D.
Kumar
a,
V.
Stoichkov
a,
E.
Brousseau
b,
G. C.
Smith
c and
J.
Kettle
*a
aSchool of Electronics, Bangor University, Dean St, Bangor, Gwynedd LL57 1UT, Wales, UK. E-mail: j.kettle@bangor.ac.uk; Fax: +44 (0)1248 382471
bDepartment of Natural Sciences, University of Chester, Thornton Science Park, Chester CH2 4NU, UK
cInstitute of Mechanical and Manufacturing Engineering, Cardiff School of Engineering, Cardiff University, Queen's buildings, The Parade, Cardiff CF24 3AA, UK
First published on 12th February 2019
A report of transparent and conducting silver nanowires (AgNWs) that produce remarkable electrical performance, surface planarity and environmental stability is given. This research presents an innovative process that relies on three sequential steps, which are roll-to-roll (R2R) compatible: thermal embossing, infrared sintering and plasma treatment. This process leads to the demonstration of a conductive film with a sheet resistance of 2.5 Ω sq−1 and high transmittance, thus demonstrating the highest reported figure-of-merit in AgNWs to date (FoM = 933). A further benefit of the process is that the surface roughness is substantially reduced compared to traditional AgNW processing techniques. The consideration of the long-term stability is given by developing an accelerated life test process that simultaneously stresses the applied bias and temperature. Regression line fitting shows that a ∼150-times improvement in stability is achieved under ‘normal operational conditions’ when compared to traditionally deposited AgNW films. X-ray photoelectron spectroscopy (XPS) is used to understand the root cause of the improvement in long-term stability, which is related to reduced chemical changes in the AgNWs.
Metallic nanowires with well-defined dimensions are a promising material for electrical and optical devices, particularly as flexible transparent conducting electrodes (TCEs), and are a strong candidate for ITO substitution.5,6 When deposited from solution processing, they combine several advantages such as high optical transmittance, low sheet resistance (RSH) and mechanical flexibility.4,7–9 These properties make them a candidate for applications such as sensors and detectors, touch screens, flat panel displays, OLEDs, light emitting electrochemical cells (LECs), printed PVs and layers for heated windows.10–12 However, challenges such as long-term environmental stability,13 contact resistance to the active materials,14 high surface roughness, electrical shorting problems and scalable fabrication must be overcome to fully integrate these new electrodes into commercial devices.15 These factors limit a more extensive use of TCE films based on silver nanowires, despite the emergence of companies such as Cambrios (US), C3 Nano (US), Seashell Technology (owned by BASF), and Toppan printing, who are currently offering silver nanowire (AgNW) suspensions.
The optical/electrical properties of AgNW based transparent electrodes depend on a number of factors including the purity of nanowires, geometry, deposition process and post-treatment of samples including hot rolling and thermal annealing.9,16,17 The conductivity relies upon the use of high aspect-ratio NWs to reduce the percolation threshold and thus to obtain a conductive network. By increasing the density of the percolation network, the conductivity can be improved, but this compromises the optical transmittance of the sample.
Post-processing has been used to improve the electrical properties of AgNWs including by annealing, ‘hot rolling’ and rinsing with chemicals that remove impurities such as polyvinylpyrrolidone (PVP).16–22 Currently the best combined electrical/optical performance was reported by Preston et al.,23 who demonstrated a TCE with a transmittance of 91% and a low sheet resistance of 13 Ω sq−1. By considering the trade-off between electrical and optical performance, a figure of merit (FoM) as defined using eqn (1) is often quoted6 which can be calculated for the work of Preston et al. as 300.3. In other work, Andrés et al. have reported a FoM value of 338 without any post-processing of AgNW electrodes with an RSh of 20 Ω sq−1 electrodes and transmittance at 550 nm of 94.7%, prepared by spray deposition.4
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In this work, the application of a roll-to-roll (R2R) compatible post-processing technique is reported which is shown to lead to one of the best reported AgNW electrode performances reported to date. The AgNWs were deposited using spray coating and post-processed using a sequential combination of thermal embossing, sintering and plasma cleaning. The produced films show performances up to RSh = 2.48 Ω sq−1 with transmittances over 85.5% in the visible-SWIR spectrum (300–2000 nm) onto polyethylene naphthalate (PEN) substrates. These result in the highest FoM of 933. Furthermore, the post-processing technique is shown to substantially reduce the surface roughness to a level comparable to that of ITO while also enhancing the stability at elevated temperature and current bias levels, with failure times shown to reduce by two orders of magnitude. The AgNWs are overcoated with ZnO nanoparticles and show significantly reduced surface roughness with excellent thermal stability (∼375 °C) and flexibility while maintaining high electrical conductivity and high optical transmittance. Combining the flexible and conductive films with the scalable roll-to-roll process, we anticipate that the commercial manufacture of a large-scale transparent electrode, replacing ITO, will be realized in the near future.24–26
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Fig. 1 Film deposition and post-processing approach: thermal embossing, photonic sintering, and N2 plasma treatment are used for post-treatment. |
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The sheet resistance (RSh) was measured using a four-probe setup (A & M FELL Ltd, UK). The surface roughness was estimated by white light interferometry (WLI) using a MicroXAM surface mapping microscope (KLA Tensor, USA). The roughness was measured in six positions and over two areas (3 × 2 mm) and (0.6 × 0.4 mm), with no discrepancy noted between the measurement areas. The roughness values were averaged across the six areas. Scanning electron microscopy (SEM) images were obtained using a Carl Zeiss 1540XB system equipped with a field-emission SEM.
