Investigation of the Photochromism of WO3, TiO2, and Composite WO3-TiO2 Nanoparticles.

We report the synthesis of WO3, TiO2, and TiO2-WO3 nanoparticles by a polyol route, with the objective of studying the influence of the preparation method on their photochromic properties. By combining transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and diffuse reflectance experiments, we show that low W6+ concentrations and high ripening temperatures allow the preparation of WO3 nanoparticles with high photochromic efficiency. WO3-TiO2 nanocomposites (NCs) prepared by the introduction of a TiO2+ solution in a WO3 nanoparticle suspension exhibit a strong coloring photochromism, which is attributed to the TiO2 coating of the WO3 nanoparticles as it involves the formation of W-O-Ti oxo-bonds in place of W5+-νO defects. Especially, after an oxidative treatment in order to obtain an initial pale-yellow material, such WO3-TiO2 NCs exhibit a fully reversible photochromism with a large contrast between the colored and bleached state. They could therefore be incorporated in hybrid smart films for solar control on building window glasses. On the other hand, while the WO3-TiO2 NCs are functionalized with DPA (n-dodecyl phosphonic acid), the as-prepared nanocomposites exhibit exacerbated coloring contrast but with a nearly nonreversible photochromism (very limited bleaching), which makes them good candidates for the fabrication of smart UV-sensor devices that can indicate the cumulative UV dose which is received.

Silver Nanowire-Based Transparent Electrodes for V2O5 Thin Films with Electrochromic Properties.

The development of electrochromic systems, known for the modulation of their optical properties under an applied voltage, depends on the replacement of the state-of-the-art ITO (In2O3:Sn) transparent electrode (TE) as well as the improvement of electrochromic films. This study presents an innovative ITO-free electrochromic film architecture utilizing oxide-coated silver nanowire (AgNW) networks as a TE and V2O5 as an electrochromic oxide layer. The TE was prepared by simple spray deposition of AgNWs that allowed for tuning different densities of the network and hence the resistance and transparency of the film. The conformal oxide coating (SnO2 or ZnO) on AgNWs was deposited by atmospheric-pressure spatial atomic layer deposition, an open-air fast and scalable process yielding a highly stable electrode. V2O5 thin films were then deposited by radio frequency magnetron sputtering on the AgNW-based TE. Independent of the oxide's nature, a 20 nm protective layer thickness was insufficient to prevent the deterioration of the AgNW network during V2O5 deposition. On the contrary, crystalline V2O5 films were grown on 30 nm thick ZnO or SnO2-coated AgNWs, exhibiting a typical orange color. Electrochromic characterization demonstrated that only V2O5 films deposited on 30 nm thick SnO2-coated AgNW showed characteristic oxidation-reduction peaks in the Li+-based liquid electrolyte associated with a reversible orange-to-blue color switch for at least 500 cycles. The electrochromic key properties of AgNW/SnO2 (30 nm)/V2O5 films are discussed in terms of structural and morphological changes due to the AgNW network and the nature and thickness of the two protective oxide coatings.

Insight into the generation of near infra-red (NIR) absorbing species in electrochromic surface-anchored metal-organic frameworks.

Due to their versatility and easy processing, Surface-Anchored Metal-Organic Frameworks (SurMOFs) have gained interest in recent times as promising electrochromic thin films. Herein a step forward in their use and characterization was achieved thanks to the integration of {Zn2(PDICl4)2} SurMOFs in a multi-layer electrochromic device (ECD), based on a membrane-like electrolyte. The optical and electrochemical properties of the ECD were fully characterized, revealing a two-step reduction process localized on the organic ligand and involving subsequent near infra-red (NIR) and cyan absorbing states, leading to optical modulation of the films. The species responsible for this absorption were isolated and identified in the reduced states. In parallel to experimental characterization, quantum chemistry was successfully used to investigate the structure-property relationship of the SurMOF, revealing additional information regarding the structure and the local environment of the electrochromic ligand.

From the Irreversible Transformation of VO2 to V2O5 Electrochromic Films.

