Design and fabrication of MoSe2/WO3 thin films for the construction of electrochromic devices on indium tin oxide based glass and flexible substrates

Electrochromic devices (ECDs) have the ability to block the heat generated by sunlight, making them ideal for use in smart windows. Herein, we report the fabrication of ECDs using MoSe₂/WO₃ (MSW) as the electrochromic material, for smart windows applications. A solvothermal method was used for the synthesis of MoSe₂, while WO₃ was synthesized using a sol-gel approach. Subsequently, MoSe₂/WO₃ (MSW) hybrids with different wt% of MoSe₂ (0.05 wt%, 0.2 wt%, 0.5 wt%) were synthesized using an ultra-sonication approach. The physicochemical features of these MSW hybrids herein termed as MSW 0.05, MSW 0.2 and MSW 0.5, were investigated using X-ray diffraction (XRD), X-ray photon electron spectroscopic (XPS), scanning electron microscope (SEM), and EDS techniques and compared with pristine MoSe₂ and WO₃. The ECDs synthesized using MSW 0.05 showed increased coloration efficiency (62 cm^2 C-1) with an applied potential range of 0 to −1.5 V. Subsequently, the ECDs based on indium tin oxide (ITO) and MSW 0.05 demonstrated excellent electrochromic performance and stability for 10,000 cycles. The enhanced electrochromic performance of the MSW-based ECDs may be attributed to the conductive nature as well as the synergistic effects between MoSe₂ and WO₃ when compared to the WO₃-based ECDs. The synthesized MSW also showed promise as an electrochromic material in flexible ECDs for smart windows applications.     

Influence of Ag incorporation on the structural,optical and electrical properties of ITO/Ag/ITO multilayers for inorganic all-solid-state electrochromic devices

Indium tin oxide/silver/indium tin oxide (ITO/Ag/ITO, IAI) multilayer structures were prepared by DC magnetron sputtering as a conductive transparent electrode for inorganic all-solid-state electrochromic devices. A thin layer of silver (Ag) with various thicknesses was inserted between two layers of ITO films. The XRD and SEM results revealed that the microscopic morphology of Ag film was closely related to the thickness. Besides, the electrical and optical properties of the IAI multilayers were significantly influenced by the Ag layer thickness. The optimized IAI multilayers demonstrated the best combination of electrical and optical properties with a figure of merit of 54.05 (sheet resistance of 6.14 Ω/cm²and optical transmittance of 90.83%) when the Ag film was 10 nm thick. In order to evaluate the IAI multilayers as a transparent electrode for electrochromic applications, two ECDs with the structures of ITO/NiO_x/LiPON/WO₃/ITO and ITO/NiO_x/LiPON/WO₃/IAI were prepared, and their electro-optical properties were characterized by cyclic voltammetry (CV), chronoamperometry (CA) and spectroscopic measurements. Compared with ECD the pure ITO top electrode (ITO/NiO_x/LiPON/WO₃/ITO), the ECD with the IAI top electrode (ITO/NiO_x/LiPON/WO₃/IAI) presented a slightly smaller optical modulation amplitude, but a faster switching speed. All our findings indicate that the IAI multilayer structure is a promising alternative to the ITO thin film for inorganic all-solid state electrochromic applications.     

Electrochromic properties of porous NiO thin film as a counter electrode for NiO/WO3 complementary electrochromic window

Highly porous nickel oxide (NiO) thin films were prepared on ITO glass by chemical bath deposition (CBD) method. SEM results show that the as-deposited NiO film is constructed by many interconnected nanoflakes with a thickness of about 20 nm. The electrochromic properties of the NiO film were investigated in a nonaqueous LiClO₄–PC electrolyte by means of optical transmittance, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements. The NiO film exhibits a noticeable electrochromic performance with a variation of transmittance up to 38.6% at 550 nm. The CV and EIS measurements reveal that the NiO film has high electrochemical reaction activity and reversibility due to its highly porous structure. The electrochromic (EC) window based on complementary WO₃/NiO structure shows an optical modulation of 83.7% at 550 nm, much higher than that of single WO₃ film (65.5% at 550 nm). The response time of the EC widow is found to be about 1.76 s for coloration and 1.54 s for bleaching, respectively. These advantages such as large optical modulation, fast switch speed and excellent cycle durability make it attractive for a practical application.     

