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New concepts for the 3D-TSV electroplating: From the tailored design to the application of suppressor additives

English title New concepts for the 3D-TSV electroplating: From the tailored design to the application of suppressor additives
Applicant Nguyen Thi Minh Hai
Number 139758
Funding scheme Marie Heim-Voegtlin grants
Research institution Departement für Chemie und Biochemie Universität Bern
Institution of higher education University of Berne - BE
Main discipline Physical Chemistry
Start/End 01.02.2012 - 31.01.2014
Approved amount 219'273.00
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All Disciplines (2)

Discipline
Physical Chemistry
Organic Chemistry

Keywords (9)

Copper electroplating; 3D-TSV; Leveler; Suppressor additive; Copper interconnect; Copper technology; Suppressor polymer; Electrochemistry; Polymer synthesis

Lay Summary (English)

Lead
Lay summary
The present project aims to develop new concepts for the superfill (bottom-up fill) of large, µm-sized copper interconnects that are mandatory for the future three-dimensional Through-Silicon-Via (3D-TSV) technology. This technology allows the 3D stacking of individual microprocessors and the integration of memory devices and other applications on one single processor unit. Copper deposition for such interconnects requires new types of chemistries that form stable suppressor ensembles at the wafer surface and the upper sidewalls of the TSV features during the entire superfill. Firstly, new suppressor additives will be synthesized based on the polymerization of various diglycidyl ethers and bivalent bases. Secondly, these polymers will be characterized by different analytical and electrochemical methods in order to obtain information on the particular polymer structure, the molecular weight/size distribution, the suppressing capabilities and the overall electrochemical stability under reactive conditions. Thirdly, the active suppressor ensemble will be isolated, identified and characterized with various spectroscopic and microscopic methods (EC-STM, MS, UV-VIS, SQUID, elementary analysis) in order to gain a fundamental atomistic understanding on the formation and the action mode of the suppressor ensembles at the copper/electrolyte interface. The copper deposition will finally be performed with the new suppressor polymers on real 3D-TSV test structures. The quality of the fill will be characterized by different wafer-scale analytic methods. The project is going to contribute a significant fundamental knowledge for the development of suppressor additives that will be applied for the future 3D-TSV technology in the semiconductor industry.
Direct link to Lay Summary Last update: 21.02.2013

Responsible applicant and co-applicants

Employees

Publications

Publication
On the role of halides and thiols in additive-assisted copper electroplating
Huynh Thi M. T., Weiss Florian, Hai Nguyen T. M., Reckien Werner, Bredow Thomas, Fluegel Alexander, Arnold Marco, Mayer Dieter, Keller Hubert, Broekmann Peter (2013), On the role of halides and thiols in additive-assisted copper electroplating, in ELECTROCHIMICA ACTA, 89, 537-548.
Polyvinylpyrrolidones (PVPs): Switchable Leveler Additives for Damascene Applications
Hai N. T. M., Furrer J., Stricker F., Huynh T. M. T., Gjuroski I., Luedi N., Brunner T., Weiss F., Fluegel A., Arnold M., Chang I., Mayer D., Broekmann P. (2013), Polyvinylpyrrolidones (PVPs): Switchable Leveler Additives for Damascene Applications, in Journal of The Electrochemical Society, 160(12), 3116-3125.
Quasi-Reversible Interaction of MPS and Chloride on Cu(100) Studied by In Situ STM
Huynh T. M. T., Hai N. T. M., Broekmann P. (2013), Quasi-Reversible Interaction of MPS and Chloride on Cu(100) Studied by In Situ STM, in Journal of The Electrochemical Society, 160(12), 3063-3069.
Tailored Design of Suppressor Additives for Copper Plating by Combining Functionalities
Hai Nguyen T. M., Janser Félice, Luedi Nicola, Broekmann Peter (2013), Tailored Design of Suppressor Additives for Copper Plating by Combining Functionalities, in ECS Electrochemistry Letters, 2(11), 52-54.
Beyond interfacial anion/cation pairing: The role of Cu(I) coordination chemistry in additive-controlled copper plating
Hai NTM, Kramer KW, Fluegel A, Arnold M, Mayer D, Broekmann P (2012), Beyond interfacial anion/cation pairing: The role of Cu(I) coordination chemistry in additive-controlled copper plating, in ELECTROCHIMICA ACTA, 83, 367-375.
Competitive anion/anion interactions on copper surfaces relevant for Damascene electroplating
Hai NTM, Huynh TTM, Fluegel A, Arnold M, Mayer D, Reckien W, Bredow T, Broekmann P (2012), Competitive anion/anion interactions on copper surfaces relevant for Damascene electroplating, in ELECTROCHIMICA ACTA, 70, 286-295.
Competitive Anion/Water and Cation/Water Interactions at Electrified Copper/Electrolyte Interfaces Probed by in Situ X-ray Diffraction
Keller H, Saracino M, Nguyen HMT, Thi MTH, Broekmann P (2012), Competitive Anion/Water and Cation/Water Interactions at Electrified Copper/Electrolyte Interfaces Probed by in Situ X-ray Diffraction, in JOURNAL OF PHYSICAL CHEMISTRY C, 116(20), 11068-11076.
On the Acceleration of Cu Electrodeposition by TBPS (3,3-thiobis-1-propanesulfonic acid): A Combined Electrochemical, STM, NMR, ESI-MS and DFT Study
Hai N. T. M., Furrer J., Gjuroski I., Bircher M. P., Cascella M., Broekmann P. (2012), On the Acceleration of Cu Electrodeposition by TBPS (3,3-thiobis-1-propanesulfonic acid): A Combined Electrochemical, STM, NMR, ESI-MS and DFT Study, in Journal of The Electrochemical Society, 160(12), 3158-3164.
Potential Oscillations in Galvanostatic Cu Electrodeposition: Antagonistic and Synergistic Effects among SPS, Chloride, and Suppressor Additives
Hai NTM, Oderrnatt J, Grimaudo V, Kramer KW, Fluegel A, Arnold M, Mayer D, Broekmann P (2012), Potential Oscillations in Galvanostatic Cu Electrodeposition: Antagonistic and Synergistic Effects among SPS, Chloride, and Suppressor Additives, in JOURNAL OF PHYSICAL CHEMISTRY C, 116(12), 6913-6924.

