Zheng, Adv - Funct.mater.2011, Nano Tungston Oxide - Properties & Applications

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FEATURE ARTICLE
Nanostructured Tungsten Oxide Properties, Synthesis, and Applications

Haidong Zheng,* Jian Zhen Ou, Michael S. Strano, Richard B. Kaner, Arnan Mitchell, and Kourosh Kalantar-zadeh*
inherently small size of nanostructured materials, that signicantly inuences charge transport, electronic band structure and optical properties. Nanostructured WOx is exceptionally versatile and offers unique characteristics. It has become one of the most investigated functional metal oxides impacting many research elds ranging from condensedmatter physics to solid-state chemistry. WOx has exceptional chromic properties and thin lms made of nanostructured WOx have been increasingly investigated and applied for the development of electrochromic devices. In comparison to many other functional metal oxide nanostructures, such as TiO2, ZnO, NiO, and their substoichiometric forms, the study of WOx chromic properties is much more advanced.[2] Nanostructured WOx is also a wellstudied material for photocatalysis and sensing.[1] While metal oxides such as SnO2, TiO2, ZnO, as well as their various substoichiometric forms, are commonly used in photocatalytic systems and sensors, the importance of WOx is growing equally in these elds.[1] For solar-cell research, nanostructured WOx in its fully oxidized form, WO3, has received relatively little attention compared to materials such as TiO2 and ZnO. However, the application of WO3 in solar cells should be encouraged, since it offers similar functional properties to TiO2 and ZnO, which are now widely used in the relevant industries. In this Feature Article, we present a general, yet comprehensive, review on WOx. In particular, we focus on the various nanostructured forms of WOx that have been presented in the literature to date. We describe the fundamental properties of nanostructured WOx and compare the nanomaterials with the bulk form. We summarize the different reported methods for the synthesis of nanostructured WOx and divide these synthesis methods into two major categories: vapor phase and liquid phase. Finally, we present a selection of the more popular and interesting applications that exploit WOx and illustrate the enhancements made possible by using nanostructures of this material.
Metal oxides are the key ingredients for the development of many advanced functional materials and smart devices. Nanostructuring has emerged as one of the best tools to unlock their full potential. Tungsten oxides (WOx) are unique materials that have been rigorously studied for their chromism, photocatalysis, and sensing capabilities. However, they exhibit further important properties and functionalities that have received relatively little attention in the past. This Feature Article presents a general review of nanostructured WOx, their properties, methods of synthesis, and a description of how they can be used in unique ways for different applications.
1. Introduction
Tungsten oxide (WOx) is a transition metal oxide with wideranging applications. Interest in WOx can be dated back to the 17th century when the properties of LiWO3 and the techniques for the synthesis of WO3 and NaWO3 were rst studied.[1] More recently, renewed research interest in WOx was sparked by the discovery of its electrochromic (EC) effect.[2] With the advent of nanotechnologies, the synthesis and analysis of WOx nanostructures has become increasingly prominent. Nanostructuring of WOx can enhance the performance of this important functional material and provides it with unique properties that do not exist in its bulk form. Exceptional qualities of nanostructured WOx compared to the bulk material include: i) increased surface-to-volume ratio, which provides more surface area for both chemical and physical interactions; ii) signicantly altered surface energies that allow tuning and engineering of the materials properties, as atomic species near the surface have different bond structures than those embedded in the bulk; and iii) quantum connement effects, due to the
H. Zheng, J. Z. Ou, Prof. A. Mitchell, Prof. K. Kalantar-zadeh School of Electrical and Computer Engineering RMIT University Melbourne, Victoria 3001, Australia E-mail: h.zheng@student.rmit.edu.au; kourosh.kalantar@rmit.edu.au Prof. M. S. Strano Department of Chemical Engineering Massachusetts Institute of Technology Cambridge, MA 02139, USA Prof. R. B. Kaner Department of Chemistry and Biochemistry University of California Los Angeles, CA 90024, USA
2. Fundamental Properties
This section focuses on the fundamental properties of nanostructured WOx and start with its various crystal structures and the conditions for phase transitions between these structures. The structures of nonstoichiometric WOx and WO3 hydrates 2175
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are also discussed. Further fundamental properties including optical, electrical, and photocatalytic characteristics, which are presented next. This section also descripbe the thermoelectric and ferroelectric properties as well as doping effects. 2.1. Crystal Structures and Phase Transition WO3 crystals are generally formed by corner and edge sharing of WO6 octahedra. The following phases are obtained by corner sharing: monoclinic II (-WO3), triclinic (-WO3), monoclinic I (-WO3), orthorhombic (-WO3), tetragonal (-WO3), and cubic WO3. However, cubic WO3 is not commonly observed experimentally. The detail of the polyhedral representations of these six structures is shown in Figure 1.[3] The phase classication is based on the tilting angles and rotation direction of WO6 octahedra with reference to the ideal cubic structure (ReO3 type). Lattice constant data for WO3 crystal phases are presented in Table 1. Like other metal oxides, WO3 crystal phase transitions can take place during annealing and cooling. It has been widely reported that for WO3, in bulk form, phase transformation occurs in the following sequence:[6,7] monoclinic II (-WO3, <43 C) triclinic (-WO3, 43 C to 17 C) monoclinic I (-WO3, 17 C to 330 C) orthorhombic (-WO3, 330 C to 740 C) tetragonal (-WO3, >740 C) The above phase transitions of WO3 has been reported to be partially reversible. At room temperature, monoclinic I (-WO3) has been reported as the most stable phase, with triclinic (WO3) also being observed.[6] When annealed at high temperature, WO3 transforms to other crystal phases (usually -WO3 and -WO3). However, WO3 is generally unable to retain these alternate phases when it is returned to room temperature. The monoclinic II phase (-WO3), is only stable at subzero temperatures, and is thus rarely encountered outside the laboratory.
Haidong Zheng is currently in the nal stage of his Ph.D. study in the School of Electrical and Computer Engineering, RMIT University, Australia. Prior to his Ph.D. candidature, he received a bachelor degree of electronic engineering from the same school in 2006. Haidongs research interest includes nanostructure synthesis for TiO2 and WO3 and their use in dye-sensitized solar cells as well as chromic devices. Kourosh Kalantar-zadeh is an Associate Professor at RMIT University, Australia. He received his B.Sc. (1993) and M.Sc. (1997) degree from Sharif University of Technology, Iran, and Tehran University, Iran, respectively, and a Ph.D. at RMIT University, Australia (2001). His research interests include chemical and biochemical sensors, nanotechnology, microsystems, materials sciences, electronic circuits, and microuidics.
Hence, unless specied, the term monoclinic will be used to refer to the monoclinic I (-WO3) phase throughout the remaining text. In addition to the aforementioned crystal phases, another possible stable phase for WO3 is hexagonal (h-WO3). Observation of this phase was rst reported by Gerand et al. in 1979,[8] and was originally obtained from the slow dehydration of tungstite. Figure 2 presents a diagram of the crystal structure of h-WO3. The crystal is again obtained from WO6 octahedra, but with the form of threeand six- membered rings in the ab-plane. These three- and six-membered rings result in the appearance of trigonal cavities and hexagonal windows, respectively.[9] In the c-axis, these octahedra stack by sharing the axial oxygen and form 4-coordinated square windows. However, this hexagonal crystal phase is metastable and reported to be transformed into a monoclinic structure when annealed at temperatures exceeding 400 C. The lattice constants reported for h-WO3 are a = 7.298 and c = 3.899 .[8] The phase transition behavior in nanostructured WOx can be quite complex, Figure 1. Tilt patterns and stability temperature domains of the different polymorphs of WO3. as it mainly depends on the materials Reproduce with permission.[3] Copyright 2000, International Union of Crystallography.
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Table 1. Lattice constant data for different WO3 crystal phases.