Crack-free fabrication of Prussian blue-based blending film for the dramatic enhancement of dual electrochromic device

We introduce a method based on particle-printing technology to facilitate the fabrication of crack-free dual electrochromic devices (ECDs). A film prepared by blending Prussian blue (PB) with antimony tin oxide (ATO) powders had a dense structure free of surface cracks and was suitable as both anode and ion storage layers. We investigated the deposition conditions as a function of substrate temperature at room temperature, 80 °C, and 150 °C. The PB/ATO blending film formed at 150 °C had a uniform surface and high crystallinity; this was the optimal substrate temperature. At 150 °C, the as-fabricated dual ECD had an improved diffusion coefficient of 8.70 × 10⁻⁹ cm²/S due to the presence of the PB/ATO blending film. Moreover, there was over 4-fold improvement in the transmittance change at 800 nm compared with that of the WO₃ film only with no anodic layer. The better ECD properties were attributed to improved ion mobility and ion storage capacity. Therefore, this blending film was successfully fabricated on the substrate without any cracks using facile particle printing technology to be served as both anodic and ion storage layer.     

Ag mesh network framework based nano composite for transparent conductive functional electrodes for capacitive touch sensor and thin film heater

We report on the development of a highly conductive, transparent and flexible Ag mesh-like network covered by an ITO/PEDOT:PSS nanocomposite for flexible conductive electronics. The electrode was deposited completely via solution-based deposition. A lower R_s value, from 7.21 Ω/□ to 5.05 Ω/□, was achieved by annealing the substrate via low-temperature plasma annealing. The low-temperature annealing was used to achieve crystallinity of the materials without deformation and degradation of PEDOT:PSS and the PET substrate. The low-cost deposition-based Ag NW-ITO/PEDOT:PSS electrode substantially decreased sheet resistance and provides the transmittance of 85.17%. The chemical stability and mechanical stability of the product were examined, and morphological studies were performed; in all of these, the substrate exhibited excellent behavior. Finally, a transparent flexible electrical heater and capacitive touch screen panel were fabricated using the Ag NW-ITO/PEDOT:PSS electrode to demonstrate the performance of the electrode and its potential applications.     

Low-temperature fabrication of sol–gel NiO film for optoelectronic devices based on the ‘fuel’ of urea

In this work, NiO coating is fabricated by a low temperature ‘combustion process’ driven by ‘chemical oven’ on quartz and indium tin oxide (ITO) substrates followed by an annealing process in air at 225 °C for 2 h. The NiO coating is analyzed by means of thermalgravimetric differential thermal analysis (TG-DTA), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electric microscopy (SEM), atomic force microscope (AFM), and UV–visible spectrometer. A prelimilary photovoltaic performance measurement of the fabricated device (ITO/NiO/poly-TPD/PC₇₁BM/Al) shows a short circuit current density (J_sc) of 5.28 mA cm⁻² and power conversion efficiency (PCE) of 1.56% under an illumination of 100 mW cm⁻². The PCE of device with combustion NiO HTLs is almost 10-fold higher than those of the devices based on common NiO HTLs. The combustion fabricated NiO coating may provide an effective approach to fabricate other NiO-based optoelectrical devices at relative low temperature.     

Effect of Ar/O2 ratio on double-sided electrochromic glass performance

This paper reports the qualities of WO₃ film and NiO film added to a counter electrode and their use in a double-sided electrochromic glass device. A mixture of argon and oxygen gasses with ratios of Ar/O₂ of 1.5, 2, 3, and 5 were used for the deposition of the working electrode of WO₃ film for EC glass. The structure of double-side EC glass consists of glass/ITO/NiO/electrolyte/WO₃/ITO/glass/ITO/WO₃/electrolyte/NiO/ITO/glass layers. The working electrode of WO₃ film controls the color presented, the applied voltage controls the color depth, and the counter electrode controls the transparency in the bleached state. The double-sided EC glass with double WO₃ films and double NiO films have faster coloration/bleaching rates than do single-sided EC glass. A mixture of Ar/O₂ ratio of 3.0 has the best coloration/bleaching property of the ratios tested. Compared to the single-sided EC glass, the double-sided EC glass has lower transmittance of about 72% and 6% than the 78% and 12% during coloration and bleaching states in the visible light region with +1.5 V and ?3.5 V applied.     

