Formation of tungsten oxide nanostructures by laser pyrolysis: stars, fibres and spheres
© Govender et al; licensee Springer. 2011
Received: 25 October 2010
Accepted: 23 February 2011
Published: 23 February 2011
In this letter, the production of multi-phase WO3 and WO3- x (where x could vary between 0.1 and 0.3) nanostructures synthesized by CO2-laser pyrolysis technique at varying laser wavelengths (9.22-10.82 mm) and power densities (17-110 W/cm2) is reported. The average spherical particle sizes for the wavelength variation samples ranged between 113 and 560 nm, and the average spherical particle sizes for power density variation samples ranged between 108 and 205 nm. Synthesis of W18O49 (= WO2.72) stars by this method is reported for the first time at a power density and wavelength of 2.2 kW/cm2 and 10.6 μm, respectively. It was found that more concentrated starting precursors result in the growth of hierarchical structures such as stars, whereas dilute starting precursors result in the growth of simpler structures such as wires.
Tungsten trioxide is known as a 'smart material', because it exhibits excellent electrochromic, photochromic and gasochromic properties. Nano-sized tungsten trioxide has been applied in many nano-photonic devices for applications such as photo-electro-chromic windows , sensor devices [2, 3] and optical modulation devices . Many techniques for synthesizing nano-sized tungsten trioxide have been reported [5–8] and this article concerns with laser pyrolysis.
Laser pyrolysis is more advantageous than most methods because the experimental orientation does not allow the reactants to make contact with any side-walls, so that the products are of high quality and purity . Laser pyrolysis is based on photon-induced chemical reactions, which is believed to rely on a resonant interaction between a laser beam's emission line and a precursor's absorption band, such that a photochemical reaction is activated . The photochemical reaction enables an otherwise inaccessible reaction pathway towards a specific product, either by dissociation, ionization or isomerisation of the precursor compound. It was shown [8, 11] that low laser power densities can also achieve the same desired products as the high power densities, presumably because of the way photon-energy is distributed into the energy levels of the precursor.
In this letter, the formation of W18O49 (= WO2.72) and the effect of the laser power, the wavelength on the morphology and structural properties of tungsten oxide nano-structured and thin films are reported.
The laser power was varied using a polarization-based attenuator, and the wavelength variation was achieved with an intra-cavity mounted grating in the laser. The different wavelengths were identified using a spectrum analyzer (Macken Instruments Inc., model 16A, Coffey Lane, Santa Rosa, California, USA) and the power output was measured with a power meter (Coherent Inc., 5100 Patrick Henry Drive, Santa Clara, CA 95054, USA).
The synthesis of WO3 and WO3- x commenced by mixing 0.1 g of greyish-blue anhydrous tungsten hexachloride (WCl6, >99.9%, Sigma Aldrich, 3050 Spruce Street, St. Louis, MO 63103, USA) powder in 100 mL of absolute ethanol (C2H5OH, >99.9%, Sigma Aldrich) to give a tungsten ethoxide W(OC2H5)6 starting precursor . Optical absorption properties of the precursor were determined using a Perkin Elmer Spotlight 400 FTIR Imaging System in the wavelength range 500-4000 cm-1.
The liquid precursor was decanted into an aerosol generator (Micro Mist, model EN, Research Triangle Park, NC 27709, USA) which was attached to the laser pyrolysis system via a multiflow nozzle that allows argon gas to carry the stream of very fine precursor droplets (5 μm droplet diameter according to the manufacturer) into the laser beam. Acetylene (C2H2) sensitizer gas and argon encasing gas flowed adjacent to the precursor, guiding it towards a substrate. The gas flow rates are chosen such that the ablated precursor collects on the substrate after interacting with the laser.
The sample was annealed for 17 h at 500°C under argon atmosphere . Morphology studies were carried out using a Jeol JSM-5600 Scanning Electron Microscopy (SEM) microscope (using the secondary electron mode). Raman spectroscopy was carried out using a Jobin-Yvon T64000 Raman Spectrograph with a wavelength of 514.5 nm from an argon ion laser set at a laser power of 0.384 mW at the sample to minimize local heating of the sample during the Raman analysis. X-ray diffraction (XRD) was carried out using a Philips Xpert powder diffractometer equipped with a CuKα wavelength of 154.184 pm. The reproducibility of the experimental procedure was not verified.
