3D Porous Cu Current Collectors Derived by Hydrogen Bubble Dynamic Template for Enhanced Li Metal Anode Performance

Lithium (Li) metal is the most ideal anode material for high‐energy density batteries. However, the high activity of Li metal, the large volume change, and Li dendrite formation during cycling hinder its practical application. Herein, 3D porous Cu synthesized through a simple time‐saving hydrogen bubble dynamic template method is used as a host for the improved performance Li metal anode. Contrary to the planar Cu foil, the synthesized 3D porous structure can reduce the local current density, suppress the mossy/dendritic Li growth, and buffer the volume change in the Li metal anode. Highly stable Coulombic efficiency is achieved at different specific current densities (0.5, 1, and 2 mA cm^?2) with a capacity of 1.0 mAh cm^?2. Moreover, symmetrical Li|Li‐3D Cu cells show more stable cyclic performance with a lower overpotential even at a high current density of 3 mA cm^?2.     

Grain Boundaries in Cu(In,Ga)Se2: A Review of Composition–Electronic Property Relationships by Atom Probe Tomography and Correlative Microscopy

Cu(In,Ga)Se₂ thin-film solar cells have attracted significant research interest in recent decades due to their high efficiency in converting solar energy into electricity for enabling a sustainable future. Although the Cu(In,Ga)Se₂ absorber can be grown as a single crystal, its polycrystalline form is dominating the market not only due to its lower costs, but also due to its unexpectedly higher cell efficiency. However, this absorber contains a high fraction of grain boundaries. These are structural defects where deep-trap states can be localized leading to an increase in recombination activity. This controversy is mirrored in the existing literature studies where two main contradictory believes exist: 1) to be crucial grain boundaries in Cu(In,Ga)Se₂ absorber are anomalous, being benign in terms of cell performance, and 2) grain boundaries are regions characterized by an increased recombination activity leading to deteriorated cell performance. Therefore, the present review tackles this issue from a novel perspective unraveling correlations between chemical composition of grain boundaries and their corresponding electronic properties. It is shown that features such as Cu depletion/In enrichment, segregation of 1-2at.% of alkali dopants, and passivation by a wide-bandgap or type inversion at grain boundaries are crucial ingredients for low open-circuit voltage loss and, hence, for superior cell performance.     

In-situ cleaning and passivation of oxidized Cu surfaces by alkanethiols and its application to wire bonding

The treatment of oxidized Cu surfaces using an alkanethiol as a reducing agent has been investigated. Exposure to a dilute solution of 1-decanethiol resulted in the complete removal and/or conversion of CuO and subsequent formation of a passivating thiolate film, a so-called self-assembled monolayer (SAM), on the underlying Cu/Cu₂O surface as evidenced by x-ray photoelectron spectroscopy (XPS) analysis. Morphological changes, monitored by scanning electron microscopy (SEM) and atomic force microscopy (AFM), revealed transformation of the rough, porous CuO layer into a comparatively smooth Cu/Cu₂O surface. Experiments performed on integrated circuit back-end-of-line (BEOL) die structures, comprising Cu/SiO₂ bond pads used as substrates for Cu wire bonding, demonstrate the potential application of a thiol-based in-situ cleaning-passivation procedure in microelectronics.     

YAP:Cu晶体的热释光性能

采用中频感应提拉法生长了高光学质量的YAP:Cu(原子数分数为0.5%)单晶,使用RisF TL/OSL-DA-15型热释光(TL)和光释光(OSL)仪系统研究了其TL性能。研究结果表明:YAP:Cu单晶存在431 K和482 K两个热释光峰,482 K处为主发光峰;TL峰位置不随辐照剂量的变化而变化,显示其为一级动力学峰;YAP:Cu单晶的TL辐射剂量响应在10-5-102Gy范围内呈较好的线性关系。YAP:Cu晶体是一种TL性能优良并具有潜在应用价值的电离辐射剂量计材料。     

Solder balling of lead-free solder pastes

Solder balling in Sn/Ag/Cu solder pastes was studied in this work. Three different solder pastes, several different reflow profiles and conditions, and two stencil thicknesses were used in the investigation. During the first phase, called the verification phase, the solder pastes were checked to ensure they met the minimum requirements. In the process-screening phase, the reflow profile was varied. Results show that besides flux chemistry, reflow atmosphere plays the major role in solder balling. The average number of solder balls with the best paste was one fifth of that with the worst paste. Furthermore, with all the pastes, the number of solder balls dropped close to zero when nitrogen atmosphere was used. Another finding during the reflow process screening was the influence of the stencil thickness on the solder-balling result. With a thinner stencil, two of the pastes exhibited significant solder balling. This is assumed to be caused by the different ability of fluxes to withstand oxidation during the preheating in the reflow process. In the last phase, the effect of the solder-paste particle size on solder balling was studied more closely. The flux chemistry was kept unchanged, and the solder particle size was varied between type 3 and type 4. The results show that, with type 4 paste, significantly more solder balls are formed compared to type 3 paste. It was also confirmed that, regarding the reflow profile, the ramp-up rate from 150°C to 217°C and the reflow atmosphere were the most significant factors that determine the solder-ball formation for both types of paste.     

