Ruthenium and ruthenium dioxide thin films deposited by atomic layer deposition using a novel zero-valent metalorganic precursor, (ethylbenzene)(1,3-butadiene)Ru(0), and molecular oxygen

Yeo, Seungmin; Park, Jiyoon; Lee, Seung-Joon; Lee, Do-Joong; Seo, Jong Hyun; Kim, Soo‐Hyun

doi:10.1016/j.mee.2015.02.026

Cited by 29 publications

(22 citation statements)

References 32 publications

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“…Therefore, developing a superior ALD-Ru process to satisfy all of the above-mentioned requirements is essential. The poor nucleation of Ru resulting in low GPC during the initial stages of film deposition is currently a bottleneck in the ALD-Ru process that must be overcome to achieve a high GPC ALD process. ,,,, The low vapor pressure of the commonly used precursors is disadvantageous for achieving deposition with deep penetration into high-aspect-ratio substrates . The size of the precursor molecule is therefore critical for achieving high GPC ALD processes for noble metals and metal oxides. − Increasing the adsorption density of the precursor molecules on the surface of the substrate may be an effective method to improve the nucleation process, consequently improving the GPC and the overall properties of the film. − …”

Section: Introductionmentioning

confidence: 99%

Atomic Layer Deposition of Ru for Replacing Cu-Interconnects

et al. 2021

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The atomic layer deposition (ALD) of Ru using a metal–organic precursor, tricarbonyl(trimethylenemethane)ruthenium [Ru(TMM)(CO)3] and O2 as a reactant is reported. The high vapor pressure, thermal stability, and relatively small ligands of the precursor facilitate efficient ALD. Typical self-limiting growth and an ALD temperature window of 220–260 °C are observed along with significantly high growth per cycle (GPC) (∼1.7 Å) and short incubation cycles (∼6) at 220 °C. Density functional theory calculations indicate that the high growth rate and self-limiting behavior can be attributed to the characteristics of the trimethylenemethane ligand. The as-grown polycrystalline films (average grain size ∼20 nm and negligible impurities) were evident from plan-view transmission electron microscopy. The variation in film resistivity with increasing film thickness and deposition temperature was investigated with and without annealing. Films deposited at 260 °C show low resistivity (∼12.9 μΩ cm), which further decreases (∼9.8 μΩ cm) postannealing at 500 °C. A thin Ru film is successfully deposited with 100% step-coverage on a dual-trench structure having an aspect ratio of ∼6.3 (minimum width: ∼15 nm). The interfacial adhesion energy measured using the four-point bending test exceeds 7 J m–2, regardless of the dielectric material and annealing treatment. The Ru precursor permits enhanced nucleation and GPC at relatively low deposition temperatures to construct high-quality Ru films with significantly low resistivity using simple, plasma-free techniques, and is suitable for the fabrication of emerging Ru films to replace Cu-based interconnects.

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Section: Introductionmentioning

confidence: 99%

Atomic Layer Deposition of Ru for Replacing Cu-Interconnects

et al. 2021

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“…From the results reported in the literature for AB-type processes using EBCHDRu precursor, the low-resistivity films are expected to consist of polycrystalline grains of hexagonal close-packed Ru without a RuO 2 fraction. 42 A thicker film (24 ± 2 nm) deposited using an optimized process of 700 ALD cycles with extended O 2 and H 2 dosing times of 45 and 15 s, respectively, showed nearly negligible oxygen contents (4 at. %) and a resistivity of 26 ± 2 μΩ cm.…”

Section: Resultsmentioning

confidence: 98%

“…25 In addition to requiring a longer process time, recipes with long nucleation delays can result in films with rough interfaces as a result of island formation during the initial growth. 40,41 It has been claimed that zerovalent precursors lead to deposition after a negligible nucleation delay on a variety of substrates, 37,38,42 although only limited experimental results supporting this claim have been reported so far. Currently, these precursor molecules are being explored for their potential to deposit ultrathin, smooth films.…”

Section: Introductionmentioning

confidence: 99%

“…43,46,47 Ru is a particularly complex material because of its propensity to form subsurface O species, which can lead to more O incorporation in the final film. 33,34 In many AB-type recipes, the primary difference between deposition of RuO 2 versus Ru metal is the ratio between the Ru precursor and O 2 pulse times or partial pressures, 38,42 suggesting that short O 2 pulse times and/or low O 2 pressures should be employed to deposit metallic Ru. However, Methaapanon et al have shown that higher O 2 pressures enhance nucleation, which, in turn, is important in determining the grain size of the final crystalline Ru film.…”

