Polymer-derived ceramic (PDC) is a new kind of material which is directly synthesized by the thermal decomposition of polymer precursors. Due to their unique structure, which consists of the amorphous matrix phase and free-carbon phase, PDCs exhibit many distinguished properties even at high-temperature environment such as oxidation and creep resistance, amorphous semiconducting behavior as well as piezoresistive behavior. These outstanding properties make PDCs become promising candidates for various applications especially for high-temperature microsensors. However, most common used PDCs in the market now are SiC, SiCN and Si(M)CN ceramics, the high price and toxicity of their raw materials as well as strict operating requirements limit their applications. SiCO ceramics are appealing increasing attentions because they can cover these shortcomings of non-oxide ceramics, but their oxidation and corrosion resistance is so weak. In this dissertation, SiAlCO ceramics are chosen as main material. The addition of Al can improve the oxidation and corrosion resistance of SiCO ceramics. In this dissertation, the SiAlCO ceramics are synthesized by using silicone resin and aluminum tri-sec-butoxide (ATSB), then ceramic samples are obtained by pyrolyzing disk green bodies at 1000, 1100, 1200, 1300, 1400°C. Firstly, the composition, microstructure and structure evolution of SiAlCO ceramics are characterized via X-Ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and Impedance spectroscopy (IS). The results indicate all ceramic samples pyrolyzed below 1400°C are amorphous and a sudden structure change point around 1100°C is observed due to the increase of degree of ordering. Si-C, Si-O, C-C/H, and C=C bonds are observed within the materials. Secondly, the room-temperature and temperature-dependent conductivity of the SiAlCO ceramics are studied. The optical absorption spectra are also measured. The conductivity increases by ~6 orders of magnitude when pyrolysis temperature increases from 1000 to 1400°C. A very high activation energy of 7.15eV is observed, and the redistribution of oxygen within the material is found to be responsible for it. Amorphous semiconductor behavior which follows the band-tail hopping (BTH) process is observed within this material. And the BTH process is resulted from unique electronic structures of the materials. Thirdly, SiAlCO ceramic exhibits extraordinary piezoresistive behavior with an extremely high gauge factor in range of 7000 ~16000, which is higher than that of any previously reported high-temperature materials. The coupling effect of pressure and temperature on the piezoresistive behavior is also studied. The piezoresistive stress coefficient increases with increasing temperature, which is contradictive to other reported materials. Such change of the piezoresistive stress coefficient is due to the change in the characteristic temperature, which is reversely related to the density of state within the band-tail level. In addition, SiAlCO also shows anomalous piezo-dielectricity with the positive pressure coefficient of the dielectric constant as high as 0.10-0.25 MPa-1, which is much higher than that of other high-temperature materials. The polarizability of the material also increases with increasing pressure. There behaviors are attributed to the unique cell-like structure of the materials. In the end, a pressure sensor is successfully developed. A supportive circuit is designed and the relationships among pressure, resistance and output voltage of the system are tested. The sensitivity of the sensor is calculated to be Δ1 V=Δ15.125 Pa, indicating the SiAlCO ceramics are promising candidates for pressure sensor materials.
Doctor of Philosophy (Ph.D.)
College of Engineering and Computer Science
Materials Science Engineering
Materials Science & Engineering
Length of Campus-only Access
Doctoral Dissertation (Open Access)
Cao, Yejie, "Electrical properties of polymer-derived silicoaluminum carboxide ceramics (SiAlCO) and their applications in micro-sensors" (2016). Electronic Theses and Dissertations. 5093.