ZrAlO ternary oxide as a candidate for high-k dielectrics

ZrAlO thin films were prepared by the pyrosol process. Four different cases were considered taking as basis a solution of 0.025 M zirconium acetylacetonate (ZrAAc) and 5 at% of aluminum acetylacetonate (AlAAc) dissolved in pure methanol. Films of case A, were deposited with the mentioned solution and subjected to rapid thermal annealing (RTA). For case B, a small volume of water was added to start solution. Case C, were similar samples of case B, but with a post-deposition RTA. Case D, were Si/Al2O3/ZrAlO/Al stacks with post-deposition RTA, using water in the start solution. XPS profiles show that the relative chemical composition of deposited materials is affected by the volume of water added (Vw). The aluminum concentration in the films acquires values as high as or higher than zirconium concentration for increasing Vw. All the prepared samples were amorphous as indicated by the X-ray diffraction (XRD) spectra, even for large integration times. Current–voltage (I–V) and capacitance measurements were carried out in metal–insulator–metal (MIM) devices (Corning-glass/TCO/ZrAlO/Al) and I–V and simultaneous capacitance–voltage (C–V) measurements were performed in metal–oxide–semiconductor (MOS) devices (Si/ZrAlO/Al and Si/Al2O3/ZrAlO/Al). Leakage currents of the order of 10−4 A/cm2, were typically obtained in MIM devices, whereas for some MOS devices, leakage currents of the order of 10−7 A/cm2 were obtained. Dielectric constant (k) values of the order of 24 were calculated for MIM devices and k values ranging from 12.5 up to 17 were calculated for MOS devices.