The measurement system used to characterize the devices consisted of a Newport solar simulator with 100 mW cm−2 AM1.5G output (calibrated using a silicon reference cell from RERA in the Netherlands). The open circuit voltage (Voc), short-circuit current density (JSC), fill factor (FF) and PCE values are averaged from twelve cells.
Process | R sh (before post-process) Ω sq−1 | R sh (after post-process) Ω sq−1 | Percentage reduction in Rsh (%) | Optical transmittance@550 nm | Optical haze | FoM (after post-process) | Average percentage change in FoM (%) |
---|---|---|---|---|---|---|---|
Embossing | 40.4 | 18.1 | 55.2 | 92.9 | 0.2 | 278.9 | 120.8 |
Sintering | 42.4 | 19.1 | 55.0 | 94.0 | 0.3 | 314.1 | 97.1 |
N2 plasma | 41.4 | 20.1 | 51.4 | 92.7 | 0.3 | 242.8 | 90.2 |
Combined | 37.6 | 2.48 | 93.4 | 89.5 | 0.2 | 932.9 | 518.4 |
Combined and with ZnO NP coating | 37.1 | 2.98 | 81.7 | 85.2 | 0.4 | 758.7 | 498.6 |
ITO on PET | 40.0 | n/a | n/a | 85.0 | 0.4 | 55.7 | n/a |
ITO on glass | 12.0 | n/a | n/a | 84.0 | 0.5 | 172.4 | n/a |
The primary reason for the increase in performance after N2 plasma treatment is related to the reduction in the impurity levels (due to the organic impurity of PVP within the AgNW being removed). This is corroborated from the data in the section titled “XPS analysis of the AgNW films”, which shows that the C 1s peak intensity decreases after N2 plasma treatment, indicating a loss of the hydrocarbon content in the AgNW material.
As discussed earlier, a FoM can often be used in transparent conducting electrodes (TCEs) to compare their performances (defined in eqn (1)). The FoM for the combined post-processing technique shows a value of 933; this is substantially higher than the highest reported value in the literature, 338, and represents the best performing TCE based upon AgNWs, or ITO-replacements. As a comparison, the performances are benchmarked against the incumbent technology (ITO) which is reported for both glass and PET substrates (Table 1). In both cases, the AgNW TCEs prepared by the post-processing technique show significantly enhanced performance over the ITO. A typical absorption profile for the AgNW film, which was used for transmission calculations, is shown in ESI-2.†
In the context of transparent conducting electrodes (TCEs), the surface roughness of the sample is important. In OLEDs and OPVs, high surface roughness can lead to AgNWs penetrating through the active regions of the devices leading to electrical shorting. This limits the application of AgNWs in large-area devices or where multiple devices are required. Changes in the surface roughness after post-processing are reported in Table 2. The data show that the root mean square surface roughness (Rq) is reduced to 3.6 nm from 6.4 nm, the average roughness (Ra) is reduced to 2.7 nm from 4.9 nm and the maximum peak-to-valley is reduced to 60.8 nm from 105.9 nm, after the post-processing techniques. The surface roughness can be benchmarked also against incumbent technology (also shown in Table 2) and it is evident that after post-processing, there is 21.5 to 45.4 percent reduction in the Ra, Rq, and Pv surface roughness parameters.
