Ag@Ni Core–Shell Nanowire Network for Robust Transparent Electrodes Against Oxidation and Sulfurization

Silver nanowire (Ag NW) based transparent electrodes are inherently unstable to moist and chemically reactive environment. A remarkable stability improvement of the Ag NW network film against oxidizing and sulfurizing environment by local electrodeposition of Ni along Ag NWs is reported. The optical transmittance and electrical resistance of the Ni deposited Ag NW network film can be easily controlled by adjusting the morphology and thickness of the Ni shell layer. The electrical conductivity of the Ag NW network film is increased by the Ni coating via welding between Ag NWs as well as additional conductive area for the electron transport by electrodeposited Ni layer. Moreover, the chemical resistance of Ag NWs against oxidation and sulfurization can be dramatically enhanced by the Ni shell layer electrodeposited along the Ag NWs, which provides the physical barrier against chemical reaction and diffusion as well as the cathodic protection from galvanic corrosion.     

Electrochromic modulation of near-infrared light by WO<Subscript>3</Subscript> films deposited on silver nanowire substrates

Silver nanowire (Ag NW) transparent conductive electrodes with high conductivity and optical transmittance are fabricated. Then, WO₃ films are deposited on Ag NW electrodes by an electrochemical deposition method. The WO₃/Ag NW films act as obvious optical modulators in the visible region. More importantly, the WO₃/Ag NW films have distinct advantage on NIR modulation over conventional WO₃/ITO electrode. Meanwhile, the WO₃/Ag NW films own high electrochromic efficiency of 86.9 cm² C^?1 at NIR region of 1100 nm. Furthermore, electrochromic devices (ECDs) based on Ag NW substrates are fabricated in this study, which exhibit excellent cycling stability and distinct modulation of near-infrared light compared with ITO-based ECDs. This work is the first study that reports the application of Ag NW-based electrochromic films and electrochromic devices in modulation of NIR light. It exhibits bright prospects that the electrochromic materials deposited on Ag NW electrodes may find potential application in thermal control and emission detectors for spacecraft.     

铜纳米线复合透明电极的构筑及应用研究进展

铜纳米线(Cu NWs)作为透明导电层,具有良好的光透过性、导电性、柔性以及低成本等特点,受到了研究者及工业界的广泛关注。然而,Cu NWs极易被氧化,严重限制了其在光电器件中的应用。针对这一难题,研究者普遍采用构筑Cu NWs复合透明电极的方式提高其稳定性。本文综述了近年来国内外在构筑Cu NWs复合透明电极方面的研究进展,重点介绍了不同构筑方式对Cu NWs透明电极结构、光电性能和稳定性的影响,简述了Cu NWs复合透明电极的应用研究进展。最后,对Cu NWs复合透明电极的应用前景和发展方向进行了展望。     

Optical haze of transparent and conductive silver nanowire films

Contemporary nanostructured transparent electrodes for use in solar cells require high transmittance and high conductivity, dictating nanostructures with high aspect ratios. Optical haze is an equally important yet unstudied parameter in transparent electrodes for solar cells that is also determined by the geometry of the nanostructures that compose the electrode. In this work, the effect of the silver nanowire diameter on the optical haze values in the visible spectrum was investigated using films composed of wires with either small diameters (～60 nm) or large diameters (～150 nm). Finite difference time domain (FDTD) simulations and experimental transmittance data confirm that smaller diameter nanowires form higher performing transparent conducting electrode (TCE) films according to the current figure of merit. While maintaining near constant transmittance and conductivity for each film, however, it was observed experimentally that films composed of silver nanowires with larger diameters have a higher haze factor than films with smaller diameters. This confirms the FDTD simulations of the haze factor for single nanowires with similarly large and small diameters. This is the first record of haze properties for Ag NWs that have been simulated or experimentally measured, and also the first evidence that the current figure of merit for TCEs is insufficient to evaluate their performance in solar cell devices.      

Topotaxial fabrication of vertical Aux Ag1-x nanowire arrays: plasmon-active in the blue region and corrosion resistant

Topotaxial growth of Au(x) Ag(1-x) alloy nanowires (NWs) by postepitaxial deposition of Ag vapor on Au NWs and investigation of their plasmonic properties are reported. Ag vapor is supplied onto the epitaxially grown Au NWs, topotaxially turning them into Au(x) Ag(1-x) alloy NWs. The original geometries and alignments of the Au nanostructures are well preserved, while the composition of the alloy NWs is controlled by varying the Ag vapor supply time. The Au(0.5) Ag(0.5) NWs show high surface-enhanced Raman scattering (SERS) activity comparable to that of Ag NWs as well as highly increased oxidation resistance. The plasmon-active wavelength range of the Au(0.5) Ag(0.5) NW is significantly extended to the blue region compared to Au NWs. The Au(x) Ag(1-x) alloy NWs that have plasmonic activity in the blue region in addition to high corrosion resistance will make a superb material for practical plasmonic devices including SERS sensors and optical nanoantennas.     

