Assessing intra- and inter-molecular charge transfer excitations in non-fullerene acceptors using electroabsorption spectroscopy.

Organic photovoltaic cells using Y6 non-fullerene acceptors have recently achieved high efficiency, and it was suggested to be attributed to the charge-transfer (CT) nature of the excitations in Y6 aggregates. Here, by combining electroabsorption spectroscopy measurements and electronic-structure calculations, we find that the charge-transfer character already exists in isolated Y6 molecules but is strongly increased when there is molecular aggregation. Surprisingly, it is found that the large enhanced charge transfer in clustered Y6 molecules is not due to an increase in excited-state dipole moment, Δµ, as observed in other organic systems, but due to a reduced polarizability change, Δp. It is proposed that such a strong charge-transfer character is promoted by the stabilization of the charge-transfer energy upon aggregation, as deduced from density functional theory and four-state model calculations. This work provides insight into the correlation between molecular electronic properties and charge-transfer characteristics in organic electronic materials.

Effect of MSX1 on the cellular function of cardiomyocytes.

MSX1 (Muscle Segment Homeobox 1) has pleiotropic effects in various tissues, including cardiomyocytes, while the effect of MSX1 on cardiomyocyte cellular function was not well known. In this study, we used AC16 cell culture, real-time fluorescence quantitative PCR (qPCR), protein blotting (Western blot), flow cytometry apoptosis assay and lactate dehydrogenase (LDH) ELISA (Enzyme-Linked Immunosorbnent Assay) to investigate the effect of the MSX1 gene on cardiomyocyte function. The results showed that MSX1 plays a protective role against hypoxia of cardiomyocytes. However, further studies are required to fully understand the role of MSX1 in the regulation of LDH expression in different cell types and under different conditions.

The use of high-resolution SNP arrays to detect congenital cardiac defects.

OBJECTIVE: Copy number variations (CNVs) detected by high-resolution single nucleotide polymorphism microarrays (SNP arrays) have been associated with congenital heart defects (CHDs). The genetic mechanism underlying the development of CHDs remains unclear. METHODS: High-resolution SNP arrays were used to detect CNVs and traditional chromosomal analyses, respectively, were carried out on 60 and 249 fetuses from gestational 12-37 weeks old, having isolated or complex CHDs that were diagnosed using prenatal ultrasound. RESULTS: Twenty of the 60 fetuses (33.5%) had abnormalities, of which 23 CNVs (12 pathogenic, five probable pathogenic and six of undetermined significance) were detected by SNP arrays, and two distinct CNVs were present in three of these fetuses. In addition, in 39 patients with isolated congenital heart disease who had normal karyotypes, abnormal CNVs were present in 28.2% (11/39), and in patients with complex coronary artery disease, 19.0% (4/21) had abnormal karyotypes and 42.9% (9/21) had abnormal CNVs. In patients with complex coronary artery disease, 19.0% (4/21) had abnormal karyotypes and 42.9% (9/21) had abnormal CNVs. CONCLUSIONS: In conclusion, genome-wide high-resolution SNP array can improve the diagnostic rate and uncover additional pathogenic CNVs. The submicroscopic deletions and duplications of Online Mendelian Inheritance in Man (OMIM) genes found in this study have haploinsufficient (deletion) or triplosensitive (duplication) traits, which further clarify the etiology and inheritance of CHDs.

Charge injection engineering at organic/inorganic heterointerfaces for high-efficiency and fast-response perovskite light-emitting diodes.

The development of advanced perovskite emitters has considerably improved the performance of perovskite light-emitting diodes (LEDs). However, the further development of perovskite LEDs requires ideal device electrical properties, which strongly depend on its interfaces. In perovskite LEDs with conventional p-i-n structures, hole injection is generally less efficient than electron injection, causing charge imbalance. Furthermore, the popular hole injection structure of NiOx/poly(9-vinylcarbazole) suffers from several issues, such as weak interfacial adhesion, high interfacial trap density and mismatched energy levels. In this work, we insert a self-assembled monolayer of [2-(9H-carbazol-9-yl)ethyl]phosphonic acid between the NiOx and poly(9-vinylcarbazole) layers to overcome these challenges at the organic/inorganic heterointerfaces by establishing a robust interface, passivating interfacial trap states and aligning the energy levels. We successfully demonstrate blue (emission at 493 nm) and green (emission at 515 nm) devices with external quantum efficiencies of 14.5% and 26.0%, respectively. More importantly, the self-assembled monolayer also gives rise to devices with much faster response speeds by reducing interfacial capacitance and resistance. Our results pave the way for developing more efficient and brighter perovskite LEDs with quick response, widening their potential application scope.

