No abstract

Titanium oxide nanoparticles have been synthesized via sputtering of a hollow cathode in an argon atmosphere. The influence of pressure and gas flow has been studied. Changing the pressure effects the nanoparticle size, increasing approximately proportional to the pressure squared. The influence of gas flow is dependent on the pressure. In the low pressure regime (107 ≤ p ≤ 143 Pa) the nanoparticle size decreases with increasing gas flow, however at high pressure (p = 215 Pa) the trend is reversed. For low pressures and high gas flows it was necessary to add oxygen for the particles to nucleate. There is also a morphological transition of the nanoparticle shape that is dependent on the pressure. Shapes such as faceted, cubic and cauliflower can be obtained.

Ti-O nanoparticles have been synthesized via hollow cathode sputtering in an Ar-O-2 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 O-2 gas flow and the latter by the independent biasing of two separate anodes in the growth zone. Nanoparticles with diameters in the range of 25-75 nm, and with different Ti-O compositions and crystalline phases, have been synthesized.

Funding Agencies|Knut and Alice Wallenberg foundation [KAW 2014.0276]; Swedish Research Council via the Linkoping Linneaus Environment LiLi-NFM [2008-6572]

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, inside which 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. 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.

In this study, we investigated means of performance enhancement in sensors based on epitaxial graphene on silicon carbide (SiC). Epitaxially grown graphene on SiC substrates were successfully decorated with metal oxide nanoparticles such as TiO2 and Fe3O4 using hollow cathode pulsed plasma sputtering. Atomic Force Microscopy and Raman data verified that no damage was added to the graphene surface. It could be shown that it was easily possible to detect benzene, which is one of the most dangerous volatile organic compounds, with the Fe3O4 decorated graphene sensor down to an ultra-low concentration of 5 ppb with a signal to noise ratio of 35 dB. Moreover, upon illumination with a UV light LED (265 nm) of the TiO2 decorated graphene sensor, the sensitivity towards a change of oxygen could be enhanced such that a clear sensor response could be seen which is a significant improvement over dark conditions, where almost no response occurred. As the last enhancement, the time derivative sensor signal was introduced for the sensor data evaluation, testing the response towards a change of oxygen. This sensor signal evaluation approach can be used to decrease the response time of the sensor by at least one order of magnitude.

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 Tiphase 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, *. 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.3 the gas temperature is the same as the vacuum chamber wall temperature. For details on the experimental arrangements, see Gunnarsson et al [4][5].

Two-dimensional materials offer a unique platform for sensing where extremely high sensitivity is a priority, since even minimal chemical interaction causes noticeable changes in electrical conductivity, which can be used for the sensor readout. However, the sensitivity has to be complemented with selectivity, and, for many applications, improved response- and recovery times are needed. This has been addressed, for example, by combining graphene (for sensitivity) with metal/oxides (for selectivity) nanoparticles (NP). On the other hand, functionalization or modification of the graphene often results in poor reproducibility. In this study, we investigate the gas sensing performance of epitaxial graphene on SiC (EG/SiC) decorated with nanostructured metallic layers as well as metal-oxide nanoparticles deposited using scalable thin-film deposition techniques, like hollow-cathode pulsed plasma sputtering. It is demonstrated that under the right modification conditions the electronic properties of the surface remain those of graphene, while the surface chemistry can be tuned to improve sensitivity, selectivity and speed of response to several gases relevant for air quality monitoring and control, such as nitrogen dioxide, benzene, and formaldehyde.

No abstract