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submitted to the
Combined Faculties for the Natural Sciences and for
of the Ruperto-Carola University of Heidelberg, Germany
for the degree of
Doctor of Natural Sciences
put forward by
Diplom-Physiker: Robert Gerald Klein
Born in: Berlin-Mitte, Germany
Oral examination: 13 of January, 2010Swift Heavy Ion Irradiated Boron Nitride
With and Without the Application
of High Pressure
Referees: Prof. Dr. R. Neumann
Prof. Dr. R. Miletich-Pawliczekfür ChristianZusammenfassung
In seiner kubischen Form ist Bornitrid (BN) nach Diamant das zweithärteste
bekannte Material. Die Struktur des hexagonalen BNs ist der des Graphits sehr
ähnlich. Doch im Gegensatz zu dessen Kohlenstoff-Allotropen muss BN künst-
lich erzeugt werden, da natürliche Vorkommen nicht existieren. Erste Hinweise
auf die Erzeugung von Diamant in mit Schwerionen bestrahltem Graphit gaben
Anlass zu Experimenten an hexagonalem (hBN), mit dem Ziel, kubisches BN
zu erzeugen. Zusätzlich angewandter Druck sollte diesen Prozess katalytisch be-
günstigen. Jedoch konnte eine solche Umwandlung nicht nachgewiesen werden.
Dennoch verursacht die von Schwerionen an das Kristallgitter abgegebene Ener-
gie sichtbare Änderungen, wie eine stark orientierungsabhängige Verfärbung im
hBN, die mit unterschiedlich ausgeprägten Gitterführungseffekten erklärt wer-
den kann. Sowohl orientierungs- als auch druckabhängig entwickeln sich Intensi-
täten charakteristischer Ramanbanden mit zunehmender Fluenz. Des Weiteren
konnte mittels Raman-Spektroskopie und Synchrotron-Röntgenbeugung in situ
gezeigt werden, dass Ionenbeschuss den Phasenübergang von hBN zum wurtzi-
tischen BN (wBN) in dem Sinne erleichtert, dass dieser im Gegensatz zu unbe-
strahltem hBN bei Druckerhöhung vollständiger abläuft.
Cubic boron nitride (cBN) is the second hardest material after diamond. The
hexagonal form (hBN) resembles graphite. However, due to speculations, de-
irradiation experiments were initialized, aiming a hBN! cBN transition. Si-
multaneous pressurization were suggested to trigger such transitions. Neverthe-
less, this goal could not be reached, but several other, irradiation and pressure-
induced effects have emerged. A strongly orientation dependent colourization is
explained by ion channeling, which is believed to be also responsible for alter-
ations in the Raman spectra of hBN crystals, irradiated under different orien-
tations under simultaneous high pressure conditions. Furthermore, the pressure
phase transition from hBN to wurtzitic BN is effected by ion irradiation, ob-
served in-situ by XRD as well as Raman spectroscopy.Acknowledgement
First of all, I would like to express my sincere thank to my supervisor and first
referee Prof. R. Neumann, who gave me the opportunity to realise this thesis
in his working group. He also enabled me to attend conferences and workshops,
where I could always gain and exchange important experience.
Furthermore, I am indebted to Prof. R. Miletich-Pawliczek, who contributed
valuable assistance throughout the time of research. His point of view of the
results and experiments, as well as the realization of the measurements at the
ESRF in Grenoble were of great value.
Prof. Takashi Taniguchi, who generously fabricated and accorded me the BN
single crystals, was also a priceless benefit, and the AIRAPT conference he has
organized, however, was a great experience.
Bayerisches Geoinstitut Bayreuth, especially the assistance of Dr. L. Dubrovin-
sky, who taught me the art of reaching highest pressures.
Dr. C. Trautmann gave me the thankworthy opportunity to a stay at the Aus-
tralian National University and initialized first SAXS-beamtimes at the Aus-
tralian Synchrotron, which was not only an unvorgettable experience, but also
the promising start of a fruitful cooperation with Dr. P. Kluth, the SAXS ex-
pert, who kindly tested our BN single crytals for track formation.
Nevertheless, this work could have never been finished without the support,
assistance and encouragement of all the members of the GSI Materials Researchii
Department. Therefore, I would like to thank espacially:
Ms. Dipl.-Phys. B. Schuster for the XRD measurement series at the APS
synchrotron, and for all her helpful advices.
Dr. K.-O. Voss for the assembling of the numerous ionoluminescence devices,
and his always patient assistance.
Mr. E. Schubert for his very active support.
Mr. Dipl.-Chem. T. Seidl for the ATR measurements.
Mr. M. Rauber and Dipl.-Phys. O. Picht for the SEM (EDX)
Dr. A. Sankarakumar for always having time and motivation for scientific chat-
Dr. D. Severin for the realisation of the luminescence measurement at the novel
M-branch irradiation site.
And all others, who contributed and offered support.
Many thanks be expressed also to the members of the Mineral Physics Group
of the Heidelberg University as:
Mr. Dipl.-Min. C. Weikusat, who was always open for a helpful discussion, and
a nightshift during beamtime. Thank you for the argon filling.
Ms. I. Glass for the XRD introduction and measurements.
Mr. Dipl.-Min. P. Schouwink for the support during ESRF beamtime.
Last but not least I would like to express sincere thanks to Ina Stützer, who
always gave more than moral support, and to my friends and to my family.
All that was not possible without your always self-forgetting help, dear Chris-
tian, though it never returned worthily. Not even when you needed it most.