Copper Bottom-up Filling for Through Silicon Via (TSV) Using Single JGB Additive

Tang, Jin; Zhu, Qing–Ling; Zhang, Y.; Zhang, X.; Guo, Jingdong; Shang, Jian Ku

doi:10.1149/2.0101509eel

Cited by 44 publications

(27 citation statements)

References 15 publications

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“…The sustained acceleration on the upward-moving "V" shaped deposit surface speeded up grain growth. 35,36 This rapid grain growth dominated by the accelerator could be reflected by the relatively coarse grain in the middle region (zone 2) along the central axis of "V" shaped filling profile, as shown in Fig. 10b.…”

Section: Resultsmentioning

confidence: 93%

Effect of Reverse Pulse on Additives Adsorption and Copper Filling for Through Silicon Via

Zhu

Zhang

Liu

et al. 2018

J. Electrochem. Soc.

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In order to develop the suitable Cu electrolyte for TSV filling using period pulse reverse (PPR) electroplating, the operating mechanism of reverse pulse on the adsorption of additives within TSV was systematically investigated. Whether the promotion or reduction of the adsorption of polyethylene glycol (PEG), bis (sodiumsulfopropyl) disulfide (SPS) and Janus Green B (JGB) by reverse pulse was determined by the charge of the formed complex of this additive with Cu + and Cl − . The charge of formed complex was dependent on the Cl − concentration. The reverse pulse had no significant effect on the adsorption of single JGB. In comparison, the composite JGB-PEG inhibitor could be repelled by reverse pulse at the microvia bottom. For the composite PEG-SPS or PEG-JGB-SPS, since the preferentially adsorbed Cu + -Cl − -PEG dense layer could effectively block the transportation of Cl − , few sites of Cl − were left for the SPS adsorption and then mainly formed positively charged SPS-Cu + , which accounted for the detachment of SPS by anodic pulse current at microvia entrance in the presence of PEG. Based on the change of the additives coverage surface by reverse pulse, the microvia filling performances in PPR plating compared to those in DC plating could be well explained. Three-dimensional integrated circuitry (3D-IC) with through Si via (TSV), is a promising technology to obtain vertical electric interconnection, high packaging density, faster signal transmission, and lower power consumption.1,2 The Cu filling by electroplating is one of the core and critical procedures in TSV fabrication. However, it is a great challenge in Cu electroplating to provide a void-free filling for the TSV with high aspect ratio (AR). The "super-filling" was widely used to obtain void-free filling for micro-sized blind via, i.e., the growth at micro-sized via or trench opening was limited and the growth at the bottom was accelerated, which could be enabled by special additives combination in Cu electrolyte.3-9 Several operating mechanisms of additives adsorption within microvia have been invoked to explain this super-filling process, such as the curvature enhanced accelerator coverage (CEAC) model, 3-5 the convection-dependent adsorption (CDA) model 6,7 and time-dependent transport-adsorption mode. 8,9 The commonly used additives can be divided into three categories: accelerator, such as bis (sodiumsulfopropyl) disulfide (SPS), inhibitor, such as polyethylene glycol (PEG), and leveler, such as Janus Green B (JGB). In addition, the chloride ion also played an essential role in Cu electrolyte to promote the additive adsorption, mass transport and Cu ion reaction. 10-13Another available approach for promoting void-free filling was the use of period pulse reverse (PPR) plating.14 Reverse pulse was an effective approach to mitigate the Cu ion depletion at the microvia bottom. 15,16 In the previous studies, Hong et al. 17 reported that an enhanced filling result was obtained by 3-step PPR using one additive. Sun et al. 18 reported that the PPR pl...

