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Thermoelectric properties of CrN alloy thin films
Linköping University, Department of Physics, Chemistry and Biology, Thin Film Physics. Linköping University, Faculty of Science & Engineering.ORCID iD: 0009-0006-4871-8734
2025 (English)Licentiate thesis, comprehensive summary (Other academic)
Abstract [en]

A thermoelectric material can be used to convert heat to electricity, and vice versa, all without moving parts. Thermoelectric devices can be used for a multitude of applications, such as thermoelectric generators (TEGs) and Peltier heaters/coolers. TEGs can be used to generate electricity from e.g. waste heat, and small and efficient Peltier coolers could have a use in microelectronics. The lack of moving parts means that thermoelectric devices generally are robust.

Transition metal nitrides are versatile, durable, and have found use in many different applications. CrN, for instance, is known for its hardness, corrosion resistance, near room-temperature magnetic phase transition as well as its thermoelectric properties. Especially crystalline CrN has interesting thermoelectric properties, including a high power-factor and low thermal conductivity. These properties are essential for the constituent materials of thermoelectric devices. For durability, the stability and mechanical properties of CrN would be a bonus. The thermoelectric properties of CrN have a strong correlation to the stoichiometry, which then becomes crucial to control.

The focus of this thesis is on the thermoelectric properties of CrN, with and without alloying transition metals V and Mo. Doping and alloying can help change properties, both electrical and thermal. I have grown thin films of CrN with and without alloying elements, using reactive magnetron sputtering. Film growth using this technique happens far from thermodynamic equilibrium and thus, not all aspects are easy to control, stoichiometry being one. The films were grown on c-plane sapphire (Al2O3 (0001)) substrates.

I investigated thin, epitaxial films of CrMoVN, i.e. CrN thin films co-doped with Mo and V. They were grown on c-plane sapphire substrates, which allows the rock-salt cubic structured CrN to be grown epitaxially, albeit with a non-negligible strain. I investigated the effect of co-doping on phase composition and thermoelectric properties. While the effects of singly doped films (CrVN and CrMoN) were similar to other reports, co-doping with V and Mo resulted in the retention of the rock-salt cubic phase at much higher Mo-content than what has previously been reported. Furthermore, I tackled the issue with stoichiometry, motivated by discrepancies in literature correlating thermoelectric properties and stoichiometry of CrN. After growing sets of thin films of CrN, some epitaxial and some mix-phased, the samples were annealed in ammonia environment to approach the thermodynamic equilibrium of Cr:N = 1:1. The films that were closest to stoichiometry before annealing turned insulator – in line with theory and some articles. The films with larger under-stoichiometry got significantly improved thermoelectric properties, one by as much as 900%.   

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2025. , p. 42
Series
Linköping Studies in Science and Technology. Licentiate Thesis, ISSN 0280-7971 ; 2017
Keywords [en]
Thermoelectrics, CrN, Magnetron sputtering, Thin films, Epitaxy
National Category
Condensed Matter Physics
Identifiers
URN: urn:nbn:se:liu:diva-213256DOI: 10.3384/9789181180763ISBN: 9789181180756 (print)ISBN: 9789181180763 (electronic)OAI: oai:DiVA.org:liu-213256DiVA, id: diva2:1954566
Presentation
2025-05-28, Jordan/Fermi, F-building, Campus Valla, Linköping, 09:00 (English)
Opponent
Supervisors
Note

Funding: This work has been supported by the Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linköping University (Faculty Grant SFO-Mat-LiU No. 2009 00971), the Knut and Alice Wallenberg foundation through the Wallenberg Academy Fellows program (grant no. KAW-2020.0196), the Swedish Research Council (VR) under project no. 2021-03826, and the Swedish Energy Agency under project number 52740-1. 