lattice -WO3[4] constant () a b c 7.378 7.378 7.664
-WO3[4]
7.309 7.522 7.686
-WO3[4]
7.306 7.540 7.692
-WO3[5]
7.384 7.512 3.846
-O3[5]
5.25 N/A 3.91
ideal cubic-WO3[2] 3.84 N/A N/A
We recently synthesized nanoplatelet WO3 with thicknesses of 2060 nm via electrochemical anodization at 50 C, and the as-prepared products were post-annealed at 400 C.[13] Roomtemperature material characterization showed that the majority of the crystal phase was orthorhombic instead of the expected monoclinic phase. In some recent literature[14,15] it was also reported that nanostructured WO3 with an orthorhombic crystal phase (obtained by post-annealing) can retain its phase stability at room temperature. 2.2. Structures of Nonstoichiometric WOx WO3 is a transition metal oxide made up of perovskite units, which is well-known for its nonstoichiometric properties, as the lattice can withstand a considerable amount of oxygen deciency.[16] Only a partial loss of the WO3 oxygen content is needed to affect its electronic band structure and increase its conductivity by a large amount.[17] However, the reduction of WO3 is usually accompanied by structural changes.[16] Some of the better known nonstoichiometric WOx compositions are W20O58, W18O49 and W24O68. Such oxides are formed by cornersharing WO6, which alternate with octahedra that are partially established by edge-sharing.[16] Elimination of oxygen occurs according to the crystal-shear (CS) mechanism.[16] As the x value in WOx decreases, groups of edge-sharing WO6 octahedra form pockets of shear planes. For x values closer to 3, these shear planes are considered as extended defects, if they are isolated or disordered. With further reduction in x, the shear planes tend to interact with each other and align in parallel, lling the space between the planes with corner-sharing WO6. If these shear planes are equidistant, a crystalline phase with a dened structure arises that belongs to the (103) CS series. For x smaller than or equal to 2.87 (i.e., W18O49 and W24O68), the above mentioned structures become unstable and further restructuring takes place involving the formation of pentagonal columns (PCs) parallel to the monoclinic b axis, which are either single or paired by edge-sharing (PCPC).[16]
morphology, which is greatly affected by the nanostructure synthesis process and the initial precursors used. Proposed by the GibbsThomson expression,[10] the reduction of the size of WOx crystallites enhances the surface energy of the system, and this enhanced surface energy decreases melting and sublimation temperatures. Therefore, generally lower annealing temperatures, compared to the ones mentioned for the bulk WOx, are needed to induce the crystal phase transitions in the nanostructured form.[11] Boulova et al.[11] used in situ Raman spectroscopy to observe phase transitions in WO3 nanoparticles with diameters in the range of 2500 nm. It was found that samples with average diameter of 60 nm began the transformation from -WO3 to WO3 at 270 C and then to -WO3 at 670 C. These phase transition temperatures were both lower than that of bulk WO3. In their work, a 35 nm sample, which was initially in the form, started to transform to -WO3 below 530 C. However, a 16 nm sample underwent a phase transition from an initial pseudo WO3 structure to -WO3 form at 430 C, which is signicantly lower than that of bulk WO3 as well as the WO3 nanoparticles with larger dimensions. Similar ndings were also reported by Lu et al.[12] using in situ Raman spectroscopy. They reported that monoclinic I (-WO3) nanowires with an average diameter of 4080 nm and a length of 1 m, started to transform reversibly into -WO3 at 230 C instead of 330 C for bulk WO3. The morphology of the nanostructures can have a signicant effect on obtaining stable phases at room temperature.
2.3. WO3 Hydrates Investigations of WO3 hydrates (WO3nH2O) or tungstic acids are important as they are closely related to WOx. The importance of WO3nH2O stems from the fact that generally in liquid-phase synthesis routes, WO3 hydrates are rst produced and subsequently annealed to obtain the desired crystal phase of WOx. The reports on these hydrates can be traced back to almost a century ago,[18,19] with the four most studied classes presented as WO32 H2O (dihydrate), WO3H2O (monohydrate), WO30.5 H2O (hemihydrate), and WO30.33 H2O. The crystal structures of WO3 hydrates are highly dependent on their water content.[19] WO32 H2O possesses a layered structure, which is composed of WO5(OH)2 single sheets in corner-sharing mode. The second water molecule of the dihydrate is found to be positioned between the layers. WO3H2O consists of highly distorted corner-sharing WO5(OH)2 units, which are coordinated by ve oxygen atoms and one water molecule. As for WO30.5 H2O, its existence is less documented 2177
Figure 2. a) The structure of h-WO3 is shown with the c-axis perpendicular to the plane. b) The structure of h-WO3 with the c-axis parallel to the plane. Reproduce with permission.[9] Copyright 2009, American Chemical Society.
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but the crystal structure is believed to be of a cubic pyrochlore-type, where the water molecules are present in a tunnel constructed by the six-membered WO6 corner-sharing octahedra.[19] Finally, WO30.33 H2O was found by Gerand et al. in 1981.[20] Recently, a study conducted by Zhou et al.[21] revealed that orthorhombic WO30.33 H2O actually contains two types of corner-sharing WO6 octahedra. The rst type is constructed by a central tungston atom that is surrounded by six oxygen atoms, while in the second type, two of the oxygen atoms are replaced by a Figure 3. a) Transmittance spectra of the RF-sputtered WO3 thin lms at different substrate shorter terminal W=O bond and a longer temperatures. b) TsEg relationship of RF-sputtered WO3 lms. Reproduce with permission.[23] W(OH)2 bond, respectively. Ultimately, the Copyright 2010, American Institute of Physics. WO30.33 H2O lattice is formed by stacking up layers consisting of these two structural units.[21] 500 C). The observed optical transmission spectra and derived bandgap energy for each value of Ts is presented in Figure 3. As seen in Figure 3a, reduction in Ts, and hence reduction in crys2.4. Electronic Band Structure tallite size, results in a blue shift of the transmission spectrum corresponding to a widening of Eg. For each of the -WO3 crysWO3 is a wide-bandgap n-type semiconductor, with an electallites obtained at 300500C, the observed bandgap energy is tronic bandgap (Eg), corresponding to the difference between higher than Eg = 2.62 eV of the typical bulk -WO3 (Figure 3b). the energy levels of the valence band, formed by lled O Further, the progressive increase of this bandgap energy with 2p orbitals and the conduction band formed by empty W 5d reduced crystal dimensions suggests that these observations orbitals.[22,23] As mentioned earlier, the crystal phase of WO3 can be ascribed to the weak QC effect. However, it should be transits in a sequence that is determined by the degree of disnoted that phase transformations caused by the increasing Ts tortion from the ideal cubic phase, and in principle, this trancan also contribute to the Eg shift.[23] sition is also accompanied by a change in Eg, as the occupied levels of the W 5d states change.[22] Amorphous WO3, with the 2.5. Optical Properties and Chromism most distorted structure, normally possesses a relatively large Eg on the order of 3.25 eV,[22] whereas monoclinic WO3, in bulk form, has been reported to show a typical Eg of 2.62 eV The optical properties of WO3 in the visible region are domiat room temperature.[22] Density of states (DOS) calculations nated by the absorption threshold, which is dened by the for the cubic WO3 band structure[24] can be used to precisely bandgap energy of the material.[27] The bandgap of nanostruccalculate the lattice constant (3.84 ). However, these calcutured WO3 is blue shifted compared to the bulk form, with lations generally fail to estimate Eg correctly. For instance, reported values ranging widely from Eg = 2.60 to 3.25 eV.[28] Granqvist et al. calculated Eg as 0.6 eV, which is signicantly Therefore, WO3 (stoichiometric) is essentially transparent smaller than the experimental values.[24] Similar discrepancies to most visible wavelengths with a slightly yellow tint for are also reported for other crystal phases of WO3. smaller bandgap samples, which absorb part of the blue In nanostructured WO3, the bandgap generally increases with spectrum.[27] For photon energies greater than the bandgap [23] reducing grain size. Experimentally, this is often observed as energy, the light absorption can be approximated by the a blue shift of the optical absorption bandedge as the nanosequation:[27] tructure dimensions are reduced. It is widely accepted that this observed blue shift can be attributed to the quantum conneg" (g E g )0 (1) [25] The QC effect is divided into two regimes, ment (QC) effect. namely strong and weak.[25] The strong QC effect occurs when where is the photon energy and = 2, indicating that for WO3 the size of the crystal is reduced to much smaller than the Bohr indirect transitions are allowed. A typical optical transmission radius for the material (3 nm for WO3[26]). This causes direct spectra for nanostructured WO3 can be seen in Figure 3a with changes to the electron wavefunctions and hence signicantly a clear absorption edge evident at ultraviolet (UV) to blue wavealters the Eg. The weak QC effect occurs when the crystal size lengths.[23] The oxygen-decient WOx (nonstoichiometric) are is larger than the Bohr radius. This causes indirect perturbamostly found to be light green, which is caused by an additional tion of the electron wavefunction due to Coulomb effects and broad absorption peak in the red to infrared with a transmisresults in more subtle changes in the bandgap energy.[25] In a sion window remaining in the blue-green range. This additional recent study conducted by Gullapalli et al.,[23] different scales of absorption peak is due to the electron transfer from W6+ to nanotextured WO3 thin lms were obtained by radio frequency W5+.[4] It is also worth mentioning that the refractive index of (RF) sputtering, where the crystallite size is controlled by the WO3 is large, in the range of 22.5, and hence it is important substrate temperature (Ts) during deposition. The crystallite to consider this parameter in the design of WO3-based optical sizes obtained ranged from 9 nm (Ts = 100 C) to 50 nm (Ts = devices.[29]
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It is well-known that the WO3 optical transmittance can be modulated, which means its physical color can reversibly change from the initial state to dark blue in the presence of external stimuli. The two most reported effects are color change in response to applied voltage (electrochromism)[3033] and reducing gases (such as H2, gasochromism);[3437] however, heat- or light-induced chromic effects of WO3 have also been studied.[12,38] The electrochemical reaction that results in the chromic response of WO3 can be described by considering the injection of a quantity (x) of positive ions (M+) and an equal quantity of electrons (e). Symbolically, this reaction can be represented as follows:[2]
WO3 + xM+ + xe Mx WO3
(2)
Typical ions can be M+ = H+, Li+ and Na+ among others, and the quantity x becomes the stoichiometric parameter of the product and can vary between 0 and 1. The electrochromic effect of WOx is strongly dependent on crystal stoichiometry, with signicantly different properties being reported for amorphous and crystalline lms.[3941] For the amorphous case, the absorption peak observed in the visible optical spectrum resulting from the injection of ions and electrons can be attributed to polaron absorption. In the amorphous lm, inserted electrons are localized in the W5+ sites and polarize their surroundings to induce lattice vibration.[42,43] The inserted cations (M+) either lie in the centers of the perovskite units or are chemically bonded with the lattice oxygen and are thus spatially separated from the electrons. This spatial separation creates a polaron.[44] In the crystalline case, there is no spatial separation between the inserted cations and electrons, as the inserted electrons behave as Drude-model-like free electrons, which enter the extended states in the WO3 band structure and undergo scattering by impurities.[24] This makes the material slightly metallic with a small increase in absorption across the spectrum and a slight increase in reection at infrared wavelengths. Therefore, the crystalline WO3 lms tend to have a smaller degree of color change compared to their amorphous counterpart.[45] In contrast to electrochromism, there are still many unknown issues regarding the fundamental understanding of WO3 gasochromism. Two models are widely accepted for describing the gasochromic effect in WO3, which both agree that the coloration of the WO3 lm is caused by the transition of the W valence state from 6+ to 5+. One model is called the double injection of ions,[36] which is the same as the electrochromic mechanism. The other is the generation of oxygen vacancies,[35] which is illustrated in Figure 4. For a reducing gas such as H2, this mechanism can be briey described as follows (generally a catalytic material such as Pt or Au is required to enhance the effect): i) adsorption and dissociation of H2 onto the catalyst layer; ii) diffusion of H atoms along surfaces; iii) formation of an oxygen vacancy and H2O; iv) diffusion of oxygen vacancies into WO3; and v) eventually escape of H2O. This model argues that the nal gasochromic products are WO3x together with surface water molecules instead of the hydrogen tungsten bronze (HxWO3), which is suggested by the double injection of ions. Interestingly, both models are backed by experimental results to some extent.[35,36]
