Thin Solid Films 490 (2005) 59 67 www.elsevier.

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Initial stages of WO3 growth on silicon substrates

L. Ottaviano*, M. Rossi, S. Santucci
INFM-CNR-Laboratorio CASTI and Dipartimento di Fisica Universita ` degli Studi dellAquila Via Vetoio 10, I-67010 Coppito-LAquila, Italy Available online 19 May 2005

Abstract Ultrathin films (5 nm, 10 nm and 20 nm effective thickness) of WO3 have been deposited in high vacuum (106 Torr) onto single crystal Si(100) substrates and studied with X-ray diffraction, atomic force microscopy, scanning tunneling microscopy and spectroscopy. The experiments have been carried out on as-deposited thin films or after 1 h post-deposition annealing at various temperatures (ranging from 300 -C to 500 -C). A size induced increase of the amorphous to crystalline (monoclinic) phase transition has been observed for the 5 nm and 10 nm films, with a critical crystallite size of 25 T 5 nm and a critical temperature of 345 T 5 -C. All the experimental evidences show that, upon annealing, there is a diffusion limited aggregation growth of WO3 that forms large flat two-dimensional islands composed by aggregates of individual crystallites approximately uniform in size and shape. These islands are isolated in the 5 nm thin films, are connected in the 10 nm case and form a uniform patchwork in the 20 nm thin films. Scanning tunneling spectroscopy shows the opening of a large surface band gap (2.7 eV) in the 500 -C annealed films and the significant presence of in gap states for thin films prepared with a lower (below 400 -C) annealing temperature. These findings are discussed in view of the optimization of the best morphological, structural and electronic parameters to fabricate WO3 gas sensing devices at the sub-micrometer length scale. D 2005 Elsevier B.V. All rights reserved.
Keywords: X-ray diffraction; Atomic force microscopy (AFM); Scanning tunneling microscopy (STM); Tungsten oxide

1. Introduction Transition metal oxides (TMOs) belong to a wide class of materials, with insulating, semiconducting and conducting electronic properties [1]. This variety makes such materials extremely interesting from both the fundamental and technological point of view [2]. For bulk insulating TMOs, like SnO2, ZnO, TiO2 and WO3, one specific technological application is their use in the fabrication of solid-state devices used as gas sensors. WO3, in particular, is showing one of the best performances for such application (see for example Ref. [3]). In recent years, our group has carried out a systematic experimental investigation of the structural, morphological and electronic properties of thin (150 500 nm) films of WO3 [3 10]. In such studies, we made use of various techniques like X-ray diffraction (XRD) [4], photoemission spectroscopy (PES) [3 7] and scanning probe microscopies
* Corresponding author. Tel.: +39 0862 433097/433035; fax: +39 0862 433033. E-mail address: luca.ottaviano@aquila.infn.it (L. Ottaviano). 0040-6090/$ - see front matter D 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.tsf.2005.04.010

and spectroscopies [5 10]. This long term work has produced a microscopic understanding of the gas sensing response (investigated with classical resistance measurements [3]) of WO3 gas sensing devices based on the thin film technology [9,10]. State of the art WO3 based gas sensing devices make use of substrates with patterned circuits with a typical spacing of 20 Am between the electrodes [3]. The WO3 deposited thin film has an effective thickness of 150 nm [3]. The efforts toward miniaturization of gas sensing devices are not only related to the obvious requirement of downscaling their size for a better integration into always smaller electronic devices. Beside this, one can observe that downscaling the size intrinsically implies an increase in the surface to volume ratio of the sensing layer. Accordingly, the gas sensitivity should increase. Moreover, it is very likely that one can also expect the recovery times of a sensor to be shorter if its typical dimensions are smaller. 5 Am spaced prototype sensors have already been fabricated [11], and the breakthrough toward the nanometer scaled devices can be foreseen in the very near future.

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Fig. 1. XRD spectrum of a WO3 film (5 nm effective thickness) after 1 h 350 -C annealing in air. The wide range of the scanned angle shows the presence of the (002) and the (220) peaks of the monoclinic phase. The spectral region of the most intense (002) peak is the only one monitored in the spectra of Figs. 2 4.

