COVER SHEET

Tesfamichael, T. and Motta, N. and Bostrom, T. and Bell, J. M. (2006) Development of Porous Metal Oxide Thin Films by Co-evaporation. Applied Surface Science 253(11):pp. 4853-4859.

Accessed from http://eprints.qut.edu.au

Copyright 2006 Elsevier

Development of Porous Metal Oxide Thin Films by Co-evaporation

a a

*T. Tesfamichael, aNunzio Motta, bThor Bostrom, and cJ. M. Bell

Faculty of Built Environment and Engineering, School of Engineering Systems,

b

Faculty of Science, Analytical Electron Microscopy Facility

c

Centre for Built Environment and Engineering Research

Queensland University of Technology, 2 George Street, Brisbane, QLD 4000, Australia Fax: +61 7 38641516 *Corresponding author: Dr Tuquabo Tesfamichael, Phone: +61 7 38641988, t.tesfamichael@qut.edu.au

Abstract
This paper focuses on the development of mixed metal oxide thin films and physical characterization of the films. The films were produced by co-evaporation of titanium oxide and tungsten oxide powders. This allowed the development of titanium oxidetungsten oxide films as analyzed using XPS. Examination in the SEM and AFM showed that the films were nano-porous with the pore size and pore orientation varying as a function of the deposition angle. UV-Vis spectra of the films show an increase of transmittance with increasing deposition angle which is attributed to the structure and porosity of the films. Raman analysis indicated that the as-deposited films have broad and weak Raman characteristics, attributed to the nanocrystal nature of the films and the presence of defects, and the peak broadening deceases after annealing the film, as expected. PACS: 81.05.Rm; 61.43.Gt; 78.66.Qn; 68.55.Jk; 07.07.Df; 61.72.y

Keywords: metal oxide gas sensors; oblique deposition; co-evaporated TiO2-WO3 thin film; surface characterization; porosity

1. Introduction
To protect people and property from gas-related accidents, gas sensors with higher detecting capacity and gas selectivity are needed. A common sensing mechanism involves measuring an electrical conductance change caused by gas adsorption. This requires a sensitive layer that converts a change in the chemical state of some species into an electrical signal. Metal oxide materials such as TiO2, SnO2, ZnO and WO3 have been used for gas-sensing devices because of their simplicity and low cost [1-9]. However, they have poor selectivity and are affected by humidity and thus commonly operate at temperatures between 200-400 oC. The gas sensing properties of these oxides are determined by their intrinsic properties, but can be modified by addition of impurities and/or modifying the microstructure including particle size, distribution and orientation, surface morphology and porosity [6; 8; 10-13]. The

materials have band gap energies between 2.6 to 3.3eV at room temperature. They behave like n-type semiconducting oxides due to non-stoichiometry and they show good chemo-sensitivity toward reducing gas pollutants. Among these oxides SnO2 is one of the most widely used sensors but recent research shows the other metal oxides are able to detect pollutants and toxic gas emissions such as ammonia, carbon monoxide, hydrogen sulfide, nitrogen dioxide. The response behavior of various metal oxide films to a specific gas suggests that oxygen vacancy and charge transport mechanisms are dependent on film microstructure [14]. Thin films are usually compact and the active layer is limited to the surface whereas thick films are commonly porous and hence the whole layer can interact with the gas species. If a controlled porosity can be achieved in thin films, then the gas sensing properties can

be enhanced. Gas detecting sensitivity also depends on the reactivity of film surface as sensors are strongly influenced by the presence of oxidizing or reducing gases on the surface. The reactivity can be enhanced by impurities, defects and active species on the surface of the films, increasing the adsorption of gas species. It has been shown that inclusion of different doping metals in the oxide films increased the sensitivity to specific gases [3; 10-12; 15-17]. Gas sensitivity and selectivity can also be enhanced by appropriate choice of material and proper control of the film microstructure. Each material has its own response and co-deposition of various materials can add selectivity to specific gas species and also often improves sensor quality and performance [8; 18]. Various techniques have been used to develop films for gas sensor applications. This includes sol-gel, chemical vapor deposition (CVD) and physical vapor deposition (PVD) [19-24]. Each of the film deposition techniques has its own advantages and limitations. TiO2-WO3 thin film sensors have been produced by sputtering and sol-gel techniques [18; 25]. In this work, we expand the use of metal oxide sensors by coevaporation of titanium oxide and tungsten oxide producing porous metal oxide thin films. The experiment investigated the development of titanium oxide-tungsten oxide films by adjusting deposition angle to optimize the microstructure of the thin film to achieve high performance gas sensors. Deposition onto a substrate held at an angle to the incoming atom or ion flux is known to create columnar structures which often exhibit higher porosity and rougher surfaces than films deposited with the ion or atom flux normal to the substrate [26]. The combination of co-deposition to provide doping and off-normal deposition to change the porosity and surface roughness should provide real opportunities to improve sensitivity and selectivity.

