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The pulse length dependence of a reactive high power impulse magnetron sputtering (HiP-IMS) with a tungsten cathode in an argon+oxygen gas mixture gas was investigated. The HiPIMS discharge is operated with a variable pulse length of 20–500 µs. Discharge current, optical emission spectroscopy of neutral Ar, O, and W lines, and energy-resolved ion mass spectrometry are employed. A pronounced dependence of the discharge current on pulse length is noted while the initial discharge voltage is maintained constant. Energy-resolved mass spectrometry shows that the oxygen-to-tungsten (O+/W+) and the tungsten oxide-to-tungsten (WO+/W+) ion ratio decreases with pulse length due to target cleaning. Simulation results employing the SDTrimSP prrogram show the formation of a non-stoichiometric subsurface layer of oxygen which depends on the impingig ion composition and thus on the pulse length.

Abstract A hollow cathode discharge with a Ti cathode and a positively biased ring anode was operated in Ar + N$$_2$$ 2 or Ar + O$$_2$$ 2 gas mixtures. The energy distribution of plasma ions is investigated with the help of energy-resolved mass spectrometry. Singly and doubly charged Ar$$^+$$ + and Ar$$^{2+}$$ 2 + ions and molecular N$$_2^+$$ 2 + or O$$_2^+$$ 2 + ions are the most abundant ionic species. The kinetic energy of all plasma ions is enhanced by a positive anode voltage. Graphical abstract

The pyrite iron disulfide thin films are regarded as suitable candidates for construction of low-cost photoelectrochemical (PEC) solar cells. Iron oxide hematite has attracted much attention as possibly convenient material for hydrogen production via PEC water splitting. We refer on preparation of pyrite thin films via thermal sulfidation of hematite films synthetized by a physical methodology of high power impulse magnetron sputtering (HiPIMS) and purely chemical approach of sol-gel. We studied for the first time the correlation between PEC functionality of hematite films and after their sulfidation into pyrite. The highest PEC activity of hematite films of 560 μA cm−2 at 700 mV vs. Ag/AgCl was achieved with the HiPIMS photoelectrodes. The photoefficiency dropped dramatically to 4 μA cm−2 at 600 mV vs. Ag/AgCl after the sulfidation. A significant increase of grains‘ size, residual unreacted hematite, surface defects were the main reasons for the poor photoactivity. The sol-gel produced hematite yielded photocurrent of 30 μA cm−2 and a slight increase to 40 μA cm−2 (recorded at 500 mV vs. Ag/AgCl) of the corresponding pyrite version. Both these electrodes showed also similar morphological characteristics. The structural, electronic and optical properties of the deposited films were determined using various methods e.g. Raman spectroscopy, SEM, and PDS.

The paper reports controlled deposition of optically transparent and electrically conductive ITO films prepared by a combination of rf (13.56 MHz) and High Power Impulse Magnetron Sputtering (HiPIMS) systems without any post deposition thermal treatment/annealing. It is shown that (i) reactive admixture of N2 gas to the process and (ii) pressure in the deposition chamber enable to optimize optical properties of ITO films. Furthermore, the changes of electrical resistivity were observed, too. The variation of these ITO properties is attributed to change of crystalline structure measured by XRD methods.

Titanium dioxide in the form of one-dimensional (1D) nanostructure arrays represent widely studied morphological arrangement for light harvesting and charge transfer applications such as photocatalysis and photoelectrochemistry (PEC). Here we report a comparative structural and PEC study of variously grown 1D TiO2 nanostructures including i) nanorod arrays prepared by a hydrothermal method (TNR), ii) nanotube arrays fabricated by a two-step hydrothermal method using a ZnO nanorod array film as a template (THNT) and finally iii) nanotubes grown by self-organized electrochemical anodization of Ti films deposited on the FTO substrate (TNT). These nanostructures are assumed to be utilized as photoanodes in PEC water splitting devices. Field-emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), TEM images and UV–vis absorption spectra were used to characterize TiO2 nanostructures. The SEM and TEM morphology images revealed that the main difference among the nanostructures grown on the FTO are the shape and diameter of the individual nanotubes/nanorods and also the array’s density in the range of TNR > THNT > TNT and the degree of organization in the range of TNT > TNR > THNT. The obtained photocurrents at 0 V vs. Ag/AgCl increased in the order of THNT (110 μA cm−2)

