The effects of Si addition on the structure and mechanical properties of ZrN thin films deposited by an r.f. reactive sputtering method

Mae, Takehiko; Nosé, M.; Mei, Zhou; Nagae, T.; Shimamura, Kisaburo

doi:10.1016/s0257-8972(01)01187-2

Cited by 68 publications

(31 citation statements)

References 12 publications

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“…Independently of their Ge content, amorphous-like Zr-Ge -N films exhibit a constant hardness of 17.5 T 0.5 GPa. This value is close to that reported for amorphous Zr -Si -N films [12,14,15], indicating that in amorphous-like Zr -X -N films (X = Si or Ge), the hardness seems to be independent of the Si or Ge concentration. On the other hand, crystallised Zr -Ge -N films with Ge concentration lower than about 1 at.% exhibit a hardness higher than 30 GPa.…”

Section: Effect Of the Bias Voltagesupporting

confidence: 88%

Effect of germanium addition on the properties of reactively sputtered ZrN films

et al. 2005

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For the first time, Zr -Ge -N films were deposited on silicon and steel substrates by sputtering a Zr -Ge composite target in reactive Ar -N 2 mixture. The films were characterised by electron probe microanalysis, X-ray diffraction, micro-Raman spectroscopy and depth-sensing indentation. The effects of the Ge content and substrate bias voltage on the films' structure, internal stress, hardness and oxidation resistance were investigated. Substrate bias strongly influenced the chemical composition of the films being observed by means of a steep decrease in the Ge content for negative bias voltages higher than À80 V. In these cases, a significant hardness improvement was registered. For À100 V biased films, in the Ge concentrations range tested in this study, only ZrN grains were evidenced by X-ray diffraction. The film compressive stresses increased with the germanium concentration. An unexpected effect of the Ge content on the films' hardness was observed. In spite of the increase in the compressive stresses of the films with increasing Ge content, the hardness monotonously dropped from 38 GPa for pure ZrN down to 21.5 GPa for 4.6 at.% Ge. Addition of Ge into ZrN-based coatings induced an improvement of the oxidation resistance and it favoured the tetragonal form of zirconia in oxidised Zr -Ge -N coatings. D

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Section: Effect Of the Bias Voltagesupporting

confidence: 88%

Effect of germanium addition on the properties of reactively sputtered ZrN films

et al. 2005

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“…The similar relationship was also observed in the previous report of Zr-Si-N films. 11,12) On the other hand, the Ti-Si-N films containing more than 15%Si shows hardness lower than that of TiN films despite the films consisting of nanocrystallites less than 10 nm. Ti-Si-N films containing about 20%Si indicated low hardness of $20 GPa, which is similar to the results reported by other researchers.…”

Section: Methodsmentioning

confidence: 99%

“…3,4) Recent studies of transition metal nitride films of wear-protective coatings have been aiming to explore multi component systems for improving hardness and/or oxidation resistance. Since Vepřek et al presented a theoretical concept for the super-hard ''nanocomposite'' films and their experimental verification on the Ti-Si-N systems prepared by plasma assisted CVD (PACVD), 5,6) many researchers have extensively studied mechanical properties and/or oxidation resistance of Ti-Si-N coatings [7][8][9][10] and other systems such as ZrSi-N, 11,12) Cr-Ni-N, 13) Ti-Mo-N 13) deposited by PVD. Among the previous studies on Ti-Si-N coatings, some films fabricated by PVD showed super hardness.…”

Section: Introductionmentioning

confidence: 99%

Influence of Target Material on the Microstructure and Properties of Ti–Si–N Coatings Prepared by r.f.-Reactive Sputtering

Nosé¹,

Deguchi

Honbo

et al. 2005

Mater. Trans.

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We examined the effects of sputtering conditions and target materials on the microstructure and mechanical properties of Ti-Si-N coatings prepared by r.f.-reactive sputtering. We used composite targets consisting of a Ti (99.99%) plate and Si 3 N 4 chips as well as the target consisting of a Ti plate and Si chips. Thin films were synthesized by an r.f. sputtering machine in a facing target-type (FTS) on the substrates of high speed steel. During the deposition, the substrate was heated from room temperature up to $300 C and a d.c. bias up to À100 V was applied. Without substrate heating and bias, the hardness of the films increased from 30 GPa for a binary system, reaching a maximum of 37 GPa for a ternary system with a small amount (3-8 at%) of Si. It then decreased to values lower than those of binary systems when Si was more than 10 at%. The hardness of high Si films (containing $20 at%Si) showed a lower value of 20 GPa. The hardness of high Si films deposited from the Ti-Si target increased and reached to a maximum value of 40 GPa around at a bias of À30 V, but the crystallite size of the film increased to $30 nm. On the other hand, the hardness of the films (containing $20 at%Si) deposited from the Ti-Si 3 N 4 target increased with increasing negative bias voltage, being saturated at 38 GPa over À80 V. Although the crystallite size of the films increased gradually with increasing negative bias, it still remained at about 7 nm at À80 V. The characteristics of the latter film could be attributed to the formation of a nano-composite structure defined by Vepřek et al.

