Inkjet-printed Ag grid combined with Ag nanowires to form a transparent hybrid electrode for organic electronics

Networks of silver nanowires (AgNW) have been shown to facilitate high transparency, high conductivity, and good mechanical stability. However,the loose characteristic and local insulation problems due to gaps between the nanowires limit their application as electrodes. This study investigates an inkjet-printed Ag grid combined with AgNW to form a transparent hybrid electrode. The printed Ag grid on AgNW film connects the gaps between the Ag nanowires to increase the overall electric conductivity. The printed Ag-grid/AgNW hybrid electrodes have low resistivity (22.5 Ω/□) while maintaining a high transmittance (87.5%). These values are similar to standard indium tin oxide (ITO) on glass which has resistivity of 20Ω/□ and transmittance of 89% at 550 nm. In addition, these hybrid electrodes are also very flexible when fabricated on a photopolymer substrate. A spin-coating process combined with a peel-off process enable the fabrication of flexible ultra-smooth Ag-grid/AgNW electrodes. We tested the transparent and flexible electrode as the anode of a flexible organic light emitting diode (F-OLED). The light emitting layer of the F-OLED is 35 nm thick tris-(8-hydroxyquinoline) aluminum doped with 0.5% 10-(2-benzothiazolyl)-2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H,5H,11H-(1)-benzopyropyrano(6,7-8-I,j)quinolizin-11-one. The maximum brightness and current efficiency of the F-OLED are 10000 cd/m² and 12 cd/A, respectively, even when bent around a radius of 2 mm. The good performance of the device with Ag-grid/AgNW hybrid electrodes show that enhanced conductive inkjet-printed Ag nanoparticles combined with Ag nanowires can produce high quality electrodes for flexible organic optoelectronic devices.     

Transparent conductive PVP/AgNWs films for flexible organic light emitting diodes by spraying method

In this study, a simple spraying method is used to prepare the transparent conductive films (TCFs) based on Ag nanowires (AgNWs). Polyvinylpyrrolidone (PVP) is introduced to modify the interface of substrate. The transmittance and bending performance are improved by optimizing the number of spraying times and the solution concentration and controlling the annealing time. The spraying times of 20, the concentration of 2 mg/mL and the annealing time of 10 min are chosen to fabricate the PVP/AgNWs films. The transmittance of PVP/AgNWs films is 53.4%—67.9% at 380—780 nm, and the sheet resistance is 30 Ω/□ which is equivalent to that of commercial indium tin oxide (ITO). During cyclic bending tests to 500 cycles with bending radius of 5 mm, the changes of resistivity are negligible. The performance of PVP/AgNW transparent electrodes has little change after being exposed to the normal environment for 1 000 h. The adhesion to polymeric substrate and the ability to endure bending stress in AgNWs network films are both significantly improved by introducing PVP. Spraying method makes AgNWs form a stratified structure on large-area polymer substrates, and the vacuum annealing method is used to weld the AgNWs together at junctions and substrates, which can improve the electrical conductivity. The experimental results indicate that PVP/AgNW transparent electrodes can be used as transparent conductive electrodes in flexible organic light emitting diodes (OLEDs).     

Ice-Templated,Large-Area Silver Nanowire Pattern for Flexible Transparent Electrode

Flexible transparent electrodes are critically important for the emerging flexible and stretchable electronic and optoelectronic devices. To this end, transparent polymer films coated with silver nanowires (AgNWs) have been intensively studied in the past decade. However, it remains a grand challenge to achieve both high conductivity and transmittance in large-area films, mainly due to the poor alignment of AgNWs and their high junction resistance. Here, the successful attempt to realize large-area AgNW patterns on various substrates by a 2D ice-templating approach is reported. With a relatively low dosage of AgNWs (4 µg·cm⁻²), the resulted flexible electrode simultaneously achieves high optical transmittance (≈91%) and low sheet resistance (20 Ω·sq⁻¹). In addition, the electrode exhibits excellent durability during cyclic bending (≈10 000 times) and stretching (50% strain). The potential applications of the flexible transparent electrode in both touch screen and electronic skin sensor, which can monitor the sliding pressure and direction in real-time, are demonstrated. More importantly, it is believed that the study represents a facile and low-cost approach to assemble various nanomaterials into large-area functional patterns for advanced flexible devices.     

