Reducing Depletion Region Width at Electrode Interface via a Hole-transport Layer for Over 18% Efficiency in Organic Solar Cells.

The large depletion region width at the electrode interface may cause serious energy loss in charge collection of organic solar cells (OSCs), depressing the open-circuit voltage and power conversion efficiency (PCE). Herein, a pH neutral solution-processed conjugated polyelectrolyte PIDT-F:IMC as hole transport layer (HTL) to reduce the depletion region width in efficient OSCs is developed. By utilizing "mutual doping" strategy, the doping density of PIDT-F:IMC is increased by more than two orders of magnitude, which significantly reduces the depletion region width at the anode interface from 55 to 7.4 nm, playing an effective role in decreasing the energy loss in hole collection. It is also revealed that the optimal thickness of HTL should be consistent with the depletion region width for achieving the minimum energy loss. The OSC modified by PIDT-F:IMC shows a high PCE of 18.2%, along with an amazing fill factor of 0.79. Moreover, a PCE of 16.5% is achieved in the 1 cm2 OSC by using a blade-coated PIDT-F:IMC HTL, indicating the good compatibility of PIDT-F:IMC with large-area processing technology. The PIDT-F:IMC-modified OCS exhibits a lifetime of 400 h under operational conditions, which is ten times longer than that of the PEDOT:PSS device.

Non-ionic Perylene-Diimide Polymer as Universal Cathode Interlayer for Conventional, Inverted, and Blade-Coated Organic Solar Cells.

As a class of predominantly used cathode interlayers (CILs) in organic solar cells (OSCs), perylene-diimide (PDI)-based polymers exhibit intriguing characteristics of excellent charge transporting capacity and suitable energy levels. Despite that, PDI-based CILs with satisfied film-forming ability and adequate solvent resistance are rather rare, which not only limits the further advance of OSC performances but also hinders the practical use of PDI CILs. Herein, we designed and synthesized two non-conjugated PDI polymers for achieving high power conversion efficiency (PCE) in diverse types of OSCs. The utilization of oligo (ethylene glycol) (OEG) linkage enhanced the n-doping effect of PDI polymers, leading to an improved ability of the CIL to reduce work function and improve electron transporting capability. Moreover, the introduction of the non-ionic OEG chain effectively improve the wetting property and solvent resistance of PDI polymers, so the PPDINN CIL can withstand diverse processing conditions in fabricating different OSCs, including conventional, inverted and blade-coated devices. The binary OSC with conventional structure using PPDINN CIL showed a PCE of 18.6%, along with an improved device stability. Besides, PPDINN is compatible with the large-area blade-coating technique, and a PCE of 16.6% was achieved in the 1-cm2 OSC where a blade-coated PPDINN was used.

Nanoscale Two-Dimensional FeII- and CoII-Based Metal-Organic Frameworks of Porphyrin Ligand for the Photodynamic Therapy of Breast Cancer.

The delivery of biocompatible reagents into cancer cells can elicit an anticancer effect by taking advantage of the unique characteristics of the tumor microenvironment (TME). In this work, we report that nanoscale two-dimensional FeII- and CoII-based metal-organic frameworks (NMOFs) of porphyrin ligand meso-tetrakis (6-(hydroxymethyl) pyridin-3-yl) porphyrin (THPP) can catalyze the generation of hydroxyl radicals (•OH) and O2 in the presence of H2O2 that is overexpressed in the TME. Photodynamic therapy consumes the generated O2 to produce a singlet oxygen (1O2). Both •OH and 1O2 are reactive oxygen species (ROS) that inhibit cancer cell proliferation. The FeII- and CoII-based NMOFs were non-toxic in the dark but cytotoxic when irradiated with 660 nm light. This preliminary work points to the potential of porphyrin-based ligands of transition metals as anticancer drugs by synergizing different therapeutic modalities.

Self-Doped n-Type Quinoidal Compounds with Good Air Stability and High Electrical Conductivity for Organic Electronics.