Since its discovery, electrochromism, known as the modulation of optical properties under an applied voltage, has attracted strong interest from the scientific community and has proved to be of significant utility in various applications. Although vanadium dioxide (VO2) has been a candidate for extensive research for its thermochromic properties, its intrinsic electrochromism has scarcely been reported so far. In this study, multi-electrochromism is described for VO2 thick films. Indeed, a VO2 opaque film, doctor bladed from homemade monoclinic VO2 powder, shows a pronounced color modulation from orange to green and blue associated with an amorphization-recrystallization phenomenon upon cycling in a lithium-based electrolyte. The strong memory effect allows us to follow the coloration mechanism by combining various ex situ and in situ characterizations addressing both structural and electronic aspects. Upon cycling, the multichromism of VO2 finds its origin in the transformation of VO2 into orange V2O5 upon oxidation, while in reduction, the blue lithiated state illustrates a mixed vanadium oxidation state.

Toward the Prediction of Electrochromic Properties of WO3 Films: Combination of Experimental and Machine Learning Approaches.

WO3 is the state of the art of electrochromic oxide materials finding technological application in smart windows. In this work, a set of WO3 thin films were deposited by magnetron sputtering by varying total pressure, oxygen partial pressure, and power. On each film two properties were measured, the electrochemical reversibility and the blue color persistence of LixWO3 films in simulated ambient conditions. With the help of machine learning, prediction maps for such electrochromic properties, namely, color persistence and reversibility, were designed. High-performance WO3 films were targeted by a global score which is the product of these two properties. The combined approach of experimental measurements and machine learning led to a complete picture of electrochromic properties depending of sputtering parameters providing an efficient tool in regards to time saving.

Synthesis and Characterization of Micro/Nanoscale VO2(M) through Vanadylethylene Glycolate Decomposition.

Thanks to a homemade dynamic vacuum system, fully crystallized VO2 (M) is successfully synthesized in a merged step of vanadyl ethylene glycolate (VEG) decomposition and crystallization of VO2 at high temperatures (>500 °C). During the whole process, vanadium valence (+4) is well maintained, and VEG microstructure plays an important role in the end-product size and shape. Finally, the suggested route appears well suitable for the mass production of VO2 nanoparticles.

Doubling of the Phase Transition Temperature of VO2 by Fe Doping.

Vanadium dioxide (VO2) undergoes a fully reversible first-order metal-insulator transition from the M1 monoclinic phase (P21/c) to a high-temperature tetragonal phase (P42/mnm) at around 68 °C. Modulation of the phase transition of VO2 by chemical doping is of fundamental and technological interest. Here, we report the synthesis of highly crystallized Fe-doped VO2 powders by a carbo-thermal reduction process. The impact of Fe doping on the structural and phase transition of VO2 is studied. The as-prepared Fe-doped VO2 samples crystallize in the M2 monoclinic form (C2/m), which is linked to segregation of the doping ions in the V2 zigzag chains. A large increase in the transition temperature to 134 °C is observed, which does correspond to a breakthrough in VO2-type thermochromic materials.

Influence of Quenching on the Opto-Electronic Properties of F:SnO2 Layers.

For many opto-electronic applications, F:SnO2 materials must benefit from high transparency, high conductivity, and high mechanical strength even after quenching. The purpose of this study was to investigate the influence of quenching on the opto-electronic properties of the F:SnO2 layers synthesized at high temperature on Si x C y O-coated soda-lime glass by atmospheric chemical vapor deposition. The morphology, structure, and composition of the layers were studied before and after quenching in air- and oxygen-rich atmospheres at 670 °C. The free carrier concentration was reduced by oxygen vacancy (VO) passivation, as well as by F and Na diffusion, with all effects scaling up with quenching time in air. The transmittance also decreased with quenching time as Na impurities acted as absorption and electron recombination centers. In an oxygen-rich atmosphere, the VO passivation was even more emphasized, with however a moderate contribution to conductivity loss. The F:SnO2 layer microstructure and composition were rather fringed through high-temperature deposition. The almost invariable free carrier concentration and transmittance of the F:SnO2 samples quenched in O2 versus air were related to a moderation in Na diffusion. For long quenching times (>20 min) in air, Na and F diffusion prevailed explaining the conductivity drop.

Toward Simplified Electrochromic Devices Using Silver as Counter Electrode Material.

