Perovskite solar cells (PSCs) are among the most promising photovoltaic technologies owing to their exceptional optoelectronic properties1,2. However, the lower efficiency, poor stability and reproducibility issues of large-area PSCs compared with laboratory-scale PSCs are notable drawbacks that hinder their commercialization3. Here we report a synergistic dopant-additive combination strategy using methylammonium chloride (MACl) as the dopant and a Lewis-basic ionic-liquid additive, 1,3-bis(cyanomethyl)imidazolium chloride ([Bcmim]Cl). This strategy effectively inhibits the degradation of the perovskite precursor solution (PPS), suppresses the aggregation of MACl and results in phase-homogeneous and stable perovskite films with high crystallinity and fewer defects. This approach enabled the fabrication of perovskite solar modules (PSMs) that achieved a certified efficiency of 23.30% and ultimately stabilized at 22.97% over a 27.22-cm2 aperture area, marking the highest certified PSM performance. Furthermore, the PSMs showed long-term operational stability, maintaining 94.66% of the initial efficiency after 1,000 h under continuous one-sun illumination at room temperature. The interaction between [Bcmim]Cl and MACl was extensively studied to unravel the mechanism leading to an enhancement of device properties. Our approach holds substantial promise for bridging the benchtop-to-rooftop gap and advancing the production and commercialization of large-area perovskite photovoltaics.
Purpose: The purpose of this study was to investigate and compare the corresponding alterations of the pupillary response between acute and chronic central serous chorioretinopathy (CSC) and between different disease categories. Methods: We recruited patients with unilateral acute and chronic CSC. An eye tracker was applied to determine the pupillary light reflex (PLR) and evaluate the following PLR metrics in healthy eyes: pupil diameter, diameter changes, including relative constriction amplitude (AMP%), and re-dilation ratio (D1%). Baseline optical coherence tomography (OCT), and fluorescein and indocyanine green angiography (FA/ICGA) were performed to analyze the relationship between pupillary response and retinal/choroidal architecture. Results: In total, 52 patients were enrolled, including 25 with acute CSC and 27 with chronic CSC. Compared to the chronic CSC group, the acute CSC group displayed a significantly larger baseline pupil diameter (BPD; of 5.51 mm, P = 0.015), lower AMP% (34.40%, P = 0.004), and higher D1% (93.01%, P = 0.002), indicating sympathetic overactivity. On OCT, the total macular volume was positively correlated with the D1% (r = 0.48, P = 0.005) and negatively with AMP (r = -0.47, P = 0.007). On ICGA, the intense choroidal vascular hyperpermeability (CVH) group displayed a greater BPD than the nonintense CVH group. Additionally, 9 cases with later recurrent episodes following therapy showed a lower AMP% and higher D1% than the nonrecurrent group. Conclusions: The PLR revealed sympathetic excitation in patients with acute CSC. The stronger D1% was significantly associated with greater total macular volume, and it may be a potential biomarker for predicting the later recurrence of CSC.