Solution-processed flexible polymer solar cells with silver nanowire electrodes

The conventional anode for organic photovoltaics (OPVs), indium tin oxide (ITO), is expensive and brittle, and thus is not suitable for use in roll-to-roll manufacturing of OPVs. In this study, fully solution-processed polymer bulk heterojunction (BHJ) solar cells with anodes made from silver nanowires (Ag NWs) have been successfully fabricated with a configuration of Ag NWs/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/polymer:phenyl-C(61)-butyric acid methyl ester (PCBM)/Ca/Al. Efficiencies of 2.8 and 2.5% are obtained for devices with Ag NW network on glass and on poly(ethylene terephthalate) (PET), respectively. The efficiency of the devices is limited by the low work function of the Ag NWs/PEDOT:PSS film and the non-ideal ohmic contact between the Ag NW anode and the active layer. Compared with devices based on the ITO anode, the open-circuit voltage (V(oc)) of solar cells based on the Ag NW anode is lower by ~0.3 V. More importantly, highly flexible BHJ solar cells have been firstly fabricated on Ag NWs/PET anode with recoverable efficiency of 2.5% under large deformation up to 120°. This study indicates that, with improved engineering of the nanowires/polymer interface, Ag NW electrodes can serve as a low-cost, flexible alternative to ITO, and thereby improve the economic viability and mechanical stability of OPVs.     

Pressure Welding of Silver Nanowires Networks at Room Temperature as Transparent Electrodes for Efficient Organic Light‐Emitting Diodes

In this work, polymethylmethacrylate (PMMA) as a superior mediate for the pressure welding of silver nanowires (Ag NWs) networks as transparent electrodes without any thermal treatment is demonstrated. After a pressing of 200 kg cm^?2, not only the sheet resistance but also the surface roughness of the PMMA‐mediated Ag NWs networks decreases from 2.6 kΩ sq^?1 to 34.3 Ω sq^?1 and from 76.1 to 12.6 nm, respectively. On the other hand, high transparency of an average transmittance in the visible wavelengths of 93.5% together with a low haze value of 2.58% can be achieved. In terms of optoelectronic applications, the promising potential of the PMMA‐mediated pressure‐welded Ag NWs networks used as a transparent electrode in a green organic light‐emitting diode (OLED) device is also demonstrated. In comparison with the OLED based on commercial tin‐doped indium oxide electrode, the increments of power efficiency and external quantum efficiency (EQE) from 80.1 to 85.9 lm w^?1 and 19.2% to 19.9% are demonstrated. In addition, the PMMA‐mediated pressure welding succeeds in transferring Ag NWs networks to flexible polyethylene naphthalate and polyimide substrates with the sheet resistance of 42 and 91 Ω sq^?1 after 10 000 times of bending, respectively.     

Reverse‐Offset Printed Ultrathin Ag Mesh for Robust Conformal Transparent Electrodes for High‐Performance Organic Photovoltaics

Mechanically durable transparent electrodes are needed in flexible optoelectronic devices to realize their long‐term stable functioning, for applications in various fields such as energy, healthcare, and soft robotics. Several promising transparent electrodes based on nanomaterials have been previously reported to replace the conventional and fragile indium‐tin oxide (ITO); however, obtaining feasible printed transparent electrodes for ultraflexible devices with a multistack structure is still a great challenge. Here, a printed ultrathin (uniform thickness of 100 nm) Ag mesh transparent electrode is demonstrated, simultaneously achieving high conductance, high transparency, and good mechanical properties. It shows a 17 Ω sq^?1 sheet resistance (R_sh) with 93.2% transmittance, which surpasses the performance of sputtered ITO electrodes and other ultrathin Ag mesh transparent electrodes. The conductance is stable after 500 cycles of 100% stretch/release deformation, with an insignificant increase (10.6%) in R_sh by adopting a buckling structure. Furthermore, organic photovoltaics (OPVs) using our Ag mesh transparent electrodes achieve a power conversion efficiency of 8.3%, which is comparable to the performance of ITO‐based OPVs.     

