1.

0 Background Study Titanium dioxide (TiO2) doped with dopant recently has been used in many applications in electronic components such as varistor due to its high dielectric properties and this has replaced the Zinc Oxide (ZnO) based components earlier due to its failure at low permittivity that weakens its ability to absorb the sparks and restricts its application in low voltage circuits [1]. Titanium dioxide is relatively inert, corrosion resistant, less toxic and cheaper. Varistor are used to protect circuits from high transient voltage and its function is to increase current drastically when the voltage is excessive [2]. Varistor are also known as non-ohmic resistors. Dopants are elements that used to alter the properties of a substance where it is inserted into the substance [3]. The main objective of the present investigation is to vary the percentage of dopant used to achieve good mechanical properties of the Titanium dioxide (TiO2) ceramic with dopant for the application in semiconductor elements.

2.0 Literature Review Titanium dioxide or titania is a natural occurring oxide of titanium where it exist in mineral form as rutile, anatase and brookite phase [4]. All the phase condition may be found at room temperature but however, octahedrite will turn to rutile phase where it is the most thermodynamically stable [4]. Anatase and rutile phase is more stable thermodynamically and rutile phase is used in semiconductor elements contrast to the brookite phase that is only stable at very low temperature and thus it is not suitable in semiconductor applications [4]. Furthermore, Xia et al. [5] found that that octahedrite type has better chemical properties and photon characteristic due to its good absorbability and lower elecrtron combining rate which makes the varistor to absorb sparks better. Recently, research has been done towards titanium dioxide to be used in semiconductor elements such as in varistors and capacitors as it has large dielectric constants that protects the electrical circuit. In polycrystalline material semiconductor material, the electrical properties are based on the microstructure of the ceramic such as the grain boundary and lattice defects. The grain boundary formation is formed by the bicrystal procedure where two single crystals are combined at a particular temperature by solid reaction to achieve crystal boundary. Nevertheless, the most practical grain boundaries in ceramic composition show significant difference due to complexity. The current actual state of grain boundary data in titanium dioxide semiconductor ceramic is insufficient [4]. Rutile and anatase phase plays any role is titanium dioxide application since it is more stable and their interest has been studied in surface science techniques. In both phase surface of titanium dioxide, the basic building block is consisting of a titanium atom that is surrounded by six oxygen atoms in distorted octahedral configuration. In each of the structure, the two bonds between the titanium and oxygen at the octahedron are quite longer. The sizable 900 of bond angle is seen in the anatase phase. In rutile phase the

neighbouring octahedral share one corner along <1 0 0> type direction and are stacked with their long axis alternating by 900. In anatase, the corner-sharing octahedral form (0 0 1) plane. In all three phase of titanium dioxide structures, the stacking of octahedral results in threefold coordinated oxygen atoms. The unit cells are shown in figure;

Brookite

Figure 1.0 : Bulk structure of anatase, brookite and rutile phase. The bond lengths and angles of octahedrally coordinated titanium atoms are indicated and the stacking of the octahedral of both structure are on the right side [4].

Properties of elements and the experimental method used Introduction to titanium dioxide properties Properties Molecular formula Molar mass Appearance Density Melting point Boiling point Refractive index (nD) TiO2 79.866 g/mol White solid 4.23 g/cm3 1843 C 2972 C 2.488 2.583 2.609 (rutile) (anatase) (brookite)

Table 1.0 : Properties of Titanium Dioxide (TiO2) [6].

2.1 Application of titanium dioxide Titanium dioxide is used in heterogeneous catalysis as a photocatalyst in solar cell for the production of hydrogen and electric energy, gas sensor, white pigment, in ceramics and electric elements such as varistors. Most heterogeneous catalyst consist of small metal clusters on an oxide support, many studies on titanium dioxide was performed. Traditionally, titanium dioxide is a component in mixed vanadia/titania catalyst used for selective oxidation reactions[7 ]. Titanium dioxide is not suitable in structural support material but small addition of titania can be modify metal- based catalyst. The usage of titanium dioxide is also researched in photoelectric and photocatalyst properties. The work initially done by Fujiama and Honda[8 ] on the photolysis of water on titanium dioxide electrodes without external bias shows the surface defect may play a role in decomposition of water into H2 and O2. The sheer volume of titanium dioxide produced worldwide is about 4 million tan per year[9 ]. This pigment is used virtually in every kind of paints because of its high refractive index as shown in table 1.0. the surface properties plays an important role in this applications such as photocatalytic degradation of binder in paints is a problem in paint industry[9]. Titanium dioxide is non-toxic and safe to be dispersed where it is also used in food additive, pharmaceutical and cosmetic products [9].

