Plasma Enhanced Chemical Vapor Deposition of Manganese on Low-k Dielectrics for Copper Diffusion Barrier Application

Jourdan, N.; Barbarin, Y.; Croes, Kristof; Siew, Yong Kong; Elshocht, Sven Van; Tőkei, Zsolt; Vancoille, E.

doi:10.1149/2.002303ssl

Cited by 12 publications

(16 citation statements)

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“…9 Therefore, one of the primary targets for interconnect research is the integration of selfforming Cu diffusion barrier layers with porous low dielectric constant SiOC:H based materials. 10 Recent studies have shown that the formation of Mn silicate barriers on carbon doped low-κ dielectrics can result in the removal of carbon from the dielectric, 11 while the use of porous low-κ materials can result in the integration of gaseous Mn precursors within the dielectric pore structure. 12 As such, investigating the formation of Mn based self-forming barrier layers on SiO 2 in this paper is intended to act as an important base line study before investigating the more complex Mn/SiOC:H interface.…”

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confidence: 99%

Scanning transmission electron microscopy investigations of self-forming diffusion barrier formation in Cu(Mn) alloys on SiO2

et al. 2013

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Scanning transmission electron microscopy in high angle annular dark field mode has been used to undertake a characterisation study with sub-nanometric spatial resolution of the barrier formation process for a Cu(Mn) alloy (90%/10%) deposited on SiO2. Electron energy loss spectroscopy (EELS) measurements provide clear evidence for the expulsion of the alloying element to the dielectric interface as a function of thermal annealing where it chemically reacts with the SiO2. Analysis of the Mn L23 intensity ratio in the EELS spectra indicates that the chemical composition in the barrier region which has a measured thickness of 2.6 nm is MnSiO3.

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confidence: 99%

Scanning transmission electron microscopy investigations of self-forming diffusion barrier formation in Cu(Mn) alloys on SiO2

et al. 2013

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“…Mnbased films (∼1.5 nm thickness) were deposited by chemical vapor deposition 3,4 on a 100 nm thick tetraethylorthosilicate (TEOS)-based BD layer on 300 mm Si wafers and then annealed at ∼450…”

Section: Methodsmentioning

confidence: 99%

“…X-ray fluorescence (XRF).-The deposition of Mn-based, on BD films (∼2 nm thickness) was developed earlier by Jourdan et al 4 and the thickness of these films was confirmed by Transmission Electron Microscopy (TEM). 4 Based on this deposition technique, ∼1.5 nm thick Mn films were prepared and diced to 1" × 1.14" sized coupons.…”

Section: Methodsmentioning

confidence: 99%

“…4 Based on this deposition technique, ∼1.5 nm thick Mn films were prepared and diced to 1" × 1.14" sized coupons. X-ray fluorescence analysis was performed on these coupons using the SPECTRO XEPOS energy dispersive X-ray fluorescence spectrometer and Palladium Kα X-ray source (21.2 keV) available at IMEC.…”

Section: Methodsmentioning

confidence: 99%

“…1 Hence, it has become necessary to replace these Ta/TaN barrier-liner films with thinner and more functional candidate materials. One such candidate is a Mn/Mnbased film since it can form a very thin (∼1 nm) self-forming and excellent Cu diffusion barrier layer of amorphous manganese silicate (MnSi x O y ) at the Mn/low-k (black diamond or SiCOH with k = 2.9 or lower) [1][2][3][4][5][6][7][8][9][10] interface. However, this MnSi x O y layer is not conductive enough and requires a thin conductive liner for the deposition of a Cu seed layer.…”

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Chemical Mechanical Polishing and Planarization of Mn-Based Barrier/Ru Liner Films in Cu Interconnects for Advanced Metallization Nodes

Sagi¹,

Teugels²,

Veen³

et al. 2017

ECS J. Solid State Sci. Technol.

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Mn-based (referred to simply as Mn in the following) barrier/Ru liner stack has been proposed to replace TaN/Ta barrier-liner in Cu interconnects for 7 nm and 5 nm technology nodes. During chemical mechanical planarization (CMP) of the associated Cu/Ru/Mn/SiCOH pattern structures, the usual galvanic corrosion and removal rate selectivity issues need to be resolved. In this study, we investigated the polishing and electrochemical behavior of Cu, Mn, Ru and SiCOH films on the relevant substrates in the alkaline region using silica dispersions containing potassium permanganate (KMnO 4 ), guanidine carbonate (GC) and benzotriazole (BTA) and identified compositions that address these challenges. An XPS study of the as-deposited and annealed Mn films confirmed the formation of amorphous manganese silicate (MnSi x O y ), a self-forming dielectric layer, at the Mn/SiCOH interface. A crosssectional TEM analysis of the polished Cu/Ru/Mn/SiCOH patterned wafers (32 nm half pitch Cu lines) with our candidate slurry showed excellent post-polish performance with no corrosion and no post-CMP loss of either Cu or the Mn barrier/Ru liner film. As the node sizes continue to diminish, the 5∼7 nm thick Ta/TaN barrier-liner will occupy a significant portion of the Cu trench resulting in higher effective resistance and increased resistance-capacitance delay.1 Also, with the even smaller feature sizes and high-aspect-ratio trenches of these nodes, deposition of a conformal Cu seed layer on the Ta liner is a major challenge with any discontinuities in it leading to voids in the copper fill and limiting the yield.1 Hence, it has become necessary to replace these Ta/TaN barrier-liner films with thinner and more functional candidate materials. One such candidate is a Mn/Mnbased film since it can form a very thin (∼1 nm) self-forming and excellent Cu diffusion barrier layer of amorphous manganese silicate (MnSi x O y ) at the Mn/low-k (black diamond or SiCOH with k = 2.9 or lower) 1-10 interface. However, this MnSi x O y layer is not conductive enough and requires a thin conductive liner for the deposition of a Cu seed layer. A ∼2 nm thick Ru film with a resistivity of ∼7 μ cm, much lower than that of Ta's ∼13 μ cm, has been proposed 10,11 as such a liner. As always, these film stacks need to be planarized and for effective planarization, as shown in Figure 1, the removal rate (RR) selectivities among the Cu, Ru, Mn and SiCOH or BD layers and the galvanic corrosion between Cu/Ru and Ru/Mn couples need to be controlled. With that goal in mind, we investigated the polishing and electrochemical behavior of the relevant Mn-based barrier/Ru liner stack using silica based dispersions and various additives. For convenience, in the following the Mn-based films will be addressed simply as Mn films.Cu and Ru polishing behavior 12-18 and related corrosion issues [19][20][21][22][23] for barrier applications have been studied by several authors. Among these, Amanapu et al. 18 showed that the underlying substrate can modify the crystalline orientation o...

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Group 7 and 8 Compounds for Chemical Vapor Deposition

Winter

Upadhyay

Overbeek

et al. 2021

Comprehensive Coordination Chemistry III

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Plasma Enhanced Chemical Vapor Deposition of Manganese on Low-k Dielectrics for Copper Diffusion Barrier Application

Cited by 12 publications

References 0 publications

Scanning transmission electron microscopy investigations of self-forming diffusion barrier formation in Cu(Mn) alloys on SiO2

Scanning transmission electron microscopy investigations of self-forming diffusion barrier formation in Cu(Mn) alloys on SiO2

Chemical Mechanical Polishing and Planarization of Mn-Based Barrier/Ru Liner Films in Cu Interconnects for Advanced Metallization Nodes

Group 7 and 8 Compounds for Chemical Vapor Deposition

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