An n-n Heterojunction Configuration for Efficient Electron Transport in Organic Photovoltaic Devices

Selective electron transport and extraction are essential to the operation of photovoltaic devices. Electron transport layer (ETL) is therefore critical to organic photovoltaics (OPV). Herein, an ETL configuration is presented comprising a solution-processed n-n organic heterojunction to enhance electron transport and hole blocking, and boost power conversion efficiency (PCE) in OPV. Specifically, the n-n heterojunction is constructed by stacking a narrow-band n-type conjugated polymer layer (PNDIT-F3N) and a wide-band n-type conjugated molecule layer (Phen-NaDPO). Based on the ultraviolet photoelectron spectroscopy measurement and numerical simulation of current density-voltage characteristics, the formation of the built-in potential is investigated. In three OPVs with different active layers, substantial improvements are observed in performance following the introduction of this ETL configuration. The performance enhancement arises from the combination of selective carrier transport properties and reduced recombination. Another contributing factor is the good film-forming quality of the new ETL configuration, where the surface energies of the related materials are well-matched. The n-n organic heterojunction represents a viable and promising ETL construction strategy for efficient OPV devices.     

Durable Ultraflexible Organic Photovoltaics with Novel Metal‐Oxide‐Free Cathode

Flexible and stretchable organic photovoltaics (OPVs) are promising as a power source for wearable devices with multifunctions ranging from sensing to locomotion. Achieving mechanical robustness and high power conversion efficiency for ultraflexible OPVs is essential for their successful application. However, it is challenging to simultaneously achieve these features by the difficulty to maintain stable performance under a microscale bending radius. Ultraflexible OPVs are proposed by employing a novel metal‐oxide‐free cathode that consists of a printed ultrathin metallic transparent electrode and an organic electron transport layer to achieve high electron‐collecting capabilities and mechanical robustness. In fact, the proposed ultraflexible OPV achieves a power conversion efficiency of 9.7% and durability with 74% efficiency retention after 500 cycles of deformation at 37% compression through buckling. The proposed approach can be applied to active layers with different morphologies, thus suggesting its universality and potential for high‐performance ultraflexible OPV devices.     

Insights into charge balance and its limitations in simplified phosphorescent organic light-emitting devices

Simplified phosphorescent organic light-emitting device (PHOLED), which utilizes only two organic layers, showed record-high efficiency when first introduced. It is quite surprising that this device can have such high efficiency without the use of complex carrier and exciton confinement layers that are common in the state-of-the-art PHOLEDs nowadays. Therefore, it is important to understand how good charge balance is in simplified PHOLED and why. In this work, we study the effects of altering charge balance in simplified PHOLED through means of changing layer thickness in the hole transport layer (HTL) and electron transport layer (ETL) as well as intentionally doping hole and electron traps in the HTL and ETL, respectively, on device efficiency. The results show that when using high carrier mobility charge transport materials, changing layer thickness does not impact charge balance appreciably. On the other hand, introducing charge traps in a thin layer within the HTL or ETL can, in comparison, influence charge balance more significantly, and proves to be a more effective approach for studying the factors limiting charge balance in these devices. The results reveal that simplified PHOLEDs are generally hole-rich, and that the leakage of electrons to the counter electrode is also a major mechanism behind the poor charge balance and efficiency loss in these devices. In order to optimize charge balance in simplified PHOLED, it is important to reduce hole transport in the device so that e-h ratio can be brought closer to unity, as well as eliminate electron leakage. Finally, we show that by simply using an electron blocking HTL, the efficiency of the device can be enhanced by as much as 25%, representing the highest reported for simplified PHOLEDs.     

