Stanislav Mráz

Influence of the negative oxygen ions on the structure evolution of transition metal oxide thin films

The energy distributions of O− ions of magnetron sputtered Nb, Ta, Zr, and Hf in an Ar∕O2 atmosphere were measured as a function of the oxygen partial pressure. Three ion populations were detected in the plasma: high, medium, and low energy ions, with energies corresponding to the target potential, half of the target potential, and <150eV, respectively. The ion energy distribution functions were compared to distributions obtained based on Sigmund’s linear collision cascade sputtering theory. If the surface binding energy is assumed to be equal to the heat of formation, good agreement between the experiment and theory was achieved. From correlating the measured ion energy distributions with previously published phase stability data [Ngaruiya et al., Appl. Phys. Lett. 85, 748 (2004)], it can be deduced that large fluxes of medium and high energy O− ions comparable to the fluxes of the low energy O− ions enable formation of crystalline transition metal oxide thin films during low temperature growth. The pres...

Energy distribution of O- ions during reactive magnetron sputtering

Low, medium, and high energy O− ion populations were experimentally detected during magnetron sputtering of Al in an Ar∕O2 atmosphere. Based on calculations, the authors propose that nonsputtered O− ions originating from the target surface are accelerated in the cathode fall, while sputtered O− ions may be excluded as a significant contribution to the high energy ion population. Furthermore, the formation of medium energy O− ions is consistent with the notion of sputtered, in the cathode fall accelerated, and subsequently dissociated AlO− and AlO2− clusters. These findings may be of importance for understanding plasma energetics and growth involving electronegative species.

Experiment and simulation of the compositional evolution of Ti-B thin films deposited by sputtering of a compound target

The evolution of the coating stoichiometry with pressure, target-substrate distance, and angle was analyzed for dc sputtering of TixB (x=0.5, 1, 1.6) compound targets by elastic recoil detection analysis. For an investigation of the underlying fundamental processes primarily Ar was used as sputter gas. Additionally, the effect of a reactive gas (N2) as well as bias voltage (floating up to −200 V) was briefly cross-checked. For deposition along the target normal (90°) a pronounced Ti-deficiency of up to 20% is detected. Increasing the pressure or distance from 0.5 to 2 Pa and from 5 to 20 cm, respectively, leads to an almost equivalent linear increase in Ti/B ratio surpassing even the target composition. Off-axis depositions at lower angles (30° and 60°) on the other hand result in a higher Ti/B ratio. This is consistent with results obtained from Monte Carlo simulations combining the respective emission characteristics from the sputter process as well as the gas-phase transport. Hence, the pressure, dista...

Structure evolution of magnetron sputtered TiO2 thin films

The structure evolution of TiO2 thin films deposited by rf and dc magnetron sputtering onto nonintentionally heated, floating, glass and Si (100) substrates was investigated. As the total pressure was varied from 0.15 to 4.0 Pa, corresponding to the pressure-distance product values from 10.5 to 280 Pa mm, rutile, anatase, and a mixture thereof were deposited. The pressure-distance induced changes in ion energy were quantified by probing the ion energy distribution functions. The ion energy during synthesis was additionally varied by applying a substrate bias potential ranging from floating to −100 V revealing a similar phase formation characteristic. While the structure evolution of the TiO2 thin films reported in the literature exhibits a rather complex dependence on the process parameters, a simple correlation between the structure evolution and the ratio between the ion energy flux and the deposition flux was identified here. Phase pure anatase films were grown below 540 eV/Ti atom and phase pure rutil...

Venting temperature determines surface chemistry of magnetron sputtered TiN films

Surface properties of refractory ceramic transition metal nitride thin films grown by magnetron sputtering are essential for resistance towards oxidation necessary in all modern applications. Here, typically neglected factors, including exposure to residual process gases following the growth and the venting temperature Tv, each affecting the surface chemistry, are addressed. It is demonstrated for the TiN model materials system that Tv has a substantial effect on the composition and thickness-evolution of the reacted surface layer and should therefore be reported. The phenomena are also shown to have impact on the reliable surface characterization by x-ray photoelectron spectroscopy.

