Flash‐Assisted Processing of Highly Conductive Zinc Oxide Electrodes from Water

Fabricating high‐quality transparent conductors using inexpensive and industrially viable techniques is a major challenge toward developing low cost optoelectronic devices such as solar cells, light emitting diodes, and touch panel displays. In this work, highly transparent and conductive ZnO thin films are prepared from a low‐temperature, aqueous deposition method through the careful control of the reaction chemistry. A robotic synthetic platform is used to explore the wide parameter space of a chemical bath system that uses only cheap and earth abundant chemicals for thin film deposition. As‐deposited films are found to be highly resistive, however, through exposure to several millisecond pulses of high‐intensity, broadband light, intrinsically doped ZnO films with sheet resistances as low as 40 Ω □^?1 can be readily prepared. Such values are comparable with state‐of‐the‐art‐doped transparent conducting oxides. The mild processing conditions (<150 °C) of the ZnO electrodes also enable their deposition on temperature sensitive substrates such as PET, paving the way for their use in various flexible optoelectronic devices. Proof‐of‐concept light emitting devices employing ZnO as a transparent electrode are presented.     

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%.     

Flexible Multifunctionalized Carbon Nanotubes‐Based Hybrid Nanowires

In this work, flexible multifunctionalized carbon nanotube (CNT)‐based hybrid nanowires are synthesized through surface modification processes. The good dispersability of the hybrid nanowire in polar solvents facilitates directly making fine patterns with a minimum width of 40 μm for applications of flexible and stretchable circuits (FSCs). The hybrid nanowire possesses a flexible and highly conductive structure which demonstrates stable electro‐mechanical properties on polydimethylsiloxane (PDMS) substrates under large structural deformation. FSCs fabricated from the hybrid nanowires show a constant resistance of 0.096 Ω □^?1 (equivalent of a resistivity 0.96 Ω μm) under repeated bending cycles. The FSCs also have a low and stable sheet resistance of 0.4 Ω □^?1 for strains up to 30%, which is almost four orders of magnitude lower than that of pure CNT samples (1316 Ω □^?1). Further improved stretchability and electro‐mechanical properties (0.1 Ω □^?1, at the strain of 100%) are achieved with a prestrain PDMS substrate. Repeated deformation tests demonstrate the high reliability of FSCs. The observed stable and reliable electro‐mechanical performance of FSCs suggests the potential use of the material in wearable and portable electronics.     

Oxidised carbon nanotubes as solution processable,high work function hole-extraction layers for organic solar cells

For efficient hole-extraction in solution processed organic solar cells the transparent indium-tin oxide (ITO) electrode is invariably pre-coated with a thin layer of the high work function conducting polymer poly(3,4-ethylenedioxythiophene) doped with poly(styrenesulfonate). Herein we show that thin films of partially oxidised multi-wall and single-wall carbon nanotubes are equally effective at facilitating hole-extraction in efficient (～2.7%) bulk-heterojunction organic solar cells based on poly(3-hexylthiophene) (P3HT): [6,6]-phenyl-C₆₁ butyric acid methyl ester (PCBM) blends. Crucially, in contrast to PEDOT:PSS, deposition is from aqueous solutions of low acidity (pH 6–7) ensuring compatibility with ITO and other emerging conducting oxides. Furthermore, thin oxidised carbon nanotube films offer greater transparency in the near-infrared as compared to PEDOT:PSS films of comparable thickness. The functionality of these nano-structured films is demonstrated in relatively large area devices (～0.35 cm²) and the performance rationalised based on measurements of the electronic structure and morphology.     

Spin‐ and Spray‐Deposited Single‐Walled Carbon‐Nanotube Electrodes for Organic Solar Cells

Organic bulk‐heterojunction solar cells using thin‐film single‐walled carbon‐nanotube (SWCNT) anodes deposited on glass are reported. Two types of SWCNT films are investigated: spin‐coated films from dichloroethane (DCE), and spray‐coated films from deionized water using sodium dodecyl sulphate (SDS) or sodium dodecyl benzene sulphonate (SDBS) as the surfactant. All of the films are found to be mechanically robust, with no tendency to delaminate from the underlying substrate during handling. Acid treatment with HNO₃ yields high conductivities >1000 S cm^?1 for all of the films, with values of up to 7694 ± 800 S cm^?1 being obtained when using SDS as the surfactant. Sheet resistances of around 100 Ω sq^?1 are obtained at reasonable transmission, for example, 128 ± 2 Ω sq^?1 at 90% for DCE, 57 ± 3 Ω sq^?1 at 65% for H₂O:SDS, and 68 ± 5 Ω sq^?1 at 70% for H₂O:SDBS. Solar cells are fabricated by successively coating the SWCNT films with poly(3,4‐ethylenedioxythiophene):poly(styrene sulphonate) (PEDOT:PSS), a blend of regioregular poly(3‐hexylthiophene) (P3HT) and 1‐(3‐methoxy‐carbonyl)‐propyl‐1‐phenyl‐(6,6)C₆₁ (PCBM), and LiF/Al. The resultant devices have respective power conversions of 2.3, 2.2 and 1.2% for DCE, H₂O:SDS and H₂O:SDBS, with the first two being at a virtual parity with reference devices using ITO‐coated glass as the anode (2.3%).     