Importance of Electric-Field-Independent Mobilities in Thick-Film Organic Solar Cells.

In organic solar cells (OSCs), a thick active layer usually yields a higher photocurrent with broader optical absorption than a thin active layer. In fact, a ∼300 nm thick active layer is more compatible with large-area processing methods and theoretically should be a better spot for efficiency optimization. However, the bottleneck of developing high-efficiency thick-film OSCs is the loss in fill factor (FF). The origin of the FF loss is not clearly understood, and there a direct method to identify photoactive materials for high-efficiency thick-film OSCs is lacking. Here, we demonstrate that the mobility field-dependent coefficient is an important parameter directly determining the FF loss in thick-film OSCs. Simulation results based on the drift-diffusion model reveal that a mobility field-dependent coefficient smaller than 10-3 (V/cm)-1/2 is required to maintain a good FF in thick-film devices. To confirm our simulation results, we studied the performance of two ternary bulk heterojunction (BHJ) blends, PTQ10:N3:PC71BM and PM6:N3:PC71BM. We found that the PTQ10 blend film has weaker field-dependent mobilities, giving rise to a more balanced electron-hole transport at low fields. While both the PM6 blend and PTQ10 blend yield good performance in thin-film devices (∼100 nm), only the PTQ10 blend can retain a FF = 74% with an active layer thickness of up to 300 nm. Combining the benefits of a higher JSC in thick-film devices, we achieved a PCE of 16.8% in a 300 nm thick PTQ10:N3:PC71BM OSC. Such a high FF in the thick-film PTQ10 blend is also consistent with the observation of lower charge recombination from light-intensity-dependent measurements and lower energetic disorder observed in photothermal deflection spectroscopy.

Dually Modified Wide-Bandgap Perovskites by Phenylethylammonium Acetate toward Highly Efficient Solar Cells with Low Photovoltage Loss.

Wide-bandgap perovskites as a class of promising top-cell materials have shown great promise in constructing efficient perovskite-based tandem solar cells, but their intrinsic relatively low radiative efficiency results in a large open-circuit voltage (VOC) deficit and thereby limits the whole device performance. Reducing film flaws or optimizing interfacial energy level alignments in wide-bandgap perovskite devices can efficiently inhibit nonradiative recombination to boost device VOC and efficiency. However, the simultaneous regulation on both sides and their underlying mechanism are less explored. Herein, a bifunctional modification approach is proposed to optimize the wide-bandgap perovskite surface with an ultrathin layer of phenylethylammonium acetate (PEAAc) to synchronously decrease the surface imperfection and mitigate the interfacial energy barrier. This treatment effectively heals under-coordinated surface defects through the formation of chemical interaction between the perovskite and PEAAc, bringing about a much slower charge trapping process and dramatically decreasing nonradiative recombination losses. Meanwhile, the passivation-induced upshifted Fermi level of the perovskite contributes to accelerated electron extraction and larger Fermi-level splitting under illumination. Consequently, the PEAAc-modified wide-bandgap (1.68 eV) device achieves an optimal efficiency of 20.66% with a high VOC of 1.25 V, among the highest reported VOC values for wide-bandgap perovskite devices, enormously outperforming that (18.86% and 1.18 V) of the device without passivation. In addition, the radiative limit of VOC for both cells is determined to be 1.42 V, delivering nonradiative recombination losses of 0.24 and 0.17 V for the control and PEAAc-modified devices, respectively. These results highlight the significance of the bifunctional modification strategy in achieving high-performance wide-bandgap perovskite devices.

Heat Transfer Enhancement of n-Type Organic Semiconductors by an Insulator Blend Approach.

The transfer of heat energy in organic semiconductors (OSCs) plays an important role in advancing the applications of organic electronics, especially for lifetime issues. However, compared with crystalline inorganic semiconductors, the thermal transport of OSCs is less efficient and a relevant understanding is very limited. In this contribution, we show that the heat conduction of OSCs can be enhanced by blending with a "commodity" insulator (both thermal and electrical). PC71BM, a well-known electron transporter but poor thermal conductor, was selected as the host OSC material. The blending of a small amount of polystyrene (PS), a commonly used insulating polymer, can facilitate the heat transfer of PC71BM films, as substantiated by the scanning photothermal deflection technique and an infrared thermal camera. The phase thermodynamics of PC71BM/PS blends indicates that the efficient heat transfer preferably occurs in the OSC/insulator blends with better intimate mixing, where isolated PC71BM domains can be effectively bridged by PS that thread through the regions. The applicability of this approach can be observed in blends with another host material─ITIC. This work provides a facile strategy for designing thermally durable organic electronic devices.