Central Serous Chorioretinopathy , Humans , Central Serous Chorioretinopathy/diagnosis , Indocyanine Green , Coloring Agents , Fluorescein Angiography/methods , Tomography, Optical Coherence/methods , Choroid , Chronic Disease , Multimodal Imaging , Retrospective Studies
Room-temperature ionic liquids (RTILs) have attracted significant attention owing to their unique nature and a variety of potential applications. The archetypal RTIL comprising an aliphatic primary ammonium was discovered over a century ago, but this cation is seldom used in modern RTILs because other bulky cations (e.g., quaternary ammonium-, pyridine-, and imidazole-based cations) are prominent in current major applications, such as electrolytes and solvents, which require low and/or reversible reactivities. However, although the design of materials should change according to the intended application, RTIL designs remain conventional even when applied in unexplored fields, limiting their functions. Herein, RTIL consisting of an archetypal aliphatic primary ammonium (i.e., n-octylammonium: OA) cation and a modern bis(trifluoromethylsulfonyl)imide (TFSI) anion is proposed and demonstrated as a highly functional additive for a 2,2',7,7'-tetrakis(N,N-di-4-methoxyphenylamino)-9,9'-spirobifluorene (Spiro-OMeTAD), which is the most common hole transport material (HTM), in perovskite solar cells (PSCs). The OA-TFSI additive exhibits prominent functions via permanent reactions of the component ions with the PSC components, thus providing several advantages. The OA cations spontaneously and densely passivate the perovskite layer during the HTM deposition process, leading to both suppression of carrier recombination at the HTM/perovskite interface and hydrophobic perovskite surfaces. Meanwhile, the TFSI anions effectively improve the HTM function most likely via efficient stabilization of the Spiro-OMeTAD radical, enhancing hole collection properties in the PSCs. Consequently, PSC performances involving long-term stability were significantly improved using the OA-TFSI additive. Based on the present results, this study advocates that reconsidering the RTIL design, even when it differs from the current major designs yet is suitable for a target application, can provide functions superior to conventional ones. The insights obtained in this work will spur further study of RTIL designs and aid the development of the broad materials science field including PSCs.
Smart eyeglasses with an integrated electrooculogram (EOG) device (JINS MEME ES_R®, JINS Inc.) were evaluated as a quantitative diagnostic tool for blepharospasm. Participants without blepharospasm (n = 21) and patients with blepharospasm (n = 19) undertook two voluntary blinking tests (light and fast) while wearing the smart eyeglasses. Vertical (Vv) and horizontal (Vh) components were extracted from time-series voltage waveforms recorded during 30 s of the blinking tests. Two parameters, the ratio between the maximum and minimum values in the power spectrum (peak-bottom ratio, Fourier transform analysis) and the mean amplitude of the EOG waveform (peak amplitude analysis) were calculated. The mean amplitude of Vh from light and fast blinking was significantly higher in the blepharospasm group than in the control group (P < 0.05 and P < 0.05). Similarly, the peak-bottom ratio of Vv from light and fast blinking was significantly lower in the blepharospasm group than in the control group (P < 0.05 and P < 0.05). The mean amplitude of Vh and peak-bottom ratio of Vv correlated with the scores determined using the Jankovic rating scale (P < 0.05 and P < 0.01). Therefore, these parameters are sufficiently accurate for objective blepharospasm classification and diagnosis.
Blepharospasm , Blinking , Electrooculography , Eyeglasses , Humans , Blepharospasm/diagnosis , Time Factors
All-inorganic CsPbI3 perovskite solar cells (PSCs) with efficiencies exceeding 20% are ideal candidates for application in large-scale tandem solar cells. However, there are still two major obstacles hindering their scale-up: (i) the inhomogeneous solid-state synthesis process and (ii) the inferior stability of the photoactive CsPbI3 black phase. Here, we have used a thermally stable ionic liquid, bis(triphenylphosphine)iminium bis(trifluoromethylsulfonyl)imide ([PPN][TFSI]), to retard the high-temperature solid-state reaction between Cs4PbI6 and DMAPbI3 [dimethylammonium (DMA)], which enables the preparation of high-quality and large-area CsPbI3 films in the air. Because of the strong Pb-O contacts, [PPN][TFSI] increases the formation energy of superficial vacancies and prevents the undesired phase degradation of CsPbI3. The resulting PSCs attained a power conversion efficiency (PCE) of 20.64% (certified 19.69%) with long-term operational stability over 1000 hours. A record efficiency of 16.89% for an all-inorganic perovskite solar module was achieved, with an active area of 28.17 cm2.
