Structures and Generation Mechanisms of Defects in High-k Dielectric Films for Silicon ULSIs

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For the coming sub-65 nm complementary metal-oxide-semiconductor (CMOS) technology, high-k materials such as hafnia (HfO_2), hafnium silicate (Hf_xSi_<1-x>O_y), zirconia (ZrO_2), and zirconium silicate (Zr_xSi_<1-x>O_y) are expected to take the place of SiO_2 as the basic material for gate dielectrics. However, there is a high possibility that a lot of localized states due to defects are present in the band gap of these high-k candidates. These localized states are assumed to cause various dielectric malfunctions such as high leakage current, low breakdown voltage, and threshold variation. Therefore, detailed and systematic research on the localized states is indispensable to understand the effects of the defects on electrical properties.From this viewpoint, we have carried out basic studies on HfO_2, Hf_xSi_<1-x>O_y, ZrO_2, and ZrxSi_<1-x>O_y, using photoluminescence (PL) as a common tool that can provide fundamental information about the band gap energy and localized states. X-ray ph … More otoelectron spectroscopy (XPS) analyses were also carried out to investigate the band profiles. Furthermore, the effects of postannealing on the electrical properties of the high-k materials were also studied.Energy band profiles were investigated by XPS for amorphous hafnia and hafnium silicate films sandwiched between an evaporated Au electrode and a Si substrate. Valence band offset and conduction band offset decrease until they become almost constant with an increase in hafnium content at both Si and Au sides. In literature, similar decrease in the valence band offset was reported in zirconium silicate.Photoluminescence spectra induced by UV photons were measured for amorphous hafnia and zirconia deposited by plasma-enhanced chemical-vapor deposition, amorphous hafnia deposited by pulse laser deposition, and crystalline yttria-stabilized zirconia (YSZ). A PL peak appears around 2.7 to 2.9 eV similarly in all hafnia and zirconia samples, irrespective of the difference in crystallinity, oxygen deficiency, source alkoxide, deposition method, or the substrate material. The decay profile of the PL is also similar in all the samples. These results indicate that the PL is inherent in hafnia and zirconia, and is not due to impurities, oxygen vacancy, or interface defects between the sample and the substrate. From PL excitation (PLE) and vacuum-ultraviolet (VUV) absorption measurements, the PL was found to be excited by UV photons to tail states at the band edges. When the samples were annealed at 900℃, a new PL peak appears around 4.2 eV in all the samples except YSZ. The PLE and VUV absorption measurements indicate that the 4.2-eV PL is excited due to the interband absorption.Mechanisms of PLs induced in hafnium and zirconium silicates were also discussed. A broad PL spectrum was observed from 2.0 to 5.0 eV similarly in both silicates. This PL has two components with peaks around 2.8 to 3.0 eV and 3.8 eV for hafnium silicates and those around 2.7 to 3.0 eV and 3.8 eV for zirconium silicates. Time-resolved PL and PL decay measurements indicate that the origin of the PL component around 2.7(2.8) to 3.0 eV is the same as that of the PL component around 2.7 to 2.9 eV in hafnia and zirconia. Furthermore, PLE and VUV absorption measurements show that both the PL components around 2.7(2.8) to 3.0 eV and 3.8 eV are excited to tail states at the band edges. Through these studies, it is assumed that hafnium silicate, zirconium silicate, hafnia, and zirconia have luminescent centers in their band gaps with their respective upper and lower states that have a certain fixed energy difference irrespective of the hafnium or zirconium content.Furthermore, effects of postannealing on the electrical properties of hafnium and zirconium silicates were investigated. When the samples were postannealed in nitrogen monoxide (NO). leakage current and capacitance-voltage (C-V) hysteresis width are decreased drastically. From ESR measurement, it is assumed that paramagnetic defects at the interface between the sample and the Si substrate are responsible for the leakage current and the C-V hysteresis. Furthermore, depth profile by XPS shows that the postnitridation effectively terminates these interface defects and contributes to the improvement in electrical properties. Less