Reducible‐Shell‐Derived Pure‐Copper‐Nanowire Network and Its Application to Transparent Conducting Electrodes

The concept of using core Cu nanowires (CuNWs) that are conformally encapsulated by a reducible fugitive material for transparent conducting electrodes (TCEs) with high oxidation stability is presented. By the chemical reaction of an acid with surface oxide and hydroxide, a uniform surface shell layer is readily obtained on each CuNW upon adding lactic acid to the CuNW dispersion. The Cu lactate shell prevents the core CuNW from oxidizing during storage and film formation, enabling the core Cu nanowires to maintain their characteristic optoelectronic properties. Through simple thermal annealing under a nitrogen atmosphere, the Cu lactate shell is easily decomposed to expose the underlying pure Cu, providing an effective way to produce a pure‐CuNW‐network TCE with a sheet resistance of 19.8 Ω sq^?1 and an optical transmittance of 85.5% at 550 nm. The application of the CuNW‐based TCE to the transparent top electrode in organometallic halide perovskite solar cells is further demonstrated for the first time, yielding a power‐conversion efficiency 9.88% as compared to that of 13.39% for conventional perovskite solar cells with an indium–tin‐oxide electrode. This study proposes the high feasibility of these CuNWs as a vacuum‐free and noble‐metal‐free transparent‐window electrode in perovskite solar cells.     

Does Electronic Type Matter when Single‐Walled Carbon Nanotubes are Used for Electrode Applications?

Single‐walled carbon nanotube (SWNT) electrodes that are chemically and mechanically robust are fabricated using a simple drop cast method with thermal annealing and acid treatment. An electronic‐type selective decrease in sheet resistance of SWNT electrodes with HNO₃ treatment is shown. Semiconducting SWNTs show a significantly higher affinity toward hole doping in comparison to metallic SWNTs; a ≈12‐fold and a ≈fivefold drop in sheet resistance, respectively. The results suggest the insignificance of the electronic type of the SWNTs for the film conductivity after hole doping. The SWNT films have been employed as transparent hole extracting electrodes in bulk heterojunction (BHJ) organic photovoltaics. Performances of the devices enlighten the fact that the electrode film morphology dominates over the electronic type of the doped SWNTs with similar sheet resistance and optical transmission. The power conversion efficiency (PCE) of 4.4% for the best performing device is the best carbon nanotube transparent electrode incorporated large area BHJ solar cell reported to date. This PCE is 90% in terms of PCEs achieved using indium tin oxide (ITO) based reference devices with identical film fabrication parameters indicating the potential of the SWNT electrodes as an ITO replacement toward realization of all carbon solar cells.     

High-Performance ITO-Free Perovskite Solar Cells Enabled by Single-Walled Carbon Nanotube Films

The unprecedented advancement in power conversion efficiencies (PCEs) of perovskite solar cells (PSCs) has rendered them a promising game-changer in photovoltaics. However, unsatisfactory environmental stability and high manufacturing cost of window electrodes are bottlenecks impeding their commercialization. Here, a strategy is introduced to address these bottlenecks by replacing the costly indium tin oxide (ITO) window electrodes via a simple transfer technique with single-walled carbon nanotubes (SWCNTs) films, which are made of earth-abundant elements with superior chemical and environmental stability. The resultant devices exhibit PCEs of ≈19% on rigid substrates, which is the highest value reported to date for ITO-free PSCs. The facile approach for SWCNTs also enables application in flexible PSCs (f-PSCs), delivering a PCE of ≈18% with superior mechanical robustness over their ITO-based counterparts due to the excellent mechanical properties of SWCNTs. The SWCNT-based PSCs also deliver satisfactory performances on large-area (1 cm² active area in this work). Furthermore, these SWCNT-based PSCs can retain over 80% of original PCEs after exposure to air over 700 h while ITO-based devices only sustain ≈60% of initial PCEs. This work paves a promising way to accelerate the commercialization of ITO-free PSCs with reduced material cost and prolonged lifetimes.     