A reactive high-power impulse magnetron sputtering (r-HiPIMS) and a reactive high-power impulse magnetron sputtering combined with electron cyclotron wave resonance plasma source (r-HiPIMS + ECWR) were used for the deposition of p-type CuFexOy thin films on glass with SnO2F conductive layer (FTO). The aim of this work was to deposit CuFexOy films with different atomic ratio of Cu and Fe atoms contained in the films by these two reactive sputtering methods and find deposition conditions that lead to growth of films with maximum amount of delafossite phase CuFeO2. Deposited copper iron oxide films were subjected to photoelectrochemical measurement in cathodic region in order to test the possibility of application of these films as photocathodes in solar hydrogen production. The time stability of the deposited films during photoelectrochemical measurement was evaluated. In the system r-HiPIMS + ECWR, an additional plasma source based on special modification of inductively coupled plasma, which works with an electron cyclotron wave resonance ECWR, was used for further enhancement of plasma density ne and electron temperature Te at the substrate during the reactive sputtering deposition process. A radio frequency (RF) planar probe was used for the determination of time evolution of ion flux density iionflux at the position of the substrate during the discharge pulses. Special modification of this probe to fast sweep the probe system made it possible to determine the time evolution of the tail electron temperature Te at energies around floating potential Vfl and the time evolution of ion concentration ni. This plasma diagnostics was done at particular deposition conditions in pure r-HiPIMS plasma and in r-HiPIMS with additional ECWR plasma. Generally, it was found that the obtained ion flux density iionflux and the tail electron temperature Te were systematically higher in case of r-HiPIMS + ECWR plasma than in pure r-HiPIMS during the active part of discharge pulses. Furthermore, in case of hybrid discharge plasma excitation, r-HiPIMS + ECWR plasma has also constant plasma density all the time between active discharge pulses ni &asymp, 7 &times, 1016 m&minus, 3 and electron temperature Te &asymp, 4 eV, on the contrary in pure r-HiPIMS ni and Te were negligible during the &ldquo, OFF&rdquo, time between active discharge pulses. CuFexOy thin films with different atomic ration of Cu/Fe were deposited at different conditions and various crystal structures were achieved after annealing in air, in argon and in vacuum. Photocurrents in cathodic region for different achieved crystal structures were observed by chopped light linear voltammetry and material stability by chronoamperometry under simulated solar light and X-ray diffraction (XRD). Optimization of depositions conditions results in the desired Cu/Fe ratio in deposited films. Optimized r-HiPIMS and r-HiPIMS + ECWR plasma deposition at 500 &deg, C together with post deposition heat treatment at 650 &deg, C in vacuum is essential for the formation of stable and photoactive CuFeO2 phase.

We explored the effect of magnetic field strength | B | and geometry (degree of balancing) on the deposition rate and ionized flux fraction F flux in dc magnetron sputtering (dcMS) and high power impulse magnetron sputtering (HiPIMS) when depositing titanium. The HiPIMS discharge was run in two different operating modes. The first one we refer to as &ldquo, fixed voltage mode&rdquo, where the cathode voltage was kept fixed at 625 V while the pulse repetition frequency was varied to achieve the desired time average power (300 W). The second mode we refer to as &ldquo, fixed peak current mode&rdquo, and was carried out by adjusting the cathode voltage to maintain a fixed peak discharge current and by varying the frequency to achieve the same average power. Our results show that the dcMS deposition rate was weakly sensitive to variations in the magnetic field while the deposition rate during HiPIMS operated in fixed voltage mode changed from 30% to 90% of the dcMS deposition rate as | B | decreased. In contrast, when operating the HiPIMS discharge in fixed peak current mode, the deposition rate increased only slightly with decreasing | B | . In fixed voltage mode, for weaker | B | , the higher was the deposition rate, the lower was the F flux . In the fixed peak current mode, both deposition rate and F flux increased with decreasing | B | . Deposition rate uniformity measurements illustrated that the dcMS deposition uniformity was rather insensitive to changes in | B | while both HiPIMS operating modes were highly sensitive. The HiPIMS deposition rate uniformity could be 10% lower or up to 10% higher than the dcMS deposition rate uniformity depending on | B | and in particular the magnetic field topology. We related the measured quantities, the deposition rate and ionized flux fraction, to the ionization probability &alpha, t and the back attraction probability of the sputtered species &beta, t . We showed that the fraction of the ions of the sputtered material that escape back attraction increased by 30% when | B | was reduced during operation in fixed peak current mode while the ionization probability of the sputtered species increased with increasing | B | , due to increased discharge current, when operating in fixed voltage mode.

A magnetron sputtering discharge with a positively biased anode in argon gas is investigated by Langmuir probe diagnostics and by energy-resolved mass spectrometry. The discharge is operated in continuous (direct current) and in pulsed (high power impulse magnetron sputtering, Hi) mode with a Ti target and in Ar gas. Singly-charged Ar +, Ti +, and Ar 2 + and doubly-charged Ar 2 + and Ti 2 + ions are observed. A novel approach is to bias the magnetron anode. Application of a positive anode voltage shifts the kinetic energies of plasma ions by q e 0 V a, where V a is the anode voltage and q e 0 is the ion charge. It allows for an effective control of plasma ion energies.

The performance of a positively biased external ring anode in combination with a hollow cathode (HC) discharge or a magnetron sputtering (MS) discharge, both with a Ti cathode and with Ar as working gas, is investigated. Plasma and floating potential increase as function of anode voltage. Energy-resolved mass spectrometry reveals that the kinetic energy of argon and titanium ions is enhanced by a positive anode voltage allowing for an effective energy control of plasma ions.