Novel design of electrochromic devices (ECDs) known for their ability to modify optical properties under an applied voltage, based on a minimization of the number of layers is reported. The use of a metallic electrode, playing the role of both the conductive layer and the counter electrode, allows us to simplify the assembly of a commonly five-layer battery-type device to four-layer ECD. Further minimization of the number of layers is achieved using a conductive and electrochromic material. The novelty of the device configuration is illustrated using poly(3,4-ethylenedioxythiophene) (PEDOT)-based materials as EC layer, lithium-based ionic liquid as electrolyte, and Ag as counter electrode. Such a four- or three-layer ECD deposited on paper substrate switches from light to deep blue in a narrow 0.7 V voltage window. Preliminary investigations of the mechanism indicate traces of Ag on the PEDOT layer upon cycling. Finally, the printed ECD is successfully activated using a mobile phone.

Geometric considerations of the monoclinic-rutile structural transition in VO2.

The mechanism of the displacive phase transition in VO2 near the transition temperature is discussed in terms of a geometrical approach, combining simple calculations based on the Brown's band valence model and in situ X-ray diffraction experimental results. Considering that the structural origin is well linked to the electrostatic potential optimization as in a Peierls model, our geometrical calculations and experimental studies are in agreement and suggest that VO2 phase transition is the consequence of very short atomic shifts mainly associated to a decrease of the 2nd sphere coulombic interactions. Hence, at a given temperature, the allotropic form (monoclinic versus rutile form) offering the largest unit-cell volume is stabilized over the lower unit-cell volume allotropic, while the transition occurs at the intercept of the unit cell variation versus temperature of the two forms, which exhibit significantly different thermal expansion coefficients.

Color Tuning by Oxide Addition in PEDOT:PSS-Based Electrochromic Devices.

Poly(3,4-ethylenedi-oxythiophene) (PEDOT) derivatives conducting polymers are known for their great electrochromic (EC) properties offering a reversible blue switch under an applied voltage. Characterizations of symmetrical EC devices, built on combinations of PEDOT thin films, deposited with a bar coater from commercial inks, and separated by a lithium-based ionic membrane, show highest performance for 800 nm thickness. Tuning of the color is further achieved by mixing the PEDOT film with oxides. Taking, in particular, the example of optically inactive iron oxide Fe2O3, a dark blue to reddish switch, of which intensity depends on the oxide content, is reported. Careful evaluation of the chromaticity parameters L*, a*, and b*, with oxidizing/reducing potentials, evidences a possible monitoring of the bluish tint.

Carbon-reduction as an easy route for the synthesis of VO2 (M1) and further Al, Ti doping.

A low-cost and facile method to synthesize highly crystallized VO2 (M1) particles is proposed, using carbon black as the reducing agent mixed with V2O5 nanopowders comparing two types of vacuum systems for the thermal activation. In a sealed vacuum system, CO gas is generated in the first reductive step, and continues to reduce the new born VO2, until all the V (+4) is reduced to V (+3), resulting in V2O3 formation at 1000 °C. In contrast, in a dynamic vacuum system, CO gas is ejected through pumping as soon as it is generated, leading to the formation of pure VO2 (M1) at high temperatures (i.e. in the range 700 °C ≤ T ≤ 1000 °C). The evolution of the carbon content, determined by CHNS, of each sample versus the synthesis conditions, namely temperature and type of vacuum system, confirms that the transformation of V (+5) into V (+4) or V (+3) can be controlled. The characterization of the morphologies and crystal structures of two synthesized VO2 (M1) at 700 °C and 1000 °C shows the possibility to tune the crystallite size from 1.8 to more than 5 µm, with a uniform size distribution and highly crystallized powders. High purity VO2 (M1) leads to strong physical properties illustrated by a high latent energy (∼55 J g-1) during the phase transition obtained from DSC as well as high resistivity changes. In addition, with this method, dopants such as Ti4+ or Al3+ can be successfully introduced into VO2 (M1) thanks to the preparation of Al or Ti-doped nano-V2O5 by co-precipitation in polyol medium before carbon-reduction.

Structural transformations of the La2-xPrxNiO4+δ system probed by high-resolution synchrotron and neutron powder diffraction.

