Copper Chalcogenide–Copper Tetrahedrite Composites—A New Concept for Stable Thermoelectric Materials Based on the Chalcogenide System

For the first time, an alternative way of improving the stability of Cu-based thermoelectric materials is proposed, with the investigation of two different copper chalcogenide–copper tetrahedrite composites, rich in sulfur and selenium anions, respectively. Based on the preliminary DFT results, which indicate the instability of Sb-doped copper chalcogenide, the Cu1.97S–Cu12Sb4S13 and Cu2−xSe–Cu3SbSe3 composites are obtained using melt-solidification techniques, with the tetrahedrite phase concentration varying from 1 to 10 wt.%. Room temperature structural analysis (XRD, SEM) indicates the two-phase structure of the materials, with ternary phase precipitates embed within the copper chalcogenide matrix. The proposed solution allows for successful blocking of excessive Cu migration, with stable electrical conductivity and Seebeck coefficient values over subsequent thermal cycles. The materials exhibit a p-type, semimetallic character with high stability, represented by a near-constant power factor (PF)—temperature dependences between individual cycles. Finally, the thermoelectric figure-of-merit ZT parameter reaches about 0.26 (623 K) for the Cu1.97S–Cu12Sb4S13 system, in which case increasing content of tetrahedrite is a beneficial effect, and about 0.44 (623 K) for the Cu2−xSe–Cu3SbSe3 system, where increasing the content of Cu3SbSe3 negatively influences the thermoelectric performance.

Cu diffusion into the glass under bias temperature stress condition for through glass vias (TGV) applications

For Through Glass Via (TGV) applications, significant copper migration in-between vias would result in failure of the device. The Cu migration occurs due to a combination of thermal and applied electrical field. Thus, it is critical to generate data of Cu diffusivity through glass as function of temperature and electrical field to determine whether a Cu diffusion barrier is required for this application. In this study, the Cu diffusion profiles in the Corning SG 3.4 glass, under varying electrical fields and temperature are evaluated. Using a planar capacitance test structure and a bias temperature stress test at elevated temperature, an Arrhenius plot of Cu diffusivity was obtained. Cu diffusion in the SG 3.4 glass has an activation energy of 1.1 eV which is in the range of thermal SiO2 and low-k of the references. Based on this Arrhenius plot, Cu diffusion depth at various combinations of operating temperatures and electrical fields can be determined. Based on the calculated diffusion lengths we infer that Cu diffusion barrier may not be required in most TGV applications.

A comparison of the Cu electrochemical migration behavior between Cu lines with 5 um L/S realized by conventional Semi Additive Process (SAP) and an innovative Excimer Laser Damascene Process

The technological evolution regarding multi-chip integrated Fan-Out packages and chip scale packages (CSPs) with high amounts of I/O demands for even higher routing densities. Conventional used technologies and materials like mask aligner and photosensitive polymers used for semi additive process (SAP) in the BEOL have reached its limits to push the resolution down to two um. New materials and technologies are necessary to overcome these limits. As the routing density increases, so does the reliability requirements. The electrochemical migration between Cu lines cannot be neglected and need to be analyzed as the distance between the Cu lines is decreasing. A new approach for fine-line multi redistribution layers (RDL) realized by an excimer laser dual damascene process was presented in the past, using laser ablation and Cu chemical mechanical planarization (CMP) to realize embedded Cu lines. This approach has several advantages regarding the processing but one of the most important characteristics of the damascene approach is the improved electrochemical migration behavior. The Cu lines are partially cladded by the Ti part of the seed layer due to the way of processing. The Ti acts as a barrier layer and inhibits the Cu migration into the surrounding polymer. RDL structures realized by conventional SAP have Ti only under and not between the Cu lines. In this study different test samples with interdigital structures (resp. interdigital capacitor IDC) with five um line and space width (L/S) were realized to analyze the electrochemical migration behavior between the fingers of the IDC. The samples were realized by SAP and by the excimer laser damascene process and were subsequently tested by the temperature humidity bias (THB) test resp. biased High Accelerated Stress Test (bHAST). With the help of this work, we were able to compare the reliability of both process variants and to demonstrate and prove the reliability of embedded copper lines realized by the excimer laser damascene process.

Novel Low Temperature Curable Photo-Patternable Polyamide with High Planarity for Wafer Level Fan-Out Packaging (WLFO)

As Wafer Level Fan-Out Packaging (WLFO) designs continue to evolve, higher pattern densities for Cu lines and interconnects continue to increase while thickness continues to decrease. As Cu densities increase, the patterning resolution of the RDL dielectric needs to shrink to allow increased bump density. The higher Cu density in turn requires enhanced dielectric performance to minimize Cu migration, whilst utilizing lower temperature and shorter cure times which result in lower levels of wafer warpage. Minimizing mechanical stress, continues to be a critical function of the RDL dielectric. Warpage leads to poor yields, distorting the planarity of the package and ultimately leading to stress induced failure from cracking and delamination. Reduction of the thermal budget is the primary means of reducing mechanical stress in WLFO designs. The amount of Cu in the package continues to increase. Differences in thermal expansions of such and the dielectric increase with temperature. Further, conventional solder reflow processes and set points will continue to be used, therefore the RDL dielectric must continue to be thermally and mechanically stable but capable of being cured at lower temperatures, 180–200 °C to minimize overall mechanical stresses from thermal expansion. We present a novel polyamide based RDL dielectric, KMRD, designed to achieve current and future WLFO design requirements. KMRD is a low temperature curable, aqueous (2.38%TMAH) developable dielectric capable of meeting industry standards for mechanical and electrical requirements, with a high level of reliability while utilizing a single stage cure at 185 °C. KMRD provides clear advantages over incumbent materials, with low temperature cure, improved pattern resolution, wide process latitudes, superior adhesion, chemical compatibility, and cost benefits using standard processing equipment and chemistry.