Solar driven photoelectrochemical water splitting (PEC-WS) using semiconductor photoelectrodes represents a promising approach for a sustainable and environmentally friendly production of renewable energy vectors and fuel sources, such as dihydrogen (H2). In this context, titanium dioxide (TiO$_2$) and iron oxide (hematite, $\alpha$-Fe$_2$O$_3$) are among the most investigated candidates as photoanode materials, mainly owing to their resistance to photocorrosion, non-toxicity, natural abundance, and low production cost. Major drawbacks are, however, an inherently low electrical conductivity and a limited hole diffusion length that significantly affect the performance of TiO$_2$ and $\alpha$-Fe$_2$O$_3$ in PEC devices. To this regard, one-dimensional (1D) nanostructuring is typically applied as it provides several superior features such as a significant enlargement of the material surface area, extended contact between the semiconductor and the electrolyte and, most remarkably, preferential electrical transport that overall suppress charge carrier recombination and improve TiO$_2$ and $\alpha$-Fe$_2$O$_3$ photo-electrocatalytic properties. The present review describes various synthetic methods, properties and PEC applications of 1D-photoanodes (nanotubes, nanorods, nanofibers, nanowires) based on titania, hematite, and on $\alpha$-Fe$_2$O$_3$/TiO$_2$ heterostructures. Various routes towards modification and enhancement of PEC activity of 1D photoanodes are also discussed including doping, decoration with co-catalysts and heterojunction engineering. Finally, the challenges related to the optimization of charge transfer kinetics in both oxides are highlighted.

TiO 2 nanotube (TNT) arrays directly grown on a transparent conductive support such as e.g. a layer of fluorine doped tin oxide (FTO) are highly desirable for solar energy application including dye-sensitized solar cells (DSSC) and photoelectrochemical water splitting (PEC-WS). In this paper we report on the fabrication of fully transparent TNT arrays formed by complete self-organizing electrochemical anodization of metallic Ti thin layers deposited on the FTO glass substrate by using electron beam evaporation and/or magnetron sputtering. It is clearly shown for the first time that the quality of the deposited titanium film (e.g. amount and size of pinholes) governs its adherence to the substrate and subsequently the anodization process itself. Mechanical properties of the deposited Ti films were investigated by tribology experiments. The main difference between the sputtered and evaporated titanium layers are the lower film density and considerably higher amount of pinholes of the latter. The grown TNT films were further characterized by SEM, X-ray diffraction, and UV–Vis spectroscopy. The sputtered layers overperformed the evaporated layers by 20% when applied for DSSC. An even greater difference was observed in the case of aqueous electrolyte based PEC-WS, where the sputtered layers showed five times higher activity.

Bipolar high power impulse magnetron sputtering (HiPIMS) with a yttrium target is investigated with the help of time-resolved diagnostics. The bipolar HiPIMS discharge is operated with a negative pulse with a width of 100 μ s, which is immediately followed by a positive pulse (pulse voltage up to +60 V) with a duration of ∼ 310 μ s. The time-resolved floating potential first rises to a large positive voltage of ∼ 55 V at the beginning of the positive pulse (+60 V) and after 30 μ s drops to ∼ 38 V. It indicates the ignition of a reversed discharge. Further evidence of such a reversed discharge is confirmed by time-resolved mass spectrometry and time-resolved optical emission spectroscopy.

The sideways (radial) deposition rate and ionized flux fraction in a high power impulse magnetron sputtering (HiPIMS) discharge are studied and compared to a dc magnetron sputtering (dcMS) discharge, while the magnetic field strength | B | and degree of balancing are varied. A significant deposition of the film forming material perpendicular to the target surface is observed for both sputter techniques. This sideways deposition decreases with increasing axial distance from the target surface. The sideways deposition rate is always the highest in dc operation, while it is lower for HiPIMS operation. The magnetic field strength has a strong influence on the sideways deposition rate in HiPIMS but not in dcMS. Furthermore, in HiPIMS operation, the radial ion deposition rate is always at least as large as the axial ion deposition rate and often around two times higher. Thus, there are a significantly higher number of ions traveling radially in the HiPIMS discharge. A comparison of the total radial as well as axial fluxes across the entire investigated plasma volume between the target and the substrate position allows for revised estimates of radial over axial flux fractions for different magnetic field configurations. It is here found that the relative radial flux of the film forming material is greater in dcMS compared to HiPIMS for almost all cases investigated. It is therefore concluded that the commonly reported reduction of the (axial) deposition rate in HiPIMS compared to dcMS does not seem to be linked with an increase in sideways material transport in HiPIMS.

Metal nanoparticles embedded into a semiconductive matrix represent a promising material for widely sought advanced technological applications. We focused our interest on the preparation of TiO2 matrix with embedded Cu nanoparticles. In particular, we studied the effect of reactive discharge (Ar/O2) exposition on copper oxidation, which can result in two stable forms: cuprous oxide (Cu2O) and cupric oxide (CuO). Copper nanoparticles, of size in range 10–50 nm, were produced by magnetron sputtering in combination with gas aggregation. The beam of Cu nanoparticles was impinging onto a silicon substrate which was directly exposed to a reactive Ar/O2 magnetron discharge providing sputtering of Ti target at the same time. The properties of deposited nanocomposite Cu(xO)–TiO2 were investigated by X-ray photoelectron spectroscopy, grazing incidence X-ray diffractometry, X-ray reflectometry and scanning electron microscopy techniques to reveal the nanocomposite properties and to understand the oxidation process of embedded Cu nanoparticles. It was found that CuO is preferentially formed if copper is exposed to active oxygen species (O+, O−, O⁎ etc.) produced in the reactive magnetron discharge. On the other hand, Cu2O was observed in the case of copper reaction in ambient Ar/O2 atmosphere. As a result, two possible copper oxidation mechanisms are proposed, employing chemical kinetics.

