| 1. |
- Arvizu, Miguel A, et al.
(författare)
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Electrochemical pretreatment of electrochromic WO3 films gives greatly improved cycling durability
- 2018
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Ingår i: Thin Solid Films. - : ELSEVIER SCIENCE SA. - 0040-6090 .- 1879-2731. ; 653, s. 1-3
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Tidskriftsartikel (refereegranskat)abstract
- Electrochromic WO3 thin films have important applications in devices such as smart windows for energy-efficient buildings. Long-term electrochemical cycling durability of these films is essential and challenging. Here we investigate reactively sputter-deposited WO3 films, backed by indium-tin oxide layers and immersed in electrolytes of LiClO4 in propylene carbonate, and demonstrate unprecedented electrochemical cycling durability after straight-forward electrochemical pretreatments by the application of a voltage of 6 V vs. Li/Li+ for several hours.
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| 2. |
- Arvizu, Miguel A., et al.
(författare)
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Electrochromic dc sputtered W1-x-y Moy Tix O3 thin films: : Optical properties and durability.
- 2016
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Konferensbidrag (refereegranskat)abstract
- The key component in an electrochromic (EC) device is its primary EC thin film. The outstanding intrinsic ECproperties of tungsten oxide (WO3) make this material the best option available for the cathodic layer in an ECdevice. Nevertheless much research remains in order to optimize WO3 with regard to optical properties, durability,etc. It is well known that addition of titanium (Ti) into the matrix of WO3 increases significantly the resistance of the film to electrochemical cycling both under norma loperation and during accelerated aging in extended voltage ranges [1]. On the other hand, using molybdenum (Mo) as an additive in small concentrations helps to improve the color rendering by shifting th eposition of the maximum of the coloration band to higher energies [2]. The present work reports our recent investigations on thin films of mixed oxides with a focus on ways to optimize tungsten oxide thin films regarding both their durability and color by the addition of Ti and Mo. The films were deposited by reactive DC cosputtering from Mo and W-Ti alloy targets. Cyclic voltammetry, in a three-electrode system consisting of the film and lithium foils, was performed in a solution 1 MLiClO4 in propylene carbonate (Li–PC) as electrolyte. Insitu and ex-situ optical characterization was done for the EC films, and the transmittance switching and coloration efficiency were determined. Durability was studied by analyzing how the charge density evolved and how rapidly the transmittance modulation deteriorated during cycling for the different concentrations of Mo and Ti .References[1] M.A. Arvizu, C.A. Triana, B.I. Stefanov, C.G.Granqvist , G.A. Niklasson, “Electrochromism in SputterdepositedW-Ti Oxide Films: Durability Enhancement dueto Ti”, Solar Energy Materials & Solar Cells 125 (2014)184-189 (and references therein).[2] M.A. Arvizu, C.G. Granqvist and G.A. Niklasson,“Electrochromism in sputter deposited W1–yMoyO3 thinfilms”, Journal of Physics: Conference Series 682 (2016)012005 (and references therein).
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| 3. |
- Arvizu, Miguel A, et al.
(författare)
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Electrochromic W(1-x-y)Ti(x)lo(y)O(3) Thin Films Made by Sputter Deposition : Large Optical Modulation, Good Cycling Durability, and Approximate Color Neutrality
- 2017
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 29:5, s. 2246-2253
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Tidskriftsartikel (refereegranskat)abstract
- Tungsten oxide thin films are used in electrochromic devices such as variable-transmittance "smart windows" for energy efficient buildings with good indoor comfort. Two long-standing issues for WO3 thin films are their limited durability under electrochemical cycling and their blue color in transmission. Here, we show that both of these problems can be significantly alleviated by additions of titanium and molybdenum. We found that similar to 300 nm-thick films of sputter deposited W1-x-yTixMoyO3 are able to combine a midluminous transmittance modulation of 0.4 similar to 70% with good color neutrality and durability under extended electrochemical cycling. The Ti content should be similar to 10 at. % in order to achieve durability without impairing transmittance modulation significantly, and the Mo content preferably should be no larger than 6 at. % in order to maintain durability. Hence, our results give clear guidelines for making three-component mixed-oxide thin films that are suitable for electrochromic "smart windows".
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| 4. |
- Arvizu, Miguel A, et al.