Carbon Nanotube Based Inverted Flexible Perovskite Solar Cells with All‐Inorganic Charge Contacts

Organolead halide perovskite solar cells (PSC) are arising as promising candidates for next‐generation renewable energy conversion devices. Currently, inverted PSCs typically employ expensive organic semiconductor as electron transport material and thermally deposited metal as cathode (such as Ag, Au, or Al), which are incompatible with their large‐scale production. Moreover, the use of metal cathode also limits the long‐term device stability under normal operation conditions. Herein, a novel inverted PSC employs a SnO₂‐coated carbon nanotube (SnO₂@CSCNT) film as cathode in both rigid and flexible substrates (substrate/NiO‐perovskite/Al₂O₃‐perovskite/SnO₂@CSCNT‐perovskite). Inverted PSCs with SnO₂@CSCNT cathode exhibit considerable enhancement in photovoltaic performance in comparison with the devices without SnO₂ coating owing to the significantly reduced charge recombination. As a result, a power conversion efficiency of 14.3% can be obtained on rigid substrates while the flexible ones achieve 10.5% efficiency. More importantly, SnO₂@CSCNT‐based inverted PSCs exhibit significantly improved stability compared to the standard inverted devices made with silver cathode, retaining over 88% of their original efficiencies after 550 h of full light soaking or thermal stress. The results indicate that SnO₂@CSCNT is a promising cathode material for long‐term device operation and pave the way toward realistic commercialization of flexible PSCs.     

Zr‐Doped Indium Oxide (IZRO) Transparent Electrodes for Perovskite‐Based Tandem Solar Cells

Parasitic absorption in transparent electrodes is one of the main roadblocks to enabling power conversion efficiencies (PCEs) for perovskite‐based tandem solar cells beyond 30%. To reduce such losses and maximize light coupling, the broadband transparency of such electrodes should be improved, especially at the front of the device. Here, the excellent properties of Zr‐doped indium oxide (IZRO) transparent electrodes for such applications, with improved near‐infrared (NIR) response, compared to conventional tin‐doped indium oxide (ITO) electrodes, are shown. Optimized IZRO films feature a very high electron mobility (up to ≈77 cm² V^?1 s^?1), enabling highly infrared transparent films with a very low sheet resistance (≈18 Ω □^?1 for annealed 100 nm films). For devices, this translates in a parasitic absorption of only ≈5% for IZRO within the solar spectrum (250–2500 nm range), to be compared with ≈10% for commercial ITO. Fundamentally, it is found that the high conductivity of annealed IZRO films is directly linked to promoted crystallinity of the indium oxide (In₂O₃) films due to Zr‐doping. Overall, on a four‐terminal perovskite/silicon tandem device level, an absolute 3.5 mA cm^?2 short‐circuit current improvement in silicon bottom cells is obtained by replacing commercial ITO electrodes with IZRO, resulting in improving the PCE from 23.3% to 26.2%.     

A Self‐Powered and Stable All‐Perovskite Photodetector–Solar Cell Nanosystem

Hybrid organic–inorganic perovskites have attracted intensive interest as light absorbing materials in solid‐state solar cells. Herein, we demonstrate a high‐performance CH₃NH₃PbI₃‐based perovskite photodetector constructed on the flexible indium tin oxide (ITO) coated substrate even after 200 bending cycles. The as‐fabricated devices show high responsivity, broad spectrum response from ultraviolet to whole visible light, long‐term stability, and high on‐off ratio. Particularly, atomic layer deposition technique was used to deposit the ultrathin Al₂O₃ film on devices, functioning as a protection layer to effectively enhance the stability and durability of perovskite photodetectors. The first all‐perovskite self‐powered nanosystem was successfully assembled by integrating a perovskite solar cell with a perovskite photodetector. Driven by the perovskite solar cell, the photodetector exhibits fast and stable response to illuminated light at a low working voltage less than 1.0 V. This stable integrated nanosystem has promising applications in which photodetectors can work in harsh environments without external power sources.     