Hematite, α-Fe2O3, is considered as one of the most promising materials for sustainable hydrogen production via photoelectrochemical water splitting with a theoretical solar-to-hydrogen efficiency of 17%. However, the poor electrical conductivity of hematite is a substantial limitation reducing its efficiency in real experimental conditions. Despite of computing models suggesting that the electrical conductivity is extremely anisotropic, revealing up to 4 orders of magnitude higher electron transport with conduction along the (110) hematite crystal plane, synthetic approaches allowing the sole growth in that direction have not been reported yet. Here, we present a strategy for controlling the crystal orientation of very thin hematite films by adjusting energy of ion flux during advanced pulsed reactive magnetron sputtering technique. The texture and effect of the deposition mode on the film properties were monitored by XRD, conversion electron Mössbauer spectroscopy, XPS, SEM, AFM, PEC water splitting, IPCE, transient photocurrent measurements, and Mott-Schottky analysis. The precise control of the synthetic conditions allowed to fabricate hematite photoanodes exhibiting fully textured structures along (110) and (104) crystal planes with huge differences in photocurrents of 0.65 and 0.02 mA cm(-2) (both at 1.55 V versus RHE), respectively. The photocurrent registered for fully textured (110) film is among record values reported for thin planar films. Moreover, the developed fine-tuning of crystal orientation having a huge impact on the photoefficiency would induce further improvement of thin hematite films mainly if cation doping will be combined with the controllable texture.

Transfer of semiconductor thin films on transparent and or flexible substrates is a highly desirable process to enable photonic, catalytic, and sensing technologies. A promising approach to fabricate nanostructured TiO2 films on transparent substrates is self-ordering by anodizing of thin metal films on fluorine-doped tin oxide (FTO). Here, we report pulsed direct current (DC) magnetron sputtering for the deposition of titanium thin films on conductive glass substrates at temperatures ranging from room temperature to 450 °C. We describe in detail the influence that deposition temperature has on mechanical, adhesion and microstructural properties of titanium film, as well as on the corresponding TiO2 nanotube array obtained after anodization and annealing. Finally, we measure the photoelectrochemical water splitting activity of different TiO2 nanotube samples showing that the film deposited at 150 °C has much higher activity correlating well with the lower crystallite size and the higher degree of self-organization observed in comparison with the nanotubes obtained at different temperatures. Importantly, the film showing higher water splitting activity does not have the best adhesion on glass substrate, highlighting an important trade-off for future optimization.

Titanium oxide (TiO2) and iron oxide (α-Fe2O3) hematite films have potential applications as photoanodes in electrochemical water splitting. In the present work TiO2 and α-Fe2O3 thin films were prepared by two methods, e.g., sol-gel and High Power Impulse Magnetron Sputtering (HiPIMS) and judged on the basis of physical properties such as crystalline structure and surface topography and functional properties such as simulated photoelectrochemical (PEC) water splitting conditions. It was revealed that the HiPIMS method already provides crystalline structures of anatase TiO2 and hematite Fe2O3 during the deposition, whereas to finalize the sol-gel route the as-deposited films must always be annealed to obtain the crystalline phase. Regarding the PEC activity, both TiO2 films show similar photocurrent density, but only when illuminated by UV light. A different situation was observed for hematite films where plasmatic films showed a tenfold enhancement of the stable photocurrent density over the sol-gel hematite films for both UV and visible irradiation. The superior properties of plasmatic films could be explained by ability to address some of the hematite drawbacks by the deposition of very thin films (25 nm) consisting of small densely packed particles and by doping with Sn.

Solar driven photoelectrochemical water splitting (PEC-WS) using semiconductor photoelectrodes represents a promising approach for a sustainable and environmentally friendly production of renewable energy vectors and fuel sources, such as dihydrogen (H

High power impulse magnetron sputtering (HiPIMS) of a cobalt cathode in argon gas was investigated by time-resolved electrical (Langmuir) probe diagnostics and by time-integrated energy-resolved mass spectrometry. The HiPIMS discharge was operated with a bipolar pulsed power supply, providing a large negative voltage with a typical pulse width of 100 μs followed by a long positive pulse with a pulse width of about 310 μs. The time-resolved Langmuir probe results yield a small negative plasma potential in the negative pulse regime and a large positive floating potential and plasma potential in the positive pulse regime. The electron density is significantly reduced during the positive pulse regime. The probe results are supported by ion energy measurements.

Carbon nanostructures were deposited by surface wave discharge using various Ar/CH4/ CO2 gas mixture ratios. The morphology was controlled by adjusting of gas concentration and was investigated by scanning electron microscopy (SEM). Also, the influence of the low temperature plasma treatment and process time on the wettability of the diamond films has been studied. The results indicate that for hydrogen termination of diamond surface indicate that the temperature as low as 400°C and treatment time of 15 min is sufficient to attain the p-type surface conductivity of diamond.

