Copper diffusion into single-crystalline TiN studied by transmission electron microscopy and atom probe tomography
Abstract TiN/Cu bilayers were grown by unbalanced DC magnetron sputter deposition on (001)-oriented MgO substrates. Pole figures and electron back-scatter diffraction orientation maps indicate that both layers in the as-deposited state are single-crystalline with a cube-on-cube epitaxial relationship with the substrate. This is confirmed by selected area electron diffraction patterns. To study the efficiency of the TiN barrier layer against in-diffusion of Cu, we annealed samples at 900 °C for 1 h in vacuum and at 1000 °C for 12 h in Ar atmosphere. The single-crystalline structure of the TiN layer is stable up to annealing temperatures of 1000 °C as shown by high resolution transmission electron microscopy. While no Cu diffusion was evident after annealing at 900 °C, scanning transmission electron microscopy images and energy-dispersive X-ray spectrometry maps show a uniform diffusion layer of about 12 nm after annealing at 1000 °C for 12 h. Concentration depth profiles obtained from 3D atom probe tomography reconstructions confirm these findings and reveal that the TiN film is slightly substoichiometric with a N/Ti ratio of 0.92. Considering this composition, we propose a lattice diffusion mechanism of Cu in TiN via the formation of Cu–N vacancy complexes. The excellent diffusion barrier properties of single-crystalline TiN are further attributed to the lack of fast diffusion paths such as grain boundaries.
Correlation between microstructure and barrier properties of TiN thin films used Cu interconnects
Abstract In order to develop a fabrication process to prepare thermally stable TiN thin films, the TiN films were prepared by the sputter-deposition technique with various process parameters. The barrier property of the TiN films which prevented the Cu diffusion into Si or SiO2 were found to be influenced by the radio-frequency power, Ar/N2 gas ratio, and substrate temperature of the sputtering system. By adjusting these process parameters, the 25-nm-thick TiN films with excellent thermal stability that prevented the Cu diffusion at 850 °C for 30 min were successfully prepared. Microstructural analysis by X-ray diffraction and transmission electron microscopy indicated that the microstructure of the TiN films was sensitive to the thermal stability and that the TiN films with strong fiber structure and large grain size had higher resistance to the Cu diffusion into Si.
Phase formation during mechanical alloying in the Ti–Si system
Abstract Mechanical alloying of Ti–Si powder mixture or TiH 1.924 –Si powder mixture was performed by high-energy ball milling, in which the Ti to Si mole ratio was 1:2. The phase formations in both mixtures during milling were investigated by X-ray diffraction. Mechanical alloying a mixture of elemental powders led to the formation of TiSi 2 equilibrium compound, while when starting from Si + TiH 1.924 , a metastable phase was formed. The metastable phase completely transforms to TiSi 2 when the mechanically alloyed powder is annealed at temperatures above 800 °C. Two different pathways of phase transitions during mechanical alloying are attributed to the existence of hydrogen atoms, i.e., when starting from Si + TiH 1.924 compared to Si + Ti, the kinetics for the formation of the TiSi 2 intermetallic compound slows down. The kinetics related to the different phase transitions depending on the starting powder mixture are discussed.