Lightwave irradiation-assisted low-temperature solution synthesis of indium-tin-oxide transparent conductive films

Transparent conductive oxide (TCO) films have important applications in many areas. Unfortunately, TCOs are usually fabricated using vacuum and high-temperature methods, preventing them from applications in low-cost flexible devices. In this paper, facile low-temperature sol-gel method is described that can be used to fabricate high-quality TCO films. This study uses lightwave (LW) irradiation (at ～280 °C) with indium-tin-oxide (ITO) as a typical example. Both structure and key properties of ITO films are investigated for different LW irradiation conditions. ITO can be formed via LW irradiation after a period as short as 5 min. Furthermore, it is found that LW irradiation can promote the formation of M ? O framework, effectively remove Cl impurities, and facilitate the elimination of hydroxyl oxygen defects - even at temperatures as low as ～280 °C. The optimal ITO films show excellent electronic properties, including low sheet-resistance (14.5 Ω·sq^?1) and high conductivity (1.7 × 10³ S cm^?1). Moreover, ITO films also show high transmittance (above 87%). Overall, our ITO films have a figure of merit (FOM) of 1.72 × 10^?2 Ω^?1, which is comparable to (or higher than) those of previous ITO films that were produced using conventional vacuum and high-temperature methods. Our LW irradiation method provides facile and effective approach to produce high-performance TCO films at remarkably low cost. This means these films could be used in affordable flexible large-area devices.     

Stability-enhanced indium hexacyanoferrate electrodes: Morphological characterization, in situ EQCM analysis in nonaqueous electrolytes and application to a WO3 electrochromic device

This paper presents a promising transparent counterelectrode system for a WO₃ electrochromic device (ECD) on the basis of a stability-enhanced indium hexacyanoferrate (InHCF) electrode and a NaClO₄/propylene carbonate (PC) electrolyte. Through SEM characterization it was found that clusters of granular InHCF nanoparticles (ca. 80-140 nm) were deposited on ITO substrates in HCl and KCl-stabilized plating solutions, and uniform micrometer thick films with high charge capacity could be obtained. From in situ electrochemical quartz crystal microbalance study, it was discovered that Na⁺ would enter or move out from the InHCF film in the “desolvated” form during the redox process in a PC electrolyte. Besides, NaClO₄/PC resulted in higher electrochemical activity and reversibility than LiClO₄/PC. With these discoveries, a durable WO₃-InHCF ECD featuring blue-to-colorless electrochromism was fabricated successfully. The device remained 73.6 and 88.7% of its initial ΔT values at 600 and 800 nm after 40,000 rapid and successive coloring/bleaching cycles, respectively. Moreover, the cycling-induced loss of electrochromic performance almost completely restored after 1-month rest and kept unchanged for another month. Thus, the applicability of this nonaqueous InHCF counterelectrode system to ECDs was verified.     

Ga and Ti co-doped In2O3 films for flexible amorphous transparent conducting oxides

We designed Ga and Ti co-doped In₂O₃ (IGTO) films to use as a flexible and transparent amorphous conducting oxide electrode in thin film heaters (TFHs) and flexible touch screen panels (FTSPs) for automobiles. The properties of the IGTO electrodes deposited on cyclic olefin copolymer (COP) at room temperature were investigated as a function of the O₂/(Ar + O₂) flow ratio, to confirm the best sputtering condition for transparent and flexible electrode. Depending on the oxygen flow ratio, the IGTO/COP electrodes showed sheet resistance of (39.3 – 1.57) × 10⁴ Ohm/sq, an average transmittance of (84.90 – 87.12) % at visible wavelength area, and a surface roughness of (0.95 – 3.23) nm. In addition, IGTO/COP samples exhibited good mechanical flexibility with critical bending radius of 3 mm, which is enough to be used as FTSPs. From the previously mentioned results, we found the amorphous IGTO/COP to be a promising flexible and transparent electrode for curved TFHs and FTSPs. The flexible IGTO/COP TFHs demonstrated a saturated temperature of 78.6 °C when applied with low operating direct current (DC) of 8 V, due to its low sheet resistance. In addition, the IGTO/COP FTSPs showed very stable touch sensitivity, even at a bent state. We found that the optimized IGTO/COP is a promising flexible and transparent electrode for next-generation automobiles.     

