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Nano Energy 81 (2021) 105620 Available online 18 November 2020 2211-2855/© 2020 The Author(s).
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Published by Elsevier Ltd.
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This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
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Full paper
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Electrochromic solar water splitting using a cathodic WO3 electrocatalyst
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A R T I C L E I N F O
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Keywords: Electrochromism Hydrogen evolution reaction Water splitting WO3 Site saturation
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A B S T R A C T
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Solar-driven water splitting is an emerging technology with high potential to generate fuel cleanly and sus- tainably.
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In this work, we show that WO3 can be used as a cathodic electrocatalyst in combination with (Ag,Cu) InGaSe2 solar cell modules to produce hydrogen and provide electrochromic functionality to water splitting devices.
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This electrochromic effect can be used to monitor the charge state or performance of the catalyst for process control or for controlling the temperature and absorbed heat due to tunable optical modulation of the electrocatalyst.
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WO3 films coated on Ni foam, using a wide range of different sputtering conditions, were investigated as cathodic electrocatalysts for the water splitting reaction.
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The solar-to-hydrogen (STH) efficiency of solar-driven water electrolysis was extracted using (Ag,Cu)InGaSe2 solar cell modules with a cell band gap varied in between 1.15 and 1.25 eV with WO3 on Ni foam-based electrolyzers and yielded up to 13% STH ef- ficiency.
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Electrochromic properties during water electrolysis were characterized for the WO3 films on transparent substrate (indium tin oxide).
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Transmittance varied between 10% and 78% and the coloration efficiency at a wavelength of 528 nm and the overpotential of 400 mV was 40 cm2 C− 1.
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Hydrogen ion consumption in ion intercalation for electrochromic and hydrogen gas production for water electrolysis processes was discussed.
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1. Introduction
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Concerns about climate change, urban air pollution, and energy se- curity have led to an increased interest of scientists, industry, and po- litical leaders to develop methods for production, usage, and storage of energy in a clean and sustainable way.
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Molecular hydrogen is here a promising and carbon-free energy carrier for energy storage for later utilization as a source for heat, electricity, or as a chemical feedstock for industry.
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Electrolysis of water is a technique that yields hydrogen with high purity and would form a sustainable solution if electricity from wind-, hydro-, or solar-harvesting were used.
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A direct production in a photocatalytic or photovoltaic (PV) system coupled to an electrolyzer can be readily used today where molecular hydrogen stores the solar energy in a carbon-free fuel for later use in vehicles or stationary ap- plications.
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The stored energy can be used as heat by combustion or as electrical power via a hydrogen fuel cell on demand or when the solar power is intermittent.
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The history of electrolysis began at the end of the 18th century (1789) when Deiman and van Troostwijk dissociated water using an electrostatic generator and two gold electrodes immersed in water [1].
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Subsequently, Nicholson and Carlisle were the first who described the process of using electricity to dissociate water into hydrogen and oxygen in their experiments on the electrolytic splitting of water using voltaic piles in the year 1800 [2].
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Following the electrifi- cation of society, over 400 industrial water electrolyzers were in use in 1902 [3].
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Light-driven electrolysis was first described by Fujishima and Honda in 1972 using TiO2 as a photoanode and platinum as a cathode [4] and has been an active field of research since then.
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In electrocatalytic water splitting, hydrogen and oxygen gases evolve from reduction and oxidation of water at the cathodic and anodic electrodes, respectively.
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For photocatalytic water splitting using pho- toelectrochemical cells (PECs), the charge carriers are created from the photovoltaic effect close to the catalytic site.
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Solar cell driven electro- catalysis instead has advantages over direct photocatalysts in terms of higher efficiency, high power per area, and the possibility to separate the light absorption process from the electrolysis process [5] allowing optimization of each function independently, and not the least, enable the removal of the photo absorbing material from the electrolyte [6].
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Proton exchange membrane (PEM) electrolysis, which occurs in acidic electrolytes (pH 0–7), has better efficiency and enhanced ramping capability over other types of electrolysis [7].
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The principle of PEM
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electrolysis_01
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electrolysis together with half-cell and overall-cell reactions can be written as 2H+ + 2e− →H2 (cathodic reaction) (1) H2O→2H+ + 1/2O2 + 2e− (anodic reaction) (2) H2O→H2 + 1/2O2 (overall reaction) (3) and are shown in Fig. 1a.
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The typical operating cell voltage for commercial electrolyzers (1.8–2.0 V) is much larger than the theoretical minimum value (1.23 V), and they are typically operated at higher current densities to produce hydrogen at a high rate in order to offset the capital cost of the materials used.
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electrolysis
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For water electrolysis, the fabrication of cost-effective non-noble metals has attracted significant interest as a replacement for expensive Pt-based catalysts.
