Mechanical integrity of hybrid indium-free electrodes for flexible devices

Maintaining electrical conductivity, optical transparency, and mechanical integrity against bending and stretching are key requirements for flexible transparent electrodes. Transparent conducting oxides (TCOs) are widely used thin film electrodes in optoelectronic devices. However, these materials are brittle and reducing film thickness to improve their mechanical integrity compromises their electrical performance. Here we combine TCO thin films with metal grids embedded in a polymer substrate to create hybrid electrodes with low sheet resistance and high resilience to bending. Amorphous zinc tin oxide (ZTO) and aluminum-doped zinc oxide (AZO) films sputtered onto polyethylene-terephthalate (PET) substrates with and without embedded metal grids are studied. The hybrid electrodes have an optical absorptance below 5% in the visible range and their electrical sheet resistance is less than 1 Ω/sq. The critical strain for tensile failure is analyzed through a combination of electrical measurements and in-situ observations of crack initiation and propagation during tensile loading. The mean critical strain for failure of the AZO/metal grid is 8.5% and that of the ZTO/metal grid is as high as 10%. The AZO and ZTO films alone present critical strain values around 0.6% and 1% respectively, demonstrating that the addition of the metal grid considerably improves the resistance onset strain of the electrodes far beyond these critical strain limits.     

Effect of Al Nanoparticles on the Microstructure,Electrical, and Optical Properties of AZO/Al/AZO Trilayer Thin Film

In this work, designed growth of aluminum (Al)/aluminum-doped zinc oxide (AZO), AZO/Al/AZO, and AZO/Al multilayer electrodes by radiofrequency (RF) magnetron sputtering on glass substrates was studied. The microstructures, optical properties, and electrical characteristics of the multilayer electrode thin films were analyzed, their structural denseness and thickness were observed by field-emission scanning electron microscopy (FE-SEM), and their crystal orientation was identified by x-ray diffraction (XRD). The resistivity and transmittance of the films were measured by four-point probe and UV–Vis–NIR spectrophotometer, respectively. The resistivity of the AZO/Al/AZO multilayer electrode thin film was 1.55 Ω cm. The average transmittance of the AZO/Al/AZO thin film over wavelengths from 400 nm to 800 nm was much better than that of other thin films, since Al nanoparticles distribute in the AZO thin film during the sputtering process, as observed by high-resolution transmission electron microscopy (HRTEM). In addition, the figure of merit of the AZO/Al/AZO trilayer film was much larger than those of the other structures.     

Large area roll-to-roll sputtering of transparent ITO/Ag/ITO cathodes for flexible inverted organic solar cell modules

We fabricated solution-processed flexible inverted organic solar cell (IOSC) modules (10 cm × 10 cm) on roll-to-roll (RTR) sputtered ITO/Ag/ITO multilayer cathodes. By using a pilot-scale RTR sputtering system equipped with mid-range frequency power for dual ITO targets and direct current power for the Ag target, we were able to continuously deposit a high-quality ITO/Ag/ITO multilayer on PET substrate with a width of 700 mm and length of 20,000 mm as a function of Ag thickness. At the Ag thickness of 12 nm, the ITO/Ag/ITO multilayer had a very low sheet resistance of 3.03 Ohm/square and high transmittance of 88.17%, which are better values than those of amorphous ITO film. A strip-type ITO/Ag/ITO cathode was successfully patterned using a RTR wet etching process. Successful operation of flexible IOSC modules on RTR sputtered ITO/Ag/ITO cathodes indicate that the RTR sputtering technique is a promising coating process for fabrication of high-quality transparent and flexible cathodes and can advance the commercialization of cost-efficient flexible IOSCs.     

All-solution-processed foldable transparent electrodes of Ag nanowire mesh and metal matrix films for flexible electronics

In this study, we developed foldable transparent electrodes composed of Ag nanowire (AgNW) networks welded by Ag nanoparticles (AgNPs) reduced from commercial Ag ink. All the processes used were solution-based. Using the Meyer rod method, uniform AgNW networks were roll-to-roll coated on large-area polymer substrates, and the spin-coated AgNPs firmly welded the AgNWs together at junctions and to substrates. The hybrid films consisting of AgNWs and the Ag film matrix exhibited higher electrical conductivity (5.0–7.3 × 10⁵ S/m) than and equivalent transparency (90–95%) to the AgNW networks. Furthermore, the hybrid films showed significantly better bending stability than AgNW networks. During cyclic bending tests to 10,000 cycles at 5 mm bending radius and even when almost folded with r_b of 1 mm, the resistivity changes were negligible because AgNWs were tightly held and adhered to the substrate by Ag films covering wires, thereby hindering fracturing of AgNWs under tension. Because the films were fabricated at a low temperature, there was no oxidation on the surfaces of the films. Hence, flexible organic light-emitting diodes (f-OLEDs) were successfully fabricated on polyethylene terephthalates (PET) coated with the hybrid films. The f-OLED in the bent state was comparable to that in the flat state, validating the potential applications of these transparent hybrid films as electrodes in various flexible electronics.     

