Precursor Chemistry of Ta and NB Nitride For MOCVD and ALD Applications

Precursor Chemistry of Tantalum and Niobium Nitride
for MOCVD and ALD Applications
Dissertation
Arne Baunemann
Precursor Chemistry of Tantalum and Niobium Nitride
for MOCVD and ALD Applications
Dissertation
zur Erlangung der Doktorwürde der Fakultät für
Chemie der Ruhr-Universität Bochum
vorgelegt von
Diplom-Chemiker Arne Baunemann
Referenten
Prof. Dr. Roland A. Fischer
Prof. Dr. William S. Sheldrick
II
Die vorliegende Arbeit entstand in der Zeit von Oktober 2003 bis Oktober 2006 am Lehrstuhl
für Anorganische Chemie II der Ruhr-Universität Bochum
Meinem Mentor und Betreuer, Professor Dr. Roland A. Fischer möchte ich an dieser Stelle
meinen außerordentlichen Dank zuteil werden lassen. Ohne seine inspirierende Vorlesung im
ersten Semester hätte ich nicht den Weg in die Chemie gefunden. Während meines gesamten
Studiums hat er mir jederzeit mit Rat und Tat zur Seite gestanden und mich in allen Plänen -
ohne Einschränkungen - unterstützt. Diese Erfahrungen haben mich zutiefst für mein weiteres
Leben geprägt.
III
“Contradictions do not exist. Whenever you think that you are facing a contradiction, check
your premises. You will find that one of them is wrong.”
(Ayn Rand in “Atlas Shrugged”, 1957)
Meinen Eltern
und Carmen
IV
Acknowledgements
Danksagung
Juniorprof. Dr. Anjana Devi Anjana und Harish danke ich außerordentlich für die
& Dr. Harish Parala Unterstützung in Form von konstruktiver Kritik in vielen
Bereichen und der Unterstützung bei XRD und TG/DTA
Messungen.
Dr. Christian Gemel Christian danke ich für den wertvollen chemischen Input, den
er mir in den letzten Jahren gegeben hat.
Marie-Kathrin Schröter Nana danke ich für die Unterstützung und den gemeinsamen
Spaß in den letzten acht Jahren, die wir fast tagein-tagaus
miteinander verbracht haben. Awesome.
Martin Lemberger Martin hat es mit nahezu unermüdlichem Eifer geschafft, mir
einen gewissen Einblick in das Mysterium der Elektrotechnik
zu geben. Vielen Dank für die Kooperation im Rahmen des
DFG.
Stephan Hermes & Andreas Stephan und Andreas danke ich für die kreative
Kempter Unterstützung, wenn es darum ging, neue Wege zu gehen und
ganz besonders für die Showvorlesung.
Denise Zacher Danke für die Motivation, Hilfe bei Syntheseproblemen und
ein immer offenes Ohr.
Sabine Masukowitz Vielen Dank für die Unterstützung in allen organisatorischen
Fragen und bei dem Umgang mit dem RUB’schen
Büroapparat.
Stephan Spöllmann Stephan danke ich für die vielen Experimente, die er mit Lucy
alias Aixtron 200 FE durchgeführt hat.
Manuela Winter Manuela danke ich für die Lösung von vielen, vielen
Kristallstrukturen und die Berücksichtung meiner wirren
Wünsche für die Bezeichnung der Atome.
Kai Richter Kai danke ich für die tatkräftige Unterstützung bei der
Synthese von Schwefel und anderen nützlichen Dingen.
Dr. Rolf Neuser Herrn Neuser danke ich für die SEM- und EDX Messungen.
Prof. Dr. Martin Feigel und Ihnen danke ich für die Unterstützung bei dem Lösen von
Priv. Doz. Dr. Iris Müller schwierigen NMR-Spektren und Kristallstrukturen.
Prof. Dr. Lauri Niinistö & Vielen Dank für die nette und herzliche Aufnahme an der
Jaako Niinistö Helsinki University of Technology.
V
Acknowledgements
Prof. Dr. Jin-Hio Boo & Vielen Dank für die sehr gastfreundliche Aufnahme an der
Jin-Ho Park Sungkyunkwan University.
H.C. Starck GmbH Ich danke Herrn Dr. Stephan Kirchmeyer, Herrn Dr. Knud
Reuter und Herrn Gerd Passing für die materielle und
wissenschaftliche Unterstützung währende der Promotion.
Desweiteren möchte ich mich bei meinem gesamten Lehrstuhl für die schöne Zeit in der
Gruppe bedanken. Dazu gehören Saeed Amirjalayer, Dr. Raghunandan Bhakta, Beatrice
Buchin, Thomas Cadenbach, Mirza Cokoja, Rolf Deibert, Daniel Esken, Lina Freitag,
Dr. Eliza Gemel, Malte Hellwig, Ursula Herrmann, Todor Hikov, Heike Kampschulte,
Andreas Kempter, Dr. Jayaprakash Khanderi, Dr. Emmanuel Lamouroux, Dr. Eva Maile,
Mikhail Meilikhov, Andrian Milanov, Maike Müller, Daniel Rische, Dr. Rochus Schmid,
Felicitas Schröder, Dr. Jelena Sekulic, Stephan Spöllmann, Tobias Thiede, Dr. Maxim
Tafipolsky, Tim Wilmsen, Manuela Winter, Dr. Wenhua Zhang und Xiaoning Zhang.
VI
Table of contents
Table of contents
Chapter 1 Introduction and motivation 1

1.1 Motivation and goals 2
1.2 Phases of group(V) nitrides and their properties 4
1.3 Applications of tantalum and niobium nitrides 7
1.4 Techniques for deposition of thin films via gasphase 11
1.4.1 Physical Vapor Deposition (PVD) 11
1.4.2 Metal Organic Chemical Vapor Deposition (MOCVD) 12
1.4.3 Atomic Layer Deposition (ALD) 16
Chapter 2 State of the art in research and motivation 19

2.1 Previously reported MOCVD experiments for group(V) nitrides 19
2.1.1 MOCVD of tantalum nitride 20
2.1.2 Conclusions of past reports about the MOCVD of tantalum nitride 24
2.1.3 MOCVD of niobium nitride 28
2.2 Previously reported ALD experiments for group(V) nitrides 29
2.2.1 ALD of tantalum nitride 29
2.2.2 ALD of niobium nitride 32
Chapter 3 Starting compounds and their synthesis 34

3.1 Synthesis of mixed amido / imido compounds of tantalum and niobium 34
3.1.1 Single crystal X-ray analysis of S8, S3 and the hydrolyzed form of S3 (S3’) 36
3.1.2 Thermal properties of the compounds S4-S9 39
3.2 Ligand synthesis 41
3.2.1 Synthesis of N-trimethylsilyl-N’,N’-bisdimethylhydrazine (Htdmh) 42
Chapter 4 Hydrazido based precursors of tantalum 44

4.1 Hydrazine derivatives as useful ligands for new MOCVD and ALD precursors 44
4.2 Synthesis of amido / imido / hydrazido complexes A1-A3 by transamination reactions 46
4.2.1 Synthetic route, purity and properties of the compounds A1-A3 46
4.2.2 Spectroscopic analysis of the compounds A1-A3 48
4.2.3 Single crystal X-ray analysis of A1 49
4.2.4 Thermal analysis of A1-A3 in respect to MOCVD / ALD 50
4.3 Destructive transamination reactions of A1-A3 with N,N-dimethyl-hydrazine (Hdmh) 52
4.3.1 Single crystal X-ray analysis of a hydrolyzed tantalum-dmh complex 54
4.4 Reactions of TaCl5 and [TaCl3(N-t-Bu)py2] with lithiated hydrazine derivatives 57
Chapter 5 Guanidinato based precursors of tantalum and niobium 60

5.1 Types of guanidinate ligands in complexes and their synthesis 60
5.2 Potential of guanidinate(-1) ligands for precursor chemistry 64
5.3 Synthesis of amido / imido / guanidinato compounds of tantalum B1-B8 65
5.3.1 Synthetic route, purity and properties of the compounds B1-B8 65
5.3.2 Spectroscopic analysis of the compounds B1-B8 68
5.3.3 Single crystal X-ray analysis of B1-B5 and B7 74
VII
Table of contents
5.4 Synthesis of amido / imido / guanidinato compounds of niobium C1-C4 83

5.4.1 Synthetic route, purity and properties of the compounds C1-C4 83
5.4.2 Spectroscopic analysis of the compounds C1-C4 84
5.4.3 Single crystal X-ray analysis of C1 and C2 85
5.5 Thermal analysis of B1-B8 and C1-C4 in respect to MOCVD / ALD 87
5.6 Investigations of the thermal decomposition of B1-B3 91
Chapter 6 MOCVD of tantalum nitride 93

6.1 Presentation of the MOCVD reactors utilized in this work 94
6.1.1 Bubbler design – Enhancement of precursor evaporation 98
6.2 Deposition experiments with simple amido / imido tantalum precursors 99
6.2.1 Depositions with [Ta(NEtMe)3(N-t-Bu)] (S5) in the selfbuilt horizontal reactor 100
6.2.2 Depositions with [Ta(NEt2)3(N-t-Bu)] (S6) in the Aixtron 200 RF reactor 104
6.2.3 Depositions with [Ta(NEt2)3(N-t-Bu)] (S6) in the 150 mm wafer reactor 112
6.2.4 Depositions with [Ta(NMeEt)3(N-t-Bu)] (S5) in the 150 mm wafer reactor 113
6.2.5 Conclusions for the use of mixed amido / imido tantalum precursors 114
6.3 Deposition experiments with mixed amido / imido / hydrazido tantalum precursors 115
6.3.1 Depositions in the selfbuilt horizontal cold wall reactor 115
6.3.2 Depositions with [Ta(NMeEt)2(tdmh)(N-t-Bu)] (A2) in the 150 mm wafer reactor 118
6.3.3 Conclusions for the use of mixed amido / imido / hydrazido tantalum precursors 119
6.4 Deposition experiments with mixed amido / imido / guanidinato tantalum precursors 121
6.4.1 Depositions with B2 in the selfbuilt horizontal reactor 121
6.4.2 Depositions with B2 in the LI – MOCVD reactor Aixtron 200 FE 125
6.4.3 Conclusions for the use of mixed amido / imido / guanidinato tantalum precursors 127
6.5 Electrical characterization of TaN films for MOS-gate structures at the FIIS (Erlangen) 128
Chapter 7 MOCVD of niobium nitride 130

7.1 Depositions with [Ta(NMe2)3(N-t-Bu)] (S8) in the selfbuilt horizontal reactor 130
7.2 Depositions with C1 in the selfbuilt horizontal reactor 133
Chapter 8 ALD of metal (oxo) nitride materials 136

8.1 Presentation of the ASM F120 ALD reactor 136
8.2 ALD experiments in a well adjusted F-120 reactor (Finland) 138
8.3 Installation of the F120 reactor in Bochum and first results 140
8.3.1 Depositions with S5 in reactor setup I 140
8.3.2 Depositions of Al2O3, TaON and NbON in reactor setup II 142
8.4 Conclusions for the ALD of tantalum and niobium nitride materials 145
Chapter 9 Summary and outlook 147
Chapter 10 Experimental 154

10.1 Analytical characterization of the precursors 154
10.2 Thin films analysis and instruments 155
10.3 Details to MOCVD and ALD experiments 161
10.3.1 Wafer treatment 161
VIII
Table of contents
10.3.2 Handling of the selfbuilt reactor 161

10.3.3 Handling of the ASM F-120 Reactor 162
10.4 General comments on synthesis and characterization 162
10.5 Synthesis of the starting compounds S1-S11 164
10.5.1 Synthesis of the chloro-containing intermediate compounds S1 - S3 164
10.5.2 Synthesis of the mixed amido / imido complexes S4 - S8 165
10.5.3 Synthesis of N-Trimethylsilyl-N’,N’-dimethylhydrazine 167
10.6 Synthesis involving hydrazines (A1-A5 and further reactions) 167
10.6.1 Synthesis of A1-A4 167
10.6.2 Synthesis of A5 169
10.6.3 Reactions with S6 (TBTDET) and dimethylhydrazine 169
10.6.4 Further reactions involving hydrazine derivatives 170
10.7 Synthesis of the guanidinato-containing complexes of tantalum (B1-B8) 171
10.8 Synthesis of the guanidinato-containing complexes of niobium (C1-C4) 175
10.9 Crystallographic data 178
10.9.1 Crystallographic data of S3’ and S8 179
10.9.2 Crystallographic data of A1, A4 and A5 180
10.9.3 Crystallographic data of B1-B5 and B7 181
10.9.4 Crystallographic data of C1 and C2 186
Appendix 187
A Content lists of figures and tables 188
A-1 List of figures 188
A-2 List of tables 194
B Own publications and contributions to conferences 196
B-1 Publications 196
B-2 Oral presentations 196
B-3 Poster presentations 196
B-4 Additional publications (not based on results from this PhD thesis) 197
C Curriculum vitae 198
D References 200
IX
Abbreviations
Abbreviations
AFM Atomic Force Microscopy

ALD Atomic Layer Deposition
APCVD Atmospheric Pressure CVD
t-Bu tert-Butyl
btdmh N,N-Bis(trimethylsilyl)-N’,N’-dimethylhydrazine
cdi Carbodiimide
cy Cyclohexyl
cy-cdi Dicylclohexylcarbodiimide
Hdmh N,N-Dimethylhydrazine
DTA Differential Thermal Analysis
EA Elemental Analysis (C,H,N-analysis)
EDX Electron Dispersive X-Ray spectroscopy
EI-MS Electron Ionization Mass Spectroscopy
Et Ethyl
fcc Face-Centered Cubic
FIIS Fraunhofer Institut für Integrierte Schaltungen, Erlangen
LICVD Liquid Injection CVD
LPCVD Low Pressure CVD
MBE Molecular Beam Epitaxy
Me Methyl
MOCVD Metal Organic Chemical Vapor Deposition
PDEAT Pentakisdiethylamidotantalum (V)
PDMAN Pentakisdimethylamidoniobium (V)
PDMAT Pentakisdimethylamidotantalum (V)
i-Pr iso-Propyl
i-Pr-cdi Di(iso-propyl)carbodiimide
PVD Physical Vapor Deposition
RBS Rutherford Back Scattering
SEM Scanning Electron Microscopy
SIMS Secondary Ion Mass Spectroscopy
SNMS Secondary Neutral Mass Spectroscopy
TAIMATA Tertiary-amylimidotris(dimethylamido)tantalum
TBTDEN Tert-butylimidotris(diethylamido)niobium
TBTDET Tert-butylimidotris(diethylamido)tantalum
TOF-ERDA Time-Of-Flight-Elastic Recoil Detection Analysis
Htdmh N-Trimethylsilyl-N’,N’-dimethylhydrazine
TGA Thermogravimetric Analysis
XPS X-Ray Photoelectron Spectroscopy
XRD X-Ray Diffraction
X
Chapter 1 Introduction
Chapter 1 Introduction and motivation
The present work deals with the synthesis of precursors used for the MOCVD and ALD of
tantalum and niobium nitride thin films and the application of the latter in deposition
processes. This field of interest, especially in the case of TaN, has gained increasing attention
in the material science research community over the last decade. Although investigations into
this field already began as early as the 1930’s, the acceleration of research efforts started with
the publication of Tsai et al. in 1995.[1] Since then, the research topic itself has begun to
maturate from a more explorative level to an application-oriented state. This development was
mainly driven by the great potential for utilizing these films as materials for microelectronic
devices. An indicator for this surge is surely the raise in the number of patents that has been
submitted for TaN (figure 1). Compared to TaN, NbN has received less attention, although the
material itself displays some additional, very interesting properties, and high potential for
various applications. Thus, we expect that the importance of NbN will also increase during
the next years. The properties of these binary metal nitride materials depend heavily on the
composition and chemical structure of the deposited phase. Due to the complexity of the
binary phase diagrams, control of the deposition process is particularly difficult. Therefore,
before going ahead with the state of the art in the deposition of these materials, the different
phases and their corresponding features will be discussed in the following paragraph (1.2).
The most relevant material properties for an application in microelectronic devices are
conductivity and hardness which correlate with the diffusion inhibition of the thin films.
Paragraph (1.3) gives an overview of the applications for the two binary materials that have
been envisaged so far.
1
Figure 1. Trends in the number of new patents for NbN and TaN materials. Left: Number of new patents per year;
Right: Number of patents accumulated.
1.1 Motivation and goals
This work was motivated by two aspects: The first is oriented towards the large variety of
applications for metal nitride thin films, specifically for those involving tantalum and niobium
nitride thin films (1.3). The most important application is considered to be the integration of
these films in microelectronic devices. The International Technology Roadmap for
Semiconductors 2005 makes the following statement:
“Barrier materials used for Cu wiring must prevent its diffusion into the adjacent dielectric,
but in addition must form a suitable, high quality interface with Cu to limit vacancy diffusion
and achieve acceptable electromigration lifetimes. TaN/Ta has become the predominant
industry solution…” [2]
Optimal techniques for the fabrication of these films are still lacking, as all concepts have
their own advantages and disadvantages (see 1.4). In order to deposit high quality films
having the desired crystal phase with excellent electrical properties the deposition of TaN and
NbN by means of MOCVD and ALD was selected. To obtain better results in these processes,
our approach was to investigate the behavior of new classes of all-nitrogen coordinated
precursors (guanidinato and hydrazido containing precursors) in deposition techniques and to
compare the results to common, structurally simpler precursor systems. The basic question
was to determine what consequences are associated with an increase in the complexity of the
precursor-molecules, thus changing the volatility, thermal stability and decomposition
characteristics (mechanisms) thereof and at the same time gaining additional degrees of
freedom for deposition control. Does the increase in complexity correspond to loosing the
2
ability to function as a precursor to the formation of TaN thin films? The underlying reasons
for choosing the discussed types of ligands are presented in the beginning of chapter 4
(hydrazido-containing precursors) and 5 (guanidinato-containing precursors).
Besides this superordinate motivation of contributing to the large area of “How to fulfill
Moore’s law in the future?”[a] as a long term objective, there is also a second driving force.
The chemistry of guanidinato and hydrazido ligands at early transition metal centers is
interesting for its own merit with the development of molecular coordination chemistry. For
example, guanidinato-groups can function as ambidentate and mono/dianionic type of ligands
and show excellent properties in the promotion of reactions (e.g. catalyst for Ring Opening
Metathesis Polymerization reactions). Investigating structural parameters and chemical /
thermal properties of the new compounds can give a deeper insight into the chemistry of the
group V metals tantalum and niobium.
[a] Moore’s law states that the number of transistors, placed on an integrated circuit (IC) will double every 18 to
24 month. The International Roadmap for Semiconductors describes the technical developments that have to be
achieved in order to keep the high growth rate.
3
1.2 Phases of group(V) nitrides and their properties
Tantalum as well as niobium nitride materials exist in a large variety of stable and metastable
phases. After the discovery of the metals Ta and Nb in the beginning of the 19th century, first
experiments for the formation of tantalum nitrides were attempted around 1850. Ta2O5 and
TaCl5 were exposed to gaseous ammonia.[3] In the 1920’s reputated scientists like A. E. van
Arkel worked further on reactions between solid TaCl5 and H2/N2 mixtures and discovered the
hexagonal phase Ta2N.[4,5] Enabled by the progresses in vacuum technology, in the following
decades, many phases of tantalum nitride have been identified. These phases were synthesized
by exposure of tantalum wires, films and powder to N2 at temperatures well above 1000°C.
Removing nitrogen by degassing the heated, nitrogen-rich phases, led to the formation of
nitrogen deficient phases of tantalum. In the 1960’s, large quantities of physical data e.g.
desorption energies, diffusion coefficients, phase diagrams were collected by calorimetric
methods and kinetic studies.[6] Another interesting method that is worth mentioning is the
method of “exploding wires” in which high voltage is applied to a tantalum wire in a nitrogen
atmosphere in order to produce tantalum nitride material.[7] The following table (table 1)
provides an overview of the known tantalum nitride phases. These phases can be roughly
divided into four groups: The phases in which atomic nitrogen is only „dissolved“ in solid
tantalum (1), the special phase Ta2N (2), phases in which the Ta:N ratio is almost 1:1 (3) and
nitrogen-rich phases (4). These phases differ fundamentally in their physical properties.
Table 1. Phases of tantalum nitride and their structure types. The phases, that have been deposited via
chemically based gasphase methods (not necessary the quoted references) are highlighted.
Phase Stochiometry Structure type / Comments Ref.
α-TaN TaN0.04 Solid solution of N in (bcc)-Ta [8,9]
β-TaN TaN0.05 Superstructure to the α-TaN-lattice [9]
γ-Ta2N TaN0.5 Hexagonal close packing of Ta, with nitrogen atoms [9,10]
occupying half of the octahedral interstetices (non statistical
distribution)
ε-TaN TaN1.0 Hexagonal structure, CoSn-type (formed at T>1100°C, black) [11,12]
δ-TaN TaN0.92-0.97 Cubic face centered structure, NaCl-type (golden) [13]
θ/ν-TaN TaN1.0 Hexagonal structure, WC-type (formed from ε-TaN by [14]
polymorphic transformation under high pressure)
Ta5N6 TaN1.2 Hexagonal [15]
Ta4N5 TaN1.25 Tetragonal [15]
Ta2N3 TaN1.5 Fluorite structure with ordered nitrogen vacancies [16]
Ta3N5 TaN1.66 Orthorhombic, Fe2TiO5-type (TaN6-octaehdrons, sharing [17]
edges and corners. Nitrogen is three and four coordinated)
4
In a 2005 review, which contains first theoretical approaches to the complex phase system of
tantalum nitride the following is stated:
”It can be noted from these experiments that TaN compounds have widely varying structural
properties, which depend sensitively on the experimental procedures and conditions. While
this flexibility and control thereof raises the possibility of new, diverse applications, it is first
necessary to gain a deeper understanding into the energetics and physical properties of these
materials.” [18]
This review comes to the conclusion that only three phases are thermodynamically stable,
namely γ-Ta2N, Ta5N6 and Ta3N5. This outcome is based on the results from calculations of
the free energy of formation of the certain phases. All other phases, including the frequently
observed cubic δ-TaN (figure 2) phase are metastable. Nevertheless, the formation of the
thermodynamically most stable phases is not heavily favored due to the remarkably small
energetic advantage over the formation of the metastable phases. Even small kinetic hindrance
during formation of nitride material can lead to metastable phases of tantalum nitride. Not
only was the stability of the phases investigated, but also the electrical resistivity of the nitride
materials depending on the phase. Unfortunately, no concrete values are given for the specific
phases, but rather a qualitative description. This description is based on the theoretical density
of states (DOS) at the Fermi-level of the different phases.[18,19] The conclusion of these
calculations is, that coming from γ-Ta2N (with nitrogen deficiency) and proceeding to nitrogen-
rich Ta3N5, the DOS at the fermi-level empties, resulting in a change of material’s property
from metallic (γ-Ta2N, ε-TaN , δ-TaN, Ta5N6) to completely insulating (Ta3N5). However, the
trend is not monotonically decreasing. The reason for this behavior that is quoted in these
references is the increasing number of Ta vacancies in the materials.
Figure 2. Structures of a) the cubic δ-TaN and b) the hexagonal δ-TaN (view from the top).
5
The related (qualitative) chemical interpretation is that the oxidation state of tantalum is
changing from zero to +V when moving from pure tantalum to nitrogen-rich Ta3N5. The
Ta3N5 system with tantalum as a d0-element is comparable to the dielectric material Ta2O5.
The specific resistivity of the metallic phases is between 263 ± 22 (TaN0.45) and 128 ± 22
(TaN1..01) μΩ·cm.[20,21] It is very difficult (or even just not possible) to find more reliable
values for the resistivity and density of the specific phases. The Ta:N ratio of the phases can
vary within certain ranges, without changing the crystal lattice of the material.
The niobium nitride system shows a similar complexity, but will not be discussed at such a
detailed level because the main emphasis of this work is directed to tantalum nitride materials.
All clearly identified phases are displayed in figure 3.[22,23,24,25] The differences are that in the
case of niobium nitrides, the existence of the dielectric Nb3N5 has not been reported thus it
can be expected that all phases of niobium nitride are conductive and show metallic behavior.
The reason for the absence of Nb in the oxidation state +5 (considering that nitrogen is in the
state –3) is its lower stability when compared to tantalum.[26] Of course, the inhibition of
oxidation plays a major role when it comes to the synthesis of this material. In addition, some
of the nitride phases of niobium show high critical temperatures (Tc, onset of
superconductivity) in particular the cubic, silver δ-NbN with Tc=17.4 K.[27]
Figure 3. Reported niobium nitride phases, arranged by increasing nitrogen content from left to right.
Besides the electrical properties of these materials, the high hardness and the extremely high
melting point of the materials can be mentioned as advantage. The cubic δ-TaN phase has an
astonishing melting point of 3095°C and thus a very rigid lattice. Cubic NbN melts at a
significant lower temperature of 2205°C.[26] An important issue which needs to be addressed
at this point is the sensitivity of tantalum and niobium towards oxygen when the nitride
6
materials thereof are handled at higher temperatures. Absolute exclusion of air is required;
otherwise the films will be contaminated with oxygen. [b]
1.3 Applications of tantalum and niobium nitrides
The application of tantalum and niobium nitride thin films can be divided into two groups, the
first group that is based on the unique mechanical properties of the materials, whereas the
second group takes advantage of the electronic features of the materials. The group, based on
the mechanical properties of the metal nitride phases, applies these materials in the formation
of thin coatings on tools in order to improve their wear resistance. The steel substrates (e.g.
for cutting or drilling tools) are coated with metal nitride films in the thickness range of a few
microns. Sputtering techniques are used for these deposition processes, because they allow
very high deposition rates on relatively large objects.[28] Multilayered films of different metal
nitrides e.g. TaN/NbN, TiN/NbN have been found to increase the hardness of the films
compared to single phase coatings. The hardness of these materials are in the order of 50 GPa
(based on a Knoop hardness test for thin films).[29] For comparison, silicon carbide has a
hardness of approximately 24 GPa and diamond of about 78 GPa. In the other group, the area
of microelectronic device technology, four different fields of application can be identified that
will be discussed in detail.
Application of TaN as liner material for diffusion barriers in Si/MN/Cu device

structures
During the past decade, the accelerating development of integrated circuits in the
microelectronic industry provided new challenges and higher requirements of the materials,
used for the fabrication of these circuits, e.g. MOSFET-devices (Metal Oxide Semiconductor
Field Effect Transistors). Following the International Technology Roadmap for
Semiconductors from 1999, the size of device nodes in sub-quarter-micron devices has to
shrink from 180 nm in 1999 to 35 nm in 2014.[30] This presupposes the use of copper (1.67
μΩ·cm)[31] or silver[32] as the wiring material due to their lower resistivity compared to
aluminum (2.65 μΩ·cm )[33] that has been used so far. From these two materials, copper is the
main focus of the microelectronic industry as the future wiring material. The major problem
[b] Actually, this is the origin of the metals’ name, based on Tantalus and his daughter Niobe from greek
mythology. The same way that Tantalus is suffering thirst in the Hades, the same way does Ta2O5 not have the
ability to react with acids in order to form salts (it cannot satisfy its thirst).
7
that is connected with the introduction of copper into the device structures is the highly
favored formation of copper-silicides (Cu3Si) due to migration of copper into silicon at Cu/Si-
interfaces. Therefore, an effective diffusion barrier for copper is needed, that is placed
between the Cu-wiring and the Si-substrate. Figure 4 displays the introduction of such a
diffusion barrier in a MOSFET-device.
Three different mechanisms are described that lead to a failure of the liner (diffusion barrier):
Diffusion of copper through bulk defects in the liner
Diffusion of copper or substrate atoms along grain boundaries
Loss of liner integrity due to a metallurgical or chemical reaction with the copper
and/or substrate
Thus, the liner material has to meet several requirements. It should be highly conductive,
thermally stable, and inert to the underlying Si-substrate as well as the Cu above the barrier.
In an ideal case it should be nanocrystalline or even amorphous in order to prevent the
diffusion of Cu along grain boundaries.[34] These boundaries typically exist in polycrystalline
materials. All these issues have to be fulfilled as good as possible with a maximum barrier
thickness of 13 (in 2002) to ideally almost zero nm in future application. One indication of a
good material for a diffusion barrier is the melting point of the material because it was
experimentally observed that lattice diffusion rates are proportional to the absolute melting
temperature of the material.[35] Materials with high melting points that come into
consideration are the refractory metals such as W, Mo, Nb and Ta, alloys and the conducting
carbides (TiC, TaC, SiC), nitrides (TiN, W2N, HfN, TaNx, SiNx) and carbodnitrides (SiCxNy,
TaCxNy) of various metals and semiconductors. The Ti and TiN systems have already been
widely employed, but they show rather poor properties as diffusion barriers. The low thermal
stability of the TiN phases, the low inertness of Ti against Cu, and the high film thickness for
adequate inhibition of Cu-diffusion (>50nm) make them less suitable for an effective use in
future integrated circuit devices.[34] Tantalum as pure metal is thermodynamically stable with
respect to Cu, but crystallization of amorphous Ta-films at higher temperatures leads to the
formation of grain boundaries that serve as diffusion channels for Cu. Nevertheless, pure Ta is
clearly more effective as a liner material than Ti or TiN. The best results have been obtained
for tungsten nitride[36,37,38] and tantalum nitride thin films.[39,40,41] TaNx-films, are even more
inert towards Si than tantalum films. Again, grain boundaries due to thermally induced
recrystallization of thin, amorphous TaN-films make up the main problem in terms of barrier
qualities.
8
Figure 4. Changes in the MOSFET-structure. Replacement of aluminium by copper and the introduction of a
TaN-diffusion barrier. Furthermore, replacement of polycrystalline Si by TaN as gate electrode material.
In order to circumvent this problem of crystallization, the incorporation of Si into TaNx thin
films was investigated and proved to be helpful for the prevention of crystallization and Cu-
[42,43,44,45]
diffusion. Niobium nitride thin films have not been tested on their suitability of
inhibition of cupper diffusion so far. Nevertheless, the relative high melting point of NbN,
good conductivity and chemical inertness against copper[46] makes it a candidate for future
investigations of liner materials.
Application of TaN and NbN as gate electrode material for MOSFETs (metal oxide
semiconductor field effect transistors)
On the left side of figure 4 it can be seen that the gate electrode of a MOSFET has
traditionally been fabricated of highly doped polycrystalline silicon. The high concentration
of the dopant, boron, leads to problems when the sub-quarter micron regime of node sizes is
reached. Diffusion of the dopant into the gate oxide material results in the malfunction of the
device structure. Therefore replacement by alternative electrode materials is necessary and the
search for such materials leads, again, to the refractory metals and binary compounds thereof
(e.g. nitrides). According to simulations, the work function[c] of these materials should be
around 4.2-4.3, or 3.8-3.9 eV in the case of n-type MOS-devices (Econducting ± 0.2 eV) and 4.8-
5.0 eV for an application in p-type-MOS devices. [47,53,d] For these values, the drive currents
through the conducting channel are supposed to run through a maximum. Many studies
underline the superior electrical properties of TaN[48,49,50,51,52] and TaSiN[45] thin films for the
[c] The work function represents the minimum energy needed to remove an electron from a solid (in this case
TaN) to a point immediately outside the solid surface. The work function of a material equals approximately half
of the materials ionization energy.
[d] Two approaches can be taken into account. Choosing one material for both types of MOS-devices that has a
work function in of 4.6-4.7 eV (midgap metal gate) or taking two different materials, one for n-MOS and one for
p-MOS devices (dual metal gates). The second method is favored by industry, and in fact is more advanced.
9
substitution of the polycrystalline silicon gate electrode. Again, not only an electrical fit of the
materials plays a role, but also stability issues with respect to chemical inertness and
resistance to thermal stress. Other materials e.g. WNx, TiNx and TaSix have values of work
function that are out of range for a proper application as gate electrode materials.[53] Based on
a recent literature search NbN was not mentioned so far and thus presumably not considered
for an application as material for gate electrodes. However, considering its work function of
approximately 4.7-4.8 eV[54] and its relative high thermal stability it is most probably only a
question of time until gate electrodes composed of NbN are tested. An interesting, new
approach is the use of tertiary materials consisting of two refractory metals and nitrogen.
These tertiary systems (e.g. TaTbxN or HfxTayN) exhibit work functions that can easily be
tuned between 4.2-4.6 eV by varying the content of the incorporated second metal (in this
case Tb or Hf).[55,56]
Application of NbN in the formation of Josephson Junctions

Superconductivity at relative high temperatures (17.4 K)[57] makes NbN one of the most used
material for Josephson Junctions.[58] Josephson Junctions consist of two thin films of a
superconducting material (e.g. NbN) that enclose a thin film that is either metallic or
insulating.[59,60,61] The phenomenon that occurs when this structure is cooled down under the
critical temperature of the superconducting material is, that a current flows across these two
superconductors. This effect is extremely sensitive towards changes in magnetic fields close
to the device. These junctions are used for various applications, e.g. for the measurements of
extremely small currents (currents of the brain and the heart) or as highly sensitive photon
detectors. Due to the complexity of this effect and since this application for NbN is not in the
main focus of this work, no further discussion of this effect is reasonable at this point.
Application of Ta3N5 as a photoelectrode material or gate dielectric