Air stable n-type conductive molecules with high electrical conductivities and excellent device performance have important applications in organic electronics, but their synthesis remains challenging. Herein, we report three self-doped n-type conductive molecules, designated QnNs, with a closed-shell quinoidal backbone and alkyl amino chains of different lengths. The QnNs are self-doped by intermolecular electron transfer from the amino groups to the quinoidal backbone. This process is ascertained unambiguously by experiments and theoretical calculations. The use of a quinoidal structure effectively improves the self-doping level, and thus increases the electrical conductivity of self-doped n-type conductive molecules achieved by a closed-shell structure from<10-4  S cm-1 to>0.03 S cm-1 . Furthermore, the closed-shell quinoidal structure results in good air stability of the QnNs, with half-lives>73 days; and Q4N shows an electrical conductivity of 0.019 S cm-1 even after exposure to air for 120 days. When applying Q6N as the cathode interlayer in organic solar cells (OSCs), an outstanding power conversion efficiency of up to 18.2 % was obtained, which represents one the best results in binary OSCs.

A Heterometallic Three-Dimensional Metal-Organic Framework Bearing an Unprecedented One-Dimensional Branched-Chain Secondary Building Unit.

A heterometallic metal-organic framework (MOF) of [Cd6Ca4(BTB)6(HCOO)2(DEF)2(H2O)12]∙DEF∙xSol (1, H3BTB = benzene-1,3,5-tribenzoic acid; DEF = N,N'-diethylformamide; xSol. = undefined solvates within the pore) was prepared by solvothermal reaction of Cd(NO3)2·4H2O, CaO and H3BTB in a mixed solvent of DEF/H2O/HNO3. The compatibility of these two divalent cations from different blocks of the periodic table results in a solid-state structure consisting of an unusual combination of a discrete V-shaped heptanuclear cluster of [Cd2Ca]2Ca' and an infinite one-dimensional (1D) chain of [Cd2CaCa']n that are orthogonally linked via a corner-shared Ca2+ ion (denoted as Ca'), giving rise to an unprecedented branched-chain secondary building unit (SBU). These SBUs propagate via tridentate BTB to yield a three-dimensional (3D) structure featuring a corner-truncated P41 helix in MOF 1. This outcome highlights the unique topologies possible via the combination of carefully chosen s- and d-block metal ions with polydentate ligands.

A Carbonylated Terthiophene-Based Twisted Polymer for Efficient Ternary Polymer Solar Cells.

In polymer solar cells (PSCs), it is difficult for twisted conjugated polymers to achieve high power-conversion efficiency (PCE) as donors due to their low charge carrier mobilities and poor bulk heterojunction morphologies. In this work, a new twisted conjugated polymer (P3TCO-1) with excellent solubilities (above 30 mg mL-1 ) in common organic solvents at room temperature is reported. UV-visible absorption spectra and cyclic voltammetry indicate that P3TCO-1 has a wide optical bandgap of 1.90 eV and deep HOMO level of -5.39 eV. In binary PSCs, P3TCO-1:ITIC-based device shows a PCE of 10.11%, with JSC of 17.05 mA cm-2 and FF of 62.89%; P3TCO-1:PC71 BM-based device gives a PCE of 6.67% with JSC of 12.31 mA cm-2 and FF of 58.00%. When the two acceptors of ITIC and PC71 BM are combined, the twisted P3TCO-1-based ternary PSCs exhibit a significantly boosted PCE of up to 11.41%, with a simultaneously improved JSC of 18.16 mA cm-2 and FF of 66.78%. These results can guide the improvement of PCE for twisted conjugated polymer-based PSCs.

Fine-Tuned Photoactive and Interconnection Layers for Achieving over 13% Efficiency in a Fullerene-Free Tandem Organic Solar Cell.

Fabricating organic solar cells (OSCs) with a tandem structure has been considered an effective method to overcome the limited light absorption spectra of organic photovoltaic materials. Currently, the most efficient tandem OSCs are fabricated by adopting fullerene derivatives as acceptors. In this work, we designed a new non-fullerene acceptor with an optical band gap (Egopt) of 1.68 eV for the front subcells and optimized the phase-separation morphology of a fullerene-free active layer with an Egopt of 1.36 eV to fabricate the rear subcell. The two subcells show a low energy loss and high external quantum efficiency, and their photoresponse spectra are complementary. In addition, an interconnection layer (ICL) composed of ZnO and a pH-neutral self-doped conductive polymer, PCP-Na, with high light transmittance in the near-IR range was developed. From the highly optimized subcells and ICL, solution-processed fullerene-free tandem OSCs with an average power conversion efficiency (PCE) greater than 13% were obtained.

