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Dense, single-phase, hard, and stress-free Ti0.32Al0.63W0.05N films grown by magnetron sputtering with dramatically reduced energy consumption
Linköping University, Department of Physics, Chemistry and Biology, Thin Film Physics. Linköping University, Faculty of Science & Engineering.
Linköping University, Department of Physics, Chemistry and Biology, Thin Film Physics. Linköping University, Faculty of Science & Engineering.
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Linköping University, Department of Physics, Chemistry and Biology, Thin Film Physics. Linköping University, Faculty of Science & Engineering. Univ Illinois, IL 61801 USA; Natl Taiwan Univ Sci & Technol, Taiwan.ORCID iD: 0000-0002-2955-4897
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2022 (English)In: Scientific Reports, E-ISSN 2045-2322, Vol. 12, no 1, article id 2166Article in journal (Refereed) Published
Abstract [en]

The quest for lowering energy consumption during thin film growth, as by magnetron sputtering, becomes of particular importance in view of sustainable development goals. A recently proposed solution combining high power impulse and direct current magnetron sputtering (HiPIMS/DCMS) relies on the use of heavy metal-ion irradiation, instead of conventionally employed resistive heating, to provide sufficient adatom mobility, in order to obtain high-quality dense films. The major fraction of process energy is used at the sputtering sources rather than for heating the entire vacuum vessel. The present study aims to investigate the W+ densification effects as a function of increasing Al content in (Ti1-yAly)(1-x)WxN films covering the entire range up to the practical solubility limits (y similar to 0.67). Layers with high Al content are attractive to industrial applications as the high temperature oxidation resistance increases with increasing Al concentration. The challenge is, however, to avoid precipitation of the hexagonal wurtzite AIN phase, which is softer. We report here that (T1-yAly)(1-x)WxN layers with y= 0.66 and x= 0.05 grown by a combination ofW-HiPIMS and TiAI-DCMS with the substrate bias V-s synchronized to the W+-rich fluxes (to provide mobility in the absence of substrate heating) possess single-phase NaCl-structure, as confirmed by XRD and SAED patterns. The evidence provided by XTEM images and the residual oxygen content obtained from ERDA analyses reveals that the alloy films are dense without discernable porosity. The nanoindentation hardness is comparable to that of TiAlN films grown at 400-500 degrees C, while the residual stresses are very low. We established that the adatom mobility due to the heavy ion W+ irradiation (in place of resistive heating) enables the growth of high-quality coatings at substrate temperatures not exceeding 130 degrees C provided that the W+ momentum transfer per deposited metal atom is sufficiently high. The benefit of this novel film growth approach is not only the reduction of the process energy consumption by 83%, but also the possibility to coat temperature-sensitive substrates.

Place, publisher, year, edition, pages
Nature Portfolio , 2022. Vol. 12, no 1, article id 2166
National Category
Manufacturing, Surface and Joining Technology
Identifiers
URN: urn:nbn:se:liu:diva-183428DOI: 10.1038/s41598-022-05975-5ISI: 000757457000032PubMedID: 35140271OAI: oai:DiVA.org:liu-183428DiVA, id: diva2:1643927
Note

Funding Agencies|Swedish Research Council VR Grant [2018-03957]; Swedish Energy AgencySwedish Energy AgencyMaterials & Energy Research Center (MERC) [51201-1]; Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation [KAW2016.0358]; Competence Center Functional Nanoscale Materials (FunMat-II) VINNOVA grantVinnova [2016-05156]; Carl Tryggers Stiftelse [CTS 20:150, CTS 15:219, CTS 14:431]; Swedish research council VR-RFISwedish Research Council [2017-00646_9]; Swedish Foundation for Strategic ResearchSwedish Foundation for Strategic Research [RIF14-0053]

Available from: 2022-03-11 Created: 2022-03-11 Last updated: 2023-05-24
In thesis
1. Toward Energy-efficient Physical Vapor Deposition: Routes for Replacing Substrate Heating during Magnetron Sputtering by Employing Metal Ion Irradiation
Open this publication in new window or tab >>Toward Energy-efficient Physical Vapor Deposition: Routes for Replacing Substrate Heating during Magnetron Sputtering by Employing Metal Ion Irradiation
2023 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In this Thesis, magnetron sputtering is perfected as an environmental-friendly deposition technique. I performed systematic studies of a novel approach - hybrid high-power impulse and dc magnetron co-sputtering (HiPIMS/DCMS) with metal-ion-synchronized substrate bias pulses. The technique relies on the use of high-mass metal ion irradiation from the HiPIMS source to densify material deposited by the primary metal targets that operate in the DCMS mode. Thermally-driven adatom mobility, conventionally used to obtain high-quality layers, is replaced by low-energy recoils that are effectively created upon heavy metal ion bombardment of the growing film surface. As a result, the need for external heating is effectively eliminated and the useful growth temperature can be as low as 130 °C.   

