A new alternative self-assembled-monolayer activation process for electroless deposition of copper interconnects without a conventional barrier

Chen, Giin-Shan; Yang, Tzong Jer; Chen, Sung-Te; Cheng, Yi-Lung; Fang, Jau–Shiung

doi:10.1016/j.elecom.2017.12.015

Cited by 18 publications

(19 citation statements)

References 24 publications

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“…However, N 1s spectra appeared in the APTMS-treated highly porous low-k dielectric, confirming the formation of a highly oriented SAMs from APTMS. Deconvoluting N 1s peak can result in two peaks at binding energies of 399.3 eV and 401.2 eV, attributed to primary (-NH 2 ) and protonated (-NH 3 + ) amino groups, respectively [30,31]. Moreover, the higher the percentage of -NH 2 groups (~82%) implies that the formation SAMs are highly oriented [31].…”

Section: Resultsmentioning

confidence: 99%

“…Deconvoluting N 1s peak can result in two peaks at binding energies of 399.3 eV and 401.2 eV, attributed to primary (-NH 2 ) and protonated (-NH 3 + ) amino groups, respectively [30,31]. Moreover, the higher the percentage of -NH 2 groups (~82%) implies that the formation SAMs are highly oriented [31]. These N-related groups in the SAMs are benefit for Cu barrier [32].…”

Section: Resultsmentioning

confidence: 99%

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Self-Assembled Monolayers on Highly Porous Low-k Dielectrics by 3-Aminopropyltrimethoxysilane Treatment

et al. 2019

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Highly porous low-dielectric-constant (low-k) dielectric materials with a dielectric constant (k) less than 2.50 are needed for 32 nm and beyond technological nodes. In this study, a highly porous low-k dielectric film with a k value of 2.25, open porosity of 32.0%, and pore diameter of 1.15 nm were treated by 3-Aminopropyltrimethoxysilane (APTMS) in wet solution in order to form self-assembled monolayers (SAMs) onto it. The effects of the formation SAMs on the electrical characteristics and reliability of highly porous low-k dielectric films were characterized. As SAMs were formed onto the highly porous low-k dielectric film by APTMS treatment, the dielectric breakdown field and the failure time were significantly improved, but at the expense of the increases in the dielectric constant and leakage current. Moreover, the formation SAMs enhanced the Cu barrier performance for highly porous low-k dielectric films. Therefore, the SAMs derived from APTMS treatment are promising for highly porous low-k dielectric films to ensure better integrity.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Self-Assembled Monolayers on Highly Porous Low-k Dielectrics by 3-Aminopropyltrimethoxysilane Treatment

et al. 2019

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“…While the method required oxidation of substrates not bearing surface hydroxyl sites to enable SAM chemisorption, the use of amine ligand functional groups ,− eliminated the need for environmentally hazardous Sn species. Direct covalent binding of Pd species by the ligands facilitated deposition of adherent EL metal films without the need for substrate surface roughening, permitting fabrication of sub-100 nm features in EL metal. − More recently, others have improved the ligand-based process by replacing costly Pd species by cheaper first row transition metal ions, such as Co, ,, Cu, − or Ni, ,,− capable of autocatalyzing EL metal deposition upon reduction to zerovalent species. Some examples have been presented in the Cobalt section, Nickel section, and Copper section.…”

Section: Discussionmentioning

confidence: 99%

Electroless Metallization of the Elements: Survey and Progress

Turró

Dressick

2022

ACS Appl. Electron. Mater.

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The electroless plating of metals and their alloys, oxides, and chalcogenides represents a critically important technology for the automotive, aerospace, machine tools, and, especially, the electronics industries. Since the initial efforts involving the plating of industrially important metals, such as Ni, Co, Cu, Ag, and Au, in the mid-20th century, the process has evolved to encompass a growing number of elements. At the same time, this expansion in the palette of accessible metals has enabled progress in these industries and evoked new nonconventional applications. In this review, we collect and survey available electroless processes in aqueous and organic solvent systems for each element organized according to position in the Periodic Table as a resource for the reader. Examples illustrating progress in the field are presented and are described in sufficient detail to be useful and understandable for both the expert and nonexpert. Given the historical importance of electronics as a driver for development of electroless processes, examples are electronics-related where possible. However, we strive to also include examples of applications in nontraditional fields to provide the reader with a sense of generality available for electroless methods. The review closes with an outlook for the field and a challenge to scientists and engineers to adapt electroless processes for new applications to continue the growth of the field.

