The relationship between local order, long range order, and sub-band-gap defects in hafnium oxide and hafnium silicate films

Abstract

We have measured x-ray absorption spectra (XAS) at the oxygen K edge for hafnium oxide (HfO2) films grown by chemical vapor deposition (CVD) and atomic layer deposition (ALD), as well as for hafnium silicate (HfSiO) films grown by CVD. The XAS results are compared to x-ray diffraction (XRD) and spectroscopic ellipsometry (SE) data from the same films. Features characteristic of crystalline HfO2 are observed in the XAS spectra from all CVD-grown HfO2 films, even for a thickness of 5 nm where XRD is not sensitive. XAS and XRD spectra from the ALD-grown HfO2 films exhibit the signature of crystallinity only for films that are 20 nm or thicker. These characteristic XAS features are absent in all HfSiO films measured, which is consistent with their being amorphous. The appearance of these peaks in XAS and XRD is correlated with sub-band-gap absorption in the SE spectra, which appears to be intrinsic to crystalline HfO2 in the monoclinic phase. © 2008 American Institute of Physics.