Cathode Interlayer Research Articles

Solution-processing induced H-aggregate of Perylene-Diimide Zwitterion Exhibiting Compact Molecular Stacking toward Efficient Cathode Modification in Organic Solar Cells.

High-performance organic cathode interlayers (CILs) play a crucial role in the advance of organic solar cells (OSCs). However, organic CILs have exhibited inferior performances to their inorganic counterparts over a long time, due to the inherent shortcoming of poor charge transporting capability. Here, we designed and synthesized a perylene-diimide (PDI) zwitterion PDI-B as high-performance organic CIL for OSCs. We revealed that an obvious H-aggregate of PDI-B was formed during the solution processing, thereby significantly enhancing the charge transporting capability of the CIL. Compared to the classic PDINN, the π-π stacking distance of PDI-B was reduced from 4.2 Å to 3.9 Å, which further facilitated the charge transport. Consequently, PDI-B showed a high conductivity of 1.81×10-3S/m; this is comparable to that of inorganic CILs. The binary OSC showed an elevated PCE of 19.23 %, which is among the highest PCE values for binary OSCs. Benefitting from improved solvent resistance and good compatibility with large-area processing method of PDI-B, the photovoltaic performances of inverted and 1-cm2 OSC were significantly improved. The results from this work provide a new approach of optimizing the condensed structure of PDI film to boost the charge conductivity, opening an avenue to develop high-performance PDI-based CILs.

Thienyltriazine Triamides: Thickness Insensitive Interlayer Materials Featuring Fine-Tuned Optoelectronic and Aggregation Characters for Efficient Organic Solar Cells.

A novel class of thienyltriazine triamides (TTTAs) was facile synthesized and firstly used as cathode interlayers (CILs) for organic solar cells (OSCs). By utilizing different aromatic arms and pendant polar groups, their optoelectronic properties and aggregation behaviors were effectively modulated. The combination of thienyltriazine (TT) core, naphthylamide arm and imidazole pendant group endows TT-N-M with suitable energy levels, intensified work function tunability, higher conductivity, and well-balanced crystallinity and film-forming ability, boosting both the performance and stability of OSCs significantly. Remarkably, the solar cell efficiency remains stable at around 90 % of the optimal efficiency even as the interlayer thickness varied from 5 to 95 nm, demonstrating its insensitivity to thickness. Moreover, TT-N-M exhibits compatibility with various active layer systems, achieving a maximum efficiency of 19.60 % for single-junction solar cell. Its exceptional tolerance to thickness fluctuations and performance establishes a new benchmark for multi-armed CIL-based OSCs, also positioning them among the most high-performing CIL materials documented thus far. This work not only broadens the scope of CIL materials for OSCs but also offers deep insights into design strategies and structure-properties relationships, being beneficial for the future development of more efficient CIL materials for organic optoelectronic applications.

Mitigating interfacial recombination enabling efficient semitransparent organic photovoltaics

Charge recombination at the interface between top electrode and active layer is a substantial current loss pathway in semitransparent organic photovoltaics (STOPVs). Reducing interfacial traps is an effective strategy to mitigate interfacial recombination and promote charge extraction, and thereby improve the power conversion efficiencies (PCEs). Herein, a facile approach of depositing 11-mercapto-undecanoic acid (11-MUA) on zinc oxide (ZnO) cathode interlayer in conventional STOPVs is demonstrated. 11-MUA can form covalent interactions with both ZnO and silver (Ag) and thus can induce the formation of high-quality ultrathin Ag electrode. Compared with that deposited on bare ZnO, the Ag electrode on ZnO/11-MUA shows higher conductivity as well as higher optical transparency. The STOPVs based on ZnO/11-MUA/Ag exhibit 2 orders of magnitude lower surface trap density than the counterparts based on ZnO/Ag. Consequently, 11-MUA simultaneously improves the PCEs from 11.2% to 12.1% and average visible transmittance from 21.6% to 27.0% in the STOPVs. Furthermore, arising from the 11-MUA-modified interface, the thermal stability of STOPVs based on ZnO/11-MUA/Ag is also improved.

Non‐Ionic Perylene‐Diimide Polymer as Universal Cathode Interlayer for Conventional, Inverted, and Blade‐Coated Organic Solar Cells

AbstractAs 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.