Approaching disorder-tolerant semiconducting polymers.

Doping has been widely used to control the charge carrier concentration in organic semiconductors. However, in conjugated polymers, n-doping is often limited by the tradeoff between doping efficiency and charge carrier mobilities, since dopants often randomly distribute within polymers, leading to significant structural and energetic disorder. Here, we screen a large number of polymer building block combinations and explore the possibility of designing n-type conjugated polymers with good tolerance to dopant-induced disorder. We show that a carefully designed conjugated polymer with a single dominant planar backbone conformation, high torsional barrier at each dihedral angle, and zigzag backbone curvature is highly dopable and can tolerate dopant-induced disorder. With these features, the designed diketopyrrolopyrrole (DPP)-based polymer can be efficiently n-doped and exhibit high n-type electrical conductivities over 120 S cm-1, much higher than the reference polymers with similar chemical structures. This work provides a polymer design concept for highly dopable and highly conductive polymeric semiconductors.

Organic indoor light harvesters achieving recorded output power over 500% enhancement under thermal radiated illuminances.

Organic photovoltaic (OPV) cells have found their potential applications in the harvest of indoor light photons. However, the output power of such indoor devices is usually far from the demand of the internet of things. Therefore, it is essential to boost the output power of indoor organic photovoltaics to a much higher level. As wildly deployed among industrial and civil luminous environments, thermal radiation-based indoor light sources are alternative candidates to supply the essential power of the off-grid electronics with a broad consecutive emission spectrum. In this work, we evaluated the photovoltaic performance of organic solar cells under indoor incandescent and halogen illuminations. Impressively, under such thermal radiations, an improvement over 500% of the output power density can be achieved in comparison with that under light-emitting diodes and fluorescent lamps, reaching a record high value of 279.1 µW cm-2 by the PM6:Y6-based device. The remarkable power output is originated from the extra near-infrared spectrum of indoor thermal lights, which restricts the effective area under 10 cm2 in achieving 1 mW output power. This work clarifies the feasibility of collecting photons radiated from indoor thermal light sources through OPV cells, and enlightens the further applications of indoor OPV cells under multiple illumination environments.

Highly Crystalline Near-Infrared Acceptor Enabling Simultaneous Efficiency and Photostability Boosting in High-Performance Ternary Organic Solar Cells.

The near-infrared (NIR) absorbing fused-ring electron acceptor, COi8DFIC, has demonstrated very good photovoltaic performance when combined with PTB7-Th as a donor in binary organic solar cells (OSCs). In this work, the NIR acceptor was added to state-of-the-art PBDBT-2F:IT4F-based solar cells as a third component, leading to (i) an efficiency increase of the ternary devices compared to the binary solar cells in the presence of the highly crystalline COi8DFIC acceptor and (ii) much-improved photostability under 1-sun illumination. The electron transport properties were investigated and revealed the origin of the enhanced device performance. Compared to the binary cells, the optimized ternary PBDBT-2F:COi8DFIC:IT4F blends exhibit improved electron transport properties in the presence of 10% COi8DFIC, which is attributed to improved COi8DFIC molecular packing. Furthermore, transient absorption spectroscopy revealed a slow recombination of charge carriers in the ternary blend. The improved electron transport properties were preserved in the ternary OSC upon aging, while in the binary devices they seriously deteriorated after simulated 1-sun illumination of 240 h. Our work demonstrates a simple approach to enhance both OSC efficiency and photostability.

Donor Polymer Can Assist Electron Transport in Bulk Heterojunction Blends with Small Energetic Offsets.

Conventional organic solar cell (OSC) systems have significant energy offsets between the donor and acceptor both at the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels. Because of this, in a bulk heterojunction (BHJ) system, electrons typically transport in acceptors, whereas holes typically transport in donors. It is not favorable for electrons to hop back and forth between the donor and acceptor because the hopping is energetically disfavored. In such conventional OSC systems, the addition of donor polymer to acceptor films should typically reduce the electron mobility. In this study, a surprisingly large increase (up to 30×) in electron mobility is observed in an OSC blend when introducing a polymer donor into small molecular acceptor. By ruling out morphology reasons, it is shown that the donor polymer can assist the electron transport by providing "bridges" or a "shortcut" for electron transport across the domains of small molecular acceptors. This can happen because, for these systems, the LUMO offset is small. The study shows the benefits of donor-assisted electron transport in BHJ systems with small energetic offsets. This finding could be also applied to other fields to tune the optimized charge transport property of organic materials or slush blends.