The XRD studies revealed peaks at 23° and 24° diffraction angles which suggests a tungsten oxide compound, but the lack of a triplet peak confirms the absence of monoclinic tungsten trioxide . The broad hump at 22° resulted from SiO2 of the substrate, and this substantially decreased the signal-to-noise ratio making it difficult to identify the peaks. XRD peaks at 11, 40 and 64° diffraction angles are also evident in tungsten oxides , but the 44° diffraction angle suggests that the tungsten oxide has a deficiency of oxygen . Based on the information from Raman spectroscopy and XRD, the most probable stoichiometry of this sample is monoclinic phase W18O49 (= WO2.72). According to the Powder Diffraction File (PDF 00-005-0392) that best matches the XRD spectrum in Figure 3, the lattice constants a, b and c are 18.28, 3.78 and 13.98 Å, respectively and the lattice angles are α = γ = 90° and β = 115.20°. The Miller indices are shown on the XRD spectrum in Figure 3.
Previously solid-vapour-solid (SVS)  and solution-liquid-solid (SLS)  mechanisms were proposed to explain the growth of nanowires of tungsten trioxide and platinum, respectively. Since the tungsten trioxide nanowires were grown with a low precursor concentration using a similar laser beam and laser parameters, the precursor concentration is seemingly the main contributor to hierarchical structure. This was confirmed by the 100 times more concentrated precursor that was used for the growth of the stars. The six-sided stars that were grown in Figure 2 looked very similar to lead (II) sulphide (PbS) stars that were grown by a concentration difference and gradient (CDG) technique . This CDG technique used a high local concentration of one reactant mixed with a low concentration of another reactant under ambient conditions, where the high concentration favoured the thermodynamic conditions for crystal growth and the low concentration resulted in a diffusion-controlled kinetic environment for growth of hierarchical structures.
It is possible that due to a Gaussian laser beam profile, which has a high intensity at the beam's centre and low intensity at the edges, the region of intensity in the beam experienced by the precursor could vary the concentration of the decomposed material. It is speculated that this variation in concentration could have led to the growth of the hierarchical structures according to the CDG technique. The growth of stars has also been reported before for gold and molybdenum oxide [21, 22], but not as yet for tungsten oxide. The literature proposes that star-shaped structures can be grown from agglomerates of more simple nanoforms under an inert atmosphere, which conditions were similar for this experiment [21, 22]. One growth mechanism of nanostructures could be due to Gibbs-Thompson effect [9, 23, 24], which proposes that the size of the critical radius is dependent on the precursor concentration and explains the increase (Ostwald ripening) or decrease (Tiller's formula) in size of nanostructures.
The higher concentration probably provided a critical radius which resulted in simple nanoforms and the growth of stars as opposed to a lower concentration which resulted in microspheres and the growth of wires. It is speculated that the critical radius influences the thermodynamic and kinetic conditions as predicted by the CDG technique. Thus, the laser beam properties together with the relative precursor concentration contribute to the growth of stars. Some stars may form with four-sides and others with six-sides depending on the crystalline plane arrangement and the elements composing the structures . It is not yet understood if the observed deficiency of oxygen plays a role in the formation of the six-sided stars or if the higher tungsten content, with a predominant valency of +6, has some correlation with the number of sides formed.
It is thought that acetylene gas acts as a photosensitizer  in laser pyrolysis, yet no evidence of absorption in the laser wavelength range 9.19-10.82 μm was found. This was verified by passing the acetylene gas through the laser beam at atmospheric pressure, and monitoring the power change during this interaction. The laser power did not appear to show any change, which implied that no radiation was absorbed by this gas. This does not, however, discount the possibility of some short-lived metastable state in acetylene induced by the laser which was undetectable by the power meter. The argon-precursor mixture, however, showed a change in power which indicated that the radiation was being absorbed, and the maximum absorbance was found at a wavelength of 9.54 μm. The absorbance of the precursor was given by the ratio of the laser power before laser-precursor interaction to the power observed during laser-precursor interaction.
The nanosphere diameters of this sample, which were easiest to measure on SEM micrograph, were distributed in the range 50-250 nm as depicted in inset of Figure 5, and micron-sized fibres were also present in this sample. The theory speculates that if the laser wavelength is resonant with the C-O absorption band of the precursor (W-O-C2H5), then the C-O bond would break and lead to the formation of tungsten oxide. However, FTIR showed that the C-O absorption band is found between 9.00-9.38 μm (see Figure 4), and despite argon carrier gas presumably broadening the precursor absorption bands to some extent , the result could correspond to a non-resonant energy transfer. A 10.48-μm wavelength photon carries 0.1 eV of energy, and so 29 photons are required to dissociate a C-O bond  which corresponds to a multi-photon process. It is known, however, that tungsten ethoxide precursor can form WO3 upon heat treatment , which implies that the 10.48-μm wavelength could have had similar effects as annealing had. We believe that the shorter wavelengths, which had higher energy photons, dissociated various bonds which led to the formation of triclinic phase or a mixture of monoclinic and triclinic phase WO3- x where x can vary between 0.1 and 0.3, depending on the laser parameters. It was also observed that the morphology of the samples became more randomized and of a disordered arrangement as the wavelength increased, and this is believed to be an effect of a corresponding decrease in energy.
