Abstract.A simple and cost effective approach to stabilize the sputtering process in the transition zone during reactive high-power impulse magnetron sputtering (HiPIMS) is proposed. The method is based on real-time monitoring and control of the discharge current waveforms. To stabilize the process conditions at a given set point, a feedback control system was implemented that automatically regulates the pulse frequency, and thereby the average sputtering power, to maintain a constant maximum discharge current. In the present study, the variation of the pulse current waveforms over a wide range of reactive gas flows and pulse frequencies during a reactive HiPIMS process of Hf-N in an Ar-N 2 atmosphere illustrates that the discharge current waveform is a an excellent indicator of the process conditions. Activating the reactive HiPIMS peak current regulation, stable process conditions were maintained when varying the N 2 flow from 2.1 to 3.5 sccm by an automatic adjustment of the pulse frequency from 600 Hz to 1150 Hz and consequently an increase of the average power from 110 to 270 W. Hf-N films deposited using peak current regulation exhibited a stable stoichiometry, a nearly constant power-normalized deposition rate, and a polycrystalline cubic phase Hf-N with (111)-preferred orientation over the entire reactive gas flow range investigated. The physical reasons for the change in the current pulse waveform for different process conditions are discussed in some detail.

Obtaining single-phase tin monosulfide (SnS) films at low temperatures is challenging since cubic (π-SnS) and orthorhombic (α-SnS) polymorphs have similar energies of formation and grow under similar conditions. Here, we show that in atomic layer deposition (ALD) of polycrystalline SnS using tin­(II) acetylacetonate and H2S precursors, the substrate surface greatly influences the SnS phase evolution. For example, a silicon (100) substrate, with a highly hydroxylated surface, favors the growth of α-SnS. Meanwhile, ozone treatment or preannealing of the same substrate leads to mainly π-SnS. Just a few ALD cycles of another oxide or sulfide can even more substantially alter the outcome. Substrates that favor α-SnS growth typically produce initially enhanced growth rates, while those promoting π-SnS are partially surface-poisoned by the acetylacetonate precursor ligands. Growth of either polymorph is self-sustained after its initiation, and the sustaining factor appears to be the surface–ligand interaction; π-SnS preferentially evolves on substrates and π-SnS surfaces that are rich in highly reactive dangling bonds, while chemically inert substrates and α-SnS surfaces promote α-SnS. While lattice matching is less central, the role of ligand bonding in SnS ALD also helps explain the previously reported phase dependence on growth temperature and H2S precursor dose and shows promise for area-selective ALD of SnS.

Low-temperature epitaxial growth of refractory transition-metal nitride thin films by means of physical vapor deposition has been a recurring theme in advanced thin-film technology for several years. In the present study, 150-nm-thick epitaxial HfN layers are grown on MgO(001) by reactive high-power impulse magnetron sputtering (HiPIMS) with no external substrate heating. Maximum film-growth temperatures T s due to plasma heating range from 70 to 150 °C, corresponding to T s /T m = 0.10-0.12 (in which T m is the HfN melting point in K). During HiPIMS, gas and sputtered metal-ion fluxes incident at the growing film surface are separated in time due to strong gas rarefaction and the transition to a metal-ion-dominated plasma. In the present experiments, a negative bias of 100 V is applied to the substrate, either continuously during the entire deposition or synchronized with the metal-rich portion of the ion flux. Two different sputtering-gas mixtures, Ar/N 2 and Kr/N 2 , are employed in order to probe effects associated with the noble-gas mass and ionization potential. The combination of x-ray diffraction, high-resolution reciprocal-lattice maps, and high-resolution cross-sectional transmission electron microscopy analyses establishes that all HfN films have a cube-on-cube orientational relationship with the substrate, i.e., [001] HfN ||[001] MgO and (100) HfN ||(100) MgO . Layers grown with a continuous substrate bias, in either Ar/N 2 or Kr/N 2 , exhibit a relatively high mosaicity and a high concentration of trapped inert gas. In distinct contrast, layers grown in Kr/N 2 with the substrate bias synchronized to the metal-ion-rich portion of HiPIMS pulses have much lower mosaicity, no measurable inert-gas incorporation, and a hardness of 25.7 GPa, in good agreement with the results for epitaxial HfN(001) layers grown at T s = 650 °C (T s /T m = 0.26). The room-temperature film resistivity is 70 μΩ cm, which is 3.2-10 times lower than reported values for polycrystalline-HfN layers grown at T s = 400 °C.

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We demonstrate that tungsten disulphide (WS2) with thicknesses ranging from monolayer (ML) to several monolayers can be grown on SiO2/Si, Si, and Al2O3 by pulsed direct current-sputtering. The presence of...