Sample | R a (before post-process), nm | R a (after post-process), nm | % Change in RA | R q (before post-process), nm | R q (after post-process), nm | % Change in Rq | P V Peak to valley (before post-process nm) | P V Peak to valley (after post-process nm) | % Change in peak to valley PV |
---|---|---|---|---|---|---|---|---|---|
AgNWs combined | 6.8 | 3.7 | 45.4 | 8.5 | 4.9 | 43.0 | 101.4 | 79.6 | 21.5 |
AgNWs and with ZnO NP coating | 4.9 | 2.7 | 44.9 | 6.4 | 3.6 | 43.8 | 105.9 | 60.8 | 42.6 |
ITO on PET | 3.38 | n/a | n/a | 4.74 | n/a | n/a | 52.2 | n/a | n/a |
ITO on glass | 1.1 | n/a | n/a | 2.2 | n/a | n/a | 10 | n/a | n/a |
Given the significant enhancements in electrical and surface topographic properties, it is necessary to discuss their origins. SEM images of AgNWs TCEs before and after post-processing are shown in Fig. 2(a) and (b). Based on this, it can be said that the percolating network of AgNWs after embossing possess a more uniform height as the variation in the SEM contrast is less obvious. While topography can be somewhat difficult to evaluate using SEM, the images do show that the embossing step leads to improved physical contact between percolating AgNWs and is therefore likely to increase the number of electrical connections in between AgNWs and the integrity of the contact junctions. As the embossing temperature is low, it is unlikely that there is any ‘fusing’ of AgNW electrodes. The reduction in the SEM contrast indicates reduced secondary electron emission and is likely to be as the AgNWs are partially embedded within the polymer substrate. The embedding of the AgNWs into the polymer surface is likely to contribute to the reduction in the surface roughness as the top surface topography is dominated by the smoothness of the nickel shim which determines the embossed surface smoothness, rather than the protrusions of the AgNWs. In Fig. 2(c), it is apparent that the AgNWs have compressed and are embedded into the PMMA layer and some appear to have fractured during the embossing stage. It is clear that the applied pressure and temperature need to be optimised as over-pressurising during the embossing stage can lead to fractures which will diminish the sheet resistance. The physical changes that occur as a result of photonic sintering are also shown in the SEM image in Fig. 2(c). The data in Table 1 show that the average RSH reduces by ∼50% after sintering. Based on the SEM images, the sintering process affects the AgNW by melting and moderately deforming the AgNW so that the formation of better electrical junctions between individual nanowires is achieved which leads to the enhanced conductivity in films. In previous work, high temperature processing has been shown to remove the residue polyvinyl propyl (PVP) in the AgNWs, leading to improved chemical purity,4,24 which is also likely to contribute to the improvement in the RSH. Because the changes related to N2 plasma treatment are most likely to be changes in the materials chemistry, this is better discussed in section 3.5, where XPS studies of the surface chemistry are discussed. The N2 plasma treatment is likely to also remove the PVP resulting in an improvement in the sheet resistance.
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Fig. 3 Surface topography images using white light interferometry (WLI): (a) the control sample, (b) post-processed sample and (c) post-processed sample with ZnO overcoating. |
The roughness is quantified in Table 2 and the combined AgNW–ZnO electrode is shown to possess a roughness much lower than the control sample and is comparable to ITO on PET. It is clear from the WLI data that the ZnO fills up the voids created by the network of AgNWs and covers any remaining AgNWs that are protruding and thus improves the surface roughness. The result is significant for a second reason; for OPVs and OLEDs, ZnO is often used as an interlayer as the energy levels are favourable for electron extraction or hole injection (for OPVs and OLEDs, respectively). Therefore, the ZnO player has a dual functionality as it planarises the AgNW electrode and ensures energy alignment between the transparent electrode and the active region.
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Fig. 4 Current–voltage characteristics for the PTB7-Th:PCBM OPV using ITO-based electrodes on PET and glass substrates and a AgNW-based electrode under 100 mW cm−2 AM1.5 illumination. |
V OC (V) | J SC (mA cm−2) | FF | PCE | Yield | |
---|---|---|---|---|---|
ITO on PET | 0.732 | −16.3 | 0.56 | 6.70 | 100% |
AgNWs on PEN | 0.716 | −16.8 | 0.58 | 7.00 | 100% |
In terms of performance, the AgNW shows a moderately improved PV performance; this is primarily due to an increase in the short circuit current density (JSC) of around 0.6 mA cm−2 and a fill factor of 2%, compared to the sample made on an ITO substrate leading to a drop in the PCE. One would expect the AgNW device to have a higher FF than the device made on ITO-PET due to the lower RSH, but the observed differences in the FF are minor. Considering the IV characteristics reported in Fig. 4, the series resistance (RS) of the AgNW device is moderately better than that of the ITO-PET device, but there appears to be a decrease in the shunt resistance (RSH). This decreased Rsh is attributed to the increased shunts and parasitic pathways between AgNW films and the PTB7-Th:PCBM active layer as ZnO might not fully planarise the gap in-between the AgNW and the active layer. In the case of a larger device or modules, the use of AgNWs would have an even greater impact upon PV performance as the RS plays a much more significant role as the area increases. The open circuit voltage (VOC) of the AgNW electrode device is slightly lower as AgNWs possess a lower work-function and this accounts for the observed decrease of VOC.25 In addition to the slight performance increase, the AgNWs do possess a number of additional advantages over ITO including the improved mechanical robustness, no post-treatment requirements and no processing under vacuum.
