Size Dependent Effects in Nucleation of Ru and Ru Oxide Thin Films by Atomic Layer Deposition Measured by Synchrotron Radiation X-ray Diffraction

Methaapanon, Rungthiwa; Geyer, Scott M.; Brennan, S.; Bent, Stacey F.

doi:10.1021/cm401585k

Cited by 26 publications

(26 citation statements)

References 33 publications

(59 reference statements)

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“…17,18 Similar observations of cation enrichment in the initial layers of related catalytic support systems like RuO 2 (Ref. 19) and NiO 20 even at high oxygen pressures (in excess of 1 mbar) have been reported and mechanisms based on critical nuclei size for oxygen incorporation into the metal and the stability of the metal clusters against oxide clusters have been proposed. This paper expands on pre-existing records on transformations in amorphous alumina thin films, deposited by an energetic plasma sputtering technique and provides direct evidence of IRZ formation and microstructural evolution on annealing.…”

Section: Introductionsupporting

confidence: 65%

A transmission electron microscopy and X-ray photoelectron spectroscopy study of annealing induced γ-phase nucleation, clustering, and interfacial dynamics in reactively sputtered amorphous alumina thin films

Kumar

Prasanna

Subramanian

et al. 2015

Journal of Applied Physics

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Pure α-Al2O3 exhibits a very high degree of thermodynamical stability among all metal oxides and forms an inert oxide scale in a range of structural alloys at high temperatures. We report that amorphous Al2O3 thin films sputter deposited over crystalline Si instead show a surprisingly active interface. On annealing, crystallization begins with nuclei of a phase closely resembling γ-Alumina forming almost randomly in an amorphous matrix, and with increasing frequency near the substrate/film interface. This nucleation is marked by the signature appearance of sharp (400) and (440) reflections and the formation of a diffuse diffraction halo with an outer maximal radius of ≈0.23 nm enveloping the direct beam. The microstructure then evolves by a cluster-coalescence growth mechanism suggestive of swift nucleation and sluggish diffusional kinetics, while locally the Al ions redistribute slowly from chemisorbed and tetrahedral sites to higher anion coordinated sites. Chemical state plots constructed from XPS data and simple calculations of the diffraction patterns from hypothetically distorted lattices suggest that the true origins of the diffuse diffraction halo are probably related to a complex change in the electronic structure spurred by the a-γ transformation rather than pure structural disorder. Concurrent to crystallization within the film, a substantially thick interfacial reaction zone also builds up at the film/substrate interface with the excess Al acting as a cationic source.

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Section: Introductionsupporting

confidence: 65%

A transmission electron microscopy and X-ray photoelectron spectroscopy study of annealing induced γ-phase nucleation, clustering, and interfacial dynamics in reactively sputtered amorphous alumina thin films

Kumar

Prasanna

Subramanian

et al. 2015

Journal of Applied Physics

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“…XRD has only been used a few times as an in situ technique. 24,31 There are however numerous examples of synchrotron based ex situ XRD studies on ALD grown layers. 30,[62][63][64][65][66] This indicates that synchrotron based XRD has several advantages to lab based XRD.…”

Section: X-ray Diffractionmentioning

confidence: 99%

In situ synchrotron based x-ray techniques as monitoring tools for atomic layer deposition

Devloo-Casier

Ludwig

Detavernier

et al. 2013

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

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Atomic layer deposition (ALD) is a thin film deposition technique that has been studied with a variety of in situ techniques. By exploiting the high photon flux and energy tunability of synchrotron based x-rays, a variety of new in situ techniques become available. X-ray reflectivity, grazing incidence small angle x-ray scattering, x-ray diffraction, x-ray fluorescence, x-ray absorption spectroscopy, and x-ray photoelectron spectroscopy are reviewed as possible in situ techniques during ALD. All these techniques are especially sensitive to changes on the (sub-)nanometer scale, allowing a unique insight into different aspects of the ALD growth mechanisms.

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“…The growth per cycle is 0.5 Å/cycle, which is higher than previously reported for ruthenium ALD. [22][23][24][25][26][27][28] There is an initiation delay of approximately 10 cycles before steady-state ALD of Ru is achieved. This delay is quite low compared to typical noble metal ALD, which often exhibits > 50-100 cycles of initiation delay.…”

mentioning

confidence: 99%

Isolating the Photovoltaic Junction: Atomic Layer Deposited TiO₂–RuO₂ Alloy Schottky Contacts for Silicon Photoanodes

Hendricks¹,

Scheuermann²,

Schmidt

et al. 2016

ACS Appl. Mater. Interfaces

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Access to the full text of the published version may require a subscription. Embargo information Access to this article is restricted until 12 months after publication by the request of the publisher. Just Accepted "Just Accepted" manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides "Just Accepted" as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. "Just Accepted" manuscripts appear in full in PDF format accompanied by an HTML abstract. "Just Accepted" manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). "Just Accepted" is an optional service offered to authors. Therefore, the "Just Accepted" Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the "Just Accepted" Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these "Just Accepted" manuscripts. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 2 transport is measured as film thickness increases from 3 to 45 nm for alloy compositions ≥ 16% Rights Embargo lift dateRu. Silicon photoanodes with a 2 nm surface SiO 2 layer that are coated by these alloy Schottky contacts having compositions in the range of 13-46% RuO 2 exhibit average photovoltages of 525 mV, with a maximum photovoltage of 570 mV achieved. Depositing TiO 2 -RuO 2 alloys on nSi sets a high effective work function for the Schottky junction with the semiconductor substrate, thus generating a large photovoltage that is isolated from the properties of an overlying oxygen evolution catalyst or protection layer.

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Size Dependent Effects in Nucleation of Ru and Ru Oxide Thin Films by Atomic Layer Deposition Measured by Synchrotron Radiation X-ray Diffraction

Cited by 26 publications

References 33 publications

A transmission electron microscopy and X-ray photoelectron spectroscopy study of annealing induced γ-phase nucleation, clustering, and interfacial dynamics in reactively sputtered amorphous alumina thin films

A transmission electron microscopy and X-ray photoelectron spectroscopy study of annealing induced γ-phase nucleation, clustering, and interfacial dynamics in reactively sputtered amorphous alumina thin films

In situ synchrotron based x-ray techniques as monitoring tools for atomic layer deposition

Isolating the Photovoltaic Junction: Atomic Layer Deposited TiO₂–RuO₂ Alloy Schottky Contacts for Silicon Photoanodes

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Size Dependent Effects in Nucleation of Ru and Ru Oxide Thin Films by Atomic Layer Deposition Measured by Synchrotron Radiation X-ray Diffraction

Cited by 26 publications

References 33 publications

A transmission electron microscopy and X-ray photoelectron spectroscopy study of annealing induced γ-phase nucleation, clustering, and interfacial dynamics in reactively sputtered amorphous alumina thin films

A transmission electron microscopy and X-ray photoelectron spectroscopy study of annealing induced γ-phase nucleation, clustering, and interfacial dynamics in reactively sputtered amorphous alumina thin films

In situ synchrotron based x-ray techniques as monitoring tools for atomic layer deposition

Isolating the Photovoltaic Junction: Atomic Layer Deposited TiO2–RuO2 Alloy Schottky Contacts for Silicon Photoanodes

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Product

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Isolating the Photovoltaic Junction: Atomic Layer Deposited TiO₂–RuO₂ Alloy Schottky Contacts for Silicon Photoanodes