Although most of the applications of TaNx-materials involve the conductive phases of
tantalum nitride, two applications of the insulator Ta3N5 have been tested or can be
considered. First it can be used as visible-light driven photoelectrode material for the
conversion of photon energy into chemical energy (e.g. the splitting of water). The band
positions (conducting band, valence band) of Ta3N5, enable this material to act as a
photocatalyst, comparable to the materials Ta2O5 or TaOxNy.[62,63,64,65,66] A second application
which is already patented is the use as a gate dielectric in the fabrication of MOSFET
10
transistor-structures.[67] Its dielectric constant is above 100[68], thus it can replace SiO2 as the
insulating layer between the gate electrode and the underlying silicon (figure 4).[e]
1.4 Techniques for deposition of thin films via gasphase
Thin metal nitride films can be either formed directly from the evaporated elements (Physical
Vapor Deposition, 1.4.1) or by thermal/chemical decomposition processes of precursor
molecules at the substrate surface (Chemical Vapor Deposition (1.4.2), Atomic Layer
Deposition (1.4.3)). PVD-techniques are the most widely used techniques in IC-fabrication.
Nonetheless, strong efforts have been undertaken to establish the more complex, but
advantageous (MO)-CVD and ALD techniques. In the following the techniques are briefly
described and their advantages and disadvantages are discussed.
1.4.1 Physical Vapor Deposition (PVD)
The term PVD includes a variety of techniques for depositing thin films. The most prominent
in semiconductor industries is the process of sputtering. Besides this technique, evaporative
deposition techniques (e.g. MBE) and pulsed laser deposition techniques belong to the group
of PVD. Sputtering processes are based on the ion bombardment of source materials (so
called “targets”) and the subsequent ejection of target material into the gas phase. This
material (in atomic form) is deposited everywhere within the reaction chamber including
substrates that are mounted within. Ionized atoms (mostly Argon-atoms) are used for the
bombardment of the target. These positively charged argon ions are created in an electron
plasma that is built up by a magnetron, whereby the target material itself serves as the cathode
of the magnetron. The bias voltage applied to the cathode of the magnetron typically lies in
the range of -300 V or more. Due to the high voltage, the ions are accelerated towards the
target and strike out neutral surface atoms. For the deposition of tantalum nitride thin films,
tantalum metal targets are used and the sputtering process takes place in a nitrogen
atmosphere. Nitrogen radicals, formed in the plasma, are incorporated into the tantalum that
deposits on the surface of the substrate thus forming cubic TaN (figure 5). When additional
reactive gases are used, the whole process is called reactive sputtering.
[e] Other materials that have been tested for this purpose are mainly oxides of the early transition metals, Ti, Zr,
Hf and Ta.
11
Figure 5. Reactive sputtering of TaN. Nitrogen (blue) is incorporated into the TaN-film (blue-yellow).
As an alternative to reactive sputtering, polycrystalline TaN-targets (no nitrogen required) can

be used for depositing stochiometric TaN-films. The only problem that occurs in this case is a
non-stochiometric deposition of TaNx in the beginning of the process due to preferential
sputtering of the lighter element nitrogen. The advantage of the sputtering technique is good
control over the stochiometry of the films without any impurities (e.g. carbon) and the high
deposition rate of this process. Disadvantageous is the incapability of depositing uniform
films on objects with high aspect ratios[f] (e.g. DRAM-devices and more complex device
structures).[69] In addition, underlying device structures on the substrate can be damaged by
this process due to the high energetic particles which are involved. Despite these
disadvantages, sputtering is so far the dominating process for the fabrication of TaN thin films
in device production. Not only TaN,[31,70,71] but also TaSiN[43,72] have been successfully
deposited and integrated as diffusion barriers for copper and metal gate electrodes. In 2004, a
new method was described for the deposition that is in between PVD and CVD. Powell et al.
made experiments for the deposition of thin TaN films via Chemically Enhanced Physical
Vapor Deposition (CE-PVD).[73] An I-PVD (Ionization-PVD) reactor was modified in such
manner that besides nitrogen and argon, a metal organic precursor could be introduced during
the sputter process (tantalum target). They found out that step coverage could be improved
compared to classical PVD or plasma-enhanced CVD processes (PECVD, see 1.4.2).
1.4.2 Metal Organic Chemical Vapor Deposition (MOCVD)
From a historic point view, CVD is a rather old method. For detailed information, the
historical preface by M. L. Hitchman and K. F. Jensen can be referred.[74] Nowadays, CVD is
[f] So called line-of-sight-growth
12
a well established technique for the deposition of various kinds of materials, including group
III/V semiconductors, oxides, nitrides, carbides and silicides of many metals as well as
magnetic materials. Its main purpose is the fabrication of materials for the microelectronic
industries. A definition of the process is cited thereby:
”Chemical vapor deposition is a process whereby a thin solid film is synthesized from the
gaseous phase by a chemical reaction. It is this reactive process which distinguishes CVD
from physical deposition processes such as evaporation, sputtering and sublimation.”[74]
This statement already implies the higher complexity of the process compared to PVD,
because not only diffusion processes have to be considered, but a large variety of thermally
induced chemical reactions in the gas phase and on the surface. Figure 6a shows the transport
and reaction steps that are involved in a typical CVD process. At first, the precursor has to
diffuse from the main flow to the substrate. Thereby it has to pass the diffusion zone above
the substrate in which the precursor has to diffuse perpendicular to the surface. As long as the
precursor is in the gas phase above the substrate, pre-reactions can occur (gas phase reactions)
that may lead to partial decomposition of the precursor and the formation of reactive
intermediates. The reactants and the precursor, after being absorbed on the surface, can either
desorb from the surface, diffuse on the surface or react (decompose) in order to form a thin
film. Temperature plays a crucial role in this system of high complexity. Three different
regimes can be identified for the CVD process in which different effects play a dominating
role in respect to film growth (figure 6b). At low temperatures (zone 1) the growth is
controlled by surface kinetic effects (growth, controlled by surface reactions). Not all
precursor molecules absorbed on the surface will be decomposed directly, but surface
diffusion processes and desorption of undecomposed precursor molecules take place. It is
obvious that in this zone, more precursor molecules would decompose at higher substrate
temperatures, thus giving a higher growth rate. This behavior can be mathematically
described by an Arrhenius expression (eq. 1).
⎛ E ⎞
growth rate = A ⋅ exp ⎜ A ⎟ eq.1
⎝ R ⋅T ⎠
In the second zone, the surface provides enough energy for the decomposition of all the
absorbed molecules. Therefore, the growth rate is mainly controlled by the amount of
precursor that diffuses to the substrate (growth, controlled by diffusion). The growth rate
shows only a low dependence on the substrate temperature (transport controlled). From a
13
certain temperature, growth rate decreases, caused by a hydrodynamic depletion of precursor

molecules in the diffusion zone above the substrate.
Figure 6. a) Scheme of the reactions involved in a CVD process; b) Arrhenius plot of the growth rate as function
of the inverse substrate temperature (1/T). Three regimes can be identified. 1: growth, controlled by surface
reactions; 2: growth, controlled by diffusion; 3: depletion of the precursor in the diffusion zone above the
substrate.
The classical CVD-process for a binary material normally utilizes two reactive chemicals.
First, a metal containing precursor and second a reactive gas, e.g. ammonia or hydrogen. In
the beginning of CVD-research, the precursors were mainly homoleptic halido-complexes of
the certain metal (e.g. TaCl5). High temperatures for evaporation and decomposition of these
precursors are required, thus setting high demands for the reactor equipment (valves, lines)
and the thermal stability of the substrates. In addition, halide incorporation into the films is
problematic due to its high negative impact on the electronic properties of the films. In order
to circumvent this problem, more volatile, less thermally stable precursors and halide free
compounds were used as precursors. These Metal Organic compounds (→ MOCVD) can also
serve as single source precursors (SSP), without the need of a second reactive gas, to form a
binary material thin film. A prominent example for such SSP is the compound BAZIGA
(Bisazido(dimethylaminopropyl)gallium) for the deposition of GaN thin films.[75] The
properties of a compound, making it a good candidate for a precursor in MOCVD-processes
are described in 1.4.2.1. A variation of the second reactive compound is the use of plasma
(e.g. hydrogen plasma) instead of simple gases. The big advantage of plasma is the higher
reactivity at low temperatures compared to gases e.g. ammonia (Plasma assisted/enhanced
CVD). However, the aggressiveness of the plasma can damage the underlying structures on
the substrate.
14
Briefly, the advantage of MOCVD is the high control over uniformity, deposition rate and
film composition by changing the parameters of the CVD-experiments (temperature, pressure,
flow rates). When the temperature is selected in such a way that the growth behavior is under
kinetic control (figure 6b, zone 1), diffusion of reactants on the surface of the substrate can
minimize problems due to line-of-sight coverage. Therefore more complex structures can be
covered with a uniform film. Main disadvantages of MOCVD are the incorporation of
impurities into the film (carbon) and the air sensitivity of most of the precursors. More
detailed descriptions of the principles of MOCVD can be found in the CVD textbooks, edited
by M. L. Hitchman[74] and Arthur Sherman[76].
1.4.2.1 Properties of a “good” precursor
The suitability of a compound to be used in Low Pressure – MOCVD[g] is given with respect
to several criteria that need to be fulfilled as good as possible.
Transport of the precursor to the substrate without decomposition

The precursor should evaporate at temperatures below its decomposition temperature.
Nevertheless, even less volatile precursors can be used, that cannot be evaporated under
normal CVD conditions. The technique that can be applied is Liquid-Injection MOCVD
where the precursor is solved e.g. in toluene and the solution is abruptly evaporated, carrying
along the precursor molecules.
Clean decomposition of the precursor at the desired temperature regime

In this work clean TaN and NbN thin films shall be deposited. The word “clean” is used in the
sense of low incorporation of carbon or other undesired parts of the precursors. Therefore the
precursor molecules should be either thermally labile with good leaving groups, or the
cleavage of ligands should be easy when the precursor reacts with the reactive gas. These
decomposition properties can be controlled by the well directed choice of ligands. Bidentate
ligands for instance elevate the thermal stability, but can lead to the incorporation of large
amounts of ligand fragments into the films.
Normally, the carbon content (and the content of halides) in the films decreases when higher
substrate temperatures are used during decomposition. The maximum temperature that can be
[g] Actually LPCVD is standard method and only very few examples for Atmospheric Pressure CVD (APCVD)
exist.
15
used during a process is normally given by the thermal stability of the substrate or the
deposited material.
Formation of the right phase in the right degree of crystallinity

The influence precursors have on the resulting film composition and crystal phase seems to be
very high, especially in this work, which deals with the deposition of TaN and NbN thin
films. It was claimed that pre-formed bonds (e.g. Ta=N-bonds) favor the formation of certain
phases. So far, no clear relation has been found between the use of a certain ligand system and
the resulting crystal phase of thin film. The grade of crystallinity however can be regulated
mainly by the substrate temperature and the amount of reactive gas, but again little is known
about which ligand system leads to which degree of crystallinity. It is still an open question
whether the ligands can direct the growth of a particular crystal phase.
Simple and up-scalable synthesis, low toxicity

Multi-gram batches of the certain precursor should be easily accessible. Nonetheless, costs of
the starting compounds do not play such an important role, compared to the role of reaction
time and the number of necessary reaction steps. In addition, it is preferable that the used
ligands and the resulting complex exhibit rather low toxicity.
Chemical and long-term thermal stability

The precursor should be as stable as possible at the evaporation temperature (in fact many
precursors are not) and it should be less reactive towards air and moisture. The latter
simplifies the handling of the precursor. Generally, metal organic precursors of early
transition metals are very sensitive towards moisture.
1.4.3 Atomic Layer Deposition (ALD)
ALD is by far the youngest technique among all deposition techniques. First reports were
published by T. Suntola et al. in the late 1970s.[77] T. Suntola is commonly known as the
inventor of this technique.[h,78] In the beginning, the process was used for processing of thin
film electroluminescent devices (TFEL) that had to be coated with a highly uniform film of
zinc sulfide.[79] Although ALD belongs – by definition – to the group of CVD-techniques one
crucial difference to CVD can be pointed out. In CVD processes the precursor is normally
decomposed by thermal reactions with a coupling of homogeneous gas-phase and
[h] However, other reports exist by a Russian group that claims to be the original inventor of the technique.
16
heterogeneous surface reactions. The substrate temperature is significantly higher than the
onset temperature of decomposition of the precursor. In the case of ALD, at first the precursor
is absorbed onto the surface of the substrate (by a chemical reaction or just by physical
absorption) and – in an ideal case – inhibits further growth.[80,81] The process is self-limiting
and forms a sub-monolayer. The compound is not thermally decomposed. In a second step a
reactive compound, e.g. water, ammonia or hydrazine is passed over the substrate leading to a
full decomposition of the adsorbed precursor. Thus, an active surface is created that can again
react with the precursor (figure 7). Inert purge gas is used to remove an excess of reactants in
the reaction chamber between each pulse of precursor and reactive compound. The process
that comes close to an ideal ALD-process is the reaction between trimethylaluminium and
water. Because of that, this process is used to test new ALD-reactors on their functionality.
Figure 7. Idealized ALD process showing one cycle of deposition. In reality, less than one monolayer is formed
and normally undesired thermal decomposition of the precursor occurs.
ALD is a technique that polarizes research groups and industry in terms of applicability. On
the one hand it offers great advantages, but on the other it suffers from serious concerns that
have not been overcome yet. Advantages are:
The growth of the film can be easily controlled by the number of cycles per
deposition.
High uniformity of the films is achieved, even on substrates having very high aspect
ratios e.g. DRAM-trenches. No line-of-sight deposition occurs due to the saturation of
the surface.
Very precise control of pressure and flow rates is not required in an ideal ALD-
process.
No gas-phase pre-reactions between the precursor and the reactive gas can take place
due to the separation of the two sources.
The major disadvantage of ALD is that in most of the cases ideal ALD-growth like behavior
is not possible.
17
Homogeneous and heterogeneous parasitic thermal decomposition occurs (CVD-

growth). This is indicated by obtaining higher growth rates at longer pulse times of the
precursors. In an ideal case the growth rate would be independent of pulse times of the
precursor and the reactive gas (saturation, self-limiting growth).
The adhesion of the thin films on silicon surfaces is rather low (e.g.TaNx).[82]
The low substrate temperatures, below the thermal decomposition temperature of the
precursor, lead to the formation of low density films that are completely amorphous. It
turns out to be quite challenging to deposit nano crystalline films at these low
temperatures
When no ideal ALD growth can be assumed, parameters e.g. flow rates, temperature
distribution in the reactor, pressure and pulse/purge times of the reactants play an
important role on the uniformity of the films.
In the case of film thicknesses in the 1-10 nm range, the first cycles of ALD raise
problems in terms of island growth.
Little is known about theoretical studies of the ALD-process. It is not a well
established technique and still problematic in application.
Contrary to all the disadvantages, ALD seems to be the only technique which shows the
ability to fulfill certain criteria given by the International Technology Roadmap for
Semiconductors in respect to film thicknesses, uniformity (covering substrates with very high
aspect ratios) and growth control in the long term perspective. New approaches have been
established for the use of plasma-enhanced ALD, with the aim to obtain denser, nano-
crystalline films of e.g. TaN at moderate temperatures.
18
Chapter 2 State of the art in research and motivation
The aim of this chapter is to give an overview of the developments in precursor synthesis for
the deposition of tantalum and niobium nitride thin films by means of CVD and ALD
techniques. The majority of the precursors have been tested under CVD conditions, with
strongly deviating results in terms of the film properties (e.g. crystallinity, phase and
resistivity). Very little was reported on the ALD of TaN and NbN using metal organic
compounds as precursors.
2.1 Previously reported MOCVD experiments for group(V) nitrides
Before starting to discuss the depositions that have been carried out in detail, it is advisable to
have a look on figure 9 (page 27, fold-out) in which the experiments are summarized (with
letters referring to the experiments, discussed in the text).
Homoleptic halido-compounds of tantalum and niobium have been used in the beginning of
MOCVD experiments. These precursors, mainly TaCl5 and NbCl5, feature a relatively low
volatility and require high temperatures for volatilization.[24,83,84,85,86] In addition, it is
necessary to use reactive, nitrogen containing co-reactants e.g. ammonia or nitrogen in order
to grow nitride thin films. This necessity on the other hand also bears the opportunity to tune
the nitrogen content within the films. Obviously one advantage of these precursors is the
absence of carbon atoms in the whole process. Therefore no undesired carbon incorporation
occurs during deposition. The major disadvantages of these precursors are the high process
temperature of about 900 °C and the incorporation of halides into the film (A). Halides tend to
have a deteriorating effect on the whole structure of the devices. Therefore they are highly
undesired, even in small amounts. In order to lower the temperature of the processes
drastically, the less stable compound TaBr5 was tested in CVD processes with the co-reactants
NH3/H2 (B) or even with a H2/N2-plasma (C).[87,88] Using plasma-assisted CVD of TaBr5
(H2/N2-plasma), films were deposited that consisted of highly conductive TaN in the face
centered cubic (fcc) rocksalt-type phase.[i] However, as it was mentioned before, PA-CVD has
[i] The resistivity of the films, deposited in these experiments were 150 μΩ·cm, which is the lowest value that
has been reported so far for TaN thin films, made by CVD-techniques. It is close to the literature value for bulk
TaN (128 μΩ·cm).
19
some drawbacks in terms of damaging the underlying substrates. In addition, approximately

3 % of bromine was incorporated into the films.
2.1.1 MOCVD of tantalum nitride
Compared to other fields of MOCVD, e.g. the deposition of titanium dioxide or hafnium
dioxide, the number of precursors that have been tested is rather low. Amido-substituted
complexes (Ta(V) and Ta(IV)) were used as precursors, followed by mixed amido/imido
compounds. Quite recently, more complex, halide containing complexes have been
investigated.
Homoleptic Ta(V)-amido-complexes
A first attempt to overcome the drawbacks, related to metal halides, was the replacement of
the chloro ligands by dialkylamido groups. Thus, PDMAT (Pentakisdimethylamidotantalum)
synthesized from TaCl5 and five equivalents of LiNMe2 [89] were used in MOCVD processes,
together with ammonia as a reactive gas (D).[90,91] Although depositions at temperatures
between 200 and 450 °C were carried out successfully, no conducting films could be
obtained. Instead of cubic TaN, insulating Ta3N5 material was deposited. The amount of
carbon in these films was below the detection limit. Again, like in the case of tantalum
halides, PA-MOCVD experiments were carried out using methane/hydrogen-,[92] ammonia-[93]
or hydrogen-plasma[93] in order to reduce tantalum from the oxidation state +V to +III (cubic
TaN) (E). Conducting films were obtained that consisted of tantalum nitride and tantalum
carbide. The authors state that cubic TaN was deposited, using the ammonia-plasma at
temperatures of about 300 °C.[93] This statement is questionable, because TaC has almost the
same positions for reflections in XRD-spectra. If the films consist of a mixture of cubic
TaN1.0 and TaC, the ratio of Ta:(N+C) should be 1:1. Instead it is 1:(1.1+0.51) (based on
XPS-studies). Therefore it could also be that the film consists of a mixture of amorphous
Ta3N5 and nanocrystalline TaC, while the tantalum carbide phase is responsible for the low
resistivity and the observed peaks in the XRD-spectra. Films, deposited using a
methane/hydrogen plasma at substrate temperatures of 225 °C resulted in the formation of
amorphous films that consisted mainly of tantalum carbide (carbon:nitrogen ratio varied from
3:1 to 10:1).[92] As expected, when methane was absent in these experiments (only hydrogen
was flown into the reactor), the deposited films contained less carbon and more nitrogen
(carbon:nitrogen ratio = 1:1.2).
20
The precursor PDEAT (Pentakisdiethylamidotantalum) is a topic on its own. This compound

was synthesized by Bradley and his co-workers in 1959, together with PDMAT.[94,95] In
contrast to PDMAT, PDEAT cannot be distilled (and therefore not evaporated) without
decomposition. At higher temperatures it decomposes to a mixture of an amido/imido
compound and the [Ta(N(Et)(CHCH3))(NEt2)3]-complex containing a η2 imido-ligand (figure
8).[96] The mechanism is supposed to involve an activation of a β-CH bond of an NEt2 ligand
and the subsequent cleavage of diethylamine. This compound in turn decomposes at higher
temperatures to [Ta(NEt)(NEt2)3] and ethylene.
Figure 8. Thermal decomposition of PDEAT during distillation.
Despite these undesired gas phase reactions, this system was investigated via MOCVD by
various research groups. Astonishingly, recent publications about the MOCVD of PDEAT do
not even mention the fact that the precursor cannot be evaporated without decomposition. The
use of PDEAT as a single source precursor is not suitable for depositing carbon free films. All
films show carbon contents of above 30%; therefore it is misleading to talk about the
deposition of tantalum nitride thin films at all (F).[97,98] As soon as ammonia participated in
the MOCVD-processes, the carbon contamination decreased below 5% and the cubic TaN-
phase could be observed in XRD-spectra of the films (G). The participation of ammonia
involves transamination reactions during growth and the release of HNEt2.[98] However, the
resistivity of these films was rather high (~12000 μΩ·cm). Plasma assisted MOCVD
depositions (H2-plasma) or the bombardment with argon/nitrogen ions during deposition did
not help to reduce the carbon content of the films significantly (G).
Mixed amido/imido compounds

Two trisamidoimido complexes of tantalum have been investigated so far. The best known
complex is TBTDET (tert-Butylimidotrisdiethylamidotantalum, [Ta(NEt2)3(N-t-Bu)]).[99] It
has been used as a single source precursor for MOCVD and also together with ammonia as
co-reactant (H).[1,100] Using TBTDET as SSP gave low resistivity films at temperatures of
21
about 600-650 °C that contained carbon below 10% and showed reflections for cubic TaN in
the XRD-spectra. So far these experiments (performed by Tsai et al. in 1995) are the only
examples of good quality TaN films deposited by a plasma free deposition process that show
a resistivity below 1000 μΩ·cm. However, reducing the carbon content in the films is highly
desirable. Attempts were made by using ammonia as co-reactant at low temperatures (~400
°C). Unfortunately no details on composition were given in the publication. The use of the
precursor TAIMATA (tert-Amylimidotrisdimetyhlamidotantalum, [Ta(NEt2)3(NCMe2Et)]) as
SSP again led to the formation of films that contained large amounts of carbon (Ta:N:C =
1:1:1, 450 °C substrate temp) (I). XRD-analysis revealed reflections that probably belong to
tantalum carbide.[51] Adding ammonia during deposition led to a decrease of the carbon
content in the films on the one hand, but on the other hand increased the amount of nitrogen
(Ta:N:C = 1:1.2:0.3) in the films (I). Most probably, the insulating phase Ta3N5 was
deposited. Another work revealed contradicting results. Again, TAIMATA was used as SSP
(500 °C substrate temperature), but this time nearly stochiometric TaN films were obtained
that showed a significantly smaller fraction of carbon in the films (J).[48]
Ta(IV)-amido complexes
The syntheses of only a few tantalum(IV)-complexes have been reported so far. Two of these
complexes have been tested for MOCVD of TaN: the homoleptic complex [Ta(NEt2)4] and
the mixed amido complex [Ta(NEt2)2(Ncy2)2]. The complex [Ta(NEt2)2(Ncy2)2] is thermally
less stable and non-volatile. The tantalum center is coordinated in the form of a distorted
tetrahedron with a slight distortion towards square planar geometry. MOCVD experiments in
presence of ammonia were carried out by aerosol assisted MOCVD in which a
precursor/mesitylene solution was nebulized by an ultrasonic nebulizer (K).[101] Thin,
amorphous films with the composition TaN1.5H0.3 were deposited at a temperature of 340 °C.
An oxidation state of tantalum in the order of +IV was determined.[j] The resistivity of the
films was rather high with values of about 250,000 μΩ·cm (which is nearly insulating). If the
oxidation state was really +IV, higher conductivity should be expected.[102, 103] The synthesis
of this complex in sub-gram batches and the use of Na/Hg-alloy make the precursor less
suitable for MOCVD of TaN in mass fabrication. In addition, the precursor was not
completely pure, but still contained some chlorine, which was incorporated into the film.
[j] The authors make the questionable assumption that tantalum (in TaN-films) favors the oxidation state that it
had in the precursor complex.
22
While the analysis of the cyclohexyl-containing complex is valid, the existence of the other
complex [Ta(NEt2)4] has still not been proven in a proper way. In contrast to the involatile
complex [Ta(NEt2)2(Ncy2)2] the homoleptic complex is described as a very volatile, liquid
compound.[k] Nevertheless MOCVD-experiments were carried out, but the results should not
be taken for granted. Depositions using [Ta(NEt2)4] in the presence of hydrogen (carrier gas),
led to the formation of conducting films that contained only small amounts of nitrogen and
mainly consisted of elemental tantalum and tantalum carbide (L). Thus it cannot be
considered as a suitable precursor for TaN in the presence of ammonia.
Halide-containing metal organic precursors

The three following precursors showed interesting behavior in MOCVD processes. However,
they all contain halides which inevitably leads to chlorine incorporation into the films - at
least to certain extend. The incorporated halides can react with moisture to form corrosive
acids. Charles Winter and his group synthesized two dichloro/amine/amido/imido complexes
of tantalum. The complex [TaCl2(N-t-Bu)(HN-t-Bu)(H2N-t-Bu)]2, synthesized from the
reaction of TaCl5 and tert-butyl-amine, is dimeric and can be sublimed at 120 °C without
decomposition. Used as a SSP (substrate temperature: 600 °C) it produces films, consisting of
insulating, nanocrystalline Ta3N5 (M).[104,105] The oligomeric, but sublimable
dimethylhydrazine congener [TaCl2(NNMe2)(HNNMe2)(H2NNMe2)]n seems to be more
interesting. MOCVD experiments using this orange, solid precursor gave thin silver colored
films, showing fcc phase TaN. Nonetheless, the values, found for the resistivities were too
high, compared to bulk cubic TaN (N).[106]
The groups around C. J Carmalt and D. J. Williams recently published data about the complex
[TaCl3(NSiMe3)(NC5H3Me2-3,5)2]. The complex is stabilized by two neutral donor-ligands.
This „precursor“ (volatilization without decomposition was not proven) led to the formation
of conducting films[l] (substrate temperature: 600 °C) that consist of tantalum and
nitrogen.[107] The formation of stochiometric TaN is indicated, but no convincing evidences
were provided (e.g. quantitative XPS or SIMS-analysis) (O).
Other precursors, not tested for CVD

Some compounds have been reported with respect to their potential as precursor for MOCVD
or ALD techniques. The synthesis of these “precursors” is described in the publications,
[k] This description of the physical properties fits more to the behavior of a mixed amido/imido Ta(V)-complex.
[l] The resistivities of the films were reported to be very low, but the results have to be taken with care.
23
normally including a comment on their volatility. However, most of the compounds were not
tested on their thermal behavior e.g. decomposition temperature or vapor pressure. Basically
all mixed amido/imido-complexes belong into this group, the simple alkyl substituted ones
and the more complex silicon complexes e.g. [Ta(NSiHMe2)(N(SiHMe2)2)3].[108] In addition,
the almost non-volatile tantalum IV-complex [Ta(NEt2)2(NPh2)2][109] and the low volatile
complex [{4,5-Me2-C6H2(NSiMe3)2)2}TaCl][110] were considered to serve as precursors for
MOCVD.
2.1.2 Conclusions of past reports about the MOCVD of tantalum nitride
At this point it is necessary to make a comment about the results regarding the MOCVD of
TaN thin films. According to the results of this dissertation, it is very difficult to make a
general statement whether a precursor is suitable for the MOCVD of TaN thin films or not. It
is obvious that compounds should fulfill the basic criteria of a precursor (e.g. volatility,
purity). As a conclusion one can only say, that a precursor is not suitable to deposit
conducting TaN thin films with a certain set of parameters (e.g. type of reactor, temperatures,
reactive gases, type of precursors). It is hardly possible to say that a precursor is not suitable
in general. Still, some basic conclusions can be drawn from the experiments. These
conclusions will be discussed in the following.
Crystalline vs. amorphous films (high vs. low substrate temperatures)

[m]
Although low substrate temperatures are desired for many processes, amorphous films
(lower temperatures) often show higher resistivities than nanocrystalline films (higher
temperatures). Many of the experiments, carried out at temperatures of about 400°C (B, F, G,
H, K) would probably lead to better conductive films when the substrate temperature is set to
600 °C. Generally it was observed that the best conductivities of the films were achieved at
the highest deposition temperature of an experimental row. The incorporation of other
elements (hydrogen, carbon, silicon) can lead to the inhibition of crystallization of the films.
Incorporation of carbon
The incorporation of carbon into the films often has a positive effect on their conductivity due
to the formation of highly conductive tantalum carbide. It is difficult to distinguish between
[m] This is a critical issue. In some papers it is stated that the device structures cannot endure deposition
temperatures above 400°C. However, based on the type of application of TaN and the type of fabrication process
deposition temperatures from 300 °C up to 700/800 °C can be tolerated (in some cases even above 900°C).
24
crystalline cubic TaC and TaN based on XRD-spectra due to their similar lattice constants of
d = 2.503 Å for TaN and 2.572 Å for TaC, respectively. Although tantalum carbide is also an
interesting material for a diffusion barrier,[111,112] pure TaN films are desired. Carbon
containing TaN films are normally less stable and more susceptible for post oxidation and
diffusion. However, this point is not clearly discussed in literature.
Ambiguous impact of ammonia

Ammonia plays an ambiguous role. When used in a deposition process it definitely reduces
the amount of carbon (originating from the precursor) that is incorporated into the films. On
the other hand resistivity of the films can either decrease or increase when ammonia is used.
The removal of carbon leads to the absence of tantalum carbide in the films. Now, if TaC was
the real cause of conductivity, resistivity of the films will decrease with increasing ammonia
flow rate (I). In addition, ammonia serves as an additional nitrogen source, which should not
be required when all-nitrogen substituted tantalum complexes are applied in MOCVD. The
excess of nitrogen could lead to preferred, but highly undesired formation of nitrogen rich
Ta3N5 (D). In some experiments ammonia seems to support the formation of nanocrystalline,
cubic TaN and thus lowers the resistivity of the films, compared to films deposited without
additional ammonia. Nevertheless, step coverage of the films decreases drastically (G). The
effect of ammonia in combination with homoleptic amido complexes was studied in detail by
means of mass spectroscopic analysis by S. Motojima et al. in 1975 and D. M. Hoffman.[90,113]
Transamination reactions seem to be favored at temperatures below 600 °C (cleavage of
HNR2), while complete thermal decomposition of the precursors occur at higher temperatures.
However, it is difficult to draw conclusions on the effect of ammonia on depositions of TaN
due to the absence of a nitrogen rich Ti3N4-phase.
Oxidation of the films

In many works, the incorporation of oxygen into the films is mentioned. This can happen
either during deposition, caused by minor leaks in the reactor, or due to post oxidation after
removal of the films from the reactor. The high oxophilicity of tantalum leads to the
formation of insulating Ta2O5, when oxygen is present in the reactor chamber. The Ta2O5 has
a strong influence on the resistivity of the whole film and can falsify the results of a whole
experimental row.
25
Use of plasma assisted MOCVD

In figure 9 it can be seen that all experiments that used ammonia-, hydrogen- or nitrogen-
plasmas as reactants in depositions led to the formation of films with low resistivity that
contained crystalline tantalum nitride and/or tantalum carbide. The substrate temperatures
were below 350°C. However, the use of plasma bears several problems, including a less-
conformal growth over the whole substrate and the derogation of the underlying substrate.
26
Figure 9. Diagram including the majority of the experiments that have been reported so far. From each experimental row, the data set of the
27
film with the lowest resistivity is displayed. The green box marks the expectations of the industry that have to be met. Yellow boxes show
experiments using the precursors as SSP. Blue boxes indicate the use of ammonia during deposition. Grey boxes show experiments using
plasma assisted CVD or certain reactive gases.
2.1.3 MOCVD of niobium nitride
The number of precursors that have been tested to deposit niobium nitride thin films is very
small compared to TaN (figure 10). In the first instance, NbCl5 was used as a precursor in
MOCVD processes. Using nitrogen and hydrogen as co-reactants, high substrate temperatures
are required in order to deposit the metal rich phases Nb2N and Nb4N3 as well as the
stochiometric NbN (as mixture of phases).[24,25,86] Together with ammonia and hydrogen,
cubic NbN is obtained (TSubstrate = 900 °C).[27] An alternative reactant is hexamethyldislazane
that gives cubic, rock salt phase NbN. This atmospheric pressure MOCVD process can be
carried out at much lower substrate temperatures of about 550°C.[85] The only metal-organic
precursors so far that have been tested in pure MOCVD-processes were [Nb(NEt2)4] and
[Nb(NMe2)5] by Hoffman et. al.[91], [NbCl2(N-t-Bu)(HN-t-Bu)(H2N-t-Bu)]2 and
[104]
[NbCl2(NNMe2)(HNNMe2)(H2NNMe2)]n by Winter et al. and [NbCl3(NSiMe2Ph)-
(NH2SiMe2Ph]2 by Williams and his group.[107] The homoleptic amido complexes gave, in
accordance with the results of Hoffmann et al. in the case of tantalum, the nitrogen richest
phase of niobium, Nb3N4, which is a conducting phase. This assumption is based on studies of
the composition of the films. XRD-measurements were not possible due to the amorphous
character of the films. The high dosage of ammonia during deposition reduced the amount of
incorporated carbon below 3%. The two dichloro-complexes, synthesized by the reactions of
NbCl5 with Hdmh and tert-butylamine respectively, were used to grow nano-crystalline, cubic
NbN thin films at substrate temperatures of 500°C. The same result was observed for the
silicon containing precursor [NbCl3(NSiMe2Ph)-(NH2SiMe2Ph]2, although it is unlikely that it
can be volatilized without decomposition. Two precursors, namely [Nb(NEt2)4] and the
pentavalent complex [{η3-N(CH2CH3N-i-Pr)}Nb(N-t-Bu)] that contains a triamidoamide-
group were tested together with hydzaine plasma to produce cubic NbN.[114]
28
Figure 10. Selected MO-precursors that have been tested for the MOCVD of NbNx thin films.
2.2 Previously reported ALD experiments for group(V) nitrides
The main emphasis in the ALD of group V nitride materials was directed to tantalum nitride
(2.2.1). Experiments for the ALD of NbN are discussed in 2.2.2.
2.2.1 ALD of tantalum nitride
The first experiment for the deposition of TaN via ALD was already performed in 1988 by
Hiltunen et al. together with other metal nitrides.[115] However, little analytical data was given
and full studies were not presented until 1999.[116] The development of the ALD of TaN is
similar to the progression in MOCVD experiments. In the beginning metal chlorides were
used for depositing thin TaN-films. The big advantage of metal chlorides is their high thermal
stability. Therefore, very high surface temperatures (500 °C) can be applied in ALD-
experiments when e.g. TaCl5 is used as a precursor. Deposition experiments with metal
organic precursors have to be carried out at much lower temperatures. Otherwise, parasitic
MOCVD-growth can be observed and the deposition is not self-limiting.
ALD using TaCl5 and TaBr5 as precursors