Solution‐Processed,Alkali Metal‐Salt‐Doped,Electron‐Transport Layers for High‐Performance Phosphorescent Organic Light‐Emitting Diodes

High‐performance, blue, phosphorescent organic light‐emitting diodes (PhOLEDs) are achieved by orthogonal solution‐processing of small‐molecule electron‐transport material doped with an alkali metal salt, including cesium carbonate (Cs₂CO₃) or lithium carbonate (Li₂CO₃). Blue PhOLEDs with solution‐processed 4,7‐diphenyl‐1,10‐phenanthroline (BPhen) electron‐transport layer (ETL) doped with Cs₂CO₃ show a luminous efficiency (LE) of 35.1 cd A^?1 with an external quantum efficiency (EQE) of 17.9%, which are two‐fold higher efficiency than a BPhen ETL without a dopant. These solution‐processed blue PhOLEDs are much superior compared to devices with vacuum‐deposited BPhen ETL/alkali metal salt cathode interfacial layer. Blue PhOLEDs with solution‐processed 1,3,5‐tris(m‐pyrid‐3‐yl‐phenyl)benzene (TmPyPB) ETL doped with Cs₂CO₃ have a luminous efficiency of 37.7 cd A^?1 with an EQE of 19.0%, which is the best performance observed to date in all‐solution‐processed blue PhOLEDs. The results show that a small‐molecule ETL doped with alkali metal salt can be realized by solution‐processing to enhance overall device performance. The solution‐processed metal salt‐doped ETLs exhibit a unique rough surface morphology that facilitates enhanced charge‐injection and transport in the devices. These results demonstrate that orthogonal solution‐processing of metal salt‐doped electron‐transport materials is a promising strategy for applications in various solution‐processed multilayered organic electronic devices.     

Solution processed WO3 layer for the replacement of PEDOT:PSS layer in organic photovoltaic cells

Tungsten oxide layer is formed uniformly by a sol–gel technique on top of indium tin oxide as a neutral and photo-stable hole extraction layer (HEL). The solution processed tungsten oxide layer (sWO₃) is fully characterized by UV–Vis, XPS, UPS, XRD, AFM, and TEM. Optical transmission of ITO/sWO₃ substrates is nearly identical to ITOs. In addition, the sWO₃ layer induces nearly ohmic contact to P3HT as PEDOT:PSS layer does, which is determined by UPS measurement. In case that an optimized thickness (～10 nm) of the sWO₃ layer is incorporated in the organic photovoltaic devices (OPVs) with a structure of ITO/sWO₃/P3HT:PCBM/Al, the power conversion efficiency (PCE) is 3.4%, comparable to that of devices utilizing PEDOT:PSS as HEL. Furthermore, the stability of OPV utilizing sWO₃ is significantly enhanced due to the air- and photo-stability of the sWO₃ layer itself. PCEs are decreased to 40% and 0% of initial values, when PEDOT:PSS layers are exposed to air and light for 192 h, respectively. In contrast, PCEs are maintained to 90% and 87% of initial PCEs respectively, when sWO₃ layers are exposed to the same conditions. Conclusively, we find that solution processed tungsten oxide layers can be prepared easily, act as an efficient hole extraction layer, and afford a much higher stability than PEDOT:PSS layers.     

Plasma-tolerant structure for organic light-emitting diodes with aluminum cathodes fabricated by DC magnetron sputtering: Using a Li-doped electron transport layer

We fabricate aluminum cathodes that are almost free from plasma damage by DC magnetron sputtering for organic light-emitting diodes (OLEDs). While sputtering is widely known to have numerous advantages over conventional evaporation for mass production of devices, it can cause serious damage to organic layers. In this report, we fabricate devices that are free from plasma damage by introducing a 1%-Li-doped electron transport layer (ETL). The difference of external electroluminescence quantum efficiency between OLEDs with the structure ITO/α-NPD/ETL/Al (where ITO is indium tin oxide and α-NPD is N,N′-di(1-naphthyl)-N,N′-diphenylbenzidine) with Al cathodes deposited by conventional evaporation or sputtering is 0.1%, and their driving voltage is identical. We find that the Li-doped ETL should be thicker than 40 nm. Analysis of the depth profile of the ETL by time-of-flight secondary ion mass spectrometry indicates that considerable damage from sputtering extended to a depth of approximately 30 nm, suggesting that high-energy particles penetrated about 30 nm into the ETL.     