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Section: Resultsmentioning

confidence: 93%

Effect of Reverse Pulse on Additives Adsorption and Copper Filling for Through Silicon Via

Zhu

Zhang

Liu

et al. 2018

J. Electrochem. Soc.

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“…High-performance levelers, therefore, play an essential role in the commercial plating formula. Levelers were generally selected from dyes in the early days of copper electroplating, such as Janus Green B [ 18 , 19 ], a classic one in the literature [ 19 , 20 , 21 ]. Early work suggested that the leveling ability of JGB originated from the electrochemical reduction and cleavage of its −N=N− group at the tip or protrusion of the cathode surface [ 22 ].…”

Section: Introductionmentioning

confidence: 99%

Structure Performance Correlation of N-Heterocyclic Oligomer Leveler for Acid Copper Plating of Advanced Interconnects

Peng

Zhai

Chen³

et al. 2023

Molecules

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Levelers, as an essential part of organic additives in copper electroplating, play a crucial role in the fabrication of sophisticated interconnects in integrated circuits, packaging substrates, and printed circuit boards. In this work, four N-heterocyclic oligomers were synthesized and characterized, along with investigations of their electrochemical behaviors and their synergism with other bath components. The corresponding effects of the oligomers on the deposited copper films were analyzed by morphological and compositional characterizations. The leveling mechanism of the oligomers was further discussed with the aid of quantum chemical calculations. The results exhibit that each of these N-heterocyclic oligomers holds a particular degree of leveling ability. The oligomer of 1,3-bis(1-imidazolyl)propane and 1,3-dichloro-2-propanol (IPIEP) is the best leveler for THs plating compared with the other three oligomers. It was found that the hydroxyl group in IPIEP enhances the hydrophilicity of the modified molecule and triggers a more stable complexation between IPIEP and H2O−Cu(I)−MPS. Moreover, imidazole demonstrates a better practicality than piperazine. This work recommends the combination of N-heterocycles in planar conformation with modification by the hydroxyl group to synthesize high-performance straight-chain levelers.

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“…Therefore, a single inhibitor that accomplishes void-free TSV filling is needed in order to reduce the time and cost of the optimisation process. Thus far, only one report, by Tang and co-workers, has demonstrated a single-component additive (Janus Green B) that could provide void-free filled-in micro-vias 11 .…”

Section: Introductionmentioning

confidence: 99%

Experiment and simulation of single inhibitor SH110 for void-free TSV copper filling

Wang

2021

Sci Rep

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Three-dimensional integration with through-silicon vias (TSVs) is a promising microelectronic interconnection technology. Three-component additives are commonly used for void-free TSV filling. However, optimising the additive concentrations is an expensive process. To avoid this, a single-component additive was developed: 3-(2-(4,5-dihydrothiazol-2-yl) disulfanyl) propane-1-sulfonic acid/sulfonate (SH110). Sodium 3,3′-dithiodipropane sulfonate (SPS) and SH110 were used as additives for TSV electroplating copper filling. SH110 resulted in void-free filling, whereas large keyhole voids were found for SPS. To understand how the additives affect the filling mechanism, linear sweep voltammetry of the plating solutions was carried out. The interactions between the Cu surface and additives were simulated by molecular dynamics (MD) analysis using Materials Studio software, and quantum chemistry calculations were conducted using GAUSSIAN 09W. SH110 adsorbs to the Cu surface by both 4,5-dihydrothiazole (DHT) and 3-mercaptopropane sulfonate (MPS) moieties, while SPS is adsorbed only by MPS moieties. MD simulations indicated that the adsorption of the coplanar MPS moiety is the main factor governing acceleration. Quantum chemistry calculations showed that DHT provides an inhibitory effect for TSV filling, while MPS acts as an accelerator for SH110. SH110 is an excellent additive exhibiting both the acceleration and the suppression necessary for achieving void-free TSV filling.

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Copper Bottom-up Filling for Through Silicon Via (TSV) Using Single JGB Additive

Cited by 44 publications

References 15 publications

Effect of Reverse Pulse on Additives Adsorption and Copper Filling for Through Silicon Via

Effect of Reverse Pulse on Additives Adsorption and Copper Filling for Through Silicon Via

Structure Performance Correlation of N-Heterocyclic Oligomer Leveler for Acid Copper Plating of Advanced Interconnects

Experiment and simulation of single inhibitor SH110 for void-free TSV copper filling

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