Table 2 gives an overview of the experiments that have been performed so far, including
structural and physical properties of the films.
29
Table 2. Experiments for the ALD of TaN thin films using metal halides.
Precursor Reactive Substrate Phase/crystallinity Resistivity Comments on Ref.
Component temperature contamination
in °C
TaCl5 NH3 200-500 °C Orthorombic Insulating Below 300 °C high 116
Ta3N5 chlorine contamination
(above 400 °C) of the films
TaCl5 NH3 and zinc 400-500 °C Cubic TaN Conducting Low level of 116
900 μΩ·cm contamination
TaCl5 NH3 and 250-400 °C Cubic TaN, or 1,300- High contamination 117
AlMe3 cubic TaC of low 7,500 with C, Cl, Al
crystallinity μΩ·cm (total: 50-60 %)
TaBr5 NH3 and Zinc 400-500 °C Comparable results to TaCl5 (ref. 106) 117
TaBr5 NH3 and 250-400 °C Low crystalline 6,600- High contamination 117
AlMe3 TaN-films 64,000 with Al, C, Cl
μΩ·cm
TaCl5 NH3 and 300-500 °C Cubic TaN and 36,000- Low contamination 118
SiH(NMe2)3 insulating Si3N4 220,000 with chlorine or carbon
(based on XPS) μΩ·cm
TaCl5 1,1-dimethyl- 300-400°C Amorphous Insulating Most probably Ta3N5 119
hydrazine was formed
TaCl5 N2/H2-plasma 100-400 °C Cubic TaN 350 μΩ·cm Film contains chlorine 120,
(300 °C) 121
The first approach that has been attempted is the alternating pulsing of the metal halide and
ammonia at substrate temperatures of 200-500 °C. It seems that ammonia is not suitable to
reduce the Ta(V)-center of TaCl5 to Ta(III) at these temperatures. Ritala et al suggested that
only liberation of HCl occurs, thus giving insulating, nanocrystalline Ta3N5 (figure 11a).[116]
Figure 11. Proposed reactions for the ALD of TaNx using a) TaCl5 and ammonia or b) ammonia and gaseous
zinc.
Hence, various metal based and organic reducing agents were tested. Metallic zinc together
with ammonia was successfully applied and cubic, conductive TaN was obtained (figure 11b).
The use of gaseous zinc requires very high temperatures (min 400 °C) for the whole transfer
line system, including the valves. Therefore industrial use does not seem to be promising. The
use of trimethylaluminum (TMA) as the reactive compound led to the formation of
conductive, nanocrystalline films. It could not be found whether cubic TaN or cubic TaC was
the conductive species. These films were heavily contaminated with aluminum, carbon and
chlorine and consisted of less than 40-50% of tantalum and nitrogen. Replacement of TaCl5
30
by TaBr5 showed no improvement in the deposition behavior. The use of organic compounds
as reducing reagents was not successful. Pulsing TDMAS (Tris(dimethylamino)silane,
HSi(NMe2)3) during the ALD-cycles led to the formation of cubic TaN, but concurrently,
insulating, amorphous Si3N4 was deposited. Thus, the films were less conductive with
resistivities above 3.6 x 105 μΩ·cm. Even higher resistivities were obtained in depositions
employing TaCl5 and unsymmetrical dimethylhydrazine. Insulating, amorphous Ta3N5 was
deposited in the temperature range from 100 to 400 °C. Most probably only transamination
reactions took place and the reductive capability of hydrazine as such was too low at these
temperatures.
Plasma-enhanced ALD (PEALD) of TaCl5 and a mixed hydrogen/nitrogen plasma showed the
best results. Highly conductive, cubic TaN was deposited even at 300 °C. Nonetheless,
applying aggressive plasmas in deposition experiments always bears the risk of surface
degradation.
In all experiments, ALD-growth (self-limitation) was observed and the films were highly
conformal. Generally, halide incorporation is a drawback (corrosion, electrical properties) that
was already discussed for the MOCVD experiments of TaN using TaCl5. The oxygen content
of the films plays an important role for the electrical properties of the films. All films (ref.
106-111) contained 5-8 % of oxygen. The main reason, given by the authors is post oxidation
of the film, once it was removed from the reactor. ALD films are generally not as dense as
bulk TaN or MOCVD deposited TaN thus displaying a certain porosity, susceptible for the
diffusion of oxygen into the films. However, small leaks in the reactor setup could be an
alternative source of oxygen.
ALD using metal organic precursors (TBTDET and TAIMATA)

The two mixed amido/imido compounds TBTDET ([Ta(NEt2)3(N-t-Bu)]) and TAIMATA
([Ta(NMe2)3(NCMe2Et)]) were tested for ALD purposes together with the co-reactants
ammonia as well as hydrogen plasma (table 3). The results regarding the use of ammonia are
contradicting. Two groups (TAIMATA[122], TBTDET[126]) reported that amorphous, almost
insulating TaNx films were deposited. These films had very low densities (~3.6 g/cm3; for
comparison: bulk TaN: 13.7 g/cm3) and were highly susceptible towards post oxidation in air.
These results agree with the general assumption that ammonia is not suitable to act as a
reducing agent at low temperatures, but only as a proton donator for transamination reactions
or the protonation of metal chlorides (see figure 11a). O. van der Straten and his co-workers
on the other hand reported the formation of completely amorphous, but very conductive TaN
31
films using TBTDET and ammonia at substrate temperatures of 250 °C. So far no other
reports exist in which completely amorphous TaNx films are conductive. Therefore these
results have to be considered with care. Unfortunately, no colors of the films are given.
Metallic, stochiometric TaN would show a golden/brown mirror-like appearance, while
thicker films of insulating TaNx (x > 1) result in green, blue and violet surface colors.
Table 3. Experiments for the ALD of TaN thin films using metal organic compounds.
Precursor Reactive Substrate Phase/crystallinity Resistivity Comments on Ref.
Component temperature contamination
in °C
TAIMATA NH3 250 °C Amorphous Ta3N5 insulating Heavily oxidized 122
(20 % oxygen)
TAIMATA H2-plasma 250 °C Cubic TaN 366 μΩ·cm 17 % carbon 122
TBTDET NH3 250 °C Amorphous TaN 500-1,000 7 % carbon, 7 % 123,
μΩ·cm oxygen 124
TBTDET NH3 260 °C Amorphous TaNx 1.4 x 106 Aging of the film is 126
μΩ·cm observed
TBTDET H2-plasma 260 °C Cubic TaN 400 μΩ·cm 20 % carbon 125,
126
The results for films, deposited from TBTDET or TAIMATA, using hydrogen plasma are
consistent. Cubic TaN (XRD) films having high conductivity and a relative high density (~7.9
g/cm3) were deposited. It seems as though hydrogen-plasma does not have the ability to
inhibit the incorporation of carbon into the films (17-20 atomic %). It can be concluded that
no significant protonation of the amido groups and consequent cleavage of amines occur. Due
to the higher density of the films, no aging effects in air (post oxidation) were observed.
2.2.2 ALD of niobium nitride
So far only NbCl5 has been used as precursor for the deposition of NbNx thin films. Due to the
fact that no insulating NbN phases are known, all depositions led to conducting films.
Experiments using ammonia as the co-reactant resulted in NbNx films that contained
significant amounts of chlorine (depending on the substrate temperature). The crystalline
phase could not be explicitly assigned (δ-NbN or Nb4N5). Time Of Flight – Elastic Recoil
Detection Analysis (TOF-ERDA) clearly showed that the films were nitrogen rich. This
indicates the formation of Nb4N5. Oxidation of the films does not play an important role. The
oxygen content always remained below 1 %. The use of zinc as an additional reducing agent
did not show fundamental improvement of the quality of the films. Likewise, no positive
32
effect was achieved when dimethylhydrazine was used as the source of nitrogen in the ALD
process.
Table 4. Experiments for the ALD of TaN thin films using metal organic compounds.
Precursor Reactive Substrate Phase/ Resistivity Comments on Ref.
Component temperatu crystallinity contamination
re in °C
NbCl5 NH3 and zinc 500 °C Crystalline δ-NbN 200 μΩ·cm Oxygen < 1%, but 127
or Nb4N5 Nb:N ratio = 2:3
NbCl5 NH3 500 °C Crystalline δ-NbN 500 μΩ·cm Oxygen < 1%, but 127
or Nb4N5 Nb:N ratio = 2:3
NbCl5 NH3 250 - Most probably 16,000 μΩ·cm Oxygen < 1%, 128
500 °C Nb4N5 (250 °C) chlorine:
600 μΩ·cm 8 % at 250°;
(500 °C) < 1% at 500 °C
NbCl5 1,1- 400 °C Low crystallinity 2,900 μΩ·cm 5 % of chlorine 119
dimethyl-
hydrazine
33
Chapter 3 Starting compounds and their synthesis
This chapter discusses the synthesis of all starting compounds that were not commercially
available. The existence of the majority of the compounds has already been reported,
including their synthesis. However, the scales of the batches were rather low, so were the
yields in some cases. The aim was to upscale the amount per badge and increase the yield.
3.1 Synthesis of mixed amido / imido compounds of tantalum and niobium
A large variety of tantalum and niobium amido and imido complexes of the type
[M(NR3)(NR1R2)3] (M = Ta, Nb; R3 = t-Bu, n-Pr; R1,R2 = Me, Et) was synthesized within this
work. The synthesis always started from the metal(V)-chloride.
Basically two synthetic routes have been reported, a one- and a two-step synthesis in which a
pyridine stabilized intermediate product is isolated. In order to synthesize the amido/imido
complex in one step, four equivalents of the lithiated amide [LiNR1R2] and one equivalent of
[LiNHR3] are added to [TaCl5] at room temperature. The reactions take place very rapidly and
the addition of both ligands at the same time seems to lead to mixture of different species.
Therefore the yields of these reactions are rather low (table 5, page 36) and the compounds
are not as pure as the products obtained from the two step synthesis.[129] Thus we decided to
use the two-step synthesis which guarantees higher yields, but on the other hand requires
higher efforts and takes longer time.[130,131,132,133,134] The first step consists of the reaction of a
secondary amine (tert-butyl amine) with a metal chloride (figure 12). Chlortrimethylsilane is
used as a catalyst and forms with the amine an intermediate silyl-amine complex (Me3Si-
NHR3). After the reaction of this complex with the metal chloride, free SiMe3Cl is re-formed.
Figure 12. Synthetic routes for S1-S3, which are the intermediate compounds for the synthesis of S4-S9.
34
Due to the lower π-donating effect of the chloro ligands in comparison to the amido-ligands in
the amido/imido-complex, the metal-chloro/imido complex is electronically not saturated and
requires stabilization by two pyridine molecules.
Instead of pyridine, it is also possible to use tetrahydrofurane as the stabilizing donor.[135] The
synthesis of S1-S3 in this work was carried out using toluene as the solvent. The hydrochloric
acid that was liberated during the reaction precipitated in the form of pyridinium and
ammonium salts. These salts could be removed by simple filtration, while the products
remained solved in toluene. The solubility of the products (S1-S3) in toluene was increased by
adding further amounts of pyridine to the reaction mixture. After recrystallization from hot
toluene (ca. 2 ml toluene per gram S1-S3) the yellow-orange products were obtained in pure
form. The yields in all reactions were about 80 % in respect to the amount of TaCl5 that is
employed. Attempts to synthesize a trichloro/imido complex using Hdmh instead of the amine
were not successful. An orange, insoluble solid was formed during the reaction.
In the second step of the reaction, the chloro-imido-compounds were brought to reaction with
three equivalents of lithiated amines in order to synthesize S4-S9 (figure 13).
Figure 13. Synthetic route for S4-S9. The second step of the two-step synthesis is shown.
The lithiated amines were added to the metal complexes as suspensions in hexane. LiNMeEt
and LiNEt2 had to be prepared from the corresponding amine and, butyllithium, prior to use.
Higher yields of the products (S4-S9) were obtained when the freshly prepared suspensions of
the lithiated amines were stirred at room temperature for 24 hours before they were brought to
reaction with the metal complex. It seems that the reactivity of the amides was reduced,
probably due to agglomeration of the particles in the suspension. This reduced reactivity led
35
to a lower amount of side products that were formed during the reactions. Our yields as well
as the batch sizes were well above the values, reported in previous publications. The range in
yields was about 50-70 % based on TaCl5 and 63-87 % based on the pyridine stabilized educts
(table 5).
Table 5. Yields of the reactions for the formation of S4-S9 from our experiments, compared to the experiments
from previous works. [129-132]
One-step Two-step This work (two- Color/
Comp M R1 R2 R3
synthesis synthesis step synthesis) phase
TaCl5 yield TaCl5 Yield TaCl5 Yield
in g in % in g in % in g in %
S4 Ta Me Me t-Bu 14.7 37 -- -- 18 59 yellow solid
yellow-
S5 Ta Me Et t-Bu -- -- 10 <40 39 68
colorless liquid
S6 Ta Et Et t-Bu -- -- 50.0 60 60 64 yellow liquid
S7 Ta Et Et n-Pr -- -- 2.4 55 9 73 orange liquid
yellow-green
S8 Nb Me Me t-Bu 11.1 18 -- -- 13.5 57
solid
S9 Nb Et Et t-Bu -- -- 3.0 18 -- -- yellow liquid
All amido/imido compounds are highly volatile and can be distilled/sublimed at temperatures
of about 60-80 °C in vacuum. The dimethylamido substituted complexes S4 and S8 are solids
at room temperature (with low melting points), while the other compounds are liquids, having
a slightly higher viscosity than water. The colors of S4-S9 varied, depending on the rapidness
of addition of the lithiated amide to the metal compounds S1-S3. The faster the addition, the
darker was the color of the crude products after removal of solvents (orange to almost black).
The same holds for the color of the products after distillation (colorless to orange). Elemental
analysis of the compounds revealed no significant amounts of impurities after a single
distillation. All NMR-data were in accordance with the data that has been published before.
The crystal structure of complex S8 has not been reported so far and will be discussed in the
following. Unintentionally, during one experiment of crystallization of S3, water diffused into
the Schlenk tube, giving crystals of the hydrolyzed form of S3 (referred to as S3’). This
complex will also be discussed in brevity.
3.1.1 Single crystal X-ray analysis of S8, S3 and the hydrolyzed form of S3 (S3’)
Crystals of S8, suitable for a structural characterization via single crystal X-Ray diffraction
were collected from the sublimation finger of the purification of the raw, as-synthesized
36
material of S8. The green-orange colored crystals were handled in inert perfluorated oil and
mounted on a glass tip. The crystals were of good quality and resulted in relatively low R-
values of the refined data (molecular structure: figure 14). The atom C(4) of the complex is
disordered. The molecule itself is highly symmetric, bearing a C3-axis along the imido-
niobium axis (figure 13). The coordination of the four nitrogen atoms around the niobium
center equals a slightly distorted tetrahedron (N(1)-Nb(1)-N(2) = 107.73 (8)°; N(1)-Nb(1)-
N(1)’ = 111.16(8)°). The imido group seems to be ideally sp-hybridized, thus donating
altogether six electrons to the niobium center. The Nb(1)-N(2)-C(3) angle is 180° and the
Nb(1)-N(2) bond length is 1.757 Å. This is slightly longer than in the case of the halide
containing complex [Nb(NCMe3)Cl3(dme)] (1.722(7) Å).[136] The difference can be explained
by the higher donor strength of the amido groups compared to the chloride ligands. More
electron density is pushed into the LUMO-orbitals of the Nb-imido bond, which lengthens the
bond. The amido groups seem to be almost ideally sp2-hybridized. The sum of the bond
angles around N(1) is exactly 360° and the out of plane angle of the amido group is about
177°. Therefore the complex can be described as an 18 valence electron d0-complex of
niobium.
Figure 14. Molecular structure of S8 in the solid state. The C3-rotation axis goes along the C(3)-N(2)-Nb(1) axis.
Crystals of S3 were obtained from a concentrated solution of toluene at -30 °C. However, the
structure has been already reported with similar R-values.[130] Thus, the parameters of this
structure are only discussed in relation to the hydrolyzed product S3’. The hydrolysis of S3
led to the formation of the colorless, yellow complex [O{Nb(N-t-Bu)Cl2(py)2}2].
Unfortunately it was not possible to reproduce the synthesis of S3’, therefore further
37
analytical data, e.g. NMR spectra and CHN-analysis cannot be provided. S3’ crystallizes in
the monoclinic crystal system with the space group P2(1)/c. The quality of the crystals was
sufficient, for solving the molecular structure of S3’ in the solid state (figure 15). Structural
analysis revealed that two toluene molecules per complex are incorporated in the crystal
lattice. These solvent molecules show no interaction with the Nb-complex and are therefore
not discussed furthermore. Both niobium atoms of the dimeric complex are coordinated in an
octahedral fashion with one oxygen atom as the bridging unit. The other five ligands are one
tert-butyl-imido group, two pyridine and two chloro-atoms. This clearly shows that one
chloro-ligand per Nb-center from the starting complex S3 has been removed by proton
transfer from a water molecule. The Nb(1)-O(1)-Nb(2) is almost linear with a bond angle of
172.6 (3)°. This feature and the Nb-O bond length are in good accordance to the comparable
structure of the complex [O{NbCl3(mecp)(OH2)}2] (mecp = methylcyclopentadienyl).[137]
The bond strength of the three ligands can be classified in the descending order NR2- > O2-1/2 >
Cl- > pyridine. The strongest, π-donating ligand [N-t-Bu2-] is arranged opposite to the relative
weak donor pyridine (which is not covalently bonded). The Nb-Cl bond length is elongated in
the case of the chloro-ligand opposite to the oxygen (Nb(1)-Cl(2): 2.468(3) Å; Nb(2)-Cl(3):
2.462(2) Å), in comparison to the chloro ligand, opposite to the neutral pyridine ligand
(Nb(1)-Cl(1): 2.426(3) Å; Nb(2)-Cl(4): 2.419 Å). All other structural issues regarding bond
length and bond angles are almost identical in the cases of S3 and S3’.
Figure 15. Molecular structure of S3 and S3’ in the solid state. The structure of S3 has already been reported.
The carbon atoms of the pyridine ligands of S3’ are omitted for reasons of clarity.
38
3.1.2 Thermal properties of the compounds S4-S9
All niobium as well as tantalum amido/imido complexes exhibit high volatility. The dimethyl-
amido substituted complexes are low melting solids (S4, S8) while the other complexes are
already liquid at room temperature (S5, S6, S7, S9). The compounds could be distilled at
temperatures between 90 and 115 °C for purpose of purification. Diethylamido-substituted
complexes (S7, S8) required the highest oil bath temperatures. The long-term stability of the
mixed amido/imido complexes at temperatures of about 60-70 °C is limited. After a heating
period of several hours, the colorless/yellow compounds turned to orange/red/brown. The
decomposition products were non-volatile. Repeated sublimation of these aged compounds
yielded pure, colorless to yellow liquids and solids. TG/DTA analysis of all compounds was
performed in aluminum crucibles with a heating rate of 5 °C/min and in inert nitrogen gas
flow (purity: 6.0) (table 6). The melting points of the two solids were determined to be
70.4 °C (S4) and 72.8 °C (S8).
Table 6. Thermal parameters of the compounds S4-S9 (n.d. = not determined; n.v. not clearly visible)
Complex Mass in M.p. 5 % weight Onset of Residual Theoretical,
g/mol in °C loss reached decomposition mass in residual mass for
at T = in ° C % pure MN in %
S4 [Ta(NMe2)3(N-t-Bu)] 384.30 70.4 103 °C n.v. 12.8 50.7
S5 [Ta(NEtMe)3(N-t-Bu)] 426.38 n.d. 101 °C 189 11.1 45.7
S6 [Ta(NEt2)3(N-t-Bu)] 468.46 n.d. 107 °C (appr. 192) 13.0 41.6
S7 [Ta(NEt2)3(N-n-Pr)] 454.43 n.d. 114 °C 189 15.4 42.9
S8 [Nb(NMe2)3(N-t-Bu)] 296.25 72.8 95 °C n.v. 13.6 36.1
S9 [Nb(NEt2)3(N-t-Bu)] 380.41 n.d. 117 °C 162 16.9 28.1
Although thermal decomposition of the compounds already occured at temperatures below

100 °C (e.g. in reservoirs for MOCVD-reactors), it is possible to identify a clear onset of
substantial decomposition for the compounds S5, S7 and S9 in the TG-spectra. The onset of
this considerable decomposition should result in a sudden mass loss of the compound in
addition to the mass loss, caused by evaporation of the undecomposed compound. Figure 16
displays this sudden increase in weight loss for S5, S7 and S9. According to these data, small
exothermic peaks can be observed in the DTA of these complexes. Figure 16 also shows the
absence of a sudden weight loss in the TG of S4, S6 and S8. The lack of clear signals for
decomposition in the DTA-spectra indicates a floating decomposition process. Recording
DTA-spectra at higher heating rates (10 °C/min) would be helpful to distinguish the onset of
thermal decomposition.
39
Figure 16. Left: Weight loss of compounds S5, S7 and S9 in µg per 5 seconds as a function of temperature
(heating rate: 5 °C/min). The sudden increase in weight loss marks the beginning of thermal decomposition. In the
case of S4, S6 and S8, this step cannot be observed (right side).
An indicator for the order of the compounds with respect to their volatility is the temperature
that has to be reached until 5 % weight loss of the compounds occur (table 6). In accordance
to the experiences during distillation of S4-S9 it can be concluded that the diethyl substituted
congeners are less volatile than the dimethyl and methyl-ethyl substituted compounds. It
would be too simple to take the difference in the molecular masses in account for the different
volatility. Comparing the pairs S4/S8 and S6/S9, the identical niobium and tantalum
complexes, the niobium containing complex S8 is more volatile than S4 (tantalum-complex),
while S9 (niobium) seems to be less volatile than S6 (figure 17). Naturally intermolecular
interactions in the solid state/liquid are the cause for the differences in volatility. In order to
get reliable data for the sequence of volatility S4-S9, isothermal studies at temperatures of
about 60-80 °C would be required. The last two columns of table 6 summarize the
experimental residual masses in TG/DTA analysis (in %) versus the theoretical residual
masses if the compound is fully decomposed to pure TaN or NbN. In all cases it is clearly
visible that most of the precursor evaporates and only partly decompose. Reducing the heating
rate from 5 °C/min to 2.5 °C/min will most presumably lead to a further reduction of the
residual masses.
40
Figure 17. Complete TG/DTA analysis of the two congeners S4 (a) and S8 (b). Comparison of the TG-curves of
the pairs S4 / S8 (c) and S6 / S9 (d).
3.2 Ligand synthesis
According to the claim of developing precursors that can be easily synthesized in larger
quantities it makes sense to avoid complex ligands that are not easily accessible. This was one
reason for taking the trimethylsilyl-substituted ligand Htdmh instead of the silicon-free ligand
trimethylhydrazine. The synthesis of HNMeNMe2 as such is rather complicated, gives only
low yields and involves the use of noble metals as catalysts. In the following the synthesis of
Htdmh and of a lithiated guanidinate-ligand is described.
41
3.2.1 Synthesis of N-trimethylsilyl-N’,N’-bisdimethylhydrazine (Htdmh)
Two ways have been described in literature to synthesize Htdmh (figure 18). W. L. Gladfelter
et al. (2003) synthesized Htdmh by a salt metathesis reaction between freshly prepared
LiHNNMe2 (MeLi + Hdmh) and trimethylchlorsilane (I).[145] The reaction involves large
amounts of MeLi-solution (> 100ml, highly pyrophoric) and gives yields of 54 % (14 g per
batch).
Figure 18. The two ways for the synthesis of Htdmh. I: Involvement of MeLi is required (W. L. Gladfelter); II:
Straightforward synthesis via liberation of HCl and consequent formation of a hydrazonium salt as an insoluble
byproduct.
The other synthetic route (II) already reported by U. Wannagat in 1966 is based on a simple
Brønstedt acid/base reaction of Hdmh and chlorotrimethylsilane. HCl is liberated in this
reaction and forms a hydrazonium salt with a second equivalent of Hdmh.[138, 139] The addition
of the silane to Hdmh is carried out at room temperature under inert gas. The yield of the
reaction after distillation is about 88 %. It is possible to synthesize 58 grams of pure Htdmh in
one batch. Certainly, the second route is advantageous for obtaining large amounts of Htdmh
by a simple one step reaction. Probably, Gladfelter et al. did not have access to the synthetic
route due to the fact that Wannagat described the synthetic route in a journal, published in
german.
Htdmh is a colorless liquid that can be distilled at temperatures of about 100-115 °C and
atmospheric pressure. Proton-NMR spectroscopy of Htdmh shows only two signals
(singuletts): one signal for the two methyl groups, bonded directly to the nitrogen atom (δ =
2.21 ppm) and one for the protons of the trimethylsilyl-group (δ = 0.13 ppm). It is important
to mention that Hdmh as well as Htdmh are highly toxic, and are suspected to cause cancer. It
42
should be strictly avoided to bring these compounds in contact with oxidizing agents, e.g.
sulfuric acid since explosive decomposition of the hydrazines can occur.
43
Chapter 4 Hydrazido based precursors of tantalum
In this chapter, all results of the reactions of tantalum compounds and hydrazine derivatives
are presented. After a short introduction regarding the interrelation of hydrazines and the
MOCVD and ALD-processes, the successful reactions of mixed amido/imido compounds of
tantalum with 1-trimethylsilyl-2,2-dimethylhydrazine (Htdmh) are described and the results
are presented. Thereafter, reactions of 1,1-dimethylhydrazine (Hdmh) and lithiated hydrazine
derivatives with tantalum compounds are described. Unfortunately, no isolable compounds
were obtained, but decomposition was observed instead.
4.1 Hydrazine derivatives as useful ligands for new MOCVD and ALD
precursors
Hydrazine derivatives possess the potential of playing an important role in the formation of
metal nitride thin films for applications as diffusion barriers or metal gate electrodes. Two
options can be considered for using hydrazine based molecules in MOCVD or ALD
processes.
First of all they may be used as a reactive gas during the formation of the thin films in the
aforementioned processes. Hydrazine derivatives are used due to their strong reducing
abilities and their relatively labile nitrogen-nitrogen single bond. This bond can be easily
broken even at lower temperatures, thus providing reactive, unsaturated nitrogen fragments.
Hydrazines also serve as nitrogen sources comparable in their chemical behavior to ammonia,
although they display higher reactivity.[140] The use of hydrazines in MOCVD processes is
well known for the formation of epitaxial gallium and indium nitride thin films.[141] Gaseous
hydrazine was also successfully applied in the direct nitridation of thin foils of early as well as
late transition metals (Co, Cr, Fe, Mo, Ta, Ti, V and W).[142] ALD-experiments have been
carried out using TaCl5 and Hdmh for the formation of TaN.[119] However, no conducting
films were obtained (formation of amorphous Ta3N5), and the deposited films contained up to
14 % of chlorine. Recently, our group tested the deposition behavior of [Hf(NEt2)4] with
dimethylhydrazine as the reactive co-reactant and it was found out that cubic, conducting
hafnium nitride could be obtained only when hydrazine was used as a reducing agent, instead
of ammonia. Problems in these experiments occur due to the dangerous properties of
hydrazines as such. When hydrazines come in contact with strong oxidizing agents e.g.
44
concentrated sulfuric or nitric acid (in the case of exhaust scrubbing), they tend to get
oxidized in an explosion-like manner.[n] Even substitution of protons at the hydrazine by
hydrocarbon groups does not significantly lower this reactivity towards oxidizing agents.[143]
In addition, hydrazine derivatives appear to be highly poisonous and they are suspected to
cause cancer. Unfortunately, even an excess of hydrazine has to be used in the deposition of
thin films, which corrodes the fittings of the reactor lines and sets high demands for cleaning
the exhaust gases.[144] In order to avoid dealing with high amounts of free hydrazine
derivatives as reactive gas, the second option is to insert these derivatives in form of ligands
into the ligand sphere of the metal complexes that are then used as precursors in MOCVD and
ALD processes (figure 19).
Figure 19. Ligands used for the synthesis of precursors mentioned either in this work or in closely related
publications.
First reports exist in which the homoleptic complexes [M1(tdmh)3] (M1=Ga, In) were
synthesized to obtain precursors for the MOCVD of gallium and indium nitride.[145] In these
cases, the ligand is supposed to serve only as a nitrogen source at low temperatures, because
gallium and indium already reside in the +III oxidation state. No MOCVD experiments were
carried out within these studies. Only two systems have been investigated for the use of
hydrazine derivatives in the precursor synthesis of early transition metals:
1. The synthesis of homoleptic, trimethylhydrazido complexes of Zr(IV) and Hf(IV) as
well as mixed chloro/trimethylhydrazido complexes thereof. The complexes are
volatile (sublimation occurs at 90 °C, 0.06 mmHg), but were not used in MOCVD-
processes.[146,147]
2. Reactions of TaCl5 and Hdmh led to the formation of a mixed
amine/amido/chloro/imido complex [TaCl2(NNMe2)(NHNMe2)(NH2NMe2)] with low
[n] Therefore, hydrazines were used as fuel for rockets from the 1940’s on, until today. One system that has the
advantage of igniting itself (so called hypergolic fuel) is the system 1,1-dimethylhydrazine / dinitrogentetroxide.
45
volatility. Surprisingly, conductive, cubic TaN films could be produced using this
compound as a MOCVD precursor.[106]
In this work, we investigate reactions between Htdmh and tantalum compounds. One reason
for using the tdmh ligand in particular is that this ligand has already been successfully tested
in the case of the aforementioned precursor synthesis for the MOCVD of GaN and InN.
Besides the transfer of this system to tantalum, containing silicon is also interesting for a
precursor in terms of silicon-incorporation into the films during MOCVD. TaSiN thin films
have already been tested on their behavior as liner materials (diffusion barriers). It has been
shown that the incorporation of silicon into TaN films drastically increases the thermal
stability of the films in comparison to silicon-free TaN-films.[148,149] The thermal stability of
the material is crucial for its performance as a diffusion barrier for copper. Additionally, it can
be expected that the reduction of Ta(V) to Ta(III) during MOCVD (the formation of
conductive TaN) is favored due to the hydrazines’ ability to act as reducing agents.
The reactions can be categorized in two different ways: Transamination-reactions (Htdmh
(4.2) or Hdmh (4.3) with mixed Ta-amido/imido compounds) and salt metathesis-type of
reactions (Li-tdmh and halide containing Ta-compounds (4.4)).
4.2 Synthesis of amido / imido / hydrazido complexes A1-A3 by

transamination reactions
Transamination (ligand exchange) reactions of the amido/imido compounds of tantalum and

the protonated form of tdmh will only take place, when the bond between the tdmh anion and
the Ta-center is favored over the Ta-NR2 (amido) bond. The two parameters that determine
the likeliness of ligand exchange are mainly the pKA-values of the two competing ligands and
the abilitity of the ligands to serve as chelating ligands. The pKA-values of dialkylamines are
[150]
typically in the range of 10.5-11.5 , while the value for hydrazine derivatives are about
7.0-8.0.[151] Therefore, it can be concluded that deprotonation of the hydrazine takes place, and
the formerly bonded amido group is protonated. In addition, the hydrazido ligand can act as a
chelating ligand, which lowers the probability of cleavage of the hydrazido ligand, once it is
attached to the tantalum center.
4.2.1 Synthetic route, purity and properties of the compounds A1-A3
The starting materials [Ta(NMe2)3(N-t-Bu)], [Ta(NMeEt)3(N-t-Bu)] and [Ta(NEt2)3(N-t-Bu)]

were treated with the ligand Htdmh under various conditions. The steric demand of the
46
hydrazido ligand typically prefers side-on coordination which significantly limits the number
of amido-groups that could be exchanged.
Figure 20. Reaction equations for the formation of A1-A3 by ligand exchange reactions between S1-S3 and
Htdmh.
In all reactions of tantalum amido/imido complexes, even with a large excess of Htdmh and
long periods of refluxing, only a single amido group was replaced (figure 20). This already
leads to a five-coordinated Ta-complex, which is an odd (and thus not favored) coordination
number for tantalum, but gives an 18 valence electron complex. One four-electron donor NR2
is replaced by the side-on coordinated two + two electron donor tdmh. The assumption that
steric hindrance is a limiting factor in the substitution reactions is supported by the increasing
reaction time for alkylamido substitution in the order NMe2, NMeEt, NEt2. The reaction rates
as well as the purity and sensitivity of these compounds towards moisture will be discussed
below.
Reaction rates
The reactions were carried out by simply adding a small excess of Htdmh to the slightly
yellow solutions of the starting compounds in hexane. In the synthesis of A3, a large excess of
Htdmh and a refluxing period of 5 days was necessary for quantitative formation of the
product. After two days at room temperature, only 10% of [Ta(NEt2)3(N-t-Bu)] reacted to
form A3 (based on 1H-NMR). NMR-scale experiments with 1.5 eq. of Htdmh and 5 eq. of
Htdmh, together with [Ta(NEt2)3(N-t-Bu)] showed that the effect of the concentration of
Htdmh on the reaction rate is significant. After a reaction time of 48 hours at 80 °C, 45 % (1.5
eq. of Htdmh) and 65 % (5 eq. of Htdmh) of A3 were formed, respectively. From these facts it
can be assumed that the rate determining step is most likely an associative step (Htdmh to the
Ta-complex), and not a dissociative one (cleavage of one amido group). Otherwise, the
reaction rate should be independent of the concentration of Htdmh. This is in good
47
accordance with the fact that unsaturated complexes usually undergo associative ligand
substitutions.
Purity and sensitivity towards moisture