Enhancing the photovoltaic performance with two similar structure polymers as donors by broadening the absorption spectrum and optimizing the molecular arrangement

Ternary organic photovoltaics (OPVs) were fabricated with two polymers (PM6 and D18) as the donor and the fullerene-free small molecule Y6 as the acceptor in an inverted structure. The blueshifted absorption spectrum of neat D18 relative to neat PM6 can enable harvesting of more short and medium wavelength photons in the ternary photoactive layer, which is beneficial to increasing the short-circuit current density (J_SC). The enhancement of the open-circuit voltage (V_OC) of the ternary OPVs can be explained by the deeper HOMO level of D18 than that of PM6, which is beneficial to broadening the energy bandgap. In addition, the combination of the cascade LUMO levels among D18, PM6 and Y6 and the enhanced crystallinity can lead to more efficient exciton dissociation and charge transport within the ternary films. As a result, the power conversion efficiency of the optimize ternary OPV is 15.85%, which is higher than those of the PM6:Y6- and D18:Y6-base binary OPVs (PCEs of 14.70% and 14.95%, respectively). The results indicate that ternary OPVs with a blend of two similar chemical structure polymers as the donor could achieve high performance by broadening the light spectrum and optimizing the phase separation and crystallinity.     

Enhanced photocurrent and stability of organic solar cells using solution-based TS-CuPc interfacial layer

Copper phthalocyanine-3,4′,4″,4‴ tetra-sulfonated acid tetrasodium salt (TS-CuPc) are promising interfacial materials for organic photovoltaics (OPVs) because of their electrical properties, solution process ability and stability. In this article, we report the fabrication of poly(3-hexylthiophene):[6,6]-phenyl-C61 butyric acid methyl ester (P3HT:PCBM) OPV devices incorporating solution-based TS-CuPc as electron transport layers that show promising enhancements of the device photocurrent and stability. We also discuss the impact of the mechanism of Photochemical and photophysical behavior and all parameters on device performance as well as the ambient degradation of these devices. In these results we showed charge extraction improvement by the use of the TS-CuPc.     

Insights into Fullerene Passivation of SnO2 Electron Transport Layers in Perovskite Solar Cells

Interfaces between the photoactive and charge transport layers are crucial for the performance of perovskite solar cells. Surface passivation of SnO₂ as electron transport layer (ETL) by fullerene derivatives is known to improve the performance of n–i–p devices, yet organic passivation layers are susceptible to removal during perovskite deposition. Understanding the nature of the passivation is important for further optimization of SnO₂ ETLs. X‐ray photoelectron spectroscopy depth profiling is a convenient tool to monitor the fullerene concentration in passivation layers at a SnO₂ interface. Through a comparative study using [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) and [6,6]‐phenyl‐C₆₁‐butyric acid (PCBA) passivation layers, a direct correlation is established between the formation of interfacial chemical bonds and the retention of passivating fullerene molecules at the SnO₂ interface that effectively reduces the number of defects and enhances electron mobility. Devices with only a PCBA‐monolayer‐passivated SnO₂ ETL exhibit significantly improved performance and reproducibility, achieving an efficiency of 18.8%. Investigating thick and solvent‐resistant C₆₀ and PCBM‐dimer layers demonstrates that the charge transport in the ETL is only improved by chemisorption of the fullerene at the SnO₂ surface.     

具有新型电子传输层的有机薄膜电致发光器件

将8-hydroxy-quinolinato lithium(Liq)掺入4'7-diphyenyl-1,10-phenanthroline(BPhen)作为n型电子传输层(ETL),将tetrafluro-tetracyano-quinodimethane(F4-TCNQ)掺入4,4',4"-tris(3-methylphenylphenylamono)triphenylamine(m-MTDATA)作为p型空穴传输层(HTL),制作了p-i-n结构有机电致发光器件.为了检验传输层传导率的改善情况,制备了一系列单一空穴器件和单一电子器件.在引入BPhen:33wt% Liq作为ETL后,x% F4-TCNQ:m-MTDATA作为HTL后,器件的电流和功率效率明显改善.与控制器件(未掺杂)相比,性能最佳的掺杂器件的电流及功率效率分别提高了51%和89%,电压下降了29%.这是由于传输层传导能力的提高使得载流子在发光区域达到有效平衡.     