(författare)
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Electrochromic WO3 thin films attain unprecedented durability by potentiostatic pretreatment
- 2019
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Ingår i: Journal of Materials Chemistry A. - : ROYAL SOC CHEMISTRY. - 2050-7488 .- 2050-7496. ; 7:6, s. 2908-2918
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Tidskriftsartikel (refereegranskat)abstract
- Electrochromic windows and glass facades are able to impart energy efficiency jointly with indoor comfort and convenience. Long-term durability is essential for practical implementation of this technology and has recently attracted broad interest. Here we show that a simple potentiostatic pretreatment of sputterdeposited thin films of amorphous WO3-the most widely studied electrochromic material-can yield unprecedented durability for charge exchange and optical modulation under harsh electrochemical cycling in a Li-ion-conducting electrolyte and effectively evades harmful trapping of Li. The pretreatment consisted of applying a voltage of 6.0 V vs. Li/Li+ for several hours to a film backed by a transparent conducting In2O3: Sn layer. Associated compositional and structural modifications were probed by several techniques, and improved durability was associated with elemental intermixing at the WO3/ITO and ITO/glass boundaries as well as with carbonaceous solid-electrolyte interfacial layers on the WO3 films. Our work provides important new insights into long-term durability of ion-exchange-based devices.
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| 5. |
- Arvizu, Miguel A., et al.
(författare)
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Electrochromism in DC sputtered W1-yMoyO3 thin films
- 2015
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Ingår i: INERA Conference 2015. - : Institute of Physics (IOP).
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Konferensbidrag (refereegranskat)abstract
- Electrochromic (EC) properties of tungsten–molybdenum oxide (W1–yMoyO3) thin films were investigated. The films were deposited on indium tin oxide covered glass by reactive DC sputtering from tungsten and molybdenum targets. Elemental compositions of the W1–yMoyO3 films were determined by Rutherford back scattering. Voltammetric cycling was performed in an electrolyte of 1 M LiClO4 in propylene carbonate. The increase in molybdenum content in the EC films caused both a shift towards higher energies and a quenching of the value of the maximum of the coloration band, as compared with WO3 EC films. Durability was also diminished for W1–yMoyO3 EC films.
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| 6. |
- Arvizu, Miguel A, et al.
(författare)
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Electrochromism in sputter-deposited W-Ti oxide films : Durability enhancement due to Ti
- 2014
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Ingår i: Solar Energy Materials and Solar Cells. - : Elsevier BV. - 0927-0248 .- 1879-3398. ; 125, s. 184-189
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Tidskriftsartikel (refereegranskat)abstract
- Thin films of W-Ti oxide were prepared by reactive DC magnetron sputtering and were characterized by Rutherford bathcattering spectrometry, X-ray diffraction, scanning electron microscopy and atomic force microscopy. The electrochromic properties were studied by cyclic voltammetry in an electrolyte of lithium perchlorate in propylene carbonate and by optical transmittance measurements. The addition of Ti significantly promoted the amorphous nature of the films and stabilized their electrochemical cycling performance and dynamic range for electrochromism. (C) 2014 Elsevier B.V. All rights reserved.
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| 7. |
- Arvizu, Miguel, et al.
(författare)
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Galvanostatic ion de-trapping rejuvenates oxide thin films
- 2015
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Ingår i: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 7:48, s. 26387-26390
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Tidskriftsartikel (refereegranskat)abstract
- Ion trapping under charge insertion-extraction is well-known to degrade the electrochemical performance of oxides. Galvano-static treatment was recently shown capable to rejuvenate the oxide, but the detailed mechanism remained uncertain. Here we report on amorphous electrochromic (EC) WO3 thin films prepared by sputtering and electrochemically cycled in a lithium-containing electrolyte under conditions leading to severe loss of charge exchange capacity and optical modulation span. Time-of-flight elastic recoil detection analysis (ToF-ERDA) documented pronounced Li+ trapping associated with the degradation of the EC properties and, importantly, that Li+ detrapping, caused by a weak constant current drawn through the film for some time, could recover the original EC performance. Thus, ToF-ERDA provided direct and unambiguous evidence for Li+ detrapping.
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| 8. |
- Atak, Gamze, et al.
(författare)
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Durability studies of annealed electrochromic tungsten oxide films
- 2021
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Ingår i: EMRS Fall Meeting 2021.