Elemental analysis revealed that the products were synthesized in sufficient purity, with batch
sizes up to 50 g. The crude products showed only small amounts of impurities. Nevertheless,
all compounds were purified by short path distillation at temperatures between 120°C and
143°C under vacuum conditions (0.01 mbar) prior to further analysis. All three compounds
are liquid, but have a higher viscosity and higher boiling points than the starting compounds
(70-90°C). In comparison to the starting compounds, the air sensitivity of A1-A3 decrease
drastically. NMR-samples sealed with normal caps showed only small signs of decomposition
of A3 (free diethylamine) after 48 hours, while samples of [Ta(NEt2)3(N-t-Bu)] were
completely decomposed after 24 hours (formation of white solid).
4.2.2 Spectroscopic analysis of the compounds A1-A3
1
H- and 13C-NMR spectra were recorded in order to characterize the compounds. Integration
of the peaks clearly shows that one amido group was replaced. In figure 21, the 1H-NMR-
spectra of A1 and A2 are displayed. As a representative example, the spectroscopic features
of compound A2 are discussed here. Due to the chirality of A2, the two diastereotopic protons
of the Ta-N-CH2-CH3 groups are split into two doublets of quartets. Nevertheless, the two
amido-groups are chemically equivalent in solution, resulting in one set of peaks. The methyl
groups, bound to one of the hydrazido nitrogen atoms (δ = 2.42 ppm) appear as one peak in
the NMR-spectrum, indicating that rotation along the N-N axis is possible in solution. EI-
Mass spectra at 30 eV or 70 eV provided no real valuable information about structural details
or decomposition pathways. The molecule peak can be observed in all three cases with
intensities of 3 and 2 % in the case of A1 and A2 and 40 % in the case of A3. Thus it can be
concluded that higher amounts of undecomposed A3 are volatilized during the measurement
or that A3 is chemically more stable than A1 and A2. In addition, the cleavage of a methyl
group can be observed in all spectra. This supports the aforementioned assumption because
the intensities are rather low for A1 and A2 (8 % and 5 %), but they are the highest (100 %)
for A3.
48
Figure 21. 1H-NMR spectra of A1 and A2 (25°C, C6D6, 250 MHz).
4.2.3 Single crystal X-ray analysis of A1
Although A1-A3 are viscous liquids at room temperature, it was possible to obtain the
molecular structure of A1 by careful crystallization at -20 °C from diethylether and further
preparation and manipulation of the crystals under continuous cooling to -10 °C. The crystals
were mounted on a capillary using inert oil and were transferred immediately to the cold gas
stream (105 °K) of the diffractometer. The compound crystallizes in the form of colorless
prisms. Crystallographic data are presented in table 28, while selected bond lengths and
angles are summarized in table 7. The molecular structure of A1 in the solid state contains
two crystallographically independent molecules in the asymmetric unit. This complex is one
of the few examples of all-nitrogen five-coordinated tantalum complexes (e.g. the homoleptic
complex [Ta(NMe2)5]). An imaginary mirror plane can be put through the atoms Ta(1)-N(11)-
N(12)-N(13), although no exact Cs symmetry exists (figure 22). The hydrazido ligand is
bound in the expected chelating fashion with a (N11)-Ta(1)-N(12) biting angle of 37.6 °. The
Ta-N bond lengths to the hydrazido ligand lie in the expected range similar to the alkylamido
starting complex and related systems. The covalent bond (Ta(1)-N(11)) is 0.379Å shorter than
the donating bond Ta(1)-N(12) of the η2-hydrazido ligand. This is comparable to the case for
[Zr(N(Me)NMe2)4] in which the difference in bond lengths is about 0.392 Å.[146] The Ta(1)-
N(13)-C(131) angle is almost 180° thus indicating that the imido group acts as a six electron
donor (sp-hybridization). In addition, the two remaining amido groups at the tantalum center
are almost planar with torsion angles of about 170° supporting the assumption of a strong sp2-
double bond character of the Ta(1)-N(14) and Ta(1)-N(15) bonds. Their bond lengths to
tantalum are in the order of 2.004 Å, almost exactly the same as in the case of [Ta(NMe2)3(N-
t-Bu)] (1.99(1)Å).[132]
49
Figure 22. Molecular structure of A1 in the solid state. Hydrogen atoms are omitted for reasons of clarity.
Table 7. Selected bond lengths and angles of the crystal structure of A1.
Bond lengths (Å) Bond angles in (°)
Ta(1)-N(11) 2.021(7) N(11)-Ta(1)-N(12) 37.6(3)
Ta(1)-N(12) 2.350(7) Ta(1)-N(13)-C(131) 179.6(6)
Ta(1)-N(13) 1.786(7)
Ta(1)-N(14) 2.013(7) Torsion angles (°)
Ta(1)-N(15) 1.995(7) Ta(1)-N(15)-C(151)-C(152) 170.3/171.2
N(11)-Si(1) 1.738(7) Ta(1)-N(14)-C(141)-C(142) 172.5/171.3
N(11)-N(12) 1.443(10) Ta(1)-N(11)-N(12)-N(13) 179.6(4)
4.2.4 Thermal analysis of A1-A3 in respect to MOCVD / ALD
Compounds A1-A3 can be quantitatively distilled under reduced pressure. Solid precursors
(e.g. the homoleptic trimethylhydrazine complexes of Ti, Zr and Hf) often result in problems
to ensure a constant mass transport of the precursor into the gas phase. Therefore, being liquid
at ambient temperature simplifies the handling of the precursor. The two tantalum compounds
A1 and A2 are significantly more volatile than the diethyl-substituted complex A3, with the
consequence of relatively low remaining masses of 4 % and 6 % in TG/DTA analyses,
respectively (figure 23). Unlike TBTDET the compounds show a higher temperature onset of
volatilization, but they have the advantage of a higher thermal stability. This is revealed by
possessing a higher decomposition temperature of about 250 °C versus 190 °C for TBTDET.
50
It is to be noted that both, A1 and A2 showed monotonic weight loss with almost negligible
residue left behind above 250 °C compared to TBTDET. The DTA spectrum of A3 showed a
peak, related to decomposition at a temperature of 280 °C. The high thermal stabilities of the
precursors make them promising candidates for ALD processes that can be carried out at
comparably high temperatures. As expected, the higher thermal stability is going along with a
lower chemical reactivity of the complexes. Testing these precursors under ALD-conditions
would be very interesting, not only in the ALD of metal nitrides, but also in the deposition of
thin oxide films, together with water as the oxygen source.
Figure 23. TG/DTA spectra of A1-A3, recorded at a heat rate of 5 °C/min and 300 sccm nitrogen flow. TG
spectrum of A1-A3 and TBTDET for comparison (bottom right).
51
4.3 Destructive transamination reactions of A1-A3 with N,N-dimethyl-

hydrazine (Hdmh)
Based on these results with Htdmh and the amido/imido compounds we were encouraged to
investigate substitution reactions of the tantalum amido/imido complex [Ta(NEt2)3(N-t-Bu)]
with the sterically less demanding 1,1-dimethylhydrazine. In 1H-NMR studies it could be
observed that two different reactions took place after adding the dimethylhydrazine to the
tantalum compound [Ta(NEt2)3(N-t-Bu)] (TBTDET). The first reaction was the formation of
an unstable intermediate analogous to compound A3, while the second reaction led to the
formation of an orange, hardly soluble precipitate in the NMR-tube (figure 24). The
intermediate compound, formed by the transamination reaction (presumably [Ta(NEt2)2(N-t-
Bu)(dmh)]), was apparently consumed by the second reaction.
Figure 24. Reaction pathway of the decomposition reaction of TBTDET, induced by Hdmh.
The rate of formation of the orange precipitate depended on the concentration of Hdmh in
solution. In time-dependent NMR-studies of TBTDET and Hdmh (one and two equivalents) a
decrease in the concentration of [Ta(NEt2)3(N-t-Bu)] and an increase in the concentration of
[Ta(NEt2)2(dmh)(N-t-Bu)] could be observed in the first stage. The concentration of the
intermediate compound passed through a maximum and decreased almost to zero after a
certain period (figure 25). Figure 26 shows the NMR spectra of the reaction of TBTDET with
one equivalent of Hdmh after certain periods of time. At higher concentrations of Hdmh
(three and four equivalents) in the beginning of the reaction, the ligand exchange reaction as
well as the decomposition reaction was faster, which led to a complete decomposition of
TBTDET already after 300 min The oligomerized product appeared in the form of two very
broad peaks (most probably oligomerized tantalum species) that can be observed in the areas
of 0.8-1.5 and 2.3-4.0 ppm. It was not possible to isolate the pure intermediate compound.
Instead it seemed that decomposition took place once the hydrazine coordinated to the
tantalum center. Even reactions in which less than one equivalent of Hdmh was used led to
the full decomposition of the amido/imido-compound. Another indication for the very high
reactivity of Hdmh as compared to Htdmh was the formation of free tert-butylamine besides
52
the expected liberation of diethylamine in the investigated reactions. The higher the amount of
Hdmh in the beginning of the reaction, the more free H2N-t-Bu could be observed.
Figure 25. Decomposition reaction of TBTDET with Hdmh. Ratio of TBTDET (left), the intermediate compound
(middle) and HNEt2 (right) to C6D6 (=1) as a function of reaction time. The ratios were determined by comparing
the integrals of the C6D6 peaks with the triplets of the NEt2-groups of the three compounds.[o]
Figure 26. Proton NMR-spectra of the reaction of TBTDET and one equivalent of Hdmh after 20 min, 70 min,
700 min and 30 hours. The peaks for TBTDET, the intermediate compound, free Hdmh and HNEt2 are marked.
This clearly shows the possibility of a total cleavage of all ligands by proton donating agents.
Of course, steric requirements have to be considered, e.g. the coordination of only one Htdmh
[o] Lines were drawn for a better overview of the trends in the change of the product-to-C6D6 ratios. Certainly,
the real curve progression could be different in terms of the position of the maximium in the spectrum (middle).
In addition the rise and fall of the values would practically have the shape of an exponential function.
53
ligand seems to effectively block further protonation of amido groups. One would expect that
a reaction between ammonia and e.g. TBTDET will also lead to full protonation and cleavage
of the amido groups. This assumption is strengthened in the MOCVD of TBTDET in
presence of ammonia. The carbon content decreased drastically once ammonia was used in
the experiments (>15 % without ammonia, <2 % with ammonia). However, for a more
detailed analysis of the reaction kinetics the concentrations of TBTDET and Hdmh at the
beginning have to be determined. In addition, the use of chemically inert substances for a
more accurate calibration of the peaks is suggested.
4.3.1 Single crystal X-ray analysis of a hydrolyzed tantalum-dmh complex
Reactions of TBTDET with a high excess of Hdmh were carried out, leading to the fast
formation of an orange solid. This solid, assumed to be oligomerized Ta-hydrazido species,
was hardly soluble in C6D6, diethylether and CH2Cl2. Small amounts could be dissolved by
extraction with pure Hdmh. The orange solution was stored at -30°C. Water diffusion into the
solution occurred after a storage time of approximately 12 months and an orange compound
crystallized in the Schlenk tube (A5). The crystals were highly reactive towards air and turned
white in inert oil after approximately ten minutes. Nevertheless, one crystal could be
measured by means of single X-ray diffraction and the structure could be determined.
Unfortunately, no further analysis could be performed due to the low amount of compound
that was formed (3-4 crystals). Although the compound was not fully analyzed, and the
synthesis could not be reproduced so far, the structure will be discussed due to its interesting
structural features (figure 27 (labeling), figure 28 (bond length/angles)).
A5 crystallizes in the triclinic crystal system having the space group P-1. The quality of the
crystal was high enough to determine the structure. The cluster molecule contains altogether
four tantalum atoms that are interconnected by bridging unsymmetrical dimethylhydrazido
ligands and most probably OH-groups. Two of the tantalum atoms are identical due to the
centrosymmetric geometry of the complex. Tantalum(1) is coordinated by four
dimethylhydrazido ligands, three of them as bidentate ligands, resulting in a coordination
number of 7.
54
Figure 27. Molecular structure of A5 in the solid state (atoms are labeled).
2.240 Å
Figure 28. Bond distances and bond angles of A5 in the solid state (deviations are omitted for reasons of clarity).
55
Two of the dimethylhydrazido ligands are only bonded to Ta(1), having bond lengths to Ta
(Ta(1)-N(31): 2.073(7) Å; Ta(1)-N(41): 2.019(7) Å) in the range of tantalum-nitrogen single
bonds with a strong π-donating character (4 electron donor). The other two dimethylhydrazido
ligands are coordinated in a μ2- fashion to Ta(1) and Ta(2) as well as a η2-fashion to Ta(1).
The eight-membered ring Ta(1)-N(11)-Ta(2)-N(21A)-Ta(1A)-N(11A)-Ta(2A)-N(21) seems
to consist of a highly delocalized π-electron system. It is difficult to give a well founded
statement on the status of the two bridging nitrogen atoms N(11) and N(21). In order to have
Ta(1) in the oxidation state +V, N(21) and N(11) must be fully deprotonated. Their two
negative charges could be distributed on Ta(1) and Ta(2) in the relation 1.5 to 0.5 (figure 29,
bond orders).
Figure 29. ChemDraw-scheme of A5, including the bond orders of the Ta-O and Ta-N bonds.
This would be in agreement with the bond lengths that are observed in the complex. On the
one hand, the bond lengths of the Ta(1)-N(21) and Ta(1)-N(11) are between the bond
distances of a tantalum-nitrogen single and double bond. On the other hand, the bond lengths
of Ta(2)-N(21) and Ta(2)-N(11) are longer than a tantalum-nitrogen single bond, but shorter
than a simple donor-bond. If Ta(1) is in the oxidation state +IV, one would expect a deep
purple to deep blue color of the complex as was observed for all Ta(IV) complexes that have
been reported so far.[109,101] The Ta(2)-atom is surrounded by two hydrazido-ligands that are
bonded in a terminal fashion (N(51), N(61)), the two μ2-hydrazido ligands (N(11), N(21)) and
56
two bridging OH-groups. This results in a six-coordinated complex, having the coordination
geometry of a distorted octahedron. The Ta(2)-N(61) bond is the only truly imido-type bond
with a very short bond distance (Ta(2)-N(61) = 1.808(6) Å) and an almost linear geometry
(Ta(2)-N(61)-N(62) = 168.6(8) °). The oxygen-tantalum bonds are too long to belong to fully
deprotonated O2- ions (Ta(2)-O(99) = 2.216(6) Å). The typical Ta-O-R-bond length is
approximately 2.00Å.[152] Therefore it can be concluded that one hydrogen is still bonded to
one oxygen ligand and that each oxygen ligand shares its charge between the two tantalum
atoms Ta(2) and Ta(2A). However, steric effects play a relevant role in such a large complex,
therefore all conclusions drawn from bond-lengths and angles on the electronic structure of
the complex, have to be considered as indications and not to be taken for granted.
4.4 Reactions of TaCl5 and [TaCl3(N-t-Bu)py2] with lithiated hydrazine

derivatives
Salt metathesis reactions applying the lithiated hydrazine ligand seem to be the
straightforward way of introducing hydrazido groups into transition metal complexes. These
reactions are adequate for the synthesis of most of the early transition metal amido complexes
[Ta(NR2)3(N-t-Bu)] (R = Me, Et) from the metal chlorides and the lithiated amines.
Homoleptic complexes like [Ta(tdmh)5] do not seem to be reasonable target molecules, when
aiming at all-nitrogen coordinated compounds due to the steric demand of the hydrazido
ligand. Nevertheless, experiments with TaCl5 and Li-tdmh were performed in order to obtain
mixed chloro/hydrazido complexes of Ta. For the synthesis of all nitrogen coordinated
tantalum complexes we used the well known tantalum complex [TaCl3(N-t-Bu)(py)2] and
studied the substitution of the chloro ligands by treatment with different equivalents of the
lithiated tdmh ligand.
Reactions of Li-tdmh with [TaCl3(N-t-Bu)py2]

The reaction of [TaCl3(N-t-Bu)py2] with Li-tdmh did not lead to the fully substituted product
[Ta(tdmh)3(N-t-Bu)]. Instead, 1H-NMR suggests the exchange of two chlorides ligands of the
tantalum compound by two hydrazido ligands. It was not possible to isolate [TaCl(N-t-
Bu)(tdmh)2] in significant amounts or sufficient purity (15% impurities) and the reaction
occurred rather slowly. An excess of lithiated hydrazine (5 equivalents) and a reaction time of
five days at high temperatures (70°C) was required to obtain the product. We observed the
formation of a pyridine stabilized complex of the type [Li(py)(tdmh)]2 (A4) as a by-product in
these reactions. This complex could not be separated to a fully satisfying extend from the
57
doubly substituted complex, even not by distillation under reduced pressure or fractionated
crystallization. The dimeric complex is described in the following paragraph.
Characterization of the complex A4

The complex [Li(tdmh)(py)]2 (A4) was synthesized independently and fully characterized,
after being identified in reactions of [TaCl3(py)2(N-t-Bu)] with Li-tdmh. Obviously, A4
exhibits only low reactivity towards salt metathesis reactions. Even refluxing three
equivalents of A4 with [TaCl3(N-t-Bu)(py)2] for 72 hours did not lead to the desired tantalum
complex. Using higher amounts of A4 in these reactions led to the previously mentioned
problems of product isolation and purification. Still, compound A4 is interesting for its own
merit and will be discussed at this point. Depending on the rapidness of addition of the
butyllithium to the ligand and the dilution of the compound, the color of the resulting solution
could vary from yellow to red. Nevertheless, no noteworthy impurities were found in the
NMR-spectra of A4. It seems though, that an equilibrium between the monomeric and
dimeric species of A4 exists in solution so that two peaks appear for the SiMe3-groups in the
1
H-NMR spectra. These two peaks varied in their intensities, depending on the concentration
of the NMR-solution. At higher temperatures (60°C) only one coalesced signal could be
observed. The pure isolated complex is very air sensitive and decomposes immediately when
exposed to air.
Single crystals of A4 suitable for X-ray structure analysis were obtained by crystallization
from hexane at -30 °C (figure 30). The complex displays Ci-symmetry with two µ2-η2
coordinated hydrazido ligands. The structure of A4 is very similar to the recently published
dimeric complex [Mg(tdmh)2]2.[153] Numerous examples of lithium-hydrazido complexes are
known and compound A4 matches the typical structural properties.[154,155,156]
58
Figure 30. Molecular structure of A4 in the solid state. Hydrogen atoms are omitted for reasons of clarity.
Reactions of Li-tdmh and [Li(tdmh)(py)]2 with TaCl5.

All reactions that were carried out using the lithiated hydrazines (freshly prepared, or pyridine
stabilized) and TaCl5 in toluene led to the formation of colorful solutions, and a white
precipitate (LiCl). Various equivalents of the lithiated hydrazines were brought to reaction
with the metal chloride (2 and 6 equivalents). However, filtration with subsequent reduction
of the amount of solvent did not lead to any crystalline material. The products of the reactions
were highly viscous, orange to dark-red oils that could be distilled by short path distillation.
NMR-analysis of these oil-like products indicated a large variety of trimethylsilyl-containing
compounds. Most likely, oligomerization reactions took place. No further investigations of
these reactions were performed due to the low prospect of obtaining isolable, pure compounds
of tantalum.
59
Chapter 5 Guanidinato based precursors of tantalum and niobium
Chapter 5 Guanidinato based precursors of tantalum and

niobium
The second type of ligands that was investigated within this work is the monoanionic
guanidinate ligand. Guanidinate ions are very versatile ligands and a large variety of
complexes has been synthesized. In 2001 P.J. Bailey wrote in a review: [157]
“The steric and electronic flexibility of guanidinates, the variety of possible coordination
modes, …, coupled with the ease with which guanidines bearing virtually any combination of
substituents may be synthesized, …, means that guanidinates have the potential to develop
into valuable ancillary ligands in coordination and organometallic chemistry”
Investigations into this ligand system are largely motivated by applications in homogeneous
catalysis, e.g. in Ring Opening Metathesis Reactions and styrene polymerization.[158,159] The
features of this ligand, its historical development in metal organic synthesis and possible
synthetic routes will be explained in 5.1. In paragraph 5.2, the use of this type of ligand for
the synthesis of precursors for MOCVD and ALD will be discussed. The results of the
experiments are presented in 5.3 (tantalum) and 5.4 (niobium). Altogether, twelve new
compounds were synthesized. All compounds were analyzed by standard methods including
NMR, EI-MS, CHN and TG/DTA-analysis. The molecular structures of eight of these twelve
complexes were elucidated by means of single crystal X-ray analysis.
5.1 Types of guanidinate ligands in complexes and their synthesis
The monoanionic guaninate ligand can be allocated to the main group of guanidine ligands.
Figure 31 shows the different types of guanidines, all containing the characteristic Y-shaped
CN3-unit.
Properties
The guanidinium ligand does not have the ability to act as a Lewis-base and thus cannot be
used as a ligand for early transition metal complexes (Lewis acids). The neutral guanidine
ligand will probably not lead to complexes that can be volatilized without decomposition and
is therefore not suitable for the synthesis of precursors. Instead, it is necessary to use charged
ligands, e.g. guanidinate (-1/-2) ligands to guarantee sufficient thermal stability of a complex.
60
Figure 31. Ionic and neutral representatives of guanidines. A large variety of derivatives is known (R = H, Me,
i-Pr, cyclohexyl, t-Bu, phenyl). In this work, the monoanionic guanidinate ligand was used.
The following discussions will focus in particular on the monoanionic guaninate ligand and
complexes containing this ligand. This monoanionic ligand has the ability to bond to a metal
either in a monodentate or bidentate, chelating fashion. As a chelating ligand, it forms highly
stable metal-guanidinate complexes. This stability can be to some extend explained by the
presence of so-called Y-aromaticity of the CN3-system in which the π-electrons of the system
are highly delocalized. Two resonance forms are possible that are shown in figure 32 A and
B. Resonance form A exhibits a π-electron system that is delocalized within the endocyclic
CN2-group. Structure type B features participation of the exocyclic amido-group in the π-
electron system of the guanidinate ligand. Theoretically, high acidity of the metal center
should lead to the preferred contribution of structure type B. One characteristic feature to
differentiate between the contributions of structure type A or B is the length of the C-N-bonds
within the CN3-system.
Figure 32. The two resonance forms of a monoanionic guanidinate ligand.
Certainly, in order to draw these conclusions the crystal structures of the complexes have to
be determined. If only resonance form A is contributing to the structure of the complex, both
endocyclic C-N-bonds shall have a partial double bond character, therefore being significantly
shorter than the exocyclic C-N single bond. The shorter the exocyclic C-N bond, the stronger
61
is the participation of resonance form B in the overall structure of such a guanidinate

complex. Complete delocalization in the CN3-system can be observed for example in the case
of the titanium complex [Ti{η2-(NPh)2CNEt2}2Cl2].[160] All C-N-bonds of the guanidinate
ligand have exactly the same bond length of 1.342 ± 0.001 Å. In order to interact fully with
the delocalized π-electron system, the exocyclic amido group (plane 1) must be in plane with
the endocyclic CN2-group (plane 2). A deviation indicates a low inclusion of the amido-group
into the π-electron system, even if the nitrogen atom of the amido group is sp2-hybridized. Sp2
hybridization of the exocyclic nitrogen atom is necessary for a participation in the guanidinate
electron system. It can easily be identified by analyzing the sum of the bond angles around the
nitrogen atom (360° = sp2-hybridization; 328.4° = sp3-hybridization). In addition, the amido-
group should form one plane, together with the central carbon atom of the guanidinate-ligand
(in contrast to resonance form A, which shows an sp3-hybridized nitrogen).
Historical development
First complexes, containing monodentate, guanidinate (-1) ligands were reported in the late
1960’s by Wade et al.[161] These metal complexes were relatively unstable and the metal
center was only coordinated by a single nitrogen atom of the ligand comparable to a metal-
amide bond. In 1996, the first complex was reported that contained a chelating guanidinate
(-1) ligand ([Cp*Rh{η2-(PhN)2CNHPh}Cl]).[162] In the following decade, a large number of
compounds, enabling the chelating guanidinate (-1) ligand, was identified. Some of the few
examples for guanidinate complexes of niobium and tantalum have been provided by D. S.
Richeson et al. and L. G. Hubert-Pfalzgraf et al. in 1999. D. S. Richeson was interested in the
coordination behavior of this ligand and the conversion of the guanidinate(-1)-ligand to a
dianionic ligand and vice versa. The most interesting compounds for this work are the all
nitrogen coordinated complexes [M(NMe2)4{η2-(NR)2CNMe2}] (M = Nb, Ta; R = i-Pr, cy).
[163,164,165]
L. G. Hubert-Pfalzgraf and her co-workers reported the synthesis of halide
containing tantalum and niobium complexes, including the first Nb(IV)-guanidinate complex
[NbCl2{η2-(Ncy)2CN(SiMe3)2}].[166] Two different types of synthetic routes were employed
for the formation of these complexes.
62
Route 1: Synthesis by salt metathesis reactions

The salt metathesis reactions are two-step reactions. First an alkalimetal-amide complex (e.g.
LiNMe2) is combined with a carbodiimide by insertion (nucleophilic attack) in order to form a
guanidinate complex (figure 33). This complex usually is oligomeric, but it is possible to
stabilize the monomeric complex by addition of a Lewis base e.g. TMEDA (N,N,N’,N’-
Tetramethylethylendiamine)[167]. In a second step, the preformed lithium-guanidinato complex
is added to a metal chloride. The formation of the guanidinate complex of the metal is going
along with the formation of lithium chloride. This synthesis procedure has been copied from
the more deeply investigated amidinate system.[168] Many guanidinate complexes of early
transition metals have been successfully synthesized using this method, e.g. W,[167,169] Ta and
Nb-complexes.[166]
Figure 33. Synthetic route for guanidinate complexes by salt metathesis reactions.
Route 2: Synthesis by insertion reactions

The synthesis by insertion of carbodiimide into transition metal amide bonds relates to the
first reaction step of route 1. The carbodiimide is added to a metal-amido complex, already
containing the target metal. Insertion reactions of this type were first reported by K. Lee et al.
in 1997.[170] He and his group synthesized a THF-stabilized bis(guanidinato)magnesium
complex. Quite recently, S. T. Barry et al. investigated the insertion of carbodiimides into Al-
and Ga-amido groups, including theoretical considerations regarding the mechanism of
guanidinato-formation.[171,172] The mechanism they proposed is displayed in figure 34.
Figure 34. Mechanism for the insertion of a carbodiimide derivative into a metal amido-bond (R1,R2,R3 = alkyl-
groups).
63
The reaction starts with a nucleophilic attack of one nitrogen atom of the carbodiimide to the
Lewis acidic tantalum center. After the migration of one amido group of the tantalum
complex to the partially positive charged carbon atom of the carbodiimide, the guanidinato
complex is formed. Mixed amido/guanidinato complexes of zinc[158] and of zirconium[173]
were synthesized by this method. The previously mentioned compounds of the type
[M(NMe2)4{η2-(NR)2CNMe2}] (M = Nb, Ta; R = i-Pr, cy) have also been prepared by
insertion reactions.
Within this work, the plan was to use mixed amido/imido complexes of tantalum and
investigate insertion reactions of carbodiimides into the metal amido-bonds of the compound
(route 2). The big advantage of insertion reactions (route 2) over reactions, involving lithiated
guanidinate complexes (route 1) is the total absence of side products (e.g. LiCl). In addition,
the presence of impurities in the form of halogenide-containing tantalum species is lower. It
can be assumed, that up to three carbodiimide complexes can be inserted into the three metal
amido bonds of the starting compounds of the type [M(NR2)3(NR’)] (M = Nb, Ta; R,R’ =
alkyl).
5.2 Potential of guanidinate(-1) ligands for precursor chemistry
Classically, complexes of tantalum and niobium having low coordination numbers were used
as precursors for the MOCVD and ALD of thin metal nitride films. Mainly mixed
amido/imido complexes and homoleptic amido-complexes of the type [M(NR2)3(NR’)] and
[M(NR2)5] were tested (M = Nb, Ta; R, R’ = alkyl). These four and five coordinated
complexes display high volatility, but in addition a very high chemical reactivity as well as
low thermal stability. The use of mixed ligand precursors involving monoanionic guanidinate-
ligands seems to be very promising in terms of tuning the thermal and chemical properties of
precursors. Introducing this chelating ligand into the ligand sphere of the metal by replacing
one amido group by one bidentate ligand will consequently lead to a higher coordination
number of the central metal. Thus, free coordination sites at the metal center will be occupied
and it can be assumed that the chemical reactivity, e.g. sensitivity towards moisture, will
decrease. In addition, the thermal stability of the complexes should be increased by this
modification. The questions that logically arise are:
How does the increase of the complexity of the ligand sphere (coordination number,
chelating ligands, heterolepticity) effect the deposition behavior of the resulting
precursor systems?
64
Will it be possible to deposit conducting TaN thin films?

Does the increase of the carbon content of the precursor lead to an increase of carbon
incorporation into the film during deposition?
Similar questions were already asked in precursor development for MO2 thin films (M = Ti,
Zr, Hf). This research area has been largely influenced by a similar move-away from simple
homoleptic [M(OR)4] complexes to heteroleptic derivatives [M(OR)2L2] (M = Ti, Zr, Hf;
R = alkyl, L = chelating ligands e.g. β-diketonate and β-ketoester derivatives). For example,
the complex [Hf(O-i-Pr)2(tbaoac)2] (tbaoac = tert-butylacetoacetate) was successfully used in
MOCVD and LI-MOCVD processes to yield carbon free, stochiometric hafnium dioxide thin
films with excellent properties as a gate oxide material.[174] Compared to the homoleptic
alkoxy complex [Hf(O-i-Pr)4], the six-fold coordinated hafnium complex shows a higher
stability towards moisture and displays a higher shelf life in solution. Recently, guanidinato
complexes of hafnium were also considered as precursors for the deposition of HfO2 and
showed the potential to yield carbon free, nanocrystalline films.[175]
5.3 Synthesis of amido / imido / guanidinato compounds of tantalum B1-B8
This chapter includes all synthesis experiments and results related to reactions of mixed
amido/imido complexes with carbodiimides. The synthetic routes are described, followed by
spectroscopic analyses of the newly synthesized compounds. Altogether, six crystal structures
were obtained and are discussed in detail. Thermal analyses by means of TG/DTA analysis
were carried out and conclusions are drawn for the potential of the complexes as precursors
for the MOCVD/ALD of TaN.
5.3.1 Synthetic route, purity and properties of the compounds B1-B8
A number of reactions with various equivalents of carbodiimide derivatives and different

tantalum complexes were carried out. The tantalum containing amido/imido complexes, used
in the reactions were [Ta(NMe2)3(N-t-Bu)] (S4), [Ta(NMeEt)3(N-t-Bu)] (S5), [Ta(NEt2)(N-t-
Bu)] (S6) and [Ta(NEt2)(N-n-Pr)] (S7). The derivatives of carbodiimides tested for insertion
reactions were tert-butyl-, trimethylsiliyl-, cyclohexyl- and iso-propyl- substituted
compounds, as well as unsubstituted carbodiimide (figure 35).
65
A major outcome of the investigations is that tert-butyl- and trimethyl-silylcarbodiimide

molecules do not insert into the metal-amido bonds of the amido/imido compounds of
tantalum. Even higher concentrations of the carbodiimide and higher reaction temperatures (5
equivalents; toluene at 110 °C) did not lead to any reactions after a refluxing period of 24
hours. On the other hand, cy-cdi, as well as i-Pr-cdi, readily reacted with the tantalum starting
compounds S4 to S7 at moderate conditions and under the release of heat (exothermic
reaction). It can thus be assumed, that the difference in the steric features of the carbodiimide
derivatives plays a decisive role in this type of reactions.
R3
R3
R3 3
R
Figure 35. Reactions of carbodiimides with S4-S7 (S1: R1,R2 = Me, R4 = t-Bu; S2: R1 = Me, R2 = Et, R4 = t-Bu;
S3: R1,R2 = Et, R4 = t-Bu; S4: R1,R2 = Et, R4 = n-Pr).
The first step of the reaction is most probably a nucleophilic attack of the nitrogen of the
carbodiimide on the lewis acidic tantalum center. In the case where R3 possesses an α-
hydrogen (i-Pr, cy), it is possible that R3 rotates in such manner, that the attack of the nitrogen
on the tantalum center is sterically less hindered (figure 36). Theoretically it is not necessary
that the first step of the insertion reaction is the differentiating step, regarding the type of
carbodiimide. However, supported by the fact that the insertion reactions seem to be very
exothermic, cleavage of the carbodiimide is rather unlikely, once it is bound to the metal
center. In addition, no strong change in the electronic structure should occur when the i-Pr
substituent is exchanged by a t-Bu group. At first - in contrast to the prior explanation - it
seems remarkable that i-Pr as well as t-Bu substituted carbodiimides insert into Al-amido
bonds.[171] The explanation for this different behavior is most probably the low steric
shielding of the aluminium-center (H2Al-NMe2) compared to the fully amido/imido
substituted Ta-complexes S4-S7.
66
Figure 36. The two carbodiimides of type a feature an α-hydrogen, thus enabling the nitrogen to coordinate to the
Ta-center. In the structure type b (t-Bu-, SiMe3-cdi) steric hindrance, evoked by the methyl groups at the
substituents of the carbodiimide cannot be avoided by rotation of the substituent.
Reactions with the unsubstituted carbodiimide (which exists in the form of H2-N-C≡N) did
not lead to an isolable product. Adding the solid, hardly soluble H2-N-C≡N to the solution of
the amido/imido-tantalum compound in hexane led to a colorless suspension, which slowly
turned orange. After all the carbodiimide had reacted, an orange solid could be isolated which
was almost insoluble in toluene and THF. Most probably, transamination reactions took place
in this experiment, leading to the formation of insoluble, oligomerized tantalum complexes.
The solid was not further investigated.
Reactions of two equivalents of i-Pr-cdi and cy-cdi with S4-S7, led to the formation of eight
hexa-coordinated compounds B1-B8. Table 8 summarizes the substitution pattern of the
compounds and their melting points as well as yields.
Table 8. Overview of the synthesized guanidinato complexes of tantalum.

