Metal nanowire-based transparent electrode for flexible and stretchable optoelectronic devices.

High-quality transparent electrodes are indispensable components of flexible optoelectronic devices as they guarantee sufficient light transparency and electrical conductivity. Compared to commercial indium tin oxide, metal nanowires are considered ideal candidates as flexible transparent electrodes (FTEs) owing to their superior optoelectronic properties, excellent mechanical flexibility, solution treatability, and higher compatibility with semiconductors. However, certain key challenges associated with material preparation and device fabrication remain for the practical application of metal nanowire-based electrodes. In this review, we discuss state-of-the-art solution-processed metal nanowire-based FTEs and their applications in flexible and stretchable optoelectronic devices. Specifically, the important properties of FTEs and a cost-benefit analysis of existing technologies are introduced, followed by a summary of the synthesis strategy, key properties, and fabrication technologies of the nanowires. Subsequently, we explore the applications of metal-nanowire-based FTEs in different optoelectronic devices including solar cells, photodetectors, and light-emitting diodes. Finally, the current status, future challenges, and emerging strategies in this field are presented.

Intrinsically stretchable organic photovoltaics by redistributing strain to PEDOT:PSS with enhanced stretchability and interfacial adhesion.

Intrinsically stretchable organic photovoltaics have emerged as a prominent candidate for the next-generation wearable power generators regarding their structural design flexibility, omnidirectional stretchability, and in-plane deformability. However, formulating strategies to fabricate intrinsically stretchable organic photovoltaics that exhibit mechanical robustness under both repetitive strain cycles and high tensile strains remains challenging. Herein, we demonstrate high-performance intrinsically stretchable organic photovoltaics with an initial power conversion efficiency of 14.2%, exceptional stretchability (80% of the initial power conversion efficiency maintained at 52% tensile strain), and cyclic mechanical durability (95% of the initial power conversion efficiency retained after 100 strain cycles at 10%). The stretchability is primarily realised by delocalising and redistributing the strain in the active layer to a highly stretchable PEDOT:PSS electrode developed with a straightforward incorporation of ION E, which simultaneously enhances the stretchability of PEDOT:PSS itself and meanwhile reinforces the interfacial adhesion with the polyurethane substrate. Both enhancements are pivotal factors ensuring the excellent mechanical durability of the PEDOT:PSS electrode, which further effectively delays the crack initiation and propagation in the top active layer, and enables the limited performance degradation under high tensile strains and repetitive strain cycles.

Waterproof and ultraflexible organic photovoltaics with improved interface adhesion.

Ultraflexible organic photovoltaics have emerged as a potential power source for wearable electronics owing to their stretchability and lightweight nature. However, waterproofing ultraflexible organic photovoltaics without compromising mechanical flexibility and conformability remains challenging. Here, we demonstrate waterproof and ultraflexible organic photovoltaics through the in-situ growth of a hole-transporting layer to strengthen interface adhesion between the active layer and anode. Specifically, a silver electrode is deposited directly on top of the active layers, followed by thermal annealing treatment. Compared with conventional sequentially-deposited hole-transporting layers, the in-situ grown hole-transporting layer exhibits higher thermodynamic adhesion between the active layers, resulting in better waterproofness. The fabricated 3 µm-thick organic photovoltaics retain 89% and 96% of their pristine performance after immersion in water for 4 h and 300 stretching/releasing cycles at 30% strain under water, respectively. Moreover, the ultraflexible devices withstand a machine-washing test with such a thin encapsulation layer, which has never been reported. Finally, we demonstrate the universality of the strategy for achieving waterproof solar cells.

Flexible Solution-Processed Electron-Transport-Layer-Free Organic Photovoltaics for Indoor Application.

Organic photovoltaics (OPVs) have unique advantages of low weight, mechanical flexibility, and solution processability, which make them exceptionally suitable for integrating low-power Internet of Things devices. However, achieving improved operational stability together with solution processes that are applicable to large-scale fabrication remains challenging. Their major limitation arises due to the instable factors that occur both inside the thick active film and from the ambient environment, which cannot be completely resolved via the current encapsulation techniques used for flexible OPVs. Additionally, thin active layers are highly vulnerable to point defects, which result in low yield rates and impede the laboratory-to-industry translation. In this study, flexible fully solution-processed OPVs with improved indoor efficiency and long-term operational stability than that of conventional OPVs with evaporated electrodes are achieved. Benefiting from the oxygen and water vapor permeation barrier of the spontaneously formed gallium oxide layers on the exposed eutectic gallium-indium surface, fast degradation of the OPVs with thick active layers is prevented, maintaining 93% of its initial Pmax after 5000 min of indoor operation under 1000 lx light-emitting diode (LED) illumination. Additionally, by using the thick active layer, spin-coated silver nanowires could be directly used as bottom electrodes without complicated flattening processes, thereby substantially simplifying the fabrication process and proposing a promising manufacturing technique for devices with high-throughput energy demands.