Compositions in the La2-xPrxNiO4+δ series offer an attractive balance of chemical stability and electrochemical performance for use as cathode materials in solid oxide fuel cells (SOFCs). A detailed crystallographic study of this system has been performed, combining both high resolution synchrotron and neutron powder diffraction data, in order to investigate structural details of the series as a function of composition, temperature and oxygen over-stoichiometry. The monoclinic structure (space group F2/m) of ambient temperature Pr-rich compositions for 1.0 < x ≤ 2.0 is discussed in terms of octahedra tilt arrangements and possible long-range structural modulations. In situ synchrotron diffraction experiments and TEM are employed to examine the role of temperature and interstitial oxygen on these structural distortions. With increasing La substitution, a region of mixed monoclinic and tetragonal phases is described for 0.5 ≤ x ≤ 1.0. La-Rich compositions are found to be single phase tetragonal (F4/mmm for 0 < x < 0.5) or orthorhombic (Fmmm for x = 0). Possible origins and electrochemical property consequences of the refined structural trends are considered.

Two-Step Synthesis of VO2 (M) with Tuned Crystallinity.

Highly crystallized monoclinic vanadium dioxide, VO2 (M), is successfully synthesized by a two-step thermal treatment: thermolysis of vanadyl ethylene glycolate (VEG) and postannealing of the poorly crystallized VO2 powder. In the first thermolysis step, the decomposition of VEG at 300 °C is investigated by X-ray diffraction and scanning electron microscopy (SEM). A poorly crystallized VO2 powder is obtained at a strict time of 3 min, and it is found that the residual carbon content in the powder played a critical role in the post crystallization of VO2 (M). After postannealing at 500 and 700 °C in an oxygen-free atmosphere, VO2 particles of various morphologies, of which the crystallite size increases with increasing temperature, are observed by SEM and transmission electron microscopy. The weight percent of crystalline VO2, calculated using the Fullprof program, increases from 44% to 79% and 100% after postannealing. The improved crystallinity leads to an improvement in metal-insulator transition behaviors demonstrated by sharper and more intense differential scanning calorimetry peaks. Moreover, V2O3 and V2O5 with novel and particular microstructures are also successfully prepared with a similar two-step method using postannealing treatment under reductive or oxidizing atmospheres, respectively.

Life-cycling and uncovering cation-trapping evidence of a monolithic inorganic electrochromic device: glass/ITO/WO3/LiTaO3/NiO/ITO.

The visualization of the microstructure change and of the depth of lithium transport inside a monolithic ElectroChromic Device (ECD) is realized using an innovative combined approach of Focused Ion Beam (FIB), Secondary Ion Mass Spectrometry (SIMS) and Glow Discharge Optical Emission Spectroscopy (GDOES). The electrochemical and optical properties of the all-thin-film inorganic ECD glass/ITO/WO3/LiTaO3/NiO/ITO, deposited by magnetron sputtering, are measured by cycling voltammetry and in situ transmittance analysis up to 11 270 cycles. A significant degradation corresponding to a decrease in the capacity of 71% after 2500 cycles and of 94% after 11 270 cycles is reported. The depth resolved microstructure evolution within the device, investigated by cross-sectional cutting with FIB, points out a progressive densification of the NiO layer upon cycling. The existence of irreversible Li ion trapping in NiO is illustrated through the comparison of the compositional distribution of the device after various cycles 0, 100, 1000, 5000 and 11 270. SIMS and GDOES depth profiles confirm an increase in the trapped Li content in NiO as the number of cycles increases. Therefore, the combination of lithium trapping and apparent morphological densification evolution in NiO is believed to account for the degradation of the ECD properties upon long term cycling of the ECD.

Double-Sided Electrochromic Device Based on Metal-Organic Frameworks.

Devices displaying controllably tunable optical properties through an applied voltage are attractive for smart glass, mirrors, and displays. Electrochromic material development aims to decrease power consumption while increasing the variety of attainable colors, their brilliance, and their longevity. We report the first electrochromic device constructed from metal organic frameworks (MOFs). Two MOF films, HKUST-1 and ZnMOF-74, are assembled so that the oxidation of one corresponds to the reduction of the other, allowing the two sides of the device to simultaneously change color. These MOF films exhibit cycling stability unrivaled by other MOFs and a significant optical contrast in a lithium-based electrolyte. HKUST-1 reversibly changed from bright blue to light blue and ZnMOF-74 from yellow to brown. The electrochromic device associates the two MOF films via a PMMA-lithium based electrolyte membrane. The color-switching of these MOFs does not arise from an organic-linker redox reaction, signaling unexplored possibilities for electrochromic MOF-based materials.

Low-Cost and Facile Synthesis of the Vanadium Oxides V2O3, VO2, and V2O5 and Their Magnetic, Thermochromic and Electrochromic Properties.