Name Amido Cdi-type Imido Yield M.p. in °C
1 2 3 4
R R R R
B1 Me Me i-Pr t-Bu 90 232
B2 Me Et i-Pr t-Bu 87 217
B3 Et Et i-Pr t-Bu 91 210
B4 Et Et i-Pr n-Pr 84 195
B5 Me Me cy t-Bu 85 210
B6 Me Et cy t-Bu 82 218
B7 Et Et cy t-Bu 87 204
B8 Et Et cy n-Pr 65 205
67
All reactions were carried out in hexane. The light yellow, clear solution of the tantalum
starting compound turned colorless during the addition of the carbodiimide-ligand. i-Pr-cdi
based compounds (B1-B4) could be synthesized the same way, by simply adding the liquid i-
Pr-cdi directly to a solution of the tantalum amido/imido compound in hexane. The solid cy-
cdi reactand had to be added in form of a solution of cy-cdi in hexane. Due to the exothermic
insertion reaction, the mixtures immediately warmed up to appr. 50 °C and slowly cooled
down to room temperature again. Removing the hexane in vacuum yielded B1-B8 in the form
of white powders. Crystalline, colorless samples of B1-B8 were obtained by crystallization
from hexane, diethylether or toluene at -30°C. The yields of the reactions were relatively high
(>80%). The compounds are white solids, having high melting points of 195-232°C (the
melting point of B7 was determined after drying the crystals at 50°C in vacuo for 24 hours in
order to remove toluene incorporated into the crystals). Elemental analysis revealed that all
compounds (besides B8) are chemically pure as prepared, even without further
recrystallization from toluene. B8 showed small amounts of excess cy-cdi in the NMR-
spectra. The compounds were highly soluble in most of the organic solvents e.g. benzene,
hexane, toluene, diethylether. Increasing the excess of the ligands (e.g. 4−5 equivalents) did
not lead to the formation of higher coordinated tantalum complexes. Experiments in which
only one equivalent of the carbodiimide was brought to reaction with the tantalum compounds
S4-S6 also led to the formation of the twofold inserted product and unreacted S4-S6. These
reactions are explained in the NMR-section (5.3.2.1). Obviously, there is a certain preference
for the bisguanidinato complexes.
5.3.2 Spectroscopic analysis of the compounds B1-B8
The compounds B1-B8 of the type [Ta(amido)(guanidinato)2(imido)] were spectroscopically

characterized by means of 1H-, 13
C-NMR (5.3.2.1) and EI-mass spectroscopy (5.3.2.2). In
addition, the NMR-results of the reactions with one equivalent of carbodiimide and the
tantalum amido/imido-compounds are discussed (5.3.2.1).
68
5.3.2.1 NMR-analysis
All compounds B1-B8 show very complex 1H-NMR spectra. Due to the mixed ligand sphere
containing four ligands of three different types, and the fact that two bidentate ligands are
involved, the compounds are chiral and a number of diasteromers are possible. In addition, the
three amido groups (NR1R2) are hindered in their rotation which furthermore increases the
complexity of the spectra (figure 37). It seems though, that no fast ligand exchange reactions,
neither inter-, nor intramolecular take place at room temperature. This results in discrete
signals for all four substituents at the nitrogen atom of the two guanidinato ligands (e.g R3 = i-
Pr).
Figure 37. The two chiral forms of the mixed amido/imido/guanidinato complexes. The specific bonds that show a
hindered rotation are marked with arrows.
All protons from the CH-groups of the i-Pr-groups are chemically not equivalent and appear
as four doublets of quartets in the area of 3.6-4.15 ppm (figure 38a, B1). The two methyl
groups from each iso-propyl group are diastereotopic and are thus chemically not equivalent.
Therefore, in the case of B1 to B4, all eight methyl-groups of the four i-Pr (R3) groups appear
as well resolved doublets at different chemical shifts (1.15 ppm-1.60 ppm) (figure 38 b),
having coupling constants of 6.4 Hz. Interestingly, one doublet is significantly low-field
shifted to ~1.60 ppm in all cases (B1-B4). This shift can be explained either by interactions
between the iso-propoxy group of one guanidinate ligand and the π-electron system of the
second guandinate ligand or by the strong electronic impact of the imido group on the trans
oriented N-i-Pr moiety. When the substituents at the guanidinato-ligand are cyclohexyl groups
(B5-B8), the protons of the cyclohexyl group cannot be clearly identified. Instead, broad
multiplets are observed. In the following, the pairs B1/B5, B2/B6, B3/B7 and B4/B8 are
discussed.
69
Figure 38. a) Full 1H-NMR-spectrum of compound B1 and b) an enlarged section of the spectrum. The doublets
of the i-Pr-groups are numbered from 1-8.
The dimethylamido substituted complexes (B1 and B5) exhibit the simplest 1H-NMR spectra.
(B1: figure 38 a). The two singlets of the Ta-N(CH3)2 - group (3.5 and 4.2 ppm, blue dots in
38 a) are also chemically not equivalent due to the sp2-character of the N-atom. At higher
temperatures (60 °C, C6D6), the two peaks become broader, indicating that rotation around the
R2N-C bond takes place (figure 39). Besides small shifts of some peaks, no other differences
can be observed at higher temperatures. At lower temperatures (-80 °C, toluene-d8) the high
field one of the two singlets at 2.50 (6 H) and 2.55 (6 H), belonging to the guandininate-
N(CH3)2 groups, divides into two smaller peaks with the intensities of 2 x 3 H. It can be
assumed, that the rotation barrier of this group, as a result of the sp2-character of the nitrogen
atom, cannot be longer overcome.
Figure 39. NMR spectra of B1 at low and high temperatures in different solvents.
70
Figure 40. 1H-NMR spectrum of B2. For each assigned methyl group, two peaks (*) can be found.
Compounds B2 and B6 give the most complex, highly temperature dependent 1H-NMR
spectra. The unsymmetrical substitution of the amido group results in the formation of
rotational isomers (figure 40). The methyl and the ethyl substitutes of the amido group,
directly bounded to the tantalum center, can occupy two different positions which leads to the
presence of two distinct diasteromers. Two peaks for the methyl group (marked with a star)
with the ratio 3.7:1 can be observed (4.4 and 3.7 ppm). The signals of the protons of the ethyl
group show the same behavior and are strongly broadened. Consequently all other peaks in
the spectrum exist twofold, visible as small additional peaks or shoulders.
Figure 41. Proton NMR spectrum of B3. Left side: full spectrum including the assignments of the α-hydrogen
atoms. Right side: enlarged section of the spectrum, showing all doublets (D) and triplets (T) of the CH3-groups.
Two triplets are not resolved.
The NMR-spectra of compounds B3 and B7 display an even higher complexity than B1 and
B5 (figure 41). In addition, to the doublets at higher field, six triplets, assigned to the ethyl
groups of the NEt2 groups are observed. Two of these triplets that belong to one guanidinate-
71
bounded NEt2-group are broadened. This again refers to dynamic processes that take place at
room temperature. At -50 °C (toluene-d8) these still broad peaks can be clearly identified as
triplets. The corresponding quartets of the ethyl-groups in the 1H-spectrum and the related
peaks in the 13C NMR spectrum are also broadened.
The protons of the CH2-groups from the Ta-N(CH2CH3)2 fragment are diastereotopic, thus
giving four different doublets of quartets (coalescence is observed at 60 °C, C6D6). Generally,
compounds B4 and B8 show the same features as the similar compounds B3 and B7. The only
difference is the substitution of the particular imido group. Figure 42 shows the corresponding
proton NMR-spectra of these two complexes in C6D6. The protons of the cyclohexyl-groups
of B8 appear as broad multiplets in the range of 1.2-2.3 ppm and 3.3-3.8 ppm (N-CH). The
same can be observed for B5 to B7.
Figure 42. Proton NMR spectra for B4 and B8 (RT, C6D6). The α-hydrogen atoms are assigned by the colored
dots and squares.
13
C NMR spectroscopy did not reveal any additional structural information. The correct
assignment of all peaks of the compounds B1-B4 at room temperature was done by 2-D
HMQC measurements. Based on this information, the peaks for B5-B8 could also be
assigned. Figure 43 shows such a spectrum of B3. The blue cross peaks belong to CH2-
groups, while the turquoise peaks can be assigned to CH or CH3-groups.
72
Figure 43. 2D-HMQC spectrum of B3. The proton-NMR data are allocated at the x-axis, while the carbon-NMR
data are allocated at the y-axis of the spectrum.
NMR investigations of reactions with one equivalent of carbodiimide

Attempts to insert only one equivalent of carbodiimide into the amido-imido compounds (S4-
S6) were partly successful. One equivalent of i-Pr-cdi was added to the starting compound S5,
dissolved in hexane. After two hours, one milliliter of the clear solution was taken and
carefully dried in vacuum. NMR spectroscopy of the viscous, gel like residue, revealed the
formation of the mono-guanidinato complex [Ta(NEtMe)2{η2-(N-i-Pr)2C(NEtMe)}(N-t-Bu)].
Figure 44. NMR spectrum of the mono-inserted product of the reaction between S5 and one i-Pr-carbodiimide.
Addtionally, small amounts of B2 (twofold inserted product) and S5 can be also observed. The peaks for the
protons of the CH2-group (Ta-N(Me)CH2CH3) cannot be clearly assigned.
The proton NMR spectrum is less complex than the spectra of B1-B8 (figure 44). Two
explanations can be given for this observation. Firstly, the molecule contains an internal
73
mirror plane along the Ta-imido-guanidinato plane and is thus not chiral. Consequently, the
substituents are chemically equivalent and show only one peak for each type of substituent.
The other explanation would be fluxional processes (fast migration of the carbodiimide-
group) that can take place, because the tantalum center is only fivefold coordinated and
enables the formation of six fold coordinated intermediate structures. Crystallization of this
mono guanidinato complex was not possible. Crystals, obtained from a concentrated solution
of this reaction turned out to be compound B2, the twofold guanidinato substituted product.
Obviously equilibrium reactions take place between the mono- and di-substituted guanidinato
complexes (figure 45).
Figure 45. Reaction of the amido/imido complexes S4-S6 (R1, R2 = Me/Et) with one equivalent of i-Pr-cdi.
Attempts to crystallize the mono-inserted product lead to the formation of the solid di-substituted complexes.
5.3.2.2 Mass spectroscopy
Mass spectral analysis of B1-B8 indicated the low volatility of cy-cdi containing compounds
(B5-B8), compared to their bis(iso-propyl)carbodiimide (i-Pr-cdi) based congeners (B1-B4).
The intensities of the M+-peaks of the cy-cdi based complexes were found to be below 1 % (if
visible at all) and in the case of the i-Pr-cdi based compounds between 10 and 13 %.
According to this information, the intensity of free cdi is much higher, indicating a higher
contribution of thermal decomposition during evaporation (see chapter 5.6 for thermal
decomposition experiments). The most intense peaks (B5-B8) could be observed at m/z = 41,
43 and 55, belonging to the cyclohexyl-fragments C3H5+, C3H7+ and C4H7+.
5.3.3 Single crystal X-ray analysis of B1-B5 and B7
Single crystals of B1-B5 and B7 in good quality were obtained by recrystallization of the
compounds from toluene (B2-B5, B7) or diethylether (B1) at -30 °C. Several attempts to
obtain crystals of B6 or B8, suitable for single-crystal X-ray analysis failed. The crystals were
colorless and appeared in form of agglomerated, needle like structures (figure 46). Crystals,
74
removed from the Schlenk tube were mounted on a capillary using inert oil, transferred to the
cold gas stream of the diffractometer and mounted on the goniometer.
Figure 46. Crystals of B1 in five-fold magnification. The different colors of particular crystals are generated by
polarized light that is refracted at the boundaries within the crystals. These boundaries clearly show that the
crystals are not single crystalline, but agglomerates of conjoined smaller crystals.
Compounds B1-B3 crystallize in an orthorhombic crystal system while the crystal systems of
B4, B5, B7 are of lower symmetry, i.e. monoclinic for B4 and B7 and triclinic for B5,
respectively. The quality of the data of the measured crystals was excellent in most of the
cases (besides B3), despite the agglomeration of the crystals (table 9). All details regarding
the crystallographic data and the refinement parameters are summarized in table 29 and 30
(page 181 and 182).
Table 9. Selected data for the crystal structures of B1-B5 and B7.
Complex Crystal system Space group R [I > 2σ(I)] R indices (all data)
R1 wR2 R1 wR2
B1 orthorhombic Pbca 0.0455 0.0707 0.0686 0.0759
B4 monoclinic P2(1)/n 0.0406 0.0977 0.0440 0.1000
B5 triclinic P-1 0.0662 0.0960 0.0861 0.1016
B7 monoclinic P2(1)/c 0.0562 0.1119 0.0797 0.1221
Only in the case of B7, solvent was incorporated into the crystals. However, the solvent
showed no interaction with B7, therefore it was excluded from further consideration. All six
crystal structures confirm the structures deduced from NMR spectroscopy and show very
75
similar bonding features. Thus the molecular structure of B1 is discussed in some detail as a
general example of the whole series. All relevant bond lengths and bond angles are
summarized in table 10 on page 82 (fold-out).
The tantalum center of B1 is hexa-coordinated in the form of a distorted octahedron,

surrounded by two guanidinate ligands in cis-position, one dimethylamido and one tert-
butylimido-group (figure 49 and 50 on page 81; fold-out). Therefore the molecule is chiral,
resulting in the complex NMR-spectra discussed above. The Ta-N(6)-C(18) unit of the imido-
ligand is almost linear (170.6(4)°) and the Ta-N(6) bond is relatively short (1.785(5) Ǻ) which
indicates an almost sp-hybridized imido-ligand. Based on the strong π-donating effect of this
imido ligand, the Ta(1)-N(3) bond of the guanidinato ligand trans to the imido-group is
elongated (2.396(5) Ǻ), while the second Ta-N bond of the same guanidinato ligand (Ta(1)-
N(4), 2.129(4) Ǻ) is considerably shorter. The π-donating amido group, attached to the
tantalum center evokes the same effect, but is expectedly less pronounced as compared to the
imido group. Obviously, the π-donating effect of the imido group results in an unsymmetrical
charge distribution within the delocalized π-system of the guanidinato ligand, which is also
well reflected in a rather large difference of the N-C bond lengths (N(3)-C(2): 1.320(7) Ǻ and
N(4)-C(2): 1.361(7) Ǻ). The second guanidinato ligand (N(1)-C(1)-N(2)) is more symmetric,
the two Ta-N bond lengths being 2.174(4) Ǻ (Ta-N(1)) and 2.254(4) Ǻ (Ta(1)-N(2)). Again
the longer Ta-N bond is found trans to the more basic ligand, i.e. the amido group.
The bite angles of the two bidentate ligands (N(1)-Ta(1)-N(2) = 59.56(18) ° and N(3)-Ta(1)-
N(4) = 58.92 °) are similar to the bite angle of the guandinate-ligand in the related complex
[Ta(NMe2)4(η2-(Cy-N)2C(NMe2))] X1 (59.90°), published by M. K. T. Tin et. al. in 1999.[163]
Another similarity is that the remaining NMe2-group at the tantalum centre of B1 is almost
planar. With a dihedral angle of nearly 180°, it indicates the strong π-donating effect of this
amido group.
A significant difference between the structure of B1 and the mono guanidinato structure
[Ta(NMe2)4(η2-(Cy-N)2C(NMe2))] (X1) can be observed in the character of the NMe2-groups
that are bonded to the guanidinate ligand. In the case of complex X1 structure type A (sp3-
hybrisation of the exocyclic nitrogen) seems to be dominating (figure 47). Compound B1 on
the other hand contains structural features of structure type A as well as B.
76
The structure types can be characterized by four specific parameters, that are explained
beneath the caption of figure 47:
Figure 47. Comparison of the structural features of the guanidinato ligand in complex X1 and B1. While X1 is
clearly present in form of structure type A, the structure of the ligand in complex B1 is in between the two
mesomeric forms A and B. The out of plane distortion angles of the C-NMe2 moiety are given (150° and 177°) as
well as the twisting angles of the amido moiety versus the endocyclic Ta-N-C-N group (Newman projection).
Sum of bond angles around exocyclic nitrogen

The sums of the bond angles around N(7) and N(8) (exocyclic amido groups) of structure B1
are almost 360°, pointing to the sp2-hybridisation of the nitrogen centers of the exocyclic
amido groups. The sum of angles around the exocyclic nitrogen atom of complex X1 is only
350°, which is in between the theoretical values for a sp2- and sp3- hybridized nitrogen atom.
77
Planarity of the amido group

For X1, the structure of the CNMe2-moiety deviates from an ideal planar structure type with a
dihedral angle of 150.2°. Contrary, the CNMe2-moieties of structure B1 are almost planar
with dihedral angles of 178.9 and 176.8°, respectively.
Twisting angle between the NMe2-plane and the metallacycle

Although the exocyclic nitrogen atom exhibits strong indications for sp2-hybridisation,
interaction with the cyclic TaCN2-system seem to be reduced. For an ideal interaction
between the π-system of the NMe2 moiety at one guanidinate ligand and the metallcycle
system itself, the planes spanned by the CN2-segment and NMe2 should be twisted by 0°. The
observed twisting angles of B1 are about 47°, thus showing a reduced π-π-interaction
(Newman projection, figure 46). However, compared to the structural parameters of the
guanidinato containing compound X1 a significantly higher interaction can be observed for
B1. The amido ligand of X1 is distorted by over 80° towards the cy-N-C-N-cy-unit and the C-
N bond with the exocyclic nitrogen atom (in our case N(7), N(8) is lengthened by 0.03 Å
(1.420 Å vs. 1.394 Å) .
N-C bond length within the CN3-system

Additionally, the type of bond between the central carbon atom (C(1), C(2)) of the
guanidinato ligand and the nitrogen atom of the amido group (N(8), N(7)) can be classified
based on the comparison of C-N-bond distances within the ligand. This comparison provides
information about the interaction of the free electron pair at the nitrogen of the amido-group
with the NCN-unit of the guanidinato ligand. If the mesomeric iminium diamide form (figure
32 B) dominates the overall structure, the C-N bond length of the NMe2 group to the
guanidinato core (C(1)-N(8), C(2)-N(7)) would be shorter than the N-C bonds of the
metallacycle. This is clearly not the case. The metallcyclic C-N bonds are 0.3 to 0.8 Å shorter
than the exocyclic C-N bond. This would point to the dominating influence of the 1,3-
diazallyl structure type (figure 46 A). The differences in the tantal-to-ligand interactions of
the two guanidinato ligands (opposite position to the imido and amido group) do not seem to
affect the bonding situation of the exocyclic amido groups of these guanidinato-ligands
(almost the same bond length for C(1)-N(8) = 1.393(7) Å and C(2)-N(7) = 1.390(7) Å).
78
Structural distinctions and similarities between B1 and the structures of B2-B5 and B7.
The main finding is that the cyclohexyl-moiety of the guanidinato ligand does not seem to
have a strong influence on the structural features of the compounds compared to i-Propyl
substituted complexes. Ortep/Povray plots are displayed in figure 92-94 in the experimental
part (chapter 10.9.3). All the studied molecular structures reveal that the Ta-N(6)-C(18) unit
of the imido-ligand is almost linear (>170°) and the Ta-N(6) bond is relatively short (1.79 Ǻ).
The sum of bond angles around the nitrogen atoms N(7) and N(8) range between 357.9 and
360° for all compounds and the amido groups are almost planar with angles above 155.5° (up
to 179.8°). Nevertheless, only reduced interaction with the delocalized π–system of the R4-N-
C-N-R4 unit is possible due to the relative high distortion angles between the planes, given by
the amido ligand and the R4-N-C-N-R4 unit (40.5 to 58.6°).
All molecular structures show the same orientation for the Ta-amido group. One carbon atom
(atom C(16), figure 48) is arranged it such manner that it is positioned within the plane,
spanned by tantalum and the two nitrogen atoms of the amido and imido group (N(5)-Ta(1)-
N(6)). The out of plane torsion angle is below 6.3 ° for B1-B5 and B7. It can be proposed that
steric reasons play a significant role in this alignment of the atoms, besides an impact of the
electronic structure of the molecular orbitals. This structural feature clearly explains the
presence of two widely separated peaks for the protons attached to C(16) and C(17) in the 1H-
NMR spectra of the compounds (see chapter 5.3.2.1). The rotation of this group is not only
hindered by the double bond character of the Ta-N(5) bond, but more by steric circumstances.
Another indication for steric constraints within the structures is the inwards orientation of the
two methyl groups of the iso-propyl moieties (B1-B4) towards the tantalum center. This is
caused by a repulsion of the iso-propyl groups and the exocyclic amido group.
79
Figure 48. Ortep/Povray plots of the structures of B1 and B2. The planes, spanned by Ta(1), N(6), N(5) and
C(16) are displayed in both molecules. Substituents, e.g. i-Pr-groups are removed for reasons of clarity.
Thus, complexes containing symmetric amido groups (NMe2, NEt2) show two peaks, having
the same intensity, since rotation of the amido groups by 180 ° lead to chemically equivalent
structures. Ethyl-methyl-amido substituted complexes (e.g. B2) generate two signals for the
methyl group as well as two sets of signals for the ethyl group. The ratio between each pair of
signals is influenced by the preference for the sterically less hindered position for the amido
group. From the molecular structure of B2 in the solid state, the favored orientation is
presumably an orientation of the methyl group towards the imido group.
80
Figure 49. Molecular structure of B1 in the solid state.
Figure 50. Clarification of the coordination sphere of the six nitrogen atoms around the tantalum center. Left:
Ortep/Povray plot of a cutout of B1. Right: The geometrical figure corresponds to a distorted octahedron. The
labeling of the nitrogen atoms is consistent for all compounds B1-B8.
81
Table 10. Selected bond length and bond angles of B1-B5 and B7.
B1 B2 B3 B4 B5 B7
Selected bond lengths (Å)

Ta(1)-N(1) 2.174(4) 2.185(7) 2.198(8) 2.192(4) 2.168(6) 2.198(4)
Ta(1)-N(2) (opp. amido) 2.254(4) 2.251(7) 2.275(8) 2.250(4) 2.279(5) 2.269(4)
Ta(1)-N(3) (opp. imido) 2.396(5) 2.409(7) 2.408(8) 2.433(4) 2.437(5) 2.408(4)
Ta(1)-N(4) 2.129(4) 2.127(7) 2.126(8) 2.122(4) 2.123(5) 2.136(4)
Ta(1)-N(5) (Ta-amido) 2.014(5) 2.002(8) 2.023(8) 2.013(4) 2.005(5) 2.008(4)
Ta(1)-N(6) (Ta-imido) 1.785(5) 1.791(8) 1.790(10) 1.780(4) 1.786(6) 1.797(4)
N(1)-C(1) 1.345(7) 1.352(11) 1.327(13) 1.329(6) 1.389(8) 1.342(6)
N(2)-C(1) 1.309(7) 1.318(11) 1.327(14) 1.325(6) 1.318(9) 1.319(6)
N(3)-C(2) 1.320(7) 1.319(11) 1.323(13) 1.308(6) 1.308(9) 1.320(6)
N(4)-C(2) 1.361(7) 1.356(11) 1.359(13) 1.359(6) 1.363(9) 1.363(6)
N(5)-C(16) 1.456(7) 1.453(12) 1.464(13) 1.471(6) 1.451(8) 1.457(7)
N(5)-C(17) 1.463(7) 1.468(13) 1.465(12) 1.454(7) 1.453(8) 1.464(6)
N(6)-C(18) 1.444(7) 1.453(12) 1.449(14) 1.439(7) 1.457(9) 1.440(7)
N(7)-C(2) 1.390(7) 1.382(11) 1.400(13) 1.388(6) 1.388(9) 1.400(6)
N(7)-C(11) 1.442(7) 1.454(12) 1.464(14) 1.467(6) 1.465(9) 1.456(7)
N(7)-C(12) 1.440(8) 1.447(12) 1.467(16) 1.457(6) 1.443(9) 1.446(7)
N(8)-C(1) 1.393(7) 1.391(11) 1.393(13) 1.393(6) 1.397(8) 1.393(7)
N(8)-C(3) 1.444(8) 1.437(13) 1.444(14) 1.451(7) 1.455(8) 1.456(8)
N(8)-C(4) 1.450(7) 1.447(12) 1.461(14) 1.463(7) 1.459(9) 1.483(10)
Selected bond angles (°)
N(1)-Ta(1)-N(2) 59.56(18) 59.4(3) 58.8(3) 59.38(14) 60.3(2) 59.14(15)
N(2)-Ta(1)-N(5) 155.36(19) 154.8(3) 158.7(3) 155.50(16) 153.7(2) 156.64(17)
N(3)-Ta(1)-N(4) 58.92(16) 58.1(3) 58.5(3) 58.05(14) 58.0(2) 58.62(14)
N(3)-Ta(1)-N(6) 162.19(19) 161.1(3) 160.6(4) 156.78(16) 161.4(2) 161.69(16)
N(1)-C(1)-N(2) 112.0(5) 111.0(7) 111.6(9) 112.1(4) 111.3(6) 111.9(4)
N(3)-C(2)-N(4) 113.2(5) 112.0(8) 112.5(8) 113.2(4) 113.0(6) 112.9(4)
C(1)-N(8)-C(3) 122.7(5) 120.6(8) 120.6(9) 120.0(4) 121.0(6) 120.3(5)
C(1)-N(8)-C(4) 121.9(5) 121.4(8) 120.1(8) 121.8(4) 119.0(5) 118.4(5)
C(3)-N(8)-C(4) 115.3(5) 117.2(8) 118.5(9) 116.9(4) 115.1(5) 120.9(5)
C(2)-N(7)-C(11) 120.7(5) 122.9(8) 121.4(8) 120.6(4) 123.0(6) 121.1(4)
C(2)-N(7)-C(12) 122.8(5) 120.7(8) 121.4(8) 119.1(4) 120.9(6) 121.1(4)
C(11)-N(7)-C(12) 116.5(5) 116.1(8) 117.2(8) 118.2(4) 115.1(6) 116.0(4)
Ta(1)-N(6)-C(18) 170.6(4) 175.7(7) 174.9(8) 176.2(4) 175.7(5) 172.3(4)
Selected torsion angles (°)
Ta(1)-N(5)-C(16)-C(17) 178.5(7) 179.4(12) 178.4(14) 178.0(5 175.7(10) 180.0(7)
C(2)-N(7)-C(11)-C(12) 179.8(9) 174.6(11) 179.0(14) 163.6(4) 169.0(10) 166.2(6)
C(1)-N(8)-C(3)-C(4) 176.3(9) 169.9 (12) 169.9(14) 166.8(5) 155.5(10) 172.4(5)
C(3)-N(8)-C(4)-plane vs. 45.5(13) 50.4(18) 53.7(14) 48.7(8) 45.3(10) 58.6(6)
N(1)-C(1)-N(2)-plane
C(11)-N(7)-C(12)-plane vs. 44.2(13) 45.0(18) 42.2(14) 45.9(6) 40.6(10) 46.2(7)
N(3)-C(2)-N(4)-plane
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5.4 Synthesis of amido / imido / guanidinato compounds of niobium C1-C4
Generally, niobium and tantalum show similar behavior in the formation of metal organic
complexes having the oxidation state +V. Following the synthesis of B1-B8, the concept of
carbodiimide-insertion into metal amido compounds was transferred to niobium. Very similar
properties can be observed for the synthesized mixed amido/imido/guanidinato complexes.
Therefore this chapter will be condensed to the most important findings.
5.4.1 Synthetic route, purity and properties of the compounds C1-C4
For the synthesis of C1-C4, two equivalents of the corresponding carbodiimide were added to
the amido/imido compound of niobium (figure 51). The products, which are highly soluble in
common organic solvents (e.g. toluene, hexane, benzene) precipitated from the reaction
solutions during removal of the solvent in vacuo.
Figure 51. Synthesis of the complexes C1-C4. The assignment of R1-R3 can be found in table 11.
Table 11. Overview of the synthesized guanidinato complexes of niobium.