Surface-Energy-Mediated Interfacial Adhesion for Mechanically Robust Ultraflexible Organic Photovoltaics.

Insufficient interfacial adhesion is a widespread problem across multilayered devices that undermines their reliability. In flexible organic photovoltaics (OPVs), poor interfacial adhesion can accelerate degradation and failure under mechanical deformations due to the intrinsic brittleness and mismatching mechanical properties between functional layers. We introduce an argon plasma treatment for OPV devices, which yields 58% strengthening in interfacial adhesion between an active layer and a MoOX hole transport layer, thus contributing to mechanical reliability. The improved adhesion is attributed to the increased surface energy of the active layer that occurred after the mild argon plasma treatment. The mechanically stabilized interface retards the flexible device degradation induced by mechanical stress and maintains a power conversion efficiency of 94.8% after 10,000 cycles of bending with a radius of 2.5 mm. In addition, a fabricated 3 µm thick ultraflexible OPV device shows excellent mechanical robustness, retaining 91.0% of the initial efficiency after 1000 compressing-stretching cycles with a 40% compression ratio. The developed ultraflexible OPV devices can operate stably at the maximum power point under continuous 1 sun illumination for 500 min with an 89.3% efficiency retention. Overall, we validate a simple interfacial linking strategy for efficient and mechanically robust flexible and ultraflexible OPVs.

Precursor Engineering to Reduce Processing Temperature of ZnO Films for Flexible Organic Solar Cells.

Sol-gel-derived ZnO is one of the most widely used electron-transport layers in inverted organic solar cells. The sol-gel ZnO precursor consists of zinc acetate dehydrate (ZAH) and ethanolamine dissolved in 2-methoxyethanol, where ethanolamine chelates with ZAH, which helps ZAH dissolve in the 2-methoxyethanol. However, an annealing temperature above 120 °C is required to convert the complexes into ZnO. High temperatures are incompatible with flexible plastic substrates such as polyethylene terephthalate. In this work, we report an amine-free recipe consisting of ZAH in methanol to prepare ZnO films. The complex formed in the amine-free precursor solution is methanol-solvated ZAH, which is simpler than that of the amine-containing precursor solution. The temperature required for converting the precursor complex into ZnO was reduced to 90 °C for the amine-free recipe. Low-temperature-processed ZnO can function efficiently as an electron-transport layer in both rigid and flexible inverted nonfullerene solar cells.

Solution-Processed Electron-Transport Layer-free Organic Photovoltaics with Liquid Metal Cathodes.

Flexible, lightweight, and large-area solar cells provide new power supply opportunities in the renewable energy field and facilitate the supply of power to internet-of-things devices and wearable devices. The choice of printing process technologies is a key parameter for such flexible power sources because of their energy-saving process technology and high throughput rate. In addition to selecting the appropriate printing method for the active and charge transport layers, the development of printed electrodes is critical. Numerous printable materials have been developed to replace conventional evaporated top electrodes. However, achieving fully solution-processed organic photovoltaics (OPVs) with power conversion efficiency (PCE) comparable to OPVs with vacuum-deposited transparent and top electrodes is challenging. This is because of the difficulty of forming a uniform interface between the top solution-processed electrode and the active layers while preventing deterioration. In this study, an electron transport layer-free, eutectic gallium-indium (EGaIn) top-cathode strategy was developed and a record PCE of 12.7% in fully solution-processed, flexible OPVs was achieved. Direct coating of EGaIn on the active layer, in a nitrogen atmosphere, is conducive for energy band matching and obtaining physically perfect interfaces without any penetrations or voids. An average PCE of 14.1% and enhanced operating stability, comparable to conventional OPVs, were achieved with indium tin oxide transparent electrodes by eliminating the electron-transport layer. The fully solution-processed flexible OPVs fabricated with the embedded silver nanowire strategy in ultrathin transparent polyimide, achieved an average PCE of 12.7%, representing a promising technique to meet green and high-throughput energy demands.