Stretchable,Electrochemically-Stable Electrochromic Devices Based on Semi-Embedded Ag@Au Nanowire Network

Stretchable electrochromic (EC) devices that can adapt the irregular and dynamic human surfaces show promising applications in wearable display, adaptive camouflage, and visual sensation. However, challenges exist in lacking transparent conductive electrodes with both tensile and electrochemical stability to assemble the complex device structure and endure harsh electrochemical redox reactions. Herein, a wrinkled, semi-embedded Ag@Au nanowire (NW) networks are constructed on elastomer substrates to fabricate stretchable, electrochemically-stable conductive electrodes. The stretchable EC devices are then fabricated by sandwiching a viologen-based gel electrolyte between two conductive electrodes with the semi-embedded Ag@Au NW network. Because the inert Au layer inhibits the oxidation of Ag NWs, the EC device exhibits much more stable color changes between yellow and green than those with pure Ag NW networks. In addition, since the wrinkled semi-embedded structure is deformable and reversibly stretched without serious fractures, the EC devices still maintain excellent color-changing stability under 40% stretching/releasing cycles.     

一维金属介质光子带隙材料的光学特性

本文描述了由不同厚度的ITO和Ag层制成的一维金属介质光子带隙材料1D M-D PBG的光学透射和反射特性。研究发现,单元尺寸小于80 nm的金属结构和较小的金属分数会导致光学透射率的提高。对于大于80 nm的单元尺寸,在可见光的低频和高频的频谱范围内反射率都相应增强。这是由于一种特殊结构和等离子体的带隙的作用。此外,在两个范围内的反射随着增加银膜厚度的增加而提高和扩大。结构引起的反射光谱随着单位尺寸的增大而增大,并且由于等离子体光子带隙的反射超出光学范围。研究结果对1D M-D PBG光学滤波器的设计有一定的参考价值。     

Tuning Light Absorption in Core/Shell Silicon Nanowire Photovoltaic Devices through Morphological Design

Subwavelength diameter semiconductor nanowires can support optical resonances with anomalously large absorption cross sections, and thus tailoring these resonances to specific frequencies could enable a number of nanophotonic applications. Here, we report the design and synthesis of core/shell p-type/intrinsic/n-type (p/i/n) Si nanowires (NWs) with different sizes and cross-sectional morphologies as well as measurement and simulation of photocurrent spectra from single-NW devices fabricated from these NW building blocks. Approximately hexagonal cross-section p/i/n coaxial NWs of various diameters (170-380 nm) were controllably synthesized by changing the Au catalyst diameter, which determines core diameter, as well as shell deposition time, which determines shell thickness. Measured polarization-resolved photocurrent spectra exhibit well-defined diameter-dependent peaks. The corresponding external quantum efficiency (EQE) spectra calculated from these data show good quantitative agreement with finite-difference time-domain (FDTD) simulations and allow assignment of the observed peaks to Fabry-Perot, whispering-gallery, and complex high-order resonant absorption modes. This comparison revealed a systematic red-shift of equivalent modes as a function of increasing NW diameter and a progressive increase in the number of resonances. In addition, tuning shell synthetic conditions to enable enhanced growth on select facets yielded NWs with approximately rectangular cross sections; analysis of transmission electron microscopy and scanning electron microscopy images demonstrate that growth of the n-type shell at 860 °C in the presence of phosphine leads to enhanced relative Si growth rates on the four {113} facets. Notably, polarization-resolved photocurrent spectra demonstrate that at longer wavelengths the rectangular cross-section NWs have narrow and significantly larger amplitude peaks with respect to similar size hexagonal NWs. A rectangular NW with a diameter of 260 nm yields a dominant mode centered at 570 nm with near-unity EQE in the transverse-electric polarized spectrum. Quantitative comparisons with FDTD simulations demonstrate that these new peaks arise from cavity modes with high symmetry that conform to the cross-sectional morphology of the rectangular NW, resulting in low optical loss of the mode. The ability to modulate absorption with changes in nanoscale morphology by controlled synthesis represents a promising route for developing new photovoltaic and optoelectronic devices.     

Nanowire encapsulation with polymer for electrical isolation and enhanced optical properties

Light management and electrical isolation are essential for the majority of optoelectronic nanowire (NW) devices.Here,we present a cost-effective technique,based on vapor-phase deposition of parylene-C and subsequent annealing,that provides conformal encapsulation,anti-reflective coating,improved optical properties,and electrical insulation for GaAs nanowires.The process presented allows facile encapsulation and insulation that is suitable for any nanowire structure.In particular,the parylene-C encapsulation functions as an efficient antireflection coating for the nanowires,with reflectivity down to ＜1％ in the visible spectrum.Furthermore,the parylene-C coating increases photoluminescence intensity,suggesting improved light guiding to the NWs.Finally,based on this process,a NW LED was fabricated,which showed good diode performance and a clear electroluminescence signal.We believe the process can expand the fabrication possibilities and improve the performance of optoelectronic nanowire devices.     