Acceptor-donor-acceptor-type molecules with large electrostatic potential difference for effective NIR photothermal therapy.

Although acceptor-donor-acceptor (A-D-A)-type molecules offer advantages in constructing NIR absorbing photothermal agents (PTAs) due to their strong intramolecular charge transfer and molecular planarity, their applications in photothermal therapy (PTT) of tumors remain insufficiently explored. In particular, the influence of ESP distribution on the optical properties of A-D-A photosensitizers has not been investigated. Herein, we analyze and compare the difference in ESP distribution between A-D-A-type small molecules and polymers to construct NIR absorbing PTAs with a high extinction coefficient (ε) and high photothermal conversion efficiency (PCE). The calculation results of density functional theory (DFT) indicate that the large ESP difference makes A-D-A-type small molecules superior to their polymer counterparts in realizing tight molecular packing and strong NIR absorbance. Among the as-prepared nanoparticles (NPs), Y6 NPs exhibited an obvious bathochromic shift of absorption peak from 711 nm to 822 nm, with the NIR-II emission extended to 1400 nm. Moreover, a high ε value of 5.69 L g-1 cm-1 and a PCE of 66.3% were attained, making Y6 NPs suitable for PTT. With a concentration of 100 µg mL-1, Y6 NPs in aqueous dispersion yielded a death rate of 93.4% for 4T1 cells upon 808 nm laser irradiation (1 W cm-2) for 10 min, which is comparable with the best results of recently reported PTT agents.

Counterion Engineering toward High-Performance and pH-Neutral Polyoxometalates-Based Hole-Transporting Materials for Efficient Organic Optoelectronic Devices.

Although protonated polyoxometalates (POMs) are promising hole-transporting layer (HTL) materials for optoelectronic devices owing to their excellent hole collection/injection property, pH neutrality, and noncorrosiveness, POMs are seldom used as high-performance HTL materials. Herein, we designed and synthesized a series of mixed-additive POMs with pH-neutral counterions (NH4+, K+, and Na+) as HTL materials. X-ray photoelectron spectroscopy and single-crystal X-ray analyses indicated that the use of the lacunary heteropolyanion [P2W15O56]12- as an intermediate ensured successful incorporation of the counterions into the mixed-addenda POMs without causing deterioration of the POM frameworks. The hole-transporting layer performance of POM-NH4, which was characterized by a high work function and good conductivity and could be prepared using a low-cost method surpassed those of its protonated counterpart POM-4 and many classic HTL materials. An organic solar cell (OSC) modified with POM-NH4 delivered a power conversion efficiency of 18.0%, which was the highest photovoltaic efficiency achieved by POM-based OSCs to date. Moreover, an HTL material based on POM-NH4 reduced the turn-on voltage of an organic light-emitting diode from 4.2 to 3.2 V. The results of this study suggest that POMs are promising alternatives to the classic HTL materials owing to their excellent hole-collection ability, low costs, neutral nature, and high-chemical stability.

Adjusting the Electron-Withdrawing Ability of Acceptors in Thermally Activated Delayed Fluorescence Conjugated Polymers for High-Performance OLEDs.

Constructing high-performance solution-processed organic light-emitting diodes (OLEDs) based on thermally activated delayed fluorescence (TADF) conjugated polymers remains a challenging issue. The electron-withdrawing ability of acceptors in TADF units significantly affects the TADF properties of the conjugated polymers. Herein, we have designed three TADF conjugated polymers, in which phenoxazine donors and anthracen-9(10H)-one acceptors are incorporated into the polymeric backbones and side chains, respectively, and the carbazole derivative is copolymerized as the host. By incorporating different heteroatoms, such as nitrogen, oxygen, or sulfur, with slightly different electronegativities into anthracen-9(10H)-one, the effect of the electron-withdrawing ability of the acceptor on the performance of conjugated TADF polymer-based OLEDs is thus systematically studied. It is found that the introduction of a nitrogen atom can enhance the spin-orbital coupling and RISC process due to the modulated energy levels and nature of the excited states. As a result, the solution-processed OLEDs based on the prepared polymer p-PXZ-XN display an excellent comprehensive performance with an EQEmax of 17.6%, a low turn-on voltage of 2.8 V, and a maximum brightness of 14750 cd m-2. Notably, the efficiency roll-off is quite low, maintaining 15.1% at 1000 cd m-2, 12.1% at 3000 cd m-2, and 6.1% at 10000 cd m-2, which ranks in the first tier among the reported TADF conjugated polymers. This work provides a guideline for constructing high-efficiency TADF polymers.