Defective and perfect sites naturally exist within electronic semiconductors, and considerable efforts to reduce defects to improve the performance of electronic devices, especially in hybrid organic-inorganic perovskites (ABX3 ), are undertaken. Herein, foldable hole-transporting materials (HTMs) are developed, and they extend the wavefunctions of A-site cations of perovskite, which, as hybridized electronic states, link the trap states (defective site) and valence band edge (perfect site) between the naturally defective and perfect sites of the perovskite surface, finally converting the discrete trap states of the perovskite as the continuous valence band to reduce trap recombination. Tailoring the foldability of the HTMs tunes the wavefunctions between defective and perfect surface sites, allowing the power conversion efficiency of a small cell to reach 23.22% and that of a mini-module (6.5 × 7 cm, active area = 30.24 cm2 ) to reach as high as 21.71% with a fill factor of 81%, the highest value reported for non-spiro-OMeTAD-based perovskite solar modules.
Hole-transporting materials (HTMs) based on the 10H, 10'H-9,9'-spirobi [acridine] core (BSA50 and BSA51) were synthesized, and their electronic properties were explored. Experimental and theoretical studies show that the presence of rigid 3,6-dimethoxy-9H-carbazole moieties in BSA 50 brings about improved hole mobility and higher work function compared to bis(4-methoxyphenyl)amine units in BSA51, which increase interfacial hole transportation from perovskite to HTM. As a result, perovskite solar cells (PSCs) based on BSA50 boost power conversion efficiency (PCE) to 22.65 %, and a PSC module using BSA50 HTM exhibits a PCE of 21.35 % (6.5×7â cm) with a Voc of 8.761â V and FF of 79.1 %. The unencapsulated PSCs exhibit superior stability to devices employing spiro-OMeTAD, retaining nearly 90 % of their initial efficiency after 1000â h operation output. This work demonstrates the high potential of molecularly engineered spirobi[acridine] derivatives as HTMs as replacements for spiro-OMeTAD.
Purpose: This study assessed the autonomic nervous system in patients with central serous chorioretinopathy (CSC) by simultaneously measuring pupillary responses and heart rate variability (HRV). Methods: We recruited 33 patients with CSC and 26 age- and sex-matched healthy controls. Using a pupillometry and acceleration plethysmography system, we measured the participants' pupillary light reflex and HRV simultaneously, and compared the following parameters between the two groups: the pupil diameters, diameter changes, and time and frequency domain HRV indices (high frequency power: HF; low frequency power: LF; log LF/HF ratio). Additional data from the Profile of Mood States (POMS) and pupillary responses during mental tasks were also analyzed. Results: The CSC group had a significantly lower constriction amplitude and a higher re-dilation ratio compared with the control group, indicating parasympathetic inhibition and sympathetic activation. For the HRV measures, the CSC group demonstrated significantly lower HF and higher LF and log LF/HF ratio, indicative of higher sympathetic activity. The CSC group also showed significantly larger pupil dilation during tasks of moderate difficulty, and higher negative/lower positive POMS mood scores. Further analyses also revealed that the baseline pupil diameter was significantly larger in patients with active as opposed to chronic CSC. Conclusions: Pupillary responses and HRV measures both revealed sympathetic activation and parasympathetic attenuation in patients with CSC. Larger pupil dilation during mental tasks in CSC could be a potential marker of psychophysiological stress.
Central Serous Chorioretinopathy , Acceleration , Autonomic Nervous System/physiology , Central Serous Chorioretinopathy/diagnosis , Heart Rate/physiology , Humans
The lack of organic non-fullerene ETMs with good electron transport and device stability is an important problem for the further development and commercialization of perovskite solar cells. Herein, the use of SubPcs as ETMs in PSCs is explored. To this end, we analyze the influence of SubPc peripheral functionalization on the efficiency and stability of p-i-n PSCs. Specifically, ETMs based on three SubPcs (with either six or twelve peripheral fluorine and chlorine atoms) have been incorporated into PSCs with the perovskite layer deposited by solution processing (CsFAMAPbIBr). The device performance and morphology of these devices are deeply analyzed using several techniques, and the interfacial effects induced by the SubPcs are studied using photoluminescence and TR-PL. It is observed that the device stability is significantly improved upon insertion the SubPc layer. Moreover, the impact of the SubPc layer-thickness is assessed. Thus, a maximum power conversion efficiency of 13.6% was achieved with the champion device.
