Methods for forming dielectric materials with selected polarization for semiconductor devices

A substrate processing method, comprising:

• forming a semiconductor device containing a heat-treated first film and a heat-treated second film, the heat-treated first film having a different crystallographic orientation than the second heat-treated film, by:
• a) forming a first film of a first zirconium oxide material on a substrate by performing a first plurality of cycles of atomic layer deposition and, thereafter, heat-treating the first film to lock in the crystallographic orientation of the first dielectric material in the heat-treated first film, wherein a thickness of the first film is below a threshold thickness needed for spontaneous polarization in the first zirconium oxide material, and the heat-treated first film in the semiconductor device is not spontaneously polarized and exhibits linear polarization in the presence of an external electric field;
• and
• b) forming a second film of a second zirconium oxide material on the substrate by performing a second plurality of cycles of atomic layer deposition and, thereafter, heat-treating the second film to lock in the crystallographic orientation in the heat-treated second dielectric film, wherein a thickness of the second film is greater than the thickness of the first film, and the heat-treated second film in the semiconductor device is ferroelectric or antiferroelectric, and wherein a) is performed before b), or b) is performed before a).