Reducing the Depletion Region Width at the Anode Interface via a Highly Doped Conjugated Polyelectrolyte Composite for Efficient Organic Solar Cells.

In the realm of organic solar cells (OSCs), the width of the depletion region at the anode interface is a critical factor that adversely impacts the open-circuit voltage (Voc) and the power conversion efficiency (PCE). To address this challenge, a novel approach involving a conjugated polyelectrolyte (CPE)-based composite, PCP-2F-Li:POM, has been developed. This composite serves as a solution-processed hole transport layer (HTL), effectively minimizing the depletion region width in high-performance OSCs. The innovative aspect of PCP-2F-Li:POM lies in its "mutual doping" mechanism. Polyoxometalate (POM) is utilized as a dopant, facilitating the formation of p-doped CPE and n-doped POM within the composite. This results in a substantial increase in doping density, nearly 2 orders of magnitude higher than that observed in unmodified CPE. Consequently, the width of depletion region is markedly reduced, shrinking from 76.4 to 6.0 nm. This reduction plays a pivotal role in enhancing hole transport via the tunneling effect. The practical impact of this development is notable. It leads to an increase in Voc from 0.84 to 0.86 V, thereby contributing significantly to an impressive PCE of 18.04% in OSCs. Moreover, the compatibility of PCP-2F-Li:POM with large-area processing techniques underscores its potential as a viable HTL material for future practical applications. Additionally, its contribution to the enhanced long-term stability of OSCs further bolsters its suitability for practical applications.

Solution-Processed Semiconductor Materials as Cathode Interlayers for Organic Solar Cells.

Cathode interlayers (CILs) play a crucial role in improving the photovoltaic efficiency and stability of OSCs. CILs generally consists of two kinds of materials, interfacial dipole-based CILs and SPS-based CILs. With good charge transporting ability, excellent compatibility with large-area processing methods, and highly tunable optoelectronic properties, the SPS-based CILs exhibit remarkable superiorities to their interfacial dipole-based counterparts in practical use, making them promising candidate in developing efficient CILs for OSCs. This mini-review highlights the great potential of SPS-based CILs in OSC applications and elucidates the working mechanism and material design strategy of SPS materials. Afterward, the SPS-based CIL materials are summarized and discussed in four sections, including organic small molecules, conjugated polymers, nonconjugated polymers, and TMOs. The structure-property-performance relationship of SPS-based CIL materials is revealed, which may provide readers new insight into the molecular design of SPS-based CILs. The mechanisms to endow SPS-based CILs with thickness insensitivity, resistance to environmental erosion, and photo-electric conversion ability are also elucidated. Finally, after a brief summary, the remaining issues and the prospects of SPS-based CILs are suggested.

Design and Application of an Asymmetric Naphthalimide-based Molecule with Improved Hydrophobicity for Highly Stable Organic Solar Cells.

With the photovoltaic efficiency of organic solar cells (OSCs) exceeding 17%, improving the stability of these systems has become the most important issue for their practical applications. In particular, moisture in the environment may erode the interlayer molecules, which has been proved to be the main reason for the efficiency decay. At present, the development of moisture-resistant interlayer molecules remains a great challenge to the field. Herein, we designed two naphthalene diimide (NDI)-based organic compounds, namely, NDI-M and NDI-S, exhibiting suitable energy level and excellent electron extraction property. In addition to this, NDI-S has extremely low hygroscopicity. An efficiency of 17.27% was achieved for the NDI-S inverted cells, and the long-term stability under continuous illumination conditions was significantly improved with a T80 lifetime (the time required to reach 80% of initial performance) of over 28 000 h. More importantly, we demonstrated that, by using a covalent bond to link the counter ions with the host molecular structure in the zwitterion, the asymmetric molecule NDI-S can transform from amorphous to crystalline hydrate at high humidity and exhibited outstanding non-hygroscopic nature; this could decrease the interaction between the cell and the moisture, obviously improving the device stability under high humidity.