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However, they would also need to operate at a rela- tively high hydrogen production rate to lower the total cost of hydrogen produced over the lifetime of the system.
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Transition metal oxides such as WO3 can be promising alternatives and have previously mainly been used as photoanodic catalystst for oxygen evolution with modest solar- to-hydrogen (STH) efficiency but has recently also been highlighted as a cathodic electrocatalys that show promising stability with HER stability maintained after 2000 cycles [8].
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PV–technologies such as crystalline– and thin film– silicon, perov- skites, and (Ag, Cu)InGaSe2 (A-CIGS) can be used to supply the energy to drive an electrolyzer [6,9–12] with theoretical STH efficiencies span- ning from about 25% from serial interconnected solar cells to 32% for tandem approaches when using un-concentrated solar illumination [13].
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High optical absorption coefficient and adjustable band gap of A-CIGS solar cells make them attractive because of the possibility to achieve high efficiency (η) in the cells.
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The band gap of the A-CIGS cells can be changed by changing the Ga/(Ga+In) ratio [14–16].
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This prop- erty is helpful in finding an optimum condition for a highly efficient solar water splitting system [17].
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Electrochromism on the other hand, is an energy-saving technology that allows control of the amount of solar heat and visible light trans- mitted by a thin film.
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Electrochromic thin films are integral parts of multi-layer devices (Fig. 1b) that are capable of varying their optical properties by application of an externally applied voltage [18,19].
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Electrochromic devices can be used as smart windows in buildings, and this technology can significantly reduce energy use for cooling, air conditioning, and illumination [20].
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The history of electrochromism starts in the 1950s with the devel- opment of qualitative theory and quantitative prediction of the shift of the absorption and emission spectra of certain organic dyes by solvent and polarization effects [21,22].
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Based on these investigations, a possible change of color in dyes by applying an electric field was sug- gested by Platt in 1961 [23].
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It was the first time that the term elec- trochromism was used.
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In 1969, electrochromism was experimentally demonstrated in an inorganic compound, WO3, by Deb [24] and in 1985, Svensson and Granqvist introduced the potential application of electrochromic materials in smart windows [25].
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A typical smart win- dow, as shown in Fig. 1b, contains five layers between two transparent substrates where a transparent ion conductive layer lies at the center of the structure.
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One side of the layer is in contact with a thin film of a cathodic electrochromic material.
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This layer is colored by the insertion of ions and charge-balancing electrons into the film.
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On the opposite side of the ion conductor, an ion storage layer is situated.
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Usually, anodic electrochromic thin films are used in this layer in order to get the highest possible modulation of the transmittance.
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The anodic layer is colored by the extraction of ions and electrons from the film.
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In current electro- chromic technology, the most common devices include thin films based on cathodically coloring WO3 and anodically coloring NiO.
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The color- ation of WO3 is attributed to intervalence electron transfer between W6+ and W5+ valence states [26].
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The most accepted model for the coloration is that polarons formed by the localization of the injected electrons at W5+ sites are hopping between adjacent Wi and Wj sites when the light is absorbed [27].
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hν + W5+ i + W6+ j → W6+ i + W5+ j (4)
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The electrochromic phenomenon in WO3 occurs with the intercala- tion of M+ cations such as H+, Li+, and Na+ from the electrolyte and the reaction mechanism is given as: WO3 + xM+ + xe− ↔ MxWO3 (5)
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The expression for the time-dependent intercalation level is [28]. x(t) = (zedANW) − 1 ∫ t 0 dt′ I(t′) (6) where z is the valence of the intercalated ion, e is the elementary charge, d film thickness, A is the active area of the electrode, NW is the tungsten number density, and I is the current during the measurement.
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Electrochromic properties are assessed by optical modulation which is the difference between the bleached (Tb) and colored transmission (TC) states; optical density is defined as OD(λ, x) = dα(λ, x)where α is the absorption coefficient at the specified optical wavelength λ and inter- calation level x; and differential coloration efficiency K(λ, x) given by [28].
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K(λ, x) = dOD(λ, x)/dq (7) where q is the inserted charge per unit area.
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Fig. 1. Schematic picture of PEM electrolysis (a) and a window type electrochromic device (b), where M+ denotes the inserting ion.
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electrolysis_01
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İ. Bayrak Pehlivan et al Nano Energy 81 (2021) 105620 3
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electrolysis_01
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Considering the relation of OD with total transmittance (Tt) and reflectance (Rt), the differential coloration efficiency K(λ, x) can be written as K(λ, x) = − 1 Tt(λ, x) dTt(λ, x) dq − 1 [1 − Rt(λ, x) ] dRt(λ, x) dq (8)
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electrolysis_01
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Transition metal oxides are of interest for many applications other than electrochromic devices, for example, as catalysts, batteries, supercapacitors, and gas sensors.
