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Rickard Gunnarsson

Publications and source records attributed to Rickard Gunnarsson.

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Nucleation of titanium nanoparticles in an oxygen-starved environment, I: Experiments

A constant supply of oxygen has been assumed to be necessary for the growth of titanium nanoparticles by sputtering. This oxygen supply can arise from a high background pressure in the vacuum system or from a purposely supplied gas. The supply of oxygen makes it difficult to grow metallic nanoparticles of titanium and can cause process problems by reacting with the target. We here report that growth of titanium nanoparticles in the metallic hexagonal titanium (αTi) phase is possible using a pulsed hollow cathode sputter plasma and adding a high partial pressure of helium to the process instead of trace amounts of oxygen. The helium cools the process gas in which the nanoparticles nucleate. This is important both for the first dimer formation and the continued growth to a thermodynamically stable size. The parameter region where the synthesis of nanoparticles is possible is mapped out experimentally and the theory of the physical processes behind this process window is outlined. A pressure limit below which no nanoparticles were produced was found at 200 Pa, and could be attributed to a low dimer formation rate, mainly caused by a more rapid dilution of the growth material. Nanoparticle production also disappeared at argon gas flows above 25 sccm. In this case the main reason was identified as a gas temperature increase within the nucleation zone, giving a too high evaporation rate from nanoparticles (clusters) in the stage of growth from dimers to stable nuclei. These two mechanisms are in depth explored in a companion paper [1]. A process stability limit was also found at low argon gas partial pressures, and could be attributed to a transition from a hollow cathode discharge to a glow discharge.

cond-mat.mtrl-sci

Nucleation of titanium nanoparticles in an oxygen-starved environment, II: Theory

The nucleation and growth of pure titanium nanoparticles in a low-pressure sputter plasma has been believed to be essentially impossible. The addition of impurities, such as oxygen or water, facilitates this and allows the growth of nanoparticles. However, it seems that this route requires so high oxygen densities that metallic nanoparticles in the hexagonal aTi-phase cannot be synthesized. Here we present a model which explains results for the nucleation and growth of titanium nanoparticles in the absent of reactive impurities. In these experiments, a high partial pressure of helium gas was added which increased the cooling rate of the process gas in the region where nucleation occurred. This is important for two reasons. First, a reduced gas temperature enhances Ti2 dimer formation mainly because a lower gas temperature gives a higher gas density, which reduces the dilution of the Ti vapor through diffusion. The same effect can be achieved by increasing the gas pressure. Second, a reduced gas temperature has a "more than exponential" effect in lowering the rate of atom evaporation from the nanoparticles during their growth from a dimer to size where they are thermodynamically stable, r*. We show that this early stage evaporation is not possible to model as a thermodynamical equilibrium. Instead, the single-event nature of the evaporation process has to be considered. This leads, counter intuitively, to an evaporation probability from nanoparticles that is exactly zero below a critical nanoparticle temperature that is size-dependent. Together, the mechanisms described above explain two experimentally found limits for nucleation in an oxygen-free environment. First, there is a lower limit to the pressure for dimer formation. Second, there is an upper limit to the gas temperature above which evaporation makes the further growth to stable nuclei impossible.

cond-mat.mtrl-sci

Synthesis of titanium-oxide nanoparticles with size and stoichiometry control

Ti-O nanoparticles have been synthesized via hollow cathode sputtering in an Ar-O2 atmosphere using high power pulsing. It is shown that the stoichiometry and the size of the nanoparticles can be varied independently, the former through controlling the O2 gas flow and the latter by the independent biasing of two separate anodes in the growth zone. Nanoparticles with diameters in the range of 25 to 75 nm, and with different Ti-O compositions and crystalline phases, have been synthesized.

cond-mat.mes-hall