The device performance has also been tested in resistive heaters and is shown in ESI-4.† The performances were demonstrated for a range of bias conditions, showing that heat can be applied very quickly and over an extended temperature range (limited by the temperature compatibility of the substrate). These data show that the post-processed electrodes can be used for a range of applications.
![]() | (3) |
![]() | (4) |
![]() | (5) |
Post-processed T10% | As used T10% | Post-processed T25% | As used T25% | |
---|---|---|---|---|
A | 7.79 × 10−7 | 2.0 × 10−6 | 9.51 × 10−8 | 3.20 × 10−7 |
B | 9359 | 7824 | 10![]() |
8440 |
n | 1.74 | 1.92 | 1.68 | 1.82 |
β | 2.47 | 2.08 | 2.42 | 2.11 |
η | 63![]() |
433 | 175![]() |
1005 |
To compare the impact of post-processing, a consistent definition of failures is needed. For this work, we calculated the time for 63% of the population of AgNW electrodes tested to show a decline in a particular value [such as 10% increase in resistance (T10%) or 25% increase (T25%)]. This value is often referred to as B(63%). By considering eqn (4), when t = η, the cumulative number of failures in the population, F(t) = 63%; therefore η is equivalent to B(63%).
Based on eqn (3), life is a function of two stress conditions; therefore, life versus temperature and life versus current density can be plotted on a logarithmic scale to show how varying temperature or current density affects the life of the AgNW films, while the other variable is kept constant. This is shown in Fig. 5(a) and (b) for life model fittings from Table 4. The general trend is to be expected; as the stress level of the current density (a) or temperature (b) is increased, the anticipated life of the AgNW film decreases. It is evident from Fig. 5 that the stability of the post-processed samples is substantially higher than that of the non-post-processed samples, by around three orders of magnitude under normal operational conditions (Ibias = 20 mA cm−2 and temperature). This is because the post-processed samples possess a lower resistance due to improved electrical contact. As the power dissipated across the electrode is related to the bias current and resistance as PD = I2·R, the ‘as used’ sample will experience 16× greater power dissipation than the post-processed sample, leading to increased Joule heating, which causes the nanowires to break up and thus create an electrical discontinuity in the nanowire film.14 As more heat is created, the probability of failures increases. Furthermore, during the post-processing procedure, the AgNWs are partially embedded within the underlying polymer, which is likely to act as a barrier layer limiting the impact of oxidation and sulphidisation.
An important characteristic often assessed in life test models is the acceleration factor (AF), which shows the ratio of the AgNW life at the ‘operational’ stress level to its life at an accelerated stress level and is defined in eqn (3). Both the post-processed and ‘as used’ samples show similar characteristics, but the ‘as used’ samples appears to degrade quicker with increases in the current density.
To evaluate the stability fully, further experiments have been conducted by applying different interlayers onto the AgNW electrodes to observe the interaction between two layers. A single stress condition was applied (Ibias = 300 mA cm−2 and temperature = 65 °C), enabling a relative comparison of stability to be made, which is reported in Fig. 6. The least stable electrode was the ‘as used’ electrode which had no post-processing conducted. The poor stability is due to thermal oxidation of AgNWs as the sample is exposed to the environment. When AgNW films are exposed to air and water, they can be easily oxidized, leading to a sharp increase of the sheet resistance and haze of the AgNW films.26 After the post-processing, the AgNWs are moderately embedded into PMMA and this appears to act as a barrier to inhibit the level of oxidation. By applying a further overcoating the stability is enhanced, although the most significant improvement is obtained by using the ZnO interlayer. The application of PEDOT + DMSO shows the lowest stability as an overcoating layer and is likely to be related to the reactive nature of Ag to environmental S which causes sulfidation.
It is worth noting that the optical properties did not change upon ageing. For example, the optical haze of the aged samples was compared to freshly prepared samples. For samples without any interlayers (i.e. ZnO/PEDOT:PSS), the optical haze of fresh samples was measured at 4.81%, which changed less than ±0.10% after ageing. This was measured from an average of three samples.