Figure 4. Illustration of generation of oxygen vacancies mechanism for the gasochromic effect.
Chromic efciency is often observed to have a strong dependency on surface morphology.[46] Nanostructured WO3 lms improve the surface-to-volume ratio, allowing more surface area available for reactions, hence producing superior optical modulation as compared to the compact lms.[31,32] Additionally, the open structure enhances species diffusion within the system, which greatly improves the chromic response time.[47] The intercalation behavior of nanostructured WO3 can be quite different from its bulk counterparts. We have recently shown that thin tungstite platelets on the order of several unit cells, greatly enhance the propensity for lithium intercalation compared to that of thick WO3 lms.[48] The effect of morphology should be considered with care, as it has been reported that high surface irregularities and the effect of the size of nanostructured WO3 might conversely suppress the optical modulation during chromic interactions.[49] Chen et al.[49] studied the electrochromic properties and relative near-infrared absorption mechanism of thermally evaporated WO3 nanowire lms with an average diameters of 50200 nm. They found that the colored lm had a relatively high transmittance compared to bulk material in the wavelength range higher than 800 nm. In addition, an extra absorption band (when compared to bulk WO3), which was t to a cation-polaron absorption, was found in the near-infrared region. The appearance of this band suggested the existence of the interactions between inserted cations and compensating electrons, which remain spatially separated forming a polaron and modify hostlattice vibration energies. Luo et al.[37] conducted Raman spectroscopic studies on gasochromism of monoclinic WO3 nanowires with an average diameter of 50 nm to prove the coexistence of oxygen vacancies together with water molecules on the nanowires after exposure to pure H2. Based on their observations, they proposed a modied mechanism for low-dimensional WO3 interactions with H2 similar to the generation of oxygen vacancies model, which describes the coloration without the presence of oxygen vacancy diffusion.
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to more trapping and scattering of free charge carriers.[55] If the size of the crystallites is smaller than the electron mean free path, grain boundary scattering dominates and hence the electrical conductivity decreases. In addition, lattice strain and crystal distortions can also affect the motion of charge, causing a decrease in conductivity.[56,57] 2.7. Photocatalytic Properties In principal, photocatalytic activity is achieved by illuminating a semiconductor material in a solvent (usually water) to photons that have energies equal to or larger than the semiconductors bandgap. This creates electronhole pairs, which generates free radicals (e.g., OH) to undergo further reactions. As a photocatalytic material, stoichiometric WO3 has a conduction band (CB) edge, which is positioned slightly more positive (versus NHE (normal hydrogen electrode)) than the H2/ H2O reduction potential (Figure 6),[58] and a valence band (VB) edge much more positive than the H2O/O2 oxidation potential, which makes WO3 capable of efciently photo-oxidising a wide range of organic compounds[59,60] such as textile dyes[6165] and bacterial pollutants.[64,65] When compared to TiO2, which is the most studied photocatalytic material so far, another advantage of WO3 is that it can be irradiated by the blue region of the visible solar spectrum, as its bandgap energy is in the 2.6 to 3.2 eV range. Furthermore, WO3 has a remarkable stability in acidic environments, making it a promising candidate for treatment of water contaminated by organic acids.[66] Nanostructuring of WO3 can greatly enhance its photocatalytic capability. The large surface-to-volume ratio, which
Figure 5. Carrier mobility, concentration, and resistivity of WO3 lms grown at different substrate temperatures. Reproduce with permission.[52] Copyright 2008, Elsevier.
2.6. Electrical Conductivity
For n-type metal oxide semiconductors, electrical conduction relies on a signicant concentration of free electrons being present in their conduction bands. The free-electron concentration in such materials is mainly determined by the concentration of stoichiometric defects, such as oxygen vacancies.[50] The electrical conductivity of single-crystal WO3 ranges from 10 to 104 S cm1 depending on the stoichiometry.[17] In addition, structural factors such as grain size, grain boundary, lm thickness, specic phase and dopants (if any) also have a great inuence on the materials conductivity.[51] Therefore, the electrical properties of WO3 are strongly dependent on the synthesis techniques and the growth conditions. For example, it has been reported that a relatively high carrier concentration (5 1019 cm3) and electron mobility (6.5 cm2 V1 s1) have been observed for WO3 lms synthesized using an elevated substrate temperature during sputtering and thermal evaporation depositions.[52] These results are presented in Figure 5. A high substrate temperature tends to detach oxygen ions under vacuum conditions, allowing more free electrons for conduction. It has been suggested that by conning the free carriers movement to within well oriented one- or two-dimensional crystal structures, with smooth boundaries, the carrier mobility increases as the scattering effects are reduced. This increase in mobility has been successfully shown in other metal oxides such as ZnO nanorods.[53] For WO3 such reports are rare. However, recently, the carrier mobility of a single W18O49 nanowire was measured by Rui et al.[54] to be as high as 40 cm2 V1 s1. Increasing the roughness of the structure, however, increases resistivity. The conductivity was reported to decrease within the WO3 nanoparticles, due to an increasing volume Figure 6. CB and VB energy levels of a number of semiconductors. Reproduce with permisof the grain boundaries, which contributes sion.[58] Copyright 2001, Nature Publishing Group. 2180
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is provided by the nanostructures, signicantly increases the effective surface area available for photocatalytic reactions. Nevertheless, one should be cautious when comparing the photocatalytic performances reported for WO3 nanoparticles of different sizes, obtained by calcinations at various temperatures. Hong et al.[67] found that 500-nm WO3 nanoparticles obtained at 800 C could induce better O2 evolution compared to 30-nm ones that were obtained at 500 C, as better crystallinity (as a result a smaller Eg) of larger particles offset their smaller surface-to-volume ratio. In addition to this, the charge-carrier separation and transport mechanisms of the nanocrystalline semiconductors under illumination are believed to be different from the bulk material.[68] It is generally accepted that minimal band bending and small spacecharge regions are developed within nanocrystalline semiconductors, allowing the photogenerated charge carriers to travel towards their surface without the need for excessive applied energies.[68] It is well known that the introduction of dopants is a common method for enhancing photocatalysis. Nanostructured WO3 allows effective intercalation of dopants to achieve optimum band structures, while it is more difcult for dopants to diffuse into bulk WO3. 2.8. Thermoelectric Properties The thermoelectric effect involves the direct conversion of a temperature difference to a voltage gradient or vice versa. The thermoelectric effect in WOx is a relatively less studied area, and measurements have usually been conducted to evaluate the thermochromism of WO3.[69] The thermoelectric effect has been shown to exist for stoichiometric WO3[69] and WO3 hydrates,[70] and their Seebeck coefcients were found to be highly dependent on temperature. From subzero temperatures to approximately 50 C, the Seebeck coefcients increase linearly with temperature. However, the Seebeck coefcient of the hydrates increases sharply when the temperature exceeds 50 C, and then drops exponentially after the temperature surpasses 100 C.[70] The largest Seebeck coefcient (480 V K1) is obtained at 90 C. In contrast, experimental data show that the Seebeck coefcient of stoichiometric WO3 increases to a maximum value of 600 V K1 by increasing the temperature to 200 C.[69] The thermoelectric effect has also been found in nonstoichiometric WOx[16], however, the temperature-dependent Seebeck coefcient is only observed in subzero conditions. Interestingly, a linear relationship between Seebeck coefcient and temperature has been found for WO2.9 and WO2.95, whereas, a nonlinear relationship is present for WO2.72 and WO2.83.[16] There is no report on the effects of nanostructuring WOx on its thermoelectric properties, which could be an interesting subject for future investigations. 2.9. Ferroelectric Properties The ferroelectric effect is usually not found in WOx, except for the monoclinic II -WO3, which is the only acentric WOx phase and stable only at cryogenic temperatures.[4] There are only few reports in this eld over the last two decades as the instability of -WO3 at room temperature has encumbered the research for its use as a ferroelectric material.[4] The -WO3 was found to
have a spontaneous electric dipole moment. The polarity comes from the displacement of tungsten atoms from the centre of each WO6 octahedra.[4] Recently Wang et al.[71] obtained stable Cr-doped WO3 nanoparticles (1530 nm), which consisted of both and phases at room temperature. It is suggested that the Cr acts as a structure stabilizing agent for the -WO3.[71] 2.10. Doping It is possible to alter the material properties of WOx through doping. Typical dopants include Li, Na, and H which can be intercalated into the structure of WO3 during or after the synthesis process.[27] Intercalation of H, Li, or Na into WO3 is often used to induce chromic effects, which were discussed in Section 2.5. Intercalation of dopants leads to intricate phase changes that are not commonly observed in pure WO3.[27] For instance, cubic WO3 has rarely been reported at room temperature; however, cubic phases can be observed for H0.5WO3, LixWO3 with 0.1 < x < 0.4, and NaxWO3 with 0.3 < x < 1.[27] Structurally, it is believed that the Li and Na atoms are positioned at the centres of the perovskite octahedral units, while the H atoms are attached to oxygen atoms to form hydroxyl groups at the corners of the perovskite octahedra.[27] WO3 also experiences an insulator-to-metal transition after the intercalation of Li, Na, or H. This can be attributed to the energy of the s level of the dopants, which are above the W 5d level of the WO3 crystal conduction band. For Li and Na, the s energy level is likely to be placed well above the conduction band edge and, and thus the contributed electrons signicantly increase the free-electron density in the conduction band.[27] When the dopant is H, the mechanism of electron donation is different,as the dopant bonds with oxygen to form a hydroxide unit. However, the net result of H intercalation is still the contribution of an electron to the bottom of the conduction band, which resembles the cases for Li or Na intercalation, and thus physical properties should not be too different. In addition to Li, Na, or H doping, N doping has also been reported. It has been found that the Eg of WO3 nanowires decreases with N doping, and that the resistivity of a single N-doped WO3 nanowire is approximately one order of magnitude less than that of the corresponding undoped crystalline WO3 nanowire.[28] It has also been found that the conductivity of WO3 can be improved by a factor of 000 through addition of Al2O3.[17] Other metal oxide dopants such as TiO2,[72] Co3O4, MnO2, and LiO2[17] have also observed to enhance the electrical conductivity of WO3. Similar to the chromic effect in nanostructured WOx, discussed in Section 2.5, doping of nanostructured WOx can be more efcient than in its bulk form due to the enhanced surface area and ease of diffusion of dopants through the structure. The doping should be conducted with care, as the surface morphology of nanostructured WOx can be signicantly altered during the process, and deterioration of the performance may result due to the reduced structural porosity.[73]
