Cohesively Enhanced Conductivity and Adhesion of Flexible Silver Nanowire Networks by Biocompatible Polymer Sol–Gel Transition

Silver nanowire (AgNW) networks are a promising candidate to replace indium tin oxide (ITO) as transparent conductors. In this paper, a novel transparent composite conductor composed of AgNW/biocompatible alginate gel on a flexible polyethylene terephthalate (PET) substrate, with synchronously enhanced adhesion and reduced resistivity, is prepared without high‐temperature annealing. The sheet resistance of the flexible AgNW/PET film reduces from 300 to 50.3 Ohm sq^?1 at transmittance of 94%. The optical and electrical performance is superior to that obtained from the flexible ITO film on PET. Meanwhile, the sheet resistance does not show great change after tape test, suggesting a good adhesion of AgNW to the polymer substrate. Moreover, the AgNW composite film shows a good stability to resist long‐term storage, solvent damage, and ultrasonication. Finally, polymer solar cells employing the composite AgNW film as the electrode are realized, displaying an efficiency of 2.44%.     

Roll‐to‐Roll Printed Silver Nanowire Semitransparent Electrodes for Fully Ambient Solution‐Processed Tandem Polymer Solar Cells

Silver nanowires (AgNWs) and zinc oxide (ZnO) are deposited on flexible substrates using fast roll‐to‐roll (R2R) processing. The AgNW film on polyethylene terephthalate (PET) shows >80% uniform optical transmission in the range of 550–900 nm. This electrode is compared to the previously reported and currently widely produced indium‐tin‐oxide (ITO) replacement comprising polyethylene terephthalate (PET)|silver grid|poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)|ZnO known as Flextrode. The AgNW/ZnO electrode shows higher transmission than Flextrode above 490 nm in the electromagnetic spectrum reaching up to 40% increased transmission at 750 nm in comparison to Flextrode. The functionality of AgNW electrodes is demonstrated in single and tandem polymer solar cells and compared with parallel devices on traditional Flextrode. All layers, apart from the semitransparent electrodes which are large‐scale R2R produced, are fabricated in ambient conditions on a laboratory roll‐coater using printing and coating methods which are directly transferrable to large‐scale R2R processing upon availability of materials. In a single cell structure, Flextrode is preferable with active layers based on poly‐3‐hexylthiophene(P3HT):phenyl‐C61‐butyric acid methylester (PCBM) and donor polymers of similar absorption characteristics while AgNW/ZnO electrodes are more compatible with low band gap polymer‐based single cells. In tandem devices, AgNW/ZnO is more preferable resulting in up to 80% improvement in PCE compared to parallel devices on Flextrode.     

Inkjet printed silver nanowire percolation networks as electrodes for highly efficient semitransparent organic solar cells

In this work, we demonstrate inkjet printing of silver nanowires (AgNW) with an average length of 10's of μm using industrial printheads with nozzle diameters in the same size range. The printed silver nanowire mesh reveals uniform distribution and a good balance between conductivity and transmittance, which is comparable to layers fabricated by conventional methods like slot-die or spray coating. Employing a novel AgNW ink formulation based on a high boiling alcohol allows printing directly on PEDOT:PSS and prevents nozzle clogging. Using silver nanowire meshes as bottom and top electrodes, a fully inkjet printed semitransparent organic solar cell with a power conversion efficiency of 4.3% for 1 cm² area is demonstrated, which is the highest value reported so far for fully inkjet printed organic photovoltaic cells.     

Transparent,dip-coated silver nanowire electrodes for small molecule organic solar cells

Percolation networks from silver nanowires can be used as a transparent electrode and promising alternative to the commonly used ITO. Here, the deposition of such a nanowire based network by dip coating, a versatile and scalable method, is described and characterized in detail. After identifying appropriate processing parameters, nanowire grids with conductivity and transmittance values rivaling ITO have been achieved. As a main issue, the roughness of the film was addressed and the influence on the device in terms of shunt paths was investigated. Using this network as anode, small molecule organic solar cells with varying stack structure were fabricated and yield efficiencies comparable to cells on ITO.     