The AFM measurements have been taken with a Digital (Nanoscope III a) microscope operating in FTapping Mode_ (TM-AFM). The STM/STS data presented for comparison with the TM-AFM images and for the investigation of the electronic properties of the thin films have been taken with a Omicron VT-100 STM operating in UHV (base pressure 2 10 10 Torr). Details of the STM tip preparation, STS measurements, parameters and data analysis are given in [8]. STS spectra are presented in this work as normalized conductance curves (d(ln(I ))/d(ln(V ))) from averages of 14,400 I V curves on a 120 120 point grid taken on homogeneous areas of a typical size of 250 250 nm2. STS data have been collected exclusively on the WO3 surface. X-ray photoemission spectroscopy (experimental details are given in [5]) has been used to check for the relative concentration of the W, O and Si atomic species on the thin films (data is not presented here to maintain brevity).

3. Results and discussion Figs. 1 4 and Tables 1 3 summarize the results of the XRD investigation of the various WO3/Si(100) interfaces prepared. As in previous works, we verified that the thin films of WO3 are in an amorphous phase soon after the thermal evaporation. Only the post-deposition annealing treatment induces a phase transition to a polycrystalline phase. The phase stable at room temperature is the monoclinic one [12] and previous XRD experiments show that bulk-like thick WO3 films on Si substrates undergo the amorphous crystalline phase transition upon annealing just above 300 -C [4]. Fig. 1 shows a typical XRD spectrum of the WO3 films in the monoclinic phase. The (002) and the (220) peaks of such phase are clearly detected at 23.1- and

To this purpose, the study and characterization of the very initial stages of deposition of such gas sensing materials is of particular importance. For these reasons, we have studied the structural, morphological and electronic properties of very thin films (5 nm, 10 nm and 20 nm) of WO3 deposited onto Si substrates. The investigation has been carried out with experimental tools like XRD, atomic force microscopy (AFM) and scanning tunneling microscopy/spectroscopy (STM/STS).

2. Experimental Thin films of WO3 from 99.998% pure powder (Aldrich) were prepared by thermal evaporation in high vacuum onto highly boron-doped (10 2 V cm) Si(100) thick SiO2 surface layer. A substrates having a 20 A thoroughly out-gassed W crucible was used for the WO3 evaporation. Prior to the evaporation, the Si substrates were cleaned with ethanol in an ultrasonic bath. The pressure during the evaporation was about 1 10 6 Torr and the deposition rate, controlled by a quartz crystal microbalance was about 0.1 nm/s. The overall nominal sample thickness has been set to three different values, namely 5 nm, 10 nm and 20 nm. The samples have been investigated as-deposited or after 1 h post-deposition annealing in air at temperatures ranging from 300 -C to 500 -C (T 1 -C). The annealing was performed with increasing and decreasing heating ramps of 1 -C/min. The crystalline phase of the films has been investigated with XRD (Siemens D5000 system) operated in the grazing angle GA (2-) mode. The system is equipped with a Cu Ka X-ray source (k = 0.154 nm) with an angular resolution of 0.005-. The angular step size used was 0.02-.

Fig. 2. XRD spectra of the 5 nm WO3 films after different post-deposition annealing temperatures. The experimental data are taken in the region of the (002) (and the (200)) peak of the monoclinic phase. From top to bottom: 500 -C, 400 -C, 350 -C and 340 -C.

L. Ottaviano et al. / Thin Solid Films 490 (2005) 59 67 Table 1 5 nm WO3 effective thickness: summary table of the WO3 crystallites sizes measured by means of the Scherrer formula from the FWHM of the (001) peak of the spectra of Fig. 2 Annealing temperature (-C) 350 400 500 Crystallite size (nm) 26 T 2 25 T 2 35 T 2

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Table 2 10 nm WO3 effective thickness: summary table of the WO3 crystallites sizes measured by means of the Scherrer formula from the FWHM of the (002) and (200) peaks of the spectra of Fig. 3 Temperature (-C) 350 400 500 Peak (nm) (002) 22 T 2 24 T 2 (200) 24 T 2 22 T 2

