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Hard Ti1-xAlxN thin films are of importance for metal-cutting applications. The hardness, thermal stability, and oxidation resistance of these coatings can be further enhanced by alloying with TaN. We use a hybrid high-power pulsed and dc magnetron co-sputtering (HIPIMS/DCMS) technique to grow dense and hard Ti0.41Al0.51Ta0.08N alloys without external heating (T-s amp;lt; 150 degrees C). Separate Ti and Al targets operating in the DCMS mode maintain a deposition rate of similar to 50 nm/min, while irradiation of the growing film by heavy Ta+/Ta2+ ions from the HIPIMS-powered Ta target, using dc bias synchronized to the metal-ion-rich part of each HIPIMS pulse, provides effective near-surface atomic mixing resulting in densification. The substrate is maintained at floating potential between the short bias pulses to minimize Ar+ bombardment, which typically leads to high compressive stress. Transmission and scanning electron microscopy analyses reveal dramatic differences in the microstructure of the co-sputtered HIPIMS/DCMS films (Ta-HIPIMS) compared to films with the same composition grown at floating potential with all targets in the DCMS mode (Ta-DCMS). The Ta-DCMS alloy films are only similar to 70% dense due to both inter-and intra-columnar porosity. In contrast, the Ta-HIPIMS layers exhibit no inter-columnar porosity and are essentially fully dense. The mechanical properties of Ta-HIPIMS films are significantly improved with hardness and elastic modulus values of 28.0 and 328 GPa compared to 15.3 and 289 GPa for reference Ta-DCMS films. Published by AIP Publishing., Funding Agencies|Swedish Research Council VR Grant [2013-4018, 2014-5790]; VINN Excellence Center Functional Nanoscale Materials (FunMat); Aforsk Foundation Grant [16-359]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [SFO-Mat-LiU 2009-00971]; Knut and Alice Wallenberg Foundation [2011.0143]

We review results on the growth of metastable Ti1-xAlxN alloy films by hybrid high-power pulsed and dc magnetron co-sputtering (HIPIMS/DCMS) using the time domain to apply substrate bias either in synchronous with the entire HIPIMS pulse or just the metal-rich portion of the pulse in mixed Ar/N-2 discharges. Depending upon which elemental target, Ti or Al, is powered by HIPIMS, distinctly different film-growth kinetic pathways are observed due to charge and mass differences in the metal-ion fluxes incident at the growth surface. Al+ ion irradiation during Al-HIPIMS/Ti-DCMS at 500 degrees C, with a negative substrate bias V-s = 60 V synchronized to the HIPIMS pulse (thus suppressing Ar+ ion irradiation due to DCMS), leads to single-phase NaCl-structure Ti1-xAlxN films (x less than= 0.60) with high hardness (greater than30 GPa with x greater than 0.55) and low stress (0.2-0.8 GPa compressive). Ar+ ion bombardment can be further suppressed in favor of predominantly Al+ ion irradiation by synchronizing the substrate bias to only the metal-ion-rich portion of the Al-HIPIMS pulse. In distinct contrast Ti-HIPIMS/Al-DCMSTi1-xAlxN layers grown with Ti+/Ti2+ metal ion irradiation and the same HIPIMS-synchronized V-s value, are two-phase mixtures, NaCl-structure Ti1-xAlxN plus wurtzite AlN, exhibiting low hardness (similar or equal to 18 GPa) with high compressive stresses, up to -3.5 GPa. In both cases, film properties are controlled by the average metal-ion momentum per deposited atom less thanp(d)greater than transferred to the film surface. During Ti-HIPIMS, the growing film is subjected to an intense flux of doubly-ionized Ti2+, while Al2+ irradiation is insignificant during Al-HIPIMS. This asymmetry is decisive since the critical less thanp(d)greater than limit for precipitation of w-AlN, 135 [eV-amu](1/2), is easily exceeded during Ti-HIPIMS, even with no intentional bias. The high Ti2+ ion flux is primarily due to the second ionization potential (IP2) of Ti being lower, Funding Agencies|European Research Council (ERC) through an Advanced Grant; VINN Excellence Center Functional Nanoscale Materials (FunMat)

A hybrid deposition process consisting of reactive high-power pulsed and dc magnetron cosputtering (HIPIMS and DCMS) from Ti and Al targets is used to grow Ti1-xAlxN alloys, with x similar to 0.6, on Si(001) at 500 degrees C. Two series of films are deposited in which the energy and momentum of metal ions incident at the growing film are individually varied. In both sets of experiments, a negative bias V-s ranging from 20 to 280 V is applied to the substrate in synchronous, as determined by in-situ mass spectrometry, with the metal-ion-rich part of the HIPIMS pulse. Ion momentum is varied by switching the HIPIMS and dc power supplies to change the mass m and average charge of the primary metal ion. Al-HIPIMS/Ti-DCMS layers grown under Al+ (m(Al) = 26.98 amu) bombardment with 20 less than= V-s less than= 160 V are single-phase NaCl-structure alloys, while films deposited with V-s greater than 160 V are two-phase, cubic plus wurtzite. The corresponding critical average metal-ion momentum transfer per deposited atom for phase separation is less than p(d)*greater than greater than= 135 [eV-amu](1/2). In distinct contrast, layers deposited in the Ti-HIPIMS/Al-DCMS configuration with Ti+/Ti2+ (m(Ti) = 47.88 amu) ion irradiation are two-phase even with the lowest bias, V-s = 20 V, for which less than p(d)*greater than greater than 135 [eV-amu](1/2). Precipitation of wurtzite-structure AlN is primarily determined by the average metal-ion momentum transfer to the growing film, rather than by the deposited metal-ion energy. Ti-HIPIMS/Al-DCMS layers grown with V-s= 20 V are two-phase with compressive stress sigma= -2 GPa which increases to -6.2 GPa at V-s= 120 V; hardness H values range from 17.5 to 27 GPa and are directly correlated with sigma. However, for Al-HIPIMS/Ti-DCMS, the relatively low mass and single charge of the Al+ ion permits tuning properties of metastable cubic Ti0.38Al0.62 N by adjusting V-s to vary, for example, the hardness from 12 to 31 GPa while maintaini