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Growth and Characterization of Amorphous Multicomponent Nitride Thin Films
Linköping University, Department of Physics, Chemistry and Biology, Thin Film Physics. Linköping University, The Institute of Technology.
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis explores deposition of amorphous thin films based on the two transition metal nitride systems, TiN and HfN. Additions of Si, Al and B have been investigated using three different deposition techniques: dc magnetron sputtering, cathodic arc evaporation, and high power impulse magnetron sputtering (HIPIMS). The effect of elemental composition, bonding structure, growth temperature, and low-energy ion bombardment during growth has been investigated and correlated to the resulting microstructure and mechanical properties of the films. The thermal stability has been investigated by annealing experiments.

Deposition by cathodic arc evaporation yields dense and homogeneous coatings with essentially fully electron-diffraction amorphous structures with additions of either Al+Si, B+Si or B+Al+Si to TiN. The B-containing coatings have unusually few macroparticles. Annealing experiments show that Ti-Al-Si-N coatings have an age hardening behavior, which is not as clear for B-containing coatings. Compositional layering, due to rotation of the sample fixture during deposition, is present but not always visible in the as-deposited state. The layering acts as a template for renucleation during annealing. The coatings recrystallize by growth of TiN-rich  domains.

Amorphous growth by conventional dc magnetron sputtering is possible over a wide range of compositions for Ti-B-Si-N thin films. The Ti content in the films is reduced compared to the content in the sputtering target. Without Si, the films consist of a BN onion-like structure surrounding TiN nanograins. With additions of Si the films eventually grows fully amorphous. The growth temperature has only minor effect on the microstructure, due to the limited surface diffusion at the investigated temperature range (100-600 °C). Ion assisted growth leads to nanoscale densification of the films and improved mechanical properties.

Ti-B-Si-N thin films are also deposited by a hybrid technique where dc magnetron sputtering is combined with HIPIMS. Here, the Ti:B ratio remains equal to the target composition. Films with low Si content are porous with TiN nanograins separated by BN-rich amorphous channels and have low hardness. Increasing Si contents yield fully electron-amorphous films with higher hardness.

Finally, Hf-Al-Si-N single-layer and multilayer films are grown by dc magnetron sputtering from a single Hf-Al-Si target. Amorphous growth is achieved when the growth temperature was kept at its minimum. Low-energy substrate bias modulation is used to grow nanocomposite/nanocolumnar multilayers from the single Hf-Al-Si target, where the layers has essentially the same composition but different Si bonding structure, and different degree of crystallinity.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2014. , 92 p.
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1595
National Category
Natural Sciences
Identifiers
URN: urn:nbn:se:liu:diva-106576DOI: 10.3384/diss.diva-106576ISBN: 978-91-7519-337-3 (print)OAI: oai:DiVA.org:liu-106576DiVA: diva2:716735
Public defence
2014-05-28, Planck, Fysikhuset, Campus Valla, Linköping, 10:00 (English)
Opponent
Supervisors
Available from: 2014-05-12 Created: 2014-05-12 Last updated: 2016-08-31Bibliographically approved
List of papers
1. Growth of Hard Amorphous Ti-Al-Si-N Thin Films by Cathodic Arc Evaporation
Open this publication in new window or tab >>Growth of Hard Amorphous Ti-Al-Si-N Thin Films by Cathodic Arc Evaporation
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2013 (English)In: Surface & Coatings Technology, ISSN 0257-8972, E-ISSN 1879-3347, Vol. 235, no 25, 376-385 p.Article in journal (Refereed) Published
Abstract [en]

Ti(1−x−y)AlxSiyNz (0.02≤x≤0.46, 0.02≤y≤0.28, and 1.08≤z≤1.29) thin films were grown on cemented carbide substrates in an industrial scale cathodic arc evaporation system using Ti-Al-Si compound cathodes in a N2 atmosphere. The microstructure of the as-deposited films changes from nanocrystalline to amorphous by addition of Al and Si to TiN. Upon incorporation of 12 at% Si and 18 at% Al, the films assume an x-ray amorphous state. Post-deposition anneals show that the films are thermally stable up to 900 ◦C. The films exhibit age hardening up to 1000 ◦C with an increase in hardness from 21.9 GPa for as-deposited films to 31.6 GPa at 1000 ◦C. At 1100 ◦C severe out-diffusion of Co and W from the substrate occur, and the films recrystallize into c-TiN and w-AlN.