Efficient flexible organic photovoltaics using silver nanowires and polymer based transparent electrodes

Planarization and filling voids between wires are key issues when using nanowire electrodes in flexible solar cells such as organic photovoltaics (OPV). For this purpose, we use poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT: PSS) which leads to an electrically well connected silver nanowire (AgNW) network. Furthermore, the use of water based PEDOT: PSS leads to humidity assisted AgNW fusing, resulting in a maximum processing temperature of only 120 °C. OPV cells using this AgNW/PEDOT: PSS transparent electrodes exhibit power conversion efficiencies up to 7.15%. Moreover, OPV devices on PET substrates with an alumina encapsulation and barrier adhesive show excellent mechanical flexibility.     

Orthogonally weaved silver nanowire networks for very efficient organic optoelectronic devices

We demonstrate a simple but effective method to control the orientation of silver nanowires (AgNWs). Shear-flow-induced AgNW preferable orientation is realized by judiciously controlling the process parameters in the bar-coating method. This controllability of the NW direction enables the formation of AgNW cross-linking networks for transparent conductive electrode (TCE) applications. We experimentally demonstrate that the orthogonally weaved AgNW networks possess predominant advantages of lower percolation limit, higher transmission, and lower sheet resistance compared with the randomly orientated AgNW counterparts. The phenomenon is also confirmed with theoretical calculation by the Monte Carlo method. These high-quality AgNW TCEs exhibit a high transmittance of ∼94% with a sheet resistance of ∼20 Ω/sq, which meet the requirements of modern optoelectronic devices. Very efficient organic light-emitting diodes (OLEDs) and organic solar cells (OSCs) prepared by these AgNW TCEs are demonstrated. The OLED exhibits exceptionally high luminance efficiency, power efficacy, and external quantum efficiency of 92 cd/A, 111 lm/W, and 26.8%, respectively. The OSCs also deliver a high power conversion efficiency of up to 7.5%.     

High‐Performance Hazy Silver Nanowire Transparent Electrodes through Diameter Tailoring for Semitransparent Photovoltaics

Solution‐processed metal nanowire networks have attracted substantial attention as clear transparent conductive electrodes (TCEs) to replace metal oxides for low‐cost and flexible touch panels and displays. While targeting photovoltaic applications, TCEs are expected to be more hazy for enhancing light absorption in the active layer, but are still required to retain high transmittance and low sheet resistance. Balancing these properties (haze, transmittance, and conductivity) in TCEs to realize high performance but high haze simultaneously is a challenge because they are mutually influenced. Here, by precisely tailoring the diameter of thick–long silver nanowires using rapid radial electrochemical etching, high hazy flexible TCEs are fabricated with high figure of merit of up to 741 (4 Ω sq^?1 at 88.4% transmittance with haze of 13.3%), surpassing those of commercialized brittle hazy metal oxides and exhibiting superiority for photovoltaic applications. Laminating such TCEs onto the perovskite solar cells as top electrodes, the obtained semitransparent devices exhibit power efficiencies up to 16.03% and 11.12% when illuminated from the bottom and top sides, respectively, outperforming reported results based on similar device architecture. This study provides a simple strategy for flexible and hazy TCEs fabrication, which is compatible with mild solution‐processed photovoltaic devices, especially those containing heat‐sensitive or chemical‐sensitive materials.     

All‐Solution‐Processed Indium‐Free Transparent Composite Electrodes based on Ag Nanowire and Metal Oxide for Thin‐Film Solar Cells