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.     

Reduced Graphene Oxide Micromesh Electrodes for Large Area,Flexible, Organic Photovoltaic Devices

A laser‐based patterning technique—compatible with flexible, temperature‐sensitive substrates—for the production of large area reduced graphene oxide micromesh (rGOMM) electrodes is presented. The mesh patterning can be accurately controlled in order to significantly enhance the electrode transparency, with a subsequent slight increase in the sheet resistance, and therefore improve the tradeoff between transparency and conductivity of reduced graphene oxide (rGO) layers. In particular, rGO films with an initial transparency of ≈20% are patterned, resulting in rGOMMs films with a ≈59% transmittance and a sheet resistance of ≈565 Ω sq^?1, that is significantly lower than the resistance of ≈780 Ω sq^?1, exhibited by the pristine rGO films at the same transparency. As a proof‐of‐concept application, rGOMMs are used as the transparent electrodes in flexible organic photovoltaic (OPV) devices, achieving power conversion efficiency of 3.05%, the highest ever reported for flexible OPV devices incorporating solution‐processed graphene‐based electrodes. The controllable and highly reproducible laser‐induced patterning of rGO hold enormous promise for both rigid and flexible large‐scale organic electronic devices, eliminating the lag between graphene‐based and indium–tin oxide electrodes, while providing conductivity and transparency tunability for next generation flexible electronics.     

Ambient‐Dried Cellulose Nanofibril Aerogel Membranes with High Tensile Strength and Their Use for Aerosol Collection and Templates for Transparent,Flexible Devices

The application potential of cellulose nanofibril (CNF) aerogels has been hindered by the slow and costly freeze‐ or supercritical drying methods. Here, CNF aerogel membranes with attractive mechanical, optical, and gas transport properties are prepared in ambient conditions with a facile and scalable process. Aqueous CNF dispersions are vacuum‐filtered and solvent exchanged to 2‐propanol and further to octane, followed by ambient drying. The resulting CNF aerogel membranes are characterized by high transparency (>90% transmittance), stiffness (6 GPa Young's modulus, 10 GPa cm³ g^?1 specific modulus), strength (97 MPa tensile strength, 161 MPa m³ kg^?1 specific strength), mesoporosity (pore diameter 10–30 nm, 208 m² g^?1 specific surface area), and low density (≈0.6 g cm^?3). They are gas permeable thus enabling collection of nanoparticles (for example, single‐walled carbon nanotubes, SWNT) from aerosols under pressure gradients. The membranes with deposited SWNT can be further compacted to transparent, conductive, and flexible conducting films (90% specular transmittance at 550 nm and 300 Ω ?^{? 1} sheet resistance with AuCl₃‐salt doping). Overall, the developed aerogel membranes pave way toward use in gas filtration and transparent, flexible devices.     

Stability of Doped Transparent Carbon Nanotube Electrodes

This paper evaluates the effectiveness of p‐doping transparent single‐walled carbon nanotube (SWNT) films via chemical treatment with HNO₃ and SOCl₂. Stability of the improvement in electrical conductivity after doping is investigated for different doping treatments as a function of exposure time to air and as a function of temperature. Doped films were found to have a greater than twofold increase in conductivity with sheet resistance values as low as 105 Ω sq^?1 with an optical transmittance of 80% at 550 nm. However, doping enhancements demonstrated limited stability in air and under thermal loading. The application of a thin capping layer of PEDOT/PSS is shown to stabilize the improvements in conductivity, evidenced by sustained lower sheet resistance in both air and under thermal loading.     

