskite solar cells, which origin is still under discussion. Here we use impedance spectroscopy to analyze these responses in methylammonium lead bromide cells treated with lithium cations at the electron-selective layer/perovskite interface and in iodide devices exposed to different relative humidity conditions. Employing the surface polarization model, we obtain a time constant associated with the kinetics of the interaction of ions/vacancies with the surface, τkin, in the range of 100-102 s for all the cases exhibiting both features. These interactions lead to a decrease in the overall recombination resistance, modifying the low-frequency perovskite response and yielding a flattening of the cyclic voltammetry. As a consequence of these results we find that negative capacitance and inverted hysteresis lead to a decrease in the fill factor and photovoltage values.

BioMeT and Algorithm Challenges: A Proposed Digital Standardized Evaluation Framework.

Technology is advancing at an extraordinary rate. Continuous flows of novel data are being generated with the potential to revolutionize how we better identify, treat, manage, and prevent disease across therapeutic areas. However, lack of security of confidence in digital health technologies is hampering adoption, particularly for biometric monitoring technologies (BioMeTs) where frontline healthcare professionals are struggling to determine which BioMeTs are fit-for-purpose and in which context. Here, we discuss the challenges to adoption and offer pragmatic guidance regarding BioMeTs, cumulating in a proposed framework to advance their development and deployment in healthcare, health research, and health promotion. Furthermore, the framework proposes a process to establish an audit trail of BioMeTs (hardware and algorithms), to instill trust amongst multidisciplinary users.

Impedance spectroscopy of perovskite/contact interface: Beneficial chemical reactivity effect.

Understanding chemical reactivity of lead halide perovskite materials with contacts is crucial to improve the stability of these optoelectronic devices. The study of the physical and chemical interactions at the interfacial region is still one of the most challenging tasks in this field. We investigate a configuration based on the direct contact of gold (Au) with highly crystalline methylammonium lead bromide perovskite (MAPbBr3), in comparison with the presence of an organic interlayer. The metal contact clearly shows the double layer capacitance that can be monitored by Impedance Spectroscopy (IS). Measurements in the dark reveal the frequencies where a reduction in charge accumulation occurs, related to ionic reactivity with the external contacts. Under light, this chemical reaction is favored and the newly formed contact improves the performance of the solar cell. The IS results show that reactivity proceeds at timescales longer than 100 s, reducing the recombination kinetics under 1 sun illumination conditions, increasing the photovoltage and photocurrent that can be extracted. This work presents IS as a nondestructive in operando tool to monitor the kinetics of the ionic double layer formation and the reactivity of methylammonium bromide perovskite material with contacts decoupling as well this information from other resistive and capacitive contributions.

Crystalline Clear or Not: Beneficial and Harmful Effects of Water in Perovskite Solar Cells.

Clarification of how water affects the photovoltaic performance of perovskite solar cells is one of the major challenges to successfully develop a large-scale low-cost fabrication process. Many authors have reported beneficial effects of moisture during the fabrication of perovskite solar cells (PSCs), such as enhanced crystallinity, photoluminescence and photovoltage. However, the highest power conversion efficiency reported until this date was obtained under completely dry atmosphere conditions, avoiding the presence of water during perovskite formulation and preserving the damage caused by moisture exposure with encapsulation techniques. This apparent contradiction makes patent the necessity of an extensive clarification to establish the conditions in which water represents a beneficial or harmful factor in the development of high efficiency and stable perovskite devices. In this review, we summarized the effects of water, both as an additive into the perovskite formulation as an additive and as moisture exposure during fabrication. We discuss in depth the structural and chemical effects, analysing also the photovoltaic consequences during operation conditions. As a final input, we remark a useful method to perform high efficiency PSCs under different lab ambient conditions and highlight the latest advances in hydrophobic devices and encapsulation techniques.

Effects of Frequency Dependence of the External Quantum Efficiency of Perovskite Solar Cells.