National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-80199 (URN)10.1016/j.surfcoat.2013.07.014 (DOI)000329596100048 ()
Available from: 2012-08-22 Created: 2012-08-22 Last updated: 2017-12-07Bibliographically approved
2. Reactive DC magnetron sputtering of amorphous (Ti0.25B0.75)1−xSixNy thin films from TiB2 and Si targets
Open this publication in new window or tab >>Reactive DC magnetron sputtering of amorphous (Ti0.25B0.75)1−xSixNy thin films from TiB2 and Si targets
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2014 (English)Manuscript (preprint) (Other academic)
Abstract [en]

(Ti0.25B0.75)1−xSixNy, 0≤x≤0.89, 0.9≤y≤1.25, thin films were reactively grown on Si(001) substrates by dc magnetron sputtering from compound TiB2 and elemental Si targets. The films can be grown in a fully electron-diffraction amorphous state with x>0.46, as evidenced by XRD and HR-TEM investigations. With x=0, BN form onion-like sheets surrounding TiNnanograins. Substrate temperatures, Ts=100-600 ◦C, has a minor effect of the film structure and properties, due to limited surface diffusion.

Ion-assisted growth with substrate bias voltages, Vb, between -50 V and -200 V, favors densification of amorphous structures over nanocrystalline formation, and improves mechanical properties. A maximum hardness value of 26.8±0.7 GPa is found for an amorphous (Ti0.25B0.75)0.39Si0.61N1.15 film grown with substrate temperature Ts=400 °C and substrate bias voltage Vb=-100 V.

National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-106572 (URN)
Available from: 2014-05-12 Created: 2014-05-12 Last updated: 2016-08-31Bibliographically approved
3. Thermal stability and mechanical properties of amorphous arc evaporated Ti-B-Si-N and Ti-B-Si-Al-N coatings grown by cathodic arc evaporation from TiB2, Ti33Al67, and Ti85Si15 cathodes
Open this publication in new window or tab >>Thermal stability and mechanical properties of amorphous arc evaporated Ti-B-Si-N and Ti-B-Si-Al-N coatings grown by cathodic arc evaporation from TiB2, Ti33Al67, and Ti85Si15 cathodes
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2014 (English)In: Journal of Vacuum Science & Technology. A. Vacuum, Surfaces, and Films, ISSN 0734-2101, E-ISSN 1520-8559, Vol. 32, no 6, 061508- p.Article in journal (Refereed) Published
Abstract [en]

Ti-B-Al-N, Ti-B-Si-N, and Ti-B-Si-Al-N coatings were grown on cemented carbide substrates in an industrial scale cathodic arc evaporation system using Ti33Al67, Ti85Si15, and TiB2 cathodes in a reactiveN2 atmosphere. The microstructure of the as-deposited coatings changes from nanocrystalline to amorphous with addition of (B+Si+Al), or high amounts of (B+Si) to TiN. In the as-deposited state, the 4 μm-thick amorphous coatings are dense and homogenous, besides slight compositional modulation with Ti-rich layers induced by rotation of the substrate holder fixture during deposition, and have unusually few macroparticles. Annealing at temperatures ranging from 700 °C to 1100 °C results in that the coatings crystallize by clustering of TiN grains. The hardness of as-deposited amorphous coatings is 17-18 GPa, and increases to 21 GPa following annealing at 800 °C. At annealing temperatures of 1000 °C and above the hardness decreases due to inter-diffusion of Co from the substrate to the coating.

