Thin Solid Films 324 1998.

4451

Physical and structural characterization of tungsten oxide thin films for NO gas detection
D. Manno ) , A. Serra, M. Di Giulio, G. Micocci, A. Tepore
Dipartimento di Scienza dei Materiali, Uniersita di Lecce and INFM, Unita di Lecce, Via Arnesano, 73100 Lecce, Italy Received 25 September 1997; accepted 27 November 1997

Abstract Tungsten trioxide WO 3 . thin films were rf sputtered from a WO 3 target in various oxygenrargon O 2rAr. atmospheres and at different total pressures. A detailed structural and morphological investigation has been carried out on all obtained films by high resolution electron microscopy and nanodiffraction methods. Optical and electrical properties have been studied as function of deposition parameters. In addition, all obtained films were tested in controlled atmosphere in order to investigate their response to NO in the interval 2100 ppm in dry air. The sputtering parameters were optimized in order to obtain the maximum sensitivity to NO gas. Finally, a close dependence between sputtering conditions, morphological features and physical properties was observed. q 1998 Elsevier Science S.A. All rights reserved.
Keywords: Diffraction; Sputtering; Electron microscopy

1. Introduction Tungsten trioxide WO 3 . is reported to have interesting physical properties which make it suitable for a variety of thin and thick film applications. In the past, WO 3 was studied for transparent electrochromic devices w1x, selective catalysts for both oxidation and reduction reactions w2x. In addition, as observed for other metal oxides, WO 3 physical properties e.g., electrical conductivity. depend on surrounding gaseous atmosphere because of physisorption, chemisorption and catalytic reactions between gases and material surface w3x. For this reason, thin films of such material were tested for gas sensing application w4x. In particular, WO 3 thin films were reported to have outstanding sensitivity to nitrogen oxides NO x w5,6x, H 2 S w7x and NH 3 w8x gases. WO 3 films can be amorphous or polycrystalline, the structural order degree depending on preparation method. At present, many deposition techniques to prepare tungsten oxide films have been developed. They are based on thermal evaporation of WO 3 powder under a vacuum w6,9x, reactive sputtering from metallic tungsten w10x or WO 3

Corresponding author.

target in ArO 2 atmospheres w11,12x, and solgel deposition w13x. The physical properties of a material are seriously affected by structural order and morphology. Different preparation methods have respective advantages in film quality and production cost in viewpoint of material applications. In fact, electrochromic devices consist of amorphous oxides, on the contrary, polycrystalline films play a fundamental role in gas sensing properties w14x. It is evident that the improvement of material properties requires a closer inspection of preparation conditions. In particular, the effect of deposition parameters on structural, morphological and physical properties of the material have to be investigated. In this work, tungsten oxide thin films were deposited by rf sputtering in various O 2 Ar atmospheres and at different total operating pressures. A detailed structural and morphological investigation has been performed by high resolution transmission electron microscopy TEM. and nanodiffraction methods in order to analyse the evolution of morphology and structure of the films as a function of deposition parameters. Optical and electrical properties of obtained films were also studied as a function of deposition parameters. Finally, tungsten oxide thin films were tested in controlled atmosphere. The close relation-

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ship that binds electrical response to different NO concentrations in dry air, film morphology and sputtering conditions will be also discussed.

2. Experimental details Tungsten oxide thin films were deposited by rf sputtering from a WO 3 target 12.7 cm in diameter and 99.99% pure. in an MRC 8620J system. The 13.56-MHz rf power was 200 W because higher power does not intentionally heat the substrate. On the other hand, power lower than 200 W does not give an acceptable deposition rate. Ultrasonically-cleaned alumina, quartz and glass slides were used as substrates. Before sputtering, a pressure of 3 = 10y7 mTorr was reached in the chamber, then the appropriate quantity of mixed ArO 2 was introduced to obtain the required pressure. The target was presputtered for 30 min before depositing coatings. The total gas pressure and the O 2 content were in the ranges of 520 mTorr and 3.330%, respectively. The different sputtering atmospheres and deposition rates for our oxide films are reported in Table 1. As one can see, the deposition rate depends on O 2 concentration and total pressure. A quartz crystal monitor Inficon XTC was employed to control on-line the growing rate of the films. The final thickness of our samples were measured by a Tencor Alpha-Step 200 stylus profilometer. Films 150-nm thick were employed for optical and electrical measurements, while films 30-nm thick were deposited for TEM analysis. Samples for TEM observation were obtained from films deposited onto glass slides overcoated with amorphous carbon. This allows the tungsten oxide films to be floated off the substrate onto distilled water after exposition to hydrofluoric acid vapor and then to be deposited onto 600 mesh grids without any additional film support. TEM observations were performed by a JEM 2010 electron microscope working at 160 kV. Small area electron diffraction SAD. has been obtained by selecting the suitable spot size, convergence angle and condenser aperture in order to obtain the diffraction patterns from chosen areas of about 100 nm in diameter with a beam approxi-