As prepared | Thermal embossing | N2 plasma treatment | Thermal embossing and N2 plasma treatment | As prepared and aged | Thermal embossing and N2 plasma treatment and aged | |
---|---|---|---|---|---|---|
C 1s | 66.66 | 72.92 | 61.73 | 62.31 | 67.42 | 70.95 |
O 1s | 19.72 | 22.15 | 27.10 | 25.12 | 22.20 | 24.91 |
Ag 3d | 7.99 | 1.58 | 7.11 | 8.19 | 5.09 | 1.01 |
S 2p | 1.66 | 0.29 | 1.86 | 2.07 | 2.13 | 0.14 |
Cl 2p | 1.00 | 0.17 | 0.96 | 0.91 | 0.83 | 0.22 |
N 1s | 2.97 | 2.89 | 1.24 | 1.40 | 1.79 | 2.32 |
Na 1s | 0.55 | 0.45 |
The C 1s spectra were typical of those obtained from a poly(methyl methacrylate) PMMA surface, with the hydrocarbon component arising from the backbone and the pendant methyl groups, and the oxygenated components arising from the two carbon–oxygen bonded components of the ester group. The variation in the presence of carbon in this form indicates that there are different levels of AgNW coverage between different samples. Samples that were embossed show higher levels of the carbon surface, indicating that they are submerged in the underlying PMMA.
The levels of Ag did not change significantly upon N2 plasma treatment; however, the embossed samples showed much lower levels of Ag (consistent with the SEM images and carbon XPS data). Nevertheless, even after thermal embossing, Ag was clearly present at the surface, indicating that Ag was not fully embedded into the substrate during this processing step. By comparison, the N2 plasma treated sample showed a decrease in the surface concentration of C and an increase in the surface concentration of O compared to the control. We speculate that the N2 plasma removes hydrocarbon impurities from the AgNW films, namely the PVP used in end-capping during the synthesis, and this leads to the reduction in C and the improved electrical properties. This is supported by the reduction in the surface concentration of N after N2 plasma treatment, which is also likely to be due to the removal of PVP. The increase in the O content after thermal embossing is likely to be because of the raised temperature in ambient air leading to increased oxidation.
On all samples, the Ag 3d5/2 – 3d3/2 doublets were sharp, intense, symmetrical in shape and typically 1.2–1.3 eV in width. In all cases the binding energy of the 3d5/2 component was found in the range 368.8–369.3 eV, somewhat higher than the internationally accepted reference value of 368.27 eV for clean metallic silver.27 In all cases, a doublet separation of 6.02 ± 0.01 eV was found. Ag is unusual among metallic elements in that its oxides tend to exhibit photoelectron peak binding energy shifts to a lower binding energy than the metallic state. Here, a shift to a higher binding energy is seen. This is occasionally seen in the presence of alloying elements, but this cannot be the case here. Instead, it is more likely that the shift is due to charge transfer between the nanowires and the (insulating) PMMA/PEN substrates. This would be consistent with the results reported by Lin & Wang28 and those from other studies of deposited Ag layers. It could alternatively be a function of a more tightly bound crystal structure of Ag in the form of nanowires compared to the bulk metal.
Ageing the as-prepared sample caused small increases in the surface concentrations of O, S and C. Ageing of the post-processed sample caused an increase in the surface concentration of C and small reductions in the surface concentrations of the other elements present, except for Ag where a significant reduction occurred from ∼8% to ∼1%, suggesting the coverage of Ag by a carbon-containing material as a consequence of the ageing process.
S was detected at low levels on all samples, with a possible correlation with the level of Ag (correlation coefficient r2 = 0.79). This is consistent with the reactive nature of Ag to environmental S and the consequent formation of silver sulphides. Inspection of the S 2p photoelectron peaks showed that the majority of S was present in a sulphide state, S2−, consistent with AgS. The thermally embossed and aged samples show low levels of S indicating why these samples remain stable. By ensuring that a greater proportion of the AgNWs are submerged in the underlying PMMA, they remain less susceptible to environmental ageing.
We have included bend testing to demonstrate the enhanced mechanical performance of the post-processed AgNW-based electrodes during repeated bending. As shown in ESI-7,† under a 100-cycle test with a bending radius of 20 mm, almost no effect was observed while dramatic failure was observed in the ITO electrode in the same test. The test shows that the mechanical flexibility of the samples is not affected by the post-processing of the AgNW films.
Footnote |
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c8nr07974a |
This journal is © The Royal Society of Chemistry 2019 |