Ultrathin and Efficient Organic Photovoltaics with Enhanced Air Stability by Suppression of Zinc Element Diffusion.

Ultrathin (thickness less than 10 µm) organic photovoltaics (OPVs) can be applied to power soft robotics and wearable electronics. In addition to high power conversion efficiency, stability under various environmental stresses is crucial for the application of ultrathin OPVs. In this study, the authors realize highly air-stable and ultrathin (≈3 µm) OPVs that possess high efficiency (15.8%) and an outstanding power-per-weight ratio of 33.8 W g-1 . Dynamic secondary-ion mass spectrometry is used to identify Zn diffusion from the electron transport layer zinc oxide (ZnO) to the interface of photoactive layer; this diffusion results in the degradation of the ultrathin OPVs in air. The suppression of the Zn diffusion by a chelating strategy results in stable ultrathin OPVs that maintain 89.6% of their initial efficiency after storage for 1574 h in air at room temperature under dark conditions and 92.4% of their initial efficiency after annealing for 172 h at 85 °C in air under dark conditions. The lightweight and stable OPVs also possess excellent deformability with 87.3% retention of the initial performance after 5000 cycles of a compressing-stretching test with 33% compression.

Robust metal ion-chelated polymer interfacial layer for ultraflexible non-fullerene organic solar cells.

Achieving high power conversion efficiency and good mechanical robustness is still challenging for the ultraflexible organic solar cells. Interlayers simultaneously having good mechanical robustness and good chemical compatibility with the active layer are highly desirable. In this work, we present an interlayer of Zn2+-chelated polyethylenimine (denoted as PEI-Zn), which can endure a maximum bending strain over twice as high as that of ZnO and is chemically compatible with the recently emerging efficient nonfullerene active layers. On 1.3 µm polyethylene naphthalate substrates, ultraflexible nonfullerene solar cells with the PEI-Zn interlayer display a power conversion efficiency of 12.3% on PEDOT:PSS electrodes and 15.0% on AgNWs electrodes. Furthermore, the ultraflexible cells show nearly unchanged power conversion efficiency during 100 continuous compression-flat deformation cycles with a compression ratio of 45%. At the end, the ultraflexible cell is demonstrated to be attached onto the finger joint and displays reversible current output during the finger bending-spreading.

Tailoring vertical phase distribution of quasi-two-dimensional perovskite films via surface modification of hole-transporting layer.

Vertical phase distribution plays an important role in the quasi-two-dimensional perovskite solar cells. So far, the driving force and how to tailor the vertical distribution of layer numbers have been not discussed. In this work, we report that the vertical distribution of layer numbers in the quasi-two-dimensional perovskite films deposited on a hole-transporting layer is different from that on glass substrate. The vertical distribution could be explained by the sedimentation equilibrium because of the colloidal feature of the perovskite precursors. Acid addition will change the precursors from colloid to solution that therefore changes the vertical distribution. A self-assembly layer is used to modify the acidic surface property of the hole-transporting layer that induces the appearance of desired vertical distribution for charge transport. The quasi-two-dimensional perovskite cells with the surface modification display a higher open-circuit voltage and a higher efficiency comparing to reference quasi-two-dimensional cells.

A low-temperature carbon electrode with good perovskite compatibility and high flexibility in carbon based perovskite solar cells.

A low-temperature carbon electrode with good perovskite compatibility is employed in hole-transport-material free perovskite solar cells, and a champion power conversion efficiency (PCE) of 11.7% is obtained. The PCE is enhanced to 14.55% by an interface modification of PEDOT:PSS. The application of this carbon on ITO/PEN substrates is also demonstrated.

12.5% Flexible Nonfullerene Solar Cells by Passivating the Chemical Interaction Between the Active Layer and Polymer Interfacial Layer.