Preparation of Al-doped ZnO transparent electrodes suitable for thin-film solar cell applications by various types of magnetron sputtering depositions

In order to determine the influence of different types of magnetron sputtering (MS) depositions on the characteristics of Al-doped ZnO (AZO) thin films appropriate for applications as transparent electrodes in thin-film solar cells, transparent conducting AZO thin films were prepared on glass substrates at 200 °C by direct current (dc) magnetron sputtering (dc-MS), radio frequency (rf)-MS and rf power superimposed dc-MS (rf + dc-MS) depositions using an MS apparatus with the same AZO target. AZO thin films prepared by an rf + dc-MS deposition exhibited both a higher deposition rate than that found with rf-MS depositions and a lower resistivity or higher Hall mobility than those found with dc-MS. The lower dc sputter voltage featured in rf-MS and rf ± dc-MS depositions, producing smoother surface morphology and better crystallinity than obtained with dc-MS depositions. The light scattering characteristics of surface-textured AZO thin films prepared by various types of MS depositions were evaluated by observing the surface texture and measuring the optical transmittance and the diffusive component; wet-chemical etching of the thin film surface was performed in a 0.1% HCl solution. The obtainable haze property in the range from visible to near infrared in AZO films prepared by an rf + dc-MS deposition was markedly better than that obtained with dc-MS depositions.     

p-Type ZnO nanowire arrays

Well-aligned ZnO nanowire (NW) arrays with durable and reproducible p-type conductivity were synthesized on alpha-sapphire substrates by using N2O as a dopant source via vapor-liquid-solid growth. The nitrogen-doped ZnO NWs are single-crystalline and grown predominantly along the [110] direction, in contrast to the [001] direction of undoped ZnO NWs. Electrical transport measurements reveal that the nondoped ZnO NWs exhibit n-type conductivity, whereas the nitrogen-doped ZnO NWs show compensated highly resistive n-type and finally p-type conductivity upon increasing N2O ratio in the reaction atmosphere. The electrical properties of p-type ZnO NWs are stable and reproducible with a hole concentration of (1-2) x 10(18) cm(-3) and a field-effect mobility of 10-17 cm2 V(-2) s(-1). Surface adsorptions have a significant effect on the transport properties of NWs. Temperature-dependent PL spectra of N-doped ZnO NWs show acceptor-bound-exciton emission, which corroborates the p-type conductivity. The realization of p-type ZnO NWs with durable and controlled transport properties is important for fabrication of nanoscale electronic and optoelectronic devices.     

Highly efficient visible light photocatalysis of novel CuS/ZnO heterostructure nanowire arrays

Here, a facile approach for the fabrication of CuS nanoparticle (NP)/ZnO nanowire (NW) heterostructures on a mesh substrate through a simple two-step solution method is demonstrated. Successive ionic layer adsorption and reaction (SILAR) was employed to uniformly deposit CuS NPs on the hydrothermally grown ZnO NW array. The synthesized CuS/ZnO heterostructure NWs exhibited superior photocatalytic activity under visible light compared to bare ZnO NWs. This strong photocatalytic activity under visible light is due to the interfacial charge transfer (IFCT) from the valence band of the ZnO NW to the CuS NP, which reduces CuS to Cu(2)S. After repeated cycles of photodecolorization of Acid Orange 7 (AO7), the photocatalytic behavior of CuS/ZnO heterostructure NWs exhibited no significant loss of activity. Furthermore, our CuS/ZnO NWs/mesh photocatalyst floats in solution via partial superhydrophobic modification of the NWs.     

Ag反射膜厚度对PbTe热电薄膜性能的影响

采用真空蒸发法制备相同厚度的PbTe薄膜,再利用RF磁控溅射法在上面制备不同厚度的Ag反射膜,采用XRD、SEM、FTIR和四探针法分别对制备样品的物相组成、表面形貌、透射率和电阻率进行测试,结果显示,所制备的薄膜具有明显的〈100〉方向择优取向,呈多晶结构,随着反射膜厚度的增加,薄膜结晶性能先降低后增加;晶粒尺寸增加,表面粗糙程度先降低后增加;薄膜光学性能在一定膜厚范围内,随着反射膜厚度的增加透射率降低,超过一定膜厚时,透射率降为零;随着反射膜厚度的增加,电阻率呈先急剧降低后缓慢降低的趋势。     