Ti-Al-N is chosen as a model materials system for the studies in this thesis due to its relevance for industrial applications and well-known challenges for phase stability control. The role of the metal ion mass on densification, phase content, nanostructure, and mechanical properties of metastable cubic Ti0.50Al0.50N-based thin films is investigated. Three series of (Ti1-yAly)1-xMexN (Me = Cr, Mo, W) films are grown with x varied intentionally by adjusting the DCMS power. There is a strong dependence of film properties on the mass of the HiPIMS-generated metal ions. All layers deposited with Cr+ irradiation exhibit porous nanostructure, high oxygen content, and poor mechanical properties. In contrast, (Ti1-yAly)1-xWxN films are fully-dense even with the lowest W concentration, x = 0.09.  

A strong coupling is found between W+ incident energy Ew+ and minimum W concentration x required to grow dense (Ti1-yAly)1-xWxN layers. With lower x, higher Ew+ is needed to obtain dense films. (Ti1-yAly)1-xWxN film growth is also studied as a function of the relative Al content on the metal lattice, y = Al / (Al + Ti), covering the entire range up to the achievable solubility limit of y ~ 0.67. High-Al content films that are desired in industrial applications (as the high temperature oxidation resistance increases with increasing y) are demonstrated, while precipitation of the softer hexagonal AlN phase is avoided. It is shown that the W+ irradiation from HiPIMS source can be used to grow high-Al content layers with high hardness and low residual stress, while avoiding wurtzite AlN precipitation.  

The critical parameter that controls the growth is shown to be the average momentum transfer per deposited metal adatom. W+ ion irradiation is shown to have a determining role in the densification of TiAlWN films grown by hybrid W-HiPIMS/TiAl-DCMS co-sputtering. Films with the same composition were grown as a function of the number of W+ ions per deposited metal atom, η = W+/ (W + Al + Ti). The latter was varied in a wide range by altering the peak target current density on the W target, as confirmed by time-resolved ion mass spectrometry analyses performed at the substrate plane. I demonstrate that the degree of porosity and the nanoindentation hardness are strong functions of η.   

Finally, high-temperature properties of TiAlWN films grown by hybrid W-HiPIMS/TiAl-DCMS co-sputtering with no external substrate heating is explored, as motivated by application requirements, where the temperature of cutting inserts during machining exceeds 900 °C. A new age hardening mechanism was discovered with Guinier-Preston (GP) zone formation in a ceramic material. Layers with low Al content maintain high hardness well above the annealing temperature characteristic of spinodal decomposition. The evidence from electron microscopy, ab initio calculations, and molecular dynamics simulations, shows that the GP effect originates from the formation of atomic-plane-thick W discs populating {111} planes of the cubic matrix. The results demonstrate for the model materials system of TiAlN that the process energy consumption can be reduced by as much as 64% with respect to conventional methods, with no compromise on coating quality. 

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2023. p. 40
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 2328
Keywords
PVD, Magnetron sputtering, Thin films, HiPIMS, TiAlN, Energy efficiency
National Category
Materials Chemistry
Identifiers
urn:nbn:se:liu:diva-194088 (URN)10.3384/9789180752428 (DOI)9789180752411 (ISBN)9789180752428 (ISBN)
Public defence
2023-09-01, Planck, F-building, Campus Valla, Linköping, 09:15 (English)
Opponent
Supervisors
Note

Funding: The research was primarily financed by the Swedish Research Council (VR) Grant 2018-03957 and the Swedish Energy Agency Grant 51201-1. Additional support was also received from a Knut and Alice Wallenberg Foundation Scholar Grant (Hultman: KAW2016.0358), the Competence Center Functional Nanoscale Materials (FunMat-II) VINNOVA grant 2016-05156,  the VINNOVA grant 2019-04882, the Carl Tryggers Stiftelse contracts CTS 17:166, CTS 15:219 and CTS 14:431.The work supported by the Swedish research council VR-RFI (2017-00646_9) for the accelerator-based ion-technological center and from the Swedish Foundation for Strategic Research (Per Persson: RIF14-0053) for the Tandem accelerator laboratory in Uppsala University is also acknowledged.

Updates:2023-05-24 The thesis was first published online. 2023-05-29 The cover was changed in the published version to match the printed version. Before this date the PDF has been downloaded 38 times.

Available from: 2023-05-24 Created: 2023-05-24 Last updated: 2023-08-01Bibliographically approved

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