Study of Chemical Vapor Deposition of Manganese on Porous SiCOH Low-k Dielectrics Using Bis(ethylcyclopentadienyl)manganese

Jourdan, N.; Krishtab, Mikhail; Baklanov, Mikhaı̈l R.; Meersschaut, Johan; Wilson, Christopher J.; Ablett, J. M.; Fonda, Emiliano; Zhao, Larry; Elshocht, Sven Van; Tőkei, Zsolt; Vancoille, E.

doi:10.1149/2.006206esl

Cited by 17 publications

(27 citation statements)

References 17 publications

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“…In that case, a couple of major drawbacks arise: i) thicker liners are needed to form pin-holes free barriers, 102,104,105 and ii) the precursor molecules deposit inside the pores before a continuous layer is actually formed on the material surface. 106 Even though the latter could help ensure a good adhesion between the two materials, it should be avoided (or limited to a few nanometers at the interface) to keep the increase in k effective at a minimum. One way to mitigate this penetration phenomena is to pre-treat the dielectric material surface prior to liner deposition.…”

Section: Ecs Journal Of Solid State Science and Technology 4 (1) N30mentioning

confidence: 99%

Toward Successful Integration of Porous Low-k Materials: Strategies Addressing Plasma Damage

Lionti

Volksen

Magbitang

et al. 2014

ECS J. Solid State Sci. Technol.

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The increasing sensitivity of porous low dielectric constant materials to process damage constitutes a major roadblock to their implementation in back-end-of-the-line (BEOL) wiring structures for advanced technology nodes. In the early 2000s and in anticipation to future low-k related integration challenges, the semiconductor industry started to investigate the possibility to repair or prevent this damage. It is remarkable that the most disruptive solutions proposed today are inspired from the work initiated more than 10 years ago. In this review we first describe the accepted mechanisms for plasma damage, followed by a quick summary of the methods used to quantify its extent on both blanket films and patterned structures. We then report on the past and current strategies developed to mitigate the plasma damage of porous, low-k materials during damascene integration processes.

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Section: Ecs Journal Of Solid State Science and Technology 4 (1) N30mentioning

confidence: 99%

Toward Successful Integration of Porous Low-k Materials: Strategies Addressing Plasma Damage

Lionti

Volksen

Magbitang

et al. 2014

ECS J. Solid State Sci. Technol.

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“…Finally, it is also noted that in contrast to previous work on similar non-treated samples, there is strong evidence of Mn diffusion into the 50% porous substrate after thermal anneal, which has been reported to occur in inter-layer dielectric (ILD) materials that were subject to plasma treatments. 17 …”

Section: Resultsmentioning

confidence: 99%

“…15 Manganese silicate (MnSiO 3 ) barrier layers have been the subject of considerable study due to their reported effectiveness as a barrier to Cu migration and improved Cu adhesion properties compared to other barrier layer candidates. 5,6,16,17 While the majority of studies to date have focused on the formation of MnSiO 3 barrier layers on SiO 2 surfaces, 6,18,19 the growth of the Mn based barrier layers on carbon containing ultra-low dielectric constant (ULK) materials has also been the subject of interest. 7,16,[20][21][22] The formation of effective barrier layers on these surfaces is essential if they are to be adopted by the industry.…”

Section: Introductionmentioning

confidence: 99%

In-situ surface and interface study of atomic oxygen modified carbon containing porous low-κ dielectric films for barrier layer applications

Bogan

Lundy

McCoy

et al. 2016

Journal of Applied Physics

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The surface treatment of ultralow-j dielectric layers by exposure to atomic oxygen is presented as a potential mechanism to modify the chemical composition of the dielectric surface to facilitate copper diffusion barrier layer formation. High carbon content, low-j dielectric films of varying porosity were exposed to atomic oxygen treatments at room temperature, and x-ray photoelectron spectroscopy studies reveal both the depletion of carbon and the incorporation of oxygen at the surface. Subsequent dynamic water contact angle measurements show that the chemically modified surfaces become more hydrophilic after treatment, suggesting that the substrates have become more "SiO 2 -like" at the near surface region. This treatment is shown to be thermally stable up to 400 C. High resolution electron energy loss spectroscopy elemental profiles confirm the localised removal of carbon from the surface region. Manganese (%1 nm) was subsequently deposited on the modified substrates and thermally annealed to form surface localized MnSiO 3 based barrier layers. The energy-dispersive X-ray spectroscopy elemental maps show that the atomic oxygen treatments facilitate the formation of a continuous manganese silicate barrier within dense low-k films, but significant manganese diffusion is observed in the case of porous substrates, negatively impacting the formation of a discrete barrier layer. Ultimately, the atomic oxygen treatment proves effective in modifying the surface of non-porous dielectrics while continuing to facilitate barrier formation. However, in the case of high porosity films, diffusion of manganese into the bulk film remains a critical issue. Published by AIP Publishing. [http://dx

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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%

“…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.…”

mentioning

confidence: 99%

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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Study of Chemical Vapor Deposition of Manganese on Porous SiCOH Low-k Dielectrics Using Bis(ethylcyclopentadienyl)manganese

Cited by 17 publications

References 17 publications

Toward Successful Integration of Porous Low-k Materials: Strategies Addressing Plasma Damage

Toward Successful Integration of Porous Low-k Materials: Strategies Addressing Plasma Damage

In-situ surface and interface study of atomic oxygen modified carbon containing porous low-κ dielectric films for barrier layer applications

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

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