Transformation of β-Ni(OH)2 to NiO nano-sheets via surface nanocrystalline zirconia coating: Shape and size retention

Shape and size of the synthesized NiO nano-sheets were retained during transformation of sheet-like β-Ni(OH)₂ to NiO at elevated temperatures via nano-sized zirconia coating on the surface of β-Ni(OH)₂. The average grain size was 6.42 nm after 600 °C treatment and slightly increased to 10 nm after 1000 °C treatment, showing effective sintering retardation between NiO nano-sheets. The excellent thermal stability revealed potential application at elevated temperatures, especially for high temperature catalysts and solid-state electrochemical devices.     

Optical and electrical properties of ITO film on flexible fluorphlogopite substrate

Indium Tin Oxide (ITO) films were prepared, at room temperature, on a fluorphlogopite substrate using magnetron sputtering technology. At various temperatures of 500 °C, 600 °C, 700 °C, 800 °C, and 900 °C, the samples were (had) annealed for 2 h (a 2-h duration). The results showed improvement in the crystalline performance of ITO film at selected annealing temperatures, with a significant reduction in resistivity at 800 °C. The lowest resistivity is 4.08 × 10^?4 Ω-cm, which is nearly an order of magnitude lower than the unannealed sample. All samples have an average light transmittance above 85% in the visible light range (400–800 nm), and with increasing annealing temperature, the average light transmittance tends to decrease. Besides, at the sensitive wavelength of 550 nm, the light transmittance is as high as 93.74%. The sheet resistance testing of the sample was through the number of bending times, which revealed that with the increase of the number of bending, the sheet resistance increases. However, after 1200 bending times, the change rate of the sheet resistance remains below 5%. Thus, the ITO film prepared on the flexible fluorphlogopite substrate revealed excellent optical and electrical properties, good flexibility, and improved stability after high-temperature annealing, which guarantees successful application in flexible electronic devices.     

Logotype-selective electrochromic glass display

This paper describes a fabrication method of a logotype-selective electrochromic (EC) glass. The EC glass performance based on the sample size, WO₃ film thickness, and internal impedances under various applied voltages are also discussed. The logotype-selective electrochromic glass was fabricated by the sputter deposition process. Both working and counter electrode were coated with ITO/WO₃ films. The specific logotypes of “NCUT” and “NUU” can be displayed with positive and negative voltages applied to the EC glass. EC glasses of various sizes (1 cm², 4 cm², 9 cm², 25 cm², and 100 cm²) were also fabricated by sputter deposition process. When voltage (?3.5 V) was applied to the device, the active layer of the assembled device changed from almost transparent to a translucent blue color (colored). The average transmittance in the visible region of the spectrum for a 100 cm² EC device was 73% in the bleached state. The best device, with a 140 nm WO₃ active layer, had average transmittances in the colored and bleached states of 11.9% and 54.8%, respectively. Cyclic voltammogram tests showed that reproducibility of the colored/bleached cycles was good. Nyquist plots showed that increasing the device size decreased the current density, and the electrolyte impedance increased because of a low conductive electrolyte in the device.     