3. Nanostructure Synthesis
Many different approaches for the syntheses of nanostructured WOx have been implemented using both vapor- and 2181
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liquid-phase-based methods. In this Feature Article, we present the most common synthetic methods and describe how they can be employed for engineering and tuning the morphology and properties of WOx.
sputtering can be controlled to become oxygen decient or nonstoichiometric.[24,76] Post-annealing in a controlled gas environment can be used to achieve enhanced crystallinity.[76] 3.1.2. Thermal Evaporation
3.1. Vapor-Phase Synthesis The category of vapor-phase deposition includes a wide range of material synthesis techniques. In general, it involves the condensation of vaporized source material onto the targeted substrates.[74] To obtain nanostructured WOx, physical vapor deposition (PVD) is more commonly used. The PVD process can be purely physical, starting with the WOx material source in the form of a solid target or powder, which is energetically evaporated (sublimed) by many possible techniques. Ion bombardment,[7578] heat,[79] electron beam,[80] and laser irradiation[81] are among the most commonly reported energetic sources. With careful control on the process parameters, the evaporated species can condense into a nanostructured form with desired dimensions, crystallinity, and nanoscale morphology. The starter material source is not necessarily WOx, it can also be W metal in the form of powder or lament.[82] In this case, oxygen gas or oxidants must be added to the vapor to form WOx. In many cases, the as-synthesized material resulting from PVD is WOx rather than WO3. The color of the deposited material is a good indicator of the species stoichiometry.[82,83] Usually black lms are obtained because of severe lack of oxygen content within the material; translucent dark blue lms are observed for WOx with x = 2.7 0.2;[82] and a pale green-yellow color is observed for WO3.[83] Generally post-annealing can be utilized to obtain the desired oxygen content as well as crystal phase and stoichiometry. 3.1.1. Sputtering Sputtering, a process in which atoms are ejected from a solid target material by bombarding it with energetic particles, is a well established PVD process with a high degree of controllability. The high energy and controllable parameters of sputtering can result in the growth of well-structured and crystalline lms. Further, sputtering can be easily implemented as a rollto-roll process for large-scale manufacturing.[24] Therefore, sputtering is among the most popular methods for the deposition of WOx in industry. Conventionally, quality anhydrous WOx (x = 3 0.1) thin lms can be obtained using direct current (DC) or RF sputtering techniques with metallic W or WOx targets in an oxygenrich environment. The as-synthesized materials usually exhibit a columnar structure that consists of micro- or nanometer-sized grains that are tightly packed.[7578] The process parameters that can be adjusted during deposition include the applied sputtering power, substrate type and temperature, and gas content and pressure. These parameters can be used to precisely control the lm deposition rate, thickness, grain size, crystallinity, and nanostructure morphology. Dopants can also be introduced during the sputtering process by either adding material to the solid target, adding a secondary target, or introducing additional species to the gas environment. The lms resulting from
Thermal evaporation deposition is achieved by vaporizing a source material using heat either in a vacuum or in a controlled gaseous environment at low pressure. For the deposition, the source material can be either W metal or WO3 in either powder or condensed form. Due to the low-pressure environment, vaporization of the source material can usually be conducted at a temperature that is lower than the melting point of WO3 (1470 C).[79] The vaporized W or WOx emanates from the material source and may interact with the gas environment within the deposition chamber before condensing on a substrate located at a distance from the heated material source. Processing parameters such as evaporation temperature, substrate temperature, gas environment and pressure, and the type of substrate play an important role in achieving the desirable outcomes. Generally post-annealing can be utilized to obtain the desired oxygen content as well as the crystal phase and the species stoichiometry. In general, WOx nanowires can be obtained under optimum thermal evaporation conditions, and the physical mechanism for the nanostructure condensation has been described using the vaporsolid growth mechanism. Thangala et al.[79] describe the vaporsolid process as follows: Firstly, the supersaturated WOx vapor condenses to form solid WOx clusters in a nucleation step. Then, the WOx clusters are further oxidized to form a nanocrystalline tip on the substrate. Finally this crystalline tip acts as a seed for further crystal growth and exhibits enhanced adsorption of the WO2/WO3 species. Depending on the crystallinity of this seed, the nucleation point will either grow preferentially in the vertical dimension, forming a one-dimensional (1D) nanowire structure, or can grow in both lateral and vertical dimensions forming small aggregated nanoparticles through the use of higher substrate temperature.[79] Most examples found in the literature[82,84,85] observe that the as-synthesized WOx nanostructures tend to grow along the (010) and (001) plane, which are more favorable for axial nanowire growth. Zhu et al.[82] presented the early studies on WOx thermal evaporation, in which they obtained treelike structures of micrometer dimensions by heating a W plate pressed against a SiO2 plate. The SiO2 plate acted as the collection substrate as well as the source of oxygen ions. Materials such as B2O3 can also be used as the oxygen source.[86] Thermal evaporation was further experimented with to produce 1D WOx nanostructures in the forms of nanowires or nanorods by heating W metal or WO3 powder in the presence of oxygen gas.[79,8487] Figure 7 shows the typical morphology of such nanowires. Thangala et al.[79] found that the density and diameters of thermally evaporated WOx nanowires were inversely proportional to the substrate temperature and both increased by boosting the oxygen partial pressure during the process. The assynthesized 1D WOx nanostructures were mostly reported to be monoclinic W18O49, and the oxygen deciency was minimized by increasing the oxygen content during the process or by postannealing.[83,84,86] Further to the previous reports, water vapor
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Figure 8. a) AFM image showing the topography of a typical WO3 lms obtained using spray pyrolysis at 250 C substrate temperature. Reproduce with permission.[100] b) SEM image of the WO3 lm with nanobre network obtained using pulsed spray pyrolysis (inset: magnied image). Reproduce with permission.[108] Copyright 2007, Elsevier. Figure 7. SEM images of WOx nanowires on quartz substrate synthesized by thermal evaporation at 1950 K. a) Low-magnication image of individual nanowires with diameters in the range of 30 to 60 nm. b) Crosssectional image of the as-synthesized vertical arrays of nanowires on a uorine-doped tin oxide (FTO) substrate. Reproduce with permission.[79]
was introduced during the thermal evaporation of WOx as the oxygen source.[88,89] In this case, relatively denser and longer WOx nanowires were obtained, and a slightly lower temperature (650 C) was required to evaporate the source material. It was suggested that water favors the formation of highly mobile species, such as WOx hydrates, allowing faster spreading of the material for nanostructural growth.[89] 3.1.3. Other PVD Methods Apart from the abovementioned vapor-phase methods, electron-beam (e-beam) deposition,[80,90,91] pulsed-laser deposition (PLD)[81,9295] and arc-discharge[96,97] deposition techniques are the alternatives available for synthesizing nanostructured WO3. For the e-beam and PLD methods, WOx targets are generally used, while W metal electrodes are employed in the arc-discharge technique. The as-synthesized WOx from these three methods are usually compact thin lms, which are textured by nanoparticles (10800 nm). The size of the particles is greatly affected by the oxygen pressure and substrate temperature as the two most important parameters for these processes.[93,98] Spray Pyrolysis: Spray pyrolysis is a typical aerosol-assisted chemical vapor deposition (CVD), which is well utilized in the glass industry and in solar cell production to deliver thin or thick lm coatings.[99] A typical spray pyrolysis process can be conducted either in vacuum or under atmospheric pressure, and the set-up usually consists of an atomizer, a precursor solution, substrate heaters, and a temperature controller.[99] During the deposition, the precursor solution is pumped to an atomizer, and then sprayed through the carrier gas as a ne mist of very small droplets onto heated substrates. Subsequently the droplets undergo evaporation, solute condensation, and thermal decomposition, which then result in lm formation.[100] WOx lms prepared by this method are generally produced from tungsten chloride or ammonium tungstate solutions, and oxygen or air is used as the carrier gas.[101105] Such lms are typically of compact structure, consisting of 100200-nm
grains as seen in Figure 8a.[103,104] Substrate temperature is considered to be the most important parameter, as it affects both the crystallinity and thickness of the as-produced lms, and also inuences the size of the deposited particles.[99] Many researchers[101107] have found that amorphous or polycrystalline WO3 is formed on substrates with temperatures less than 300 C, while monoclinic WO3 starts to dominate as the substrates temperature is raised above 300 C. Further improvement of the material crystallinity can also be achieved by postannealing at 500 C. Regragui et al.[103] found that larger grain sizes were obtained when the substrates were heated to 400500 C, due to more severe solvent evaporation and precursor decomposition. More recently, Bathe et al.[108] obtained WO3 lms of interconnected nanobres using pulsed spray pyrolysis to avoid the unwanted substrate cooling caused by continuous spraying of mist (Figure 8b). The same research group[109] later presented the growth of nanobre networks by using different quantities of precursor solutions. It was found that beads (100200 nm) were initially formed on the substrate; afterwards, nanowires (diameter: 250 nm) started to grow; and nally a network of interconnected nanobres (width: 500 nm) was obtained as the process continued.[109] Modications to the standard spray pyrolysis of WO3 were also found to enhance the materials structural morphology. Ghimbeu et al.[110] applied static voltages between 7.58 kV to the nozzle, electrically charging up the precursor droplets. Consequently, extremely porous WO3 lms were created using this method. Additionally, a laser was applied to the mist during the process, and ne nanowires of WO3 were found scattered in different densities on the substrate.[111] The application of the laser was believed to induce some photochemical reactions to the precursor droplets in the mist, which resulted in the selfassembled growth. Finally, one of the latest reports presented ame-assisted WO3 synthesis by spray pyrolysis.[112] The combustion of the precursor droplets was supported by CH4 and O2 as carrier gases, and ultrane monoclinic WO3 nanoparticles (515 nm) were produced.
3.2. Liquid-Phase Synthesis Liquid-phase synthesis (LPS) methods are generally chosen when the high capital cost of vapor-phase deposition equipment