Association between TGF-ß gene polymorphism and myopia: A systematic review and meta-analysis.

INTRODUCTION: The present study was conducted to determine the association of transforming growth factor-beta (TGF-ß) gene polymorphism and myopia. METHOD: Four hundred twelve articles were identified, of which 11 articles with 5213 participants in 4 countries were included in the final analysis. Review Manager software (RevMan, version 5.4) was used for data analysis. RESULT: Odds ratio (OR) value of TGF-ß1 rs1800469 is 1.33 (95% confidence interval [CI] = 1.15-1.54) in the allelic model; in the dominant model is 1.76 (95% CI = 1.16-2.67); in homozygous model is 5.98 (95% CI = 4.31-8.06). OR value of TGF-ß1 rs4803455 is 0.62 (95% CI = 0.43-0.88) in recessive model. TGF-ß2 is not associated with myopia. Relevant study on TGF-ß3 is scarce. CONCLUSION: Our systematic review and meta-analysis found that TGF-ß1 rs4803455 and rs1800469 were correlated with myopia.

Fluidic Manipulating of Printable Zinc Oxide for Flexible Organic Solar Cells.

As a representative electron transporting layer in organic solar cells, zinc oxide (ZnO) can be fabricated by the meniscus-guided coating with the promotion of sol-gel technology. In order to fabricate stable and flexible organic solar cells (OSCs) based on the printable ZnO layers, here, a new method for simultaneously manipulating fluidics of the sol-gel ZnO precursor and optimizing processability of the ZnO layer for flexible OSCs is developed. It is found that the Marangoni recirculation in meniscus and the annealing temperature of the sol-gel ZnO precursor can be effectively modulated by changing the Lewis base. With the use of propylamine, the high-quality ZnO layer that is suitable for flexible OSCs can be fabricated through blade coating. Under such a condition, the formation of polar facet in ZnO layer is well restrained, which favors the photostability of the cells. As a result, the best 1.00 cm2 flexible cell outputs a power conversion efficiency of 16.71%, which is the best value till now.

A Medium-Bandgap Nonfullerene Acceptor Enabling Organic Photovoltaic Cells with 30% Efficiency under Indoor Artificial Light.

The correlation between molecular structure and photovoltaic performance is lagging for constructing high-performance indoor organic photovoltaic (OPV) cells. Herein, this relationship is investigated in depth by employing two medium-bandgap nonfullerene acceptors (NFAs). The newly synthesized NFA of FTCCBr exhibits a similar bandgap and molecular energy level, but a much stronger dipole moment and larger average electrostatic potential (ESP) compared with ITCC. After blending with the polymer donor PB2, the PB2:ITCC and PB2:FTCCBr blends exhibit favorable bulk-heterojunction morphologies and the same driving force, but the PB2:FTCCBr blend exhibits a large ESP difference. In OPV cells, the PB2:ITCC-based device produces a power conversion efficiency (PCE) of 11.0%, whereas the PB2:FTCCBr-based device gives an excellent PCE of 14.8% with an open-circuit voltage (VOC ) of 1.05 V, which is the highest value among OPV cells with VOC values above 1.0 V. When both acceptor-based devices work under a 1000 lux of 3000 K light-emitting diode, the PB2:ITCC-based 1 cm2 device yields a good PCE of 25.4%; in contrast, the PB2:FTCCBr-based 1 cm2 device outputs a record PCE of 30.2%. These results suggest that a large ESP offset in photovoltaic materials is important for achieving high-performance OPV cells.

High-Efficiency ITO-Free Organic Photovoltaics with Superior Flexibility and Upscalability.