Figure 6 shows the Raman and XRD spectra with the corresponding SEM micrograph of a sample prepared at a power density of 85 W/cm2 at the 10.6-μm wavelength, which appeared to form a monoclinic phase WO3 according to the characteristic peaks.
A summary of the results obtained for the laser power and wavelength variation
Wavelength Variation (Pdensity = 51.2 W/cm2)
Power Density Variation (λ = 10.6 μm)
Wavelength, λ (mm)
Average sphere particle size (nm)
Power Density, P peak (W/cm 2 )
Average sphere particle size (nm)
m/t -WO3- x
m/t -WO3- x
Six-sided monoclinic phase WO2.72 stars were synthesized by laser pyrolysis technique using a more concentrated starting precursor and near-Gaussian laser beam profile. The higher concentrated precursors are required to obtain hierarchical structures as predicted by the literature. Laser wavelengths above 10 μm seem to favour the formation of stoichiometric WO3, but only at certain power densities, presumably to overcome possible competing reactions. Owing to the nature of photochemical reactions and the many stoichiometries and multi-phases that tungsten oxides can form, some product compositions were written as WO3- x where x most probably assumes values between 0.1 and 0.3. The higher power densities were found to be essential for the further growth of structures and for smaller particle sizes. The authors now have an idea of the possible shapes of nanostructures that can be synthesized with possible chemical compositions, and the determination of the electrical and optical properties of these structures to observe possible unique characteristics allows for the tailoring of sensor devices that operate at room temperature for example.
Conflict of interest
The authors declare that they have no conflict of interests.
- Bittencourt C, Landers R, Llobet E, Molas G, Correig X, Silva MAP, Sueiris JE, Calderer J: Effects of Oxygen Partial Pressure and Annealing Temperature on the Formation of Sputtered Tungsten Oxide Films. Electrochem Soc 2002, 149: H81. 10.1149/1.1448821View ArticleGoogle Scholar
- Kawasaki H, Namba J, Iwatsuji K, Suda Y, Wada K, Ebihara K, Ohshima T: NO x gas sensing properties of tungsten oxide thin films synthesized by pulsed laser deposition method. Appl Surf Sci 2002, 197–198: 547–551. 10.1016/S0169-4332(02)00333-1View ArticleGoogle Scholar
- Guidi V, Butturi MA, Blo M, Carotta MC, Galliera S, Giberti A, Malagù C, Martinelli G, Piga M, Sacerdoti M, Vendemiati B: Aqueous and alcoholic syntheses of tungsten trioxide powders for NO 2 detection. Sens Actuators B 2004, 100: 277. 10.1016/j.snb.2003.12.055View ArticleGoogle Scholar
- Wang SW, Chou TC, Liu CC: Nano-crystalline tungsten oxide NO 2 sensor. Sens Actuators B 2003, 94: 343. 10.1016/S0925-4005(03)00383-6View ArticleGoogle Scholar
- Wang XP, Yang BQ, Zhang HX, Feng PX: Tungsten Oxide Nanorods Array and Nanobundle Prepared by Using Chemical Vapor Deposition Technique. Nanoscale Res Lett 2007, 2: 405–409. 10.1007/s11671-007-9075-3View ArticleGoogle Scholar
- Rajagopal S, Nataraj D, Mangalaraj D, Djaoued Y, Robichaud J, Khyzhun O: Controlled Growth of WO 3 Nanostructures with Three Different Morphologies and Their Structural, Optical, and Photodecomposition Studies. Nanoscale Res Lett 2009, 4: 1335–1342. 10.1007/s11671-009-9402-yView ArticleGoogle Scholar
- Mwakikunga BW, Forbes A, Sideras-Haddad E, Scriba M, Manikandan E: Self assembly and properties of C:WO 3 nano-platelets and C:VO 2 /V 2 O 5 triangular capsules of C:VO 2 /V 2 O 5 fullerenes and quantum dots produced by laser solution photolysis. Nanoscale Res Lett 2010, 5: 389–397. 10.1007/s11671-009-9494-4View ArticleGoogle Scholar
- Mwakikunga BW, Forbes A, Sideras-Haddad E, Arendse C: Optimization, yield studies and morphology of WO 3 nanowires synthesized by laser pyrolysis in C 2 H 2 and O 2 ambients - validation of a new growth mechanism. Nanoscale Res Lett 2008, 3: 372–380. 10.1007/s11671-008-9169-6View ArticleGoogle Scholar