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cannot be justied. LPS offers better control of the material morphology when compared to the vapor-phase methods. LPS can also be implemented at relatively low temperatures, hence not deteriorating the quality of low-heat-tolerance substrates during the deposition process. Over the years, a vast number of liquid-phase synthesis routes have been developed for synthesizing WOx in various nanostructured forms. Hydrolysis, condensation, etching, and oxidation are the four most important chemical processes in LPS. 3.2.1. SolGels The solgel process is a well-known, intensively studied wetchemical technique that is widely used in materials synthesis. This method generally starts with a precursor solution (the sol) to form discrete particles or a networked gel structure. During the course of gelation (aging process), various forms of hydrolysis and polycondensation take place. Film deposition is generally conducted during the gelation process, where the solgel is dip-coated, spun, or drop-cast onto the substrates. In most WOx solgel syntheses, hydrated WO3 is produced. Sanato et al.[113] conducted a series of Raman analyses concerning the change of the solgel-produced WO3 crystal structure induced by various annealing temperatures. They found that the assynthesized material was a highly crystalline tungsten oxide hydrate; however, no specic type of hydrate could be determined. The typical Raman peaks of hydrated WO3 were still present even after calcination at 300 C, and anhydrous WO3 in a monoclinic phase started to be dominant above 400 C. For the sol preparation, a diverse range of precursor solutions are available. Early work mainly focused on dissolving W(OEt)6[114] and WOCl4[115] in various kinds of alcohols. However, these precursors are expensive and highly volatile, and the WO3 lms produced from them were rather compact and featureless.[116] WCl6 can also be used by dissolving it in organic solvents, but the resulting product was found to have tungsten bronze impurities instead of pure WO3, as the organic solvents partially reduce W6+ to W5+. Therefore, such a precursor needs to be aged for a long period of time (37days at room temperature or 48 h at 5060 C) to obtain a transparent solution indicating that the amount of W5+ has been minimized.[117] The WO3 lms obtained were reported to lack porosity unless a templating method was also used.[117,118] Aqueous solutions of tungstic acid are also widely used as precursors and are typically obtained by acidication of aqueous sodium tungstate solutions. These clear precursor solutions are more stable and easier to handle than the ones mentioned above.[116] During the tungstic acid solution aging process precipitates are found as the hydrolysis of H2WO4 proceeds, condensing to form crystalline WO3nH2O particles.[119] The as-prepared precursor can be immediately used for lm deposition; however, the resultant lms are made up of large crystallites. In contrast, by exerting some control over the tungstic acid preparation and the precursor aging process, interesting nanomorphologies can be realized. We recently reported[119] a new technique for preparing a tungstic acid solution in which the mixing of Na2WO4 solution and HNO3 was conducted using a microuidic Y connector with a controlled ow rate rather than mixing the two solutions at once. As can
Figure 9. SEM images of WO3nH2O: a) left to dry at low humidity; b) dried in a humid environment. The insets show low magnication optical images. Reproduce with permission.[119] Copyright 2010, American Chemical Society.
be seen from Figure 9, micro- and nanotextured tungsten oxide in a randomly aligned akelike structure (thickness: 1030 nm) was obtained using a slow ow rate. The humidity of the aging process was also found to affect the materials morphology, as enhanced lm porosity was obtained in a more humid environment (Figure 9b). As expected, the as-produced material was found to be a mixture of WO3nH2O where n = 1/3, 1, or 2. A mixed phase of monoclinic and orthorhombic WO3 formed after annealing at 550 C. Peroxotungstic acid solutions are probably the most widely used precursors in WO3 solgel syntheses due to their excellent stability in an ambient environment.[116] The precursor is typically obtained by dissolution of tungsten metal in concentrated hydrogen peroxide solution, which produces [WO2(O2)H2O]nH2O complexes. The gelation of peroxotungstic acid generally takes place with the addition of some organic acids at 5060 C for 2448 h, during which time WO3nH2O is formed.[30,120,121] A typical surface morphology of the WO3 lms obtained using peroxotungstic acid is a highly mesoporous network of interconnected particles (diameter: 100200 nm), as shown in Figure 10.[120] Humidity present during the precursor aging process affects the structural morphology in a similar way to using aqueous tungstic acid, as mentioned above.[122] However, the mechanism behind this is still unclear. Addition-
Figure 10. Surface morphology of a WO3 lm prepared by peroxotungstic acid solgel method, the lm was annealed at 500 C. Reproduce with permission.[120] Copyright 2007, American Chemical Society.
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ally, like the case of aqueous tungstic acid, hydrated WO3 with a degree of crystallinity is normally the direct product of the synthesis, and the WO3 formed is able to retain its hydrated nature after the post-annealing process at temperatures less than 500 C. 3.2.2. Templating Templating is a modication of the solgel synthesis technique and can be very effective for the preparation of meso- or nanostructured WOx. Templating can be divided into two main categories, namely hard templating and soft templating. In hard templating, templates such as an anodic alumina membrane (AAM) with self-organized nanopores[123,124] as well as a meso- or nanoporous silica substrate[5] are immersed in the WO3 precursor solution, which is prepared in a similar fashion to the solgel method such that the precursor solution inltrates the hard template structures. The inltrated templates Figure 12. SEM (a,b,d) and TEM (c) images of WO prepared using a colloidal crystal template. 3 are then aged to achieve gelation. After aging, a) PMMA diameter, 490 nm; calcination temperature, 773 K. b,c) 180 nm; 773 K. d) 180 nm, the WOx gels, together with the substrates, 873 K. Reproduce with permission.[127] Copyright 2008, Royal Society of Chemistry. are annealed to induce solid WO3 nanostructures and crystallinity. Finally the templates are gently removed by chemical etching. Figure 11a presents oxygenated environment to remove the templates. Figure 11b a template nanostructured WO3 lm with wire morphology and Figure 12 show the WO3 morphologies achieved by softachieved by inltrating an AAM lm with precursor, aging, and templating using PEG and PMMA microballs, respectively. then dissolving the AAM template. As is evident from Figure 12, through careful control of gelaFor the soft templating method, carbon-based structures tion and annealing processes, it is possible to achieve highly (e.g., carbon microspheres[125]) and organic compounds such ordererd meso-structures. To prevent structural collapse during as polyethylene glycol (PEG),[113,126] polymethyl methacrylate the annealing treatment, it was suggested by Yang et al.[132] that [127] [128132] (PMMA), and other block copolymers, are mostly used the conditions of the precursor-template aging process needed as the templates. These template materials are either dissolved to be controlled to promote slow hydrolysis. This is particuor dispersed in solutions, which are then added to the WO3 prelarly important for the metal oxideorganic template assembly, cursor. After thorough stirring, the mixture is aged under varwhere rapid crystallization can lead to phase separation and disious conditions, and then heated at elevated temperatures in an sociation that degrade the integrity of the lm. 3.2.3 Hydrothermal Hydrothermal treatment is a facile, cost-effective and wellstudied liquid-phase technique, which has the capability of producing WOx of different nanomorphologies. In most cases, the hydrothermal synthesis of nanostructured WOx starts with the preparation of a tungstic acid solution (H2WO4) as the precursor. This solution is then kept at an elevated temperature (120300 C) for a certain period of time,[133] allowing the nucleation and growth of crystallites. Such synthetic processes generally produce layered WO3nH2O akes of lateral dimensions in the range of several tens of nanometers to several micrometers and thicknesses in the nanometre range, as can be seen from the TEM images in Figure 13.[21,134] Recent reports have shown that high-aspect-ratio 1D WOx nanostructures, such as nanowires, nanorods, and other interesting congurations, can be synthesized using the hydrothermal technique by adding sulfates and certain types of organic acid to the tungsten acid precursor solution as structure-
Figure 11. a) SEM images of the tungsten oxide nanowires synthesized using AAM template where the inltration of WO3 precursor solution was assisted by gas-lled methods. Reproduce with permission.[124] Copyright 2006, Institute of Physics. b) Surface morphology of a WO3 lm prepared by the deposition of a tungstic acid/PEG 300 colloidal solution after annealing at 400 C. Reproduce with permission.[113] Copyright 2001, American Chemical Society.
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Figure 13. TEM images of WO30.33 H2O: hexagonal nanoakes at low (A) and high (B) magnication. The inset of (B) shows the SAED pattern. HRTEM images of the samples are shown in top (C) and cross-section (D). Reproduce with permission.[21] Copyright 2008, American Chemical Society.
Many reports claim that hydrothermal synthesis with sulfates and organic species produce hexagonal or orthorhombic WO3 phases and rely solely on X-ray diffraction (XRD) patterns as the evidence for this claim. However, it is important to consider that hexagonal WO3 is formed by dehydration of orthorhombic WO31/3 H2O,[8] thus they share similar crystal structures, which are reected by the nearly identical XRD patterns.[9,21] With the lack of detailed Raman and FTIR analysis, which are very sensitive to the presence of OH groups,[141] it is difcult to draw a decisive conclusion on the exact WOx crystal phases obtained from hydrothermal synthesis with additives. Regardless of crystallinity, the general morphologies of hydrothermally synthesized WOx, produced with and without additives, are undisputedly different, however it is still unclear what exact structural assembly mechanisms are inuenced by the addition of sulfates and acids. Some literature[136,142] suggests that certain ions in the additives are adsorbed onto the surface of seed crystals of WOx. This effect locally decreases the crystal surface energy that alters the growth mechanism. In addition, a recent report by Phuruangrat et al.[143] found that the application of microwave power during the hydrothermal process for WOx nanostructure synthesis shortens the reaction time by more than 50%.
directing and dispersing agents. The type of nanostructure and crystallinity can be controlled through the use of different kinds of sulfate and organic acid. Table 2 presents a brief summary of the nanostructured WOx types that result from hydrothermal treatment with different additives. Figure 14 presents a selection of the high-aspect-ratio structures that have been achieved using this technique.
3.2.4. Electrochemical Anodization Electrochemical anodization has long been used on an industrial scale to passivate metal surfaces for corrosion resistance; it also helps to color and glue metal surfaces more effectively by producing microscopic textures on the surfaces. In the early 90s, nanoporous structures were discovered on silicon[144] and
Table 2. Summary of WOx nanostructures obtained using hydrothermal process and their synthesis conditions.
Morphology nanowire bundles[135] nanorods[136] nanoribbon[136] cylindrical nanowire bundles[136] scattered nanorods[136] nanobelts
[137]
Dimensions [nm]a) D: 5-15 L: > 5 103 D: 5-25 L: 200-500 W: 100-1000 L: >1 104 T: 10-25 N/A N/A W: 30-100 L: >1 10 T: 15
3
Precursor H2WO4 H2WO4 H2WO4 H2WO4 H2WO4 H2WO4 H2WO4 H2WO4 WCl6
Additives Li2SO4 H2C2O4 Rb2SO4 H2C2O4 K2SO4 H2C2O4 Na2SO4 H2C2O4 (NH4)2SO4 H2C2O4 cetyltrimethylammonium bromide Na2S ethylenedi minetetraaetic Na2S citric acid urea
Temperature [C] 180 180 180 180 180 180 140180 120 180
Duration [h] 224 272 272 8 8 12 412 24 12
Crystal phaseb) h-WO3 h-WO3 h-WO3 N/A N/A
-WO3
h-WO3
nanowire bundles[138] nanoplate[139] nanowire, hollow sphere, nanotube, solid ball[140]

