Deposition behavior and substrate dependency of ALD MnO&lt;inf&gt;x&lt;/inf&gt; diffusion barrier layer

Matsumoto, Kenji; Maekawa, Kaoru; Nagai, Hiroyuki; Koike, Junichi

doi:10.1109/iitc.2013.6615566

Cited by 5 publications

(4 citation statements)

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“…Thus, one of the challenges for ASD is passivating the nongrowth surface selectively to the growth surface and the ASD-grown material, which both need to remain reactive during cyclic ASD processes. Alkyl-terminated surfaces inhibit a wide variety of deposition processes. − Organic surface functionalizations which produce multilayers or monolayers can therefore be used to prevent deposition, and versatile chemical selectivity can be provided through the head group of the organic molecules. − These organic inhibitors show great promise for a variety of ASD applications, as the organic multilayers or monolayers not only block access to the nongrowth surface but may also limit lateral overgrowth as these layers are typically a few nanometers thick. , However, some ALD and CVD processes operate outside the thermal stability window of these organic layers, and the thickness of these layers may pose challenges for the filling of narrow three-dimensional (3D) features . Alternative selective surface treatments which produce subnanometer-thin passivation layers are therefore also under investigation. − Methylsilyl compounds show promise for ASD of metals and HfO 2 by SiO 2 surface deactivation via silylation. − Dimethylamino-trimethylsilane (DMA-TMS) is an interesting candidate for SiO 2 surface silylation in terms of reaction kinetics. ,, DMA-TMS can cover a SiO 2 nongrowth surface with −Si(CH 3 ) 3 groups via a self-limiting surface reaction with surface −OH groups, and the −Si(CH 3 ) 3 -terminated surface is thermally stable up to 650 °C. , Reaction with H-terminated Si is energetically unfavorable, and DMA-TMS can as such enable ASD on Si/SiO 2 nanopatterns .…”

Section: Introductionmentioning

confidence: 99%

Insight into Selective Surface Reactions of Dimethylamino-trimethylsilane for Area-Selective Deposition of Metal, Nitride, and Oxide

et al. 2020

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Area-selective deposition (ASD) is a promising bottom-up manufacturing solution for catalysts and nanoelectronic devices. However, industrial applications are limited as highly selective ASD processes exist only for few materials. “Passivation/deposition/defect removal” cycles have been proposed to increase selectivity, but cycling requires the passivation to be selective to the growth surface as well as the ASD-grown material. Dimethylamino-trimethylsilane (DMA-TMS) can passivate SiO2 surfaces by covering them with −Si(CH3)3 groups. However, the interaction of DMA-TMS with materials other than SiO2 and Si remains largely unknown and its compatibility with cycling is not yet understood. This work investigates the selectivity of metal, nitride, and oxide atomic layer deposition (ALD) to DMA-TMS-passivated SiO2 as well as the surface chemistry and selectivity of the DMA-TMS reaction. The ALD coreagents O2, NH3, and H2O show low reactivity with the −Si(CH3)3-terminated surface at temperatures up to 300 °C, but the selectivity of ALD strongly depends on the metal precursor and temperature. We demonstrate that DMA-TMS is a selective passivation agent for ASD of and on TiO2, TiN, and Ru selective to SiO2, by TiCl4/H2O, TiCl4/NH3, and EBECHRu/O2 ALD, respectively. We investigate the DMA-TMS reaction on Ru and TiN/TiO2 growth surfaces under conditions that passivate SiO2. At least 77% of the area of the growth surface remains reactive for ALD, confirming the compatibility of DMA-TMS with cycling for ASD. We investigate the impact of changes in surface composition due to patterning before ASD and find that DMA-TMS removes F impurities on TiN and TiO2 surfaces. DMA-TMS selectively passivates SiO2 on three-dimensional (3D) nanopatterns, allowing preferential TiO2 deposition on a nonpassivated growth surface. Thus, the selectivity of DMA-TMS shows great promise to expand the ASD material space as well as to increase selectivity during ASD cycles.

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Section: Introductionmentioning

confidence: 99%

Insight into Selective Surface Reactions of Dimethylamino-trimethylsilane for Area-Selective Deposition of Metal, Nitride, and Oxide

et al. 2020

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“…Therefore, an alternative to replace the currently used Ta/TaN barrier materials and process for the aggressively scaled-down interconnects is required to overcome the above-mentioned issues, among which self-forming barrier process, chemical vapor deposition (CVD), and atomic layer deposition (ALD) technologies have been proposed [10,11,12]. Moreover, manganese (Mn), ruthenium (Ru), and cobalt (Co), along with their derivatives, are considered as potential alternative barrier materials to substitute the Ta/TaN dual layer [13,14,15].…”