Physical characterization of various films to determine film structure, composition, crystallinity and optical properties have been performed. Atomic Force Microscopy (AFM) and Scanning Electron Microscope (SEM) were used to study the surface structure and morphology of the films. The chemical composition was investigated using X-Ray Photoelectron Spectroscopy (XPS). The optical properties and crystalline nature of the films have been characterized using UV-Vis spectroscopy and Raman spectroscopy, respectively.

2. Experimental
2.1. Thin Film Preparation The present work focuses on a development of nanoporous metal oxide thin film by evaporation method. A conducting SnO2:F glass substrate (Libbey-Owens Ford TEC 8 8 /square nominal resistance) was obtained from Libbey-Owens Ford (USA). The substrate was cut in to 5.5x5.5 cm squares and cleaned using methylated spirit. The substrate was attached to a variable-angle substrate holder and mounted 10 cm above a heat resistive boat (see Figure 1). High purity commercial titanium oxide (99.9%) and tungsten oxide (99.9%) pellets were obtained from Pure Tech Inc. (USA). The pellets of equal proportion (by volume) were crushed to a fine powder, mixed and put onto the boat in a chamber (Figure 1). The chamber was evacuated by mechanical and diffusion pumps to a base pressure of about 1.5 x10-4 Torr. Coevaporation of the mixture was carried out at a partial pressure of about 10-2 Torr by applying an electric current through the boat. Film thickness was controlled using quartz thickness monitor and films of about 100 to 200 nm thick were obtained by controlling the deposition rate and time. The samples analyzed in this paper have film thickness of about 200 nm. Various samples were evaporated at different angles of incidence between normal angle and 80 degree. One sample was annealed in air in

a temperature-substrate-specimen controlled oven at 450

C for 24 hours to

investigate the change in crystalline property of the film. The effect of annealing on crystallinity and gas selectivity of the films will be studied systematically at a later stage. 2.2. Film Characterization The surface microstructure of the films deposited at various angles of incidence was examined using an FEI Quanta 200 scanning electron microscope operated at 25kV. The samples for SEM were coated with a very thin layer of gold in a sputter coater to provide electrical conduction and thereby reduce any charging effects. AFM images of the film surface were obtained using an NT-MDT Solver P47 scanning probe microscope (NT-MDT Co., Moscow, Russia) with "Golden" Si cantilevers operated in semi-contact (vibrating tip) mode. Optical properties of the film were measured using Varian Cary 50 UV-Visible conventional spectrophotometer in the wavelength range 300 to 1100 nm. As a reference, zero and 100% baseline signals were displayed before each measurement of transmittance. The composition of the film was determined using an Kratos AXIS ULTRA multi-technique X-ray Photoelectron Spectrometer (XPS) incorporating a 165 mm hemispherical electron energy analyser. XPS measurements were made at the Brisbane Surface Analysis Facility at the University of Queensland. Survey (wide) scans were taken at an analyser pass energy of 160 eV. Survey scans were carried out over 1200-0 eV binding energy range with 1.0 eV steps and a dwell time of 100 ms and atomic concentration of each element in the film were determined from peak areas of the profile. Narrow multiplex high resolution scans were run with 0.1 eV steps and 250 ms dwell time. Raman measurements were carried out using Renishaw System-1000 Raman spectrometer to determine the chemical structure and physical state of the film. A HeNe laser

excitation source of wavelength 633 nm with a 10 mW power at the sample was used. A Raman shift between the wavenumbers 200 cm-1 to 1000 cm-1 has been measured.

3. Results And Discussions

3.1 Scanning Electron Microscopy Figure 2 shows SEM images of titanium oxide-tungsten oxide films deposited at various angles of incidence. Figure 2a shows a film deposited at near normal angle of incidence. A dense film with a range of submicron particle sizes from approximately 100 nm to 500 nm can be observed. Figures 2b and c show images of titanium oxide-tungsten oxide films deposited at 70 and 80 angle of incidence. From the images, it can be observed that at higher angles of incidence nanoporous films have been obtained. The microstructures of these films are considerably different from the film deposited at near normal angle of incidence (Figure 2a). The particle size is similar, with some smaller crystallites evident in the films deposited at 80 angle of incidence, but there is considerable porosity evident at the surface of the film, with pores of about 20 nm to 100 nm in size distributed across the film. From the results it can be concluded that the porosity of the co-evaporated films was found to increase with increasing angle of deposition and those films which possess nanopores are especially desirable for gas-sensor design [10; 27; 28]. 3.2 Atomic Force Microscopy AFM images of four samples deposited between 30 to 80 degrees of incidence are shown in Figure 3a-d. The porosity of the films was found to increase with increasing deposition angle which is consistent with the SEM results discussed above. During deposition of the films, the particles cluster together forming bigger grains with grain