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
The 30th Annual SAOG Meeting (Swiss Working Group for Surface and Interface Science) Poster Redox-active Safranine/Janus Green B leveler additives at Cu(100)/electrolyte interface 24.01.2014 University of Fribourg, Switzerland Nguyen Thi Minh Hai;
The 30th Annual SAOG Meeting (Swiss Working Group for Surface and Interface Science) Poster Electrochemical oscillation in the additives-assisted copper electroplating 24.01.2014 University of Fribourg, Switzerland Nguyen Thi Minh Hai;
Dixième rencontre romande interassociations SURF-THERM : « De la fonctionnalisation à la caractérisation » Talk given at a conference Tailor design of supressor ensembles for damascene and 3D-TSV copper plating 12.07.2013 Salon EPHJ-EPMT-SMT – Palexpo – Genève, Switzerland Nguyen Thi Minh Hai;
The 24th Conference of the EPS Condensed Matter Division (CMD-24), the 29th European Conference on Surface Science (ECOSS-29) Talk given at a conference From structure to function: Towards an atomistic understanding of the action of additives relevance for the Damascene and TSV copper plating 06.09.2012 Edinburgh International Conference Centre Edinburgh, UK, Great Britain and Northern Ireland Nguyen Thi Minh Hai;
The 24th Conference of the EPS Condensed Matter Division (CMD-24), the 29th European Conference on Surface Science (ECOSS-29) Poster Redox-active Safranine/Janus Green B leveler additives at Cu(100)/electrolyte interface: EC-STM and electrochemical studies 05.09.2012 Edinburgh International Conference Centre Edinburgh, UK, Great Britain and Northern Ireland Nguyen Thi Minh Hai;
The 24th Conference of the EPS Condensed Matter Division (CMD-24), the 29th European Conference on Surface Science (ECOSS-29) Poster Electrochemical oscillation in the additives-assisted copper electroplating: A mechanistic study on the role of intermediate species at the copper/electrolyte interface 05.09.2012 Edinburgh International Conference Centre Edinburgh, UK, Great Britain and Northern Ireland Nguyen Thi Minh Hai;
Metrohm Autolab User Meeting 2012 Talk given at a conference From fundamentals to application/characterization of plating additives for the Damascene process and 3D-TSV technology 04.09.2012 Metrohm Switzerland Ltd. Zofingen, Switzerland, Switzerland Nguyen Thi Minh Hai;


Associated projects

Number Title Start Funding scheme
151238 New concepts for the 3D-TSV electroplating: From the tailored design to the application of suppressor additives 01.02.2014 Marie Heim-Voegtlin grants
149224 Copper/Electrolyte Interfaces under Reactive Conditions II 01.01.2014 Project funding (Div. I-III)

Abstract

Within the framework of this project it is intended to develop new concepts for the superfill of large, micrometer-sized copper interconnect architectures that are needed for the future 3D-TSV (Through Silicon Via) technology. This project involves the tailored design (synthesis) of new electroplating additives, mechanistic studies on the action mode of these new types of additives at the copper/electrolyte interface under reactive conditions and finally the ultimate proof-of-principle of these concepts using state-of-the-art 3D-TSV test structures. This project is therefore going to cover topics, approaches and methodologies from both fundamental and applied research.
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