The development of a scalable chemical bath deposition (CBD) process facilitates the realization of electron-transporting layers (ETLs) for large-area perovskite solar modules (PSMs). Herein, a method to prepare a uniform and scalable thick Zn2SnO4 ETL by CBD, which yielded high-performance PSMs, is reported. This Zn2SnO4 ETL exhibits excellent electrical properties and enhanced optical transmittance in the visible region. Moreover, the Zn2SnO4 ETL influences the perovskite layer formation, yielding enhanced crystallinity, increased grain size, and a smoother surface, thus facilitating electron extraction and collection from the perovskite to the ETL. Zn2SnO4 thereby yields PSMs with a remarkable photovoltaic performance, low hysteresis index, and high device reproducibility. The champion PSM exhibited a power conversion efficiency (PCE) of 22.59%, being among the highest values published so far. In addition, the CBD Zn2SnO4-based PSMs exhibit high stability, retaining more than 88% of initial efficiency over 1000 h under continuous illumination. This demonstrates that CBD Zn2SnO4 is an appropriate ETL for high-efficiency PSMs and a viable new process for their industrialization.
Despite the remarkable progress in power conversion efficiency of perovskite solar cells, going from individual small-size devices into large-area modules while preserving their commercial competitiveness compared with other thin-film solar cells remains a challenge. Major obstacles include reduction of both the resistive losses and intrinsic defects in the electron transport layers and the reliable fabrication of high-quality large-area perovskite films. Here we report a facile solvothermal method to synthesize single-crystalline TiO2 rhombohedral nanoparticles with exposed (001) facets. Owing to their low lattice mismatch and high affinity with the perovskite absorber, their high electron mobility and their lower density of defects, single-crystalline TiO2 nanoparticle-based small-size devices achieve an efficiency of 24.05% and a fill factor of 84.7%. The devices maintain about 90% of their initial performance after continuous operation for 1,400 h. We have fabricated large-area modules and obtained a certified efficiency of 22.72% with an active area of nearly 24 cm2, which represents the highest-efficiency modules with the lowest loss in efficiency when scaling up.
Hybrid lead halide perovskite solar cells (PSCs) have emerged as potential competitors to silicon-based solar cells with an unprecedented increase in power conversion efficiency (PCE), nearing the breakthrough point toward commercialization. However, for hole-transporting materials, it is generally acknowledged that complex structures often create issues such as increased costs and hazardous substances in the synthetic schemes, when translated from the laboratory to manufacture on a large scale. Here, we present cyclobutane-based hole-selective materials synthesized using simple and green-chemistry inspired protocols in order to reduce costs and adverse environmental impact. A series of novel semiconductors with molecularly engineered side arms were successfully applied in perovskite solar cells. V1366-based PSCs feature impressive efficiency of 21 %, along with long-term operational stability under atmospheric environment. Most importantly, we also fabricated perovskite solar modules exhibiting a record efficiency over 19 % with an active area of 30.24â cm2 .
Organic halide salt passivation is considered to be an essential strategy to reduce defects in state-of-the-art perovskite solar cells (PSCs). This strategy, however, suffers from the inevitable formation of in-plane favored two-dimensional (2D) perovskite layers with impaired charge transport, especially under thermal conditions, impeding photovoltaic performance and device scale-up. To overcome this limitation, we studied the energy barrier of 2D perovskite formation from ortho-, meta- and para-isomers of (phenylene)di(ethylammonium) iodide (PDEAI2) that were designed for tailored defect passivation. Treatment with the most sterically hindered ortho-isomer not only prevents the formation of surficial 2D perovskite film, even at elevated temperatures, but also maximizes the passivation effect on both shallow- and deep-level defects. The ensuing PSCs achieve an efficiency of 23.9% with long-term operational stability (over 1000 h). Importantly, a record efficiency of 21.4% for the perovskite module with an active area of 26 cm2 was achieved.