Available from: 2025-04-25 Created: 2025-04-25 Last updated: 2025-04-25Bibliographically approved
List of papers
1. Phase Composition and Thermoelectric Properties of Epitaxial CrMoVN Thin Films
Open this publication in new window or tab >>Phase Composition and Thermoelectric Properties of Epitaxial CrMoVN Thin Films
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2023 (English)In: Advanced Energy & Sustainability Research, E-ISSN 2699-9412, Vol. 4, no 12, article id 2300119Article in journal (Refereed) Published
Abstract [en]

Thin films of CrMoVN are deposited on c-plane sapphire (Al2O3 (0001)) by direct current reactive magnetron sputtering, to investigate the effects of Mo and V addition to CrN-based films. All films grow epitaxially, but Mo incorporation affects the crystal structure and nitrogen content. All films in the CrMoVN series are understoichiometric in nitrogen, but largely retain the NaCl B1 structure of stoichiometric CrN films. Addition of vanadium increases the phase-stability range of the cubic phase, allowing for higher solubility of Mo than what has previously been reported for cubic CrN. The Seebeck coefficient and electrical resistivity are greatly affected by the alloying, showing a decrease of the Seebeck coefficient along with a decrease in resistivity. Cr0.83Mo0.11V0.06Nz shows a 70% increase in power factor (S2 sigma = 0.22 mW m-1 K-2) compared to the reference CrNz (S2 sigma = 0.13 mW m-1 K-2). Thermoelectric (TE) materials are in use in several applications, but often have too low efficiency. For more widespread use of these materials, fundamental research on TE material system is necessary. In this work, alloying in CrN, with the hope of pushing a material with great promise closer to applications, is investigated.image (c) 2023 WILEY-VCH GmbH

Place, publisher, year, edition, pages
WILEY, 2023
Keywords
alloys; chromium; CrN; epitaxy; nitrides; thermoelectrics; thin films
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:liu:diva-198835 (URN)10.1002/aesr.202300119 (DOI)001080324100001 ()2-s2.0-85171194991 (Scopus ID)
Note

Funding Agencies|Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [SFO-Mat-LiU No. 2009 00971]; Knut and Alice Wallenberg foundation through the Wallenberg Academy Fellows program [KAW-2020.0196]; Swedish Research Council (VR) [2021-03826]; Swedish Energy Agency [2022-00213]; IUVSTA through the Medard W. Welch International Scholarship; Swedish Research Council VR-RFI [2019-00191]; Swedish Foundation for Strategic Research [RIF14-0053]

Available from: 2023-11-02 Created: 2023-11-02 Last updated: 2025-04-25
2. Influence of Ammonia Annealing on Cr-N Thin Films and Their Thermoelectric Properties
Open this publication in new window or tab >>Influence of Ammonia Annealing on Cr-N Thin Films and Their Thermoelectric Properties
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2024 (English)In: ACS Applied Energy Materials, E-ISSN 2574-0962, Vol. 7, no 15, p. 6785-6792Article in journal (Refereed) Published
Abstract [en]

CrN-based thin films are emerging as thermoelectric materials for energy harvesting. Their thermoelectric properties depend on phase composition and stoichiometry, necessitating control over the nitrogen content and how it affects the phase composition. Here, the effect of high-temperature ammonia annealing on the thermoelectric properties as well as crystal structure of thin films of Cr-N on c-plane sapphire (Al2O3(0001)) was investigated. Single-phase (cubic CrN) and mix-phase (cubic CrN + hexagonal-Cr2N) Cr-N films were annealed in ammonia, converting any secondary phase of hexagonal Cr2N to cubic CrN. The thermoelectric properties of the films that contained a secondary phase of hexagonal (CrN)-N-2 greatly improved upon annealing, with an increase of 900% to 0.5 x 10-3 W m(-1) K-2 for the film annealed at 800 degrees C for 2 h. Annealing of single-phase films of cubic CrN resulted in films with near-insulating electrical properties. For the thermoelectric applications of CrN, ammonia annealing can be beneficial over meticulous deposition control.

Place, publisher, year, edition, pages
AMER CHEMICAL SOC, 2024
Keywords
CrN; thermoelectrics; thin film; ammonia; annealing; chromium
National Category
Materials Chemistry
Identifiers
urn:nbn:se:liu:diva-206289 (URN)10.1021/acsaem.4c01491 (DOI)001280925300001 ()
Note

Funding Agencies|Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]; Knut and Alice Wallenberg Foundation through the Wallenberg Academy Fellows program [KAW-2020.0196]; Swedish Research Council (VR) [2021-03826]; Swedish Energy Agency [52740-1]; Swedish Research Council VR-RFI [2019-00191]; Swedish Foundation for Strategic Research [RIF14-0053]

Available from: 2024-08-14 Created: 2024-08-14 Last updated: 2025-04-25Bibliographically approved

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