Fully solution‐processed Al‐doped ZnO/silver nanowire (AgNW)/Al‐doped ZnO/ZnO multi‐stacked composite electrodes are introduced as a transparent, conductive window layer for thin‐film solar cells. Unlike conventional sol–gel synthetic pathways, a newly developed combustion reaction‐based sol–gel chemical approach allows dense and uniform composite electrodes at temperatures as low as 200 °C. The resulting composite layer exhibits high transmittance (93.4% at 550 nm) and low sheet resistance (11.3 Ω sq^‐1), which are far superior to those of other solution‐processed transparent electrodes and are comparable to their sputtered counterparts. Conductive atomic force microscopy reveals that the multi‐stacked metal‐oxide layers embedded with the AgNWs enhance the photocarrier collection efficiency by broadening the lateral conduction range. This as‐developed composite electrode is successfully applied in Cu(In_1‐x,Ga_x)S₂ (CIGS) thin‐film solar cells and exhibits a power conversion efficiency of 11.03%. The fully solution‐processed indium‐free composite films demonstrate not only good performance as transparent electrodes but also the potential for applications in various optoelectronic and photovoltaic devices as a cost‐effective and sustainable alternative electrode.     

High Power Conversion Efficiency of 13.61% for 1 cm2 Flexible Polymer Solar Cells Based on Patternable and Mass-Producible Gravure-Printed Silver Nanowire Electrodes

With the aim of developing high-performance flexible polymer solar cells, the preparation of flexible transparent electrodes (FTEs) via a high-throughput gravure printing process is reported. By varying the blend ratio of the mixture solvent and the concentration of the silver nanowire (AgNW) inks, the surface tension, volatilization rate, and viscosity of the AgNW ink can be tuned to meet the requirements of gravure printing process. Following this method, uniformly printed AgNW films are prepared. Highly conductive FTEs with a sheet resistance of 10.8 Ω sq⁻¹ and a high transparency of 95.4% (excluded substrate) are achieved, which are comparable to those of indium tin oxide electrode. In comparison with the spin-coating process, the gravure printing process exhibits advantages of the ease of large-area fabrication and improved uniformity, which are attributed to better ink droplet distribution over the substrate. 0.04 cm² polymer solar cells based on gravure-printed AgNW electrodes with PM6:Y6 as the photoactive layer show the highest power conversion efficiency (PCE) of 15.28% with an average PCE of 14.75 ± 0.35%. Owing to the good uniformity of the gravure-printed AgNW electrode, the highest PCE of 13.61% is achieved for 1 cm² polymer solar cells based on the gravure-printed FTEs.     

Ultrathin Metal films for Transparent Electrodes of Flexible Optoelectronic Devices

The need for the development of transparent conductive electrodes (TCEs) supported on flexible polymer substrates has explosively increased in response to flexible polymer‐based photovoltaic and display technologies; these TCEs replace conventional indium tin oxide (ITO) that exhibits poor performance on heat‐sensitive polymers. An efficient, flexible TCE is required to exhibit high electrical conductance and high optical transmittance, as well as excellent mechanical flexibility and long‐term stability, simultaneously. Recent advances in technologies utilizing an ultrathin noble‐metal film in a dielectric/metal/dielectric structure, or its derivatives, have attracted attention as promising alternatives that can satisfy the requirements of flexible TCEs. This review will survey the background knowledge and recent updates of synthetic strategies and design rules toward highly efficient, flexible TCEs based on ultrathin metal films, with a special focus on the principal features and available methodologies involved in the fabrication of highly transparent, conductive, ultrathin noble‐metal films. This survey will also cover the practical applications of TCEs to flexible organic solar cells and light‐emitting diodes.     

Uniformly Interconnected Silver‐Nanowire Networks for Transparent Film Heaters

The fabrication and design principles for using silver‐nanowire (AgNW) networks as transparent electrodes for flexible film heaters are described. For best practice, AgNWs are synthesized with a small diameter and network structures of the AgNW films are optimized, demonstrating a favorably low surface resistivity in transparent layouts with a high figure‐of‐merit value. To explore their potential in transparent electrodes, a transparent film heater is constructed based on uniformly interconnected AgNW networks, which yields an effective and rapid heating of the film at low input voltages. In addition, the AgNW‐based film heater is capable of accommodating a large amount of compressive or tensile strains in a completely reversible fashion, thereby yielding an excellent mechanical flexibility. The AgNW networks demonstrated here possess attractive features for both conventional and emerging applications of transparent flexible electrodes.     