Reactive high power impulse magnetron sputtering (HiPIMS) of a cobalt cathode in pure argon gas and with different oxygen admixtures was investigated by time-resolved optical emission spectroscopy (OES) and time-integrated energy-resolved mass spectrometry. The HiPIMS discharge was operated with a bipolar pulsed power supply capable of providing a large negative voltage with a typical pulse width of 100 μs followed by a long positive pulse with a pulse width of about 350 μs. The HiPIMS plasma in pure argon is dominated by Co+ ions. With the addition of oxygen, O+ ions become the second most prominent positive ion species. OES reveals the presence of Ar I, Co I, O I, and Ar II emission lines. The transition from an Ar+ to a Co+ ion sputtering discharge is inferred from time-resolved OES. The enhanced intensity of excited Ar+* ions is explained by simultaneous excitation and ionisation induced by energetic secondary electrons from the cathode. The intensity of violet Ar I lines is drastically reduced during HiPIMS. Intensity of near-infrared Ar I lines resumes during the positive pulse indicating an additional heating mechanism.

Growth of Cu nanoparticles in a pulsed gas aggregation cluster source was studied. The cluster growth is enhanced by an energy transport inside the aggregation chamber fed by argon that is delivered in short pulses repeated with low frequency. The effect of pressure, varied during the pulse, on the cluster growth was estimated from time-resolved measurements of mass/size cluster distribution. The cluster mass and the cluster production well correlate with pressure changes. Several stages of cluster growth during the gas-pulse were recognized. Not only larger clusters but also significantly enhanced particle and mass fluxes were observed.

Formation of Ti–Cu thin films with regard to controlling the copper release is reported in the paper. Copper released from films can inhibit bacterial colonization and can be utilized as an implant surface modification. The copper release has to be controlled (i) to repress the bacteria growth and (ii) to balance the Cu level tolerated by osteoblasts cells. The dual-high power impulse magnetron sputtering superimposed with mid-frequency discharge was employed for ionized vapor deposition of Ti–Cu films. It was found that the microscopical architecture of films is strongly influenced by the pressure during the deposition process. There is an indication that these structural changes are caused by the energy of deposited species (ion distribution functions were measured by time-resolved retarding field analyzer). Grain-like structure with large Cu crystals is formed at higher pressures, i.e. at low ion energies. The grain-like microstructure increases an effective film area which encourages the copper release. It is demonstrated that controlled copper release can be achieved by appropriate setting of the input experimental parameters (pressure, mean discharge current).

The effect of energetic ion bombardment on TiO 2 crystallographic phase formation was studied. Films were deposited using high-power impulse magnetron sputtering (HiPIMS) assisted by an electron cyclotron wave resonance (ECWR) plasma. The ECWR assistance allows a significant reduction of pressure down to 0.075 Pa during reactive HiPIMS deposition and subsequently enables control of the energy of the deposited species over a wide range. Films deposited at high ion energies and deposition rates form rutile with (101) a preferred orientation. With decreasing ion energy and deposition rates, rutile is formed with random crystallite orientation, and finally at low ion energies the anatase phase occurs. It is supposed that particles gain high energy during the HiPIMS pulse while the ECWR discharge is mostly responsible for substrate heating due to dissipated power. However, the energetic contribution of the ECWR discharge is not sufficient for annealing and phase transformation.

The paper focuses on time-resolved diagnostics of unipolar hybrid-dual-High Power Impulse Magnetron Sputtering (hybrid-dual-HiPIMS) discharges. The newly developed sputtering system is based on a combination of dual-HiPIMS with a mid-frequency (MF) discharge. The most important feature of hybrid-dual-HiPIMS systems is the MF pre-ionization which causes/allows: (i) a significant reduction of working pressure by more than one order of magnitude, and (ii) faster ignition and development of HiPIMS pulses. Parameters such as mean electron energy, electron density and electron energy probability function (EEPF) were obtained from time-resolved Langmuir probe diagnostics to demonstrate the aforementioned effects. Calorimetric probe diagnostics were used for determination of the total power density flux. Power flux contributions of particular species, e.g. ions, electrons and neutrals, were estimated as well.

The present paper is focused on time-resolved diagnostics of the simultaneous combination of dual mid-frequency and dual-high power impulse magnetron sputtering discharges (so-called hybrid-dual-HiPIMS systems). Combined systems are operated with the following parameters – dual-high power impulse magnetron sputtering ( f H = 100 Hz, duty cycle 1%) and dual mid-frequency discharge ( f M = 94 kHz, duty cycle 30%) – running simultaneously with two magnetron guns. The magnetrons in dual configuration are electrically confined, i.e. electrodes are alternately operated as an anode–cathode (and vice versa) during the sputtering. The dual MF discharge causes a pre-ionization effect which is an important feature because of: (i) a significant reduction of the working pressure by more than one order of magnitude, (ii) an increase of electron and ion energy, and (iii) an increase of the deposition rate. It was found that the ion velocity distribution function (IVDF) during HiPIMS pulses reaches a maximum of about 15–20 eV whereby the dual MF discharge reaches about 0.5–1.5 eV. The time-resolved IVDF measurements revealed that ions with high energy generated at the cathode arrive at the substrate position about 25–30 μs after the HiPIMS pulse ignition. The effect of the hybrid system is illustrated on the deposition of Ti–Cu films. The crystallographic phase and properties of the deposited films are strongly influenced by the energy of incoming particles and by reduced pressure in the chamber.