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“…SiO 2 can remain intact and retain its dielectric properties after the wet chemical treatments during the fabrication of SAMs because it has strong O-Si-O linkages. 10,12 However, the wet chemical activation process is readily to damage the weak, hydrophobic carboxylic (-CH 3 ) groups of the p-SiOCH, 13 thus degrading its dielectric properties and negatively affecting the degree of alignment of SAMs grown. This activation process turns out to be a critical factor that determines the barrier capacity of a SAM for Cu metallization on porous dielectric materials.…”

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confidence: 99%

“…This activation process turns out to be a critical factor that determines the barrier capacity of a SAM for Cu metallization on porous dielectric materials. 13,14 We have recently found that an aminosilane SAM after functionalization serves as a seed-trapping enhancer that catalyzes electroless Cu coatings both on SiO 2 and p-SiOCH. 12,13 The functionalized monolayer followed by a seeding process is capable of yielding finer catalytic particle and holds promising in terms of an inline (all-wet) process flow and simplified stack design (eliminating extrinsic metallic barrier) for the electroless metallization of Cu on p-SiOCH.…”

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confidence: 99%

(3-Aminopropyl)trimethoxysilane Self-Assembled Monolayer as Barrier of Porous SiOCH for Electroless Cu Metallization: Optimizations of SiOCH Hydroxylation and Monolayer Functionalization

Fang

Yang

Cheng

et al. 2021

ECS J. Solid State Sci. Technol.

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Self-assembled monolayers (SAMs) are potential diffusion barriers of nanoporous carbon-doped organosilica (p-SiOCH) for Cu metallization. A concern regarding silanization of the p-SiOCH using a wet chemical process is that its dielectric properties and bonding structures could be damaged by the chemical solution used, which is rarely addressed. In this study, the capacity of various (3-aminopropyl)trimethoxysilane self-assembled monolayers (APTMS-SAMs) as a barrier of p-SiOCH for electroless Cu metallization is evaluated. The processing of hydroxylation of the p-SiOCH (for silanization) and functionalization of APTMS-SAMs (for seeding of electroless metallization) was controlled through examining dielectric properties and bond structures of the hydroxylated p-SiOCH and functionalized APTMS-SAMs. Through tailoring the wet chemical treatments, the dielectric constant, insulating capacity, and bonding structure of post-treated p-SiOCH could be preserved at the pristine states, and the APTMS-SAM fabricated turns out to be a reliable barrier thermally stable up to 500 °C, 100 °C greater than that of the p-SiOCH without an SAM barrier. The integration of electroless Cu metallization reliably with p-SiOCH using a near-zero-thickness monolayer (free of a conventional metallic barrier) in an all-wet manner will be demonstrated. However, to make this approach working, both the hydroxylation of p-SiOCH and functionalization of APTMS-SAM have to be optimized.

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A new alternative self-assembled-monolayer activation process for electroless deposition of copper interconnects without a conventional barrier

Cited by 18 publications

References 24 publications

Self-Assembled Monolayers on Highly Porous Low-k Dielectrics by 3-Aminopropyltrimethoxysilane Treatment

Self-Assembled Monolayers on Highly Porous Low-k Dielectrics by 3-Aminopropyltrimethoxysilane Treatment

Electroless Metallization of the Elements: Survey and Progress

(3-Aminopropyl)trimethoxysilane Self-Assembled Monolayer as Barrier of Porous SiOCH for Electroless Cu Metallization: Optimizations of SiOCH Hydroxylation and Monolayer Functionalization

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