具有新型电子传输层的有机薄膜电致发光器件

将8-hydroxy-quinolinato lithium(Liq)掺入4'7-diphyenyl-1,10-phenanthroline(BPhen)作为n型电子传输层(ETL),将tetrafluro-tetracyano-quinodimethane(F4-TCNQ)掺入4,4',4"-tris(3-methylphenylphenylamono)triphenylamine(m-MTDATA)作为p型空穴传输层(HTL),制作了p-i-n结构有机电致发光器件.为了检验传输层传导率的改善情况,制备了一系列单一空穴器件和单一电子器件.在引入BPhen:33wt% Liq作为ETL后,x% F4-TCNQ:m-MTDATA作为HTL后,器件的电流和功率效率明显改善.与控制器件(未掺杂)相比,性能最佳的掺杂器件的电流及功率效率分别提高了51%和89%,电压下降了29%.这是由于传输层传导能力的提高使得载流子在发光区域达到有效平衡.     

Polymer‐Modified ZnO Nanoparticles as Electron Transport Layer for Polymer‐Based Solar Cells

The optimization of interfacial layer plays a critical role in the ultimate use of polymer‐based solar cells (PSCs). By introducing an insulating polymer, polystyrene (PS), into the ZnO nanoparticles (NPs) with large particle size, an electron transport layer (ETL) with a thickness of more than 130 nm is produced. The doping of PS not only improves the film quality of ZnO NPs to generate a denser, smoother, and more uniform ETL, but also increases the contact properties between the hydrophilic ZnO and hydrophobic active layer. In comparison to control devices, the power conversion efficiencies (PCEs), short circuit current densities, and fill factors of PSCs with the PS‐modified ETL for a typical fullerene system PTB7‐Th:PC₇₁BM and, also, a nonfullerene system PBDB‐T:ITIC are increased, with PCEs from 8.49% to 9.54% and 10.03% to 11.05%, respectively. The reproducibility, mechanical endurance, and ambient stability of the PSCs with the PS‐modified ZnO NP ETL are significantly improved. The combination of the insulating polymer and ZnO NPs provides a simple, low‐cost way to realize the commercialization of high performance, flexible PSCs.     

Inter-Flake Quantum Transport of Electrons and Holes in Inkjet-Printed Graphene Devices

2D materials have unique structural and electronic properties with potential for transformative device applications. However, such devices are usually bespoke structures made by sequential deposition of exfoliated 2D layers. There is a need for scalable manufacturing techniques capable of producing high-quality large-area devices comprising multiple 2D materials. Additive manufacturing with inks containing 2D material flakes is a promising solution. Inkjet-printed devices incorporating 2D materials have been demonstrated, however there is a need for greater understanding of quantum transport phenomena as well as their structural properties. Experimental and theoretical studies of inkjet-printed graphene structures are presented. Detailed electrical and structural characterization is reported and explained by comparison with transport modeling that include inter-flake quantum tunneling transport and percolation dynamics. The results reveal that the electrical properties are strongly influenced by the flakes packing fraction and by complex meandering electron trajectories, which traverse several printed layers. Controlling these trajectories is essential for printing high-quality devices that exploit the properties of 2D materials. Inkjet-printed graphene is used to make a field effect transistor and Ohmic contacts on an InSe phototransistor. This is the first time that inkjet-printed graphene has successfully replaced single layer graphene as a contact material for 2D metal chalcogenides.     

