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Atomic layer deposition of AlxTi1-xN via co-evaporation of metal precursors
Linköping University, Department of Physics, Chemistry and Biology, Chemistry. Linköping University, Faculty of Science & Engineering.ORCID iD: 0000-0003-0878-9248
Linköping University, Department of Physics, Chemistry and Biology, Chemistry. Linköping University, Faculty of Science & Engineering.ORCID iD: 0000-0002-2248-4291
Seco Tools AB, Sweden.
Seco Tools AB, Sweden.
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2025 (English)In: Journal of Vacuum Science & Technology. A. Vacuum, Surfaces, and Films, ISSN 0734-2101, E-ISSN 1520-8559, Vol. 43, no 3, article id 032405Article in journal (Refereed) Published
Abstract [en]

Different approaches are used in tailoring properties of thin films to meet the requirements of specific applications. This study comprises work done on atomic layer deposition of Al (x) Ti1-x N employing the co-evaporation approach using tris-dimethylamido aluminum [Al(NMe2)(3)], tetrakis(dimethylamido)titanium (IV) [Ti(NMe2)(4)], and ammonia (NH3) plasma. High Al-content, low impurity (O and C, both <5 at. %) films with uniform grain size distribution and dense morphology were deposited. The as-deposited films were x-ray amorphous, but mixed crystallographic phases were observed when the films were annealed at 700 degrees C. The deposited aluminum-rich Al (x) Ti1-x N films show an alternative way for ternary material depositions.

Place, publisher, year, edition, pages
A V S AMER INST PHYSICS , 2025. Vol. 43, no 3, article id 032405
National Category
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:liu:diva-213007DOI: 10.1116/6.0004420ISI: 001456404300002Scopus ID: 2-s2.0-105001313857OAI: oai:DiVA.org:liu-213007DiVA, id: diva2:1952385
Note

Funding Agencies|Swedish Foundation for Strategic Research through the project "Time-resolved low temperature CVD for III-nitrides" [SSF-RMA 15-0018]; Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009-00971]; Seco Tools

Available from: 2025-04-15 Created: 2025-04-15 Last updated: 2025-11-04
In thesis
1. Divide in Time to Conquer the Surface: ALD Studies to Understand Surface Chemistry of AlxTi1-xN CVD
Open this publication in new window or tab >>Divide in Time to Conquer the Surface: ALD Studies to Understand Surface Chemistry of AlxTi1-xN CVD
2025 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The production of metal objects in industry largely depends on cutting operations such as turning, milling, and drilling. Such operations use cutting tools with replaceable inserts made of cemented carbide, designed with precise geometry and material properties. To enhance the longevity of the inserts, they are typically coated with a thin layer (a few micrometers) of a hard, wear-resistant material. This use of wear-resistant protective coatings represents one of the most promising strategies for enhancing the functional properties of contact materials, thereby effectively addressing issues related to friction and wear. Multicomponent coatings formulated from e.g., cubic aluminium titanium nitride (c-AlxTi1-xN) solid solutions are recognized for their exceptional hardness, along with thermal stability and resistance to wear and oxidation. These coatings can be applied onto the cutting inserts through deposition methods such as chemical vapor deposition (CVD).

The aim of this thesis is to establish a foundation and extend the understanding of the surface chemistry during the deposition of AlxTi1-xN by CVD. Research in recent years has demonstrated that metastable c-AlxTi1-xN with high aluminium content can be deposited near thermodynamic equilibrium using CVD techniques at very low pressures. However, the underlying CVD chemistry of these processes remains poorly understood, which limits the development of these processes to speculative approaches rather than scientifically grounded strategies. Because the CVD of AlxTi1-xN is not yet fully understood, atomic layer deposition (ALD) — a time-resolved variant of CVD — can serve as a valuable model system for investigating its surface chemistry and underlying reaction mechanisms. ALD enables a stepwise, temporally separated approach to studying these complex surface processes. By dividing the ternary AlxTi1-xN into its constituent binary components (TiN and AlN) and examining each one individually before combining them into the ternary material, we can systematically unravel the surface reactions involved. This time-resolved strategy provides a more controlled and detailed pathway to understanding the overall CVD process.

Reaction mechanism studies focus on understanding how and why a thin film forms. The identification of the chemical reactions that occur during each precursor pulse allows researchers to connect the dots that lead to the overall growth process. The findings in this thesis give a basis for a comprehensive understanding of the deposition chemistry at the atomic scale using different techniques to study surface chemistry, thereby enabling the advancement of more efficient and sustainable AlxTi1-xN CVD processes. This was conducted by utilization of different precursors: trimethyl aluminium (TMA, Al(CH3)3) and tris-dimethylamido aluminium (TDMAA, Al(NMe2)3) as the Al precursors and tetrakis-dimethylamido titanium (TDMAT, Ti(NMe2)4) as the Ti precursor, while NH3 acted as the N source. Furthermore, established ALD methods for the binaries TiN and AlN were employed to create an alternative ALD approach for the ternary AlxTi1-xN deposition. In situ, operando and ex situ measurements were taken from these ALD processes and proved effective for studying surface reaction mechanisms, as they provided chemical information before, during and after the deposition process.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2025. p. 67
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 2473
National Category
Materials Chemistry
Identifiers
urn:nbn:se:liu:diva-219277 (URN)10.3384/9789181182248 (DOI)9789181182231 (ISBN)9789181182248 (ISBN)
Public defence
2025-12-04, Nobel (BL32), B Building, Campus Valla, Linköping, 09:15 (English)
Opponent
Supervisors
Note

Funding agencies: Seco Tools AB, the Swedish Foundation for Strategic Research through the project "Time-resolved low temperature CVD for III-nitrides" (SSF RMA 150018), and Vinnova through the project "Surface chemical mechanisms in atomic layer deposition of hard nitrides" (2023-02815)

Available from: 2025-11-04 Created: 2025-11-04 Last updated: 2025-11-07Bibliographically approved

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