a)
N/A W: 500 Various
-WO3
crystalline H2W1.5O5.5 H2O
D: diameter, T: thickness, L: length, W: width; b)The crystal phase is determined in the as-synthesized material without post-annealing treatment.
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temperature. Apart from the nanoporous morphology, other nanostructures can also be obtained by W anodization. We recently reported on the synthesis of a bilayered WO3 nanoplatelet structured lm of a thickness up to a few m by anodizing W foils in 1.5 M HNO3 at 50 C.[160,161] Observation of owershaped WO3 nanostructures achieved by anodization has also been reported recently.[14] 3.2.5. Electrodeposition Electrodeposition can be considered the reverse of electrochemical anodization. For anodization, a metal is oxidized by ions present in the analyte, for electrodeposition, in contrast, a metal oxide lm forms by accumulating metal ions present in the electrolyte. For the electrodeposition of WOx, the most popular choice of electrolyte is the per[162] Alcohol (isoproFigure 14. SEM and TEM (inset) images show the morphologies of the hydrothermally synthe- oxotungstic acid solution. sized WOx with different amounts of added urea in the WCl6 precursor solution: a) 0 mmol, panol or ethanol) can be added to the solution b,c) 5mmol, d,e) 10 mmol, f,g) 20 mmol, and h,i) 40 mmol. Reproduce with permission.[140] to increase the stability.[162] The deposition Copyright 2009, American Chemical Society. mechanism can be summarized as:[163] i) the formation of isolated nuclei and their growth to larger grains; ii) the aggregation of grains; and iii) the formaaluminium[145] by anodizing the respective materials. This tion of crystallites. method was then extended to other metals including Ti, Zr, Ta, Typically the process requires only a small applied voltage Hf, Cd, and Bi.[146154] (e.g.,0.5 V versus Ag/AgCl), and the deposition duration is in In a typical anodization apparatus, potential is applied the range of 130 min. Excessive applied voltages and prolonged between two samples (working electrode and the counter elecprocessing time can result in creating compact lms with low trode), which are both immersed in a liquid electrolyte. An porosity.[164,165] Under optimal conditions, electrodeposition can electrical current is then applied between them which results produce porous WOx lms with grains of 20100-nm diamein electrochemical reactions occurring at the surface of both ters. An example of such a lm is presented in Figure 16.[166,167] samples. Grimes et al.[155] reported the rst use of anodization Analyses of electrodeposited lms using XRD indicate that they to produce WOx nanostructures. This demonstration used a W are predominantly amorphous with a small degree of nanofoil in an oxalic acid electrolyte resulting in the production of a crystallinity.[164166,168,169] As with most liquid-phase synthesis thin nanoporous WOx layer on the W foil surface. This experimethods, the as-electrodeposited WOx is usually in a hydrated ment was followed by the demonstration of more uniform and form. This fact has been conrmed by numerous FTIR and thicker lms (with thickness up to 500 nm) by anodizing W Raman studies.[164166] Post-annealing above 400 C is usufoils in uorine-containing electrolyte, where the uorine speally conducted to transform the WO3n H2O to monoclinic cies were found to greatly enhance the electrochemical etching WO3. However, annealing tends to increase the grain size and and chemical corrosion processes.[156158] The authors of this decreases the porosity of the lms.[169] review later reported on the nanoporous WO3 lms obtained Apart from the above-mentioned peroxotungstic acid elecfrom anodizing the W lms, which were RF sputtered on trolyte, Baeck et al.[170] introduced sodium dodecyl sulfate into FTO glass substrates. The resulting structure is presented in the electrolyte solution, and obtained WOx lms with lamellar Figure 15.[159] crystallites, which enhanced the photocatalytic and electroThe anodization current, composition, and temperature of the chromic performance. In addition to this, WOx lms which electrolyte are among the most important parameters affecting exhibit a pebble-beach-like morphology, made up of nanoballs the WOx growth.[60] The anodic current density transient can be with diameters in the 40350-nm range, can also be obtained interpreted as a direct measurement of the electrochemical anousing an aqueous sodium tungstate solution directly as the dization. A typical anodic current density transient is presented electrolyte.[171] To achieve these results, however, it is necessary in Figure 15a. The as-anodized WOx lms are reported to be to precisely control the electrolytes pH. hydrated and mainly amorphous.[155,158,159] however, a more recent report by Ng et al.[14] claimed that subtle crystallinity peaks corresponding to monoclinic WO32 H2O were observed 3.3. Other Methods in the XRD patterns of the as-anodized WOx lms. Nonetheless, the asanodized WOx can be converted to the highly crystalline In 2008 Widenkvist et al.[172] reported a facile route for proand stoichiometric WO3 by post-annealing, with monoclinic or ducing a WO3 ake-like structure. The synthesis was conducted orthorhombic phase being present depending on the annealing
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Figure 15. a) Current transient curves recorded during anodization at different voltages with 0.5% (wt) NH4F/ethylene glycol electrolyte, and the resulting surface morphologies of anodized W lms at b) 20 V, c) 40 V, d) 60 V (inset: cross-sectional SEM image). Reproduce with permission.[159] Copyright 2009, Elsevier.
by immersing a W metal plate in a HNO3 solution at 5060 C to form layer-structured tungstite platelets. Monoclinic WO3 was obtained by a post-annealing treatment at 350 C.
Recently, we have presented an innovative method for the synthesis of atomically thin 2D WO3 structures using a threestep process that involves a wet-chemical synthesis of hydratedWO3, mechanical exfoliation of the fundamental layers and dehydration by annealing.[48] We obtained the minimum resolvable thickness of the hydrated akes as 1.4 nm, which corresponds to one unit-cell height.
4. Applications
In this section, some of the applications of WOx materials are presented. Particular emphasis is placed on the enhancements that can be achieved by exploiting the nanostructured forms of WOx. Common applications of WOx include electrochromic, photocatalytic, and gas sensing. These applications have been thoroughly investigated and reported in the literature. The exploitation of WOx for dye-sensitized solar cells, optical data storage and eld-emission displays as well as the cation-doped WO3 high-Tc superconductor are also discussed. 4.1. Electrochromic Devices
Figure 16. Surface morphology of an electrodeposited WO3 lm using peroxotungstic acid solution. Reproduce with permission.[167] Copyright 2008, Elsevier.
WO3-based electrochromic (EC) devices, which are normally seen in smart windows and EC displays, have been widely
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to evaluate the EC device performance in the literature: cyclic stability, optical modulation, color/bleach time, charge density, and coloration efciency.[31] Most of the WO3 EC devices investigated so far have focused on amorphous lms due to their high coloration efciency (55 cm2 m C1 for H+ intercalation) and fast color/bleach time.[30,31] Unfortunately, amorphous WO3 has poor structural and chemical stability, resulting in poor EC stability. Crystalline WO3 is much more stable due to its denser structure and slower dissolution rate in acidic electrolytes.[33] However, Figure 17. a) Schematic image of a typical sandwich structure EC device. b) Samples of the crystalline bulk WO3 has a relatively lower 2 1 PEC cell with solid electrolyte in the bleached state (left, short-circuit) and colored by illumina- charge density of 3 mC cm mg comtion equivalent to one sun (right, open-circuit). Reproduce with permission.[38] Copyright 2006, pared to 9 mC cm2 mg1 in the amorphous Elsevier. form,[31] as well as poor coloration efciency (25 cm2 m C1 for H+ intercalation)[15] and studied over the past few decades. These devices exhibit a good slow switching times. Recently, a nanostructured WO3 lm memory effect with low power consumption, high contrast and with a high degree of porosity has been utilized to overcome the long-term stability. There are a few types of congurations for drawbacks of crystalline WO3 for EC applications. The details EC devices.[173] The most widely used and simplest conguraare summarized in Table 3. tion is the sandwich structure, shown in Figure 17a. It includes These nanostructured WO3-based devices show signicant an EC layer (WO3), an electrolyte for ion storage, and two transimprovement in charge density,[15,3033,175,178] coloration efparent conductors, which are utilized to establish electrical conciency,[174,176] and coloration/bleach time[32,175,176] compared to tacts. Application of a voltage drives the ion into the WO3 where bulk amorphous and crystalline WO3. More importantly, it is it is intercalated, causing the chromic effect. Reversing the observed that nanostructured hexagonal WO3-based devices voltage withdraws the ions from the WO3 matrix and returns have superior charge densities when compared to triclinic, them to the electrolyte. The electrolytes are usually H2SO4 and monoclinic, and orthorhombic WO3.[9] This can be due to the + HClO4 with H serving as the intercalation ion, while LiClO4 is unique hexagonal rings and trigonal cavities of hexagonal WO3, widely used for Li+ intercalation. Five factors are normally used which provide more available sites for cation intercalation.
Table 3. Summary of nanostructured WOx-based EC devices featuring their typical performance data.
Crystal phase H+ containing-electrolyte Monoclinic[32] Orthorhombic[15] Orthorhombic Hexagonal[175] Hexagonal[33] Monoclinic[31] Li+ containing-electrolyte Monoclinic[176] Monoclinic[177] Triclinic[164] Monoclinic
[129] [174]
Surface morphology
Thickness Optical [nm] modulation
Charge density [mC cm2 nm1]
Coloration efciency [cm2 m C1]
Coloration/ bleach time [s]
Mesoporous with a pore size of 70 nm Mesoporous with a pore size of 50 nm Mesoporous with a poresize of 100 nm Mesoporous with a pore size of 35 nm Nanorod with a diameter of 100 nm, and length of 2 m Nanospheroids (diameter of 1020 nm) mixed with nanorods (diameter of 4060 nm)
350 300 400 100 N/A N/A
60% 40% 50% N/A 34% N/A
0.054 0.05 0.033 0.082 114.5 mg1 32 mg1
N/A N/A 58 49 37.6 42
2.8 10 8 11 25 N/A
9.5 25 8.1 2 18 N/A
Nanowires with a diameter of 4060 nm, and a length of 5 m Nanowires with a diameter of 6070 nm Mesoporous with a pore size of 50100 nm Mesoporous with a pore size of 7 nm Mesoporous Nanorod with a diameter of 100 nm, and a length of 2 m
N/A N/A 220 190 240 N/A
65% 65% 50% 85% 85% 66%
N/A N/A 0.068 N/A 0.06 133 mg1
61.3 56 N/A 64 N/A N/A
3 1 55 N/A N/A 38
1.5 4.2 30 N/A N/A 42
Monoclinic[178] Hexagonal[179]
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However, the downside of using hexagonal WO3 is slower coloration/bleach time and lower coloration efciency, which could be due to the existence of surface defects. These effects are still under investigation. In recent years, self-sustained EC devices such as photoelectrochromic (PEC) cells were developed as a new approach for smart windows with no external power.[1] Typically, a PEC cell can be a standard WO3-based-EC device fabricated on top of a translucent photovoltaic (PV) cell. Due to the complexity of this side-by-side device fabrication, current research on PEC cells mainly incorporate the WO3 into a dye-sensitized solar cell (DSSC) with added lithium ions to the electrolyte, taking advantage of the ease of assembly of DSSCs. Since, currents as small as 0.1 mA cm2 are required to darken the WO3-based EC layer, the sensitized-photoanode layer can afford to be thin enough to achieve high transparency.[1] Such a PEC cell was rst demonstrated in 1996, using thermally evaporated WO3 as the cathode.[180] Under short-circuited conditions, this kind of PEC cell is colored in 100 s under illumination.[180] Furthermore, a different cell conguration was explored by Georg et al.,[38] in which the WO3 nanoparticle electrochromic layer was deposited between the transparent working electrode and the photoanode. The coloration of the cell was achieved by open-circuit conditions, and inversely bleached by short-circuit conditions, as seen in Figure 17b. The porous structure of the nanotextured WO3 lms reduced the response time and enhanced the coloration efciency. 4.2. Dye-Sensitized Solar Cells Dye-sensitized solar cell (DSSC) technology is currently a hot topic in the area of photovoltaics, and its advantages and operating principles has been reported previously.[58] TiO2 is the most investigated photoanode material for DSSCs, with an overall efciency of 12%.[181] Although WO3 was mentioned by Deb[1] as a suitable alternative for replacing TiO2 due to their comparable electronic properties, few reports on WO3-based DSSCs exist. Very recently, authors of this text[182] presented the rst detailed investigation of nanoparticle WO3-based DSSC. The open-circuit voltage (Voc = 390 mV), short-circuit current density (Jsc = 4.6 mA cm2), and efciency ( = 0.75%) obtained are still not comparable to the TiO2-based DSSCs. This is due to the unfavorable CB position of WO3, which limits the Voc, along with the very acidic surface of WO3 that reduces dye adsorption, leading to severe charge recombination. However, covering the WO3 surface with a layer of TiO2 can improve the overall performance of the cell with reaching 1.46%, as seen in Figure 18. It is also worth noting that the dimension of the WO3 nanoparticles (40 nm) used in this work was twice the size of the optimum TiO2 nanoparticles in standard DSSCs. Further studies of WO3-DSSCs need to be conducted to investigate the effects of increasing surface area and changing the morphology of the WO3 nanostructures (e.g., nanowires can increase the carrier mobility). 4.3. Photocatalytic Applications A main goal in the area of photocatalysis is to nd suitable materials for efcient solar hydrogen production and organic
Figure 18. IV characteristics of WO3-DSC and TiO2-modied WO3-DSC. Inset: SEM image of the WO3 nanoparticle photoanode used in the DSC, nominal particle size = 40 nm.
pollutant degradation. In 1969, Fujishima and Honda[183] reported the rst photoelectrolysis of water using singlecrystal rutile-structured TiO2 under UV irradiation. Since then, TiO2 and other semiconductor materials including WO3 were intensively explored for their photocatalytic abilities. Recent comprehensive reviews on photocatalytic materials and their industrial applications have been previously published[59,184,185] In searching for the optimum semiconductor material for efcient photocatalytic applications, Zhang et al.[59] have summarized the key aspects as: i) nanostructured forms can provide the optimum surface to volume ratio; ii) a lower band-gap energy that can utilize the visible spectrum of solar light; iii) an optimum band structure for the desired redox reactions; and iv) material stability to withstand harsh operating environments. As mentioned earlier, nanostructuring of WOx increases its photocatalytic capability. We[159] and a number of other research groups[126,156,157] have reported more than 100% increase of photocurrent or incident photon-to-electron conversion efciency (IPCE) for WOx in various nanostructured forms in comparison to the compact WOx. This enhanced photoresponse has been mainly ascribed to a much larger effective WOx surface area provided by the nanostructures. IPCE of up to 190% was also recorded[126,184] by adding organic species (e.g., methanol) into the electrolyte due to the particularly favorable photo-oxidation kinetics between WOx and the organic species (Figure 19). In addition to the enhanced surface-to-volume ratio, the chargecarrier separation and transport mechanisms in nanostructured WOx may also play an important role. Augustynski et al.[126,186] compared the photocurrent generated by a nanocrystalline WO3 (Figure 11b) and compact WO3 lms, which can be seen in Figure 19. They found that much higher photocurrents were achieved by a nanocrystalline WO3 lm at a relatively small applied potential and that they saturated at even higher onset potentials. On the other hand, the photocurrent generated by the compact WO3 lm did not saturate and increased with higher applied potential. Less power is required to operate a nanocyrstalline WO3 based photocatalytic device as it is easier for the charge carriers to travel to the oxide surface. Other groups have now reported similar experimental results.[66,67,156]
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4.4. Optical Recording Devices Driven by the need for high-density and reversible information storage, optical recording is an advanced technology, which has seen application in everyday life.[195] The initial exploration of WOx for this eld used a combination of photochromic and electrochromic effects to record digital images.[1] Later Lu et al.[196] showed that an amorphous WO3 thin lm could be colored by a single pulse of KrF excimer laser light at 248 nm and bleached by a single pulse of Nd-Y-Al-garnet laser light at 1.06 m in air. Experiments have also been conducted that demonstrate the use of laser light to change the crystal phase of WOx lms with associated changes in optical transmission.[197] This technique has been used to achieve a storage capacity of 25 GB on a single platter. 4.5. Sensing Applications Precise and economical monitoring of chemical gases is critical for human health, industrial processes, and environmental protection. WOx has a long history for sensing applications, especially in gas sensing.[198] The response of WOx gas sensors can be based on a range of effects such as electrochemically induced changes in resistance and alteration of optical properties. An elevated operation temperature is crucial to the gas sensing capability of WOx, as it enhances the sensitivity and reduces the response and recovery times.[199] Noble metal catalysts such as Pt, Pd, and Au, which are coated on the oxide surface, are found to improve the sensing capabilities and tend to promote chemical reactions by reducing the activation energy between the oxide and the target gas.[200] The sensing mechanism of a conductometric type-WOx gas sensor is well established.[199] Upon exposure to oxidizing gases, such as O3, NO2,[201] and CO2,[202] the surface free electrons are captured to reduce these gas species forming oxygen ions which adsorb onto the oxide surface. Therefore, the conductivity of WOx is decreased proportionally to the amount of target gas adsorbed. Conversely, exposure to reducing gases such as H2, H2S, NH3, CS2, CO and some alcoholic vapors,[125] increases the conductivity of the WOx sensing layer. Nanostructured WOx has been intensively studied for gas sensing applications as it enhances sensor capabilities; reduces power consumption, and produces excellent reproducibility.[199] Many of the enhanced features of the nano-WO3 sensor are mainly ascribed to the dramatically increased surface area for reactions; single crystallinity, and possible complete depletion of carriers within the nanostructure when exposed to the target gas.[125,199,203,204] For a WOx gas sensor based on optical modulation, the fundamentals lie within the gasochromic effect of WOx, which was explained in Section 2.5. We have reported a comprehensive study on optical modulation of nanotextured-WO3 thin lm based sensors towards H2 exposure,[205] for which the WO3 surface morphology, the absorbance spectra and the dynamic response to H2 are shown in Figure 20. Examples of WO3 basedbre-optic sensors can also be found in a report by Ito et al.[206] Based on the principles of H2 sensing, WOx was also explored in biological sensing. A study was conducted by Deb and his
Figure 19. Incident photon-to-current conversion efciencypotential curves for a nanocrystalline (about 2.5 m thick) and a bulk WO3 photoelectrode (lled and open circles, respectively) recorded in a 0.1 M CH3OH/1 M H2SO4 solution: under 380 nm illumination from a 500 W Xe lamp equipped with a monochromators. Reproduce with permission.[126]
This unique charge separation and transport mechanism is still subject to further investigation, and more detailed explanations and arguments are reported elsewhere.[59,68,187,188] Although WOx is capable of absorbing in the short wavelength region of visible light, which has much higher energy than the UV region of the solar spectrum, it is thermodynamically unfavorable to reduce water to produce hydrogen, as its CB edge is more positive (versus NHE) than the H2/H2O reduction potential (Figure 6). This can be overcome by applying an external potential to help inject the photo-generated electrons into the water molecules.[113] However, passive photocatalytic systems are preferable given todays energy issues. In such systems, WOx nanoparticles are usually mixed with other metal oxides to form an overall complementary band structure, or doped with materials that can shift the WOx CB to a more negative position. Stoichiometric water splitting to H2 and O2 using Pt-loaded WO3 mixed with Pt-loaded SrTiO3 and an I3/I redox mediator, under visible light irradiation, was rst reported by Sayama et al.[189] The more negative CB of SrTiO3 facilitates H2 production, while O2 is mainly produced by water oxidation from photogenerated holes on the VB of WO3. This work was followed by investigating mixtures of WO3 and TaON, which achieved similar results.[190] There are also a number of reports on doping WOx with Mg,[191] Fe, Co, Ni, Cu, Zn,[192] Bi, Ag,[193]and Au,[194] which all show enhanced photocatalytic performance compared to the undoped WOx. However, it was found that not all metal ion dopings shift the band positions of WOx towards the H2/H2O energy level. In particular, Ni[192] and Ag[193] doping were found to be promising for H2 evolution, while the band positions of WOx doped with Fe, Cu[192] and Au[194] shifted downwards, which improved the oxidation of water.
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is highly utilized in X-ray generators, electron microscopy and spectroscopy as well as in display devices.[208] In the eldemission process, electrons travel from an emitting material (cathode) to the anode with the assistance of a high electric eld. The emitting capability is believed to be highly dependent on both the properties of the material and on the conguration of the cathode. It is know that materials with higher aspect ratios and sharp edges generally produce higher eld-emission currents.[209] Nanostructured materials are under intensive investigation for eld-emission applications due to their high current densities, fast response times, compactness, and sustainability.[209] So far mostly elongated WOx nanostructures such as nanowires and nanorods have been explored for eld emission applications. Zhou et al.[85] reported eld-emission measurements using a 3D nanowire network of WO3 with some planar oxygen defects, with which a turn-on eld (to produce 10 A cm2 current density) of 13.85 V m1 at 200 m distance between the cathode and the anode was achieved. This result is comparable to the reported eld-emission properties of MoO3 nanobelts,[210] ZnO nanowires,[209] and In2O3 nanopyramids.[211] Similar eld-emission results for WOx nanorods and nanowires were obtained by a number of research groups,[28,212] and it was found that the diameters and the chemical composition of the materials played important roles in enhancing the eld-emission results. In a recent report, Chen et al.[213] successfully fabricated a double-gated eld-emission display (FED) based on WO3 nanowire pixels, which showed high contrast and brightness. Figure 21 presents such FED devices in operation as well as the morphology of the WO3 nanowires used for the application. 4.7. High-Tc Superconductor High-temperature superconductors (HTS) are materials that have a superconducting transition temperature (Tc) above 30 K. They are used in mass spectrometers, particle accelerators, and possibly in power transmission applications to reduce loss.[1] Sheet superconductivity at 3 K in twin walls of a non-superconducting tetragonal WO3x was rst reported by Aird et al. in 1998.[214] This was followed by the discovery of sodium doped WO3 (Na0.05WO3) possessing superconductivity at 91 K.[215] Although this work attracted less attention than high-Tc cuprates, it was the rst non-cuprate HTS material.[1] Recently Reichs group obtained a possible 2D HxWO3 superconductor with a Tc of 120 K, which is very close to the highest Tc (135 K) of HTS material reported so far.[216] To date, all the reports for superconducting WOx and its compounds are based on bulk materials; hence, it will be interesting to see the effect of nanostructured WOx or its compounds in superconductor applications.
Figure 20. SEM images of (a) RF sputtered WO3 surface, (b) absorbance versus optical wavelength for Pt/WO3 lms exposed to 1% H2 at room temperature. and (c) dynamic response when exposed to different concentrations of H2 at 100 C for a single wavelength 660nm. Reproduce with permission.[205] Copyright 2010, Elsevier.
co-workers[1] using WO3 for selecting particular mutants of green algae that produced H2 in water with increased O2 pressure. On a less reported front, sensing based on perturbation in permittivity was explored by Dong et al.[207] as a capacitive humidity sensor fabricated using WO3 deposited on a Si nanotemplate. A sensitivity of over 16 000 was achieved at an optimal operating frequency of 1000 Hz. 4.6. Field-Emission Applications Field-emission, also known as FowlerNordheim tunneling, is usually considered to be a form of quantum tunneling. It 2192
5. Conclusion and Outlook

