Effect of grain orientations of Cu seed layers on the growth of <111>-oriented nanotwinned Cu.
ABSTRACT: We investigate the growth of Cu films on two different Cu seed layers: one with regular <111>-oriented grains and the other with very strong <111>-preferred orientation. It is found that densely-packed nanotwinned Cu (nt-Cu) can be grown by pulsed electroplating on the strong <111>-oriented Cu seed layer without a randomly-oriented transition layer between the nt-Cu and the Cu seed layer. The electroplated nt-Cu grow almost epitaxially on the seed layer and formed <111>-oriented columnar structures. However, with the regular <111>-oriented Cu seed, there is a randomly-oriented transition layer between the nt-Cu and the regular <111>-oriented Cu seed. The results indicate that the seed layer plays a crucial role on the regularity of <111>-oriented nanotwinned Cu.
Project description:Cu-to-Cu direct bonding has attracted attention because it has been implemented in CMOS image sensors. Prior to the bonding, the oxides on the Cu surface needs to be removed, yet the surface may oxidize right after cleaning. Thus, oxidation is an inherent issue in the application of Cu direct bonding. Our previous study reported that Cu direct bonding can be achieved below 250?°C by using (111)-oriented nanotwinned Cu because it has the fastest surface diffusivity. However, the oxidation behavior of the nanotwinned Cu is unclear. Here, we examined the oxidation behavior of highly (111) and (200) oriented, and randomly-oriented Cu films at temperatures ranging from 120 to 250?°C. Transmission electron microscopy was used to measure the oxide thickness. The results show that the oxidation rate of (111)-oriented nanotwinned Cu has the lowest oxidation rate among them. Together, it is unique to possess the combination of the fastest surface diffusivity and the lowest oxidation rate.
Project description:Nanotwinned copper (nt-Cu) shows a broad application prospects as interconnection materials in integrated circuit industry, since it combines the excellent mechanical and electrical properties. However, the formation and growth behavior of twin lamellae in pulse electrodeposited copper films are not fully understood. In this work, a series of electroplated copper films are prepared by verifying the electroplating parameters and the microstructures are analyzed using scanning electron microscope (SEM) and transmission electron microscope (TEM). The surface morphology indicates strong evidence of stacked twin terraces and layers, suggesting that nanotwins grow up layer by layer. Combined with in situ characterization by SEM and molecular dynamics (MD) simulation, it is proved that the terraces originate from the triple junction of grain boundaries and grow up by extending along the lateral (111) crystal plane. A twin terrace-growing model for nt-Cu is then deduced, which distinguishes from deformation twins or annealed twins. This growth model would be prospective to help obtain high quality of nt-Cu in industry.
Project description:Direct Cu-to-Cu bonding was achieved at temperatures of 150-250 °C using a compressive stress of 100 psi (0.69 MPa) held for 10-60 min at 10(-3) torr. The key controlling parameter for direct bonding is rapid surface diffusion on (111) surface of Cu. Instead of using (111) oriented single crystal of Cu, oriented (111) texture of extremely high degree, exceeding 90%, was fabricated using the oriented nano-twin Cu. The bonded interface between two (111) surfaces forms a twist-type grain boundary. If the grain boundary has a low angle, it has a hexagonal network of screw dislocations. Such network image was obtained by plan-view transmission electron microscopy. A simple kinetic model of surface creep is presented; and the calculated and measured time of bonding is in reasonable agreement.
Project description:We performed molecular dynamics simulation of nanoindentation on Cu/Ni nanotwinned multilayer films using a spherical indenter, aimed to investigate the effects of hetero-twin interface and twin thickness on hardness. We found that both twinning partial slip (TPS) and partial slip parallel with twin boundary (PSPTB) can reduce hardness and therefore should not be ignored when evaluating mechanical properties at nanoscale. There is a critical range of twin thickness ? (~25?Å?<???<?~31?Å), in which hardness of the multilayer films is maximized. At a smaller ?, TPSs appear due to the reaction between partial dislocations and twin boundary accounts for the softening-dominated mechanism. We also found that the combination of the lowered strengthening due to confined layer slips and the softening due to TPSs and PSPTBs results in lower hardness at a larger ?.
