Thermal stability and oxidation behavior of quaternary TiZrAlN magnetron sputtered thin films: Influence of the pristine microstructure

Abadias, G.; Saladukhin, I.A.; Углов, В.В.; Zlotski, S.V.; Eyidi, D.

doi:10.1016/j.surfcoat.2013.07.055

Cited by 34 publications

(18 citation statements)

References 56 publications

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“…In Zr-Si-N amorphous films, a worse thermal stability was reported for films with substoichiometric ZrN x < 1 phase [8]. Similar conclusions can also be made from the work of Abadias et al on quaternary TiZrAl x N y films [47]. However, the resistance to oxidation during air annealing of MeN x phase is also determined by its ability for crystallization of metal oxide (MeO x ) phases and the type of MeO x formed (dense solid vs. volatile oxides or passivating oxides) that impact coating morphology [4,9].…”

Section: Discussion On the Comparative Oxidation Resistance Of Men/sisupporting

confidence: 76%

Structural Properties and Oxidation Resistance of ZrN/SiNx, CrN/SiNx and AlN/SiNx Multilayered Films Deposited by Magnetron Sputtering Technique

et al. 2020

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In the present work, the structure, stress state and phase composition of MeN/SiNx (Me = Zr, Cr, Al) multilayered films with the thickness of elementary layers in nanoscale range, as well as their stability to high temperature oxidation, were studied. Monolithic (reference) and multilayered films were deposited on Si substrates at the temperatures of 300 °C (ZrN/SiNx and AlN/SiNx systems) or 450 °C (CrN/SiNx) by reactive magnetron sputtering. The thickness ratios of MeN to SiNx were 5 nm/2 nm, 5 nm/5 nm, 5 nm/10 nm and 2 nm/5 nm. Transmission electron microscopy (TEM), X-ray Reflectivity (XRR) and X-ray Diffraction (XRD) testified to the uniform alternation of MeN and SiNx layers with sharp interlayer boundaries. It was observed that MeN sublayers have a nanocrystalline structure with (001) preferred orientation at 5 nm, but are X-ray amorphous at 2 nm, while SiNx sublayers are always X-ray amorphous. The stability of the coatings to oxidation was investigated by in situ XRD analysis (at the temperature range of 400–950 °C) along with the methods of wavelength-dispersive X-ray spectroscopy (WDS) and scanning electron microscopy (SEM) after air annealing procedure. Reference ZrN and CrN films started to oxidize at the temperatures of 550 and 700 °C, respectively, while the AlN reference film was thermally stable up to 950 °C. Compared to reference monolithic films, MeN/SiNx multilayers have an improved oxidation resistance (onset of oxidation is shifted by more than 200 °C), and the performance is enhanced with increasing fraction of SiNx layer thickness. Overall, CrN/SiNx and AlN/SiNx multilayered films are characterized by noticeably higher resistance to oxidation as compared to ZrN/SiNx multilayers, the best performance being obtained for CrN/SiNx and AlN/SiNx with 5 nm/5 nm and 5 nm/10 nm periods, which remain stable at least up to 950 °C.

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Section: Discussion On the Comparative Oxidation Resistance Of Men/sisupporting

confidence: 76%

Structural Properties and Oxidation Resistance of ZrN/SiNx, CrN/SiNx and AlN/SiNx Multilayered Films Deposited by Magnetron Sputtering Technique

et al. 2020

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“…8 In our previous works [9][10][11] we demonstrated that the addition of Cr into the solution leads to a formation of intermediate metastable phases of (TiCr)N and (CrAl)N where Cr dissolved in the AlN delays the onset of a detrimental cubic-to-wurtzite phase transition to higher temperatures, up to above 1000 • C. Another alloy that have shown interesting high temperature properties is (ZrAl)N. [12][13][14][15][16][17][18] Also, alloying (TiAl)N with Zr have been shown to give improved high temperature properties. [19][20][21][22] However, due to a very strong tendency towards phase separation between ZrN and AlN a process similar to what was seen in (TiCrAl)N is unlikely to play a major role in this system, instead some other decomposition trends should be expected. Chen et al 19 showed that alloying Zr into bulk (TiAl)N promoted the cubic phases and retarded formation of the detrimental wurtzite AlN phases.…”