Charge transfer-induced photoluminescence in ZnO nanoparticles.

The quality of solution-processed zinc oxide (ZnO) nanoparticles (NPs) is often correlated with their photoluminescence (PL) spectral characteristics. However, the reported PL spectral characteristics lack consistency and remain controversial. Here we report that "defect-emission free" PL spectra can even be obtained in thin films composed of as-synthesized ZnO NPs. It is found that both the PL spectral line-shape and intensity are extremely sensitive to nitrogen and oxygen. By conducting time-dependent PL (t-PL) and photothermal deflection spectroscopy (PDS) measurements under vacuum and different gases, it is proposed that both inert (N2) and reactive (O2) molecules can be absorbed on the ZnO NP surface and induce charge transfer (CT). The CT states induced by N2 are non-radiative which significantly reduces the band emission. Whereas the CT states induced by O2 are radiative at the visible region, and the exciton transfer is efficient which increases the overall PL quantum yield. Owing to such effects, the previously reported correlation between defects and PL emission becomes questionable and needs to be revisited. Particularly, the visible emission from the ZnO NPs is proved to be facilitated by external effects, instead of direct recombination from defect states.

Fused Benzothiadiazole: A Building Block for n-Type Organic Acceptor to Achieve High-Performance Organic Solar Cells.

Narrow bandgap n-type organic semiconductors (n-OS) have attracted great attention in recent years as acceptors in organic solar cells (OSCs), due to their easily tuned absorption and electronic energy levels in comparison with fullerene acceptors. Herein, a new n-OS acceptor, Y5, with an electron-deficient-core-based fused structure is designed and synthesized, which exhibits a strong absorption in the 600-900 nm region with an extinction coefficient of 1.24 × 105 cm-1 , and an electron mobility of 2.11 × 10-4 cm2 V-1 s-1 . By blending Y5 with three types of common medium-bandgap polymers (J61, PBDB-T, and TTFQx-T1) as donors, all devices exhibit high short-circuit current densities over 20 mA cm-2 . As a result, the power conversion efficiency of the Y5-based OSCs with J61, TTFQx-T1, and PBDB-T reaches 11.0%, 13.1%, and 14.1%, respectively. This indicates that Y5 is a universal and highly efficient n-OS acceptor for applications in organic solar cells.

A Cryogenic Process for Antisolvent-Free High-Performance Perovskite Solar Cells.

A cryogenic process is introduced to control the crystallization of perovskite layers, eliminating the need for the use of environmentally harmful antisolvents. This process enables decoupling of the nucleation and the crystallization phases by inhibiting chemical reactions in as-cast precursor films rapidly cooled down by immersion in liquid nitrogen. The cooling is followed by blow-drying with nitrogen gas, which induces uniform precipitation of precursors due to the supersaturation of precursors in the residual solvents at very low temperature, while at the same time enhancing the evaporation of the residual solvents and preventing the ordered precursors/perovskite from redissolving into the residual solvents. Using the proposed techniques, the crystallization process can be initiated after the formation of a uniform precursor seed layer. The process is generally applicable to improve the performance of solar cells using perovskite films with different compositions, as demonstrated on three different types of mixed halide perovskites. A champion power conversion efficiency (PCE) of 21.4% with open-circuit voltage (VOC ) = 1.14 V, short-circuit current density ( JSC ) = 23.5 mA cm-2 , and fill factor (FF) = 0.80 is achieved using the proposed cryogenic process.

Versatility of Carbon Enables All Carbon Based Perovskite Solar Cells to Achieve High Efficiency and High Stability.

Carbon-based perovskite solar cells (PVSCs) without hole transport materials are promising for their high stability and low cost, but the electron transporting layer (ETL) of TiO2 is notorious for inflicting hysteresis and instability. In view of its electron accepting ability, C60 is used to replace TiO2 for the ETL, forming a so-called all carbon based PVSC. With a device structure of fluorine-doped tin oxide (FTO)/C60 /methylammonium lead iodide (MAPbI3 )/carbon, a power conversion efficiency (PCE) is attained up to 15.38% without hysteresis, much higher than that of the TiO2 ones (12.06% with obvious hysteresis). The C60 ETL is found to effectively improve electron extraction, suppress charge recombination, and reduce the sub-bandgap states at the interface with MAPbI3 . Moreover, the all carbon based PVSCs are shown to resist moisture and ion migration, leading to a much higher operational stability under ambient, humid, and light-soaking conditions. To make it an even more genuine all carbon based PVSC, it is further attempted to use graphene as the transparent conductive electrode, reaping a PCE of 13.93%. The high performance of all carbon based PVSCs stems from the bonding flexibility and electronic versatility of carbon, promising commercial developments on account of their favorable balance of cost, efficiency, and stability.

