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.     

Co‐Percolating Graphene‐Wrapped Silver Nanowire Network for High Performance,Highly Stable,Transparent Conducting Electrodes

Transparent conducting electrodes (TCEs) require high transparency and low sheet resistance for applications in photovoltaics, photodetectors, flat panel displays, touch screen devices and imagers. Indium tin oxide (ITO), or other transparent conductive oxides, have typically been used, and provide a baseline sheet resistance (R_S) vs. transparency (T) relationship. However, ITO is relatively expensive (due to limited abundance of Indium), brittle, unstable, and inflexible; moreover, ITO transparency drops rapidly for wavelengths above 1000 nm. Motivated by a need for transparent conductors with comparable (or better) R_S at a given T, as well as flexible structures, several alternative material systems have been investigated. Single‐layer graphene (SLG) or few‐layer graphene provide sufficiently high transparency (≈97% per layer) to be a potential replacement for ITO. However, large‐area synthesis approaches, including chemical vapor deposition (CVD), typically yield films with relatively high sheet resistance due to small grain sizes and high‐resistance grain boundaries (HGBs). In this paper, we report a hybrid structure employing a CVD SLG film and a network of silver nanowires (AgNWs): R_S as low as 22 Ω/□ (stabilized to 13 Ω/□ after 4 months) have been observed at high transparency (88% at λ = 550 nm) in hybrid structures employing relatively low‐cost commercial graphene with a starting R_S of 770 Ω/□. This sheet resistance is superior to typical reported values for ITO, comparable to the best reported TCEs employing graphene and/or random nanowire networks, and the film properties exhibit impressive stability under mechanical pressure, mechanical bending and over time. The design is inspired by the theory of a co‐percolating network where conduction bottlenecks of a 2D film (e.g., SLG, MoS₂) are circumvented by a 1D network (e.g., AgNWs, CNTs) and vice versa. The development of these high‐performance hybrid structures provides a route towards robust, scalable and low‐cost approaches for realizing high‐performance TCE.     

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.     

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.     

Synthetic Crystals of Silver with Carbon: 3D Epitaxy of Carbon Nanostructures in the Silver Lattice

Only minimum amounts of carbon can be incorporated into silver, gold, and copper in a thermodynamically stable form. Here, the structure of stable silver carbon alloys is described, which are produced by thermoelectrically charging molten silver with carbon ions. Transmission electron microscopy and Raman scattering are combined to establish that large amount of carbon is accommodated in the form of epitaxial graphene‐like sheets. The carbon bonds covalently to the silver matrix as predicted from density functional theory (DFT) calculations with bond energies in the range 1.1–2.2 eV per atom or vacancy. Graphitic‐like sheets embedded in the crystal lattice of silver form 3D epitaxial structures with the host metal with a strain of ≈13% compared to equilibrium graphene. The carbon nanostructures persist upon remelting and resolidification. A DFT‐based analysis of the phonon density of states confirms the presence of intense vibration modes related to the Ag? C bonds observed in the Raman spectra of the alloy. The solid silver–high carbon alloy, termed “Ag‐covetic,” displays room temperature electrical conductivity of 5.62 × 10⁷ S m^?1 even for carbon concentrations of up to ≈6 wt% (36 at%). This process of incorporation of carbon presents a new paradigm for electrocharging assisted bulk processing.     

Enhanced Electrocatalysis via 3D Graphene Aerogel Engineered with a Silver Nanowire Network for Ultrahigh‐Rate Zinc–Air Batteries

3D graphene aerogel (GA) integrated with active metal or its derivatives has emerged as a novel class of multifunctional constructs with range of potential applications. However, GA fabricated by self‐assembly in the liquid phase still suffers from low conductivity and poor knowledge related to spatial active phase distribution and 3D structure. To address these issues, a facile approach involving in situ integration of 1D silver nanowire (AgNW) during gelation of graphene oxide flakes is presented. AgNWs prevent the restacking of graphene sheets and act as an efficient electron highway and Ag source for deposition of ultrasmall Ag nanocrystals (AgNCs). When applied as the cathodic electrocatalyst in a zinc–air battery, the 3D GA integrated with 0D AgNCs and 1D AgNWs permit ultrahigh discharge rates of up to 300 mA cm^?2. Moreover, for the first time, with the help of phase‐contrast X‐ray computed microtomography, the interconnected porous network of millimeter‐sized GA and a full‐field view of the macrodistribution of Ag is delivered, offering the vitally complementary macroscopic structure information, which has been missing in previous reports.     

Highly Conductive,Bendable, Embedded Ag Nanoparticle Wire Arrays Via Convective Self‐Assembly: Hybridization into Ag Nanowire Transparent Conductors

The optoelectrical properties of Ag nanowire (NW) networks are improved by incorporating the NWs into highly conductive ordered arrays of Ag nanoparticle wires (NPWs) fabricated via surfactant‐assisted convective self‐assembly. The NPW–NW hybrid conductor displays a transmittance (T) of 90% at 550 nm and a sheet resistance (R _s) of 5.7 Ω sq^?1, which is superior to the corresponding properties of the NW network showing a R _s of 14.1 Ω sq^?1 at a similar T. By the modified wettability of a donor substrate and the capillarity of water, the sintered NPW–NW hybrid conductors are perfectly transferred onto an UV‐curable photopolymer film, and the embedded hybrid conductors exhibit excellent electromechanical properties. The R _s and T of the NPW arrays can be predicted by using a simple model developed to calculate the width and height of the hexagonal close‐packed particles formed during the convective self‐assembly. The numerical analysis reveals that the maximum Haacke figure of merit of the NW networks is increased considerably from 0.0260 to 0.0407 Ω^?1 by integration with the NPW array. The highly conductive NPW arrays generated using a simple, low‐cost, and nonlithographic process can be applied to enhancing the performances of other transparent conductors, such as carbon nanotubes, metal oxides, and graphenes.     

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

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

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.     

Prediction of Novel p‐Type Transparent Conductors in Layered Double Perovskites: A First‐Principles Study

The development of high‐performance transparent conductors (TCs) is critical to various technologies from transparent electronics to solar cells. Whereas n‐type TCs have been extensively applied in many electronic devices, their p‐type counterparts have not been largely commercialized due to the lack of ideal materials. Combining atomic replacement and first‐principles calculations, seven stable layered double perovskites are identified, i.e., Cs₄CuSb₂Cl₁₂‐like Cs₄M²⁺B³⁺₂X^VII₁₂ compounds as promising p‐type TCs with sufficiently large bandgaps, delocalized wavefunction distribution with s‐orbital components in valence band maximum (VBM) and the antibonding character of VBM to ensure their optical transparency, light hole effective masses, and intrinsic good p‐type conductivities, respectively. Taking Cs₄CdSb₂Cl₁₂ as a representative example, it is demonstrated that under Cd‐poor (Cl‐rich) conditions, Cs₄CdSb₂Cl₁₂ could exhibit excellent p‐type conductivity with high hole concentration, contributed by the intrinsic shallow‐acceptor Cd_Sb with extremely low formation energy. Generally, the other 6 Cs₄M²⁺B³⁺₂X^VII₁₂ compounds exhibit similar intrinsic p‐type defect properties as Cs₄CdSb₂Cl₁₂, which could rank them as the top p‐type TCs discovered or predicted until now.