Perovskite solar cells are known to show very long response time scales, on the order of milliseconds to seconds. This generates considerable doubt over the validity of the measured external quantum efficiency (EQE) and consequently the estimation of the short-circuit current density. We observe a variation as high as 10% in the values of the EQE of perovskite solar cells for different optical chopper frequencies between 10 and 500 Hz, indicating a need to establish well-defined protocols of EQE measurement. We also corroborate these values and obtain new insights regarding the working mechanisms of perovskite solar cells from intensity-modulated photocurrent spectroscopy measurements, identifying the evolution of the EQE over a range of frequencies, displaying a singular reduction at very low frequencies. This reduction in EQE is ascribed to additional resistive contributions hindering charge extraction in the perovskite solar cell at short-circuit conditions, which are delayed because of the concomitant large low-frequency capacitance.

Surface Polarization Model for the Dynamic Hysteresis of Perovskite Solar Cells.

The dynamic hysteresis of perovskite solar cells consists of the occurrence of significant deviations of the current density-voltage curve shapes depending on the specific conditions of measurement such as starting voltage, waiting time, scan rate, and other factors. Dynamic hysteresis is a serious impediment to stabilized and reliable measurement and operation of the perovskite solar cells. In this Letter, we formulate a model for the dynamic hysteresis based on the idea that the cell accumulates a huge quantity of surface electronic charge at forward bias that is released on voltage sweeping, causing extra current over the normal response. The charge shows a retarded dynamics due to the slow relaxation of the accompanying ionic charge, that produces variable shapes depending on scan rate or poling value and time. We show that the quantitative model provides a consistent description of experimental results and allows us to determine significant parameters of the perovskite solar cell for both the transient and steady-state performance.

Coordination Chemistry Dictates the Structural Defects in Lead Halide Perovskites.

We show the influence of species present in precursor solution during formation of lead halide perovskite materials on the structural defects of the films. The coordination of lead by competing solvent molecules and iodide ions dictate the type of complexes present in the films. Depending on the processing conditions all PbIS5 (+) , PbI2 S4, PbI3 S3 (-) , PbI4 S2 (2-) , PbI5 S2 (3-) , PbI6 (4-) and 1D (Pb2 I4 )n chains are observed by absorption measurements. Different parameters are studied such as polarity of the solvent, concentration of iodide ions, concentration of solvent molecules and temperature. It is concluded that strongly coordinating solvents will preferentially form species with a low number of iodide ions and less coordinative solvents generate high concentration of PbI6 (-) . We furthermore propose that all these plumbate ions may act as structural defects determining electronic properties of the photovoltaic films.

Interfacial Degradation of Planar Lead Halide Perovskite Solar Cells.

The stability of perovskite solar cells is one of the major challenges for this technology to reach commercialization, with water believed to be the major degradation source. In this work, a range of devices containing different cathode metal contacts in the configuration ITO/PEDOT:PSS/MAPbI3/PCBM/Metal are fully electrically characterized before and after degradation caused by steady illumination during 4 h that induces a dramatic reduction in power conversion efficiency from values of 12 to 1.8%. We show that a decrease in performance and generation of the S-shape is associated with chemical degradation of the metal contact. Alternatively, use of Cr2O3/Cr as the contact enhances the stability, but modification of the energetic profile during steady illumination takes place, significantly reducing the performance. Several techniques including capacitance-voltage, X-ray diffraction, and optical absorption results suggest that the properties of the bulk perovskite layer are little affected in the device degradation process. Capacitance-voltage and impedance spectroscopy results show that the electrical properties of the cathode contact are being modified by generation of a dipole at the cathode that causes a large shift of the flat-band potential that modifies the interfacial energy barrier and impedes efficient extraction of electrons. Ionic movement in the perovskite layer changes the energy profile close to the contacts, modifying the energy level stabilization at the cathode. These results provide insights into the degradation mechanisms of perovskite solar cells and highlight the importance to further study the use of protecting layers to avoid the chemical reactivity of the perovskite with the external contacts.

Attentional orienting to own and others' hands.