Screen‐Printed Poly(3,4‐Ethylenedioxythiophene):Poly(Styrenesulfonate) Grids as ITO‐Free Anodes for Flexible Organic Light‐Emitting Diodes

Poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT: PSS) grids have been successfully constructed by roll‐to‐roll compatible screen‐printing techniques and have been used as indium tin oxide (ITO)‐free anodes for flexible organic light‐emitting diodes (OLEDs). The grid‐type transparent conductive electrodes (TCEs) can adopt thicker PEDOT: PSS grid lines to ensure the conductivity, while the mesh‐like grid structure can play an important role to maintain high optical transparency. By adjusting grid periods, grid thickness and treatment of organic additives, PEDOT: PSS TCEs with high optical transparency, low sheet resistance, and excellent mechanical flexibility have been achieved. Using the screen‐printed PEDOT: PSS grids as the anodes, ITO‐free OLEDs achieved peak current efficiency of 3.40 cd A^?1 at the current density of 10 mA cm^?2, which are 1.56 times better than the devices with ITO glass as the anodes. The improved efficiency is attributed to the light extraction effect and improved transparency by the grid structure. The superior optoelectronic performances of OLEDs based on flexible screen‐printed PEDOT: PSS grid anodes suggest their great prospects as ITO‐free anodes for flexible and wearable electronic applications.     

Electrical performance of the embedded-type surface electrodes containing carbon and silver nanowires as fillers and one-step organosoluble polyimide as a matrix

Embedded-type surface electrodes with silver nanowire (AgNW) and carbon nanotube (CNT) as conductive fillers and organosoluble polyimide (PI) as a matrix were investigated for their electrical conductivity and electrical durability under cyclic bending. The chosen polyimide was constituted with 4,4′-oxydiphthalic dianhydride and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane through a one-step process. Two types of surface electrodes of CNT/PI and AgNW/PI were prepared at 90 °C. The flexible CNT/PI and AgNW/PI surface electrodes not only had high electrical conductivities of 6.3 and 100 S/cm, respectively, after 30 spraying cycles but also kept electrical durability after 1200-time bending tests. The ITO-coated ITO/PI and ITO/AgNW/PI electrodes, for a comparative purpose, had severe electrical failure under cyclic bending.     

Gold nanoparticles-decorated single silver nanowire as an efficient SERS-active substrate

A novel surface-enhanced Raman scattering （SERS）-active substrate based on Au nanoparticles （AuNPs）-coated silver nanowire （AgNW） is obtained by an effective and simple method. The results show that the hybrid structures prepared by this method are powerful SERS-active substrates for the detection of malachite green （MG） molecules with the limit of 1 nmol/L. The excellent enhancing, ability mainly comes from two kinds of hot spots. One is from the gaps among the adjacent AuNPs, and the other is the presence of zone between AuNPs and AgNW. In particular, the AuNPs-coated AgNW can be viewed through the objective of the confocal Raman spectrometer due to the length of the AgNW reaches microns, which can improve the repeatability of detection. Moreover, it is of great significance in research of SERS mechanism and application.     

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.     

Improved Operational Stability of Polymer Light‐Emitting Diodes Based on Silver Nanowire Electrode Through Pre‐Bias Conditioning Treatment

For the first time, highly efficient and flexible polymer light emitting diodes (PLEDs) based on silver nanowire (AgNW) electrode, with improved operational stability by simply applying pre‐bias conditioning treatment, are demonstrated. Reverse bias conditioning performed before J–V–L measurement of the PLEDs enables the rough AgNW networks to function properly as a bottom electrode by stabilizing current characteristics, and the devices continue to show consistent operational performances. Conditions of applied bias and thicknesses of active layer are controlled for optimization and it is found that high reverse voltage is required to obtain current stabilization. Adequate thickness of polymer is also necessary to avoid breakdown induced by reverse bias. The essential effect of pre‐bias conditioning on the improved performances of PLEDs is investigated, and it is found that morphological change of AgNW networks contribute to the improvement in device performance. Some of the AgNWs that appear to be pathway of leakage current are deformed, and surface roughness (RMS) of the AgNW film is decreased while the sheet resistance of the film is maintained when the reverse bias conditioning is applied. It is also revealed that pre‐bias conditioning is independent from directionality of the applied bias when utilizing insulating polymer sandwiched between two electrodes.     