High Efficiency Planar p‐i‐n Perovskite Solar Cells Using Low‐Cost Fluorene‐Based Hole Transporting Material

For commercial applications, it is a challenge to find suitable and low‐cost hole‐transporting material (HTM) in perovskite solar cells (PSCs), where high efficiency spiro‐OMeTAD and PTAA are expensive. A HTM based on 9,9‐dihexyl‐9H‐fluorene and N,N‐di‐p‐methylthiophenylamine (denoted as FMT) is designed and synthesized. High‐yield FMT with a linear structure is synthesized in two steps. The dopant‐free FMT‐based planar p‐i‐n perovskite solar cells (pp‐PSCs) exhibit a high power conversion efficiency (PCE) of 19.06%, which is among the highest PCEs reported for the pp‐PSCs based on organic HTM. For comparison, a PEDOT:PSS HTM‐based pp‐PSC is fabricated under the same conditions, and its PCE is found to be 13.9%.     

2D/3D Heterostructure for Semitransparent Perovskite Solar Cells with Engineered Bandgap Enables Efficiencies Exceeding 25% in Four‐Terminal Tandems with Silicon and CIGS

Wide‐bandgap perovskite solar cells (PSCs) with optimal bandgap (E_g) and high power conversion efficiency (PCE) are key to high‐performance perovskite‐based tandem photovoltaics. A 2D/3D perovskite heterostructure passivation is employed for double‐cation wide‐bandgap PSCs with engineered bandgap (1.65 eV ≤ E_g ≤ 1.85 eV), which results in improved stabilized PCEs and a strong enhancement in open‐circuit voltages of around 45 mV compared to reference devices for all investigated bandgaps. Making use of this strategy, semitransparent PSCs with engineered bandgap are developed, which show stabilized PCEs of up to 25.7% and 25.0% in four‐terminal perovskite/c‐Si and perovskite/CIGS tandem solar cells, respectively. Moreover, comparable tandem PCEs are observed for a broad range of perovskite bandgaps. For the first time, the robustness of the four‐terminal tandem configuration with respect to variations in the perovskite bandgap for two state‐of‐the‐art bottom solar cells is experimentally validated.     

Zwitterionic ammonium and neutral amino molecules as cathode interlayer for inverted polymer solar cells

Cathode interlayer is essential to inverted bulk heterojunction polymer solar cells (PSCs). A series of zwitterionic ammonium and neutral amino organic molecules are introduced into inverted PSCs as cathode interlayer and power conversion efficiency (PCE) as high as 8.07% is demonstrated. Compared to the devices without interlayer, all the devices exhibit significant improvements of the device parameters by reducing the work function of indium tin oxide (ITO) cathode. It is striking that the devices with neutral amino molecules as interlayer exhibit remarkably higher PCEs than the devices with zwitterionic ammonium molecules as interlayer. We attribute the improved performance to the better photoactive morphology induced by the hydrophobic properties of the neutral amino derivatives through research of ultraviolet photoelectron spectroscopy, atomic force microscopy, and contact angle measurements. Interestingly, the PCEs of the inverted PSCs with cathode interlayer are positively correlated with the hydrophobic properties of the interlayer materials, since devices with neutral amino molecules or molecules with a more hydrophobic alkyl pendant (piperidine) as interlayer exhibit higher PCEs. These results pave the way to the design of effective cathode interlayer materials.     

Light‐Responsive Ion‐Redistribution‐Induced Resistive Switching in Hybrid Perovskite Schottky Junctions

Hybrid Perovskites have emerged as a class of highly versatile functional materials with applications in solar cells, photodetectors, transistors, and lasers. Recently, there have also been reports on perovskite‐based resistive switching (RS) memories, but there remain open questions regarding device stability and switching mechanism. Here, an RS memory based on a high‐quality capacitor structure made of an MAPbBr₃ (CH₃NH₃PbBr₃) perovskite layer sandwiched between Au and indium tin oxide (ITO) electrodes is reported. Such perovskite devices exhibit reliable RS with an ON/OFF ratio greater than 10³, endurance over 10³ cycles, and a retention time of 10⁴ s. The analysis suggests that the RS operation hinges on the migration of charged ions, most likely MA vacancies, which reversibly modifies the perovskite bulk transport and the Schottky barrier at the MAPbBr₃/ITO interface. Such perovskite memory devices can also be fabricated on flexible polyethylene terephthalate substrates with high bendability and reliability. Furthermore, it is found that reference devices made of another hybrid perovskite MAPbI₃ consistently exhibit filament‐type switching behavior. This work elucidates the important role of processing‐dependent defects in the charge transport of hybrid perovskites and provides insights on the ion‐redistribution‐based RS in perovskite memory devices.     