We have presented an overview and explanation of the fundamental properties of nanostructured WOx, have surveyed a broad selection of methods of synthesis and observed material characteristics, and have reviewed a number of possible applications
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WOx. A vast range of WOx nanostructures have already been reported, including nanoparticles, nanoplates, nanowires, nanoribbons, and nanoporous thin lms, among others. In fact, this variety is vital for the commercialization of nanostructured WOxbased devices, since certain morphologies and dimensions are better suited for particular applications than others, and different synthesis techniques provide exibility within the constraints of particular industrial circumstances. Therefore, it is very important for researchers to continue the exploration of nanostructured WOx synthesis in more innovative routes as well as the investigation of Figure 21. a) Arabic numerals and Chinese characters displayed by the double-gated FED, the growth control and mechanism. b) the cross-sectional view of the WO3 nanowires used for the FED fabrication. Reproduce with Finally, for the applications of WOx, we permission.[213] Copyright 2007, American Institute of Physics. have detailed the traditionally popular areas such as electrochromic devices, photocatalysis, and sensing devices. The studies in these areas are for this material. The key points that can be summarized from relatively advanced. However, there is still signicant room for this review are as follows. improvement of the capabilities of these devices through exploiIt was shown that WOx can be obtained in a range of crystal tation of nanostructured WOx. In addition, we have reviewed phases and that its phase transitions are rather complex. Reports some pioneering studies of WOx, which are used in dye-senindicate that by nanostructuring WOx, the energy required to sitized solar cells, optical data storage, eld-emission displays, transform the phases was considerably less than that of the of high-Tc superconductors. Although WOx may not be the bulk material, and that uniquely the orthorhombic phase can be optimal material for each of these applications, it can provide retained at room temperature. This is a very important property an effective alternative in circumstances where the optimal of nanostructured WOx, as in addition to amorphous, triclinic, material is simply not practical. Furthermore, since WOx can monoclinic and hexagonal phases, which are stable at room be well dispersed in liquid in a variety of nanostructured forms, temperature, the orthorhombic phase can also be evaluated as a one should consider the opportunity for its use in drug delivery possible candidate for the inclusion in practical devices. and sensors in microuidic systems. There have been few studies on the effects of reducing the dimensions of nonstoichiometric WO3 and WO3 hydrates and Received: November 24, 2010 this may represent an important area for future research. Revised: January 31, 2011 Although the electronic band structure, electrical conducPublished online: May 24, 2011 tivity, optical properties, chromic effect, and photocatalytic properties of WOx as well as the respective changes induced by nanostructuring are well documented, there are still many [1] S. K. Deb, Sol. Energ. Mat. Sol.. 2008, 92, 245. fundamental issues that need to be addressed. For instance, [2] C. G. Granqvist, Appl. Phys. A, Mater. Sci. Process 1993, 57, 3. [3] P. Roussel, P. Labbe, D. Groult, Acta. Crystallogr. B 2000, 56, 377. the high carrier mobility observed for WOx nanowires requires [4] P. M. Woodward, A. W. Sleight, T. Vogt, J. Solid State Chem. 1997, thorough experimental conrmation, and it will be interesting 131, 9. to see computational modelling of the electronic behavior [5] K. K. Zhu, H. Y. He, S. H. Xie, X. Zhang, W. Z. Zhou, S. L. Jin, within the nanostructures of WOx. B. Yue, Chem. Phys. Lett. 2003, 377, 317. 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Mater. 1997, 8, 687. bility to obtain atomically thin WOx layers using exfoliation, [11] M. Boulova, G. Lucazeau, J. Solid State Chem. 2002, 167, 425. presents new opportunities for ion intercalation with signi[12] D. Y. Lu, J. Chen, H. J. Chen, L. Gong, S. Z. Deng, N. S. Xu, Y. L. Liu, cantly enhanced chromic response. Appl. Phys. Lett. 2007, 90. Investigating the synthesis techniques of nanostructured [13] A. Z. Sadek, H. D. Zheng, K. Latham, W. Wlodarski, WOx is equally important for understanding its fundamental K. Kalantar-Zadeh, Langmuir 2009, 25, 509. properties as well as its practical applications. We have presented [14] C. Ng, C. H. Ye, Y. H. Ng, R. Amal, Cryst. Growth. Des. 2010, 10, a variety of synthesis techniques for producing nanostructured 3794.
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Adv. Funct. Mater. 2011, 21, 21752196