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.     

Large-Area Flexible Organic Solar Cells with a Robust Silver Nanowire-Polymer Composite as Transparent Top Electrode

Upscaling of efficient flexible organic solar cells (OSCs) is still a challenging task, where flexible transparent electrode is a key limiting factor. Silver nanowires (AgNWs) are widely used as flexible transparent electrodes to fabricate efficient small-area flexible OSCs, but the high surface roughness of AgNWs electrodes causes large leakage current and performance deterioration in large-area OSCs. In this study, it is reported that a strategy of switching the bottom AgNWs electrode and the top Ag film electrode to avoid the detrimental effect of the high surface roughness of AgNWs electrodes. Mechanical robustness of the AgNWs has been enhanced by introducing a cross-linked poly(sodium 4-styrenesulfonate) layer. The AgNWs-polymer transparent film is fabricated by water transfer printing as the top electrode. 21 cm² flexible organic modules containing 10 sub-cells are fabricated and delivered power conversion efficiencies of 12.3% with the design of switched electrodes.     

Neutral-pH PEDOT:PSS as over-coating layer for stable silver nanowire flexible transparent conductive films

The silver nanowire (AgNW) mesh film with poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as the over-coating layer is a promising flexible transparent conductive film technology. In this work, experimental studies show that the hygroscopic and acid properties of the common PEDOT:PSS lead to poor stabilities of the composite films, due to the conductivity degradation of PEDOT:PSS by the water absorption and the acid corrosion of AgNWs by PEDOT:PSS. By using the modified PEDOT:PSS of neutral pH as the over-coating layer, the long term shelf-life time, thermal and current stressing stabilities are all significantly improved without sacrifice of transparency, electrical conductivity and mechanical flexibility. Under both cases of thermal aging test at 210 °C for 20 min and 12 h continuous current stressing at a current density of 30 mA/cm², no obvious change of the conductivity is observed. The results clearly demonstrate that using the neutral-pH PEDOT:PSS as an over-coating layer can help to achieve flexible AgNW transparent conductive films with superior stability for flexible optoelectronic devices.     

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.     

Intense-pulsed-light irradiation of Ag nanowire-based transparent electrodes for use in flexible organic light emitting diodes

Silver nanowire (AgNW) based transparent electrodes are inherently coarse and therefore typically are only ever weakly bonded to a substrate. A remarkable improvement in the characteristics of a AgNW network film has, however, been achieved through a simple and short process of irradiating it with intense pulsed light (IPL). This not only avoids any severe deterioration in the optical characteristics of the AgNW film, but also significantly improves its electrical conductivity, adhesion to a polymeric substrate, and ability to endure bending stress. Most important of all, however, is the finding that the surface roughness of AgNW networks can also be improved by radiation. In a series of measurements made of organic light emitting diodes fabricated using these treated electrodes, it was revealed that the leakage current can be notably reduced by IPL treatment.     

A highly conductive and smooth AgNW/PEDOT:PSS film treated by hot-pressing as electrode for organic light emitting diode

A highly conductive, smooth and transparent electrode is developed by coating poly (3,4-ethylenedioxythiophene):poly (styrenesulfonate) (PEDOT:PSS) over silver nanowires (AgNWs) followed by a hot-pressing method. The hot-pressed AgNW/PEDOT:PSS film shows a low sheet resistance of 12 Ω/square, a transmittance of 83% at 550 nm and a smooth surface. The improvement of the conductivity and smoothness are ascribed to the fusion of nanowires resulted from the mechanical hot-pressing. The AgNW/PEDOT:PSS film on polyethylene naphthalate (PEN) substrate exhibits higher conductive stability against the bending test than commonly used indium tin oxide (ITO). Using the hot-pressed AgNW/PEDOT:PSS film as the anode, we have fabricated ITO-free organic light emitting diode with a maximum current efficiency of 58.2 cd/A, which is higher than the device with ITO anode. This proves that such AgNW/PEDOT:PSS film treated by hot-pressing is a promising candidate for flexible optoelectronic devices.     

