Nanocrystalline copper for direct copper-to-copper bonding with improved cross-interface formation at low thermal budget.

Direct copper-to-copper (Cu-Cu) bonding is a promising technology for advanced electronic packaging. Nanocrystalline (NC) Cu receives increasing attention due to its unique ability to promote grain growth across the bonding interface. However, achieving sufficient grain growth still requires a high thermal budget. This study explores how reducing grain size and controlling impurity concentration in NC Cu leads to substantial grain growth at low temperatures. The fabricated NC Cu has a uniform nanograin size of around 50 nm and a low impurity level of 300 ppm. To prevent ungrown NC and void formation caused by impurity aggregation, we propose a double-layer (DL) structure comprising a normal coarse-grained (CG) layer underneath the NC layer. The CG layer, with a grain size of 1 µm and an impurity level of 3 ppm, acts as a sink, facilitating impurity diffusion from the NC layer to the CG layer. Thanks to sufficient grain growth throughout the entire NC layer, cross-interface Cu-Cu bonding becomes possible under a low thermal budget, either at 100 °C for 60 min or at 200 °C for only 5 min.

Electrodeposition of (111)-oriented and nanotwin-doped nanocrystalline Cu with ultrahigh strength for 3D IC application.

The mechanical performance of electroplated Cu plays a crucial role in next-generation Cu-to-Cu direct bonding for the three-dimension integrated circuit (3D IC). This work reports direct-current electroplated (111)-preferred and nanotwin-doped nanocrystalline Cu, of which strength is at the forefront performance compared with all reported electroplated Cu materials. Tension and compression tests are performed to present the ultrahigh ultimate strength of 977 MPa and 1158 MPa, respectively. The microstructure of nanoscale Cu grains with an average grain size around 61 nm greatly contributes to the ultrahigh strength as described by the grain refinement effect. A gap between the obtained yield strength and the Hall-Petch relationship indicates the presence of extra strengthening mechanisms. X-ray diffraction and transmission electron microscopy analysis identify the highly (111) oriented texture and sporadic twins with optimum thicknesses, which can effectively impede intragranular dislocation movements, thus further advance the strength. Via filling capability and high throughput are also demonstrated in the patterned wafer plating. The combination of ultrahigh tensile/compressive strength, (111) preferred texture, superfilling capability and high throughput satisfies the critical requirement of Cu interconnects plating technology towards the industrial manufacturing in advanced 3D IC packaging application.

Functions of self-assembled ultrafine TiO2 nanocrystals for high efficient dye-sensitized solar cells.

In this paper, we demonstrate a simple approach of self-assembled process to form a very smooth and compacted TiO2 underlayer film from ultrafine titanium oxide (TiO2) nanocrystals with dimension of 4 nm for improving the electrical properties and device performances of dye-sensitized solar cells (DSSCs). Because the TiO2 film self-assembles by simply casting the TiO2 on fluorine-doped tin oxide (FTO) substrate, it can save a lot of materials in the process. As compared with control DSSC without the self-assembled TiO2 (SA-TiO2) layer, short-circuit current density (Jsc) improves from 14.9 mA/cm(2) for control DSSC to 17.3 mA/cm(2) for masked DSSC with the SA-TiO2 layer. With the very smooth SA-TiO2 layer, the power conversion efficiency is enhanced from 8.22% (control) to 9.35% for the DSSCs with mask and from 9.79% (control) to 11.87% for the DSSCs without mask. To explain the improvement, we have studied the optical properties, morphology, and workfunction of the SA-TiO2 layer on FTO substrate as well as the impedance spectrum of DSSCs. Importantly, we find that the SA-TiO2 layers have better morphology, uniformity, and contact with FTO electrode, increased workfunction and optical transmission, as well as reduced charge recombination at the contact of FTO substrate contributing to the improved device performances. Consequently, our results show that the simple self-assembly of TiO2 ultrafine nanocrystals forms a very good electron extraction layer with both improved optical and electrical properties for enhancing performances of DSSCs.