Effect of the thicknesses of the Al2SiO5 ion conductor on the opto-electrical properties for all-solid electrochromic devices

In this study, an all-solid-state electrochromic device (ECD) with the structure of ITO/WO₃/Al₂SiO₅/NiO_x/ITO was prepared, and the effect of the Al₂SiO₅ solid electrolyte thicknesses on the opto-electrical performance was investigated. The microstructure and surface morphology were characterized using XRD, SEM and AFM, and the surface morphology and degree of surface looseness demonstrate a significant influence on the opto-electrical properties of ECDs. The charge transfer dynamics at the solid-solid interface were characterized using EIS to obtain an ionic conductivity of 4.637 × 10^-8 S/cm. CV, CA and UV–Visible spectra were employed to record the in situ electrochemical and optical properties. The results revealed that the highest optical modulation was 44.58%, the coloring and bleaching times were 14.8 s and 3.7 s, and the highest coloring efficiency was 98.17 cm²/C, which indicates that excellent opto-electrical properties were obtained. When the thickness increases, the degree of surface dense morphology transforms, and the loose morphology is more favorable for ion conductivity, which improves the opto-electrical properties. The results in this study provide insights into the understanding of Al³⁺-based all-solid-state ECDs, which promote the exploration of new types of Al³⁺ ionic conductors for all-solid-state ECDs.     

Preparation and gas-sensing performance of GO/SnO2/NiO gas-sensitive composite materials

In this study, a SnO₂/NiO composite material was prepared via a co-precipitation method. After calcination at 400 °C for 2 h, a binary composite material (SnO₂/NiO) with good crystallization was obtained. Then, a graphene oxide (GO)/SnO₂/NiO ternary composite material was prepared using a hydrothermal method, in which SnO₂/NiO performed secondary growth on the GO surface. The XRD results showed that SnO₂/NiO exhibited good crystallinity and proved the existence of a chemical bond, Sn–O–C, which was due to the formation of a chemical bond between GO and SnO₂/NiO. Lastly, GO/SnO₂/NiO was successfully prepared and coated on the surface of a gold electrode for gas sensitivity test. A good response to acetone gas in the concentration range of 10–500 ppm at 350 °C was determined. Compared with SnO₂/NiO, GO/SnO₂/NiO showed remarkable improvements in response time, recovery time, and sensitivity. At 350 °C, the sensitivity of acetone with a concentration of 50 ppm was 21.11, the response time was only 5 s, and the recovery time was 150 s. GO/SnO₂/NiO comprised two structures, chemical bond and p-n junction, which exerted a synergistic effect. GO/SnO₂/NiO indicated an excellent application prospect in acetone gas detection.     

Trends in sputter deposited tungsten oxide structures for electrochromic applications: A review

Electrochromic devices (ECD) show reversible color change under applied electric field and are predicted to become indispensable in many applications such as low power displays, smart windows to develop energy-saving buildings as well as light-adapting mirrors in high-end cars and aircrafts. Despite the assiduous research work, ECD faces several challenges for practical usage including delamination, durability, lifetime and their integration into multifunctional devices. To improve the performance, different techniques have already been used to deposit single-layered thin film, or a stack of promising EC layers on several substrates including transparent conductive oxides (TCO) coated glass and different conducting polymers. These layers can be flat enough or have a definite shape or structure to satisfy the needs of the designed device. Based on their low resistivity and high transparency, fluorine and indium doped tin oxides (FTO, ITO) are mostly used as TCOs whereas polyaniline, polypyrrole and ethylenedioxythiophene are the trending future polymers. In this review, the critical parameters of magnetron sputtering are delineated for the deposited tungsten oxide (WO₃) films focused on ITO and FTO layered glass. The main focus of interest is to highlight the recent progress and future trends in this technique, structure introduced with sputtered electrochromic film and their carefully review along with effect of altering these parameters on physical, optical, electrochemical, durability and thus overall performance of the ECD. Finally, it will be intended to underline the future perspectives in realizing smart EC devices with various factual characteristics.     

