Atomic Layer Deposition of HfO₂ Films Using TDMAH and Water or Ammonia Water

Atomic layer deposition of HfO2 from TDMAH and water or ammonia water at different temperatures below 400 degrees C is studied. Growth per cycle (GPC) has been recorded in the range of 1.2-1.6 angstrom. At low temperatures (<= 100 degrees C), the films grew faster and are structurally more disordered, amorphous and/or polycrystalline with crystal sizes up to 29 nm, compared to the films grown at higher temperatures. At high temperatures of 240 degrees C, the films are better crystallized with crystal sizes of 38-40 nm but grew slower. GPC, dielectric constant, and crystalline structure are improved by depositing at temperatures above 300 degrees C. The dielectric constant value and the roughness of the films have been determined for monoclinic HfO2, a mixture of orthorhombic and monoclinic, as well as for amorphous HfO2. Moreover, the present study shows that the increase in the dielectric constant of the films can be achieved by using ammonia water as an oxygen precursor in the ALD growth. The detailed investigations of the relationship between HfO2 properties and growth parameters presented here have not been reported so far, and the possibilities of fine-tuning and controlling the structure and performance of these layers are still being sought.