34.1-, respectively. The former one is the most intense peak. In the case of XRD diffraction patterns of bulk powders of monoclinic WO3, this peak is accompanied by the presence of the (020) and the (200) peaks at 23.50- and 24.32-, respectively, which show similar intensities [13]. For this reason, we chose to monitor the region 22 25- in detail, to investigate, as a function of the post-deposition annealing temperature, the onset of the amorphous to crystalline phase transition and the occurrence of preferential growth modes on the Si(100) substrate. Such spectra, taken in a narrow scan angle window, are shown in Figs. 2 4. Fig. 2 shows the evolution of the (002) peak of the WO3 monoclinic phase for the 5 nm thin films as a function of the post-deposition annealing temperature. Noteworthy, there is no such transition up to 350 -C and the 5 nm films remain amorphous up to 340 -C, whereas 300 -C is the phase transition temperature observed for more bulk-like WO3 films in previous studies [5]. This effect must be evidently assigned to the existence of a critical crystallite size that makes the monoclinic crystalline phase more energetically favourable with respect to an amorphous phase. The occurrence of size induced phase transitions is a well known subject of investigation [14] and our experimental evidences add another notable example to similar observed phenomena in the class of metal oxide compounds and perovskites [14]. There, similarly to our findings, the

crystalline phase transition temperature is increasing with decreasing the crystallites size [14]. Table 1 summarizes the sizes estimated, with the Scherrer formula from the full width at half maximum (FWHM) of the (002) diffraction peak, for the crystallites in the 5 nm WO3 thin film after the occurrence of the phase transition to the monoclinic phase. The crystallite size of about 25 nm significantly increases (up to 35 nm) only upon a 500 -C annealing. Fig. 3 shows the result of the XRD investigation for the 10 nm WO3 thin films. Also in this case, the amorphous to crystalline phase transition takes place above 340 -C and is clearly observed at 350 -C. Differently from the 5 nm case, there is a coexistence of two diffraction peaks, namely the (002) and the (200) at 23.1- and 24.2-, respectively, indicating that the WO3 crystallites belong to two subclasses, one exposing the (002) face to the substrate interface and the other one the (200) face. The typical thicknesses of these two types of crystallites are not significantly dependent on the type of orientation (see Table 2). This is not too surprising as the WO3 monoclinic phase is only a very slight distortion of an ideal cubic phase [15]. Similarly to the 5 nm case, the size of the crystallites is about 25 nm for a post-deposition annealing temperature

Fig. 3. XRD spectra of the 10 nm WO3 films after different post-deposition annealing temperatures. The experimental data are taken in the region of the (002) (and the (200)) peak of the monoclinic phase. From top to bottom: 500 -C, 400 -C, 350 -C and 340 -C.

Fig. 4. XRD spectra of the 20 nm WO3 films after different post-deposition annealing temperatures. The experimental data are taken in the region of the (002) (and the (200)) peak of the monoclinic phase. From top to bottom: 500 -C, 400 -C, 350 -C, 325 -C, 310 -C and 300 -C.

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Table 3 20 nm WO3 effective thickness: summary table of the WO3 crystallites sizes measured by means of the Scherrer formula from the FWHM of the (200) peaks of the spectra of Fig. 4 Annealing temperature (-C) 310 325 350 400 500 Crystallites size (nm) 44 T 2 46 T 2 40 T 2 44 T 2 46 T 2

ranging from 350 -C to 500 -C. We observed a significant size increase (to about 42 nm) only upon annealing the WO3 10 nm films to 600 -C (the corresponding XRD spectrum is not shown for brevity). A different scenario is observed for the 20 nm WO3 films. In this case, we obtained, as a function of the annealing temperature, experimental results very similar to those reported previously for thicker films [4]. The amorphous crystalline phase transition takes place just slightly above 300 -C (see the 310 -C spectrum of Fig. 4). There is only the (200) peak and the crystallites are significantly larger (about 44 nm, see Table 3) than those observed in the 5 nm and 10 nm case. This bulk-like behaviour is explained by the images presented in the following. After the post-deposition annealing, already at 310 -C, WO3 coalesces into clusters with size larger than the 25 nm. This is the critical size needed to trigger the amorphous crystalline phase transition. The comparison of the XRD results with the AFM and STM images is further explaining the structural and morphological properties of the WO3 thin films under investigation.