Stable and Efficient Organo-Metal Halide Hybrid Perovskite Solar Cells via π-Conjugated Lewis Base Polymer Induced Trap Passivation and Charge Extraction.

High-quality pinhole-free perovskite film with optimal crystalline morphology is critical for achieving high-efficiency and high-stability perovskite solar cells (PSCs). In this study, a p-type π-conjugated polymer poly[(2,6-(4,8-bis(5-(2-ethylhexyl) thiophen-2-yl)-benzo[1,2-b:4,5-b'] dithiophene))-alt-(5,5-(1',3'-di-2-thienyl-5',7'-bis(2-ethylhexyl) benzo[1',2'-c:4',5'-c'] dithiophene-4,8-dione))] (PBDB-T) is introduced into chlorobenzene to form a facile and effective template-agent during the anti-solvent process of perovskite film formation. The π-conjugated polymer PBDB-T is found to trigger a heterogeneous nucleation over the perovskite precursor film and passivate the trap states of the mixed perovskite film through the formation of Lewis adducts between lead and oxygen atom in PBDB-T. The p-type semiconducting and hydrophobic PBDB-T polymer fills in the perovskite grain boundaries to improve charge transfer for better conductivity and prevent moisture invasion into the perovskite active layers. Consequently, the PSCs with PBDB-T modified anti-solvent processing leads to a high-efficiency close to 20%, and the devices show excellent stability, retaining about 90% of the initial power conversion efficiency after 150 d storage in dry air.

Pinning Down the Anomalous Light Soaking Effect toward High-Performance and Fast-Response Perovskite Solar Cells: The Ion-Migration-Induced Charge Accumulation.

The light soaking effect (LSE) is widely known in perovskite solar cells (PVSCs), but its origin is still elusive. In this study, we show that in common with hysteresis, the LSE is owed to the ion migration in PVSCs. Driven by the photovoltage, the mobile ions in the perovskite materials (MA+/I-) migrate to the selective contacts, forming a boosted P-i-N junction resulting in enhanced charge separation. Besides, the mobile ions (MA+) can soften and suture the PCBM/perovskite interface and thus reduce the trap density, in keeping with a higher open-circuit voltage. Finally, almost LSE-free PVSCs can be prepared by using 0.1 wt % MAI-doped PCBM as the electron transport material, whereas overdoping (1 wt % MAI doping) makes the LSE even more pronounced due to excess mobile ions that need time to migrate to reach a new quasi-static state.

Naphthalene diimide-difluorobenzene-based polymer acceptors for all-polymer solar cells.

Regio-random (P1) and -regular (P2) difluorobenzene-naphthalene-containing polymer acceptors were developed for bulk-heterojunction all-polymer solar cells (all-PSCs). P2 exhibited significantly higher crystallinity in thin films, providing high spectral absorptivity and electron mobility than P1. When used in all-PSC devices, P2 afforded a respectably higher power conversion efficiency of over 5%.

Crystal Engineering for Low Defect Density and High Efficiency Hybrid Chemical Vapor Deposition Grown Perovskite Solar Cells.

Synthesis of high quality perovskite absorber is a key factor in determining the performance of the solar cells. We demonstrate that hybrid chemical vapor deposition (HCVD) growth technique can provide high level of versatility and repeatability to ensure the optimal conditions for the growth of the perovskite films as well as potential for batch processing. It is found that the growth ambient and degree of crystallization of CH3NH3PbI3 (MAPI) have strong impact on the defect density of MAPI. We demonstrate that HCVD process with slow postdeposition cooling rate can significantly reduce the density of shallow and deep traps in the MAPI due to enhanced material crystallization, while a mixed O2/N2 carrier gas is effective in passivating both shallow and deep traps. By careful control of the perovskite growth process, a champion device with power conversion efficiency of 17.6% is achieved. Our work complements the existing theoretical studies on different types of trap states in MAPI and fills the gap on the theoretical analysis of the interaction between deep levels and oxygen. The experimental results are consistent with the theoretical predictions.