All‐Carbon Nanotube‐Based Flexible Field‐Emission Devices: From Cathode to Anode

The fabrication of a flexible field‐emission device (FED) using single‐walled carbon nanotube (SWNT) network films as the conducting electrodes (anode and cathode) and thin multi‐walled CNT/TEOS hybrid films as the emitters is reported. P‐type doping with gold ions and passivation with tetraethylorthosilicate (TEOS) made the SWNT network film highly conductive and environmentally stable, and hence a good alternative to conventional indium tin oxide electrodes. CNT/TEOS hybrid emitters showed high current density, low turn‐on field, and long‐term emission stability, compared with CNT emitters; these characteristics can be attributed to the TEOS sol, acting both as a protective layer surrounding the nanotube tip, and as an adhesive layer enhancing the nanotube adhesion to the substrate. All‐CNT‐based flexible FEDs fabricated by this approach showed high flexibility in field emission characteristics and extremely bright electron emission patterns.     

An Ultrathin Ferroelectric Perovskite Oxide Layer for High‐Performance Hole Transport Material Free Carbon Based Halide Perovskite Solar Cells

The hole transport material (HTM) free carbon based perovskite solar cells (C‐PSCs) are promising for its manufactural simplicity, but they currently suffer from low power conversion efficiencies (PCE) largely because of the voltage loss. Here, a new strategy to increase the PCE by incorporating an ultrathin ferroelectric oxide PbTiO₃ layer between the electron transport material and the halide perovskite is reported. The resulting C‐PSCs have achieved PCEs up to 16.37%, which is the highest record for HTM‐free C‐PSCs to date, mainly ascribable to the ferroelectric layer enhanced open circuit voltage. Detail measurements and analysis show an enhanced built‐in potential in the C‐PSCs as well as suppression of the non‐radiative recombination due to the ferroelectric PbTiO₃ layer incorporation, accounting for the boosted V_OC and photovoltaic performance.     

High Responsivity and Response Speed Single‐Layer Mixed‐Cation Lead Mixed‐Halide Perovskite Photodetectors Based on Nanogap Electrodes Manufactured on Large‐Area Rigid and Flexible Substrates

Mixed‐cation lead mixed‐halide perovskites are employed as the photoactive material in single‐layer solution‐processed photodetectors fabricated with coplanar asymmetric nanogap Al–Au and indium tin oxide–Al electrodes. The nanogap electrodes, bearing an interelectrode distance of ≈10 nm, are patterned via adhesion lithography, a simple, low‐cost, and high‐throughput technique. Different electrode shapes and sizes are demonstrated on glass and flexible plastic substrates, effectively engineering the device architecture, and, along with perovskite film and material optimization, paving the way toward devices with tunable operational characteristics. The optimized coplanar nanogap junction perovskite photodetectors show responsivities up to 33 A W^?1, specific detectivity on the order of 10¹¹ Jones, and response times below 260 ns, while retaining a low dark current (0.3 nA) under ?2 V reverse bias. These values outperform the vast majority of perovskite photodetectors reported so far, while avoiding the complicated fabrication steps involved in conventional multilayer device structures. This work highlights the promising potential of the proposed asymmetric nanogap electrode architecture for application in the field of flexible optoelectronics.     

Spray‐Coated Silver Nanowires as Top Electrode Layer in Semitransparent P3HT:PCBM‐Based Organic Solar Cell Devices

Silver nanowire (Ag NW) thin films are investigated as top electrodes in semitransparent inverted organic solar cells. The performance of semitransparent poly(3‐hexylthiophene‐2,5‐diyl):[6,6]‐phenyl‐C61‐butyric acid methyl ester (P3HT:PCBM) organic solar cells with Ag NW top electrode layers is found to match very closely the performance of reference devices based on thermally evaporated, highly reflective metal silver top electrodes. The optical losses of the semitransparent electrodes are investigated in detail and analyzed in terms of transmission, scattering, and reflection losses. The impact on an external back reflector is shown to increase the light harvesting efficiency of optically thin devices. Further analysis of transparent devices under illumination from the indium tin oxide (ITO) backside and through the Ag NW front electrode open the possibility to gain deep insight into the vertical microstructure related devices performance. Overall, Ag NW top electrodes are established as a serious alternative to TCO based electrodes. Semitransparent devices with efficiencies of over η = 2.0% are realized.     