High-density electroencephalographic recordings were used to investigate the level of analysis at which attentional expectations modulate the processing of specific stimuli from the same perceptual category but differentiated in terms of a particular non-perceptual feature: body ownership. We used a task in which colour cues predicted whether a picture of a hand stimulus belonged to the participant or to somebody else. Participants were instructed to respond whether the target was a left or a right hand. Results revealed that the ERP pattern depended on stimulus ownership and attention orienting, which influenced the visual processing of own and someone else's hands differentially. Larger amplitude for others' than for own hands was shown at the N1 deflection (at the right hemisphere). Attentional effects were found at the P2 and P3 potentials. The P2 reflected an interaction between stimulus ownership and attentional orienting, due to a larger validity effect for others' hands. At the P3 level, the data showed a significant validity effect only for self-hand stimuli. In sum, our results suggest that (1) differences as a function of stimulus ownership can be detected at early levels of stimulus processing; (2) endogenous attention can be directed to exemplars within the same category, hand stimuli in this case; (3) the effects of attention are modulated by ownership.

Attention to individual identities modulates face processing.

The ability of attention to apply in a flexible manner to several types of information at various stages of processing has been studied extensively. However, the susceptibility of these effects to the nature of the idiosyncratic items being attended is less understood. In the current study, we used symbolic cues to orient the attention of participants to the subsequent appearance of the face of a famous person (the former king of Spain) or an unfamiliar face. These were matched in perceptual characteristics. Behavioral effects showed that face-specific attention optimized response speed in an orthogonal task when the target matched the cue (valid trials) compared to when it did not (invalid trials). According to topographical analyses of the electrophysiological data, the famous and unfamiliar faces engaged dissociable brain circuits in two different temporal windows, from 144 to 300 ms after target processing, and at a later 456-492 ms epoch. In addition, orienting attention to specific faces modulated the perceptual stages reflected in the P1 and N170 potentials but with a different laterality pattern that depended on the familiarity of the faces. Whereas only attention to the famous face enhanced the P1 potential at left posterior electrodes, with no corresponding effect for the unfamiliar face at this stage, the N170 was modulated at left posterior sites for the famous item and at right homologous electrodes for the unfamiliar face. Intermediate processing stages, previously linked to facial identity processing indexed by the P2 and N2 potentials, reflected item familiarity but were not affected by the cueing manipulation. At the P3 level, attention influenced again item processing but did so in an equivalent manner for the famous and unfamiliar face. Our results, showing that identity-specific attention modulates perceptual stages of facial processing at different locations depending on idiosyncratic stimulus familiarity, may inform comparison of studies employing items with different degrees of novelty.

Focusing on the bodily self: the influence of endogenous attention on visual body processing.

The present study explores whether endogenous attention can modulate body perception. A modified version of the Posner paradigm was used to direct participants' attention toward the appearance of distinct body images, which differed only in detailed idiosyncratic features: one's own and another person's hands. Hand stimuli were preceded by symbolic cues that predicted their identity with high probability, which made it possible to compare the processing of expected (valid) and unexpected (invalid) targets. Results revealed that endogenous attention influenced the processing of participants' own hands by speeding participants' responses to valid in contrast to invalid trials. Crucially, no validity effect was found for the hands of another person. These findings cannot be explained in terms of perceptual familiarity, since an optimization of the processing for both familiar and unfamiliar faces by symbolic cues was observed. In light of these results, it is suggested that participants are able to anticipate particular stimuli within the same perceptual category as long as these stimuli appear to be remarkably distinct to them, which is probably the case for particular faces and their own bodies, in contrast to other people's bodies.

Category expectations: a differential modulation of the N170 potential for faces and words.

The goal of the present study was to explore whether endogenous attention can be oriented to different perceptual categories and to examine how these expectations modulate visual stimulus processing. We designed a cueing paradigm that prepared participants, on a trial-by-trial basis, for the most likely stimulus category of the target, which could be either a face or a word. Participants were asked to discriminate the gender of the stimuli, regardless of their category. We measured participants' brain activity by means of a high-density electroencephalographic recording system to investigate the neural correlates of orienting attention to faces and words. As expected, we observed a behavioural facilitation for valid compared to invalid trials. In addition, target expectations influenced stimulus processing at several points in time. Most importantly, attention modulated the lateralized N170 component in a category-specific fashion. These results show that, at least under certain circumstances, orienting endogenous attention to different categories can influence the perceptual stages of face and word visual processing.