This work aims at the utilization of nanostructured surfaces for advanced mass spectrometry [laser desorption/ionization mass spectrometry (LDI MS)]. The authors demonstrate that prepared nanostructures enable independent mass-to-charge calibration and also effectively substitute protonation agent for low-mass molecules instead of conventionally used matrices. Silver nanostructured surfaces were formed as homogeneous thin film, isolated nanoislands, and spherical nanoparticles. Besides the surface characterization, the paper focuses on the impact of LDI MS laser, irradiating the nanostructured surfaces, which results in the production of charged Ag clusters. Irradiated nanoparticle-based surfaces mostly provide single ionized species Ag+ while positive (Agn+, n ≤ 5) and negative ions (Agn−, n ≤ 7) were observed from the nanoislands film. It is shown that the ratio between particular ion line intensities can be tailored by the deposition time. The pattern of silver ions Agn (due to two natural isotopes) can be used for mass-to-charge calibration up to 1000 m/z. Additionally, the silver protonation improves the identification of small molecules. It is demonstrated on detection of sucrose (342.3 g/mol), fructose (180.2 g/mol), and creatinine (113.1 g/mol) molecules.

Thin films of SiC have been deposited using a hollow cathode sputtering technique. Several methods have been used including DC, RF, and pulsed sputtering. The films reported here have been deposited using DC and pulsed sputtering.

This work analyzes the processing of Pb(Zr,Ti)O3 (PZT) thin films directly on copper-coated polymer films. PZT thin film deposition was performed onto the metallized Kapton® films using a single RF plasma jet. In order to reduce the interaction of PZT and Cu during the initial growth stage, an ultrathin amorphous TiO2-x seeding layer was sputter-deposited prior to PZT deposition. The film texture was a mixture of (111)-oriented perovskite nanocrystals, rutile and pyrochlore. Topography and piezoelectric in-plane and out-of-plane response of the films were evaluated using a commercial AFM adapted for piezoforce measurements. The as-deposited films were self-polarized with polarization pointing at the surface of the sample. Polarization was switchable and a piezoelectric hysteresis was obtained.

Phthalocyanines (Pcs) may act as efficient absorbents of photons in the visible region. These structures upon contact with photons from well-defined regions, specifically between 600 and 700 nm, may produce an excited triple state. Its extinction is accompanied by the formation of highly active singlet oxygen species. Its utilization ranges from sensors to selective medical diagnosis tools. In this work we report on preparation of Al and Zn phthalocyanines thin layers of a constant thickness via a method of vacuum sublimation. The produced films were smooth, homogeneous, resistant and well transparent. The films were examined by means of AFM, SEM, profilometry, ellipsometry, Raman spectroscopy and UV–VIS. Special attention was paid to the crystallinity changes with temperature observable by XRD. Light absorption properties of the Pcs films were compared with those recorded in solution (sulphonated Pcs dissolved in water).

Pulse modulated double hollow cathode RF plasma jet system with two separate independent nozzles made of BaTiO3 (BTO) and SrTiO3 (STO) was used for deposition of BSTO thin films on Si and on multi-layer Si/SiO2/TiO2/Pt substrates. Dielectric properties of BSTO layers strongly depend on ratio composition expressed by parameter x = Ba/(Ba+Sr) and on accuracy in presence of other elements. Space resolved optical emission spectroscopy (OES) was used mainly for monitoring of concentration of particles sputtered from the hollow cathode and for feedback correction of power supplied in both nozzles because applied power was responsible for sputtering speed of Ba and Sr particles. Main attention was focused on relation between ratio of spectral intensity of Ba, Ba+, Sr and Sr+ lines close to substrate and ratio of Ba and Sr concentration in the deposited film. 2D map of emission lines intensity distribution for Ba, Ba+, Sr, Sr+, Ti, Ar, and Ar+ for double hollow cathode plasma jet system with BTO and STO nozzles was created. OES was also used for observing of excess of Ti particles in final layer with negative effect on layer properties and for measurement of rotational temperature of OH radicals. Preliminary results of all these optical measurements are published in this paper. Deposited thin films were analyzed by X-ray diffraction, which confirmed presence of BSTO and STO perovskite phase in the films, by atomic force microscopy (AFM), by electron microprobe and by micro-Raman scattering measurement.

Thin films of SiC were deposited using DC, RF and pulsed sputtering of a hollow cathode. The majority of the films were deposited using RF sputtering at temperatures ranging from 610 to 858 degrees C. Initial films were deposited onto Si substrates in order to determine deposition rates, film uniformity, and film composition. The introduction of a rotating substrate holder greatly improved the film thickness and composition uniformity. The samples were characterized using X-ray diffraction (XRD), Raman spectroscopy, optical absorption, and infrared ellipsometry. The initial films were polycrystalline in nature independent of the substrate used for deposition. The 4H/3C polytype ratio increases strongly for elevated substrate temperatures for the films which were grown homo-epitaxially on 4H SiC. This observation suggests a new avenue for homo-epitaxial growth of SiC onto 4H SiC and rapid hollow cathode sputtering is envisioned for the growth of single crystal films of 4H SiC for future device applications.