mately parallel the convergence angle of incoming beam was of about 5 = 10y5 rad. w15x. Spectral transmittance and reflectance of the films deposited onto quartz substrates were measured in the UV VISNIR regions by using a double-beam Varian Cary5 spectrophotometer at normal incidence with unpolarized light. An integrating sphere was used to measure reflectivity. Electrical measurements were carried-out by means of the four-point direct current method of Van der Pauw w16x in a Biorad System in order to obtain information about the electrical properties of the oxide films deposited onto alumina substrates. Several measurements were carried out by making all possible contact combinations and reversing the direction of current. Finally, to test tungsten oxide thin films as sensor, two ohmic gold contacts 5-mm spaced were sputtered onto the surface of the films in the gap configuration one on the right side and the other one on the left side of the sensor surface.. The measurements of the electrical response to different gas species were made in a dynamic flow system implemented in the laboratory. The samples under test were placed in a stainless steel cell 100 cm3 . and exposed to different gas concentrations. Constant flow rates of 100 sccm were obtained by means of MKS 647 mass-flow controller, by diluting the various gases in dry air. The temperature was controlled in the 1004008C range by means of an Eurotherm thermoregulator. A personal computer equipped by an IEEE interface board was used both to control all parameters and to acquire the data of the sensor electrical response.

3. Experimental results 3.1. Structural and morphological analysis Because of short range order in tungsten oxide thin films, only high resolution TEM allows to obtain careful information about their morphology. Fig. 1 reports typical high resolution images recorded from films deposited at 5 mTorr in Ar3.3, 10 and 30% O 2 atmosphere pictures a, b and c, respectively.. The images have the same magnification so a direct comparison is possible. In particular, it is evident that the films are made by small crystalline grains whose size depends on the partial pressure of O 2 in the reactive atmosphere. In order to reveal more quantitatively the evolution of the film morphology, the grain diameters were measured and the obtained values were reported in histograms also reported in Fig. 1 for each of the three films.. By comparing the histograms, one can see that, given a value of total pressure, the grain size generally increases as the ratio O 2rAr increases, too. With regards to statistical distribution of grain size values, this is Gaussian only for films obtained at 10% O 2 . Fig. 2 reports the

Table 1 Deposition parameters of tungsten oxide thin films P mTorr. 5 5 5 10 10 10 20 20 20 O2 % 3.3 10 30 3.3 10 30 3.3 10 30 Deposition rate nmrs. 0.20 0.16 0.08 0.15 0.13 0.07 0.13 0.11 0.07

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Fig. 1. Typical high resolution images recorded from films deposited at 5 mTorr in Ar5, 10, and 30% O 2 atmosphere pictures a, b and c, respectively. together with the related histograms of grain size.

related SAD patterns recorded from films deposited at 5 mTorr in Ar3.3, 10 and 30% O 2 atmosphere pictures a, b and c, respectively.. The SAD pattern in Fig. 2a is made by a superposition of diffuse rings and sharp ones, according to the corresponding high resolution image Fig. 1a., the more broadening rings coming from the matrix of Fig. 1a and the sharp ones from small grain. As the grain size increases Fig. 1b and c., the rings become sharper Fig.

2b and c.. The analysis of diffraction patterns allows us to attribute the observed diffraction rings to an orthorhombic cell with a s 0.73 nm, b s 0.76 nm and c s 0.78 nm independently on O 2 content in sputtering atmosphere. These data are in fairly good agreement with the WO 3 orthorhombic structural modification w17x. The morphological changes of tungsten oxide thin films due to total pressure are evident from comparison of the

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Fig. 3. Histograms of grain size obtained from films deposited in Ar10% O 2 atmosphere at 5, 10 and 20 mTorr pictures a, b and c, respectively..

histograms of grain size reported in Fig. 3. It is evident that in all cases, the grain size distribution is Gaussian, but the peak shifts towards higher values as the total pressure increases.

Fig. 2. SAD patterns coming from films deposited at 5 mTorr in Ar5, 10, and 30% O 2 atmosphere pictures a, b and c, respectively..

Fig. 4. Electrical resistivity of tungsten oxide thin films vs. sputtering pressure, for different O 2 concentrations.

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Fig. 7. Linear plot of Y r Y as a function of photon energy for tungsten oxide thin film deposited at 5 mTorr in Ar10% O 2 .

Fig. 5. Transmittance a. and reflectance b. spectra of tungsten oxide thin films deposited at 5 mTorr in different O 2 concentrations.