boundaries clearly shown between particles and also between grains. From the images, it is apparent that angular deposition at a higher angle can significantly change the porosity and morphology of the film. The effect of surface morphology on gas sensitivity has been reported elsewhere [13]. Using the Nova and Image Analysis software from NT-MDT, the average grain size was calculated from the AFM scans and is shown in Table 1. Generally the grain size remained similar as a function deposition angle with pronounced clustering of the individual particles at lower angles. At the highest angle of deposition (80 degree) the clustering of the particles was lower and as a result the average grain size was reduced (Table 1). In order to improve the gas-sensing characteristic of a film, optimizations of the grain size and porosity are important factors. Overall the analyses have shown that a change in deposition angle leads to the change in film microstructure. 3.3 X-Ray Photo-electron Spectroscopy Figure 4a shows XPS spectra obtained from survey scans on the surface of the coevaporated film between binding energies 0 to 1200 eV. As expected elements of C, O, Ti and W were detected. From the spectra, impurities of K and P were also detected. From high resolution spectra (Figure 4b), the core level of Ti 2p1/2 and Ti 2p3/2 are found at binding energy of 465.6 eV and 459 eV, respectively with a peak separation of 6.6 eV. Figure 4c shows the core level of W 4f5/2 (38.2 eV) and W 4f7/2 (36 eV) obtained from high resolution measurements and the two peaks are separated by 2.2 eV. The Ti 2p3/2 peak obtained from the co-evaporated film (459 eV) is in close agreement with the literature value (459.2 eV) which corresponds to the fully oxidized Ti+4 in titanium dioxide [29]. This shows that the Ti in the metal oxide film can be assigned to the TiO2. The binding energy of W 4f7/2 obtained in this

work (36 eV) was found to be in reasonable agreement with the corresponding characteristic binding energy of W 4f (35.8 eV) in tungsten trioxide film reported elsewhere [5; 14; 24]. The peak position of O 1s was at 531 eV (see table 2) but this value is shifted, for example by 1.1 eV when compared with the core level of O 1s (529.9 eV) of the anatase TiO2 film reported elsewhere [30]. This can be due to the nanocrystal nature of the mixed oxide thin film which may cause a shift of the core levels. From the peak area profile and the FWHM, the atomic concentrations of the elements before and after etching the film using argon gas have been determined. As shown in Table 2 and Figure 5, the amount of C decreased significantly after 5 minutes of etching which indicated that the C was not introduced during the deposition process. However, the concentrations of K and P remained significant after etching for up to 40 minutes. The source of these impurities was not known. The slight shift of the core level peaks of Ti 2p and W 4f observed above may be influenced by the K and P impurities in the nano-porous metal oxide film. The concentrations of Ti and W across the depth of the film remained fairly constant with about 8 at% and 19 at%, respectively. This is equivalent to a volume fraction of about 0.3 of TiO2 compared to WO3 in the film.

3.4 Raman spectroscopy Raman spectroscopy was used to characterize the chemical and crystalline nature of the film. As shown in Figure 6, the as-deposited film has broad and weak Raman characteristic peaks around 645 and 696 cm-1. Raman peak broadening is associated with various structural and microstructural features, including nano-size crystals, presence of grain boundary and defects [31]. The 645 cm-1 peak position

corresponds to anatase titanium oxide Raman active mode Eg and the 696 cm-1 peak corresponding to the vibrational frequency Raman mode of monoclinic tungsten trioxide. From literature the expected vibrational frequencies of the most intense Raman mode of anatase titanium oxide and monoclinic tungsten oxide are 639 cm-1 and 700 cm-1 respectively. The results for these films show a small shift from the anticipated results [18; 32; 33]. This can be due to the nano-structure of the film that can have a wide distribution of Ti-O and W-O bond angles which may cause a shift of Raman peaks. In Figure 6, Raman spectrum of the film after annealing at 450 C for 24 hours is also shown. The intensity of the absorption bands at 645 and 696 cm-1 increased and the peak width deceases. This indicates a more crystalline film after heat treatment. In addition a weak Raman peak appeared at about 320 cm1 which is most likely from the tungsten trioxide hexagonal phase, which is normally seen at 310 cm-1 [18]. 3.5 Optical Spectrophotometer Transmittance of various films deposited at different angles of incidence measured in the wavelength range 300 to 1100 nm is shown in Figure 7. From the figure, the transmittance increases significantly with increasing deposition angle over the measured wavelength range. The most likely cause for the increase is the reduced overall electron density as the porosity increases. Luminous transmittance of the films were determined by weighting the transmittance of the films (Figure 7) in the wavelength range 380 to 760 nm to the intensity of the corresponding visible spectrum for air mass 1.5 as shown in Table 3. The films deposited at higher angle are fairly transparent having a luminous transmittance of about 60% which is closer to the transmittance value of the conducting glass substrate (65%). The anatase phase of titanium oxide has a band gap energy of 3.2 eV whereas tungsten trioxide

has a band gap energy of 2.6 eV. Their corresponding optical transition wavelengths for these oxides are 385 nm and 475 nm, respectively. The co-evaporated nanocrystalline metal oxide films containing defects thus have not shown a sharp absorption edge (see Figure 7).