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Konferensbidrag (övrigt vetenskapligt/konstnärligt)abstract
- In electrochromic (EC) applications, annealing is a crucial parameter not only for an individual layer but also for a full device. For the fabrication of a complete EC device, indium tin oxide (ITO) is often preferred as a transparent conductor layer. ITO films with high transparency and low electrical resistance are usually obtained by sputtering at high substrate temperatures. Consequently, the effect of high temperature on the EC layers can be very significant during sputtering of the ITO top layer for EC devices consisting of five sputtered layers on a single substrate. The role of annealing of a single layer of WO3 may also be important for EC performance. In the present work, we studied the effects of annealing on the durability of WO3 films. Thin films of WO3 were deposited by reactive DC magnetron sputtering in a mixture of Ar and O2 gases using an oxygen to argon ratio of 0.15. The total gas pressure was set to 4.0 Pa, and the sputtering power was 200 W. The WO3 films were deposited onto (i) unheated glass plates, (ii) such plates pre-coated with transparent and electrically conducting ITO with a sheet resistance of 60 Ω/square, and (iii) glass plates pre-coated with fluorine-doped tin oxide (FTO) with a sheet resistance of 14 Ω/square. Film thicknesses were 300±10 nm. After deposition of the films, the samples were annealed at 150, 300, 450, and 600 °C in ambient air for one h using a heating rate of 10 °C min-1. Cyclic voltammetry (CV) was performed for up to 500 cycles between 2.0 and 4.0 V vs. Li/Li+ at a scan rate of 20 mV s–1. Annealing at temperatures at and above 300 °C resulted in deteriorated electrochromic properties of the WO3 films i.e., a decreased transmittance variation. Charge density and coloration efficiency changes during extended electrochemical cycling were also observed as a function of cycle number and annealing temperature. It was found that the maximum optical transmittance modulation at a wavelength of 528 nm after 500 CV cycles was 69.3% for the film annealed at 150 °C.
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| 9. |
- Atak, Gamze, et al.
(författare)
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Electrochromic tungsten oxide films prepared by sputtering : Optimizing cycling durability by judicious choice of deposition parameters
- 2021
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Ingår i: Electrochimica Acta. - : Elsevier. - 0013-4686 .- 1873-3859. ; 367
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Tidskriftsartikel (refereegranskat)abstract
- Thin films of W oxide were prepared by reactive DC magnetron sputtering (5 cm-diameter W target), and their electrochromic (EC) properties were investigated in an electrolyte of LiClO4 in propylene carbonate. The purpose of the study was to elucidate the role of critical deposition parameters-oxygen/argon gas flow ratio for the sputter plasma Gamma, total pressure in the sputter plasma p(tot) , and sputtering power P-s - on the EC performance with foci on electrochemical cycling durability and optical modulation range Delta T. Specifically, we used 0.15 <= Gamma <= 0.90, 5 <= p(tot) <= 30 mTorr, and 200 <= P-s <= 400 W and studied cycling durability for up to 500 voltammetric cycles in the range 2.0-4.0 V vs. Li/Li+ together with optical properties at a wavelength of 528 nm. Most significantly, we discovered that a judicious choice of deposition parameters could yield films with superior cycling durability. Thus a similar to 300 nm-thick film prepared at Gamma = 0.90, p(tot) = 10 mTorr, and P-s = 200 W showed Delta T approximate to 65% after an initial "training" during similar to 100 voltammetric cycles; higher values of p(tot), on the other hand, yielded films whose Delta Ts degraded by similar to 10% during the cycling, and a lower value of p(tot) led to dark films with only marginal electrochromism. Hence our work delineates a pathway towards W oxide films with excellent durability of the EC properties.
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| 10. |
- Atak, Gamze, et al.
(författare)
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Nitrogen doped W oxide films for electrochromic applications
- 2019
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Ingår i: EMRS Spring Meeting 2019.
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Konferensbidrag (refereegranskat)abstract
- Electrochromic (EC) materials are able to change their optical properties such as transmission, absorption and reflection reversibly by application of an external voltage. EC metal oxides are divided into two groups: cathodic (coloring under ion insertion) and anodic (coloring under ion extraction). W oxide is a well-known cathodic EC material and its color changes from transparent to dark blue when ions are inserted.A desirable electrochromic material must have and maintain a high optical modulation, high coloration efficiency, fast coloration/bleaching switching kinetics and a stable charge/ discharge reversibility. In this study, W oxide films with different nitrogen levels were deposited by using reactive DC sputtering onto glass and ITO coated glass in Ar+O2+N2 atmosphere. For all films, the total gas pressure was set to 4.0 Pa, the Ar flow rate was kept at 50 ml/min, and the O2+N2 flow rate was kept at 7.5 ml/min. The optical, structural and electrochromic properties of undoped and N-doped W oxide films were investigated. The optical studies revealed that the average optical transmittance and band gap decreased (from 3.43 to 3.08 eV) due to N doping. It is shown that a small amount of nitrogen has promising effects on the EC performance (i.e. charge/discharge reversibility, optical modulation, coloration efficiency) of the WO3 films. It is observed that CE values increased by increasing N2 flow rate and its maximum value was 33.8 cm2/C. The maximum ΔT at 537 nm was 73.6% for an optimized N doped W oxide film.
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