Atomic layer deposition of HfO2 films using carbon-free tetrakis(tetrahydroborato)hafnium and water

Thin hafnium oxide films were prepared by atomic layer deposition using a carbon-free precursor, tetrakis(tetrahydroborato)hafnium [Hf(BH4)(4)], and H2O. Film growth was studied using an in situ quartz crystal microbalance and Fourier transform infrared spectroscopy measurements. Self-limiting growth was observed between 100 and 175 degrees C, but the thermal decomposition of the Hf precursor occurred at higher temperatures. The film properties were investigated using x-ray photoelectron spectroscopy, x-ray reflectivity, x-ray diffraction, ellipsometry, time-of-flight secondary ion mass spectrometry, and x-ray absorption spectroscopy. The as-deposited films were found to consist of an amorphous mixture of HfO2 and B2O3, and had a lower density and lower refractive index compared to pure HfO2 thin films. Annealing the films to >750 degrees C yielded crystalline monoclinic HfO2 with a density of 9g/cm(3) and a refractive index of 2.10.