4. Conclusions
Co-evaporated titanium oxide-tungsten oxide films with submicron grain sizes have been deposited at various angles of incidence. With angular deposition a nanoporous film was produced with an increase of pore size and orientation at higher deposition angles. Optimum porosity is one of the parameters in metal oxide films that best control gas response and sensing properties. The transmittance of the films increased with increasing angle of deposition most likely due to the reduced overall electron density as the porosity increases. The XPS and Raman analyses show a mixed oxide film containing anatase TiO2 and monoclinic WO3 phases. Due to the mixed nature of the TiO2-WO3, it is anticipated that the material would have a broad gas selectivity. The gas sensing properties and selectivity of the films will be further investigated.

Acknowledgments
This work was financially supported by Queensland University of Technology (QUT). The authors are indebted to Dr Barry Wood for assistance with the XPS analyses. References [1] [2] A. Dieguez, A. Romano-Rodriguez, J.R. Morante, U. Weimar, M. SchweizerBerberich, W. Gopel, Sensors and Actuators B: Chemical 31 (1996) 1-8. X. He, J. Li, X. Gao, L. Wang, Sensors and Actuators B: Chemical Proceedings of the Ninth International Meeting on Chemical Sensors 93 (2003) 463-467.

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[24]

[25] [26] [27] [28] [29] [30] [31] [32] [33]

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Figures and Figure Captions

Figure 1. Schematic diagram of the evaporative deposition as a function of angles of incidence, .

13

Figure 2 SEM images of titanium oxide-tungsten oxide film co-evaporated at (a) near normal (b) 70 degree and (c) 80 degree angles of incidence.

14

15

Figure 3 AFM images of co-evaporated thin films deposited at (a) 30 degree, (b) 50

degree, (c) 70 degree and (d) 80 degree angles of incidence.

16

Figure 4 XPS spectra of co-evaporated titanium oxide-tungsten oxide film: (a) survey (wide) scan between binding energy 0 to 1200 eV on the surface of the film before etching, and (b), (c) narrow high resolution peaks for Ti 2p and W 4f, respectively after etching the film.

17

70

O Atomic Concentration (%)

60 50 40 30 20 10 0 0 10 20 30

C W

Ti

K P
40

Etching Time (min)

Figure 5 Atomic concentrations of C 1s, O 1s, Ti 2p, W 4f, K 2s and P 2p as a function

of etching time for titanium oxide-tungsten oxide film analyzed using high resolution XPS.

Figure 6 Raman shift of co-evaporated film before and after annealing at 450oC for 24

hours measured using 633 nm HeNe laser source and a power of 10 mW at the sample.

18

80 70

Substrate
80
o

Transmittance (%)

60 50 40 30 20 10 0

50

30

300

500

700

900

1100

Wavelength (nm)
Figure 7 Transmittance of titanium oxide-tungsten oxide films deposited at different angles of incidence as a function of wavelength between 300 nm to 1100 nm. For comparison the transmittance of the substrate (conducting glass) is shown.

19

Tables and Table captions

Table Captions

Angle of deposition 30 50 70 80

Average grain size 300 nm 346 nm 387 nm 250 nm

Table 1. Grain sizes of titanium oxide-tungsten oxide film deposited between 30 and 80 angles of incidence, determined from AFM scans.

Element

Peak Position Be (eV)

at % min)

(0

at % min)

(5

at % (10 min)

at % (20 min)

at % (30 min)

at % (40 min)

C 1s O 1s Ti 2p W 4f K 2s P 2p

285 531 459 36 378 134

40.7 43.2 3.3 8.7 1.2 3.0

11.4 55.9 7.3 15.7 6.9 2.8

9.2 61.7 7.7 18.7 1.1 1.7

6.8 62.6 7.7 21.4 0.2 1.3

5.1 56.6 9.1 20.5 4.8 3.9

9.4 54.8 8.0 19.9 5.6 2.3

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Table 2. Atomic concentration of co-evaporated titanium oxide-tungsten oxide film for various etching times obtained using XPS analysis.

Deposition Angle 30 50 70 80
o

Luminous Transmittance 53% 55% 59% 60% 65%

substrate

Table 3. Luminous transmittance (%) of co-evaporated titanium oxide-tungsten oxide films for various deposition angles.

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