Section: Introductionmentioning

confidence: 79%

High temperature phase decomposition in TixZryAlzN

et al. 2014

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Through a combination of theoretical and experimental observations we study the high temperature decomposition behavior of c-(TixZryAlzN) alloys. We show that for most concentrations the high formation energy of (ZrAl)N causes a strong tendency for spinodal decomposition between ZrN and AlN while other decompositions tendencies are suppressed. In addition we observe that entropic effects due to configurational disorder favor a formation of a stable Zr-rich (TiZr)N phase with increasing temperature. Our calculations also predict that at high temperatures a Zr rich (TiZrAl)N disordered phase should become more resistant against the spinodal decomposition despite its high and positive formation energy due to the specific topology of the free energy surface at the relevant concentrations. Our experimental observations confirm this prediction by showing strong tendency towards decomposition in a Zr-poor sample while a Zr-rich alloy shows a greatly reduced decomposition rate, which is mostly attributable to binodal decomposition processes. This result highlights the importance of considering the second derivative of the free energy, in addition to its absolute value in predicting decomposition trends of thermodynamically unstable alloys.

On the day of the defence date the status of this article was Manuscript.

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“…[4][5][6] The subsequent transformation of c-AlN to wurtzite (w)-AlN results in a loss of coherency between the binary phases and a concomitant decrease in hardness. 2,3 Recent efforts at improving the thermal stability of these coatings have focused on ways to stabilize the cubic MeAlN phase, for example, alloying [7][8][9][10][11][12] or multilayer structures. 3,13,14 ZrAlN, a related MeAlN, also exhibits good high temperature properties [15][16][17][18][19][20][21][22][23] and, under specific circumstances, high toughness due to a stress-induced phase transformation.…”

mentioning

confidence: 99%

Thermal stability of wurtzite Zr1−xAlxN coatings studied by in situ high-energy x-ray diffraction during annealing

Rogström

Ghafoor

Schroeder

et al. 2015

Journal of Applied Physics

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We study the thermal stability of wurtzite (w) structure ZrAlN coatings by a combination of in situ high-energy x-ray scattering techniques during annealing and electron microscopy. Wurtzite structure Zr 1Àx Al x N coatings with Al-contents from x ¼ 0.46 to x ¼ 0.71 were grown by cathodic arc evaporation. The stability of the w-ZrAlN phase depends on chemical composition where the higher Al-content coatings are more stable. The wurtzite ZrAlN phase was found to phase separate through spinodal decomposition, resulting in nanoscale compositional modulations, i.e., alternating Al-rich ZrAlN layers and Zr-rich ZrAlN layers, forming within the hexagonal lattice. The period of the compositional modulations varies between 1.7 and 2.5 nm and depends on the chemical composition of the coating where smaller periods form in the more unstable, high Zr-content coatings. In addition, Zr leaves the w-ZrAlN lattice to form cubic ZrN precipitates in the column boundaries.

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Thermal stability and oxidation behavior of quaternary TiZrAlN magnetron sputtered thin films: Influence of the pristine microstructure

Cited by 34 publications

References 56 publications

Structural Properties and Oxidation Resistance of ZrN/SiNx, CrN/SiNx and AlN/SiNx Multilayered Films Deposited by Magnetron Sputtering Technique

Structural Properties and Oxidation Resistance of ZrN/SiNx, CrN/SiNx and AlN/SiNx Multilayered Films Deposited by Magnetron Sputtering Technique

High temperature phase decomposition in TixZryAlzN

Thermal stability of wurtzite Zr1−xAlxN coatings studied by in situ high-energy x-ray diffraction during annealing

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