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.

Application of isoindigo-based small molecule conjugated electrolytes at interfaces with organic solar cells

Zwitterionic small molecule materials are widely employed in the cathode interface layer of organic solar cells (OSCs). Nevertheless, the exploration of superior cathode interface materials with the objective of enhancing the performance of OSCs remains a significant challenge. Two water/alcohol soluble n-type self-doped small molecule conjugated electrolytes were synthesized using isoindigo as the acceptor unit and triphenylamine (TPA) as the donor unit. Quaternary ammonium salts or pyridine salts were used as the polar side chains. When applied to organic solar cells (OSCs) with PTB7-Th: PC71BM as the active layer, the devices showed improved performance. The power conversion efficiency (PCE) reached 8.59 % (IIDN2TPA) and 8.81 % (IIDPy2TPA), respectively. These results demonstrate the water/alcohol-soluble D-A-D-type small-molecule conjugated electrolytes offer an effective strategy in designing cathode interlayer (CIL) and preparing the high-performance OSCs.

Naphthalene diimide-based cathode interlayer material enables 20.2% efficiency in organic photovoltaic cells

Naphthalene diimide-based cathode interlayer material enables 20.2% efficiency in organic photovoltaic cells

Selenophene-fused Perylene Diimide-Based Cathode Interlayer Enables 19 % Efficiency Binary Organic Solar Cells via Stimulative Charge Extraction.

The cathode interlayer is crucial for the development of organic solar cells (OSCs), but the research on simple and efficient interlayer materials is lagging behind. Here, a donor-acceptor (D-A) typed selenophene-fused perylene diimide (PDI) derivative (SePDI3) is developed as cathode interlayer material (CIM) for OSCs, and a non-fused PDI derivative (PDI3) is used as the control CIM for comparison. Compared to PDI3, SePDI3 shows a stronger self-doping effect and better crystallinity, resulting in better charge transport ability. Furthermore, the interaction between SePDI3 and L8-BO can form an efficient extraction channel, leading to superior charge extraction behavior. Finally, benefitting from significantly enhanced charge transport and extraction capacity, the SePDI3-based device displays a champion PCE of 19.04 % with an ultrahigh fill factor of 81.65 % for binary OSCs based on PM6 : L8-BO active layer, which is one of the top efficiencies reported to date in binary OSCs based novel CIMs. Our work prescribes a facile and effective fusion strategy to develop high-efficiency CIMs for OSCs.

Selenophene‐fused Perylene Diimide‐Based Cathode Interlayer Enables 19 % Efficiency Binary Organic Solar Cells via Stimulative Charge Extraction

AbstractThe cathode interlayer is crucial for the development of organic solar cells (OSCs), but the research on simple and efficient interlayer materials is lagging behind. Here, a donor‐acceptor (D–A) typed selenophene‐fused perylene diimide (PDI) derivative (SePDI3) is developed as cathode interlayer material (CIM) for OSCs, and a non‐fused PDI derivative (PDI3) is used as the control CIM for comparison. Compared to PDI3, SePDI3 shows a stronger self‐doping effect and better crystallinity, resulting in better charge transport ability. Furthermore, the interaction between SePDI3 and L8‐BO can form an efficient extraction channel, leading to superior charge extraction behavior. Finally, benefitting from significantly enhanced charge transport and extraction capacity, the SePDI3‐based device displays a champion PCE of 19.04 % with an ultrahigh fill factor of 81.65 % for binary OSCs based on PM6 : L8‐BO active layer, which is one of the top efficiencies reported to date in binary OSCs based novel CIMs. Our work prescribes a facile and effective fusion strategy to develop high‐efficiency CIMs for OSCs.

Electron Transporting Polymeric Materials with Partial Quaternization for High-Performance Organic Solar Cells.

Efficient cathode interfacial layers (CILs) have become a crucial component of organic solar cells (OSCs). Charge extraction barriers, interfacial trap states, and significant transport resistance may be induced due to the unfavorable cathode interlayer, limiting the device performance. In this study, poly(4-vinylpyridine) is used as the CIL for OSCs, and a new type of CIL named P4VP-I is synthesized through the quaternization strategy. Compared to P4VP, P4VP-I CIL exhibits enhanced conductivity and optimized work function. OSCs employing the P4VP-I ETL demonstrate prolonged carrier lifetime, suppressed charge recombination, and achieve higher power conversion efficiencies (PCE) than the commonly used ETLs such as PFN-Br and Phen-NaDPO.