In this study, vanadium sesquioxide (V2O3), dioxide (VO2), and pentoxide (V2O5) were all synthesized from a single polyol route through the precipitation of an intermediate precursor: vanadium ethylene glycolate (VEG). Various annealing treatments of the VEG precursor, under controlled atmosphere and temperature, led to the successful synthesis of the three pure oxides, with sub-micrometer crystallite size. To the best of our knowledge, the synthesis of the three oxides V2O5, VO2, and V2O3 from a single polyol batch has never been reported in the literature. In a second part of the study, the potentialities brought about by the successful preparation of sub-micrometer V2O5, VO2, and V2O3 are illustrated by the characterization of the electrochromic properties of V2O5 films, a discussion about the metal to insulator transition of VO2 on the basis of in situ measurements versus temperature of its electrical and optical properties, and the characterization of the magnetic transition of V2O3 powder from SQUID measurements. For the latter compound, the influence of the crystallite size on the magnetic properties is discussed.

Polyol Synthesis of Ti-V2O5 Nanoparticles and Their Use as Electrochromic Films.

Herein, the successful synthesis of Ti-doped vanadium pentoxide from a polyol process is reported. A high Ti concentration (up to 8.5 mol % of the total metallic content) can be inserted in vanadium oxide thanks to the synthesis route leading to nanometric crystallites. X-ray diffraction patterns were refined showing the insertion of the titanium ions inside the free pentacoordinated sites in opposition to the vanadium square pyramidal sites. This crystal organization was shown in good agreement with the ab initio positioning performed from valence calculation. The nanoparticles, NPs, of Ti-doped V2O5 compounds were characterized as electrochromic materials. Films elaborated from a dip-coating process from oxide particle suspensions exhibited three distinct colorations during the redox cycling in lithium-based electrolyte. These colors were associated with three distinct oxidation states for the vanadium ions: +III (blue), +IV (green), and +V (orange). The morphology of the films was shown to drastically impact the electrochromic performances in terms of electrochemical capacity and stability.

Structure and reactivity with oxygen of Pr2NiO(4+δ): an in situ synchrotron X-ray powder diffraction study.

The promising SOFC cathode material Pr2NiO(4.22) has been studied in situ under a pure oxygen atmosphere from 25 to 950 °C by high resolution synchrotron X-ray powder diffraction. At room temperature (RT) δ = 0.22(1), the average crystal structure turns out to be monoclinic. The subtle monoclinic distortion (γ = 90.066(1)° at RT), retained up to 460 °C, is interpreted in terms of specific tilt schemes of the NiO6 octahedra. It is also shown that Pr2NiO(4.22) is incommensurately structurally modulated already at room temperature, in the same manner as the homologous cobaltate La2CoO(4.14). The phase transition to the High Temperature Tetragonal (HTT) phase was completed at 480 °C without any evidence for the Low Temperature Orthorhombic (LTO) phase allowing clarifying the phase diagram of this K2NiF4-type ternary oxide. Moreover, it turns out that above 800 °C, the HTT phase transforms reversibly into two coexisting isomorphous tetragonal phases. The incommensurate modulation subsists up to 950 °C, although modified concomitantly with the two abovementioned phase transformations. In addition, the role of kinetics on the decomposition process is highlighted through thermo-gravimetric analyses.

The oxygen vacancy in crystal phases of WO(3).

The oxygen vacancy in WO(3) has previously been implicated in the electrochromism mechanism in this material. Previous theoretical calculations on the oxygen vacancy in WO(3) have not considered the full range of crystal structures adopted by the material. Here we report studies of the oxygen vacancy in seven crystal phases. The use of a very accurate tungsten plane-wave pseudopotential means that a byproduct of this study is a more detailed and complete picture of undefected WO(3) than previously available. Electronic structures of the crystal phases in both undefected and defected systems have been calculated and are discussed. The band gap in WO(3) is dependent upon bonding-antibonding interactions, these being dependent upon overlap in each direction. The effect of an oxygen vacancy is dependent upon the availability of both Op and Wd electrons, this being different for the various phases. A variety of behavior is predicted, which may be explained in terms of O2p-W5d mixing, including the formation of long W-W dimer bonds. It is found that the nature of a polaron in this material is dependent upon both the crystal structure and distribution of oxygen vacancies.