Fig. 5 shows the result of an STM investigation of a 5 nm WO3 thin film, as-deposited, with no post-deposition annealing. The metal oxide thin film, that is amorphous as demonstrated with XRD, is quite homogeneously deposited on the substrate. In addition, there are no exposed substrate regions observed with STM and AFM on thin films before post-deposition annealing. The gas sensing response of amorphous WO3 (a-WO3) is rather poor and we will not focus any further in this paper on its morphological properties. Noteworthy, the morphology observed for the 5 nm thin films was also observed in our experiments with AFM and STM in the case of the 10 nm and 20 nm as-deposited cases, with no significant changes in the surface morphology. Fig. 6 summarizes the morphological properties, investigated with AFM, of the 5 nm 350 -C annealed film. Similar images are obtained after 400 -C annealing. In these images, the WO3 has evidently coalesced into large and flat aggregates with lateral size ranging from few tens of nanometers to approximately 500 nm. These islands are shown with different magnification in the upper panels of the figure. In the lower panels of the same figure, the internal morphology of the surface of these islands is shown. There are small grains with approximately uniform lateral size of about 20 to 30 nm. Looking at the section profile shown in the upper panel of Fig. 7, the height of the large islands with respect to the Si substrate is 25 T 5 nm in excellent agreement with the crystallite size along the (002) direction as obtained from XRD (see Table 1). The section profile in the lower panel of the same figure indicates that the typical roughness of the surface of the large flat WO3 islands is about 2 nm (peak-to-peak value)

Fig. 5. STM image (280 280 nm2 tunneling setpoint 7.0 V, 0.5 nA) of an as-deposited 5 nm WO3 film.

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Fig. 6. TM-AFM images of a 5 nm WO3 film after 350 -C annealing. The lower panels report (with increasing magnification from left to right) the fine structure of the crystallites inside the two-dimensional island visible at different magnifications in the upper panels.

Fig. 7. Line sections taken on the TM-AFM data shown in Fig. 6. Top: line section showing the height of the islands of crystallites. Bottom: line section taken on the surface of an island showing the typical size of the crystallites. The profiles are taken, from left to right, along the white reference lines shown on the thumbnail references images reported on the right.

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and gives an estimate for the lateral size of each individual particle composing the island. On the basis of the XRD investigation, and with direct comparison of the AFM images of Fig. 6 and complimentary line profiles in Fig. 7, we conclude that these particles are individual crystallites approximately cubic in shape with 25 nm edge size. The two-dimensional large islands are thus formed by aggregates of such individual crystallites. The fact that the Si substrate is exposed in the 5 nm thin films after the annealing process is testified by many experimental evidences. First of all, the height of the large islands formed by the individual WO3 crystallites is by far larger (25 nm) than the effective film thickness of the deposition. A homogeneously covered surface should thus have a 25 nm effective thickness. Instead, a rough estimate from the upper left panel of Fig. 6 indicates that approximately only 20% (one-fifth) of the sample surface is covered by the WO3 islands. These results yield an average effective WO3 thickness of 5 nm. Secondly, the roughness of the lower uncovered sample areas is of few tenths of nanometers. This value is similar to the one measured on the clean flat Si(100) substrates, and it is almost one order of magnitude lower than the peak-to-peak roughness measured on the WO3 islands. Furthermore, Xray photoemission spectroscopy checks indicate (both in the 5 nm and in the 10 nm case) that, after 350 -C annealing, the Si 2p signal drastically increases its intensity (while the W 4f signal does not decrease). Thus, it is highly probable that significant portions of the Si substrate surface become exposed to the interface with vacuum and are no longer