Ag Nanowire Reinforced Highly Stretchable Conductive Fibers for Wearable Electronics

Stretchable conductive fibers have received significant attention due to their possibility of being utilized in wearable and foldable electronics. Here, highly stretchable conductive fiber composed of silver nanowires (AgNWs) and silver nanoparticles (AgNPs) embedded in a styrene–butadiene–styrene (SBS) elastomeric matrix is fabricated. An AgNW‐embedded SBS fiber is fabricated by a simple wet spinning method. Then, the AgNPs are formed on both the surface and inner region of the AgNW‐embedded fiber via repeated cycles of silver precursor absorption and reduction processes. The AgNW‐embedded conductive fiber exhibits superior initial electrical conductivity (σ₀ = 2450 S cm^?1) and elongation at break (900% strain) due to the high weight percentage of the conductive fillers and the use of a highly stretchable SBS elastomer matrix. During the stretching, the embedded AgNWs act as conducting bridges between AgNPs, resulting in the preservation of electrical conductivity under high strain (the rate of conductivity degradation, σ/σ₀ = 4.4% at 100% strain). The AgNW‐embedded conductive fibers show the strain‐sensing behavior with a broad range of applied tensile strain. The AgNW reinforced highly stretchable conductive fibers can be embedded into a smart glove for detecting sign language by integrating five composite fibers in the glove, which can successfully perceive human motions.     

全透明低回滞s-SWCNT/AgNW薄膜晶体管的可控制备

利用高纯度、高均一性的半导体型单壁碳纳米管(s-SWCNT)网络薄膜作为薄膜晶体管的沟道材料,以高透明度、低薄膜电阻的银纳米线(Ag NW)网络薄膜作为源、漏电极,在玻璃基底上制备了大面积、高透明度的碳纳米管薄膜晶体管阵列,并使用聚甲基丙烯酸甲酯(PMMA)薄膜在器件表面通过干法封装获得了较低回滞的电子器件,得到了整体透明度达到82%以上的器件。提出的器件制备方法不仅制备材料易得,不需要高温过程,而且能够实现器件的大面积制备,对碳纳米管薄膜晶体管的全透明柔性化进程具有推进作用。     

Well‐Ordered and High Density Coordination‐Type Bonding to Strengthen Contact of Silver Nanowires on Highly Stretchable Polydimethylsiloxane

Recently, Ag nanowires (AgNWs) has had a great interest as a conducting material for flexible and transparent devices, but it still shows several problems such as the ultimate detachment of AgNWs from substrate and a high contact resistance on AgNW junctions. Therefore, the novel concept to enhance permanent and closed attachment of AgNWs by silane modification to polydimethylsilaoxane (PDMS) substrate well known as high stretchable film with extremly low adhesive is suggested. According to this experiment, higher sigma (σ)‐donating ability and hydrophilicity indicate better electrical and mechanical properties in real device. Especially, densely amine self‐assembled PDMS surface exhibits the strongest contact force to the AgNWs, especially for junction side, and the longest maintenance of hydrophilicity by coordination‐type bonding. In addition, AgNWs adhere permanently to stretchable substrates while simultaneously maintaining high transparency (87%) and high conductivity (27 Ω sq^–1). Consequently, the resulting AgNW film shows excellent mechanical durability which includes enhanced performance of both flexibility and stretchability.     

Electrochromic Switch Devices Mixing Small‐ and Large‐Sized Upconverting Nanocrystals