Name Amido cdi-type Imido Yield m.p.
1 2 3
R R R in % in °C
C1 Me Me i-Pr t-Bu 86 211
C2 Et Et i-Pr t-Bu 79 184
C3 Me Me cy t-Bu 82 210
C4 Et Et cy t-Bu 72 197
The color of the products in powder form is white to yellow, whereas the clean product is
supposed to be completely colorless. No drastic color change was observed during the
reactions. This is a bit surprising, considering the previously reported reactions of
[Nb(NMe2)5] (PDMAN) with i-Pr-cdi and cy-cdi in which formation of a “blood red” solution
was reported after combination of the almost colorless starting compounds.[163] It was
suspected that this color change is based on the formation of minor products during the
reactions. The CHN-analysis of the compounds C1-C4 indicated sufficient purity of the
83
compounds for their use as MOCVD - precursors. In the case of reactions with i-Pr-cdi, a
small excess of the ligand was not problematic as it could be easily removed under vacuum
overnight. This was not the case with the solid, less volatile cy-cdi.
5.4.2 Spectroscopic analysis of the compounds C1-C4
13
Proton and C-NMR spectroscopy of the hexa-coordinated complexes C1-C4 resulted in
spectra, very similar to the corresponding tantalum congeners. The spectra of the tantalum
compounds were already extensively discussed, thus no thorough discussion of the spectra is
necessary here. Nevertheless, some differences in the 13C-NMR spectra should be pointed out.
It seems that going from tantalum to niobium, as the central atom of a nitrogen-coordinated
complex, has an influence on the appearance and broadness of peaks for carbon atoms, which
are directly bounded to the M-N species. The quaternary carbon atom of the imido group does
not appear in all 13C-NMR spectra of C1-C4. This effect was already observed in the case of
[Nb(NCMe2Et)Cl3(dme)] (dme = dimethoxyethane).[136] The reason for this is probably the
existence of relaxation parts in the niobium complexes different to their tantalum analogs,
which could broaden the peaks and thus make them difficult to detect. In addition, the peaks
for the α-carbon atoms of the Nb-amido group in the complexes C1-C4 are broadened
(positions: ~48 and ~58 ppm). However, the reason for this broadening can be a rotational
13
barrier with its rotating frequency within the order of the time scale of the C-NMR-
spectroscopy. Recording high temperature NMR-spectra can be considered in order to support
this assumption. Another phenomenon that can be observed in the case of the TBTDEN-based
13
complexes C2 and C4 is the complete absence or at least an extreme broadness of the C-
peaks of the diethylamidogroup from one guanidinato-ligand (altogether four peaks). So far
the only explanation for this situation is the structural difference of the two guanidinato
ligands (5.4.3). The mass spectra of the compounds revealed similar decomposition products
as observed for the mixed amido/imido/guanidinato complexes of tantalum. One difference
was the low intensity or the complete absence of the molecular peak in all cases (C1: 1 %,
C2-C4: not present). This could indicate either a decomposition of the compounds before they
evaporate or a lower chemical stability during the electron bombardment.
84
5.4.3 Single crystal X-ray analysis of C1 and C2
Crystals were obtained by slow crystallization from a concentrated solution of C1-C4 in

toluene at -30°C. The colorless, clear crystals were strongly agglomerated, making it difficult
to isolate a distinct single crystal. Therefore, the quality of the crystal data of C2 was
relatively low and crystals from C3 and C4 did not even show sufficient quality for solving
the structures (table 31). The bonding parameters of the molecular structures of C1 and C2 in
the solid state are almost equal and can be discussed together (table 12). In general, the
parameters are similar to the corresponding tantalum compounds (chapter 5.3).
Figure 52. Ortep/Povray plot of the molecular structure of C1 in the solid state. The N(6)-Nb(1)-N(5)-C(16) plane
is colored in yellow. The distortion of the endocyclic planes (green) and the planes, spanned by the exocyclic
amido groups (red) are indicated.
The hexa-coordinated complexes show coordination of the nitrogen atoms around the niobium
in distorted octahedral fashion (figure 52). The orientation of the amido group bonded to
niobium (sp2-hybridized; sum of bond angles ~360 °, almost planar) is most likely influenced
by a steric effect as it was already observed in the case of the tantalum congeners (figure 52,
yellow plane). The guanidinato ligands are cis-oriented, which is in contrast to the compound
[NbCl2{(N-cy)2C(N(SiMe3)2)}2][166], containing the two guanidinato ligands in trans
orientation. The main reason for that is most probably the strong donating effect of the imido-
group which is unlikely to be in trans-position to the amido group (trans effect). The Nb(1)-
N(6) bond of the imido group is a Nb-N triple bond with a very short distance of 1.770 Å (in
average). In addition to that, the imido-group is almost linear with an Nb(1)-N(6)-C(18) angle
of 175.8 °. The two guanidinates differ in terms of symmetry. Although their bite angles are
85
almost equal, the distance from the nitrogen atoms to the Nb center varies. Opposite to the
imido group and the amido group, the Nb(1)-N(3) and the Nb(1)-N(2) bonds are lengthened
compared to the Nb(1)-N(1) and Nb(1)-N(4) bonds. As expected, this effect is stronger in the
case of the Nb(1)-N(3)-bond, opposite to the six electron donating imido group. This
difference of the ligands possibly explains why only one amido group (of the guanidinato-
ligand) is broadened in the 13C-NMR-spectrum of C1-C4 (5.4.2). The endocyclic C-N-bonds
of the guanidinato ligands are shorter than their exocyclic C-N-bond to the amido groups
(C(1)-N(8); C(2)-N(7)). This issue, and the fact that these amido groups are twisted towards
the guanidinato-center by 41.6 to 56.0° indicate a low conjugation of the partially sp2-
hybridized nitrogen atoms N(7) and N(8) (green and red planes in figure 52). Their
hybridization is indicated by a sum of bond angles around N(7) and N(8) of almost 360° and a
high planarity of the C(1)-N(8)-C(3)-C(4) and the C(2)-N(7)-C(11)-C(12) system.
Table 12. Selected bond length and bond angles of C1 and C2.
Selected bond C1 C2 Selected bond lengths in Å C1 C2
lengths in Å
Nb(1)-N(1) 2.201(2) 2.199(5) N(5)-C(17) 1.460(3) 1.468(8)
Nb(1)-N(2) 2.298(2) 2.293(6) N(6)-C(18) 1.458(3) 1.471(9)
Nb(1)-N(3) 2.4170(19) 2.411(6) N(7)-C(2) 1.393(3) 1.390(8)
Nb(1)-N(4) 2.1427(19) 2.153(5) N(7)-C(11) 1.442(7) 1.454(12)
Nb(1)-N(5) 2.013(2) 2.012(6) N(7)-C(12) 1.440(8) 1.447(12)
Nb(1)-N(6) 1.777(2) 1.764(6) N(7)-C(11) 1.453(3) 1.440(8)
N(1)-C(1) 1.336(3) 1.342(8) N(7)-C(12) 1.445(3) 1.460(8)
N(2)-C(1) 1.319(3) 1.340(8) N(8)-C(1) 1.403(3) 1.399(8)
N(3)-C(2) 1.313(3) 1.334(8) N(8)-C(3) 1.440(4) 1.427(10)
N(4)-C(2) 1.357(3) 1.363(8) N(8)-C(4) 1.446(4) 1.446(9)
N(5)-C(16) 1.457(3) 1.460(9)
Selected bond Selected bond angles in °

angles in °
N(1)-Nb(1)-N(2) 58.81(7) 59.20(19) C(11)-N(7)-C(12) 115.0(2) 117.7(6)
N(2)-Nb(1)-N(5) 156.30(8) 159.7(2) Nb(1)-N(6)-C(18) 176.43(17) 175.3(6)
N(3)-Nb(1)-N(4) 58.20(7) 58.5(2)
N(3)-Nb(1)-N(6) 161.32(8) 161.9(2) Selected torsion angles (°)
N(1)-C(1)-N(2) 112.7(2) 111.8(6) Nb(1)-N(5)-C(16)-C(17) 179.4(2) 179.7(7)
N(3)-C(2)-N(4) 113.3(2) 112.4(6) C(2)-N(7)-C(11)-C(12) 168.5(4) 178.9(9)
C(1)-N(8)-C(3) 121.1(2) 121.3(7) C(1)-N(8)-C(3)-C(4) 171.6(4) 175.2(9)
C(1)-N(8)-C(4) 122.3(2) 119.3(6) C(3)-N(8)-C(4)-plane vs.
47.6(4) 56.0(11)
C(3)-N(8)-C(4) 116.0(2) 119.3(7) N(1)-C(1)-N(2)-plane
C(2)-N(7)-C(11) 121.3(2) 121.9(6) C(11)-N(7)-C(12)-plane vs.
41.6(4) 43.3(10)
C(2)-N(7)-C(12) 122.6(2) 120.4(6) N(3)-C(2)-N(4)-plane
86
5.5 Thermal analysis of B1-B8 and C1-C4 in respect to MOCVD / ALD
The thermal properties of compounds B1-B8 as well as C1-C4 were analyzed by classic
melting point determinations, standard TG/DTA measurements, isothermal analyses and
sublimation experiments under vacuum conditions. The melting points of all compounds were
relatively high (184-232 °C, table 13) and could not be rationalized by the type of ligand
substitution (R1-R4), nor by the central metal atom (niobium or tantalum). The compounds did
not melt fully at the documented temperatures, but underwent some sort of waxen transition
phase over a temperature range of approximately 5-10 °C (vide infra). At temperatures
between 177 and 245 °C (table 13) three processes occurred parallel to each other. Melting
and decomposition of the compounds as well as significant evaporation took place. Therefore
it was difficult to interpret the TG/DTA-spectra in this temperature range properly. Figure 53
displays exemplarily the two TG-DTA spectra of compounds B4 and B8. The spectrum of B4
is one of the few examples where the melting point was clearly separated from the onset of
decomposition (DTA-curve, blue). In the case of B8 the onset of melting was in coincidence
with the onset of decomposition of the product.
Table 13. Thermal parameters of the compounds B1-B8 and C1-C4 (n.v. not clearly visible). The results for the
melting point as well as the exact onset of decomposition have to be taken with care (large errors are possible).
Complex R1 R2 R3 R4 Mass in M.p. 5% Onset of Residual Theoretical,
g/mol in weight decom- mass in % residual
°C loss position in mass for
reached °C pure MN in
at T = %
B1 (Ta) Me Me i-Pr t-Bu 637.19 232 177 °C 224 28 31
B2 (Ta) Me Et i-Pr t-Bu 679.26 217 206 °C 222 12 29
B3 (Ta) Et Et i-Pr t-Bu 721.34 210 199 °C 214 11 27
B4 (Ta) Et Et i-Pr n-Pr 706.84 195 210 °C 245 13 28
C1 (Nb) Me Me i-Pr t-Bu 549.15 211 188 °C 216 15 17
C2 (Nb) Et Et i-Pr t-Bu 633.30 184 173 °C 193 21 15
B5 (Ta) Me Me cy t-Bu 796.96 210 217 °C n.v. 36 24
B6 (Ta) Me Et cy t-Bu 839.03 218 193 °C 219 32 23
B7 (Ta) Et Et cy t-Bu 881.11 204 191 °C 207 32 22
B8 (Ta) Et Et cy n-Pr 866.61 205 224 °C 216 29 22
C3 (Nb) Me Me cy t-Bu 708.92 210 207 °C 217 22 13
C4 (Nb) Et Et cy t-Bu 793.07 197 180 °C n.v. 29 12
87
Figure 53. TG/DTA spectra of B4 and B8. The stars indicate the endothermic peaks for a phase change. In
addition, the melting point and the onset of decomposition of B4 and B8 are assigned.
At temperatures noticeably below the melting or decomposition point, one to two endothermic
peaks could be observed (figure 53, marked with a star) for the spectra of all compounds
except B6 and C4. No weight loss was observed at these temperatures which indicated that
certain solid state reactions took place. The most probable reaction is a recrystallization
process (phase change) leading to a thermodynamically more stable phase of the particular
compound at these conditions. Solid state NMR-spectroscopy at higher temperatures and
temperature dependent powder XRD-analysis could prove helpful in explaining the
observation. However, studies of that kind were beyond the scope of this work. The presence
of different phases in the solid state of B1-B8 and C1-C4 could probably be the reason for the
problems in terms of crystallization. This phase change was not reversible, that means,
running a program in which the sample (B1) was heated, cooled down and heated again
showed the endothermic peaks only in the first period of heating. This spectrum is shown in
figure 54. The position of the peaks is strongly dependent on the nature of the alkyl
substituents R1, R2 (amido group) and R3 (guanidinato substituent). Going from methyl to
ethyl for the amido substituents R1 and R2, resulted in a shift of these peaks to higher
temperatures:
B1 (NMe2) → B2 (NMeEt) →B3 (NEt2): 52 °C → 70 °C → 110 °C;
B5 (NMe2) → B7 (NEt2): 112 °C→139 °C
C1 (NMe2) →C2 (NEt2): 43 °C→100 °C
The same is observed for the variation of R3 from i-Pr to cyclohexyl (cy):
B1 (i-Pr) →B5 (cy): 52 °C → 112 °C
B3 (i-Pr) →B7 (cy): 110 °C →139 °C
B4 (i-Pr) →B8 (cy): 82 °C → 140 °C
C1 (i-Pr) →C3 (cy): 43 °C → 97 °C
88
Figure 54. TG-DTA spectrum of B1 as a function of time. The heating rate was 5 °C per minute. The absence of
the endothermic peak during the second period of heating can be clearly observed. No weight loss was observed,
i.e. the loss of solvent can be excluded.
This sequence was valid for all compounds. It can be concluded, that the onset of the
temperature for the postulated phase changes depends on the mobility of the molecules in the
solid state, which supposedly increases with higher chain lengths and/or size of the
substituents.
The impact of the different substituents in the positions R1, R2, R3, R4 on the thermal
properties of the compounds was investigated by means of TG/DTA analysis and isothermal
TG-studies. The nature of the carbodiimide substituents (cy vs. i-Pr, R3) has the most
significant influence on the volatility of the compounds. Thus B1-B4, C1 and C2 (i-Pr-cdi
substituted) could be sublimed without any residues at 120°C in vacuo (10-4 mbar).
Compounds B5-B8, C3 and C4 (cy-cdi substituted) did not sublime at all under these
conditions. Isothermal studies at 120°C underlined these results. After 240 min under ambient
pressure, the weight loss of B1-B4 was approximately 10 % in all cases, while e.g.
compounds B5 and B6 showed a weight loss of only 2.5 % (figure 55). The mass transport of
the compounds was the highest for B4 (4.9µg/min) and significantly lower for B5 and B6
(0.93 and 0.59 µg/min). The simplest explanation for this observation are the higher
molecular masses of the cy-cdi compounds. However, by changing R1 and R2 from methyl to
ethyl (e.g. B1 vs. B3) no significant effect on the volatility is observed. Obviously, the
variation of R3 has a significant effect on the interactions between the molecules in the solid
state, e.g. by a different packing of the moieties (which is also reflected in the temperatures of
89
the postulated phase changes of the compounds). The niobium containing compounds showed
higher rates for evaporation. C1 and C2 evaporated with 12.8 and 10.3 µg/min, respectively.
The cyclohexyl substituted complexes C3 and C4 were again less volatile at 120°C (C3: 0.37
µg/min; C4: 3.06 µg/min).
Figure 55. Isothermal studies of the compounds B1-B6. Compounds, synthesized by insertion of iso-propyl
carbodiimide (B1-B4) are significantly more volatile (higher mass loss), than the cyclohexyl-substituted complexes
(B5 and B6).
Having a look at the residual masses after TG/DTA measurements (table 13) shows again the
clear difference in volatility and decomposition behavior of the i-Pr-cdi (B1-B4 and C1-C2)
substituted complexes and the cy-cdi substituted complexes in general. In almost every TG-
spectrum of the compounds B1-B4 and C1-C2 the residual masses were considerably lower
than the theoretical contents of TaN or NbN within the compounds. Clearly, evaporation of
the undecomposed compound took place during the measurements. Only TG measurements of
compounds B1 and C2 resulted in residual masses in the range of the theoretical content of
the metal nitride. In contrast, the residual masses from cy-cdi complexes (B5-B8 and C1-C2)
after TG/DTA measurements were higher than the theoretical masses of pure TaN or NbN
(table 13). This indicates an incorporation of significant amounts of carbon during
decomposition and a low tendency towards evaporation.
Variations of the rests R1, R2 and R3 or the exchange of the central metal atom gave no
consistent picture of the order of the complexes in terms of volatility or decomposition
behavior.
90
5.6 Investigations of the thermal decomposition of B1-B3
For the precursors, having potential for MOCVD of metal nitrides, the nature of their thermal
decomposition leading to the desired materials is crucial. Thus, compounds B1-B3 were
evaporated at 120°C in vacuo, a constant flow of argon providing a continuous transport of
the precursor through a decomposition tube at 600° C (figure 56).
Figure 56. Device for testing the decomposition behavior of B1-B3. The bubbler as well as the glas joints were
heated by heating tapes, while a quartz glas tube was heated to 600 °C in a tube shaped oven. The length of the
tube was 40 cm in order to ensure complete decomposition of the precursor.
The decomposition products were subsequently trapped at -196 °C (liquid nitrogen) in a

slightly modified cooling trap. After full evaporation of the precursor (300 mg), deuterated
benzene was injected into the cooling trap and the resulting C6D6 solutions were analyzed by
1
H-NMR and GC-MS measurements. The 1H-NMR spectra revealed the formation of the
corresponding free amines for B1-B3 (HNMe2, HNMeEt and HNEt2), small amounts of t-Bu-
amine (resulting from the former imido ligand) as well as free carbodiimide (figure 57). The
precursors were fully decomposed. It should be noted that although these compounds
represent a considerable part of the decomposition products, additional peaks were present,
which could not be unequivocally assigned. GC-MS measurements confirmed these 1H-NMR
results and additionally showed the presence of small amounts of i-Pr-amine as well as
several unidentified species containing the carbodiimine group. The relatively large variety of
decomposition products suggests rather complex decomposition mechanisms. The liberation
of free carbodiimide during decomposition was considered by S. T. Barry et al. as it is likely
[171, 172]
that the insertion of the carbodiimide is reversible under these drastic conditions.
Indications for this reversibility of insertion were already observed in equilibrium reactions
between mono- and bisguanidinato complexes (Chapter 5.3.2.1). The ratio of free
carbodiimide to other signals in the NMR spectra varied strongly, depending on the type of
the precursor. The volatility of other decomposition products (e.g. dimethylamine),
determined the intensity of the cdi-peaks.
91
Figure 57. 1H-NMR spectrum of the decomposition products of B3 at 600 °C, ingested by C6D6. Free
diethylamine as well as i-Pr-cdi can be observed. The peaks, marked with a star can probably be assigned to
decomposition products, still containing diethyl and iso-propyl groups.
92
Chapter 6 MOCVD experiments of tantalum nitride
Chapter 6 MOCVD of tantalum nitride
A selection of the new compounds, A1-A3, B1-B8, was tested in MOCVD experiments for
the deposition of tantalum nitride thin films (chapter 6.3 and 6.4). For reasons of comparison,
MOCVD experiments of reference precursors, namely the starting compounds S4-S8 were
carried out as well (chapter 6.2). The temperature regime that was tested was 500-800 °C.
Nevertheless it should be mentioned that all experiments have been made in the focus of
screening the precursors. A full elucidation of the deposition properties was not intended.
Four types of reactors have been used. Three of them are presented in chapter 6.1: One
selfbuilt MOCVD-reactor,[176] one large-wafer reactor (User: Martin Lemberger, Fraunhofer
Institut für Integrierte Schaltungen in Erlangen) and the industrial scale reactor Aixtron 200
RF (User: Stephan Spöllmann). The LI-MOCVD Aixtron 200 FE reactor is not described in
detail.
In the following table (table 14) the combinations of the precursors and the reactors, as well
as a qualitative description of the results are listed.
Table 14. Compounds that were used for MOCVD experiments including a short summary of the results.
Formula Reactor Chapter Qualitative results

type/user
S5 [Ta(NMeEt)3(N-t-Bu)] Selfbuilt 6.2.1 Cubic TaN was deposited having

(Bochum) high level of impurities (O, C)
S6 [Ta(NEt2)3(N-t-Bu)] Aixtron 200 RF 6.2.2 Cubic TaN was deposited. Low level
(Bochum, of impurities (with ammonia as
S. Spöllmann) reactive gas)
S6 [Ta(NEt2)3(N-t-Bu)] Large wafer 6.2.3 Heavily oxidized TaN was deposited.
(Erlangen, Still, the films showed good
M. Lemberger) electrical properties
S5 [Ta(NMeEt)3(N-t-Bu)] Large wafer 6.2.4 Heavily oxidized TaN was deposited.
(Erlangen,
M. Lemberger)
A3 [Ta(NEt2)2(tdmh)(N-t-Bu)] Selfbuilt 6.3.1 Amorphous and insulating TaSixNy
(Bochum) was deposited.
A2 [Ta(NMeEt)2(tdmh)(N-t-Bu)] Large wafer 6.3.2 Heavily oxidized TaSixNx was
(Erlangen, deposited. The films were completely
M. Lemberger) insulating.
B2 [Ta(NMeEt){η2-(N-i- Selfbuilt 6.4.1 Cubic TaN with almost no impurities
Pr)2C(NMeEt)}(N-t-Bu)] (Bochum) was deposited without ammonia.
B2 [Ta(NMeEt){η2-(N-i- LI-MOCVD 6.4.2 Oxidized and insulating, but carbon
Pr)2C(NMeEt)}(N-t-Bu)] Aixtron 200 FE free TaNx was deposited.
(Bochum)
93
The films were analyzed by several techniques that are described in chapter 10.2, including
X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Electron Dispersive X-ray
spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), Rutherford Backscattering
(RBS), Secondary Neutral Mass Spectroscopy (SNMS) and Four-Probe resistivity
measurements. Besides these techniques for answering the “standard” questions of precursor
tests (morphology, growth rate, crystallinity, composition of the films), further electrical
characterization of the thin films was performed in cooperation with our partner in Erlangen.
These analyses aim at a specific application of the TaN films as gate electrode materials.
Although the electrical characterization was completely carried out by our collaborating
partner the results are interesting in terms of applicability of the films for electronic devices
and some discussions will be given. An extra chapter is addressed to explain the electrical
characteristics and results of the measurements (Chapter 6.5). All results of the experiments
are summarized in a diagram (Chapter 9, summary), similar to the figure that summarized
experiments of other works (figure 9, chapter 2.1.1).
6.1 Presentation of the MOCVD reactors utilized in this work
In the following the three reactor systems that have been used for the MOCVD experiments
are described.
Selfbuilt, coldwall MOCVD reactor

The cold wall reactor consists of a tube shaped glas-part that contains the graphite susceptor
(inductive heating) and the substrates, which are placed on the susceptor. The area of the
reactor around the substrate holder is constantly cooled by a thermostat (water-filled, T = 40
to 80 °C, depending on the evaporation temperature). However, the inner wall of the reactor
has probably a higher temperature due to radiation of the heated susceptor. The whole
delivery system for the precursor system is heated by an airbath and additional heating tapes
to the preselected vaporization temperature to ensure the transport of the precursor at almost
isothermal conditions. Therefore, cold spots in the delivery system should be excluded. The
reactor scheme is shown in figure 58. Precursor is filled in the glove box into the thoroughly
dried bubbler under inert gas atmosphere in order to prevent an oxidation of the product. A
continuous flow of the carrier gas led through the bubbler is achieved by using a mass flow
controller. The gas/precursor mixture flows over the susceptor holder, which is tilted by
approx. 15° to allow a more uniform mass flow distribution over the whole sample. Unreacted
94
precursor and decomposition byproducts are collected in a cold trap at liquid nitrogen
temperature.
Figure 58. Scheme of the selfbuilt horizontal cold wall reactor (substrate size: 1.4 x 2.0 cm2).
Pieces of Si(100) wafers with a thermally generated silicon dioxide layer (20 nm) were used
for depositions. The sizes of the Si(100) wafers were approximately 1.4 cm x 2.0 cm. Before
use they were cleaned in a flow of pure argon in order to remove all macroscopic residues
together with any dust on the surface. No further treatment of the wafers was necessary before
loading them into the reactor. The reactor itself was kept under nitrogen to prevent absorption
of oxygen and moisture on the reactor wall. It was cleaned after each deposition with iso-
propanol to remove undecomposed precursor. The base pressure was around 4·10-6 mbar.
Experiments were carried out at pressures of 1-10 mbar. The studies focused on the properties
of the compounds as single source precursors. Therefore, in most of the experiments, ultra
pure nitrogen (purity 6.0) was used as inert carrier gas without addition of reactive gases.
Additional ammonia gas was only applied in experiments with the tdmh ligand containing
precursor A3. The advantage of this reactor is the simplicity of the setup which enables up to
three experiments per day without causing the high costs associated with the use of semi-
industrial equipment.
Nonetheless, the drawback of this type of reactor is the lack of reproducibility of the
experiments as a result of the rather simple setup. Thereby, the most crucial point is the
95
quantitative control over the precursor transport into the reactor. Small variations in the
openings (teflon valves) of the bubblers have a high impact on the fluid dynamics of the
carrier gas and thus of the mass transport of the precursor into the reactor. Thus, drawing
exact conclusions on the growth rate of a precursor under certain conditions cannot be
recommended. More reliable results can be achieved in terms of temperature dependence of
the growth. The temperature can be precisely determined and regulated by a pyrometer.
Large-scale reactor (Erlangen)

The selfbuilt reactor from our partner in Erlangen is designed to deposit thin films
simultaneously on two 150 mm wafers. [177] It is a horizontal cold wall reactor (base pressure:
approx. 10-2 mbar; quartz tube dimensions: length: 80 cm, diameter: 20 cm, figure 59). The p-
type Si(100) wafers with 20 nm thermal oxide are placed on a horizontally mounted graphite
susceptor, that is heated by halogen lamps to temperatures of 400 to 700 °C. Temperature
control is done by using thermo couples within the susceptor. The precursor is kept in a metal
or glass bubbler (chapter 6.1.1) and is electrically heated. The pre-heated carrier gas
(nitrogen) is led directly through the liquid precursor in order to guarantee a constant mass
transport into the reactor. All gas lines (length appr. 100 cm) are heated electrically to
temperatures above the evaporation temperature of the precursor. By using this reactor, it is
possible to deposit thin metal nitride films on pre-structured Si-wafers in order to form
MOSFET gate structures and measure the electrical properties of the metal nitride gate
materials. Due to the design of the reactor (large volume, complex fluiddynamics) it is
difficult to acquire control over the growth behavior of the thin films. Gas phase pre-reactions
are likely to occur, either thermally induced, or caused by contact with reactive ammonia.
This could lead to particle formation. The wafers are lying flat on the substrate holder and are
not tilted towards the gas stream. Thus, obtaining uniform films is more difficult. On the other
hand this allows the deposition (and the analysis) of gate structures having various film
thicknesses in dependence of the position of the structure on the wafer. The high base
pressure is critical as it indicates the presence of small leakages.
96
Figure 59. Scheme of the horizontal cold wall reactor in Erlangen. The reactor is constructed for two 150 mm
wafers.
Aixtron 200 RF – reactor

The industrial scale reactor Aixtron 200 RF was originally built for high volatile precursors
for the deposition of III-V semidconductors, e.g. trimethylgallium. In principle, this reactor is
constructed similar to the reactor in Erlangen (figure 60 and 61). All gas flows are regulated
by computer controlled mass flow controllers and valves. Modifications were made to enable
the transport of less volatile metal organic precursors into the reactor. All lines and valves are
covered by heating tapes and can be heated up to 100 °C.
Figure 60. Scheme of the Aixtron 200 RF reactor.
The wafer is placed on a rotating disc, actuated by a hydrogen gas flow, to enhance the
uniformity of the deposited thin films. Samples are loaded from an attached glovebox (argon)
into the open reactor without air contact. Exhaust gases are led through a 30 % aqueous
solution of sulfuric acid.
97
Figure 61. Left: Picture of the Aixtron 200 RF MOCVD reactor. The reactor part in operation is shown in the right
picture.
6.1.1 Bubbler design – Enhancement of precursor evaporation
The standard containers (bubbler) for storage of precursors in industrial and semi-industrial
MOCVD reactors consist of stainless steel. Although they have a high mechanical stability,
the precursor is hidden in a, more or less, black box and the bubbler has to be disconnected
and transferred into a glove box in order to check the precursor’s fill height and condition. In
this work, precursor reservoirs for liquid precursors, made out of glass, were constructed for
the Aixtron 200 RF reactor and the reactor in Erlangen (figure 62). They facilitate a rough
control of the precursor consumption in a certain number of experiments (e.g. 2 ml per 5 runs)
and the changes of the precursor over time. The majority of liquid metal organic precursors
partly decompose after long exposure to evaporation temperatures. This is reflected in
changes of the color of the liquid precursor as well as the formation of precipitates. For the
small, selfbuilt reactor, all bubblers are made out of glass with simple Teflon valves. The
bubbler and its content is exchanged after each deposition.
98
Figure 62. Glass bubblers for a) the Aixtron 200 RF reactor and b) the reactor in Erlangen (large wafer
instrument). In order to ensure a minimum filling height, glass pearls can be added to the precursor to reduce the
required amount of precursor.
6.2 Deposition experiments with simple amido / imido tantalum precursors
MOCVD experiments using the established amido/imido-type precursors for TaN deposition
(S5, S6) were carried out for several reasons in this work. First, the obtained data can be used
as a benchmark for screening the more complex precursor systems A1-A3, B1-B4, and C1-
C2. This is necessary, although reports of depositions applying amido/imido compounds
already exist. In fact, the published results differ quite significantly, depending on the reactor
that has been used and the particular conditions. Second, the obtained data are interesting for
their own merit due to the fact that a systematic study of alkylamido/imido-type TaN
precursors with small variations of the alkyl substitution patterns has not yet been performed.
Third, in a collaborative project with the research group in Erlangen, the formation of thin
metal nitride films for complex gate structure devices is relevant and not necessarily the type
of precursor that is used.
99
6.2.1 Depositions with [Ta(NEtMe)3(N-t-Bu)] (S5) in the selfbuilt horizontal reactor
The liquid compound S5 is highly volatile and requires comparably low temperatures of
evaporation for a sufficient mass transport into the reactor (bubbler temperature range: 30 to
45 °C). The focus of these preliminary experiments was to optimize the deposition conditions
in terms of evaporation temperature at substrate temperatures of 600 and 700°C. The pressure
(8 mbar) as well as the flow rate of the carrier gas (nitrogen, 25 sccm) were kept constant in
all experiments. Lower pressures and higher flow rates of nitrogen induced non-uniform
growth due to very high growth rates, even at a source temperature of 40 °C. The conditions
of the experiments are summarized in table 15.
Table 15. Parameters and results of the depositions using S5 as precursor. Film thickness is determined via
SEM-measurements or weight gain of the films (in combination with the density of fcc-TaN (13.7 g/cm3)).
Exp-Nr Tevap Tsubstr. Growth tdep. Film Film Calc. resistivity XRD
rate thickness thickness density (weight)
(weight) (weight) (SEM) (SEM)
in °C in °C in in min in µm in µm in in μΩ·cm phase
nm/min g/cm3
S5-1 30 600 6.4 60 0.39 0.38 13.9 5.0·105 -
5
S5-2 35 600 10.0 60 0.60 0.68 12.2 1.1·10 fcc TaN
3
S5-3 40 600 25.1 60 1.51 1.55 13.3 4.2·10 fcc TaN
4
S5-4 45 600 27.5 30 0.81 0.80 14.0 2.1·10 fcc TaN
S5-5 40 700 9.0 60 0.54 0.73 10.1 3.1·103 fcc TaN
The deposited films were shiny, metal-like with a slightly brown/golden color. In the case of
S5-1 and S5-2, no grains could be observed on the surface (completely uniform) while S5-3,
S5-4 and S5-5 showed small grains on the surface (see SEM-discussions).
Two ways were used to determine the growth rate under various conditions. The film
thickness can be directly quantified by SEM-cross section measurements or indirectly by
using the weight gain and the surface area of the samples. On the one hand, the advantage of
determining the film thickness by its weight gain is that the average thickness over the whole
substrate is measured. SEM-measurements show only one section of the whole film.
Therefore the validity is not given for the whole sample. On the other hand, the density of the
films is required to calculate the film thickness, based on the weight gain of the substrate
(ρ(fcc-TaN) = 13.7 g/cm3). Both sets of values for the film thickness were determined and
show good correspondence (table 15). Thus it can be assumed that the density of the films is
somewhat close to the film thickness of bulk fcc-TaN and that the films are very compact in
100
terms of the absence of cavities which can serve as diffusion pathways for oxygen. This is in
contrast to the films, obtained by M. Kodoshima et al,[51] having densities of about 7.4 g/cm3
(TAIMATA, 450°C). A higher compactness of the film is desired, because only compact
films effectively act as diffusion barriers for copper. Generally the growth rate of the film
deposition was very high, ranging from 6 to 28 nm/min For achieving lower deposition rates,
it would be advisable to increase the pressure and lower the flow rate in order to reduce the
precursor transport rate. However, this could lead to a less uniform growth (higher variation
of thickness over the substrate).
XRD-analysis
XRD-analyses of the films clearly showed the formation of cubic TaN. Only in the case of
S5-1 reflections for TaN were not observed (figure 63). The theoretical positions for the TaC
and TaN reflections are marked. It can be almost excluded that tantalum carbide was formed.
It seemed that the lattice constant of the cubic structure of the films, 2.46-2.48 Å based on the
(111)-peak, was slightly smaller than the lattice constant for cubic TaN (2.503 Å for the
TaN(111)-peak). Maybe the films were slightly tantalum rich which reduced the distances of
the lattices. As it would be expected, the film, deposited at 700 °C was more crystalline than
the other films. More exact conclusions can only be drawn when information about the
composition of the films are available.
Figure 63. XRD-spectra of films deposited by means of MOCVD using S5 at different evaporation temperatures
and a substrate temperature of 600 °C.
101
SEM characterization
SEM-analysis of the films revealed the nanocrystalline structure of these thin films. Cross
sectional SEM pictures (figure 64 a) show the growth of TaN in form of linear crystallites,
perpendicular to the silicon surface. These crystallites had diameters in the range of 50-90 nm.
This growth behavior was observed in all experiments using S5 as a precursor. On top of the
surface, the heads of these linear columns can be seen (figure 64 b).
Figure 64. a) Cross sectional and b) top view on a section of the sample S5-2. The columnar growth of the
crystallites can clearly be seen.
102
The nature of the grains, observed on the samples is displayed in SEM-pictures (figure 65 a,
b, d). These grains were particles that were formed on the reactor walls during deposition.
The particles fell on the surface and were incorporated into the films as it can be seen.
Therefore, they showed the same morphology as the surrounding films. As a consequence of
the growth on the particle nucleus, the inner diameter of the discrete particle increased during
growth (relative to its growth axis, figure 65 c). Nevertheless, large areas existed in which no
particles contaminate the surface.
Figure 65. SEM-recordings of the particles on the samples S5-2 and S5-3. Pictures a, b and d show the top of a
particle from above, while c shows a partially dissected particle. One can clearly see the cone-shaped form of the
particle (the arrows indicate the growth directions).
The minimum resistivity of a film was found at an evaporation temperature of 40 °C. The
variation of the substrate temperature from 600 to 700 °C seemed to have only a small impact
on the resistivity. At lower evaporation temperatures the resistivity increased drastically,
although peaks for cubic TaN could be observed in XRD spectra of S5-1. However, in the
literature the effect of precursor transport rate (and thus the growth rate) has not been
discussed so far. One explanation can be that at lower evaporation temperatures no stable (i.e.
103
constant) growth behavior was established. Thus, certain mass transport would be required
(e. g. at 40 °C) to get reproducible and meaningful results for the growth rate (10-25 nm/min)
and the films’ properties. This is in discrepancy to the results presented at a later stage for
other precursors (e.g. guanidinato-containing precursors, chapter 6.3) where reliable results
were obtained at much lower growth rates of approximately 1-4 nm/min. Investigating these
effects more extensively would be interesting in terms of optimizing the growth behavior of a
certain precursor.
Based on these results, the precursor was sent to our cooperation partner in Erlangen and will
be tested for its potential in the formation of TaN gate electrodes. The experiments are
currently under investigation and will only be discussed in brevity (6.2.3.).
6.2.2 Depositions with [Ta(NEt2)3(N-t-Bu)] (S6) in the Aixtron 200 RF reactor
The MOCVD depositions using TBTDET (S6) in the 200 RF reactor were the first successful
set of experiments, carried out in this reactor, modified for low volatile OM-precursors. In the
beginning, the main problem that had to be overcome was the condensation of precursor at
cold spots within the line system between the bubbler and the reactor. Two additional lines,
that are not included in figure 60, were connected to the precursor transport line and were not
used during deposition. Condensation within these parts occurred, though the parts, close to
transport line were heated. It seems that the gaseous precursor diffused widely into these
lines, condensed at the colder spots and assembled in the line system as liquid. The area of
assembling was between the valve that is opened to start a deposition processes and the
reactor. Thus, as soon as vacuum was applied to the reactor and the substrate was heated,
deposition took place. In order to overcome this problem in the following experiments, all
lines were constantly flushed with hydrogen and heated to temperatures above the evaporation
temperature before and during the deposition experiment.
104
The depth profile of the atomic composition of such a film (deposition caused by condensed
precursor in the lines) is shown in figure 66.
Figure 66. SNMS spectrum of a deposition in the Aixtron 200 RF reactor using S6 and NH3 as precursor and
reactive gas, respectively (Tsubstr = 600 °C). The film consists of app. 70-80 nm, deposited during the experiment
time and appr. 160 nm deposited during the warm up phase in which condensed precursor in the lines caused the
growth.
It is very interesting to see that the layer that was deposited before the experiment started
(without ammonia) showed heavy contaminations of carbon, while the addition of ammonia
directly led to a significant decrease of the carbon content in the film.
Experimental parameters
The influence of two variables was investigated in these experiments. First, the deposition
temperature (range 550-800 °C) and second the quantity of ammonia that was added to the
reactor (NH3-flow 0-400 sccm). The parameters are summarized in table 16. The evaporation
temperature of the precursor was set to a relative high temperature (91 °C) to guarantee
sufficient transport of precursor into the reactor. After several runs, the precursor slowly
started to change its color from yellow to orange/red. No precipitation was observed in the
glass bubbler; therefore it can be assumed that only little decomposition occurred. After the
deposition was complete, the samples remained for 2 minutes in the ammonia/hydrogen
atmosphere at the selected substrate temperature. The reactor pressure was set to the
105
minimum value of 1 mbar. At this pressure, complete control over fluctuations or the precise
setting of the pressure cannot be guaranteed.
Appearance, growth behavior and crystallinity of the films (SEM, XRD)