Phase control of low-dimensional metal-halide perovskites (LDPs) greatly affects their optoelectronic properties, and phase-pure LDPs are desirable to achieve efficient perovskite optoelectronic devices such as solar cells and light-emitting diodes. Herein, we introduce a method to obtain phase-pure LDP by using a neutral amine, cyclohexylmethyl amine (CHMA). The incorporation of CHMA into a formamidinium lead bromide (FAPbBr3) precursor solution leads to the protonation of the amine that allows the phase transition of 3D FAPbBr3 to phase-pure quasi-2D perovskite (n = 2). For comparison, cyclohexylmethylammonium bromide (CHMABr), which is a conventional form of ammonium halide salt with the same organic moiety to the amine, is used, which resulted in a 2D perovskite (n = 1). The perovskite films fabricated by the two different methodologies are characterized. This study paves the way for further research on the realization of phase-pure perovskites and their relevant optoelectronic devices.
Hybrid lead halide perovskites have reached comparable efficiencies to state-of-the-art silicon solar cell technologies. However, a remaining key challenge toward commercialization is the resolution of the perovskite device instability. In this work, we identify for the first time the mobile nature of bis(trifluoromethanesulfonyl)imide (TFSI-), a typical anion extensively employed in p-type dopants for 2,2'7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'spirofluorene (spiro-OMeTAD). We demonstrate that TFSI- can migrate through the perovskite layer via the grain boundaries and accumulate at the perovskite/electron-transporting layer (ETL) interface. Our findings reveal that the migration of TFSI- enhances the device performance and stability, resulting in highly stable p-i-n cells that retain 90% of their initial performance after 1600 h of continuous testing. Our systematic study, which targeted the effect of the nature of the dopant and its concentration, also shows that TFSI- acts as a dynamic defect-healing agent, which self-passivates the perovskite crystal defects during the migration process and thereby decreases nonradiative recombination pathways.
A set of novel branched molecules bearing a different number of 3,6-bis(4,4'-dimethoxydiphenylamino)carbazole-based (Cz-OMeDPA) periphery arms linked together by aliphatic chains have been developed, and their performance has been tested in perovskite solar cells (PSCs). Electrical and photovoltaic properties have been evaluated with respect to the number of Cz-OMeDPA moieties and the nature of the linking aliphatic chain. The isolated compounds possess sufficient thermal stability and are amorphous having high glass-transition temperatures (>120 °C) minimizing the risk of direct layer crystallization. The highest hole-drift mobility of µ0 = 3.1 × 10-5 cm2 V-1 s-1 is comparable to that of the reference standard spiro-OMeTAD (4.1 × 10-5 cm2 V-1 s-1) under identical conditions. Finally, PSCs employing two new HTMs (2Cz-OMeDPA and 3Cz-OMeDPA-OH) bearing two and three substituted carbazole chromophores, linked by an aliphatic chain, show a performance of around 20%, which is on par with devices using spiro-OMeTAD and demonstrates slightly enhanced device stability.
The emerging CsPbI3 perovskites are highly efficient and thermally stable materials for wide-band gap perovskite solar cells (PSCs), but the doped hole transport materials (HTMs) accelerate the undesirable phase transition of CsPbI3 in ambient. Herein, a dopant-free D-π-A type HTM named CI-TTIN-2F has been developed which overcomes this problem. The suitable optoelectronic properties and energy-level alignment endow CI-TTIN-2F with excellent charge collection properties. Moreover, CI-TTIN-2F provides multisite defect-healing effects on the defective sites of CsPbI3 surface. Inorganic CsPbI3 PSCs with CI-TTIN-2F HTM feature high efficiencies up to 15.9 %, along with 86 % efficiency retention after 1000â h under ambient conditions. Inorganic perovskite solar modules were also fabricated that exhibiting an efficiency of 11.0 % with a record area of 27â cm2 . This work confirms that using efficient dopant-free HTMs is an attractive strategy to stabilize inorganic PSCs for their future scale-up.