covered by a homogeneous WO3 film (like in the asdeposited case), which can attenuate the Si 2p signal. The occurrence of the surface diffusion of WO3 upon post-deposition annealing treatments to form aggregates of crystallites is also observed with STM for a 5 nm film after 350 -C, as show in Fig. 8. There, three adjacent islands of various sizes emerge from the flat Si substrate. Interestingly enough, the WO3 island shape and morphology measured either with AFM (Fig. 6) or with STM (Fig. 8) is clearly indicating a two-dimensional diffusion of the WO3 particles in very good consistence with a model of diffusion limited aggregation (DLA) [16]. These islands, in the case of a 10 nm film, after annealing between 350 -C and 400 -C, are connected to one another as shown in the AFM image of Fig. 9. In this case, the portions of uncovered substrate correspond to approximately 30% of the sample area. There is, evidently in this case, a percolation path between the WO3 crystallites of the whole film. This is of great importance, as discussed in the following, in view of a successful fabrication of WO3 sensing devices made of ultrathin WO3 films. Also in the 10 nm case, the height (estimated with AFM line section profiles which are not shown for brevity) with respect to the Si substrate of the two-dimensional islands is in very good agreement with the crystallites size measured with XRD for the same films (see Table 2). Further morphological information is summarized in the AFM images of Fig. 10(a) and (b). In Fig. 10(a) and (b), the typical morphology observed after 500 -C annealing for a 5 nm thin film and a 10 nm

Fig. 8. STM image (tunneling setpoint 7.0 V, 0.5 nA) of a 5 nm WO3 film after 350 -C annealing (as in Fig. 7).

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Fig. 9. TM-AFM image of WO3 film with 10 nm effective thickness after 350 -C annealing.

thin film is shown, respectively. The aggregates of crystallite are no longer uniform in height, as typically occurs for thin film annealed at 350 -C and 400 -C. Still, the height of such disordered aggregates is consistent with the crystallite sizes estimated at 500 -C annealing with XRD in Tables 1 and 2. Finally, Fig. 11 shows the AFM images taken on the 20 nm WO3 thin films after annealing at 350 -C (upper panel), 400 -C (middle panel) and 500 -C (lower panel). In this case, the 20 nm 350 -C annealed films do not show portions of uncovered Si substrate. There is a continuous patchwork, without holes, of the two-dimensional aggregates of crystallites otherwise observed partially connected (10 nm case) or isolated (5 nm case). The morphology of the 20 nm thin film remains substantially unaltered after 400 -C annealing, while large cracks in the

WO3 film are evident in the case of a 500 -C annealed film (lower panel in Fig. 11). The results of the STS investigation of the electronic properties of the WO3 thin films as a function of the annealing temperatures are reported in Figs. 12 (5 nm thin films) and 13 (20 nm thin films). STS data for the 10 nm thin films are in very good agreement with those of the 20 nm case and are not shown for brevity. The STS curves have been taken only on the WO3 islands. Direct comparison of the STS spectra of Figs. 12 and 13 taken at corresponding temperatures shows that the electronic properties are highly dependent on temperature and follows a similar trend for different thicknesses. STS spectra are presented in the form of normalized conductance curves. In this form, within some approximation, they are proportional to the total electronic density of states of the surface under investigation [17]. For a semiconducting surface, the information readily accessible with STS is the value of the band gap (corresponding to the sample bias voltage energy window where the spectra are below the unit value [8]). Noteworthy, the 500 -C annealed thin films show always the opening of a large band gap that we estimated to be about 2.7 T 0.2 eV when averaged over all temperatures. This value is in very good agreement with the bulk band gap value of bulk stoichiometric monoclinic WO3 [12]. At lower annealing temperature, the band gap is almost closed and drops to about 0.5 eV. This value is measured both for the a-WO3 thin films (Fig. 12, 340 -C spectrum, and Fig. 13, As Dep. spectrum) and also for the films annealed up to 400 -C (see Fig. 12). Furthermore, as better evidenced in Fig. 12, the density of states in the bulk band gap region is decreasing with the increase of the annealing temperature. Thus, this work has shown that a 500 -C postdeposition annealing onto very thin films of WO3 (5

Fig. 10. TM-AFM images of WO3 films after 500 -C annealing: (a) 5 nm effective thickness and (b) 10 nm effective thickness. The two images are taken with different magnification.