The hasty progress in smart, portable, flexible, and transparent integrated electronics and optoelectronics is currently one of the driving forces in nanoscience and nanotechnology. A promising approach is the combination of transparent conducting electrode materials (e.g., silver nanowires, AgNWs) and upconverting nanoparticles (UCNPs). Here, electrochromic devices based on transparent nanocomposite films of poly(methyl methacrylate) and AgNWs covered by UCNPs of different sizes and compositions are developed. By combining the electrical control of the heat dissipation in AgNW networks with size‐dependent thermal properties of UCNPs, tunable electrochromic transparent devices covering a broad range of the chromatic diagrams are fabricated. As illustrative examples, devices mixing large‐sized (>70 nm) β‐NaYF₄:Yb,Ln and small‐sized (<15 nm) NaGdF₄:Yb,Ln@NaYF₄ core@shell UCNPs (Ln = Tm, Er, Ce/Ho) are presented, permitting to monitor the temperature‐dependent emission of the particles by the intensity ratio of the Er^{3+ 2}H_11/2 and ⁴S_3/2 → ⁴I_15/2 emission lines, while externally controlling the current flow in the AgNW network. Moreover, by defining a new thermometric parameter involving the intensity ratio of transitions of large‐ and small‐sized UCNPs, a relative thermal sensitivity of 5.88% K^?1 (at 339 K) is obtained, a sixfold improvement over the values reported so far.     

Highly Efficient and Bendable Organic Solar Cells with Solution‐Processed Silver Nanowire Electrodes

Highly efficient and bendable organic solar cells (OSCs) are fabricated using solution‐processed silver nanowire (Ag NW) electrodes. The Ag NW films were highly transparent (diffusive transmittance ≈ 95% at a wavelength of 550 nm), highly conductive (sheet resistance ≈ 10 Ω sq^?1), and highly flexible (change in resistance ≈ 1.1 ± 1% at a bending radius of ≈200 μm). Power conversion efficiencies of ≈5.80 and 5.02% were obtained for devices fabricated on Ag NWs/glass and Ag NWs/poly(ethylene terephthalate) (PET), respectively. Moreover, the bendable devices fabricated using the Ag NWs/PET films decrease slightly in their efficiency (to ≈96% of the initial value) even after the devices had been bent 1000 times with a radius of ≈1.5 mm.     

Production of Flexible Transparent Conducting Films of Self‐Fused Nanowires via One‐Step Supersonic Spraying

Scalable and economical manufacturing of flexible transparent conducting films (TCF) is a key barrier to widespread adoption of low‐cost flexible electronics. Here, a simple, robust, and scalable method of flexible TCF formation using supersonic kinetic spraying is demonstrated. Silver nanowire (AgNW) suspensions are sprayed at supersonic speed to produce self‐sintered films of AgNWs on flexible substrates. These films display remarkably low sheet resistance, <10 Ω sq^?1, combined with high transmittance, >90%. These electrically conducting, transparent, and flexible coatings can be deposited over a 100 cm² area in ≈30 s. Theoretical analysis reveals the underlying physical mechanism behind self‐sintering, showing that self‐sintering is enabled by the high velocity of impact in supersonic spraying.     

Highly conductive silver nanowire networks by organic matrix assisted low-temperature fusing

In silver nanowire (AgNW) percolation network electrodes, the junction resistance at the wire-to-wire contact is crucial for the electrode performance. We introduce an organic sublayer between the substrate and the AgNW electrode to improve the sheet resistance and avoid the frequently applied high-temperature post-annealing process. Upon introduction of such a sublayer, a strong reduction of the sheet resistance (R_S) in the same order as it would be expected from a post-annealing process (e.g. 90 min@210 °C) is observed. This effect is investigated in-depth by using different sublayer material classes such as polyelectrolytes, tensides or differently charged polymers. Independent of charge and material class, especially those materials with hydrophobic and hydrophilic parts, dramatically reduce the sheet resistance. Consequently, hydrophobic interaction between substrate and nanowires and capillary forces during drying can be attributed as driving force. Using polyvinylpyrrolidone (PVP), also used as stabilizer for the AgNWs, leads to the largest reduction in sheet resistance of the investigated materials resulting in AgNW electrodes exhibiting R_S = 10.8 Ω/□ at 80.4% transparency (including substrate) without additional post-annealing at high temperatures.     