Phase identification and growth kinetics of the intermetallic compounds formed during in-49Sn/Cu soldering reactions

For the application of In-49Sn solder in bonding recycled-sputtering targets to Cu back plates, the intermetallic compounds formed at the In-49Sn/Cu interface are investigated. Scanning electron microscopy (SEM) observations show that the interfacial intermetallics consist of a planar layer preceded by an elongated scalloped structure. Electron-probe microanalyzer analyses indicate that the chemical compositions of the planar layer and the scalloped structure are Cu_74.8In_12.2Sn_13.0 and Cu_56.2In_20.1Sn_23.7, respectively, which correspond to the ε-Cu₃(In,Sn) and η-Cu₆(In,Sn)₅ phases. Kinetics analyses show that the growth of both intermetallic compounds is diffusion controlled. The activation energies for the growth of η- and ε-intermetallics are calculated to be 28.9 kJ/mol and 186.1 kJ/mol. Furthermore, the formation mechanism of intermetallic compounds during the In-49Sn/Cu soldering reaction is clarified by marking the original interface with a Ta-thin film. Wetting tests are also performed, which reveal that the contact angles of liquid In-49Sn drops on Cu substrates decline to an equilibrium value of 25°C.     

Adhesion studies of CVD copper metallization

The adhesion of chemical vapor deposition (CVD) Cu thin films to various barriers was observed to improve with a post-deposition anneal or a physical vapor deposition (PVD) Cu flash layer on the barrier before depositing CVD Cu. The ambient exposure of the barrier before the deposition of CVD Cu has been observed to lead to degradation of adhesion in both CVD Cu seed and CVD/PVD Cu high vacuum integrated metallization schemes. The integrated CVD and PVD Cu deposition scheme exhibits better adhesion due to the inherent annealing provided during the PVD deposition which is carried out at temperatures between 300 and 400°C. We have evaluated both qualitative and quantitative tests — tape test, Stud pull test and 4-point bend test — in understanding adhesion and observed that each of these tests give different details of interface breakdown.     

Post electrochemical Cu deposition anneal impact on stress-voiding in individual vias

Stress-voiding is a critical reliability issue in Cu dual-damascene interconnects which could induce via openings. In our case, voids are typically observed at the edges at the bottom of vias. This location is correlated to a local delamination at Cu/Ta interface [E.T. Ogawa, J.W. McPherson, J.A. Rosal, M.J. Dickerson, T.-C. Chiu, L.Y. Tsung, M.K. Jain, T.D. Bonifield, J.C. Ondrusek, W.R. McKee, IEEE Int. Rel. Phys. Symp. Proc. (2002) 312-321; Y.K. Lim et al., Stress-induced voiding in multi-level copper/low-k interconnects, IEEE Int. Rel. Phys. Symp. Proc. (2004) 240-245]. Then, Cu/Ta interface properties at the bottom of via seem to be in the critical path for stress-voiding. In this paper, stress-voiding on 300 mm wafers in individual vias for different post electrochemical Cu deposition (ECD) anneals is studied. Electrical results show the clear benefit of hot plate and short furnace annealings. Microstructural characterizations indicate that impurities accumulation at Cu/Ta interface during long annealings could drive preferred void nucleation.     

Microstructure characterization of Sn-Ag solder joints between stud bumps and metal pads

The microstructure of the flip-chip solder joints fabricated using stud bumps and Pb-free solder was characterized. The Au or Cu stud bumps formed on Al pads on Si die were aligned to corresponding metal pads in the substrate, which was printed with Sn-3.5Ag paste. Joints were fabricated by reflowing the solder paste. In the solder joints fabricated using Au stud bumps, Au-Sn intermetallics spread over the whole joints, and the solder remained randomly island-shaped. The δ-AuSn, ε-AuSn₂, and η-AuSn₄ intermetallic compounds formed sequentially from the Au stud bump. The microstructure of the solder joints did not change significantly even after multiple reflows. The AuSn₄ was the main phase after reflow because of the fast dissolution of Au. In the solder joints fabricated using Cu stud bumps, the scallop-type Cu₆Sn₅ intermetallic was formed only at the Cu interface, and the solder was the main phase. The difference in the microstructure of the solder joints with Au and Cu stud bumps resulted from the dissolution-rate difference of Au and Cu into the solder.     

铜钼化合物氢还原制备铜钼复合粉研究

通过对铜钼化合物氢还原过程进行热力学分析,找到了制备均匀细颗粒铜钼复合粉的热力学途径。设计了封闭还原系统,用此系统进行氢气热还原,不仅使氢气得到充分利用,而且容易判断反应终点。通过系统内的特殊装置除水,降低了还原温度,在650℃下还原得到了混合均匀的铜钼复合粉。系统能彻底快速除去反应生成的水分,使反应物的湿度大大降低,确保能得到细颗粒的铜钼复合粉,其平均粒径小于70nm。