All films were of mirror like, golden appearance and completely uniform. No particles or
grains on the surface could be observed by SEM. Therefore, it can be expected that no
significant pre-reactions took place in the gas phase during the mixture of NH3 and the
precursor. The most challenging, and only partially satisfying analysis was the exact
determination of the film thickness which was typically much below 100 nm. Three different
approaches were made: 1) determination by weight gain (presumed density of TaN = 13.7
g/cm3), 2) by cross section recordings via SEM and 3) by SNMS-measurements. Not all
samples were measured by all analytical techniques, thus no complete set of data can be given
(table 17). It can be clearly seen that the film thicknesses calculated on the bases of the weight
gain of the samples are too low. SEM-pictures of 60-80 nm thick films were very difficult to
be analyzed properly. For comparison one thicker sample was prepared at average substrate
temperature and medium flow of ammonia (S6-3’’; 30 min deposition time; table 16 and 17,
last line). Most probably, the density of the films was not 13.7 g/cm3, but around 11.0 g/cm3
(SEM-thickness versus weight gain). Qualitatively it can be stated that with higher
temperatures and higher ammonia flow rate, lower growth rates (film thicknesses) can be
observed.
106
Table 16. Parameters of the depositions using S6 as precursor in the Aixtron 200 RF reactor. Repeated
experiments are marked with an apostrophe. The experiments S6-3 and S6-3’ are listed twice due to their
relevance for both experimental rows (bold entries, substrate temperature (first row) and NH3-flow (second row)).
Exp-Nr T p Flow Flow Flow Ratio T p Depos.
(prec) (prec) H2 H2 NH3 NH3/H2 (substr) (reactor) time
(prec) (sum)
in °C in mbar in sccm in in sccm in °C in mbar in min
sccm
S6-1 91 50 21 600 200 0.33 550 1 5
S6-2 91 50 60 600 200 0.33 600 1 5
S6-2’ 91 50 21 600 200 0.33 600 1 5
S6-3 91 50 21 600 200 0.33 650 1 5
S6-3’ 91 60 60 600 200 0.33 650 1 5
S6-4 91 60 60 600 200 0.33 700 1 5
S6-5 91 60 60 600 200 0.33 800 1 5
S6-5’ 91 60 60 600 200 0.33 800 1 5
S6-7 91 60 60 600 0 0 650 1 5
S6-8 91 60 60 600 50 0.08 650 1 5
S6-9 91 60 60 600 100 0.17 650 1 5
S6-3 91 60 60 600 200 0.33 650 1 5
S6-3’ 91 60 60 600 200 0.33 650 1 5
S6-10 91 60 60 600 400 0.67 650 1 5
S6-3’’ 91 60 60 600 200 0.33 650 1 30
Table 17. Results of the depositions using S6 as precursor in the Aixtron 200 RF reactor. The results for the
thicknesses are afflicted with large errors of appr. ± 10 nm. Therefore thicknesses were defined, based on the
trend that was concluded from the less precise results of weight gain-, SEM- and SNMS measurements.
Exp-Nr Flow T Film Film Film Defined Resistivity Resistivity XRD
NH3 (substr) thickn. thickn. thickn. thickn. (defined
(weight) (SEM) (SNMS) thickn.)
in in °C in nm in nm in Ω/cm2 in μΩ·cm phase
sccm
S6-1 200 550 -- 80 -- 70 541 3.7·103 fcc TaN
S6-2 200 600 -- -- -- 70 -- -- fcc TaN
S6-2’ 200 600 -- 78 -- 70 358 2.5·103 fcc TaN
3
S6-3 200 650 -- 59 -- 60 417 2.5·10 fcc TaN
S6-3’ 200 650 44.1 -- -- 60 -- -- fcc TaN
3
S6-4 200 700 -- 61 -- 60 374 2.2·10 fcc TaN
3
S6-5 200 800 -- 65 45 60 597 3.5·10 fcc TaN
S6-5’ 200 800 32.5 -- -- 50 -- -- fcc TaN
3
S6-7 0 650 54.4 -- 82 70 695 4.8·10 fcc TaN
3
S6-8 50 650 58.4 -- 73 70 438 3.0·10 fcc TaN
3
S6-9 100 650 56.8 -- -- 60 347 2.1·10 fcc TaN
3
S6-3 200 650 -- 59 -- 60 417 2.5·10 fcc TaN
S6-3’ 200 650 44.1 -- -- 60 -- -- fcc TaN
3
S6-10 400 650 49.5 -- 55 60 392 2.3·10 fcc TaN
3
S6-3’’ 200 650 285 354 369.5 354 130 4.6·10 fcc TaN
107
Higher substrate / susceptor temperatures could lead to decomposition of precursor in the area
in front of the sample (on the susceptor). Consequently, depletion of the precursor in the gas
phase above the substrate occurred and the growth rate was lowered. In all experiments the
growth rate was in the range of 12 ± 4 nm/min. For calculation of the resistivity of the films,
values for film thickness were defined, meeting the concerns of the above mentioned trends in
thicknesses. These thicknesses were roughly estimated, based on the conversion factors for
the analytical methods resulting from the data of the deposition S6-3’’ (full analysis of this
film by all methods). The trend for the growth rates, deduced from these estimations is
contrary to the results reported for depositions using a similar amido/imido precursor
(TAIMATA).[51] Here, the growth rate slightly decreased with higher flow rates of ammonia.
The SEM pictures also reveal the nano-crystalline texture of the thin films (figure 67).
According to the growth using S5 (chapter 6.2.1), compact, but linearly grown crystals can be
identified.
Figure 67. SEM – picture of a) a cross section and b) an on-top view of sample S6-3’’. The other, thinner samples
show no good resolution.
XRD-patterns of the films testified the successful formation of cubic tantalum nitride thin
films. Theoretically it could be possible that cubic tantalum carbide is the reason for the
appearance of the peaks, but the films were almost carbon free (see SNMS-analysis). Figures
68 and 69 show the dependence of the crystallinity of the films on the temperature and the
ammonia flow rate. The peak positions for the (111) and the (200) planes differ from the
theoretical values for cubic TaN, according to the experiments using S5 in the selfbuilt
reactor.
108
Figure 68. XRD spectra of films deposited at various temperatures using S6 ([Ta(NEt2)3(N-t-Bu)]) in the Aixtron
200 RF reactor. The peaks are slightly broadened at lower substrate temperatures and the peak positions deviate
from the peaks expected for bulk TaN.
Figure 69. XRD spectra of films deposited at various NH3-flow rates (Tsubstrate = 650 °C; Precursor: S6; Aixtron
200 RF reactor). Crystallinity of the films does not differ significantly at different amounts of ammonia that are
added during deposition.
109
At lower temperatures (550, 600°C) or without additional ammonia the XRD-peaks broaden
which indicates lower degree of crystallinity.
Composition of the films (SNMS)

SNMS-analysis is a powerful tool for analyzing the composition of thin films. The only
disadvantage is, that the effects of preferential sputtering lead to a blurring of interfaces
(lighter elements are more easily removed than heavier elements, figure 70 a). At the
beginning nitrogen is preferentially sputtered over tantalum. Approximately a “buffer” of 10
to 15 nm thickness is needed before the equilibrium is adjusted.
The composition of thin films clearly reflected the effect of ammonia as a reactive component
in the process of deposition. As soon as small amounts of ammonia (50 sccm NH3 vs. 600
sccm of H2) were added during deposition, the carbon content decreased drastically. Most
likely transamination reactions occured (either in the gas phase or on the substrate), which
caused the liberation of diethylamine (cleavage of carbon containing ligands at the metal
center). This type of reaction was already investigated by Musher et al.[178] for the formation
of TiN from [Ti(NMe2)4] and ammonia. Higher amounts of ammonia caused only small
further changes in the composition. Carbon concentration decreased slightly, while the N : Ta
- ratio changed from 1.13 (50 sccm NH3) to 1.31 (400 sccm NH3) with higher ammonia
concentrations. Stochiometric TaN-films with a N : Ta - ratio of 1.00 would be desired the
most. Nitrogen rich films tended to be less conducting (insulating Ta3N5 has a N : Ta - ratio of
1.67). However, resistivity measurements (table 16) gave no indications for this relation
between the N : Ta - ratio and the resistivity. Changing the temperature from 650 to 800 °C at
constant ammonia flow rate (200 sccm) only led to minor changes in the composition of the
films. The tantalum concentration decreased slightly (43.4 at. % (650 °C); 41.0 at. % (800
°C)) while the nitrogen concentration increased (51.7 at. % (650 °C); 53.1 at. % (800 °C)).
Generally, the low oxygen content is surprising, especially in the case of depositions carried
out without additional ammonia (4 %). The oxygen level never exceeded 2 % in experiments
when ammonia was used (figure 70b). In literature oxygen content was normally above 5-
10 %. Perhaps the additional use of hydrogen caused a high compactness of the films (density
above 11 g/cm3) which protected the film from post oxidation. In addition, this reactor was
designed for industrial application and even small leakages that lead to oxygen contamination
can be fully excluded.
110
Figure 70. a) SNMS-spectrum of sample S6-8 (50 sccm NH3, Tsubstr = 650 °C) and b) the change in film
composition as a function of the ammonia flow rate.
Electrical properties (Four point probe)

In table 17 the resistivities of the films are listed. For calculation of these values, thicknesses
were defined. These thicknesses are afflicted with large errors. Thus, it can only be stated that
the resistivities of all films were between 1.5 and 5 x 103 Ω · cm. These values are acceptable
in comparison to experiments of other groups (table 18), but can probably be optimized by:
Alteration of the ammonia flow rate and the growth rate
111
Direct processing of the fresh samples (the resistivities of the samples were measured
(in Erlangen) three weeks after their formation).
Rapid thermal annealing (RTA) at higher temperatures (e.g. 900 °C) in an argon or
nitrogen atmosphere, or in vacuum.
Table 18. Results for the depositions of other groups using TBTDET (S6, [Ta(NEt2)3(N-t-Bu)]), TAIMATA
([Ta(NEt2)3(NCMe2Et]) or [Ta(N(Me)(t-Bu))3(N-t-Bu)].
Precursor Formula T Reactive Resistivity Reference
(substr) gases
in °C in μΩ·cm
TBTDET [Ta(NEt2)3(N-t-Bu] 650 -- 0.9·103 [1]
3
TAIMATA [Ta(NEt2)3(NCMe2Et] 450 -- 4.0·10 [51]
4
TAIMATA [Ta(NEt2)3(NCMe2Et] 450 NH3 5.0·10 [51]
4
TAIMATA [Ta(NEt2)3(NCMe2Et] 500 1.0·10 [48]
3
-- [Ta(N(Me)(t-Bu))3(N-t-Bu)] 60 1.7·10 [64]
At this stage of experiments, it can be concluded that the addition of ammonia during
depositions in the Aixtron 200 FE reactor using S6 ([Ta(NEt2)3(N-t-Bu)]) helps to improve
the film’s quality regarding the composition and the conductivity. Thereby, the amount of
added ammonia only affects the growth rate, but no other characteristics.
6.2.3 Depositions with [Ta(NEt2)3(N-t-Bu)] (S6) in the 150 mm wafer reactor
The experiments were performed by our cooperation partner in Erlangen (Martin Lemberger)
using TBTDET that was synthesized in our research group (Bochum). The temperature range
was 400 to 600 °C at pressures between 0.5 and 4 mbar, with and without adding NH3. The
temperature of the precursor was regulated to 80 °C.
The trends that could be identified are the following:
At a deposition temperature of 500 °C and the lowest reactor pressure (0.5 mbar)
and no additional ammonia optimum values for resistivity were obtained (growth rate
appr. 0.4 nm/min). The resistivity of these films was extremely low with 230 μΩ·cm.
Increasing or lowering the substrate temperature (400 or 600 °C) led to higher
deposition rates, but also significant higher resistivities of the films (>12,000 μΩ·cm).
Also an increase of the pressure yielded lower growth rates and higher resistivities.
Reactor pressures above 4 mbar caused volume reactions (particle formation).
112
Addition of ammonia consequently lowered the uniformity of the films. The more
ammonia was added, less uniform films were obtained with higher resistivities (14
sccm NH3 (500 °C, 1 mbar): 2000 μΩ·cm; 200 sccm NH3 (500 °C, 1mbar): >2·106
μΩ·cm). This behavior completely contradicts the results obtained with the same
precursor using the Aixtron 200 FE reactor. The reasons for these results cannot be
explained to a satisfying extent. However, two assumptions can be made as
explanations for this phenomenon. Either the differences in terms of reactor
geometries between both reactors (e.g. pre-reactions during mixture of ammonia and
the precursor) or the presence of oxygen in the reactor (Erlangen) due to leakages lead
to these totally different results. Surely, the results collected at the Aixtron 200 FE
reactor can be considered as the more reliable results (optimal reactor design and
exlusion of leakages).
The films were completely amorphous, based on SEM and TEM measurements.
Films deposited at 450 °C were in general homogeneous and carbon free (< 0.5
atomic %), but noteworthy amounts of oxygen (ca. 15 %) were detected. The sources
of oxygen incorporation were most likely leakages in the reactor and/or post oxidation
of the films.
Post deposition RTA (rapid thermal annealing) was performed at various conditions
(e.g. in nitrogen- or ammonia atmosphere) in order to lower the oxygen content of the
films and to investigate the impact on the electrical properties of the films. Only
annealing in ammonia atmosphere significantly lowered the oxygen content of the
films. However, it seemed that insulating, nitrogen rich Ta3N5 was formed, which
furthermore increased the resistivity of the films instead of lowering it.
6.2.4 Depositions with [Ta(NMeEt)3(N-t-Bu)] (S5) in the 150 mm wafer reactor
Experiments similar to those using TBTDET (6.2.3) were also performed by our cooperation
partner in Erlangen. Compound S5 was tested in the temperature range of 400 to 650 °C at
pressures between 0.15 and 0.5 mbar. Pressures above 0.5 mbar led to volume reactions
(particle formation). All experiments were carried out without adding NH3. The temperature
of the precursor was again regulated to 80 °C. The trends that could be identified in this series
of experiments are the following:
At the maximum deposition temperature of 650 °C and low reactor pressures (0.15
- 0.25 mbar) optimum values for resistivity were obtained (growth rate: approximately
0.1 nm/min). The resistivity of these films was still low (~1300 μΩ·cm), but higher
113
than in the case of experiments using S6 as precursor (~ 230 μΩ·cm). The observed
trend (higher temperatures = lower resistivity) agrees with the theory and other
experimental findings. This is contrary to the previous experiments (S6, 6.2.3) in
which the optimum of resistivity was reached at 500 °C and increased again at 600 °C.
Films deposited at 400 °C were in general homogeneous and - as in the case of S6 -
carbon free (< 0.5 atomic %). However, high amounts of oxygen (ca. 20-30 %) were
detected in all films (even at temperatures of 650 °C). The sources of oxygen
incorporation were most likely leakages in the reactor and/or post oxidation of the
films.
6.2.5 Conclusions for the use of mixed amido / imido tantalum precursors
Although some differences in the results in terms of composition and resistivities of the films
can be observed, some assumptive conclusions can be drawn. Generally, using ammonia as an
additional reactant lowers the carbon content in the films significantly (< 4 %). Without an
additional flow of ammonia, the results did not match the expectations. Surprisingly, it was
found that at higher temperatures (≥ 600 °C, no ammonia) significant amounts of carbon
(>15-20 at. %) were incorporated into the films, while at low temperatures (≤ 450 °C, no
ammonia) almost carbon-free films were obtained (6.2.3 & 6.2.4 (at high and low
temperatures), 6.2.2 (only high temperatures)). A survey of the literature gives ambiguous
results for this occurrence. Using TAIMATA [Ta(NMe2)3(NCMe2Et)] as a precursor (without
ammonia) at reactor temperatures of 300 °C and 500 °C led to similar results (Carbon content:
300°C: < 2 %; 500 °C ~ 15 %).[48] On the other hand, M. Kadoshima et al. reported the
formation of heavily carbon contaminated films (20-30%) using the same precursor
(TAIMATA) at low temperatures in the range of 300 °C to 450 °C.[51] Results, reported by
M. H. Tsai et al. (TBTDET, Tsubstrate = 450 to 650 °C) comprised the incorporation of carbon
(~10%) independently of the substrate temperature.[1] In order to clarify this issue, further
depositions at lower deposition temperatures (350-550 °C) in the Aixtron reactor should be
performed using TBTDET as a single source precursor.
To prevent films from oxidizing in the process of formation (caused by leakages in the
reactor) is critical for the quality of the films (e.g. nanocrystallinity). This source (i.e.
leakages) of oxygen is the most probable explanation for the difference in the results applying
TBTDET (S6) as precursor. Films, obtained in Erlangen had in average seven times higher
contents of oxygen than the films produced by the Aixtron 200 FE reactor. Nevertheless, the
114
influence of oxygen contamination on the electrical properties of the film is not clear. Films,
deposited in Erlangen did show lower resistivities than the films, deposited with the Aixtron
200 RF reactor regardless of their oxygen content. Other effects, e.g. grain boundaries within
the films etc. may have stronger impact on the final resistivity. In addition, the resistivities of
the films, deposited in Erlangen were directly measured after deposition. Thus, post oxidation
of the uppermost layer of the films may not have occurred. Substrates, prepared with the
Aixtron reactor were exposed to air for at least one week prior to analysis.
An important finding is that the reactor design has a strong influence on the results of
deposition. The results, produced with the Aixtron 200 RF reactor are the best in terms of
reliability, reproducibility and the exclusion of air-contact during deposition.
6.3 Deposition experiments with mixed amido / imido / hydrazido tantalum

precursors
In this chapter, first experiments of the newly synthesized compound A2

([Ta(NMeEt)2(tdmh)(N-t-Bu)]) are discussed. This precursor was tested in the selfbuilt
horizontal cold-wall reactor in Bochum as well as in Erlangen using the 150 mm - wafer
instrument.
6.3.1 Depositions in the selfbuilt horizontal cold wall reactor
The depositions were carried out in the selfbuilt horizontal MOCVD reactor, mainly at a
substrate temperature of 600 °C. The bubbler temperature was kept constant at 140 °C at
reduced pressure (0.5-100 mbar). Precursor A3 ([Ta(NEt2)2(tdmh)(N-t-Bu)]) was synthesized
first (followed by A1 and A2) and was used in these experiments although A1 and A2 turned
out to be more volatile. High evaporation temperatures were required to enable sufficient
precursor-transport at higher pressures. In addition to the inert carrier gas nitrogen (200
sccm), ammonia was used as reactive gas in some of the depositions.
6.3.1.1 Characterization of the films
The films fabricated by MOCVD of A3 were shiny and particle free, but had no golden-
metallic color (cubic TaN). Moreover, the films had violet to blue colors. This already
indicated the formation of an insulating material. The growth rate as a function of pressure
dependence was investigated, after common reactor pressures of about 1 mbar produced very
low growth rates. At these low pressures, the contact time of the precursor and the substrate
115
was presumably relatively short. This resulted in little decomposition of the precursor based
on the high thermal stability of A3. Higher reactor/evaporation pressures led to higher growth
rates with a maximum of 1.5 nm/min (35 mbar, figure 71).
Figure 71. Growth rate vs. reactor pressure in experiments using A3 at substrate temperature of 600 °C. The
growth rate was determined by the weight gain of the samples and a density, considered to be 13.7 g/cm3.
Morphology and crystallinity

All films deposited without additional ammonia were completely amorphous, showing no
peaks in XRD spectra. SEM - analyses underlined these results. Best uniformity and lowest
roughness of the films (rms (root mean square) = 1.6 nm) were obtained at 700 °C with
additional ammonia (figure 72). Only very small, non columnar crystallites could be
observed.
116
Figure 72. a) Surface AFM (rms = 1.6 nm) and b) SEM-cross section of a film, deposited at 700 °C using A3 and
additional ammonia.
Composition of the films

Films, deposited without additional ammonia exhibited significant amounts of carbon
contamination (~ 25-30 %) as shown by RBS-measurements as well as a high level of oxygen
impurities (~20-25 %) (figure 73). While the source of carbon was clearly the precursor, the
source of oxygen could be either leaks in the reactor or post-oxidation processes. All films
deposited without ammonia showed an oxygen contamination, while films deposited with
ammonia showed no oxygen impurities. Thus, it can be assumed that leakages during
deposition did not occur. More likely, the films containing carbon were less stable and
compact, thus being more susceptible to post deposition oxidation upon handling and storage
of the films.
Figure 73. RBS-measurements of samples, deposited without (a, 600 °C) and with (b, 700 °C) additional
ammonia.
117
Feeding of ammonia also reduced the amount of incorporated carbon below the detection
limit of RBS. Interestingly, independent of the presence of ammonia, Si was detected in the
films by RBS measurements. The films were nitrogen rich, which indicates the presence of
amorphous Ta3N5 and Si3N4. Based on the energy of the collected, back-scatterd helium ions,
it could be differentiated between the silicon in the film and the silicon from the substrate
(figure 73).
The amount of incorporated silicon was relatively high (~ 10 - 15 %) and was not expected,
especially if one considers the small amount of incorporated carbon (in the case of ammonia
as reactive gas). Somehow, a decomposition mechanism has to take place during deposition in
which the methyl groups of the trimethylsilyl moiety are chemically split off under the impact
of ammonia. Most likely in experiments without ammonia, the carbon in the films does not
come from the trimethylsilyl group, but from the dimethylamido-groups and the tert-butyl-
imido group, similar to the results for depositions using S5 and S6 as precursors. Other silicon
containing compounds do not show any incorporation of silicon. One example is the 3,5-
lutidine stabilized compound [TaCl3(NSiMe3)(NC5H3Me2-3,5)2], tested by J. E. Bleau et al.
that contains a trimethylsilyl-imido group.[107] It can be ruled out that Si diffused from the
Si(100) substrate through pin-hole defects (not seen by SEM) into the deposited films. To
investigate this issue, samples were prepared in this work using sapphire as substrate material.
Based on EDX-analysis, significant amounts of silicon were clearly identified in the films.
All films from this experimental row showed higher resistivities than those of pure silicon
substrates. The high levels of oxygen in the films and/or the formation of nitrogen rich TaNx-
films may be the reason for these results.
6.3.2 Depositions with [Ta(NMeEt)2(tdmh)(N-t-Bu)] (A2) in the 150 mm wafer reactor
Before the precursor A2 was tested in the large wafer reactor (Erlangen) one preliminary
experiment using compound A2 was carried out in the selfbuilt reactor (Bochum) in which
also A3 was tested. Due to the higher volatility of the precursor A2 compared to A3, an
evaporation temperature of 80 °C was sufficient to obtain a thin, golden film. In the
following, this precursor was synthesized in larger amounts (40 g) and tested in the 150 mm –
wafer reactor in Erlangen. The carrier gas (nitrogen, 200 sccm) was passed over the precursor
and an additional flow (nitrogen, 10 sccm) was directly bubbled through the liquid precursor,
which was heated to 85 °C. The substrates were 150 mm (100) p-type Si wafers with a
118
thermal SiO2 oxide film (thickness 20 nm). The depositions were performed at substrate
temperatures of 500 to 700 °C at a pressure of 0.5 to 2 mbar with additional ammonia (70
sccm) as reactive gas. Some of the samples received a rapid thermal annealing at 1050 °C for
30 s in different atmospheres (argon, nitrogen, ammonia).
Results
All films deposited using compound A2 in this reactor were non crystalline films. SEM
measurements revealed smooth films without a significant morphology. The XPS analysis of
films deposited from compound A2 in the large scale reactor (Erlangen, 150 mm wafer
instrument) again revealed a carbon content below the detection limit of XPS (except the very
surface, but this carbon level of ca. 20 % is caused by atmospheric influence). However, the
films were heavily contaminated with oxygen. The film composition was determined to
Ta0.13Si0.16N0.07O0.64 at the surface and to Ta0.20Si0.11N0.19O0.50 within the bulk, respectively.
XPS analyses revealed an extremely high O content, which was even higher at the surface.
The origin of the O content may be due to both, continuous incorporation during film growth
as a result of leakage in the reactor and post-deposition oxidation as the films showed an
amorphous structure, which is in general more susceptible to oxygen diffusion than dense
films. This result contrasts with our previous experience in depositions using A3 in the
selfbuilt reactor in Bochum (6.3.2). In that case, the films exhibited oxygen levels below the
detection limit of Rutherford-Backscattering analysis. It can be concluded that minor leaks in
the larger reactor set-up were responsible for the high oxygen contamination in this
experimental series. Not surprisingly, the films deposited from precursor A2 were insulating.
The sheet resistance of a 100 nm thick as-deposited film could not be measured using either
the automatic four-point probe equipment or external testing. This pointed to a resistivity even
higher than 10 kΩ·cm (i.e., films behave like dielectrics), which was expected from the O-rich
composition. Annealing the films at 1050 °C for 30 s reduced the resistivities significantly to
values of 26.3 (nitrogen), 17.0 (argon), and 0.4 Ω·cm (ammonia atmosphere) which are in the
order of bulk silicon substrates.
6.3.3 Conclusions for the use of mixed amido / imido / hydrazido tantalum
precursors
The tdmh-containing compounds A1-A3 are generally usable as precursors for MOCVD
purposes. However, ammonia is definitely required in order to avoid impurities of carbon and
oxygen. Experiments in a large scale reactor using the liquid precursor A3 at least showed
119
that - in principle - this type of precursor is suitable for covering large wafers in terms of
precursor transport and reactor geometry. Nonetheless, it could not be managed to avoid
undesired heavy oxygen contamination in the large wafer reactor set-up in Erlangen. The
intrinsic incorporation of Si into the layers is interesting as such and points to a special ligand
fragmentation of the hydrazido moiety of A2 and A3, which warrants further studies. But on
the other hand, this property most probably rules out the deposition of phase pure crystalline
cubic TaN using this class of precursors. Nevertheless, TaSixNy thin films are supposed to act
as a more effective diffusion barrier than pure TaN due to the inhibition of the crystallization
of TaN at higher temperatures by the incorporated silicon. Furthermore it can be assumed that
certain variation of process parameters e.g. substrate temperature, lower ammonia-flow rates
or mass transport of the precursor into the reactor can influence the nitrogen as well as the
silicon content in the films. It could be possible to obtain nitrogen-poor, carbon-free films,
having low resistivities by an optimum addition of ammonia.
Another idea would be to transfer this ligand concept to niobium, because no insulation NbN-
phases are known. This could enable the formation of conducting NbSixNy thin films using
the niobium congeners of A1-A3.
120
6.4 Deposition experiments with mixed amido / imido / guanidinato tantalum

precursors
The guanidinato ligand containing compound B2 was tested first in the self-built reactor in
Bochum (6.4.1).
The fact that this precursor is solid and requires high evaporation temperatures makes testing
in the industrial Aixtron 200 RF reactor rather difficult due to the limitations given by the
precursor feeding setup. Nevertheless, several precursor reservoirs were fabricated and tested.
These reservoirs were constructed in such a fashion that the gas flow was led downwards
through a round glass filter on which the precursor was placed. The diameter of the filter had
to be increased to 40 mm in order to avoid overpressure above the precursor. Unfortunately,
even at the highest possible evaporation temperatures and the lowest pressure, none of these
reservoirs enabled sufficient transport of precursor into the reactor. Consequently the Liquid-
Injection technique was tested as an alternative process to classical evaporation of the
precursor. Therefore, another reactor (Aixtron 200 FE) had to be used, which was routinely
employed for the deposition of oxide thin films and was available for these experiments (see
6.4.2).
6.4.1 Depositions with B2 in the selfbuilt horizontal reactor
In the MOCVD experiments of B2, the same reactor and the same substrate type as for
compound S5 were used. The precursor was transported into the reactor using nitrogen carrier
gas, without additional reactive gases, in particular no ammonia. However, the vaporizer had
to be heated up to 120 °C in order to guarantee sufficient transport of B2 into the reactor. The
pressure in the reactor was kept at 1 mbar and the nitrogen carrier gas flow was set to 50
sccm. The substrate temperature was varied between 500 and 800 °C in order to investigate
the films’ properties as a function of the growth temperature at constant mass flow.