Another major application of titanium dioxide is in varistors. Titanium dioxide is doped with dopants to achieve better mechanical properties in order to have better dielectric properties such as Chromium. Chromium growth, interfacial reaction, film structure and thermal stability have investigated by Pan et al [10]. This growth characteristics suits the early transition metals with an intermediate layer formed over chromium deposition and wetting process of the substrate by an oxidized overlayer. This wetting shows the formation of reduced Ti species as resulted under XPS. Therefore, Chromium is soluble in titanium dioxide and is suitable to be used in varistors[4 ]and investigation are underway to study the influence of Chromium. The properties of Chromium dioxide is shown below;

Properties Molecular formula Molar mass Exact mass Appearance Density Melting point Boiling point Solubility in water Solubility in alcohol Cr2O3 151.9904 g/mol 151.865768 light to dark green, fine crystals 5.22 g/cm3 2435 C, 2708 K, 4415 F 4000 C, 4273 K, 7232 F insoluble insoluble in alcohol, acetone, acids

Refractive index(nD) 2.551 Table 2.0: Properties of Chromium Dioxide (Cr2O3) [11]

Tantalum (Ta) had also been used as a dopant to titanium dioxide to improve electroceramic non-linear electrical properties. Titanium dioxide and tantalum are doped using the standard ceramic technique. The composition of tantalum was varied to get the optimum microstructure that results in better non-linear properties. When starting powders are anatase phase, the sintered pellet always contained cracks. This may be due to the change in unit cell dimensions during phase transition between anatase and rutile occurring around 1000 K and rutile powders are obtained by annealing titanium dioxide powders at 1000 K for 24 h [13]. Figure shows the microstructure of the fractured surface of sintered pellets. The average grain size obtained by the linear intercept method is in the range of 45 mm. When tantalum content is used more than 0.1%, the sample shows insulating characteristics. Only when tantalum content is around 0.1 %, the samples shows high nonlinear electrical behavior[13]. Generally, only low voltage varistors based on Titanium dioxide are reported [12 ]. This is because higher grain growth is obtained during sintering process. Nevertheless, present results shows that for specific compositions based on titanium dioxide, high voltage varistors can also be obtained. The main advantage of this electroceramic is it only needs one additive dopants to achieve better dielectric constant wherelse the zinc oxide based varistor need sevaral dopants to achive the same condition[13 ]. Figure below shows the microstructure of samples doped at different percentages;

Figure 1.0: Microstructure of (a) 0.1% and (b) 0.5% Ta doped TiO2 [13]

Properties Molecular formula Molar mass Appearance Density Melting point Solubility in water Solubility Ta2O5 441.893 g/mol white, odorless powder 8.20 g/cm3 [1] 1872 C insoluble insoluble in ethanol, most acid soluble in hot conc.HF

Table 3.0: Properties of Tantalum Pentoxide (Ta2O5)[14]

Recently, titanium dioxide has also been doped with niobium pentoxide (Nb2O5) as to improve semiconductor ceramics such as varistors. The attempts to characterize sintering conditions, grain boundary and electrical properties has been done[15 ] . XRD analysis, HTREM analysis and surface morphology has been established based on the experiment done. The experiment was done by using the standard ceramic technique. Titanium dioxide and niobium pentoxide was mixed together with bismuth trioxide where bismuth trioxide lowers the sintering temperature of the ceramic. The powders were prepared by ball milling and with de-ionized water for 24 hours in order to obtain even mixing of composites and particle sizes. The mixing was then dried at 85 oC for 10 hours in a drying chamber and then homogenized in an agate kettle. Next, the mixing were pressed by a hydraulic press into discs of 12.5mm in diameter and 23mm in thickness with a pressure of 100Mpa[16]. All samples were sintered in a furnace as in table 4.0

The components and Sintering process process of samples Composites (mol%) Sample A TiO2 1450 C, air B TiO2 + 0.5 mol% 1450 C, air Nb2O5 C TiO2 + 0.5 mol% 1340 C, air Nb2O5 + 0.4 mol% Bi2O3 D TiO2 + 0.7 mol% 1420 C, air Nb2O5 E TiO2 + 0.7 mol% 1340 C, air Nb2O5 + 0.4 mol% Bi2O3 Table 4.0: The components and process of samples[16] Based SEM analysis, some sintering characteristics are obtained from the SEM micrograph. The images of the microstructure of each samples are shown below ;

Figure 2.0: SEM image of Sample A[16]

Figure 3.0: SEM image of Sample B[16]

Figure 4.0: SEM image of Sample C[16]

Figure 5.0: SEM image of Sample D[16]