Nanostructured Cu:CuCNx composite coatings with high static and dynamic stiffness were synthesized by means of plasma-enhanced chemical vapor deposition (PECVD) combined with high power impulse magnetron sputtering (HiPIMS). Scanning electron microscope (SEM) images and energy-dispersive X-ray spectroscopy (EDS) mapping from cross-sectioned samples reveals a multi-layered nanostructure enriched in Cu, C, N, and O in different ratios. Mechanical properties of the coatings were investigated by Vickers micro-indention and model tests. It was observed that copper inclusions as well as copper interlayers in the CNx matrix can increase mechanical damping by up to 160%. Mechanical properties such as hardness, elastic modulus and loss factor were significantly improved by increasing the discharge power of the sputtering process. Moreover the coatings loss modulus was evaluated on the basis of indentation creep measurements under room temperature. The coating with optimum properties exhibited loss modulus of 2.6 GPa. The composite with the highest damping loss modulus were applied on the clamping region of a milling machining tool to verify their effect in suppressing regenerative tool chatter. The high dynamic stiffness coatings were found to effectively improve the critical stability limit of a milling tool by at least 300%, suggesting a significant increase of the dynamic stiffness. QC 20160209 HiPPOCAMP

Technology aspects and characterization of BaxSr1-xTiO3 (BST) films fabricated with low pressure plasma jet technique are presented. BST films were deposited on silicon coated with Pt/TiO2/SiO2 and on bare Si substrates. The nozzles-type RF hollow cathode has been fabricated from hot pressed BaTiO3, SrTiO3, and BST ceramics. Controlling of RF voltage, RF current and substrate temperature allowed us to deposit reproducible films with controlled grain size. Hysteresis loops, ellipsometric and micro-Raman investigation results are presented and discussed.

The atmospheric plasma > jet system was investigated for deposition of oxide layes on polymet (kapton) thin films on kapton, silicon and quartz glass substrates. As growth precursors for ZnO films, Zn-acetylacetonate vapors were used. Deposited ZnO films on both kapton and quartz glass contained hexagonal crystalline phase. They were optically transparent and had an electrical conductivity σ 10 - 1 -10 0 S.cm - 1 .

Iron oxide films were deposited using high power impulse magnetron sputtering (HiPIMS) of an iron cathode in an argon/oxygen gas mixture at different gas pressures (0.5~Pa, 1.5~Pa, and 5.0~Pa). The HiPIMS system was operated at a repetition frequency $f = 100$~Hz with a duty cycle of 1~\%. A main goal is a comparison of film growth during conventional and electron cyclotron wave resonance-assisted HiPIMS. The deposition plasma was investigated by means of optical emission spectroscopy and energy-resolved mass spectrometry. Active oxygen species were detected and their kinetic energy was found to depend on the gas pressure. Deposited films were characterized by means of spectroscopic ellipsometry and grazing incidence x-ray diffraction. Optical properties and crystallinity of as-deposited films were found to depend on the deposition conditions. Deposition of hematite iron oxide films with the HiPIMS-ECWR discharge is attributed to the enhanced production of reactive oxygen species.

CuIn 1−x Ga x Se 2 (CIGS) thin films with x = 0, 0.28 and 1 were prepared by the sputtering of Cu, In and Ga in HiPIMS (High Power Impulse Magnetron Sputtering) or DC magnetron and subsequently selenized in an Ar+Se atmosphere. Optical emission spectroscopy (OES) was used to monitor differences in HiPIMS and DC plasma during sputtering of metallic precursors. Thin film characteristics were measured using X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, energy-dispersive X-ray spectroscopy (EDX) and other techniques.

High quality hydrogenated amorphous silicon, a-Si:H, thin films were deposited by means of a dc hollow cathode plasma-jet with magnetic field confinement. Single-crystal silicon nozzles were reactively sputtered in a high density hollow cathode discharge. Only nontoxic gases, argon and hydrogen, were used for this purpose. Different configurations of the dc hollow cathode were used for the deposition process. Electronic quality a-Si:H thin films were achieved with light to dark conductivity ratios >106, with light conductivity near 10−5 S/cm and dark conductivity between 10−11 and 10−12 S/cm. This was accomplished with a specific configuration of the hollow cathode discharge in the silicon nozzle. Our best films have a Tauc band gap near 1.8 eV and an atomic hydrogen concentration of about 14%. The growth rate achieved for the electronic quality a-Si:H films was in the range of 2–3 μm/h.

The paper is focused on a study of formation of TiO x N y thin films prepared by pulsed magnetron sputtering of metallic Ti target. Oxygen and nitrogen were delivered into the discharge in the form of reactive gases O2 and N2. The films were deposited by high-power impulse magnetron sputtering working with discharge repetition frequency f = 250 Hz at low (p = 0.75 Pa) and high (p = 10 Pa) pressure. The substrates were on floating potential and thermally stabilized at room temperature during the deposition process. Post-deposition thermal annealing was not employed. The chemical composition from x-ray photoelectron spectroscopy diagnostic reveals formation of TiO x N y structure at low flow rate of oxygen in the discharge gas mixture. This result is confirmed by XRD investigation of N element's incorporation into the Ti–O lattice. Decrease in band-gap to values E g ∼ 1.6 eV in TiO x N y thin film is attributed to formed Ti–N bonds. The discharge properties were investigated by time-resolved optical emission spectroscopy. Time evolution of particular spectral lines (Ar+, Ti+, Ti) is presented together with peak discharge current.

