Taehong Gwon

Grain size engineering for ferroelectric Hf0.5Zr0.5O2 films by an insertion of Al2O3 interlayer

The degradation of ferroelectric (FE) properties of atomic layer deposited Hf0.5Zr0.5O2 films with increasing thickness was mitigated by inserting 1 nm-thick Al2O3 interlayer at middle position of the thickness of the FE film. The large Pr of 10 μC/cm2, which is 11 times larger than that of single layer Hf0.5Zr0.5O2 film with equivalent thickness, was achieved from the films as thick as 40 nm. The Al2O3 interlayer could interrupt the continual growth of Hf0.5Zr0.5O2 films, and the resulting decrease of grain size prevented the formation of non-ferroelectric monoclinic phase. The Al2O3 interlayer also largely decreased the leakage current of the Hf0.5Zr0.5O2 films.

Ferroelectricity in undoped-HfO2 thin films induced by deposition temperature control during atomic layer deposition

HfO2 thin films, extensively studied as high-k gate dielectric layers in metal-oxide-semiconductor field effect transistors, have attracted interest of late due to their newly discovered ferroelectricity in doped HfO2. The appearance of the ferroelectric orthorhombic phase of HfO2 was previously examined in variously doped and undoped systems, but the effects of process-variable changes on the physical and chemical characteristics of a thin film and the resulting ferroelectricity have not been studied systematically. Here, the evolution of ferroelectricity in HfO2 thin films through deposition temperature control during atomic layer deposition was systematically examined without the intentional doping of metallic elements other than Hf. The lower-temperature-deposited HfO2 showed an increased impurity concentration, which was mainly carbon, and the involvement of these impurities suppressed the lateral grain growth during the crystallization thermal treatment. The grain size reduction could stabilize the metastable orthorhombic phase, whose surface and grain boundary energies are lower than those of the room-temperature-stable monoclinic phase, by increasing the grain boundary areas. The 9 nm-thick HfO2 thin film deposited at 220 °C exhibited a remanent polarization value of 10.4 μC cm−2 and endured up to 108 switching cycles, which is a 102-fold improvement compared to the previously reported undoped 6 nm-thick HfO2. This can be ascribed to the decrease in the relative portion of defective interfacial layers by increasing the total film thickness. The strategy of using deposition temperature control is a feasible method for the fabrication of these new lead-free binary ferroelectric thin films.

Chemical interaction and ligand exchange between a [(CH3)3Si]3Sb precursor and atomic layer deposited Sb2Te3 films

The chemical interaction between the [(CH3)3Si]3Sb precursor and atomic layer deposited Sb2Te3 thin films was examined at temperatures ranging from 70 to 220 °C. The trimethylsilyl group [(CH3)3Si] displays greater affinity for Te than for Sb, and this drives replacement of Te in the film with Sb from the [(CH3)3Si]3Sb precursor, while eliminating volatile [(CH3)3Si]2Te, especially at elevated temperatures. The compositions of the resulting Sb–Te layers lie on the Sb2Te3–Sb tie line. The incorporation behavior of [(CH3)3Si]3Sb was explained in terms of a Lewis acid–base reaction. The exchange reactions occurred to relieve the unfavorable hard–soft Lewis acid–base pair between the trimethylsilyl group and Sb in [(CH3)3Si]3Sb. Such a reaction could be usefully adopted to control the chemical composition of ternary Ge–Sb–Te thin films.

Structural Analyses of Phase Stability in Amorphous and Partially Crystallized Ge-Rich GeTe Films Prepared by Atomic Layer Deposition

The local bonding structures of GexTe1-x (x = 0.5, 0.6, and 0.7) films prepared through atomic layer deposition (ALD) with Ge(N(Si(CH3)3)2)2 and ((CH3)3Si)2Te precursors were investigated using Ge K-edge X-ray absorption spectroscopy (XAS). The results of the X-ray absorption fine structure analyses show that for all of the compositions, the as-grown films were amorphous with a tetrahedral Ge coordination of a mixture of Ge-Te and Ge-Ge bonds but without any signature of Ge-GeTe decomposition. The compositional evolution in the valence band electronic structures probed through X-ray photoelectron spectroscopy suggests a substantial chemical influence of additional Ge on the nonstoichiometric GeTe. This implies that the ALD process can stabilize Ge-abundant bonding networks like -Te-Ge-Ge-Te- in amorphous GeTe. Meanwhile, the XAS results on the Ge-rich films that had undergone post-deposition annealing at 350 °C show that the parts of the crystalline Ge-rich GeTe became separated into Ge crystallites and rhombohedral GeTe in accordance with the bulk phase diagram, whereas the disordered GeTe domains still remained, consistent with the observations of transmission electron microscopy and Raman spectroscopy. Therefore, amorphousness in GeTe may be essential for the nonsegregated Ge-rich phases and the low growth temperature of the ALD enables the achievement of the structurally metastable phases.