Nonfullerene (NF) organic solar cells (OSCs) have been attracting significant attention in the past several years. It is still challenging to achieve high-performance flexible NF OSCs. NF acceptors are chemically reactive and tend to react with the low-temperature-processed low-work-function (low-WF) interfacial layers, such as polyethylenimine ethoxylated (PEIE), which leads to the "S" shape in the current-density characteristics of the cells. In this work, the chemical interaction between the NF active layer and the polymer interfacial layer of PEIE is deactivated by increasing its protonation. The PEIE processed from aqueous solution shows more protonated N+ than that processed from isopropyl alcohol solution, observed from X-ray photoelectron spectroscopy. NF solar cells (active layer: PCE-10:IEICO-4F) with the protonated PEIE interfacial layer show an efficiency of 13.2%, which is higher than the reference cells with a ZnO interlayer (12.6%). More importantly, the protonated PEIE interfacial layer processed from aqueous solution does not require a further thermal annealing treatment (only processing at room temperature). The room-temperature processing and effective WF reduction enable the demonstration of high-performance (12.5%) flexible NF OSCs.

Flexible and Transparent Organic-Inorganic Hybrid Thermoelectric Modules.

Light-weight, mechanically flexible, transparent thermoelectric modules are promising as portable and easy-to-integrate energy sources. Here, we demonstrate flexible, transparent thermoelectric modules by using a conducting polymer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as the p-type leg and indium tin oxide (ITO)-PEDOT:PSS as the n-type leg. Main observations include the following: (1) the bilayer combination of ITO-PEDOT:PSS (PEDOT:PSS coated on top of the ITO) displays a negative Seebeck coefficient ( S) and the value is similar to that of the ITO single layer; (2) the S value of the ITO-PEDOT:PSS is almost not dependent on the area ratio of the stacked PEDOT:PSS and ITO; and (3) the conducting polymer PEDOT:PSS deposition on top of ITO helps the ITO not to generate cracks during bending, which enhances the mechanical flexibility of the ITO. On the basis of these observations, thermoelectric modules with eight pairs of junctions are fabricated and the thermoelectric modules' Δ V/Δ T (modules' generated thermovoltage per temperature difference) is nearly the addition of S values of all legs. Thermoelectric modules show good mechanical flexibility and air stability. Applications of thermoelectric modules have also been demonstrated to produce thermovoltage via the temperature difference produced by a human hand or warm water.

Vertical Stratification Engineering for Organic Bulk-Heterojunction Devices.

High-efficiency organic solar cells (OSCs) can be produced through optimization of component molecular design, coupled with interfacial engineering and control of active layer morphology. However, vertical stratification of the bulk-heterojunction (BHJ), a spontaneous activity that occurs during the drying process, remains an intricate problem yet to be solved. Routes toward regulating the vertical separation profile and evaluating the effects on the final device should be explored to further enhance the performance of OSCs. Herein, we establish a connection between the material surface energy, absorption, and vertical stratification, which can then be linked to photovoltaic conversion characteristics. Through assessing the performance of temporary, artificial vertically stratified layers created by the sequential casting of the individual components to form a multilayered structure, optimal vertical stratification can be achieved. Adjusting the surface energy offset between the substrate results in donor and acceptor stabilization of that stratified layer. Further, a trade-off between the photocurrent generated in the visible region and the amount of donor or acceptor in close proximity to the electrode was observed. Modification of the substrate surface energy was achieved using self-assembled small molecules (SASM), which, in turn, directly impacted the polymer donor to acceptor ratio at the interface. Using three different donor polymers in conjunction with two alternative acceptors in an inverted organic solar cell architecture, the concentration of polymer donor molecules at the ITO (indium tin oxide)/BHJ interface could be increased relative to the acceptor. Appropriate selection of SASM facilitated a synchronized enhancement in external quantum efficiency and power conversion efficiencies over 10.5%.

Suppressing generation of iodine impurity via an amidine additive in perovskite solar cells.

In perovskite solar cells, I- tends to oxidize to I2 due to its low redox potential. The generated I2 has been proved to be detrimental to device performance. Herein, for the first time, an amidine DBU is introduced as an additive into the precursor of the perovskite layer. The reductive DBU can suppress the formation of iodine impurity, resulting in a highly pure perovskite polycrystalline film. The efficiency and stability of the perovskite solar cells are thus improved.

A green route to a novel hyperbranched electrolyte interlayer for nonfullerene polymer solar cells with over 11% efficiency.

A novel environmentally-friendly hyperbranched electrolyte PNSO3Na organic interfacial layer has been synthesized; this can tune the interfacial energy alignment and induce the upper active layer to form a bi-continuous nano-micro phase separation face-on orientation. Based on a PBDB-T:ITIC active layer, the device with a ZnO/PNSO3Na ETL exhibits a high efficiency of 11.2%.