In the present article, the effect of magnetic field design on electron and ion properties in both a metallic Ti/Ar and a reactive Ti/Ar + O2 high power impulse magnetron sputtering (HiPIMS) discharges is investigated. For the purpose, a variable magnetron with defined imbalance and geometrical coefficients K and , respectively, was utilized. The electron density, the mean electron energy, the plasma potential, and the floating potential were determined by employing time-resolved Langmuir probe measurements, for four specified magnetic field configurations. Mass spectroscopy was used in order to determine the energy distribution function of metal (Ti+ , Ti2+) and gaseous (Ar+ , Ar2+ , O+ , O) ions. Analysis of the measured data shows that the magnetic field design dramatically affects the charged particles energy- and spatial-distribution, causing a change in the plasma properties. It is concluded that a well-determined configuration of the magnetic field is necessary in order to insure discharge stability and reproducibility.

The paper is focused on investigation of enhanced metal (Cu) cluster growth in a source of Haberland's type using pulsed gas aggregation. The aggregation Ar gas was delivered into the cluster source in a pulse regime, which results in the formation of well pronounced aggregation pressure peaks. The pressure peaks were varied by varying the different pulse gas frequency at the same mean pressure kept for all experiments. Hence, we were able to study the effect of enhanced aggregation pressure on cluster formation. Time-resolved measurements of cluster mass distribution were performed to estimate the mass and particle flux. The paper demonstrates that pulse gas aggregation influences growth of Cu nanoparticles, i.e., cluster mass/size, mass flux, and particle flux emitted from the cluster source. It was found that cluster mass related quantities are strongly influenced by pulsed gas frequency; the highest value of mass flux appears at the most pronounced pressure peaks. On the other hand, the particle flux depends only slightly on the gas pulse frequency. The explanation based on cooling and thermalization of sputtered particles is discussed in the paper.

The metal ionized flux fraction and production of double charged metal ions Me2+ of different materials (Al, Cu, Fe, Ti) by High Power Impulse Magnetron Sputtering (HiPIMS) operated with and without a pre-ionization assistance is compared in the paper. The Electron Cyclotron Wave Resonance (ECWR) discharge was employed as the pre-ionization agent providing a seed of charge in the idle time of HiPIMS pulses. A modified grid-free biased quartz crystal microbalance was used to estimate the metal ionized flux fraction ξ. The energy-resolved mass spectrometry served as a complementary method to distinguish particular ion contributions to the total ionized flux onto the substrate. The ratio between densities of doubly Me2+ and singly Me+ charged metal ions was determined. It is shown that ECWR assistance enhances Me2+ production with respect of absorbed rf-power. The ECWR discharge also increases the metal ionized flux fraction of about 30% especially in the region of lower pressures. Further, the suppression o...

This paper reports on an investigation of the hybrid pulsed sputtering source based on the combination of electron cyclotron wave resonance (ECWR) inductively coupled plasma and high power impulse magnetron sputtering (HiPIMS) of a Ti target. The plasma source, operated in an Ar atmosphere at a very low pressure of 0.03 Pa, provides plasma where the major fraction of sputtered particles is ionized. It was found that ECWR assistance increases the electron temperature during the HiPIMS pulse. The discharge current and electron density can achieve their stable maximum 10 μs after the onset of the HiPIMS pulse. Further, a high concentration of double charged Ti++ with energies of up to 160 eV was detected. All of these facts were verified experimentally by time-resolved emission spectroscopy, retarding field analyzer measurement, Langmuir probe, and energy-resolved mass spectrometry.

Highly ionized discharge for physical vapor deposition at very low pressure is presented in the paper. The discharge is generated by electron cyclotron wave resonance (ECWR) which assists with ignition of high power impulse magnetron sputtering (HiPIMS) discharge. The magnetron gun (with Ti target) was built into the single-turn coil RF electrode of the ECWR facility. ECWR assistance provides pre-ionization effect which allows significant reduction of pressure during HiPIMS operation down to p = 0.05 Pa; this is nearly more than an order of magnitude lower than at typical pressure ranges of HiPIMS discharges. We can confirm that nearly all sputtered particles are ionized (only Ti+ and Ti++ peaks are observed in the mass scan spectra). This corresponds well with high plasma density ne ∼ 1018 m−3, measured during the HiPIMS pulse.

Time-resolved comparative study of dual magnetron sputtering (dual-MS) and dual high power impulse magnetron sputtering (dual-HiPIMS) systems arranged with closed magnetic field is presented. The dual-MS system was operated with a repetition frequency 4.65 kHz (duty cycle ≈50%). The frequency during dual-HiPIMS is lower as well as its duty cycle (f=100 Hz, duty 1%). Different metallic targets (Ti, Cu) and different cathode voltages were applied to get required stoichiometry of Ti–Cu thin films. The plasma parameters of the interspace between magnetrons in the substrate position were investigated by time-resolved optical emission spectroscopy, Langmuir probe technique, and measurement of ion fluxes to the substrate. It is shown that plasma density as well as ion flux is higher about two orders of magnitude in dual-HiPIMS system. This fact is partially caused by low diffusion of ionized sputtered particles (Ti+,Cu+) which creates a preionized medium.