Evaluation of the Near-Zero Temperature Coefficient of Resistivity (NZ-TCR) of ALD TiSixn Films

Abstract

Atomic Layer Deposition (ALD) of ternary TiSixN leads to nanocomposites of metallic TiN atomically mixed with insulating Si3N4. Formulating TiSixN films with various Ti:Si ratios lead to the emergence of a temperature regime where resistivity is independent of thermal drift, denoted as near-zero temperature coefficient of resistivity (nz-TCR). Further, the ease with which nanocomposites of TiSixN can be deposited using ALD offer precise tunability in Ti:Si ratio, thickness, mass density, crystallinity and electrical properties.Recently, our group explored TiSixN films deposited using a Eugenus® 300 mm commercial QXP mini-batch system by modulating the ratio of Ti and Si precursors with NH3 as a co-reactant. Si-content was varied from 0 at % (pure TiN) to 24.2 at % Si while maintaining thickness ~ 140 nm. The X-ray reflectivity and grazing incidence X-ray diffraction measurements showed a reduction in film density and transition from nano-crystalline to pure amorphous phase with increase in Si-fraction. Spectroscopic ellipsometry revealed the optical constants, composition, and electrical resistivities and were supported by X-ray photoelectron spectroscopy and electrical measurements. Room-temperature resistivity measurements show an increase in film resistivity with increasing at % Si. Temperature-dependent Van der Pauw measurements found a nz-TCR of -23 ppm K-1 in the temperature range of 298 K – 398 K and at 3.4 at % Si content.We have now discovered that an at % Si = 3.0% induces a nz-TCR of -5.7 ppm K-1 from 80 K – 420 K – one of the best reported nz-TCR values for ALD thin films. Fine tuning the at % Si in TiSixN films, possible only via ALD, significantly elongated the temperature window of nz-TCR behavior. Mapping the local conductivity of individual grains through conductive atomic force microscopy (c-AFM) indicated higher resistance at the grain boundaries. The local composition at the grain boundaries may play a major role in determining the nz-TCR behavior of TiSixN films. In addition, variable temperature Hall effect measurements were performed to provide deeper insights into the nz-TCR mechanism, decoupling carrier concentration from carrier mobility effects while determining film resistivity.Compared to other nz-TCR films, which are deposited using physical vapor deposition techniques, ALD based nz-TCR films presents a unique synthesis platform for interconnect technology in topologically complex, 3D devices, circuits and sensors that undergo large temperature variation during operation but need to maintain stability in their electrical characteristics.