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Fig. 12. STS (normalized conductance) spectra taken on the 5 nm WO3 films after 340 -C, 400 -C and 500 -C annealing.

not show the presence of in-gap states. The surface band gap at 500 -C corresponds to the bulk band gap of stoichiometric monoclinic WO3. This behavior is explained from the microscopic point of view and comparisons are made to our previous studies on thicker WO3 films annealed at 500 -C [6,7]. We have evidenced that this annealing in air produces a very stable, highly stoichiometric WO3, with no surface oxygen vacancies. Accordingly, there are no active sites at the surface for the

Fig. 11. TM-AFM images of a WO3 film with 20 nm effective thickness after 350 -C (top panel), 400 -C (middle panel) and 500 -C (bottom panel) annealing.

nm and 10 nm) has dramatic consequences on the morphological homogeneity of the WO3 layer. The layer coalesces into large islands in the 5 nm and 10 nm films, and opens large cracks in the 20 nm film. The film is thus discontinuous and, moreover, the WO3 film surface does

Fig. 13. STS (normalized conductance) spectra taken on the 20 nm WO3 films as-deposited, and after 325 -C and 500 -C annealing.

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interaction with gases. From an electronic structure point of view, the absence of the oxygen vacancy induced electronic states in the gap, that such strongly contribute to the modification of the transport properties of a WO3 thin film after interaction with gases, is responsible for the poor gas sensitivity of 500 -C WO3 films annealed in air. On the other side of the interval of the annealing temperature, we have also found that the as-deposited WO3 even for the thinnest case (5 nm) forms a continuous film on the Si(100) substrate, but a-WO3 does not show good performances in terms of its gas sensing response. For the 5 nm case just above the phase transition temperature, the films appears too much discontinuous to be used successfully in patterned substrates with a length scale of even a micrometer in the electrode spacing. The most interesting case is the 10 nm thin film annealed at 350 -C. It is the thinnest film fabricated so far that is showing a continuous network of WO3 islands. These islands are composed of WO3 crystallites in the monoclinic phase, but the surface (and, according to [5], also the bulk of the crystallites) is highly defective, there is a significant presence of in gap states evidently created by surface oxygen vacancies [6,7]. This 10 nm 350 -C annealed WO3 thin film is likely the most promising for gas sensing applications.

(as evidenced with X-ray photoemission spectroscopy). A DLA-like growth mode takes place with formation of islands made of WO3 crystallites. At 10 nm effective thickness of as-deposited WO3, followed by 350 -C annealing in air, these islands become interconnected making possible a percolation path in the micrometer length scale, which is typical of the spacing of Pt electrodes in state of the art gas sensors. Thus, our study indicates that a 10 nm WO3 thin film post-annealed at 350 -C is the minimum thickness for the layer of the sensing material still exhibiting electronic and morphological properties suitable for the fabrication of a gas sensor. Acknowledgement Valuable experimental support from Dr. E. Maccallini during XRD measurements is acknowledged.

References
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4. Conclusions In conclusion, the growth mode of WO3 films onto amorphous substrates like SiO2 (typical of the interelectrode region of state of the art inter-digitized electrodes) has been studied systematically in order to obtain a fabrication recipe for minimum film thickness and optimized morphological and electronic properties for gas sensing applications. In particular, ultrathin films (5, 10 and 20 nm) of WO3 have been deposited in high vacuum (106 Torr) onto atomically flat Si(100) substrates with a native oxide layer and studied either as grown or after postdeposition annealing treatments at various temperatures in the range 300 500 -C. Films of similar thickness have never been investigated before. XRD shows that an amorphous to monoclinic phase transition takes place at temperatures ranging from 300 -C to 350 -C depending on the as-deposited film thickness. At this post-deposition annealing temperature STS shows the highest density of states in the bulk band gap of WO3. These states are due to oxygen vacancies and are ultimately responsible for the gas sensitivity of WO3. It was found that amorphous WO3 uniformly wets the Si substrate, while post-deposition annealing gives rise to de-wetting with re-exposure of Si