Section: Introductionmentioning

confidence: 99%

Electrical Characteristics and Reliability of Nitrogen-Stuffed Porous Low-k SiOCH/Mn2O3−xN/Cu Integration

et al. 2019

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In our previous study, a novel barrier processing on a porous low-dielectric constant (low-k) film was developed: an ultrathin Mn oxide on a nitrogen-stuffed porous carbon-doped organosilica film (p-SiOCH(N)) as a barrier of the Cu film was fabricated. To form a better barrier Mn2O3−xN film, additional annealing at 450 °C was implemented. In this study, the electrical characteristics and reliability of this integrated Cu/Mn2O3−xN/p-SiOCH(N)/Si structure were investigated. The proposed Cu/Mn2O3−xN/p-SiOCH(N)/Si capacitors exhibited poor dielectric breakdown characteristics in the as-fabricated stage, although, less degradation was found after thermal stress. Moreover, its time-dependence-dielectric-breakdown electric-field acceleration factor slightly increased after thermal stress, leading to a larger dielectric lifetime in a low electric-field as compared to other metal-insulator-silicon (MIS) capacitors. Furthermore, its Cu barrier ability under electrical or thermal stress was improved. As a consequence, the proposed Cu/Mn2O3−xN/p-SiCOH(N) scheme is promising integrity for back-end-of-line interconnects.

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“…In order to achieve sufficient precursor dose, groups utilizing (EtCp) 2 Mn have held the precursor at 75–100 °C, many in conjunction with a bubbler. Films prepared using (EtCp) 2 Mn and H 2 O have a stoichiometry of MnO and a reported growth rate of ∼1 Å/cy. − …”

Section: Introductionmentioning

confidence: 99%

Saturation Behavior of Atomic Layer Deposition MnO_x from Bis(Ethylcyclopentadienyl) Manganese and Water: Saturation Effect on Coverage of Porous Oxygen Reduction Electrodes for Metal–Air Batteries

Clark

Muneshwar

Xiong

et al. 2018

ACS Appl. Nano Mater.

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MnO x deposits on porous gas diffusion layer (GDL) substrates for application as catalysts for the oxygen reduction reaction (ORR) in metal−air batteries have been prepared using atomic layer deposition (ALD). The saturation behavior of the bis(ethylcyclopentiadienyl) manganese ((EtCp) 2 Mn) and H 2 O ALD system has been investigated. The observed saturation behavior is in disagreement with previous reports in literature. (EtCp) 2 Mn + H 2 O depositions exhibited non-ALD behavior, as demonstrated by a high growth per cycle (GPC) at substrate temperatures (T sub ) = 40−50 °C and nonsaturating reactions at T sub ≥ 60 °C. The introduction of a forming gas (FG) (95% N 2 + 5% H 2 ) plasma between the (EtCp) 2 Mn and H 2 O doses promoted precursor saturation with a constant GPC (1.15 Å/cy) in the T sub range of 100−200 °C. The effect of saturation behavior on porosity coverage was investigated by coating porous carbon electrodes with ALD MnO x . Energy dispersive X-ray (EDX) spectroscopy, electrochemical surface area measurements, and oxygen reduction activity all indicate that the saturating behavior of the (EtCp) 2 Mn + FG + H 2 O deposition resulted in superior coverage compared with the (EtCp) 2 Mn + H 2 O depositions.

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Deposition behavior and substrate dependency of ALD MnO<inf>x</inf> diffusion barrier layer

Cited by 5 publications

References 12 publications

Insight into Selective Surface Reactions of Dimethylamino-trimethylsilane for Area-Selective Deposition of Metal, Nitride, and Oxide

Insight into Selective Surface Reactions of Dimethylamino-trimethylsilane for Area-Selective Deposition of Metal, Nitride, and Oxide

Electrical Characteristics and Reliability of Nitrogen-Stuffed Porous Low-k SiOCH/Mn2O3−xN/Cu Integration

Saturation Behavior of Atomic Layer Deposition MnO_x from Bis(Ethylcyclopentadienyl) Manganese and Water: Saturation Effect on Coverage of Porous Oxygen Reduction Electrodes for Metal–Air Batteries

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Deposition behavior and substrate dependency of ALD MnO<inf>x</inf> diffusion barrier layer

Cited by 5 publications

References 12 publications

Insight into Selective Surface Reactions of Dimethylamino-trimethylsilane for Area-Selective Deposition of Metal, Nitride, and Oxide

Insight into Selective Surface Reactions of Dimethylamino-trimethylsilane for Area-Selective Deposition of Metal, Nitride, and Oxide

Electrical Characteristics and Reliability of Nitrogen-Stuffed Porous Low-k SiOCH/Mn2O3−xN/Cu Integration

Saturation Behavior of Atomic Layer Deposition MnOx from Bis(Ethylcyclopentadienyl) Manganese and Water: Saturation Effect on Coverage of Porous Oxygen Reduction Electrodes for Metal–Air Batteries

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Saturation Behavior of Atomic Layer Deposition MnO_x from Bis(Ethylcyclopentadienyl) Manganese and Water: Saturation Effect on Coverage of Porous Oxygen Reduction Electrodes for Metal–Air Batteries