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.
Improved diffusion barrier by stuffing the grain boundaries of TiN with a thin Al interlayer for Cu metallization
A laterally segregated diffusion barrier was investigated for Cu metallization. In this scheme, the intended final structure is composed of two different barrier materials; one is the parent barrier layer (TiN, in our case) and the other (Al2O3, in this case) is segregated laterally along the grain boundaries of the parent barrier layer. As a result, the fast diffusion paths, the so-called grain boundaries of the parent diffusion barrier, are effectively passivated. To realize this type of barrier experimentally, the TiN(5 nm)/Al(2 nm)/TiN(5 nm) structure was fabricated by sequential sputtering and compared with TiN(10 nm) as a diffusion barrier against Cu. The etch pit test results indicated that the barrier with the Al interlayer prevented Cu diffusion into the Si up to 650 °C, which is 250 °C higher than achieved by a TiN(10 nm) barrier.
Measuring Sheet Resistances of Dielectrics Using Co‐Planar Hydrogel Electrochemical Cells with Practical Applications to Characterize the Protective Quality of Paints on Sculptures
Electrical properties of thin dielectric films at the solid-liquid phase boundary are an important performance characteristic of many devices, coatings and sensors. In this paper, co-polymeric hydrogels of polyacrylic acid co-sulfonic acid, swollen with a salt solution to act as the solid electrolyte, were used to assess interfaces using electrochemical impedance spectroscopy (EIS) in a co-planar geometry. Silane-modified glasses were characterized by the co-planar hydrogel EIS cell and found to be distinguishable based on their surface monolayer chemistry. EIS measurements were also made on primed and painted metal substrates, using both test panels and an outdoor sculpture, Tony Smith's Stinger. The panels were then exposed to accelerated and outdoor weathering and showed degradation on the surface paint layers, which was observable electrochemically using EIS and confirmed visually by SEM. Electrochemical spectral features were compared between data from a standard paint-test cell versus this co-planar hydrogel cell; both cell types were able to measure coating capacitance, providing useful information about the condition of the bulk coating. Yet, sheet resistance (Rs) was a spectral feature seen only by the co-planar hydrogel cell. Thus, it can be concluded that the use of such co-planar hydrogel cells can provide an earlier warning sign to coating degradation and such cells provide a new type of spectral information that is not assessable by the standard geometry.