Electroplated Copper Additives for Advanced Packaging: A Review.

Acid copper electroplating stands as a core technology in advanced packaging processes, facilitating the realization of metal interconnects, bumps, vias, and substrate wiring between transistors. The deposition quality of copper interconnect materials has a crucial impact on the final performance of chips, directly influencing their yield, reliability, and stability. In this intricate process, additives play a pivotal role in regulating the deposition quality and behavior of metal copper. This mini-review comprehensively summarizes the recent research progress in the field of electroplating copper additives for advanced packaging, both domestically and internationally, delving into the types and mechanisms of various additive molecules, including accelerators, inhibitors, and leveling agents. Through in-depth research on these additives, we gain a profound understanding of their specific roles in the electroplating process and the intricate interaction mechanisms among them, providing theoretical support for optimizing the electroplating process. Furthermore, this mini-review also delves into a thorough analysis of the current issues and challenges facing acid copper electroplating, exploring the key factors that constrain the further development of electroplating copper technology. Based on this analysis, we propose several potential solutions and research directions, offering crucial references for the development and application of electroplating copper additives in advanced packaging. In conclusion, this mini-review aims to provide a comprehensive perspective and profound understanding of the development and application of electroplating copper additives through a review and analysis of recent research progress, ultimately aiming to promote the further advancement of advanced packaging technology.

Influence of PUB2 on the Leveling Effect of Chip Copper Connection Electroplating: Mechanism and Applications.

The copper connectivity technique is essential for achieving electrical interconnection in wafer level packaging (WLP), system in packaging (SiP), and 3D packaging. The essential processing material for copper connectivity is a copper sulfate electroplating solution in which organic additives play a crucial role in the regularity of copper electrodeposition. In this study, electrochemical tests, X-ray diffraction, 3D profiling, and scanning electron microscopy were used to investigate the leveling effect and mechanism of polyquaternary ammonium urea-containing polymer (PUB2) in the process of copper electrodeposition on-chip copper connections. PUB2 has excellent polarization ability on the target surface, remains unaffected by the sulfur additive SPS and poly(ethylene glycol), and displays a strong ability to regulate the copper deposition rate of through-holes and surface wiring. The waviness of the wafer surface wiring was reduced from 130 to approximately 70 nm after optimizing the PUB2 concentration, and the surface roughness was reduced from 10 to approximately 7 nm. The coating was dispersed evenly, and the rate of through-hole filling was improved by 57%. This study not only examined PUB2 leveling performance and mechanisms but also devised a research method and system for electroplating additives to facilitate the development and application of new electroplating additives.

Prediction and Effect Verification of Thiamine as a Leveling Agent in Chip Wafer Electroplating.

Thiamine, a nitrogen-containing heterocyclic compound, is explored for the first time as a novel leveling agent in this study. Based on the density functional theory (DFT) calculations and molecular dynamics (MD) simulations of the adsorption process of thiamine and the commonly used leveling agent JGB, the average values of the binding energies after equilibrium of thiamine and JGB are similar, which indicates that the thiamine molecules have strong bonding ability with the surface of copper and can be adsorbed tightly on the surface of copper. By cyclic voltammetry (CV) curve, thiamine was found to inhibit copper deposition and the inhibition effect was stronger than JGB. The chrono potential curve (CP) test found that the potential difference △η = 87 > 50 mV at high and low speeds of thiamine, which indicates that thiamine has the potential to be used as a leveling agent. Electrochemical impedance spectroscopy (EIS) testing found that thiamine inhibited copper precipitation by inhibiting the reactions of Cu2+ → Cu+ and Cu+ → Cu. According to electroplating experiments, thiamine has a leveling effect on wafer electroplating and can be used as a leveling agent because the copper layer on the wafer obtained by adding it has a smoother surface compared to the copper layer obtained without adding it. It was found that wafer electroplating does not require PEG, and only adding 55 mg/L Cl-, 6 mg/L SPS, and 4 mg/L thiamine as additives can achieve a good filling effect.

Role of Additives: Modified Hemihydrate Phosphogypsum Morphology and Enhanced Filtration Performance of Wet-Process Phosphoric Acid.

The morphology of hemihydrate phosphogypsum crystals is of vital importance in the hemihydrate-dihydrate (HH-DH) wet-process phosphoric acid production for high filtration strength. The morphology of hemihydrate phosphogypsum is commonly needlelike due to the strong acidic crystallization environment, which is unfavorable to the following filtration process. In this study, the crystal habit of hemihydrate phosphogypsum with a large aspect ratio was skillfully modified by additives to achieve a higher filtration strength. d-Glucitol (DG) reduces the theoretical aspect ratio of hemihydrate phosphogypsum crystals from 2.076 to 1.583 by interacting with the (002) face of CaSO4·0.5H2O preferentially, and poly(vinyl alcohol) (PVA) facilitates the aggregation of small grains to gather into a clusterlike structure. The modified morphologies of hemihydrate phosphogypsum have a lower bulk density and a larger porosity of the formed filter cake, which increases the filtration strength up to 45.9% when DG is added. Our work provides an in-depth explanation of the evolution mechanism of hemihydrate phosphogypsum morphology with the additives and its influence on the filtration performance. The improved filtration strength would reduce the water content of hemihydrate phosphogypsum and relieve the storage pressure of the phosphogypsum slag dump, which is meaningful to the clean production and process emission reduction of the phosphorus chemical industry.