- Haggerty JS, Cannon WR: Sinterable powders from laser-driven reactions. In Laser Induced Chemical Reactions. Edited by: J. I. Steinfield. New York, Plenum Press; 1981:165–241.View ArticleGoogle Scholar
- Mwakikunga BW, Forbes A, Sideras-Haddad E, Erasmus RM, Katumba G, Masina B: Synthesis of tungsten oxide nanostructures by laser pyrolysis. Int J Nanopart 2008, 1: 185–200. 10.1504/IJNP.2008.020895View ArticleGoogle Scholar
- Bowden CM, Stettler JD, Witriol NM: An excitation model for laser-induced photochemical reactions. J Phys B Atom Mol Phys 1977, 10: 1789. 10.1088/0022-3700/10/9/028View ArticleGoogle Scholar
- Sakka S: Handbook of Sol-Gel Science and Technology: Processing, Characterization and Applications. Boston: Kluwer Academic Publishers; 2004.Google Scholar
- Lu DY, Chen J, Zhou J, Deng SZ, Xu NS, Xu JB: Raman spectroscopic study of oxidation and phase transition in W 18 O 49 nanowires. J Raman Spectrosc 2007, 38: 176–180. 10.1002/jrs.1620View ArticleGoogle Scholar
- Lu DY, Chen J, Deng SZ, Xu NS, Zhang WH: The most powerful tool for the structural analysis of tungsten suboxide nanowires: Raman spectroscopy. J Mater Res 2008, 23: 402–408. 10.1557/jmr.2008.0056View ArticleGoogle Scholar
- Mwakikunga BW, Sidera-Haddad E, Forbes A, Arndse C: Raman spectroscopy of WO 3 nano-wires and thermo-chromism study of VO 2 belts produced by ultrasonic spray and laser pyrolysis techniques. Phys Status Solidi A 2004, 205: 150–154.View ArticleGoogle Scholar
- Arora AK, Rajalakshmi M, Ravindran TR: Phonon Confinement in Nanostructured Materials. In Encyclopedia of Nanoscience and Nanotechnology, Volume X. Edited by: Nalwa HS. Los Angeles: American Scientific Publishers; 2003:1–13.Google Scholar
- Ganesan R, Gedanken A: Synthesis of WO 3 nanoparticles using a biopolymer as a template for electrocatalytic hydrogen evolution. Nanotechnology 2008, 19: 025702. 10.1088/0957-4484/19/02/025702View ArticleGoogle Scholar
- Microelectronic capacitor with capacitor plate layer formed of tungsten rich tungsten oxide material2002. [http://www.surechem.org] Patent 6456482
- Chen J, Wiley BJ, Xia Y: One-dimensional nanostructures of metals: large-scale synthesis and some potential applications. Langmuir 2007, 27: 4120–4129. 10.1021/la063193yView ArticleGoogle Scholar
- Chu H, Li X, Chen G, Jin Z, Zhang Y, Li Y: Inorganic hierarchical nanostructures induced by concentration difference and gradient. Nano Res 2008, 1: 213–220. 10.1007/s12274-008-8024-5View ArticleGoogle Scholar
- Kharissova OV, Kharisov BI, García TH, Méndez UO: A Review on Less-common Nanostructures. Synth React Inorg Met-Org Nano-Met Chem 2009, 39: 662–684.Google Scholar
- Khademi A, Azimirad R, Zavarian AA, Moshfegh AZ: Growth and Field Emission Study of Molybdenum Oxide Nanostars. J Phys Chem C 2009, 44: 19298–19304. 10.1021/jp9056237View ArticleGoogle Scholar
- Qin-bo W, Finsy R, Hai-bo X, Xi L: On the critical radius in generalized Ostwald ripening. J Zhejiang Univ 2005, 6B: 705–707. 10.1631/jzus.2005.B0705View ArticleGoogle Scholar
- Tiller WA: The Science of Crystallization: Microscopic Interfacial Phenomenon. New York: Cambridge University Press; 1991.View ArticleGoogle Scholar
- El-Diasty F: Simulation of CO 2 laser pyrolysis during preparation of SiC nanopowders. Opt Commun 2004, 241: 121–135. 10.1016/j.optcom.2004.07.006View ArticleGoogle Scholar
- Glockler G: Carbon Halogen Bond Energies and Bond Distances. J Phys Chem 1958, 62: 1049–1054. 10.1021/j150567a006View ArticleGoogle Scholar
- Bomatí-Miguel O, Zhao XQ, Martelli S, Di Nunzio PE, Veintemillas-Verdaguer S: Modeling of the laser pyrolysis process by means of the aerosol theory: Case of iron nanoparticles. J Appl Phys 2010, 107: 014906.View ArticleGoogle Scholar
This article is published under license to BioMed Central Ltd. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.