Over 1.1 eV Workfunction Tuning of Cesium Intercalated Metal Oxides for Functioning as Both Electron and Hole Transport Layers in Organic Optoelectronic Devices

In this paper, over 1.1 eV continuous tuning of metal oxides workfunction is realized by cesium intercalation, making the metal oxide function as both electron transport layer and hole transport layer in organic optoelectronic devices. The demonstrated metal oxides are commonly used molybdenum oxide and vanadium oxide. The proposed approach of synthesizing cesium intercalated metal oxides has interesting properties of room‐temperature, ambient atmosphere, water free and solution process, favoring the formation of metal oxides as carrier transport layers at different regions in multilayered devices and large scale fabrication of organic optoelectronics at low cost. Besides the wide range of controllable workfunction adjustment, band structures, and electrical properties are investigated in detail, to understand the effects of cesium intercalation on metal oxides. The device results show that, using the proposed cesium intercalation approach, each of the two investigated metal oxides can function as both ETL and HTL in organic solar cells and organic light emitting diodes with very good device performances. Consequently, with the interesting properties in film synthesis, the proposed cesium intercalated metal oxides can achieve continuously workfunction tuning over a large range and contribute to evolution of the simple route for fabricating high performance organic optoelectronic devices.     

Blade Coating of Alloy as Top Electrodes for Efficient All-Printed Organic Photovoltaics

All printing of organic photovoltaics (OPVs) including the top electrode is highly desirable for achieving cost-effective, high-throughput, and large-area photovoltaic manufacturing. Here, the printing of a low-melting-point alloy as top electrodes in OPVs via blade coating is investigated. The Field's metal (FM) with the melting point of 62 °C is adopted for the top electrodes, because FM can be printed under moderate temperatures without harming the active layers while remaining solid state under solar irradiation. The correlations between the processing parameters and properties of the blade-coated electrodes are elucidated. OPVs based on the D18:Y6 active layer and blade-coated FM electrodes achieve a highest power conversion efficiency of 17.28%. The OPVs with FM-electrode demonstrate much higher thermal stability than that of the Ag-electrode devices. All-printed OPVs, in which the FM electrode is blade coated and the other layers are prepared by flexible micro-comb printing, exhibit an efficiency of 16.07%. The results represent the records of evaporation-free and all-printed OPVs, demonstrating that printing FM as OPV electrodes is a cost-effective and time-saving strategy to substitute the vacuum-evaporated metals, as well as a feasible route toward high-performance all-printed OPVs.     

High Performance Roll‐to‐Roll Produced Fullerene‐Free Organic Photovoltaic Devices via Temperature‐Controlled Slot Die Coating

Solution‐processed organic photovoltaics (OPVs) have continued to show their potential as a low‐cost power generation technology; however, there has been a significant gap between device efficiencies fabricated with lab‐scale techniques—i.e., spin coating—and scalable deposition methods. Herein, temperature‐controlled slot die deposition is developed for the photoactive layer of OPVs. The influence of solution and substrate temperatures on photoactive films and their effects on power conversion efficiency (PCE) in slot die coated OPVs using a 3D printer‐based slot die coater are studied on the basis of device performance, molecular structure, film morphology, and carrier transport behavior. These studies clearly demonstrate that both substrate and solution temperatures during slot die coating can influence device performance, and the combination of hot substrate (120 °C) and hot solution (90 °C) conditions result in mechanically robust films with PCE values up to 10.0% using this scalable deposition method in air. The efficiency is close to that of state‐of‐the‐art devices fabricated by spin coating. The deposition condition is translated to roll‐to‐roll processing without further modification and results in flexible OPVs with PCE values above 7%. The results underscore the promising potential of temperature‐controlled slot die coating for roll‐to‐roll manufacturing of high performance OPVs.     

Ambient Layer‐by‐Layer ZnO Assembly for Highly Efficient Polymer Bulk Heterojunction Solar Cells

The use of metal oxide interlayers in polymer solar cells has great potential because metal oxides are abundant, thermally stable, and can be used in flexible devices. Here, a layer‐by‐layer (LbL) protocol is reported as a facile, room‐temperature, solution‐processed method to prepare electron transport layers from commercial ZnO nanoparticles and polyacrylic acid (PAA) with a controlled and tunable porous structure, which provides large interfacial contacts with the active layer. Applying the LbL approach to bulk heterojunction polymer solar cells with an optimized ZnO layer thickness of ≈25 nm yields solar cell power‐conversion efficiencies (PCEs) of ≈6%, exceeding the efficiency of amorphous ZnO interlayers formed by conventional sputtering methods. Interestingly, annealing the ZnO/PAA interlayers in nitrogen and air environments in the range of 60–300 °C reduces the device PCEs by almost 20% to 50%, indicating the importance of conformational changes inherent to the PAA polymer in the LbL‐deposited films to solar cell performance. This protocol suggests a new fabrication method for solution‐processed polymer solar cell devices that does not require postprocessing thermal annealing treatments and that is applicable to flexible devices printed on plastic substrates.     