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“…They show similar types of structures to nc-TiN/a-Si3N4 yet demonstrate different behaviors in phase segregation [154][155]. While Zr atoms have a similar electronic structure to Ti, they are significantly larger and the lattice parameter of bulk c-ZrN is much larger than that of c-TiN.…”

Section: Zrn-sinmentioning

confidence: 97%

Theoretical understanding of stability of alloys for hard-coating applications and design

Lind¹

2015

Linköping Studies in Science and Technology. Dissertations

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The performance of modern hard coating materials puts high demands on properties such as hardness, thermal stability and oxidation resistance. These properties not only depend on the chemical composition, but also on the structure of the material on a nanoscale. This kind of nanostructuring will change during use and can be both beneficial and detrimental as materials grown under non-equilibrium conditions transforms under heat treatment or pressure into other structures with significantly different properties. This thesis aims to reveal the physics behind the processes of phase stability and transformations and how this can be utilized to improve on the properties of this class of alloys. This has been achieved through the application of various methods of first-principles calculations and analysis of the results on the basis of thermodynamics and electronic structure theory.Within multicomponent transition metal aluminum nitride alloys (TMAlN) a number of studies have been carried out and presented here on ways of improving high temperature stability and hardness. Most (TMAl)N and TMN prefer a cubic B1 structure while AlN is stable in a hexagonal B4 phase, but for the purposes of hard coatings the metastable cubic B1 AlN phase, isostructural with the TMN phase is desired. It will be shown how the introduction of additional alloying components, such as Cr, into (TiAl)N changes the thermodynamic stability of phases so that new intermediary and metastable phases are formed during decomposition. In the case of such a (CrAl)N phase it is shown to have greater thermodynamic stability in the cubic phase than the pure AlN, resulting in improved high temperature hardness. Also, the importance of treating not just the binodal decomposition through the formation energy relative to end products but also the impact of spinodal decomposition from its second derivative due to the topology of formation energy surfaces is emphasized in the thesis. The impact of pressure on the AlN phase has also been studied through the calculation of a P-T diagram of AlN as part of a (TiAl)N alloy.During the study of chemical alloying of TM components into AlN the alloying of low concentrations of these TM were treated in great detail. What is generally referred to as the AlN phase in decomposition is not entirely pure and can be expected to contain traces of any alloying components, such as Ti and Cr or whatever other metals may be present. Low concentration alloying of Cr, on the order of 5-10% is also shown to be stable with regard to isostructural decomposition. Detailed analysis of the effect of Ti and Cr impurities in AlN has been carried out along with a systematic search of AlN alloyed with small amounts of other TM components. The impact of these impurities on the electronic structure and thermodynamic properties is analyzed and the general trends will be explained through the occupation of impurity states by d-like electrons.iv Theoretical treatment of such impurities is not straightforward however. AlN is an s-p semiconduct...

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The effects of Si addition on the structure and mechanical properties of ZrN thin films deposited by an r.f. reactive sputtering method

Cited by 68 publications

References 12 publications

Effect of germanium addition on the properties of reactively sputtered ZrN films

Effect of germanium addition on the properties of reactively sputtered ZrN films

Influence of Target Material on the Microstructure and Properties of Ti–Si–N Coatings Prepared by r.f.-Reactive Sputtering

Theoretical understanding of stability of alloys for hard-coating applications and design

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The effects of Si addition on the structure and mechanical properties of ZrN thin films deposited by an r.f. reactive sputtering method

Cited by 68 publications

References 12 publications

Effect of germanium addition on the properties of reactively sputtered ZrN films

Effect of germanium addition on the properties of reactively sputtered ZrN films

Influence of Target Material on the Microstructure and Properties of Ti&ndash;Si&ndash;N Coatings Prepared by r.f.-Reactive Sputtering

Theoretical understanding of stability of alloys for hard-coating applications and design

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Influence of Target Material on the Microstructure and Properties of Ti–Si–N Coatings Prepared by r.f.-Reactive Sputtering