An Indium‐Free Anode for Large‐Area Flexible OLEDs: Defect‐Free Transparent Conductive Zinc Tin Oxide

Flexible large‐area organic light‐emitting diodes (OLEDs) require highly conductive and transparent anodes for efficient and uniform light emission. Tin‐doped indium oxide (ITO) is the standard anode in industry. However, due to the scarcity of indium, alternative anodes that eliminate its use are highly desired. Here an indium‐free anode is developed by a combinatorial study of zinc oxide (ZnO) and tin oxide (SnO₂), both composed of earth‐abundant elements. The optimized Zn–Sn–O (ZTO) films have electron mobilities of up to 21 cm² V^?1 s^?1, a conductivity of 245 S cm^?1, and <5% absorptance in the visible range of the spectrum. The high electron mobilities and low surface roughness (<0.2 nm) are achieved by producing dense and void‐free amorphous layers as confirmed by transmission electron microscopy. These ZTO layers are evaluated for OLEDs in two anode configurations: i) 10 cm² devices with ZTO/Ag/ZTO and ii) 41 cm² devices with ZTO plus a metal grid. The ZTO layers are compatible with OLED processing steps and large‐area white OLEDs fabricated with the ZTO/grid anode show better performance than those with ITO/grid anodes. These results confirm that ZTO has the potential as an In‐free and Earth‐abundant alternative to ITO for large‐area flexible OLEDs.     

Bendable Solar Cells from Stable,Flexible, and Transparent Conducting Electrodes Fabricated Using a Nitrogen‐Doped Ultrathin Copper Film

Copper has attracted significant interests as an abundant and low‐cost alternative material for flexible transparent conducting electrodes (FTCEs). However, Cu‐based FTCEs still present unsolved technical issues, such as their inferior light transmittance and oxidation durability compared to conventional indium tin oxide (ITO) and silver metal electrodes. This study reports a novel technique for fabricating highly efficient FTCEs composed of a copper ultrathin film sandwiched between zinc oxides, with enhanced transparency and antioxidation performances. A completely continuous and smooth copper ultrathin film is fabricated by a simple room‐temperature reactive sputtering process involving controlled nitrogen doping (<1%) due to a dramatic improvement in the wettability of copper on zinc oxide surfaces. The electrode based on the nitrogen‐doped copper film exhibits an optimized average transmittance of 84% over a spectral range of 380 ?1000 nm and a sheet resistance lower than 20 Ω sq^?1, with no electrical degradation after exposure to strong oxidation conditions for 760 h. Remarkably, a flexible organic solar cell based on the present Cu‐based FTCE achieves a power conversion efficiency of 7.1%, clearly exceeding that (6.6%) of solar cells utilizing the conventional ITO film, and this excellent performance is maintained even in almost completely bent configurations.     

Dual Effect of ITO‐Interlayer on Inverted Top‐Illuminated Polymer Solar Cells: Wetting of Polyelectrolyte and Tuning of Cavity

Flexible inverted top‐illuminated polymer solar cells (IT‐PSCs) are fabricated by wetting of polyelectrolyte and designing a microcavity structure by laying an indium‐tin‐oxide (ITO) interlayer on top of an Ag reflector. The ITO‐coated Ag makes the surface hydrophilic, thereby improving wettability of polyethyleneimine (PEIE). This increased wettability of PEIE yields a reflective cathode with low work function of 3.73 eV. The ITO layer also tunes the light absorption spectrum in the active layer. Finite‐domain time‐difference simulation provides evidence that the ITO layer played a role in both the shift in resonant wavelength in the microcavity and confinement of the electric field to the active layer. Time‐dependent simulation suggests that the time to reach steady‐state light absorption is longer (6.6 fs) when a microcavity is present than when it is not present (3.8 fs); i.e., the microcavity increases light absorption in the active layer. The designed IT‐PSCs show a maximum photo‐conversion efficiency of 6.4% on plastic film and 6.1% on opaque copper foil; these are the highest values obtained by top‐illuminated PSCs on a metallic substrate. The IT‐PSCs have excellent mechanical flexibility and more stable in air than conventional normal structured devices.     