Inorganic Electron Transport Materials in Perovskite Solar Cells

In the past decade, the perovskite solar cell (PSC) has attracted tremendous attention thanks to the substantial efforts in improving the power conversion efficiency from 3.8% to 25.5% for single-junction devices and even perovskite-silicon tandems have reached 29.15%. This is a result of improvement in composition, solvent, interface, and dimensionality engineering. Furthermore, the long-term stability of PSCs has also been significantly improved. Such rapid developments have made PSCs a competitive candidate for next-generation photovoltaics. The electron transport layer (ETL) is one of the most important functional layers in PSCs, due to its crucial role in contributing to the overall performance of devices. This review provides an up-to-date summary of the developments in inorganic electron transport materials (ETMs) for PSCs. The three most prevalent inorganic ETMs (TiO₂, SnO_2, and ZnO) are examined with a focus on the effects of synthesis and preparation methods, as well as an introduction to their application in tandem devices. The emerging trends in inorganic ETMs used for PSC research are also reviewed. Finally, strategies to optimize the performance of ETL in PSCs, effects the ETL has on J–V hysteresis phenomenon and long-term stability with an outlook on current challenges and further development are discussed.     

Monolayer Hexagonal Boron Nitride: An Efficient Electron Blocking Layer in Organic Photovoltaics

In this study, monolayer hexagonal boron nitride (h-BN) grown via chemical vapor deposition (CVD) as an effective electron blocking layer (EBL) for the organic photovoltaics (OPVs) is proposed. Unexpectedly, it is found that h-BN can replace the commonly used hole transport layers (HTLs), i.e., molybdenum trioxide (MoO₃) and poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) in an inverted device architecture. Here, a wet-transfer technique is employed and a single layer of h-BN on top of the PV2000:PC₆₀BM blend is successfully placed. Analysis of the bandgap diagram shows that the monolayer h-BN makes smaller barrier for holes but significantly larger barrier for electrons. This makes the h-BN effective in blocking electrons while creating a possible path for the holes through tunneling to the electrode, due to the low energy barrier at the PV2000/h-BN interface. Using h-BN as an EBL, efficient inverted OPVs are achieved with an average solar-to-power conversion efficiency of 6.13%, which is comparable with that of reference devices based on MoO₃ (7.3%) and PEDOT:PSS (7.6%) as HTLs. Interestingly, the devices with h-BN shows great light-soak stability. The study reveals that the monolayer h-BN grown by CVD could be an effective alternative EBL for the fabrication of efficient, lightweight, and stable OPVs.     

Analysis of electron traps formed in organic films with a sputtered cathode

To understand why performance degradation is reduced for sputtered cathodes on organic devices when the electron transport layer (ETL) is doped with Li, we analyze electron-only devices using the thermally stimulated current (TSC) technique and modeling of temperature-dependent current–voltage characteristics with a trapped-charge-limited current (TCLC) model. The combined results suggest that the trap density measured by TSC might also include a portion of the density of the hopping sites in the lowest unoccupied molecular orbital levels, which contributes to charge transport. Compared to undoped devices, doped devices maintain a high density of hopping sites even when the Al is sputtered. We propose that the reduced effect of sputtering on electron injection and transport properties is because radical anions of Alq₃ might still be formed by the strong reducer Li even if the organic material is partially damaged. An additional TSC peak and increased driving voltage for doped tris(8-hydroxyquinoline)aluminum (Alq₃) as an ETL with a sputtered cathode suggests the formation of new traps possibly because of damage even though the transport is better compared to the undoped device. Such traps are not found in doped bathophenanthroline (Bphen) as an ETL, which shows no change in driving voltage.