3.2. Optical and electrical properties All the tungsten oxide thin films investigated were n-type semiconductors in the temperature range between 300 and 800 K. Fig. 4 shows the dependence of the electrical resistivity of tungsten oxide films on the O 2 concentration in the sputtering chamber as a function of the total operating pressure. The tested samples were deposited on alumina substrates. As shown in Fig. 4, the resistivity of our oxide films increases remarkably with increasing O 2 concentration and increasing total operating pressure in the sputtering chamber. The lower resistivity was measured on films deposited at 5 mTorr. The tungsten oxide films deposited at 5 mTorr in Ar3.3% O 2 atmosphere are blue, while the others are transparent. Typical transmittance T and reflectance R

spectra for different tungsten oxide thin films are shown in Fig. 5. The oscillations in T and R with wavelength are due to interference effect. An abrupt decrease in transmission at high energies indicates the onset of interband absorption. From transmission and reflection spectra, the absorption coefficient was evaluated by a numerical procedure deduced by the model of Heaven w18x. The optical band gap was determined from the analysis of the spectral dependence of the absorption near the fundamental absorption edge Fig. 6.. In this region, the absorption coefficient a is well described by the relation w19x: Y s a hn s B hn y Eg .
m

1.

where hn is the energy of incident photons and Eg is the value of the optical band gap corresponding to transitions indicated by the value of m. The factor B depends on the transition probability and can be assumed to be constant within the optical frequency range. Taking the first derivative Y X of Eq. 1. with respect to photon energy, we obtain, YrY X s hn y Eg . rm .

2.

The values of Y and Y X can be deduced from experiTable 2 Electrical and optical properties of sputtered tungsten oxide thin films P mTorr. O 2 % s Vy1 cmy 1 . 5 5 5 10 10 10 20 20 20 3.3 10 30 3.3 10 30 3.3 10 30 1.7=10 4.0=10y6 1.1=10y7 8.1=10y6 1.8=10y7 1.2=10y7 9.0=10y7 2.8=10y7 1.4=10y8
y5

m 1.89 1.97 2.02 2.01 1.93 1.98 2.05 1.94 2.01

Eg eV. Sensitivity %. 2.95 3.15 3.20 3.31 3.32 3.35 3.33 3.35 3.36 110 1200 990 370 910 840 570 800 890

Fig. 6. Variation of the optical absorption coefficient with incident photon energy for tungsten oxide thin films deposited at a. 5 mTorr in Ar10% O 2 and b. 10 Torr in Ar30% O 2 .

The sensitivity values are those obtained at 10 ppm NO and 1808C operating temperature.

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mental data and the linear plot of Eq. 2. as a function of the photon energy can be drawn. Both m and Eg can easily be determined from the slope and the intercept, respectively. This procedure is shown in Fig. 7 for a sample deposited at 5 mTorr in Ar10% O 2 atmosphere. In the picture, a linear region is evident and m is about 2. This dependence is peculiar of indirect allowed interband transitions. A similar analysis was performed for all prepared oxide films. The experimental values of m and Eg for each sample are listed in Table 2, together with the values of electrical conductivity at room temperature. As evident from Table 2, the optical band gap of the tungsten oxide thin films depends on the total sputtering pressure and the O 2 concentration in sputtering atmosphere. In particular, for tungsten oxide films deposited at 5 mTorr, Eg increases with increasing O 2 , while it is almost constant in films deposited at higher pressures. The optical energy gap ranges from 2.95 to 3.36 eV. These values are in good agreement with literature data. In fact, sputtered tungsten oxide polycrystalline thin films exhibit an indirect allowed interband transition with an energy ranging between 2.83.3 eV. w11,12,20x. 3.3. Gas sensing test The deposited films were exposed to different NO gas concentrations in the 2100 ppm range at different working temperatures in the 1004008C range. In stationary conditions, nitrogen oxide gas oxidizes n-type metal oxide semiconductors, such as tungsten oxide, and causes electrical resistance to increase. Figs. 8 and 9 show the sensitivity at 10 ppm of NO as a function of working temperature for different tungsten oxide thin films. The sensitivity S is defined in this work as the ratio: Ss Rg y Ra Ra

Fig. 9. Sensitivity to 10 ppm NO gas in synthetic dry air vs. working temperature of tungsten oxide thin film deposited in 5 mTorr for different ArO 2 concentrations in the sputtering atmosphere.

where R g is the resistance in the gas atmosphere and R a is the resistance in dry air.