Section: Introductionmentioning

confidence: 99%

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Atomic layer deposition of ruthenium using an ABC-type process: Role of oxygen exposure during nucleation

Chopra

Vos

Verheijen

et al. 2020

Journal of Vacuum Science &Amp; Technology A: Vacuum, Surfaces, and Films

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DOI to the publisher's website.• The final author version and the galley proof are versions of the publication after peer review.• The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication General rightsCopyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights.• Users may download and print one copy of any publication from the public portal for the purpose of private study or research. • You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal.If the publication is distributed under the terms of Article 25fa of the Dutch Copyright Act, indicated by the "Taverne" license above, please follow below link for the End User Agreement:

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“… 17 The peaks at 25.3, 37.8, 48.0, 53.9, 55.1, 62.7, and 75.0° correspond to (101), (004), (200), (105), (211), (204), and (215) of anatase (JCPDS 21-1272), respectively, and those at 28 and 35° correspond to (110) and (101) of RuO 2 , respectively. 26 , 27 26 , 27 There are two unsaturated coordination sites on the RuO 2 (110) crystal plane, namely, Ru unsaturated coordination site (Ru cus ) and bridge O (O br ). Ru cus has a strong adsorption capacity for reactive gas molecules, and the adsorbed reactive gas molecules can react with O br at low temperatures.…”

Section: Resultsmentioning

confidence: 99%

Effect of Calcination Temperature on the Activation Performance and Reaction Mechanism of Ce–Mn–Ru/TiO₂ Catalysts for Selective Catalytic Reduction of NO with NH₃

et al. 2020

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In this study, anatase TiO 2 -supported cerium, manganese, and ruthenium mixed oxides (CeO x −MnO x −RuO x / TiO 2 ; CMRT catalysts) were synthesized at different calcination temperatures via conventional impregnation methods and used for selective catalytic reduction (SCR) of NO x with NH 3 . The effect of calcination temperature on the structure, redox properties, activation performance, surface-acidity properties, and catalytic properties of the CMRT catalysts was investigated. The results show that the CMRT catalyst calcined at 350 °C exhibits the most efficient lowtemperature (<120 °C) denitration activity. Moreover, the selective catalytic oxidation (SCO) reaction of ammonia is intensified when the reaction temperature is >200 °C, which leads to a decrease in the N 2 selectivity of the CMRT catalysts and further results in an increase in the production of NO and N 2 O byproducts. X-ray photoelectron spectroscopy and in situ diffuse reflectance infrared Fourier transform spectroscopy show that the CMRT catalyst calcined at 350 °C contains more Ce 4+ , Mn 4+ , Ru 4+ , and lattice oxygen, which greatly improve the catalyst's ability to activate NO that promotes the NH 3 -SCR reaction. The Ru n+ sites of the CMRT catalyst calcined at 250 °C are the competitive adsorption sites of NO and NH 3 molecules, while those of the CMRT catalyst calcined at 350 and 450 °C are active sites. Both the Langmuir−Hinshelwood (L−H) mechanism and the Eley−Rideal (E−R) mechanism occur on the surface of the CMRT catalyst at the low reaction temperature (100 °C).

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Ruthenium and ruthenium dioxide thin films deposited by atomic layer deposition using a novel zero-valent metalorganic precursor, (ethylbenzene)(1,3-butadiene)Ru(0), and molecular oxygen

Cited by 29 publications

References 32 publications

Atomic Layer Deposition of Ru for Replacing Cu-Interconnects

Atomic Layer Deposition of Ru for Replacing Cu-Interconnects

Atomic layer deposition of ruthenium using an ABC-type process: Role of oxygen exposure during nucleation

Effect of Calcination Temperature on the Activation Performance and Reaction Mechanism of Ce–Mn–Ru/TiO₂ Catalysts for Selective Catalytic Reduction of NO with NH₃

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Ruthenium and ruthenium dioxide thin films deposited by atomic layer deposition using a novel zero-valent metalorganic precursor, (ethylbenzene)(1,3-butadiene)Ru(0), and molecular oxygen

Cited by 29 publications

References 32 publications

Atomic Layer Deposition of Ru for Replacing Cu-Interconnects

Atomic Layer Deposition of Ru for Replacing Cu-Interconnects

Atomic layer deposition of ruthenium using an ABC-type process: Role of oxygen exposure during nucleation

Effect of Calcination Temperature on the Activation Performance and Reaction Mechanism of Ce–Mn–Ru/TiO2 Catalysts for Selective Catalytic Reduction of NO with NH3

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Effect of Calcination Temperature on the Activation Performance and Reaction Mechanism of Ce–Mn–Ru/TiO₂ Catalysts for Selective Catalytic Reduction of NO with NH₃