A decade after the report of the first efficient perovskite-based solar cell, development of novel hole-transporting materials (HTMs) is still one of the main topics in this research field. Two of the main advance vectors of this topic lie in obtaining materials with enhanced hole-extracting capability and in easing their synthetic cost. The use of anthra[1,9-bc:5,10-b'c']dithiophene (ADT) as a flat π-conjugated frame for bearing arylamine electroactive moieties allows obtaining two novel highly efficient HTMs from very cheap precursors. The solar cells fabricated making use of the mixed composition (FAPbI3)0.85(MAPbBr3)0.15 perovskite and the novel ADT-based HTMs show power conversion efficiencies up to 17.6% under 1 sun illumination compared to the 18.1% observed when using the benchmark compound 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene (spiro-OMeTAD). Detailed density functional theory calculations allow rationalization of the observed opto-electrochemical properties and predict a flat molecular structure with a low reorganization energy that supports the high conductivity measured for the best-performing HTM.
Triarylamine-substituted bithiophene (BT-4D), terthiophene (TT-4D), and quarterthiophene (QT-4D) small molecules are synthesized and used as low-cost hole-transporting materials (HTMs) for perovskite solar cells (PSCs). The optoelectronic, electrochemical, and thermal properties of the compounds are investigated systematically. The BT-4D, TT-4D, and QT-4D compounds exhibit thermal decomposition temperature over 400 °C. The n-i-p configured perovskite solar cells (PSCs) fabricated with BT-4D as HTM show the maximum power conversion efficiency (PCE) of 19.34% owing to its better hole-extracting properties and film formation compared to TT-4D and QT-4D, which exhibit PCE of 17% and 16%, respectively. Importantly, PSCs using BT-4D demonstrate exceptional stability by retaining 98% of its initial PCE after 1186 h of continuous 1 sun illumination. The remarkable long-term stability and facile synthetic procedure of BT-4D show a great promise for efficient, stable, and low-cost HTMs for PSCs for commercial applications.
Purpose: This study was conducted to investigate the feasibility of a newly developed wide-field dual-array suprachoroidal-transretinal stimulation (STS) prosthesis in dogs and to examine its biocompatibility and stability over a 4-month period. Methods: Three types of STS dual arrays were designed and tested. The STS dual-array was implanted into a scleral pocket of the left eye of six healthy beagle dogs. Ophthalmic examinations, fundus photography, fluorescein angiography (FA), electroretinography (ERG), and functional testing of this system were conducted postoperatively. The dogs were euthanatized at the end of the experiment, and their eyes were enucleated and histologically examined. Results: All prostheses were successfully implanted without complications, and no serious adverse event occurred during the postoperative period. Fundus photographs and FA showed no serious damage in the retina surrounding the arrays. The ERGs recorded from the implanted eyes showed no significant differences from those from control eyes. Histological evaluations demonstrated good preservation of the retina over the array. However, system failure occurred in 50% of the dogs owing to dog-specific habits. Conclusions: Implantation of this prosthesis system in dogs is feasible and can be performed without significant damage to the eye. The biocompatibility and stability of the array were good during the observation period, but the low durability of the system against dogs (not humans) is an issue to be resolved in the future. Translational Relevance: This study suggests that this wide-field dual-array prosthesis might widen the visual field and might be useful for patients with retinitis pigmentosa.
Visual Prosthesis , Animals , Dogs , Electric Stimulation , Electrodes, Implanted , Electroretinography , Evoked Potentials, Visual , Humans