Stacking Sequence and Acceptor Dependence of Photocurrent Spectra and Photovoltage in Organic Two-Junction Devices.

Both single-junction and tandem organic photovoltaic cells have been well developed. A tandem cell contains two junctions with a charge recombination layer (CRL) inserted between the two junctions. So far, there is no detailed report on how the device will perform that contains two junctions but without a CRL in between. In this work, we report the photocurrent spectra and photovoltage output of the devices that contains two bulk-heterojunctions (BHJ) stacked directly on top of each other without a CRL. The top active layer is prepared by transfer printing. The photocurrent response spectra and photovoltage are found to be sensitive to stacking sequence and the selection of electron acceptors. The open-circuit voltage of the devices (up to 1.09 V) can be higher than the devices containing either junction layer. The new phenomenon in the new device architecture increases the versatility of the optoelectronic devices based on organic semiconductors.

Universal Strategy To Reduce Noise Current for Sensitive Organic Photodetectors.

Low noise current is critical for achieving high-detectivity organic photodetectors. Inserting charge-blocking layers is an effective approach to suppress the reverse-biased dark current. However, in solution-processed organic photodetectors, the charge-transport material needs to be dissolved in solvents that do not dissolve the underneath light-absorbing layer, which is not always possible for all kinds of light-absorbing materials developed. Here, we introduce a universal strategy of transfer-printing a conjugated polymer, poly(3-hexylthiophene) (P3HT), as the electron-blocking layer to realize highly sensitive photodetectors. The transfer-printed P3HT layers substantially and universally reduced the reverse-biased dark current by about 3 orders of magnitude for various photodetectors with different active layers. These photodetectors can detect the light signal as weak as several picowatts per square centimeter, and the device detectivity is over 1012 Jones. The results suggest that the strategy of transfer-printing P3HT films as the electron-blocking layer is universal and effective for the fabrication of sensitive organic photodetectors.

Nonreduction-Active Hole-Transporting Layers Enhancing Open-Circuit Voltage and Efficiency of Planar Perovskite Solar Cells.

Inverted planar perovskite solar cells using poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as the hole-transporting layer (HTL) are very attractive because of their low-temperature and easy processing. However, the planar cells with the PEDOT:PSS HTL typically display lower open-circuit voltage (VOC) (about 0.90 V) than that of devices with TiO2-based conventional structure (1.0-1.1 V). The underlying reasons are still not clear. In this work, we report the PEDOT:PSS that is intrinsically p-doped can be chemically reduced by methylamine iodide (MAI) and MAPbI3. The reaction reduces the work function (WF) of PEDOT:PSS, which suppresses the efficient hole collection and yields lower VOC. To overcome this issue, we adopt undoped semiconducting polymers that are intrinsically nonreduction-active (NRA) as the HTL for inverted planar perovskite solar cells. The cells display enhanced VOC from 0.88 ± 0.04 V (PEDOT:PSS HTL, reference cells) to 1.02 ± 0.03 V (P3HT HTL) and 1.04 ± 0.03 V (PTB7 and PTB-Th HTL). The power conversion efficiency (PCE) of the devices with these NRA HTL reaches about 17%.

Efficient Colorful Perovskite Solar Cells Using a Top Polymer Electrode Simultaneously as Spectrally Selective Antireflection Coating.

Organometal halide perovskites have shown excellent optoelectronic properties and have been used to demonstrate a variety of semiconductor devices. Colorful solar cells are desirable for photovoltaic integration in buildings and other aesthetically appealing applications. However, the realization of colorful perovskite solar cells is challenging because of their broad and large absorption coefficient that commonly leads to cells with dark-brown colors. Herein, for the first time, we report a simple and efficient strategy to achieve colorful perovskite solar cells by using the transparent conducting polymer (poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate), PEDOT:PSS) as a top electrode and simultaneously as an spectrally selective antireflection coating. Vivid colors across the visible spectrum are attained by engineering optical interference effects among the transparent PEDOT:PSS polymer electrode, the hole-transporting layer and the perovskite layer. The colored perovskite solar cells display power conversion efficiency values from 12.8 to 15.1% (from red to blue) when illuminated from the FTO glass side and from 11.6 to 13.8% (from red to blue) when illuminated from the PEDOT:PSS side. The new approach provides an advanced solution for fabricating colorful perovskite solar cells with easy processing and high efficiency.