On the phase formation of sputtered hafnium oxide and oxynitride films

Hafnium oxynitride films are deposited from a Hf target employing direct current magnetron sputtering in an Ar-O(2)-N(2) atmosphere. It is shown that the presence of N(2) allows for the stabilizati ...

Charge-state-resolved ion energy distributions of aluminum vacuum arcs in the absence and presence of a magnetic field

The charge-state-resolved ion energy distributions (IEDs) of aluminum vacuum arc plasma species were measured and analyzed for different geometric and magnetic field configurations. The IEDs were fitted by shifted Maxwellian distributions. Plasma expansion in the absence of a magnetic field showed higher ion energies for higher charge states. The introduction of a magnetic field (independent of geometric configuration) resulted in a broader distribution and increased average ion energies. The energy gain was approximately proportional to the charge state, which may be due to the presence of electric fields in the magnetized plasma. The evolution of ion energy distributions is relevant to thin-film growth, and it is shown that the IEDs can be modified by suitable magnetic field configurations.

Influence of argon and oxygen on charge-state-resolved ion energy distributions of filtered aluminum arcs

The charge-state-resolved ion energy distributions (IEDs) in filtered aluminum vacuum arc plasmas were measured and analyzed at different oxygen and argon pressures in the range 0.5 8.0 mTorr. A significant reduction of the ion energy was detected as the pressure was increased, most pronounced in an argon environment and for the higher charge states. The corresponding average charge state decreased from 1.87 to 1.0 with increasing pressure. The IEDs of all metal ions in oxygen were fitted with shifted Maxwellian distributions. The results show that it is possible to obtain a plasma composition with a narrow charge-state distribution as well as a narrow IED. These data may enable tailoring thin-film properties through selecting growth conditions that are characterized by predefined charge state and energy distributions.

Reducing the impurity incorporation from residual gas by ion bombardment during high vacuum magnetron sputtering

The influence of ion energy on the hydrogen incorporation has been investigated for alumina thin films, deposited by reactive magnetron sputtering in an Ar/O2/H2O environment. Ar+ with an average kinetic energy of ~5 eV was determined to be the dominating species in the plasma. The films were analyzed with x-ray diffraction, x-ray photoelectron spectroscopy, and elastic recoil detection analysis, demonstrating evidence for amorphous films with stoichiometric O/Al ratio. As the substrate bias potential was increased from –15 V (floating potential) to –100 V, the hydrogen content decreased by ~70%, from 9.1 to 2.8 at. %. Based on ab initio calculations, these results may be understood by thermodynamic principles, where a supply of energy enables surface diffusion, H2 formation, and desorption [Rosen et al., J. Phys.: Condens. Matter 17, L137 (2005)]. These findings are of importance for the understanding of the correlation between ion energy and film composition and also show a pathway to reduce impurity incorporation during film growth in a high vacuum ambient.

Ab initio study of the effect of Si on the phase stability and electronic structure of γ- and α-Al2O3

Using density functional theory, the effect of Si on the stability and electronic structure of γ- and α-Al2O3 has been investigated. The concentration range from 0 to 5 at.% is probed and the additive is positioned at different substitutional sites in the γ-phase. The calculations for (Al,Si)2O3 predict a trend towards spontaneous decomposition into α-/γ-Al2O3 and SiO2. Therefore, the formation of the metastable γ-(Al,Si)2O3 phase can only be expected during non-equilibrium processing where the decomposition is kinetically hindered. The Si-induced changes in stability of this metastable solid solution may be understood based on the electronic structure. As the Si concentration is increased, stiff silicon-oxygen bonds are formed giving rise to the observed stabilization of the γ-phase.