In memoriam of Prof. Dan Dascalu
IntroductionHafnium oxide (HfO 2 ) is the dielectric commonly used in fieldeffect transistors (FETs) fabricated in complementary metal oxide semiconductor (CMOS) technologies and, as such, retrieved in any very large-scale integrated (VLSI) circuits. Examples of such circuits include microprocessors or complex analog integrated circuits found in daily applications, for instance, in computers, smartphones, laptops, or incorporated in cars, airplanes, or medical equipments. Since the discovery of HfO 2 as a dielectric for modern integrated circuits, increasing its permittivity was a leading research issue in itself because higher permittivity values allow decreasing the effective oxide thickness (EOT), and so the leakage current; this is especially important when billions of Si FETs are integrated on a single chip. The solution found to boost the permittivity of HfO 2 is represented by structural phase transformations. [1] HfO 2 has its lowest electrical permittivity (ε r % 18) in its stable phase, which is the monoclinic phase. Higher permittivity values, of ε r % 27 in the cubic phase and ε r % 70 in the tetragonal phase, are achieved, nonetheless, in phases that are stable only at very high temperatures, exceeding 1700 C. The decrease in these temperatures is possible, however, by HfO 2 doping. Thus, the cubic and the tetragonal phases were first obtained at lower temperatures via Y doping [1] and, respectively, Si doping, [2] whereas a stable HfO 2 tetragonal phase at nearly room temperature was observed by growing HfO 2 via atomic layer deposition (ALD) and doping it with ZrO 2 . [3,4] As described in the recent review, [5] the stabilization of these phases is determined by the concentration of dopants, the annealing temperature, and the growing methods.These initial investigations focused on increasing the permittivity of HfO 2 lead eventually to the discovery of the orthorhombic phase of HfO 2 , which was associated with HfO 2 ferroelectricity. [6,7] This phase is obtained under different growth conditions in the presence of dopants, including those mentioned earlier, and requires strict control of dopant concentration, temperature, and mechanical strain. The most used orthorhombic HfO 2 -based ferroelectric, named further as Hf ZrO, is doped with Zr and is usually grown at the wafer level, up to 300 mm, using ALD. It thus benefits from the state-of-the-art CMOS technology. More recently, using Zr-doping and pulsed laser deposition (PLD), another rhombohedral phase of HfO 2 was discovered to be also ferroelectric. [7] The rhombohedral or orthorhombic Hf ZrO are ferroelectrics with similar electric performances; the origin of stable ferroelectricity in both cases being due to the induced strain between the top and/or down substrates sandwiching Hf ZrO. [8] Doping or strain application modifies the atomic structure of a material and can induce a phase transition, in particular can induce ferroelectricity in HfO 2 . Similarly, HfO 2 can transform into a weak magnetic material [9...