Electrohydrodynamic NanoDrip Printing of High Aspect Ratio Metal Grid Transparent Electrodes

The transparent conducting electrode is an essential component in many contemporary and future devices, ranging from displays to solar cells. Fabricating transparent electrodes requires a balancing act between sufficient electrical conductivity and high light transmittance, both affected by the involved materials, fabrication methodology, and design. While metal films possess the highest conductivity at room temperature, a decent optical transmittance can only be achieved with ultrathin films. Structuring the metal into optically invisible nanowires has been shown to be promising to complement or even substitute transparent conductive oxides as dominant transparent electrode material. Here the out‐of‐plane fabrication capability of the recently developed method of electrohydrodynamic NanoDrip printing to pattern gold and silver nanogrids with line widths from 80 to 500 nm is demonstrated. This fully additive process enables the printing of high aspect ratio nanowalls and by that significantly improves the electrical performance, while maintaining the optical transmittance at a high level. Metal grid transparent electrodes optimized for low sheet resistances (8 Ω sq^?1 at a relative transmittance of 94%) as well as optimized for high transmittance (97% at a sheet resistance of 20 Ω sq^?1) are reported, which can be tailored on demand for the use in various applications.     

Trilayer Nanomesh Films with Tunable Wettability as Highly Transparent,Flexible, and Recyclable Electrodes

Metallic mesh materials are promising candidates to replace traditional transparent conductive oxides such as indium tin oxide (ITO) that is restricted by the limited indium resource and its brittle nature. The challenge of metal based transparent conductive networks is to achieve high transmittance, low sheet resistance, and small perforation size simultaneously, all of which significantly relate to device performances in optoelectronics. In this work, trilayer dielectric/metal/dielectric (D/M/D) nanomesh electrodes are reported with precisely controlled perforation size, wire width, and uniform hole distribution employing the nanosphere lithography technique. TiO₂/Au/TiO₂ nanomesh films with small hole diameter (≤700 nm) and low thickness (≤50 nm) are shown to yield high transmittance (>90%), low sheet resistance (≤70 Ω sq^?1), as well as outstanding flexural endurance and feasibility for large area patterning. Further, by tuning the surface wettability, these films are applied as easily recyclable flexible electrodes for electrochromic devices. The simple and cost‐effective fabrication of diverse D/M/D nanomesh transparent conductive films with tunable optoelectronic properties paves a way for the design and realization of specialized transparent electrodes in optoelectronics.     

Highly Conductive and Transparent PEDOT:PSS Films with a Fluorosurfactant for Stretchable and Flexible Transparent Electrodes

Highly conductive and transparent poly‐(3,4‐ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) films, incorporating a fluorosurfactant as an additive, have been prepared for stretchable and transparent electrodes. The fluorosurfactant‐treated PEDOT:PSS films show a 35% improvement in sheet resistance (R_s) compared to untreated films. In addition, the fluorosurfactant renders PEDOT:PSS solutions amenable for deposition on hydrophobic surfaces, including pre‐deposited, annealed films of PEDOT:PSS (enabling the deposition of thick, highly conductive, multilayer films) and stretchable poly(dimethylsiloxane) (PDMS) substrates (enabling stretchable electronics). Four‐layer PEDOT:PSS films have an R_s of 46 Ω per square with 82% transmittance (at 550 nm). These films, deposited on a pre‐strained PDMS substrate and buckled, are shown to be reversibly stretchable, with no change to R_s, during the course of over 5000 cycles of 0 to 10% strain. Using the multilayer PEDOT:PSS films as anodes, indium tin oxide (ITO)‐free organic photovoltaics are prepared and shown to have power conversion efficiencies comparable to that of devices with ITO as the anode. These results show that these highly conductive PEDOT:PSS films can not only be used as transparent electrodes in novel devices (where ITO cannot be used), such as stretchable OPVs, but also have the potential to replace ITO in conventional 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.     

Layer‐Controlled and Wafer‐Scale Synthesis of Uniform and High‐Quality Graphene Films on a Polycrystalline Nickel Catalyst

Chemical vapor deposition (CVD) provides a synthesis route for large‐area and high‐quality graphene films. However, layer‐controlled synthesis remains a great challenge on polycrystalline metallic films. Here, a facile and viable synthesis of layer‐controlled and high‐quality graphene films on wafer‐scale Ni surface by the sequentially separated steps of gas carburization, hydrogen exposure, and segregation is developed. The layer numbers of graphene films with large domain sizes are controlled precisely at ambient pressure by modulating the simplified CVD process conditions and hydrogen exposure. The hydrogen exposure assisted with a Ni catalyst plays a critical role in promoting the preferential segregation through removing the carbon layers on the Ni surface and reducing carbon content in the Ni. Excellent electrical and transparent conductive performance, with a room‐temperature mobility of ≈3000 cm² V^?1 s^?1 and a sheet resistance as low as ≈100 Ω per square at ≈90% transmittance, of the twisted few‐layer grapheme films grown on the Ni catalyst is demonstrated.     

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.     