Transparent conducting silver nanowire networks

We present a transparent conducting electrode composed of a periodic two-dimensional network of silver nanowires. Networks of Ag nanowires are made with wire diameters of 45-110 nm and a pitch of 500, 700, and 1000 nm. Anomalous optical transmission is observed, with an averaged transmission up to 91% for the best transmitting network and sheet resistances as low as 6.5 Ω/sq for the best conducting network. Our most dilute networks show lower sheet resistance and higher optical transmittance than an 80 nm thick layer of ITO sputtered on glass. By comparing measurements and simulations, we identify four distinct physical phenomena that govern the transmission of light through the networks: all related to the excitation of localized surface plasmons and surface plasmon polaritons on the wires. The insights given in this paper provide the key guidelines for designing high-transmittance and low-resistance nanowire electrodes for optoelectronic devices, including thin-film solar cells. For the latter, we discuss the general design principles to use the nanowire electrodes also as a light trapping scheme.     

Photocurrent polarization anisotropy of randomly oriented nanowire networks

While the polarization sensitivity of single or aligned NW ensembles is well-known, this article reports on the existence of residual photocurrent polarization sensitivities in random NW networks. In these studies, CdSe and CdTe NWs were deposited onto glass substrates and contacted with Au electrodes separated by 30-110 microm gaps. SEM and AFM images of resulting devices show isotropically distributed NWs between the electrodes. Complementary high resolution TEM micrographs reveal component NWs to be highly crystalline with diameters between 10 and 20 nm and with lengths ranging from 1 to 10 microm. When illuminated with visible (linearly polarized) light, such random NW networks exhibit significant photocurrent anisotropies rho = 0.25 (sigma = 0.04) [rho = 0.22 (sigma = 0.04)] for CdSe (CdTe) NWs. Corresponding bandwidth measurements yield device polarization sensitivities up to 100 Hz. Additional studies have investigated the effects of varying the electrode potential, gap width, and spatial excitation profile. These experiments suggest electrode orientation as the determining factor behind the polarization sensitivity of NW devices. A simple geometric model has been developed to qualitatively explain the phenomenon. The main conclusion from these studies, however, is that polarization sensitive devices can be made from random NW networks without the need to align component wires.     

Femtosecond laser irradiation induced heterojunctions between carbon nanofibers and silver nanowires for a flexible strain sensor

We report the direct joining of carbon nanofibers(CNFs)to silver nanowire(Ag NWs)by controlled irradiation with femtosecond(fs)laser pulses.Two separate types of nano-junction dependent on joint geometry,laser fluence and irradiation time are identified in irradiated mixtures.In one type of junction,the tip of an Ag NW is melted and flows to form a bond with an adjacent CNF.The second type of junction occurs without significant heating of the Ag NW and involves the softening and flow of carbon in the CNF in response to the transfer of plasmonic energy from the Ag NW into the CNF.Bonding in a T-type joint configuration can be of either kind depending on the relative orientation of the incident optical field and the long axis of the Ag NW.FDTD simulations were used to explore this effect for different joint geometries and laser polarization.The electrical properties of a heterojunction involving a single Ag NW-CNF structure have been measured,and it is found that the junction resistance can be reduced by six orders of magnitude after laser joining.Finally,we have investigated the properties of a strain sensor based on an Ag NW-CNF hybrid nanowire network and find that this device can exhibit high sensitivity.This sensitivity occurs as nano-junctions induced by fs laser irradiation greatly reduces the initial resistance.This laser-based technique for direct nanojoining of CNF and Ag NWs may enable the design of robust nanowire structures for application in a variety of new devices.     

A study of silicon oxynitride film prepared by ion beam assisted deposition

A SOI-based optoelectronic device needs a high-quality antireflection coating on both faces of the device to minimize the optical reflectance from the face. In this work amorphous silicon oxynitride films were deposited on silicon substrates by ion beam assisted deposition (IBAD). The main purpose was to use silicon oxynitride film as single layer anti-reflection coating for SOI-based optoelectronic devices. This application is primarily based on the ability to tune the silicon oxynitride optical functions to the optimal values by changing deposition parameters. The chemical information was measured by X-ray photoelectron spectroscopy (XPS). Spectroscopic ellipsometry (SE) was applied to measure the refractive index and thickness. Single-side polished silicon substrate that was coated with silicon oxynitride film exhibited low reflectance. Double-side polished silicon substrate that was coated with silicon oxynitride film exhibited high transmittance. In addition, the Fresnel losses could be reduced to 0.08 dB by depositing silicon oxynitride films onto double-side polished silicon substrates. The results suggested silicon oxynitride film was a very attractive single layer anti-reflection coating for SOI-based optoelectronic device.