纳米银线-环氧树脂复合导电薄膜的制备及其在柔性触控上的应用

纳米银线透明导电薄膜具有优异的光电性能和机械性能,有望取代传统的氧化铟锡材料应用于柔性光电器件中。为解决纳米银线的黏附性、柔韧性和稳定性问题,结合转印法和烷基硫醇修饰法制备了纳米银线-环氧树脂复合导电薄膜。在此过程中,首先应用十八烷基三氯硅烷对转移衬底进行疏水化处理以提升透明电极转印的良率;接着,对转印后的纳米银线进行烷基硫醇分子的自组装修饰,以进一步提升纳米银线透明导电薄膜的稳定性;最后在此基础上制备了柔性投射式电容触控屏。所制备的透明导电薄膜具有优异的综合性能:品质因数约为300(Rs=29.7Ω/□,T=96.2%);薄膜经过100次胶带测试后,电阻变化小于25%;在1 000次弯曲(弯曲半径为1mm)测试后,电阻几乎不发生变化;高温高湿下老化一个月,电阻变化小于20%。本文结合转印工艺以及分子修饰技术开发的纳米银线-环氧树脂复合导电薄膜以及柔性触控工艺,有望推广应用至其他柔性电子元件中。     

Applied Voltage and Near‐Infrared Light Enable Healing of Superhydrophobicity Loss Caused by Severe Scratches in Conductive Superhydrophobic Films

The fabrication of self‐healing/healable superhydrophobic films that can conveniently and repeatedly restore the loss of superhydrophobicity caused by severe mechanical damage, such as deep and wide surface scratches, remains challenging. In the present work, conductive superhydrophobic films that are healable by means of an applied voltage or near infrared (NIR) light irradiation are fabricated by depositing a layer of Ag nanoparticles and Ag nanowires (AgNPs‐AgNWs) on a thermally healable polycaprolactone (PCL)/poly(vinyl alcohol) (PVA) composite film, followed by the deposition of 1H,1H,2H,2H‐perfluorodecanethiol. The AgNPs‐AgNWs layer not only provides micro‐ and nanoscaled hierarchical structures in support of superhydrophobicity but also serves as an electrothermal or photothermal heater to enable healing of the underlying PCL/PVA film under the assistance of a low applied voltage or low‐power NIR light irradiation. Because of the strong adhesion between the PCL/PVA film and the AgNPs‐AgNWs layer, the healability of the PCL/PVA film is successfully conveyed to the conductive superhydrophobic layer, which can rapidly and repeatedly restore the loss of superhydrophobicity caused by cuts several hundreds of micrometers wide. The combined electrothermal and superhydrophobic properties endow the healable conductive superhydrophobic films with improved durability and usefulness as self‐cleaning, antiicing, and snow‐removing surfaces.     

Improving the flexibility of large-area transparent conductive oxide electrodes on polymer substrates for flexible organic light emitting diodes by introducing surface roughness

In this study, transparent conductive oxide (TCO) electrodes with highly enhanced flexibility were developed on polymer substrates for application in flexible organic emitting diodes (OLEDs). TCOs, particularly indium tin oxide (ITO), have superior functional properties as electrodes compared to other materials but are inherently brittle, which significantly limits the bendability of the flexible devices. To improve the fracture strength of ITO on a polymer substrate under bending, we investigated the effect of expanding the film surface areas on the reduction of the stresses induced by an external bending force. Regularly spaced channels were imprinted at an elevated temperature onto polymer substrate surfaces using Teflon^®. Then, both amorphous (a-ITO) and crystalline ITOs (c-ITO) were dc magnetron sputter deposited. As the channel patterns on the substrate surfaces were reflected into the growing film surfaces, the ITO surfaces became unidirectionally wavy, which increased the surface area by approximately 500%. The electrical and optical properties of the wavy ITOs were measured using a four-point probe and a UV–visible spectrophotometer, respectively, and the flexibility was evaluated with cyclic bending tests. For comparison, flexible OLEDs were also fabricated on both wavy ITO and conventional ITO. Our results revealed that the functional properties of ITOs with expanded surfaces are equivalent to those of conventional ITOs on the polymer substrates. However, their cyclic bending stability was significantly improved. After 10,000 cycles at a bending radius of 10 mm, the electrical resistivity change was less than half of the conventional ITO. The current density–voltage (J–V) characteristics of the flexible OLEDs on the wavy ITOs were also nearly equal to those on conventional ITOs.     

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.