In particular, Fig. 8 indicates the sensitivity as a function of the working temperature for films deposited at different sputtering pressures. This figure shows that as sputtering pressure increases, the sensitivity decreases substantially, e.g., tungsten oxide films grown at 5 mTorr present higher sensitivity. Fig. 9 shows the sensitivity as a function of the working temperature for films deposited with different O 2 concentrations in the sputtering atmosphere. One can see that oxide films deposited in Ar10% O 2 gas mixture have high sensitivity to NO gas. The films deposited with 5 mTorr in Ar10% O 2 atmosphere are very good NO gas detectors with a sensitivity of about 1200% at 10 ppm NO. All deposited tungsten oxide thin films exhibit maximum sensitivity at 1808C. The gas sensitivity values for different deposited oxide films are reported in Table 2. Fig. 10 shows the electrical response of a tungsten oxide film deposited at 5 mTorr in Ar10% O 2 atmosphere when the sensor is exposed to different NO gas concentrations 2, 4, 6, 10 ppm. in dry air at the temperature corresponding to the maximum sensitivity. It is clear that the electrical resistivity of the films returns to starting values as the NO gas flow is switched off and the atmosphere is pure dry air. So we can conclude that the process is reversible.

Fig. 8. Sensitivity to 10 ppm NO gas in air vs. working temperature of tungsten oxide thin film deposited in Ar10% O 2 for different sputtering pressures.

Fig. 10. Electrical resistance variation of tungsten oxide film deposited at 5 mTorr in Ar10% O 2 following exposure to different NO gas concentrations.

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4. Conclusions All obtained tungsten oxide thin films consist of nanosized crystal grains in the WO 3 orthorhombic structural modification. The deposition parameters affect only the film morphology, e.g., the grain size dispersion and mean value. In particular, the grain size dispersion is Gaussian only for films deposited in Ar10% O 2 sputtering atmosphere, while the grain size and the structural order degree increase as the total pressure increases. The electrical and optical properties of thin rf sputtered tungsten oxide films were evaluated as a function of sputtering gas pressure and ArrO 2 ratio. The results can be summarized as in the following. The electrical resistivity increases with increasing O 2 concentration and sputtering gas pressure. The optical band gap ranges from 2.95 to 3.36 eV. In particular, tungsten oxide films deposited at 5 mTorr in Ar3.3% O 2 atmosphere are blue, while films deposited using other conditions are transparent, with a transmittivity greater than 85%. Sputtered tungsten oxide thin films are very sensitive to low concentrations of NO gas in air - 10 ppm., and display response times of about 40 s to have a resistance variations of 100%. All WO 3 thin films have the maximum sensitivity at an operating temperature of about 1808C. The highest sensitivity is observed in films deposited in 5 mTorr of Ar10% O 2 . It is important to stress that not appreciable structural, optical and electrical modifications are evident after repeated heating cycles 100 4008C. in the test atmosphere. Finally, it is interesting to remark that the sensitivity increases with grain sizes, reaches an optimal value, then decreases a little. In addition, the films showing the optimal sensitivity consist of crystal grains having mean radius comparable to the Debye length.

Fig. 11. Tungsten oxide thin film sensitivity at 1808C operating temperature and 10 ppm NO vs. mean diameter values of crystal grains.

The gas sensing properties of tungsten oxide thin films depend on deposition parameters and are strictly related to observed morphological changes. In a previous work w21x, we observed that gas sensing properties of vanadium oxide sputtered thin films depend both on morphology and crystal structure. In the present case, our tungsten oxide thin films turned out to be WO 3 in the orthorhombic structural modification, independently on sputtering conditions. This represents a particular and interesting case because we can analyse the effects of morphology only on gas sensing properties. Fig. 11 shows the WO 3 thin films sensitivity at 1808C operating temperature and 10 ppm NO vs. mean diameter values of crystal grains. It is evident that the sensitivity increases with the grain size, reaches an optimal value, then decreases a little. It is worth stressing that the films showing the optimal sensitivity are made by crystal grains having mean radius equal to Debye length L D . LD s

0 kT
ne 2

1r 2

3.

For our films, by using typical values r 0 f 10, n f 4.0 = 10 15 cmy 3 w22,23x in Eq. 3., we obtain a Debye length of about 10 nm at 1808C. It is well known that for grains having radius larger compared to the Debye length L D e.g., diameter d ) 2 L D ., the depletion layer affects sensitively the local electron concentration of the conduction path within the intergrain region w24x. On the contrary, for crystal grains having d - 2 L D , the depletion layer stretches the whole grain. In this case, flat-band conditions are fulfilled w24x to a good approximation. In addition, the electron concentration changes drastically and homogeneously within the grain upon variation in the occupation of surface states due to gas adsorption w25x. The variation of electron concentration upon exposure to gas is proportional to the resistance variation and also to the material sensitivity. As the grain size increases, the depletion layer increases, too. This allows the electron concentration variation to increase until an optimal value when the grain diameter equals twice the Debye length.

Acknowledgements The authors are grateful to Miss A.R. De Bartolomeo and Sig. G. DElia for valuable technical support.

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