Highly flexible organic light-emitting diodes based on ZnS/Ag/WO3 multilayer transparent electrodes

We report our study on highly flexible organic light-emitting diodes based on ZnS/Ag/WO₃ (ZAW) multilayer transparent electrodes in which high conductivity and ductility of Ag layers allow for efficient sheet conduction and flexibility while ZnS and WO₃ layers provide a means for enhancement in optical transmission and/or carrier-injection. Devices with ZAW anodes fabricated on planarized plastic substrates not only exhibit a performance and operational stability comparable to or better than those of ITO-based devices but also show a mechanical flexibility that is far superior to that of ITO-based devices. Experimental results show that a consistent performance can be obtained in ZAW-based devices upon repeated bending down to a radius of curvature of 5 mm, below which the flexibility of the devices is limited ultimately by the delamination occurring at cathode/organic interfaces rather than by the ZAW electrodes themselves.     

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).     

Transparent Flexible Substrates Based on Polyimides with Aluminum Doped Zinc Oxide (AZO) Thin Films

In this paper, transparent flexible substrates based on polyimides (PIs) with aluminum doped zinc oxide (AZO) thin films for organic electroluminescent devices have been prepared. PI film based on 2,2'-bis-(3,4-dicarboxyphenyl) hexafluoropropanedianhydride (6FDA) and 2,2'-bis-(trifluoromethyl)-4,4'-diaminobiphenyl (TFDB) were used for transparent flexible substrates. AZO thin films were prepared at two substrate deposition temperatures of 100/spl deg/C and 200/spl deg/C with a typical radio-frequency (r.f.) planar magnetron sputtering system. The sheet resistance and the optical transmission properties for AZO films on the fluorinated PI substrate were comparable with those for the AZO films on a glass substrate. The substrate properties were better when the deposition temperature was higher.     

室温下制备的ZnO/Ag/ZnO多层膜的性能

采用射频磁控溅射ZnO陶瓷靶、直流磁控溅射Ag靶的方法在室温下制备了不同厚度的ZnO/Ag/ZnO多层膜。对样品进行了研究。结果表明:随着Ag层厚度的增加,ZnO(002)衍射峰的强度先增加后减小,Ag(111)衍射峰的强度增强,ZnO/Ag/ZnO多层膜的面电阻先减小后趋于稳定。ZnO膜厚度增加,Ag膜易形成晶状结构,ZnO/Ag/ZnO多层膜的透射峰向长波方向移动。ZnO(60nm)/Ag(11nm)/ZnO(60nm)膜在554nm处的透过率高达92.3%,面电阻为4.2?/□,品质常数?TC最佳,约40×10–3/?。     

Efficient and ultraviolet durable inverted polymer solar cells using thermal stable GZO-AgTi-GZO multilayers as a transparent electrode

The optical and electrical properties of GZO/AgTi/AZO (GATG) multilayer transparent conducting films fabricated by magnetron sputtering method were investigated. The sheet resistance and maximum optical transmittance of GATG films are 5 Ω/sq and 86%, respectively. The sheet resistance of GATG still retains stable under annealing at 400 °C, which shows better thermal stability compared to GZO/Ag/AZO (GAG) film. The enhanced thermal stability of GATG is attributed to the formation of TiO_X in Ti doped Ag nanostructure film, which can inhibit Ag atom diffusion and aggregation. PTB7-TH:PC₇₁BM based inverted polymer solar cells (PSCs) with GATG electrode gave PCE of 9.20%, which is comparable to PCE (9.23%) of the control PSCs with ITO electrode. The PCE of PSCs with GATG and ITO electrodes respectively remain 59% and 23% of the original PCE values after UV exposure for 20 min with relativize humidity of 68% in air, indicating that PSCs with GATG show better UV durability. Our results suggest that GATG as an alternative to ITO electrode can obtain efficient inverted PSCs and have stronger anti-UV ability due to its low UV transparency.     