Work‐Function Engineering of Graphene Anode by Bis(trifluoromethanesulfonyl)amide Doping for Efficient Polymer Light‐Emitting Diodes

Graphene has been considered to be a potential alternative transparent and flexible electrode for replacing commercially available indium tin oxide (ITO) anode. However, the relatively high sheet resistance and low work function of graphene compared with ITO limit the application of graphene as an anode for organic or polymer light‐emitting diodes (OLEDs or PLEDs). Here, flexible PLEDs made by using bis(trifluoromethanesulfonyl)amide (TFSA, [CF₃SO₂]₂NH) doped graphene anodes are demonstrated to have low sheet resistance and high work function. The graphene is easily doped with TFSA by means of a simple spin‐coating process. After TFSA doping, the sheet resistance of the TFSA‐doped five‐layer graphene, with optical transmittance of ≈88%, is as low as ≈90 Ω sq^?1. The maximum current efficiency and power efficiency of the PLED fabricated on the TFSA‐doped graphene anode are 9.6 cd A^?1 and 10.5 lm W^?1, respectively; these values are markedly higher than those of the PLED fabricated on pristine graphene anode and comparable to those of an ITO anode.     

Inverted Layer‐By‐Layer Fabrication of an Ultraflexible and Transparent Ag Nanowire/Conductive Polymer Composite Electrode for Use in High‐Performance Organic Solar Cells

A highly flexible and transparent conductive electrode based on consecutively stacked layers of conductive polymer (CP) and silver nanowires (AgNWs) fully embedded in a colorless polyimide (cPI) is achieved by utilizing an inverted layer‐by‐layer processing method. This CP‐AgNW composite electrode exhibits a high transparency of >92% at wavelengths of 450–700 nm and a low resistivity of 7.7 Ω ?^?1, while its ultrasmooth surface provides a large contact area for conductive pathways. Furthermore, it demonstrates an unprecedentedly high flexibility and good mechanical durability during both outward and inward bending to a radius of 40 μm. Subsequent application of this composite electrode in organic solar cells achieves power conversion efficiencies as high as 7.42%, which represents a significant improvement over simply embedding AgNWs in cPI. This is attributed to a reduction in bimolecular recombination and an increased charge collection efficiency, resulting in performance comparable to that of indium tin oxide‐based devices. More importantly, the high mechanical stability means that only a very slight reduction in efficiency is observed with bending (<5%) to a radius of 40 μm. This newly developed composite electrode is therefore expected to be directly applicable to a wide range of high‐performance, low‐cost flexible electronic devices.     

Room‐Temperature Nanosoldering of a Very Long Metal Nanowire Network by Conducting‐Polymer‐Assisted Joining for a Flexible Touch‐Panel Application

As an alternative to the brittle and expensive indium tin oxide (ITO) transparent conductor, a very simple, room‐temperature nanosoldering method of Ag nanowire percolation network is developed with conducting polymer to demonstrate highly flexible and even stretchable transparent conductors. The drying conducting polymer on Ag nanowire percolation network is used as a nanosoldering material inducing strong capillary‐force‐assisted stiction of the nanowires to other nanowires or to the substrate to enhance the electrical conductivity, mechanical stability, and adhesion to the substrate of the nanowire percolation network without the conventional high‐temperature annealing step. Highly bendable Ag nanowire/conducting polymer hybrid films with low sheet resistance and high transmittance are demonstrated on a plastic substrate. The fabricated flexible transparent electrode maintains its conductivity over 20 000 cyclic bends and 5 to 10% stretching. Finally, a large area (A4‐size) transparent conductor and a flexible touch panel on a non‐flat surface are fabricated to demonstrate the possibility of cost‐effective mass production as well as the applicability to the unconventional arbitrary soft surfaces. These results suggest that this is an important step toward producing intelligent and multifunctional soft electric devices as friendly human/electronics interface, and it may ultimately contribute to the applications in wearable computers.