Locally Welded Silver Nano‐Network Transparent Electrodes with High Operational Stability by a Simple Alcohol‐Based Chemical Approach

As an indispensable aspect of emerging flexible optoelectronics, flexible transparent electrodes, especially those comprised of metal nanowires, have attracted great attentions recently. Welding the nanowire junctions is an effective strategy for reducing the sheet resistance and improving the operational stability of flexible nanowire electrode in practical applications. Herein, a simple alcohol‐based solution approach is proposed to weld crossed silver nanowires by chemically growing silver “solder” at the junctions of the nanowires, forming transparent silver nano‐network electrodes with improved electrical conductivity and operational stability. Remarkably, silver nano‐networks can be rapidly formed by this simple approach under ambient condition and room temperature, requiring no assistance from heat, light, electrical current, or mechanical pressure. Furthermore, our results show that the nano‐network electrode formed from large diameter nanowires offers a better operational stability, whose trend is opposite to that of the untreated electrodes. To demonstrate the potential application of the highly stable silver nano‐network from large diameter nanowires, organic solar cells fabricated on the nano‐network electrode incorporated with silicon dioxide nanoparticles achieve comparable performance to the ITO control device. Consequently, strategy demonstrated in this work can contribute to low‐cost and highly stable transparent electrodes in emerging flexible optoelectronics.     

纳米银线柔性透明导电薄膜研究进展

随着时代的发展,柔性电子产品的应用越来越广。柔性透明导电薄膜是柔性电子器件中的重要组成部分,由于氧化铟锡并不适合应用到柔性电子器件中,寻找新一代材料引起了研究者的广泛关注。纳米银线作为一种新型的纳米材料,在纳米尺度上有很多新奇的性能,其优良的导电性及良好的光学性能被认为是替代氧化铟锡的最佳材料。本文主要综述了纳米银线柔性导电薄膜的研究进展,主要包括纳米银线导电油墨的物化性能、纳米银线柔性透明导电薄膜的常用制备方法以及主要应用领域。此外,还结合国内外纳米银线柔性透明导电膜的研究现状,指出该研究方向仍存在的一些挑战。     

Conductive nonwetting flexible substrate

In this paper an easy method to prepare flexible conductive substrates has been demonstrated. The substrates are mainly PET (PolyEthyleneTerephthalate), on which AgNW (silver nanowire) were deposited by spin casting method. For adhesion purpose a common cosmetic material has been utilized. The material provides versatile features to these coated substrates, including robustness, hydrophobicity with transparent bracing of nanowires (NW) with the flexible substrate. Four probe conductivity measurement shows the resistivity is 12 Ω/cm and is comparable to that of commercially available indium tin oxide (ITO) coated substrates. This method is cheap, easy and can be used for different objectives like flexible thin film photovoltaic, light emitting diodes, photosensors etc.     

Silver grid transparent conducting electrodes for organic light emitting diodes

Polymer organic light emitting diodes (OLEDs) were fabricated using thin silver hexagonal grids replacing indium tin oxide (ITO) as the transparent conducting electrodes (TCE). Previous literature has assumed that thick metal grids (several hundred nanometres thick) with a lower sheet resistance (<10 Ω/□) and a similar light transmission (>80%) compared to thinner grids would lead to OLEDs with better performance than when thinner metal grid lines are used. This assumption is critically examined using OLEDs on various metal grids with different thicknesses and studying their performances. The experimental results show that a 20 nm thick silver grid TCE resulted in more efficient OLEDs with higher luminance (10 cd/A and 1460 cd/m² at 6.5 V) than a 111 nm thick silver grid TCE (5 cd/A and 159 cd/m² at 6.5 V). Furthermore, the 20 nm thick silver grid OLED has a higher luminous efficiency than the ITO OLED (6 cd/A and 1540 cd/m² at 6.5 V) at low voltages. The data shows that thinner metal grid TCEs (about 20 nm) make the most efficient OLEDs, contrary to previous expectations.