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electrolysis_01
train3
electrolysis
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Therefore, there is a growing interest in multi-functional electrochromic devices, which can provide energy storage and energy production functionality together with control over light and/or heat [29,30].
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electrolysis_01
train3
electrolysis
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Photoelectrochromic devices combine elec- trochromism with photovoltaic electricity generation in an integrated device [31,32].
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electrolysis_01
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The energy need of the electrochromic devices can be supplied from the photovoltaic part and directly used for the optical modulation without any demand for external power.
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electrolysis_01
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electrolysis
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Very recently, it was found that electrochromic devices can also exhibit tunable micro- wave dielectric properties [33].
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electrolysis_01
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Electrochromic batteries and electro- chromic supercapacitors integrate energy storage functions with optical modulation [34,35].
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electrolysis_01
train3
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In particular, the ability to monitor the level of energy stored in the devices by the color variation makes electrochromic energy storage devices attractive.
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electrolysis_01
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electrolysis_01
Electrolysis in electrochromic devices was investigated to examine the role of water on device performance [36,37].
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MEASUREMENT
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electrolysis_01
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The optical modulation has been shown to increase and the coloration and bleaching times decreased with the presence of water in the ion-conductive layer [38].
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In this study, we combine investigations of electrocatalytic and electrochromic properties of WO3 thin films.
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electrolysis
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The study consists of three main parts.
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['Motivation']
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train3
electrolysis
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First, cathodic electrocatalytic properties of WO3 thin films deposited using a wide range of sputter conditions on Ni foam were investigated in the potential range of the hydrogen evolution reaction (HER) in an acidic electrolyte and compared with a well-known NiMo electrocatalyst for the overall water splitting reaction.
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electrolysis_01
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electrolysis
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Second, optimum STH efficiency was investigated for electrolyzers combining films pro- duced using different sputtering conditions of the WO3 (cathode) with Ni foam (anode) and A-CIGS solar cell modules with cell band gaps varying in-between 1.15 and 1.25 eV.
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electrolysis_01
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electrolysis
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In addition, electrochromic and electrocatalytic properties of WO3 films coated on indium tin oxide (ITO) substrates were investigated in a potential range relevant for the HER, where the coloration efficiency was quantified.
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Finally, we discuss H+ ion intercalation and the relation to the hydrogen evaluation process and possible applications of the reported effect.
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2. Experimental
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2.1. Sample preparation
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WO3 films were deposited on 1.6 mm thick Ni foam (350 g/m2 sur- face density and sheet resistance of 0.1 Ω/□) and ITO coated glass (sheet resistance of 60 Ω/□) substrates by reactive DC magnetron sputtering using a Balzers UTT 400 unit.
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electrolysis_01
train3
electrolysis
electrolysis_01
The target consisted of a 5 cm diameter metallic W (99.99% purity, Plasmaterials) disc.
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The target to substrate distance was 13 cm, and the system was evacuated to ~8 × 10–5 Pa.
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electrolysis_01
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Pre-sputtering was performed for 5 min in argon plasma in order to remove surface impurities.
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electrolysis_01
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The substrate holder was rotated at 3 rpm to improve the homogeneity of the films.
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Coating parameters are given in Table S1.
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electrolysis_01
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The film thickness determined by a Veeco Dektak 150 surface profilometry instrument was 165 ± 10 and 300 ± 25 nm for films coated on Ni foam and ITO substrates, respectively.
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electrolysis_01
train3
electrolysis
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Ni foam surface coverage of the WO3 thin film and its homogeneity were analyzed by energy–dispersive X-ray spectroscopy (EDS).
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MEASUREMENT
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The uniform elemental coverage of the WO3 on the Ni foam substrates was identified by EDS (Fig. 2).
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Due to the shadowing effect in EDS, one could not get the same quantification from the lower and the upper surfaces of the porous Ni foam substrate.
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However, since sputtering is a highly directional process, only the surface of Ni foam that was facing the sputter target should be expected to be coated.
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2.1.2.
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The A-CIGS material and subsequent solar cell modules were fabri- cated on soda-lime glass substrates cut to a 5 × 5 cm2 sample size.
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Fig. 2.
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Electron image and elemental mapping of WO3 thin film on Ni foam.
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İ. Bayrak Pehlivan et al Nano Energy 81 (2021) 105620 4
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sample structure consists of a stack of thin layers of Mo, NaF, A-CIGS, CdS, ZnO, and ZnO:Al.
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The Mo layer was fabricated by DC magnetron sputtering to a thickness of 300–400 nm.
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