Based on the samples obtained, it is observed that the average grain size that is resulted is about 10m and has large porosity degree. In sample A, there are there are trapped air that is unable to diffuse because did not mix with bismuth trioxide that acts in liquid infiltration during sintering. In contrast to sample B, shows a greater grain size and a high area fraction of porous are clearly observed throughout the grains. It is evident that niobium pentoxide doping can lowers the sintering temperature mildly[16 ]. Furthermore, when sintered at the same condition as pure titanium dioxide as sample A, the smaller grains that forming large grains resulting in a pronounced porosity in its region. At sample D, significant porosity was observed at the grain boundaries indicating absence of coalescing of the grains. For sample C, there are less porous due to liquid sintering caused by the melting bismuth trioxide. In this case, the trapped air is are to diffuse out during sintering. These sintered samples are potentially good semiconductors and the resistance is significantly lower than other samples. Addition of bismuth trioxide causes the diffusion of niobium ions more uniformly in titanium dioxide crystal lattice[16]. For the bismuth troxide free sample, such sample B and C, the grains growth during sintering occurred at a higher porosity and hence better electric resistance. The XRD anaysis are shown below ;

Figure 6.0: XRD spectra of samples B, C, E and the of rutile titanium dioxide [16 ]

Figure 7.0: HRTEM of pure titanium dioxide ceramics [16 ]

Figure 8.0: Lattice and grain boundary image of sample C [16 ]

3.0Sintering process Sintering of ceramic material is a process that involves consolidate the ceramic powder particles by heating the green body that is compacted to a firing temperature below the melting point when the material of the separate particles diffuse with the neighboring powder particles. During the diffusion process, the pores of the green body comes closer up together where it results in better densification and thus better mechanical properties. The porosity of the microstructure also decreases determined by the initial porosity of the green body that is created and also the influence of the sintering temperature and time. Applying pressure during sintering results in shorter sintering time and porosity [17]. 3.1Conventional Ceramic Sintering

Weigh raw materials

Ball milling process and addition of deionization water

Dry and calcination process

Ball milling process

Drying, mesh sieving and binder addition

Press powder into compact disk

Sinter compact disk to obtain final ceramics

4.0 Problem Encountered There are problems that I have faced such as the resources of information to get is quite limited to research based journals that is available by the UNITEN library only. The sources from internet are limited and not credible. The dopants that chosen to be used are also not confirmed due to the availability and price factor. The experiment method and equipment availability is also to be confirmed after the dopants are finalized and the method of experiment is discussed with my supervisor. To overcome these problems, I need to find the dopants criteria by contacting local vendors and need to get more information for my research from other library and credible sources for me to have sufficient information to successfully conduct my final year project.

5.0 CONCLUSION As for week 7, the progress for this project is on track as planned in the Gantt-chart. The work left to be done is to continue studying more science research papers for literature review, preparation of materials and experimentation methods, preparation of progress report 2, preparation of project logbook and finally the planning and preparations for the final oral presentation. 6.0 Reference [1] D.R. Clarke, J. Am. Ceram. Soc. 82 (1999) page 485 [2] T.K. Gupta, J. Am. Ceram. Soc. 73 (1990) page 1817 [3] http://en.wikipedia.org/wiki/Dopant (downloaded 15/03/2012) [4] Ulrike Diebold, Surface Science Report 48 (2003) page 53-229 [5] W.B. Su, J.F.Wang, H.C. Chen,W.X.Wang, G.Z. Zhang, C.P. Li, J. Appl. Phys. 92 (2002) page 4779. [6] http://en.wikipedia.org/wiki/Titanium_dioxide(downloaded 15/03/2012) [7] C.N Satterfield, Heterogeneous Catalysis in Industrial Practise, 2nd ed, McGraw-Hill, New York, 1991. [8] A.Fujishima, K.Honda , Nature 238 (1972) page 37. [9] Kronos International, 1996. [10] J.M Pan, T.E Madey, J. Vac, Sci,Technol. A11 (1993) page 1667 [11] http://en.wikipedia.org/wiki/Chromium (downloaded 15/03/2012) [12] Y.Nakano, N.Ishinese, J. Mater Res 5 (1990) page 2910

[13] S.C Navale, A.Vadivel Murugan, V.Ravi, Ceramics International 33 (2007) page301-303 [14] http://en.wikipedia.org/wiki/Tantalum_pentoxide [15] D.J Wallis, N.D Browning, P.D Nellist, S.J PennyCook et al., J.Am Ceram Soc 80 (1997) page 499-502 [16] Xiangyi, Fang, J.T Oh, Material Science and Eng B 136 (2007) page 15-19 [17] http://www.substech.com/dokuwiki/doku.php?id=sintering_of_ceramics (downloaded 15/03/2012)