In‐Situ Removable Solid Additive Optimizing Active Layer and Cathode Interlayer of Organic Solar Cells

AbstractIn situ removable (ISR) solid additive can employ cold sublimation process to optimize active layer morphology for organic solar cells (OSCs), thus remaining unique potential. Herein, a feasible guideline is proposed to discover a new ISR solid additive 1‐bromo‐4‐chlorobenzene (CBB), whose removing time (TR) is between those of reported ISR solid additives 1,4‐dichlorobenzene (DCB) and 1‐chloro‐4‐iodobenzene (CIB). The CBB with a moderate TR is beneficial for affording the optimal active layer morphology and achieving the highest power conversion efficiency (PCE) of 18.58% for D18:L8‐BO binary active layer, as supported by the most efficient exciton splitting, the fastest exciton transfer, and the most balanced carrier transports. Due to the unique ISR ability, DCB, CBB, and CIB are further proposed to optimize the aggregation of PDINN cathode interlayer. Particularly, the CBB‐ and CIB‐treated PDINN interlayers afforded the D18:L8‐BO based binary OSCs with excellent PCEs of 19.38% and 19.26%, along with remarkable fill factors of 80.98% and 81.37%, respectively. The CBB‐ and CIB‐treated PDINN interlayers can suppress non‐radiative recombination of the devices, resulting in higher open‐circuit voltage. This work not only provides an effective approach to flourish ISR solid additives but also expands the application of the ISR solid additive in OSCs.

Indoor organic photovoltaic module with 30.6 % efficiency for efficient wireless power transfer

Organic photovoltaic (OPV) cells possess substantial advantages for indoor applications. However, the underdeveloped cathode interlayer hinders the industrialization of indoor OPV cells. Here, we introduce a phenanthroline derivative with weak nucleophilicity, dicarbolong-phenanthroline (DCP), as the cathode interlayer and comprehensively examine its utilization in indoor OPV cells. DCP exhibits thin depletion region width, which is beneficial for the charge extraction at the interface, thereby contributing to improved power conversion efficiency (PCE). Moreover, DCP presents high adaptability for coating process due to its thickness insensitivity. A DCP-based OPV module is fabricated by blade-coating method, reaching a high maximum output voltage of 4.00 V and a remarkable PCE of 30.6 % at 1000 lux. The OPV module can be successfully applied for efficient wireless power transfer. Furthermore, the DCP-based cell demonstrates outstanding device stability with a lifetime of 32000 hours under indoor lighting. These results demonstrate the promising potential of DCP-based OPV cells for indoor applications.

Ligand‐Triggered MXene Quantum Dots with Tunable Work Function as Anode and Cathode Interlayers for Organic Solar Cells

The interfacial layers of organic optoelectronic devices generally suffer from the problems of difficulty in regulating the work function (WF) and low mobility, which are prone to mismatch of interfacial energy levels and loss of carrier transport energy. Herein, O‐terminated and NH2‐terminated Ti3C2Tx MXenes quantum dots (MQDs) are synthesized to develop efficient O‐MQD hole transfer layer (HTL) and E‐MQD electron transfer layer (ETL) for organic optoelectronic devices of organic solar cells (OSCs) and organic photodetectors (OPDs). It is found that the strong electronic coupling interaction between the surface terminations and matrices enables O‐MQD and E‐MQD with tunable WF and satisfactory conductivity. Consequently, in a binary D18:L8‐BO system, the power conversion efficiencies of the OSC device based on O‐MQD HTL and E‐MQD ETL are 18.62% and 18.15%, respectively. Moreover, the OPDs with O‐MQD HTL and E‐MQD ETL exhibit higher shot‐noise‐limited detectivity (Dshot*) of 1.24 × 1013 and 1.10 × 1013 Jones, respectively, compared to the devices using classic interlayers. These findings provide some insights into the design of advanced dual‐function interlayers for organic optoelectronic devices.

Advancing Detectivity and Stability of Near-Infrared Organic Photodetectors via a Facile and Efficient Cathode Interlayer.