Zheng, Adv - Funct.mater.2011, Nano Tungston Oxide - Properties & Applications

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Nanostructured Tungsten Oxide Properties, Synthesis, and Applications

Adv. Funct. Mater. 2011, 21, 21752196

2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Funct. Mater. 2011, 21, 21752196

Table 1. Lattice constant data for different WO3 crystal phases.

ideal cubic-WO3[2] 3.84 N/A N/A

Adv. Funct. Mater. 2011, 21, 21752196

2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Funct. Mater. 2011, 21, 21752196

Adv. Funct. Mater. 2011, 21, 21752196

2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

2.6. Electrical Conductivity

Adv. Funct. Mater. 2011, 21, 21752196

Adv. Funct. Mater. 2011, 21, 21752196

2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Funct. Mater. 2011, 21, 21752196

Adv. Funct. Mater. 2011, 21, 21752196

2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Funct. Mater. 2011, 21, 21752196

Adv. Funct. Mater. 2011, 21, 21752196

2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Duration [h] 224 272 272 8 8 12 412 24 12

Crystal phaseb) h-WO3 h-WO3 h-WO3 N/A N/A

nanowire bundles[138] nanoplate[139] nanowire, hollow sphere, nanotube, solid ball[140]

N/A W: 500 Various

2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Funct. Mater. 2011, 21, 21752196

2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Funct. Mater. 2011, 21, 21752196

Thickness Optical [nm] modulation

Charge density [mC cm2 nm1]

Coloration efciency [cm2 m C1]

Coloration/ bleach time [s]

350 300 400 100 N/A N/A

60% 40% 50% N/A 34% N/A

0.054 0.05 0.033 0.082 114.5 mg1 32 mg1

N/A N/A 58 49 37.6 42

9.5 25 8.1 2 18 N/A

N/A N/A 220 190 240 N/A

65% 65% 50% 85% 85% 66%

N/A N/A 0.068 N/A 0.06 133 mg1

61.3 56 N/A 64 N/A N/A

1.5 4.2 30 N/A N/A 42

Adv. Funct. Mater. 2011, 21, 21752196

2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Funct. Mater. 2011, 21, 21752196

Adv. Funct. Mater. 2011, 21, 21752196

2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

5. Conclusion and Outlook

2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Funct. Mater. 2011, 21, 21752196

Adv. Funct. Mater. 2011, 21, 21752196

2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Funct. Mater. 2011, 21, 21752196

Adv. Funct. Mater. 2011, 21, 21752196