Developing indium-tin-oxide (ITO)-free flexible organic photovoltaics (OPVs) with upscaling capacity is of great significance for practical applications of OPVs. Unfortunately, the efficiencies of the corresponding devices lag far behind those of ITO-based rigid small-area counterparts. To address this issue, an advanced device configuration is designed and fabricated featuring a top-illuminated structure with ultrathin Ag as the transparent electrode. First, a conjugated polyelectrolyte layer, i.e., PCP-Li, is inserted to effectively connect the bottom Ag anode and the hole transport layer, achieving good photon to electron conversion. Second, charge collecting grids are deposited to suppress the increased resistance loss with the upscaling of the device area, realizing almost full retention of device efficiency from 0.06 to 1 cm2 . Third, the designed device delivers the best efficiency of 15.56% with the area of 1 cm2 on polyimide substrate, representing as the record among the ITO-free, large-area, flexible OPVs. Interestingly, the device exhibits no degradation after 100 000 bending cycles with a radius of 4 mm, which is the best result for flexible OPVs. This work provides insight into device structure design and optimization for OPVs with high efficiency, low cost, superior flexibility, and upscaling capacity, indicating the potential for the future commercialization of OPVs.

Tailoring and Modifying an Organic Electron Acceptor toward the Cathode Interlayer for Highly Efficient Organic Solar Cells.

With the rapid advance of organic photovoltaic materials, the energy level structure, active layer morphology, and fabrication procedure of organic solar cells (OSCs) are changed significantly. Thus, the photoelectronic properties of many traditional electrode interlayers have become unsuitable for modifying new active layers; this limits the further enhancement in OSC efficiencies. Herein, a new design strategy of tailoring the end-capping unit, ITIC, to develop a cathode interlayer (CIL) material for achieving high power conversion efficiency (PCE) in OSCs is demonstrated. The excellent electron accepting capacity, suitable energy level, and good film-forming ability endow the S-3 molecule with an outstanding electron extraction property. A device with S-3 shows a PCE of 16.6%, which is among the top values in the field of OSCs. More importantly, it is demonstrated that the electrostatic potential difference between the CIL molecule and the polymer donor plays a crucial role in promoting exciton dissociation at the CIL/active layer interface, contributing to additional charge generation; this is crucial for enhancement of the current density. The results of this work not only develop a new design strategy for high-performance CIL, but also demonstrate a reliable approach of density functional theory (DFT) calculation to predict the effect of the CIL chemical structure on exciton dissociation in OSCs.

Inorganic Molecular Clusters with Facile Preparation and Neutral pH for Efficient Hole Extraction in Organic Solar Cells.

The development of electrode interlayers for hole extraction is a great challenge in the field of organic solar cells (OSCs). At present, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is the only solution-processed anode interlayer (AIL) that can be used to achieve power conversion efficiencies (PCEs) over 15% in OSC devices, even though there are several well-known drawbacks in practical applications of PEDOT:PSS. Herein, we use an inorganic molecular cluster (IMC) as the AIL for making highly efficient and large-area OSCs. The IMC possesses several advantages in serving as the AIL, such as neutral pH, excellent optical transmittance, high work function, good film-forming properties, and low cost. OSCs using the IMC can achieve a high PCE of 13.38%, which is superior to the PCE of the PEDOT:PSS device. This is among the few examples of OSC devices with solution-processed and pH neutral AILs showing higher PCE than PEDOT:PSS devices. Ultraviolet photoelectron spectroscopy and electron spin resonance results indicate the formation of inorganic-organic heterojunction, which is crucial for efficient hole extraction. More importantly, the IMC is compatible with printing processing. Using a blade-coated IMC film, we fabricated a large-area OSC of 1 cm2 and a high PCE of 9.5% was achieved.

An N,N'-diethylformamide solvent-induced conversion cascade within a metal-organic framework single crystal.

Crystals of a two-dimensional (2D) metal-organic framework (MOF) [Cd3(BTB)2(DEF)4]·2(DEF)0.5 (1; BTB = benzene-1,3,5-tribenzolate; DEF = N,N'-diethylformamide) immersed in a solution of trans-1,2-bis(4-pyridyl)ethylene (BPEE) yields an interpenetrated three-dimensional (3D) MOF of [Cd3(BTB)2(BPEE)(H2O)2]·(BPEE)·xSol (2). Crystals of MOF 2, in turn, undergo a cascade conversion when immersed in DEF, yielding [Cd3(BTB)2(BPEE)1.8(DEF)0.9(H2O)0.8]·xSol (3a) over 100 seconds and [Cd3(BTB)2(BPEE)2(DEF)2]·xSol (4) after one hour, before finally shuttling back to MOF 1 after six hours.