ZnO/Ag/ZnO多层膜的制备和性质研究

采用射频磁控溅射ZnO陶瓷靶和直流磁控溅射Ag靶的方法制备了ZnO/Ag/ZnO多层膜。用X射线衍射仪、紫外–可见分光光度计、四探针测试仪和金相显微镜对ZnO/Ag/ZnO薄膜的结构、光学透过率、方阻和稳定性进行了研究。结果表明,ZnO(60nm)/Ag/(10nm)/ZnO(60nm)薄膜呈现多晶结构,薄膜在520nm处的光学透过率高达87.5%,方阻Rs为6.2Ω/□。随着顶层ZnO薄膜厚度的增加,ZnO/Ag/ZnO薄膜的稳定性提高。     

Electrical and photoelectrochemical characteristics of flexible CdS nanocomposite/conducting polymer heterojunction

The electrical properties of CdS-polyvinyl alcohol (CdS-PVA) nanocomposites have been investigated in details. The junction behavior of CdS-PVA and a conducting polymer poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) heterojunction have been studied. The current–voltage characteristics of the nanocomposite samples have also performed at different bending angles. The bending study has been carried out after deposition of CdS-PVA and CdS-PVA/PEDOT:PSS heterojunction films on indium tin oxide coated (ITO) flexible polyethylene terephthalate (PET) substrates. Spectral dependent photoconductive properties of the nanocomposite-polymer heterojunctions have been investigated. The electrochemical photosensing behaviors have been demonstrated using CdS-PVA nanocomposites and CdS-PVA/PEDOT:PSS heterojunction films as photoanodes.     

Low resistive transparent and flexible ZnO/Ag/ZnO/Ag/WO3 electrode for organic light-emitting diodes

Transparent electrodes cannot easily be created with high transmittance and low sheet resistance simultaneously, although some optoelectronic devices, such as large organic light-emitting diode (OLED) displays and lightings, require very low resistive transparent electrodes. Here, we propose a very low resistive transparent electrode (～1.6 Ω/sq) with a high transmittance (～75%) for OLED devices, the transmittance level of which represents the highest reported value to date given such a low sheet resistance level. It consists of a stacked silver (Ag)/zinc oxide (ZnO)/Ag multilayer covered by high refractive index dielectric layers. The proposed multilayer electrode with optimal layer thicknesses has a high and wide spectral transmittance peak due to interference. The low sheet resistance is a result of two Ag layers connected via the sandwiched ZnO layer. In addition to its low sheet resistance coupled with high transmittance, the proposed multilayer electrode has good flexibility. An OLED with an anode of the stacked Ag/ZnO/Ag multilayer shows performance comparable to that of an anode of indium tin oxide.     

Micro-deformation of flexible substrate for electronic devices during handling prior to lithography patterning

The dimensional stability of poly(ethylene naphthalene-2,6-dicarboxylate) (PEN) foils during the handling and production process, is crucial for the quality of the final multilayer flexible electronic devices. The foil-on-carrier (FOC) - foil/adhesive/Si-wafer sandwich - is a handling method, which is currently used to temporary attach the foil to a Si-wafer carrier during the lithography processing. This handling method ensures good surface flatness of the foils during the processing. However this technique has two drawbacks: (1) it creates an in-plane micro-deformation of the PEN foil and (2) bending of FOC due to the lamination procedure and lithography processing. In this article the temperature dependence of in-plane foil deformation and bending of FOC was reported and the final curing step of lamination procedure was identified as the main source of in-plane deformation and bending. Finally the resultant stresses introduced to FOC by the curing step derived from the experimental measurements were compared to stress values calculated from the Stoney’s and Ohring’s equations.     

Ag层的厚度对ZnO/Ag/ZnO多层膜性能的影响

采用射频磁控溅射ZnO陶瓷靶、直流磁控溅射Ag靶的方法制备了不同厚度Ag夹层的ZnO(60nm)/Ag/ZnO(60nm)多层膜.分别用X射线衍射仪、紫外可见分光光度计、四探针测试仪对样品的结构、光学性质、电学性质进行了研究.结果表明:随着Ag层厚度的增加,ZnO/Ag/ZnO多层膜呈现多晶结构,Ag(111)衍射峰的强度增强.Ag夹层厚度为11nm时,ZnO(60nm)/Ag/ZnO(60nm)膜在554nm处的透过率高达92.3%.随着Ag层厚度的增加,Ag膜的特征吸收峰呈现红移和宽化,ZnO/Ag/ZnO多层膜的面电阻先减小后趋于稳定.     

