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   <dc:title>Ionised deposition for the structural control of carbon nickel thin films</dc:title>
   <dc:identifier xsi:type="dcterms:DOI">10.17863/CAM.14287</dc:identifier>
   <dc:creator>Bosworth, David</dc:creator>
   <dcterms:abstract>Carbon encapsulated metal nanoparticles are an increasingly important class&#xd;
of materials due to the wide range of electronic, magnetic and mechanical&#xd;
properties they display. However, traditional deposition techniques are often&#xd;
complex or lead to a poor quality film. Ionised magnetron sputter deposition&#xd;
is a promising development to traditional magnetron sputtering which&#xd;
combines film deposition with ion bombardment. By adding an RF powered,&#xd;
inductively coupled plasma positioned between the deposition targets and the&#xd;
substrate, the ionisation fraction of the depositing &#xd;
flux is greatly increased.&#xd;
This additional ion &#xd;
flux can then be controlled through the use of an electrical&#xd;
substrate biasing. This controls the energy &#xd;
flux to the surface and therefore&#xd;
the resulting microstructure.&#xd;
Carbon-nickel thin films were grown by ionised magnetron sputter deposition.&#xd;
The films themselves were characterised using a wide variety of techniques&#xd;
to measure not only their structure but their properties. Additionally, the&#xd;
inductively coupled plasma itself was characterised using a Langmuir probe.&#xd;
It was determined that upon application of a negative substrate biasing, the&#xd;
ion &#xd;
flux to the growing film remained constant, however the energy of the&#xd;
species increased. This resulted in a columnar structure of nickel carbide which&#xd;
coarsened as the bias (and therefore the energy of the ions) was increased.&#xd;
Conversely the application of a positive bias gives a large &#xd;
flux of low energy&#xd;
bombardment. This led to the formation of metallic nickel nanoparticles (≈&#xd;
30 nm diameter) which were surrounded by several layers of ordered graphitic&#xd;
shells forming a so-called "nano-onion" structure.&#xd;
The transition between these phases is a result of an increase in adatom mobility&#xd;
when there is a high &#xd;
flux, low energy ion bombardment which allows the&#xd;
nickel and carbon to phase separate. Upon separating, the nickel templates&#xd;
graphite growth due to their similar bond lengths leading to the formation of&#xd;
the graphitic cages.&#xd;
The transition between these two structures is measured through X-ray diffraction&#xd;
which shows a transition from the hexagonal carbide phase to the cubic&#xd;
nickel phase. This is accompanied by an increase in ordering of the carbon&#xd;
as the bias is increased as measured by Raman spectroscopy. Additionally,&#xd;
it is observed that there is an increase in carbon ordering when a negative&#xd;
bias is applied, due to the additional energy from ion bombardment leading&#xd;
to graphite formation.&#xd;
Magnetic measurements showed a transition from a non-magnetic state when&#xd;
the structures were largely carbide, to a magnetic state when metallic. However&#xd;
at room temperature the structures display superparamagnetic behaviour&#xd;
due to the small size of the particles.&#xd;
Measurements of electronic conductivity showed a negative temperature coeffcient of resistivity for all samples demonstrating no metallic conduction&#xd;
path was present. A large drop in resistivity as the temperature increases&#xd;
was assigned to thermally activated conduction. At low temperatures the&#xd;
conductivity is dependent on tunnelling across small regions of amorphous&#xd;
carbon, while at higher temperatures it is possible to excite the electrons into&#xd;
a conduction band allowing them to conduct more easily.</dcterms:abstract>
   <uketdterms:institution>University of Cambridge</uketdterms:institution>
   <dcterms:issued>2013-06-11</dcterms:issued>
   <dc:type>Thesis</dc:type>
   <uketdterms:qualificationlevel>Doctoral</uketdterms:qualificationlevel>
   <uketdterms:qualificationname>Doctor of Philosophy (PhD)</uketdterms:qualificationname>
   <dc:language>en</dc:language>
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