Project description:Synthesized nanotwinned cubic boron nitride (nt-cBN) and nanotwinned diamond (nt-diamond) exhibit extremely high hardness and excellent stability, in which nanotwinned structure plays a crucial role. Here we reveal by first-principles calculations a strengthening mechanism of detwinning, which is induced by partial slip on a glide-set plane. We found that continuous partial slip in the nanotwinned structure under large shear strain can effectively delay the structural graphitization and promote the phase transition from twin structure to cubic structure, which helps to increase the maximum strain range and peak stress. Moreover, ab initio molecular dynamics simulation reveals a stabilization mechanism for nanotwin. These results can help us to understand the unprecedented strength and stability arising from the twin boundaries.
Project description:Experimental results (Huang et al.) indicated that nanotwinned diamond (nt-diamond) has unprecedented hardness, whose physical mechanism has remained elusive. In this report, we categorize interaction modes between dislocations and twin planes in nt-diamond and calculate the associated reaction heat, activation energies, and barrier strength using molecular dynamics. On the basis of the Sachs model, twin thickness dependence of nt-diamond hardness is evaluated, which is in good agreement with the experimental data. We show that two factors contribute to the unusually high hardness of nt-diamond: high lattice frictional stress by the nature of carbon bonding in diamond and high athermal stress due to the Hall-Petch effect. Both factors stem from the low activation volumes and high activation energy for dislocation nucleation and propagation in diamond twin planes. This work provides new insights into hardening mechanisms in nt-diamond and will be helpful for developing new superhard materials in the future.
Project description:The mechanism of radiation-induced detwinning is different from that of deformation detwinning as the former is dominated by supersaturated radiation-induced defects while the latter is usually triggered by global stress. In situ Kr ion irradiation was performed to study the detwinning mechanism of nanotwinned Cu films with various twin thicknesses. Two types of incoherent twin boundaries (ITBs), so-called fixed ITBs and free ITBs, are characterized based on their structural features, and the difference in their migration behavior is investigated. It is observed that detwinning during radiation is attributed to the frequent migration of free ITBs, while the migration of fixed ITBs is absent. Statistics shows that the migration distance of free ITBs is thickness and dose dependent. Potential migration mechanisms are discussed.
Project description:The self-assembly of 1,3,5-benzenetribenzoic acid (BTB) molecules on both Cu(111) and epitaxial graphene grown on Cu(111) were studied by scanning tunneling microscopy (STM) and low-energy electron diffraction (LEED) under ultrahigh vacuum conditions. On Cu(111), the BTB molecules were found to mainly arrange in close-packed structures through H-bonding between the (partially) deprotonated carboxylic acid groups. In addition, porous structures formed by intact BTB molecules-and also based on H-bonding-were observed. On graphene grown on Cu(111) the BTB molecules mainly form porous structures accompanied by small patches of disordered close-packed structures. Upon annealing, BTB adsorbed on Cu(111) is fully deprotonated and arranges in the close-packed structure while in contrast on graphene/Cu(111) the porous network is exclusively formed. This shows that the molecular self-assembly behavior is highly dependent on the first substrate layer: one graphene layer is sufficient to considerably alter the interplay of molecule substrate and intermolecular interactions in favor of the latter interactions.
Project description:A comparative study on the self-assembly of sexiphenyl-dicarbonitrile on highly oriented pyrolytic graphite and single-layer graphene on Cu(111) is presented. Despite an overall low molecule-substrate interaction, the close-packed structures exhibit a peculiar shift repeating every four to five molecules. This shift has hitherto not been reported for similar systems and is hence a unique feature induced by the graphitic substrates.
Project description:Material performance in extreme radiation environments is central to the design of future nuclear reactors. Radiation induces significant damage in the form of dislocation loops and voids in irradiated materials, and continuous radiation often leads to void growth and subsequent void swelling in metals with low stacking fault energy. Here we show that by using in situ heavy ion irradiation in a transmission electron microscope, pre-introduced nanovoids in nanotwinned Cu efficiently absorb radiation-induced defects accompanied by gradual elimination of nanovoids, enhancing radiation tolerance of Cu. In situ studies and atomistic simulations reveal that such remarkable self-healing capability stems from high density of coherent and incoherent twin boundaries that rapidly capture and transport point defects and dislocation loops to nanovoids, which act as storage bins for interstitial loops. This study describes a counterintuitive yet significant concept: deliberate introduction of nanovoids in conjunction with nanotwins enables unprecedented damage tolerance in metallic materials.