Place, publisher, year, edition, pages
American Vacuum Society, 2014
National Category
Physical Sciences
Identifiers
urn:nbn:se:liu:diva-106573 (URN)10.1116/1.4897170 (DOI)000345215500021 ()
Available from: 2014-05-12 Created: 2014-05-12 Last updated: 2017-12-05Bibliographically approved
4. Growth and properties of amorphous Ti-B-Si-N thin films deposited by hybrid HIPIMS/DC-magnetron co-sputtering from TiB2 and Si targets
Open this publication in new window or tab >>Growth and properties of amorphous Ti-B-Si-N thin films deposited by hybrid HIPIMS/DC-magnetron co-sputtering from TiB2 and Si targets
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2014 (English)In: Surface & Coatings Technology, ISSN 0257-8972, E-ISSN 1879-3347, Vol. 259, 442-447 p.Article in journal (Refereed) Published
Abstract [en]

Amorphous nitrides are explored for their homogenous structure and potential use as wear-resistant coatings, beyond their much studied nano-and microcrystalline counterparts. (TiB2)1−xSixNy thin films were deposited on Si(001) substrates by a hybrid technique of high power impulse magnetron sputtering (HIPIMS) combined with dc magnetron sputtering (DCMS) using TiB2 and Si targets in a N2/Ar atmosphere. By varying the sputtering dc power to the Si target from 200 to 2000 W while keeping the average power to the TiB2-target, operated in HIPIMS mode, constant at 4000 W, the Si content in the films increased gradually from x=0.01 to x=0.43. The influence of the Si content on the microstructure, phase constituents, and mechanical properties were systematically investigated. The results show that the microstructure of as-deposited (TiB2)1−xSixNy films changes from nanocrystalline with 2-4 nm TiN grains for x=0.01 to fully electron diffraction amorphous for x=0.22. With increasing Si content, the hardness of the films increases from 8.5 GPa with x=0.01 to 17.2 GPa with x=0.43.

Place, publisher, year, edition, pages
Elsevier, 2014
National Category
Physical Sciences
Identifiers
urn:nbn:se:liu:diva-106574 (URN)10.1016/j.surfcoat.2014.10.053 (DOI)000347605200010 ()
Available from: 2014-05-12 Created: 2014-05-12 Last updated: 2017-12-05Bibliographically approved
5. Hf-Al-Si-N multilayers deposited by reactive magnetron sputtering from a single Hf0.6Al0.2Si0.2 target using high-flux, low-energy modulated substrate bias: film growth and properties
Open this publication in new window or tab >>Hf-Al-Si-N multilayers deposited by reactive magnetron sputtering from a single Hf0.6Al0.2Si0.2 target using high-flux, low-energy modulated substrate bias: film growth and properties
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2014 (English)Manuscript (preprint) (Other academic)
Abstract [en]

Hf1−x−yAlxSiyN (0≤x≤0.14, 0≤y≤0.13) single layers and multilayer films are grown on Si(001) at a substrate temperature Ts=250 °C using ultrahigh vacuum magnetically-unbalanced reactive magnetron sputtering from a single Hf0.6Al0.2Si0.2 target in a 5%-N2/Ar atmosphere at a total pressure of 20 mTorr (2.67 Pa). The composition and nanostructure of Hf1−x−yAlxSiyN is controlled during growth by varying the ion energy (Ei) of the ions incident at the film surface, keeping the ion-to-metal flux ratio (Ji/JMe) constant at 8. By sequentially switching Ei between 10 and 40 eV, Hf0.77Al0.10Si0.13N/Hf0.78Al0.14Si0.08N multilayers with bilayer periods Λ = 2-20 nm are grown, in which the Si2p bonding state changes from predominantly Si-Si bonds for films grown at Ei = 10 eV, to mainly Si-N bonds at Ei = 40 eV. Multilayer hardness values increase monotonically from 20 GPa with Λ = 20 nm to 27 GPa with Λ = 2 nm, while multilayer fracture toughness increases with increasing Λ. Multilayers with Λ = 10 nm have the optimized property combination of being bothrelatively hard, H∼24 GPa, and fracture tough.

National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-106575 (URN)
Available from: 2014-05-12 Created: 2014-05-12 Last updated: 2016-08-31Bibliographically approved

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