Near-infrared (NIR) organic photodetectors (OPDs) are pivotal in numerous technological applications due to their excellent responsivity within the NIR region. Polyethylenimine ethoxylated (PEIE) has conventionally been employed as an electron transport layer (hole-blocking layer) to suppress dark current (JD) and enhance charge transport. However, the limitations of PEIE in chemical stability, processing conditions, environmental impact, and absorption range have spurred the development of alternative materials. In this study, we introduced a novel solution: a hybrid of sol-gel zinc oxide (ZnO) and N,N'-bis(N,N-dimethylpropan-1-amine oxide)perylene-3,4,9,10-tetracarboxylic diimide (PDINO) as the electron transport layer for NIR-OPDs. Our fabricated OPD exhibited significantly improved responsivity, reduced internal traps, and enhanced charge transfer efficiency. The detectivity, spanning from 400 to 1100 nm, surpassed ∼5 × 1012 Jones, reaching ∼1.1 × 1012 Jones at 1000 nm, accompanied by an increased responsivity of 0.47 A/W. Also, the unpackaged OPD remarkedly demonstrated stable JD and external quantum efficiency (EQE) over 1000 h under dark storage conditions. This innovative approach not only addresses the drawbacks of conventional PEIE-based OPDs but also offers promising avenues for the development of high-performance OPDs in the future.

A new alcohol-soluble dye-tetraphenyl porphyrin functionalized copolymer: Inside the role as a third component/cathode interlayer in halogen-free OSCs

Development and step-by-step characterizations of a novel cationic thiophene based copolymer (P1buP), including ionic phosphonium salt and dye-tetraphenylporphyrin (TPP) moiety in side chains, with an iconic property of solubility in a wide range of polar solvents is reported. Synthesized by using simple, low-cost, and straightforward procedures, the material is used to fabricate completely halogen-free (i.e., from ethanol) ternary organic solar cells (OSCs), in the presence of an alcohol-soluble ionic 3,4-dialkoxythiophene based homopolymer (P2buP) and a serinol-fullerene derivative (C60-Ser). Indeed, thanks to co-sensitization techniques, where multiple dyes harvest different parts of the solar spectrum, the power conversion efficiency of the best final device dramatically increases up to nearly 5.0%, as the light absorption is usually optimized. Additionally, since the use of a cathode interlayer in OSCs also plays a pivotal role in electron extraction and device stability, a possible application of the ionic TPP material as the interfacial layer is also investigated. Furthermore, to improve and optimize the best performing device, a successful post-metalation with Zn of the porphyrin core is carried out, and a ternary OSC (P1buP:P2buP:C60-Ser = 0.33:0.67:1 w/w) is fabricated, resulting in a photoconversion efficiency (PCE) of ∼6.0%.

Revealing the AcOH-Induced Dissolution Mechanism of Alcohol-Soluble Interlayers.

Water/alcohol-soluble cathode interlayers are widely utilized in organic electronic devices. However, the mechanism by which acetic acid (AcOH) facilitates the solubility of neutral cathode interlayers in water/alcohol remains unclear. This paper focuses on the AcOH-induced dissolution mechanism of neutral cathode interlayer materials and establishes quantitative relationships for chemical reactions. It was found that AcOH could react acid-base with the amino groups of PFN or PDIN, resulting in the formation of trace amounts of quaternary ammonium salts, which ultimately enhance the solubility of PFN and PDIN in methanol. Additionally, this study clarifies the debate about the role of neutral cathode interlayers in organic electronic devices: It is primarily the unprotonated groups of water/alcohol-soluble cathode interlayers that play a critical role in interfacial modification rather than the protonated groups produced by postacid reaction, which lays an important theoretical foundation for the development of high-performance interfacial materials.