Effects of second-phase particles and elemental distributions of ITO targets on the properties of deposited ITO films

As the key material of transparent electrodes in various optoelectronic devices, ITO targets with uniform microstructure and homogeneous elemental distributions are vital to obtain high-quality ITO films in industrial production. In this paper, the differences in the crystalline structure, sheet resistance and transmittance of ITO films with 40 nm, 70 nm and 100 nm thickness were studied between two ITO targets that were respectively sintered at 1580 °C for 10 h (target A) and 1600 °C for 5 h (target B). Surface morphology, surface roughness and thickness uniformity of ITO films with 100 nm thickness and etching property of ITO films with 40 nm and 70 nm thickness in mixed acids were further focused in the paper. The results indicate that target A, which owns homogeneous distributions of second-phase particles and elements, could be conductive to obtain the ITO films with low crystallinity that are easy to be etched leaving less and smaller residual particles. Based on the analysis, the change of sintering process has a great influence on the electrical and etching properties, but it has only a little influence on the optical property.     

Enhanced electrochromic performance of macroporous WO3 films formed by anodic oxidation of DC-sputtered tungsten layers

Self-organized macroporous tungsten trioxide (WO₃) films are obtained by anodic oxidation of DC-sputtered tungsten (W) layers on 10 mm × 25 mm indium tin oxide (ITO)-coated glass. Under optimized experimental conditions, uniformly macroporous WO₃ films with a thickness of ca. 350 nm are formed. The film shows a connected network with average pore size of 100 nm and a pore wall thickness of approximately 30 nm. The anodized film becomes transparent after annealing without significant change in macroporous structure. In 0.1 M H₂SO₄, the macroporous WO₃ films show enhanced electrochromic properties with a coloration efficiency of 58 cm² C⁻¹. Large modulation of transmittance (∼50% at 632.8 nm) and a switching speed of about 8 s are also achieved with this macroporous film.     

Low-temperature conducting performance of transparent indium tin oxide/antimony tin oxide electrodes

We fabricated transparent indium tin oxide (ITO)/antimony tin oxide (ATO) electrodes using a combined process of spin-coating of hybrid ITO nanoinks, electrospraying of ATO, and hydrogen (H₂) activation carried out at a low annealing temperature of 200 °C. The produced ITO electrode exhibited an enhanced surface densification and phase conversion of In(OH)₃ to ITO. As a result, the H₂-activated ITO/ATO electrodes exhibited excellent transparent conducting performances with a superior sheet resistance of ~47.5 Ω/□ and a good transmittance of ~85.3% as compared to the ITO and ITO/ATO electrodes. Despite the use of the low annealing temperature, the achieved improvement in the conducting performance could be attributed to the synergistic effect of the enhanced carrier concentration and the Hall mobility related to the improved surface densification achieved with the electrosprayed ATO thin film and reduction of the residual In(OH)₃ phase by H₂ activation. Therefore, our method can be used as a novel strategy for obtaining high-performance solution-processed transparent conducting oxides at a low annealing temperature of 200 °C for use in various optoelectronic applications.     

Multispectral photodetection using low-cost sputtered NiO/Ag/ITO heterostructure: From design concept to elaboration

High-performance multispectral photodetectors (PDs) are highly attractive for the emerging optoelectronic applications. In this work, a new broadband PD based on p-NiO/Ag/n-ITO heterostructure was fabricated by RF magnetron sputtering technique at room temperature. The tri-layered structure offering multispectral detection property was first identified using theoretical calculations based on combined FDTD and Particle Swarm Optimization (PSO) techniques. The crystal structure of the elaborated sensor was analyzed using X-ray diffraction (XRD) method. The device optical properties were investigated by UV–Vis–NIR spectroscopy. The NiO/Ag/ITO heterostructured PD shows a high average absorbance of 63% over a wide spectrum range of [200 nm–1100nm]. Compared with NiO and ITO thin-films, the performances of the heterostructured device are considerably enhanced. It was found that the prepared PD with NiO/Ag/ITO heterostructure merges the benefits of multispectral photodetection with reduced optical losses and efficient transfer of photo-induced carrier. The device demonstrated a high I_ON/I_OFF ratio of 78 dB and an enhanced responsivity under UV, visible and NIR lights (171 mA/W at 365 nm, 67 mA/W at 550 nm and 93 mA/W at 850 nm). The broadband photodetection property enabled by the optimized NiO/Ag/ITO heterostructure opens a new route for the elaboration of low-cost devices that can offer multiple sensing purposes, which are highly suitable for optoelectronic applications.