Thermal Oxidation of Reactively Sputtered Titanium Nitride and Hafnium Nitride Films

Abstract

The oxidation behavior of reactively sputtered normalTiN and normalHfN thin films was investigated for oxide formation in dry and wet oxidizing ambient in the temperature range of 425°–800°C. For both cases, formation of a single‐oxide phase, rutile TiO2 for oxidized normalTiN and monoclinic HfO2 for oxidized normalHfN , was observed. The oxidation process is thermally activated, and it has a parabolic time dependence, except in the case of wet oxidized normalHfN where nonuniform oxidation behavior was observed. The parabolic time dependence of the oxide growth is attributed to a transport‐controlled process which is limited by the diffusivity of the oxidant in the oxide. The dry oxidation of normalTiN is much faster than the dry oxidation of normalHfN at a given temperature. The oxidation rate is always higher in a wet than in a dry ambient.

Nanolink-based thermal devices : integration of ALD tin thin films

“…For the parabolic regime, the oxidation is limited by the diffusion of oxidizing species through the oxide layer. The oxidation rate of TiN is extracted from slope of the linear parts of the oxidation curves at several temperatures, these rates are used to construct Arrhenius plots as shown in Figure 3 The activation energies for the parabolic regime are in agreement (within 13 %) to those obtained for sputtered TiN [94], the initial oxidation regime is not reported in the literature to our best knowledge.…”

“…At t = 0 min, a TiN thickness of 8 nm is observed and a TiO 2 thickness of 3.5 nm. This initial TiO 2 layer is the native oxide formed by oxidation in air [94]. The MSE increases during the first part of the oxidation and decreases for the last part.…”

“…However, the properties of TiN are strongly influenced by the film stoichiometry, crystallinity, morphology and hence the deposition method [83,93]. Sputtered TiN layers with 1:1 stoichiometry are known to oxidize significantly in dry ambient (O 2 ) above 500 ºC [94,95], non-stoichiometric TiN layers (Ti 1 N 1-x ) even at room temperature [96].…”

(Ba,Sr)TiO3 Thin Films for Dram’s

“…In some structures, the diffusion barrier is directly exposed to oxygen during the BST deposition. The oxidation rate has been calculated and plotted versus time for a range of temperatures in Figure 27 using experimentally determined rate constants and activation energies by Suni et al [121]. When TiN oxidizes to Ti02, it undergoes a large volume expansion and the thickness of the resulting Ti02 will be 1.6 times the thickness of the consumed TiN as shown in Figure 28.…”

Kinetics and mechanisms of TiN oxidation beneath Pt thin films

“…For a capacitor with Pt bottom electrode, this oxidation process occurs by diffusion of ͑presumably, atomic͒ oxygen through the Pt grain boundaries, diffusion across a TiO x oxidation product, and reaction at the TiO x /TiN interface. Previous investigations of the oxidation kinetics of bare TiN films have used Rutherford backscattering spectrometry ͑RBS͒ 8,9 and ellipsometry 10 to measure the thickness of the oxide product. These techniques are much less useful in the case of oxidation under a continuous metal film.…”