Tailoring cathode interfaces for high-performance perovskite solar cells using perylene diimide derivatives with ionic diversity

Addressing the global demand for clean energy, perovskite solar cells (PVSCs) have emerged as one of the promising candidates. However, ensuring the stability of PVSCs under various environmental factors remains a critical issue for commercialization. Various ionic functionalities are incorporated into perylene diimide (PDIN) derivatives for altering the work function of aluminum electrodes. Well-known amino N-oxide terminal (PDIN-O), and quaternary ammonium salts (PDIN-Br and PDIN-I) were applied as cathode interlayer (CIL) materials in inverted PVSCs. Within the PDIN derivatives, PDIN-I stands out for its superior electron injection effectiveness, minimized energy losses, and enhanced interface contacts, resulting in an optimal device efficiency of 15.9 %. The research emphasizes the role of efficient interlayer engineering in enhancing layer contact and coverage, inhibiting moisture permeation, and improving device stability. PDIN derivatives emerge as eco-friendly alternatives, offering promising prospects for stable and high-performance inverted PVSCs.

A simply prepared amine oxide molecule as a low work function cathode modifier in organic photovoltaics for harvesting ambient light

Organic photovoltaics (OPV) that possibly convert ambient lights to electric energy are under the spotlight as a power supplier for portable, wearable, and Internet of Things devices. In order to enable the commercialization of ambient light harvesters, it is imperative to design and synthesize device components that offer cost-effectiveness, uniform deposition, and efficient charge extraction/collection. Here, we introduce a simple cathode interlayer (CIL) named EtNO for OPV-based ambient light harvesters. EtNO is designed with a chemical structure that does not require complicated conjugated units and is synthesized through a one-step procedure. EtNO CIL shows efficient reductions in the work function of electrodes, attributed to an interfacial dipole induced from an interaction between amine oxide group of EtNO and electrodes. Furthermore, EtNO forms a uniform layer through solution-processing without deteriorative effects on the surface of photoactive layer in OPVs. Therefore, the OPV with EtNO CIL exhibits an improved performance with an output power density of 79.2 μW cm–2 under light emitting diode illumination (1000 lx, 254 μW cm–2) compared to the device with conventional PDINO CIL (73.1 μW cm–2). Studies conducted on OPVs under halogen light illumination and on large-area devices further demonstrate the significant potential of EtNO as a CIL.

Vacuum-assisted reforming cathode interlayer orientation for efficient and stable perovskite solar cells

The cathode interlayer (CIL) is vital for enhancing the performance of inverted (p-i-n) perovskite solar cells (PSCs) by preventing charge recombination and ion diffusion, thereby achieving superior efficiency. Herein, we introduce cost-effective perylene-diimide (PDI)-based CILs—PDIN-S, PDIN, and PDIN-L—with varying spacer lengths. Among them, PDIN-S exhibits exceptional attributes in thermal evaporation processability, optical absorbance, and charge transfer capabilities. Molecular orientations of PDIN-S are studied through two deposition techniques: vacuum thermal evaporation (VE) and spin-coating (SC). The face-on orientation observed in PDIN-S (VE) confers significant advantages, including improved π–π stacking, efficient charge carrier transfer, reduced interfacial resistance, and inhibited ion diffusion. Furthermore, PDIN-S (VE) also lowers the energy barrier towards cathode, boosting PSC efficiency to 23.82%. Moreover, it enhances both thermal and light stability, maintaining over 90% initial efficiency for 2036 h at 85 °C and sustaining 80% efficiency for 1848 h under continuous illumination. Our application of a straightforward VE method enables the manipulation of molecular orientation, resulting in a concurrent enhancement of efficiency and stability. These findings underscore the potential of PDIN-S as a promising component for highly efficient and stable PSCs.

Zirconium Oxide Doped Organosilica Nanodots as Light- and Charge-Management Cathode Interlayer for Highly Efficient and Stable Inverted Organic Solar Cells.

In this work, it is reported that zirconium oxide (ZrO2) doped organosilica nanodots (OSiNDs: ZrO2) with light- and charge-management properties serve as efficient cathode interlayers for high-efficiency inverted organic solar cells (i-OSCs). ZrO2 doping effectively improves the light harvesting of the active layer, the physical contact between the active layer, as well as the electron collection property by habiting charge recombination loss. Consequently, all devices utilizing the OSiNDs: ZrO2 cathode interlayer exhibit enhanced power conversion efficiency (PCE). Specifically, i-OSCs based on PM6:Y6 and PM6:BTP-eC9 achieve remarkable PCEs of 17.16% and 18.43%, respectively. Furthermore, the PCE of device based on PM6:Y6 maintains over 97.2% of its original value following AM 1.5G illumination (including UV light) at 100mWcm-2 for 600min.