Reflecting p-contact based on thin ITO films for AlGaInN flip-chip LEDs

A reflecting contact to a p-GaN layer, used in fabrication of blue flip-chip light-emitting diodes, has been produced by deposition of thin indium tin oxide (ITO) films by electron-beam evaporation. The high reflectance of the contact, which exceeds that of a Ni/Ag contact, provides a 15–20% increase in the external quantum efficiency of light-emitting crystals. The forward voltage drops for crystals with an ITO(5 nm)/Ag(220 nm) contact are comparable with the corresponding values for crystals with a Ni(1.5 nm)/Ag(220 nm) contact. The specific resistance of the contact with an ITO layer is 3.7 × 10^?3 Ω cm². It is shown that, for ITO films produced by the given method, the optimal thicknesses providing the best electrical and optical characteristics of the crystals are in the range 2.5–5.0 nm.

     

Growth of Transparent and Conductive Polycrystalline (0001)‐ZnO Films on Glass Substrates Under Low‐Temperature Hydrothermal Conditions

Flat panel display technology seems to be an ever‐expanding field developing into a multibillion dollar market. A set of technical solutions involve a transparent conducting film (TCF) that is today still dominated by indium‐tin‐oxide (ITO). In a race to find alternatives that would avoid the indium pitfalls, mainly due to its increasing price and limited natural availablity, replacement materials have been extensively investigated. This work demonstrates that by exploiting basic principles of crystal growth in geometrically constrained conditions, zinc oxide (ZnO) could easily be utilized for this purpose. ZnO layers were grown on inexpensive glass substrates via low‐temperature citrate‐assisted hydrothermal (HT) method. It was shown that in the nucleation stage the crystal growth can be efficiently controlled by spatially confined oriented growth (SCOG) mechanism to produce smooth and dense (0001) oriented polycrystalline ZnO films with superb optical properties. Our products show optical transparency of 82% and surprisingly low sheet resistance for undoped ZnO, only in the order of few 100 Ω sq^?1. We believe that a very high degree of self‐organization between the ZnO crystals in our polycrystalline films grown under controlled SCOG conditions is main reason for the highest so far reported transparency to conductivity ratio for undoped ZnO thin film ceramics.     

Fabrication of Superstrong Ultrathin Free‐Standing Single‐Walled Carbon Nanotube Films via a Wet Process

A one‐pot and readily practical approach is described for the preparation of superstrong, ultrathin, free‐standing single‐walled carbon nanotube (SWNT) films. The SWNT films, with controlled thicknesses of tens to hundreds of nanometers, are prepared from commonly commercialized SWNTs via a wet process. The SWNTs could be easily transferred onto any substrates after self‐releasing from filter membranes without further treatment. The obtained films exhibit excellent performances with sheet resistance of 223 Ω sq^?1 and a transparency of 90% at 550 nm was obtained. Most important is that the as‐prepared free‐standing SWNT ultrathin films showed extremely high tensile strength up to 850 MPa for only about a 20‐nm thick film, which has great significance for practical applications, for example, as flexible electrode materials. The SWNT film is used to construct a capacitive touch‐screen prototype, which has a highly sensitive and quick signal touch response.     

Hybrid Silver Nanowire and Graphene‐Based Solution‐Processed Transparent Electrode for Organic Optoelectronics

The research on transparent conductive electrodes is in rapid ascent in order to respond to the requests of novel optoelectronic devices. The synergic coupling of silver nanowires (AgNWs) and high‐quality solution‐processable exfoliated graphene (EG) enables an efficient transparent conductor with low‐surface roughness of 4.6 nm, low sheet resistance of 13.7 Ω sq^?1 at high transmittance, and superior mechanical and chemical stabilities. The developed AgNWs–EG films are versatile for a wide variety of optoelectronics. As an example, when used as a bottom electrode in organic solar cell and polymer light‐emitting diode, the devices exhibit a power conversion efficiency of 6.6% and an external quantum efficiency of 4.4%, respectively, comparable to their commercial indium tin oxide counterparts.     

ITO‐Free and Flexible Organic Photovoltaic Device Based on High Transparent and Conductive Polyaniline/Carbon Nanotube Thin Films

The synthesis and characterization of thin films of polyaniline/carbon nanotubes nanocomposites is reported, as well as their utilization as transparent electrodes in ITO‐free organic photovoltaic devices. These films are generated by interfacial synthesis, which provides them with the unique ability to be deposited onto any substrate as transparent films, thus enabling the production of flexible solar cells using substrates like PET. Very high carbon nanotube loadings can be achieved using these films without significantly affecting their transparency (≈80–90% transmittance at 550 nm). Sheet resistances as low as 300 Ω/□ are obtained using secondary polyaniline doping in the presence of carbon nanotubes. These films present excellent mechanical stability, exhibiting no lack in performance after 100 bend cycles. Flexible and completely ITO‐free organic photovoltaic devices are built using these films as transparent electrodes, and high efficiencies (up to 2.27%) are achieved.