Mechanical and environmental durability of roll-to-roll printed silver nanoparticle film using a rapid laser annealing process for flexible electronics

We investigate the mechanical durability and environmental stability of laser annealed silver (Ag) nanoparticle (NP) film. Roll-to-roll printed Ag NP film on polyethylene terephthalate substrate is annealed with a rapid laser annealing process in ambient conditions as an alternative to the conventional thermal annealing process. The laser annealed Ag NP film exhibits superior electrical and mechanical properties, with fast annealing time and no damage on the substrate. The outer/inner bending test results demonstrate that the flexibility of the laser annealed Ag film is excellent. The failure bending radii in the outer/inner bending tests are 3 mm. The laser annealed film can withstand 10,000 bending cycles. A nano-scratch test indicates that the adhesion strength of the laser annealed film is comparable to that of the thermal annealed film. The environmental reliability of Ag NP film is investigated under different high-temperature and high-humidity conditions, while being subjected to cyclic bending fatigue stress. The durability of printed Ag film is found to be influenced by temperature and humidity. The laser annealed film shows relatively large increase in resistance during the bending fatigue test under high temperature and humidity condition (60 °C/90% RH), which is attributed to the oxidation of Ag nanoparticles and initiation of cracks. Generation of cracks is accelerated owing to the combinational effects of the cyclic stress and humidity. These results suggest that, even though the laser annealed Ag film demonstrates sufficient mechanical durability, further improvement of the film properties is required for use in extreme mechanical and environmental conditions.     

不同柔性衬底上CdS薄膜退火前后的性能比较

采用磁控溅射法分别在柔性PI衬底、柔性AZO衬底和柔性ITO衬底上制备CdS薄膜,并在干燥空气中以CdCl2为源380℃退火,分别研究了不同柔性衬底及退火工艺对CdS薄膜形貌、结构和光学性能的影响。研究结果表明:退火前在不同柔性衬底上的CdS薄膜形貌依赖于衬底类型,退火后CdS薄膜的晶粒再结晶,晶粒度增大明显,且不再依赖于衬底类型。不同柔性衬底上CdS薄膜均为立方相和六角相的混相结构,退火后,六角相比例增大,薄膜的结晶质量提高。透过率退火后改善明显,其中,在柔性AZO衬底上的CdS薄膜透过率超过80%。     

Humidity‐Driven Mechanical and Electrical Response of Graphene/Cloisite Hybrid Films

Humidity‐driven and electrically responsive graphene/cloisite hybrid films are obtained by casting water dispersions of graphene oxide and cloisite Na⁺. Coupling hydrophilicity and a high water vapor barrier in a homogenous film enables to realize humidity‐driven actuators which exploit the water gradient generated across the film section under asymmetric exposure to humidity. The hybrid films are self‐standing, flexible, and exhibit fast humidity‐triggered bidirectional bending up to 75°, which is tuned by varying the relative amount of the two components. Up to 60% of the bending angle can be preserved at the steady state, providing a large and reliable response to humidity. Moreover, thermal treatment results in the reduction of graphene oxide, endowing the films with humidity‐dependent electrical conductivity, which increases from 1.5 × 10^?6 S at 20% relative humidity (RH) up to 2.7 × 10^?5 S at 90% RH. The films are used to realize a humidity‐sensitive electrical switching system in which the reversible actuation is due to water desorption induced by the Joule effect. Due to their ease of preparation and tunable properties, this new class of graphene‐based materials is suitable for the realization of humidity‐driven and electrically responsive actuators and sensors.     

Flexible organic light-emitting diodes on a polyestersulfone (PES) substrate using Al-doped ZnO anode grown by dual-plasma-enhanced metalorganic deposition system

This study proposes flexible organic light-emitting diodes (OLEDs) grown on polyestersulfone (PES) using Al-doped zinc oxide (AZO) as the anode, fabricated by the dual-plasma-enhanced chemical vapor deposition (DPEMOCVD) system. The experimental results including crystalline structure, optical, and electrical characteristics indicate that the quality of AZO films grown on PES depends on the deposition temperature and Al content. The optimal deposition temperature and Al content for AZO film are 185  C and 2.88 at%, respectively. Further increasing or decreasing the deposition temperature and Al content degrades the quality of AZO films. The optimal AZO film deposited on the PES substrate was used as the anode for flexible OLED. It shows a similar performance compared to OLEDs using commercial indium–tin-oxide (ITO) as the anode on glass, and represents enhanced characteristics to that of the commercial ITO anode on a flexible polyethylene naphthalate (PEN) substrate. This indicates that the DPEMOCVD-deposited AZO film on the PES substrate can be the anode for flexible OLEDs.     

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.