All films deposited with compound B2 as precursor were completely uniform showing no
particle formation (figure 75 a, page 124). The films were slightly brown-golden and had a
mirror-like appearance. In case significant amounts of oxygen leak into the reactor it would
lead to the formation of dielectric Ta2O5-films, resulting in blue/colorful appearance of the
films. The growth rate in all experiments with compound B2 was between 1.5 and 4 nm/min
which is much lower than in experiments using compound S5 in this reactor. No clear
121
dependence of the growth rate in respect to the substrate temperature could be identified. This
is due to the fact that the precursor was solid even at 120 °C, which did not ensure a constant
mass transport into the reactor - at least using our simple setup. The growth rate was thus
limited by delivery, and the reproducibility of the growth rate at certain temperatures was not
given. The density (12.8 ± 1.3 g/cm3) of the films, obtained using B2, was slightly lower than
the density of bulk TaN-material and the films grown using S5, as discussed above.
Figure 74. XRD spectra of depositions using B2. Very high crystallinity is observed at 800 °C. Below 650 °C no
peaks can be observed.
All XRD spectra of the deposited films using B2 showed the two specific reflexes for cubic
TaN (111, 200) (figure 74). Interestingly, the ratios of the (111) and the (200) reflexes did not
show the ratio expected for pure cubic TaN. Pure cubic TaN exhibits a ratio of the (111) :
(200) peaks of 1 : 0.8. In this case, the (200) peak was dominant, being at least five times
more intense than the (111) peak. Thus, a preferred orientation towards the (200) plane was
observed. As expected, the typical crystalline domain sizes of the films increased with higher
substrate temperature. Between 750 and 800 °C well crystalline films were grown, indicated
by the drastic rise of the XRD peak intensities. At 600 and 650 °C, the films were very
smooth and showed almost no morphology in SEM cross sectional measurements.
Films deposited at higher temperatures showed a nanocrystalline morphology, with increasing

grain sizes as the substrate temperature was raised (figure 75 a, b). One representative sample
deposited at 750 °C using B2 was analyzed by SNMS analysis (figure 75 c). Most
surprisingly, the sample was almost carbon free (below 0.5 %), although the precursor was
122
used as a single source in the absence of ammonia. Due to the presence of amido as well as
imido groups one would expect the incorporation of carbon at least to a certain extent, in
accordance to the behavior of S5 and S6 at these temperatures (carbon content of the films
~15-20 %). If the decomposition reaction of the amido group that leads to the incorporation of
carbon passes over a η2-C-N-Ta transition state, this way could be blocked in the case of the
six-coordinated tantalum guanidinato-complex B2. However, this requires that the
carbodiimide is not eliminated (reverse reaction of the synthesis) before decomposition
occurs. In comparison, the tantalum center in the case of S5 and S6 is low-coordinated (four
fold coordination).
In addition to the low carbon content, the tantalum to nitrogen ratio was close to 1:1, with
atomic percentages of 46 ± 1 at. % for Ta and 47 ± 1 at. % for N. The data revealed a constant
oxygen contamination of 5 at. % throughout the bulk of the film that was likely to be caused
by a leakage. Leakages can occur at these high evaporation temperatures (120 °C).
Considering this oxygen level, the films were slightly nitrogen rich with respect to tantalum.
The higher nitrogen content close to the surface can be explained by a preferential sputtering
of nitrogen in the beginning of the analysis. Another source of oxygen in the films could also
be post-deposition oxidation by diffusion of oxygen along grain boundaries. The intermediate
20 nm thick SiO2 layer can be clearly observed in the spectrum. Compared to literature and
the previous experiments, described in this work, these are the best TaN films in terms of
composition.
123
Figure 75. Cross sectional SEM-analysis (a,b) and SNMS analysis (c) of a film deposited at 750 °C using B2 as
precursor. The high uniformity of the film is displayed in the SEM recordings.
Conductivity measurements showed that the films deposited from precursor B2 displayed fair
conductivity (resistivity: 7,000-15,000 µΩ·cm). We expected better values closer to the
properties of samples grown from e.g. S6 in the reactor in Erlangen. However, even the
samples grown at 750 to 800°C with high crystallinity were fairly poor in terms of
conductivity. So far there is no clear explanation for this behavior, since the film composition,
morphology and crystallinity appear to be almost excellent. It is possible that longer contact
to air (2-3 weeks) prior to the resistivity measurements caused an oxidation of the uppermost
layer of the films which drastically reduced the experimental value for resistivities.
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6.4.2 Depositions with B2 in the LI – MOCVD reactor Aixtron 200 FE
Encouraged by the positive results of the preliminary tests of B2 by means of MOCVD, the
precursor was prepared for LI-MOCVD. A colorless, clear solution of B2 in toluene (0.05
mmol/l, toluene is a standard solvent for LI-MOCVD) was attached to the LI-MOCVD-
reactor and 1000 (~8 µl per puls) pulses were injected onto the vaporizer (T = 200 °C).
Caused by the rapid evaporation of the solvent, the precursor was carried into the gas phase
and transported to the reactor. The substrate temperature (Si(100), 20 nm thermal SiO2) was
varied between 500 and 700 °C in 50 ° steps. Although “pulses” are mentioned, this process
has nothing to do with ALD, because the mode of operation bases completely on thermal
decomposition of the precursor.
During growth, high contamination (black solid) of the reactor walls in the heated area around
the substrate could be observed. Most probably, carbon deposited on the reactor walls due to
thermal decomposition of toluene. The films, obtained on the 1x1 cm2 substrates, were
slightly bluish/greenish and had a mirror-like appearance. However, the different colors of the
wafers indicated non-uniformity. XRD spectra as well as SEM-analysis showed that all films
were completely amorphous. No peaks for cubic tantalum nitride could be observed. Based on
SEM-analyses a growth rate of approximately 0.08 nm per pulse could be estimated. The only
possibility to get more information about the films is to analyze their chemical composition
e.g. by SNMS. SNMS analyses revealed similar composition of two samples, prepared at 600
and 700 °C, respectively (figure 76). As a consequence of the high contaminations on the
reactor walls we suspected to find significant traces of carbon in the films. Interestingly, these
concerns were not validated. The carbon content of the films was below 2 %.
125
Figure 76. SNMS analysis of a film, deposited using B2 as precursor in the Aixtron 200 FE reactor at 600 °C. It
can be assumed that a mixture of Ta3N5 and Ta2O5 was formed.
Even the high excess of toluene in the gasphase without additional reactive gases did not lead
to carbon contamination of the films. A comparison of the composition of the two analyzed
samples with the sample from experiments in the selfbuilt reactor (6.4.1) is given in table 19.
Table 19. Composition of the films, deposited using B2 as precursor in two different reactor setups.
Prec. Reactor type Tsubstr. Ta N C O Phase Comment
in °C in % in % in % in % (XRD)
B2 Self-built reactor 750 46 47 <0.5 5 fcc TaN Stochiometric TaN
B2 LI – Aixtron 200 FE 600 34 50 2 13 amorph. Ta3N5 + Ta2O5
B2 LI – Aixtron 200 FE 700 35 51 1 11 amorph. Ta3N5 + Ta2O5
The surprisingly low carbon content is the only property that the films, produced in the two
reactors have in common. While B2 created cubic, stochiometric TaN with low oxygen
content in the selfbuilt reactor, the films, deposited in the industrial LI-Aixtron reactor,
consisted of a mixture of insulating Ta3N5 and tantalum oxide (based on stochiometry). It is
very interesting that toluene seems to inhibit the formation of crystalline material and leads to
the formation of nitrogen rich TaN-films.
126
Several sources for the oxygen in the films can be assumed:

The nitrogen carrier gas could contain oxygen or rests of water (e.g. the purification
unit needs to be replaced).
Small leakages in the reactor led to oxygen incorporation.
The films were oxidized after deposition in air contact.
Without further investigations this issue cannot be clarified. So far, this reactor was only used
for the deposition of metal oxide films (with oxygen as reactive gas), thus no information
about the absence or presence of oxygen in the reactor can be given. One indication that the
oxidation already occurred in the reactor (point 1 and 2) is that the films were not uniform.
The problem of uniformity is known from the selfbuilt reactor when leakages appeared during
the experiment. Therefore not only the toluene, but also the presence of oxygen during
deposition could have led to the formation of nitrogen rich thin TaN-films. According to the
composition of the films, a mixture of insulating Ta3N5 and insulating Ta2O5, it was expected
and confirmed that the films exhibit very high resistivities (>1·106 Ω·cm).
6.4.3 Conclusions for the use of mixed amido / imido / guanidinato tantalum
precursors
The results of the experiments clearly show that an increase of the complexity of a precursor
(higher coordination number, higher atomic percentage of carbon, heterolepticety) for TaN-
depositions does not necessarily conflict with the thin film quality regarding carbon
incorporation and the formation of cubic, conductive tantalum nitride. Interestingly, ammonia
seems not to be a stringent requirement for the formation of conductive cubic TaN using B2
as precursor. The guanidinato ligand appears to be a good choice for further tuning the
precursor properties. Thus, guanidinato complexes may have quite a potential for the
MOCVD of metal nitrides, although sufficient mass transport by classical evaporation of the
precursor to the reactor remains a challenge. This problem can be overcome by Liquid
Injection MOCVD. However, the reactor should be designed for oxygen free depositions.
Although the presence of toluene probably favors the deposition of nitrogen rich phases, other
solvents (e.g. less polar solvents) could enable the formation of cubic tantalum nitride.
127
6.5 Electrical characterization of TaN films for MOS-gate structures at the

FIIS (Erlangen)
For the evaluation of the applicability of tantalum nitride thin films as gate electrode material,
several parameters were determined from J-V (Current density – Voltage) and C-V
(Capacitance – Voltage) measurements of the thin films. For this purpose, the thin films were
deposited on SiO2 thin films on p-doped Si (100)-substrates to form MOS-capacitors. The
information that was extracted from these measurements were the work function of the gate
electrode, the quality of the SiO2/TaN interface and the contribution of the TaN film to
capacitance equivalent thickness (CET = d(SiO2) + x·d(TaN); x > 0 if the resistivity of the
TaN - film is too low). The interpretation of the J-V and C-V is highly complex and would go
beyond the scope of this work.[179] Therefore only the results for the TaN films are discussed.
Films, using the compounds S6, A2 and B2 have been deposited for these purposes.
[Ta(NEt2)3(N-t-Bu)] (S6): Films, having film thicknesses of 10-60 nm were deposited at a
substrate temperature of 450 °C. These films exhibited well behaved characteristics with no
indication of charge trapping or gate oxide degradation. Thus, it can be assumed that the
SiO2-TaN interface is almost defect-free. The value for the experimentally determined CET
was found to match the thickness of the silicon dioxide films (dOx). Therefore, the TaN-film
did not act as a dielectric. The work function (ΦM) of the metal was determined as 4.6 and
4.4 eV for 10 and 60 nm thick films, respectively. According to theoretical considerations for
metal gates with these values, this material can be used as a midgap gate material (figure 77)
Figure 77. Energy diagram for an MOS-capacitor structure. The unit consists of p-doped silicon (with constant
work-function, ФS and band gap), the insulation oxide and the metal gate material (here: TaN) that can have
miscellaneous work functions (ФM).
128
[Ta(NMeEt)2(tdmh)(N-t-Bu)] A2: C-V and J-V measurements were performed on MOS

capacitors with 10 to 60 nm thick ammonia annealed TaSiN(O) films. However, as expected
from stoichiometry and four point probe characterization, electrical results were poor
regarding an application as metal gate material. It turned out that these TaSiN(O) films acted
as an additional dielectric layer (i.e. larger CET (~7 nm) compared to d(SiO2) (5 nm)) with
large amount of bulk charge (i.e. high defect density), which makes an integration into the
MOS gate stack rather unlikely.
[Ta(NMeEt)(η2-(N-i-Pr)2CNMeEt)(N-t-Bu)] B2: The results from the electrical
characterization of TaN films indicated a small series resistance (i.e. the TaN films are highly
conductive). The CET of 20.6 nm, extracted from the maximum value of the C-V curves
agreed well with the ellipsometrically measured physical thickness (d(SiO2)). Nonetheless,
the C-V curves measured at various frequencies differed in the flatband region, which was
due to voltage dependent interface traps as they were not saturated with hydrogen (e.g., a
forming gas anneal will eliminate this feature). Indications were found for an electron
trapping near the injecting interface (metal gate/SiO2) and further investigations are required
to optimize that interface. A value for ΦM of 3.9 V was obtained, which is rather low for TaN
[180]
films and fits more to reported values for pure tantalum of about 4 V. For the work
function this value seems to be ideal for a use in N-MOS devices.
129
Chapter 7 MOCVD experiments of niobium nitride
Chapter 7 MOCVD of niobium nitride
Niobium nitride thin films were prepared using precursors, comparable to the tantalum
compounds S5 and B2. In this work only preliminary experiments were performed in order to
check whether the niobium precursors (S8, C1) exhibit similar behavior as the comparable
tantalum compounds. Both compounds, the amido/imido complex [Nb(NMe2)3(N-t-Bu)]
(TBTDMN, S8) and the mixed amido/guanidinato/imido precursor [Nb(NMe2)1(N-t-Bu){η2-
(N-i-Pr)2C(NMe2)}2] (C1) were tested in the horizontal selfbuilt reactor without additional
ammonia. Besides the results published by D. Hoffmann et al., no experiments using all-
nitrogen coordinated niobium precursors as singles source precursors have been reported so
far (to the best of our knowledge).[91]
7.1 Depositions with [Ta(NMe2)3(N-t-Bu)] (S8) in the selfbuilt horizontal

reactor
The experiments with compound S8 were carried out under similar conditions as the
experiments using S5. In contrast to S5, S8 is a solid at room temperature and remained as
such during the deposition process. The evaporation temperature was varied in the range of 30
to 40 °C. Optimum growth was observed at Tevap. = 37.5 °C (growth rate: 12-50 nm/min). The
pressure was kept constant at 1 mbar and the nitrogen carrier gas flow was adjusted to 25
sccm. The substrate temperature was varied between 500 and 700 °C.

All films, deposited above 550 °C were completely uniform and showed almost no particle
deposition on the surface of the films. In fact, the films were silver-metallic with only a slight
shade of brown, which made it very difficult to identify whether formation of a film took
place at all. Experiments carried out at 500 °C repeatedly led to non-uniform growth and the
formation of large particles on the substrate. Although XRD spectra of the uniform films
indicated the presence of cubic NbN (figure 78a), the films were not as dense as the bulk
material. The lattice constant for the (111) plane (d = 2.554 nm) was in between the lattice
constant of cubic NbN (d = 2.5360 nm) and cubic NbC (2.581). The density of the films was
in average 5.6 ± 0.4 g/cm3 compared to 8.4 g/cm3 for bulk NbN. This equals a deviation of
33 %. In the case of S5 ([Ta(NMeEt)3(N-t-Bu)]) the difference between the density of the
films and bulk TaN was only 3 %. Maybe the rather high growth rates observed using S8 are
130
responsible for the formation of these “low-density” films (S8: 12-50 nm/min; S5: 6-25
nm/min). SEM-measurements revealed the crystallinity of the thin films showing columnar
growth with diameters of the crystallites in the order of 30-40 nm (figure 78 b/c).
Figure 78. a) XRD of films deposited at 600-700 °C using S8. The reflexes are slightly shifted in comparison to
the theoretical positions for cubic NbN. This can be caused by the presence of cubic niobium carbide. b) / c) SEM
pictures (600°C, precursor: S8). No particle formation could be observed.
Composition:
In the light of the experience, gathered from tantalum amido/imido complexes we expected to
find high concentrations of carbon in the films, caused by unfavorable decomposition of the
precursors. In addition, relatively high levels of oxygen were expected. Two samples
(substrate temperature: 600 and 700 °C) were examined by SNMS and the outcome supports
the aforementioned results for tantalum precursors (figure 79). The films contained 18.8 %
(600 °C) and 26.3 % (700 °C) of carbon, respectively. Finding higher contents of carbon in
the films at higher substrate temperatures is in line with the theory that two pathways of
decomposition mechanisms compete during formation of the films. Only one of these two
131
pathways leads to incorporation of carbon and is dominating the deposition at higher

temperatures. The low density of the films in combination with the presence of grain
boundaries along the columnar crystallites seems to favor post-oxidation of the films. Thus,
11-12 % oxygen was found in the films. The oxygen content of the films slightly decreased
within the sample (Tsubstrate = 700 °C; sputter depth = 100 nm: 14.6 % oxygen; sputter depth =
3000 nm: 11 % oxygen) which furthermore indicates post oxidation processes. However,
leakages within the reactor during deposition can also contribute to the overall oxygen
concentration in the films.
Figure 79. SNMS-analysis of a film using S8 ([Nb(NMe2)3(N-t-Bu)]), deposited at 700 °C. The oxygen
concentrations at a sputter depth of 100 and 2750 nm are displayed.
The resistivities of the films were in the range of 3600-4000 μΩ·cm, which is relatively high.
Higher resistivity can be caused by the formation of insulating Nb2O5, or the contact
resistivity at the grain boundaries within the films. Most probably, lower growth rates would
lead to more compact films with higher resistance towards oxidation and lower resistivities.
132
7.2 Depositions with C1 in the selfbuilt horizontal reactor
The results obtained for C1 were very similar to the results obtained for B2. However, films
deposited at temperatures as low as 500 °C were fully analyzed, including information about
their chemical composition. Precursor C1 is more volatile than B2 and required a lower
evaporation temperature of 110 °C for appropriate film growth. The reactor pressure was kept
at 1 mbar and the carrier gas flow was set to 50 sccm (parameters see table 20).
Table 20. Results and parameters of the depositions using C1 as precursor in the self-built reactor (n.d. = not
determined). Results for one film using B2 as precursor are listed for comparison of the compositions.
Exp-Nr T Film Growth Density XRD Compositon (SNMS) Resistivity
(substr) thickn. rate. in %
in °C in nm nm/min g/cm3 M* N C O in μΩ·cm
C1-1 500 255 4.2 6.4 fcc NbN 41.7 39.6 3.3 14.7 7700
C1-2 600 85 1.4 7.4 fcc NbN 42.7 43.1 1.7 11.9 5400
C1-3 700 56 0.9 n.d. fcc NbN n.d. n.d. n.d. n.d. 3100
B2 (Ta) 750 -- -- -- fcc TaN 47 46 <1 5
* M = Nb for C1-1 to C1-3; M = Ta for B2.

Films deposited in these experiments showed smooth, uniform and silver-colored surfaces. No
particle formation was observed. The growth rates (determined by SEM-thickness) were
between 0.9 and 4.2 nm/min, comparable to the growth rate determined for experiments with
B2. At higher temperatures, lower growth rates, but higher density of the films could be
observed (table 18). Calculations for the density of the films gave values that were closer to
the literature value for cubic NbN than the films obtained using S8. XRD-measurements
clearly showed the formation of cubic NbN even at low temperatures. Comparable to the
results for films deposited using the Ta-congener (B2), the lattice constant of the (111)-planes
was smaller (d = 2.48 nm) than the value for bulk NbN (d = 2.5360 nm). Based on the
dependence of the intensity of the peaks in XRD from the film thickness, no correlation
between the substrate temperature and the degree of crystallinity of the films could be
identified.
Composition
Regarding the composition of the films, this time, in comparison to experiments with B2 (also
listed in table 18), samples, that were deposited at lower temperatures (500, 600 °C) were
analyzed. SNMS-analyses revealed, that even at these temperatures, stochiometric cubic
133
niobium nitride films were deposited. Although the carbon content was again very low, higher
amounts of oxygen were found in the film. Assuming that exchanging tantalum and niobium
does not change the decomposition behavior drastically, it can be concluded that higher
substrate temperatures lead to lower carbon incorporation into the films and to a lower
tendency towards post-oxidation or oxidation by leakages. In the cases of C1-1 and C1-2, the
SNMS analyses were performed already 72-96 hours after sample preparation. The spectra
clearly show that the oxygen content decreases with further sputter depth of the samples
(figure 80). This indicates that at least a significant fraction of the oxygen content in the films
is a result of post oxidation processes. Therefore, it is clear, that less dense films (e.g. at
500 °C) have a higher affinity towards post oxidation. Fast processing or exclusion of air of
the samples after preparation will eliminate this problem.
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Figure 80. SNMS-analyses of niobium nitride films, deposited using C1 at a) 500 °C and b) 600 °C, respectively.
The oxygen concentrations at directly below the surface and close to the silicon substrate are marked.
Four point probe measurements gave values for the sheet resistivities of the films. With
increasing deposition temperature, the films showed better conductivity (table 18). However,
post oxidation of the films due to long exposure to air (approximately 2-3 weeks) deteriorated
the conductivity of the films.
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Chapter 8 ALD experiments of metal (oxo) nitride materials
Chapter 8 ALD of metal (oxo) nitride materials
This chapter deals with the attempts to grow metal nitride thin films via ALD by using metal
organic amido/imido complexes of niobium and tantalum. In the beginning, the ASM F 120
ALD reactor, that was installed in Bochum in the context of this work (8.1), will be described.
Foregoing to the installation, experiments were performed in an ASM F 120 reactor in
Helsinki, Finland (Group of Prof. L. Niinistö, Helsinki University of Technology) using the
precursor S5 (8.2). Initial experiments using the new reactor were carried out with two
different reactor setups (8.3) using S6, S9 and trimethylaluminum.
8.1 Presentation of the ASM F120 ALD reactor
The ASM F120 reactor is one of the first commercially available ALD-reactors (figure 81).
Figure 81. Picture of the ASM F-120 ALD reactor in Bochum.
It has been designed to serve as a versatile reactor for research activities in the 1980’s and
remained almost unchanged since then. The whole reactor and precursor transport system is
placed in a 1.20 m long quartz glass tube that has a diameter of 20 cm (figure 82 a). Due to
the evacuation of the whole quartz tube leakages can only occur at the valves and fittings on
the left side of the glass tube, or at the O-rings, with which the glass tube is sealed. The
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precursor transport system consists of altogether six glass tubes (only three are displayed in
figure 82 a)) that are attached to the reactor part.
Figure 82. Scheme of the ASM F120 reactor. a) The whole tube-system; only three of the six glass tubes are
displayed. b) Enlarged scheme of one of the tubes with the inner and outer tube and the precursor boat. c)
Switching mechanism of the valves.
Consequently, up to six sources can be used in ALD-experiments. While gaseous or highly

volatile substances (water, ammonia, trimethylaluminum) are stored in containers outside the
glass tube, less volatile compounds (e.g. metal organic Ta, Nb, Hf – compounds) are placed in
a boat within one of the glass tubes (figure 82 b). Each of the six glass tubes consists of an
inner (r = 0.6 cm) and an outer tube (r = 0.8 cm). The precursor boat is placed in the inner
tube. Control of the evaporation and the reactor temperatures is given by five independent
temperature zones (T1, T2, T3, T4, T5-8) that are addressed by a software program. External
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heating coils are used to heat the particular zones to temperatures of 40 - 500 °C. Ultra pure
nitrogen (purity 6.0) is used as carrier gas and is equally distributed by small capillaries to the
six glass tubes of the precursor transport system (primary flow). An additional gas flow goes
into the large glass tube (secondary flow). For an ALD-process (alternating sources), it is
necessary to operate the six glass tubes separately with the possibility to switch them “Off” or
“On”. The valves control the gas flow in such manner, that the gas only flows through the
outer glass tube (figure 82 c) when the valve is closed (“Off”, left picture) and through both
tubes (inner and outer) when the valve is open (“On”, right picture). This allows fast
switching between precursor sources due to the constant gas flow (less fluctuation) in the
system.
Two different reactor setups can be used in the reactor (figure 83). The standard reactor setup
consists of two glass tubes (diameter 10.2 cm) that are plugged into each other (Setup I).
Within this reactor wafers with diameters up to 100 mm can be placed. The reactor volume is
approximately 1000 cm3 and the temperature of the reactor is controlled by a thermocouple
which is placed on the outside of the reactor wall (in temperature zone 7). Reactor setup II
consists of three quartz plates (two sample holders and one spacer plate) that are
perpendicularly arranged in the large glass tube. The precursor passes the samples in a vertical
flow. The samples are placed face-to-face in the reactor with a gap of only 2 mm. Therefore
the whole reactor volume is approximately 7 ml and most of the surface is covered by the
substrates. The temperature of the reactor is measured in the center of the plates.
Figure 83. Schemes of the two reactor types for the ASM F-120 reactor (left: setup I, right: setup II).
8.2 ALD experiments in a well adjusted F-120 reactor (Finland)
Before installing the reactor in Bochum, experiments were carried out in a comparable F-120
reactor (setup I) at the Helsinki University of Technology, Finland together with J. Niinistö
and Dr. M. Puttkonen in the group of Prof. Dr. L. Niinistö. The depositions were carried out
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at substrate temperatures of 200-300 °C using the liquid precursor S5 ([Ta(NEtMe)3(N-t-

Bu)]) and ammonia in an alternating fashion. The scope of these experiments was to test,
whether uniform films can be deposited, and whether the precursor is suitable to be used as a
reference for the installation of the new reactor in Bochum. Thin glass plates (5 x 5 cm2)
served as substrates. Evaporation temperatures of 50 °C (zone T2, figure 83a) allowed
sufficient mass transport of the precursor to the reactor. The primary gas flow (nitrogen) was
set at 300 sccm, which corresponds to 50 sccm per glass tube. In between the pulses of the
precursor (0.6 - 2.0 s) and ammonia (6 sccm, 4 s), purge times of 1.0 - 4.0 s were applied to
remove the excess of the precursor and ammonia. Typically 1500 cycles (precursor, purge,
ammonia, purge) were accomplished for each experiment.
Results
Based on the decomposition temperature of S5 (189 °C), it was assumed that substrate
temperatures, noticeably above 200 °C will lead to the contribution of simple CVD-like
growth. This assumption was confirmed. CVD-growth could be observed without using a
second reactive compound (ammonia). However, at exactly 200 °C no thermal decomposition
of the precursor and no film growth were observed. Thus the growth could be considered as
self limiting.
The color of each film was uniform over the whole substrate. Light blue to violet films were
obtained, depending on the number of cycles, hence the thickness of the films. The color of
the films and its dependence of the film thickness already indicated that colorless films were
deposited. Thus, the observed colors are a product of a thin, transparent film (TaOxNy) having
a different refractive index than the underlying substrate (glas, n = 1.46). This destructive
interferential effect can be described by the following equation (3).[p]
1 λ
d= ⋅ (eq. 3)
n 4
Accordingly, films that appear to be blue extinguish light in the wavelength of approximately
590 nm (yellow). This would give a film thickness of 590 nm/(4 · 2.1) = 70.2 nm.
[p] d = thickness of the film; n = refractive index of the deposited film = ~2.1 (determined by ellipsometry); λ =
wavelength of the extinguished light;
139
Unfortunately, all techniques that were used to quantify the film thicknesses gave no
consistent values. Ellipsometry- (Helsinki), RBS- (Bochum) and SEM-measurements
(Bochum) of the films revealed film thicknesses in the range of 50-90 nm for the samples.
Indications were found, that the films did not show uniformity over the whole substrate and
that the density of the films (appr. 6 ± 2 g/cm3) was much lower than the density of bulk TaN
(13.7 g/cm3). These low density films did not exhibit any peaks in XRD measurements and
were completely insulating (four-point probe measurements).
The composition of the films was investigated by RBS-measurements. Although the results
were afflicted with high errors the values were consistent within these error limits for all
samples, prepared at 200 °C. The films consisted of 25 ± 5 % tantalum, 40 ± 5 % nitrogen,
5 ± 5 % carbon, and 30 ± 5 % oxygen. Clearly, the films were heavily oxidized, either by
post-oxidation, impurities in the ammonia or nitrogen gases or leakages in the reactor during
deposition. Due to transamination reactions of ammonia with the precursor, that were likely to
occur, low contents of carbon could be observed.
8.3 Installation of the F120 reactor in Bochum and first results
Experiments with reactor setup I (8.3.1) were performed after installation of the AFM-120
apparatus. Compound S5 was used as precursor at the same conditions which were applied in
previous experiments in the ALD reactor in Finland (8.2). In chapter 8.3.2 experiments with
setup II are presented.
8.3.1 Depositions with S5 in reactor setup I
Theoretically, one would expect the same results (i.e. almost uniform films) in experiments
when the same reactor type (F-120) is used under the same experimental conditions. The only
differences between both reactor setups were the types of the nitrogen (Bochum: purity 6.0;
Finland: nitrogen generator) and ammonia source (Bochum: high-purity NH3, adjustment by a
needle valve; Finland: Mass flow controller). Nevertheless, the expected reproducibility was
not given. Altogether, 15 experiments were carried out at a substrate temperature of 200 °C
while a specialist of the ASM company (T. Asikainen) was present. The pulse time of the
precursor (0.6 – 2.5 s) and ammonia (4.0 – 15.0 s), as well as the purge time after the
particular pulse were varied in a broad range (2.0-15 s). In addition, the primary gas flow
(carrier gas flow) was changed in the range of 300 to 800 sccm. In all cases, highly non-
uniform, non conducting, colorful films were deposited on the substrates (100 mm Si(100)
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wafers), almost independent of the parameters that were adjusted for the experiment. Precise
and reliable ellipsometric measurements were performed in Erlangen to reveal the non-
uniformity of the films (figure 84)
Figure 84. One film, having one of the highest uniformities is shown as an image (left side: pulse(precursor) =
1.2 s; 2000 cycles, 300 sccm N2). The blue sides of the wafer correspond to a film thickness of appr. 80 nm. On
the right side, the 3 dimensional thickness profile of the film is displayed.
All films were of higher thickness at both sides of the wafer that are directed to the precursor
inlet and the exhaust, respectively. This effect was more or less pronounced, depending on the
experimental conditions. Figure 85 shows the variations of the precursor pulse time, the
number of cycles and the primary nitrogen flow. Some trends are visible, as for example that
a higher primary flow or higher precursor pulse time led to more uniform films. However, in
an ideal ALD process, a variation of the number of cycles should have no influence on the
percentage of the standard deviation of the film thickness. In order to exclude effects of
leakages, the reactor was dissembled, rebuild and a leakage test was performed.
It can be concluded that the growth rate and its behavior in this reactor type is strongly
dependent on the variation of flow rates and pulse times. Reasons for this occurrence can be a
non uniform temperature distribution over the wafer or strong fluctuations in the reactor. With
this precursor / reactive gas combination in this reactor type it seems not possible to fabricate
uniform thin films.
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Figure 85. Dependence of the uniformity of the films on the variation of certain parameters (precursor S5). The
standard deviation and its percentage of the average thickness of the film are listed. A variation of the ammonia
flow rate (not displayed) also did not lead to higher uniformity.
8.3.2 Depositions of Al2O3, TaON and NbON in reactor setup II
As a consequence of the unsuccessful experiments in reactor setup I, a low volume reactor

(type II) was installed. This reactor was first tested with the standard process,
trimethylaluminum and water on 5 x 5 cm2 silicon substrates. The samples were highly
uniform with standard deviations of less than 3.6 nm and average film thicknesses of 83 to
112 nm. The results are listed in table 21. In accordance with these data, the reactor had no
leaks and could be considered to work properly.
Table 21. Results and parameters of the depositions using trimethylaluminum (TMA) and water (T(substrate) =
300 °C), primary flow = 700 sccm N2, secondary flow = 100 sccm N2 on Si(100) substrates.
Exp. Cycles Pulse Purge Pulse Purge Avg. dmax dmin Growth rate RMS
(TMA). (H20) Thickn.
in s in s in s in s in nm in nm in nm in Å/cycle in nm
Test12 1000 0.5 1.0 1.0 1.5 99.8 106.3 95.7 0.100 ± 0.005 3.57
Test13 1000 1.5 3.0 3.0 4.5 112.3 117.9 108.7 0.112 ± 0.005 3.53
Test14 800 1.0 2.0 2.0 3.0 82.8 88.4 80.3 0.104 ± 0.004 3.10
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Experiments using S6 [Ta(NEt2)3(N-t-Bu)]

Instead of S5 (in setup I), S6 was tested in the new reactor setup II. S6 has already been used
successfully to produce TaN thin films.[123,125] However, in both literature references
completely different deposition behavior in terms of pulse times of the precursor and
ammonia were reported that are required to obtain self-limiting growth (0.2 vs. 4 seconds).
One author (J.-S. Park et al.) concludes that at 260 °C substrate temperature (60 °C over the
thermal decomposition temperature of the precursor) amorphous, low density, almost
insulating and chemically unstable films are formed, while in the other publication (O. van
der Straten et al.) the formation of conducting, stable and stochiometric TaN films was
reported (Tsubstrate = 250 °C). We decided to choose a lower substrate temperature of 200 °C
and 150 °C in order to minimize the contribution of thermal CVD during deposition (table
22).
Table 22. Results and parameters of the depositions using S6 and ammonia, primary flow = 700 sccm N2,
secondary flow = 100 sccm N2 on Si(100) substrates (20 nm SiO2); T(precursor) = 55 °C.1500 cycles.
Exp. T Pulse Purge Pulse Purge Avg. dmax dmin Growth RMS
(substr.) (S6). (NH3) Thickn. rate
20-24 in °C in s in s in s in s in nm in nm in nm in Å/cycle in nm
TaN-1 200 1.2 3.0 4.0 4.0 102* - - 0.73 -
TaN-2 200 3.0 3.0 6.0 6.0 123* - - 0.82 -
TaN-3 200 0.6 3.0 6.0 6.0 98** 112 94 0.65 8.4
TaN-4 150 0.6 3.0 6.0 6.0 116** 134 102.9 0.77 10.5
TaN-5 150 3.0 3.0 6.0 6.0 121* - - 0.81 -
*Based on weight gain ** Based on ellipsometric measurement
Results of this set of experiments are hereby briefly summarized. By variation of the
deposition parameters, optimal conditions were found to deposit uniform films at a substrate
temperature of 200 °C (TaN-3, see figure 86). The films, deposited at 150 °C were less
uniform. It can be assumed that longer purge times are required to remove absorbed ammonia
or an excess of the precursor from the reactor and substrate walls. Generally a divergence can
be observed between ideal ALD growth and the results from the experiments. In an ideal case,
more uniform films should be obtained and the growth rate should be independent of the
pulse time of the precursor. A satisfactory explanation cannot be given. Leakages could be
excluded and high purity carrier gas, as well as high purity ammonia were used. The films
were blue, amorphous and completely insulating. This indicated the formation of either
Ta3N5, or more likely highly amorphous films of a mixture of TaNxCy and not fully
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decomposed precursor fragments. Based on these negative results the samples were not
further analyzed. The results are in accordance to the results from the work of J.-S. Park et al..
Figure 86. 3-dimensional plot of the film thicknesses of a) TaN-3 and b) TaN-2. Film thickness was determined at
the white and black spots.
Experiments using S9 [Nb(NEt2)3(N-t-Bu)]

The reason for using this precursor was to investigate whether conducting NbNx films could
be obtained. In the case of tantalum, Ta3N5 can be formed as an insulating film, which is not
possible for niobium. Taking into account the previous experiences with compound S6, the
purge time after the ammonia-flow was increased to 10 seconds to guarantee that excess of
ammonia was completely removed from the reactor. All other parameters besides this value
were adopted from the experiments using S6 and are summarized in table 23.
Table 23. Parameters and results of the depositions using S9 and ammonia, primary flow = 700 sccm N2,
secondary flow = 100 sccm N2 on Si(100) substrates (20 nm SiO2); T(precursor) = 60 °C. Purge times: 3 s (after
precursor pulse) and 10 s (after ammonia pulse). Thickness measurements were performed by ellipsometry.
Exp. T Pulse Pulse Avg. Deviation Growth rate Calculated Refractive
(substr.) (S9). (NH3) Thickn. on the density** index
wafer*
20-24 in °C in s in s in nm in % in Å/cycle in g/cm3
NbN1 200 0.5 3.0 36.8 2 0.37 4.8 2.26
NbN2 200 0.75 3.0 45.1 3 0.45 5.4 2.27
NbN3 200 1.0 3.0 44.1 3 0.44 n.d. 2.26
NbN4 200 1.5 3.0 55.0 3 0.55 4.2 2.25
NbN5 200 3.0 3.0 69.5 5 0.70 5.4 2.27
NbN6 200 5.0 3.0 87.9 6 0.88 5.4 2.21
NbN7 250 1.0 3.0 42.7 2 0.43 5.2 2.45
* Percentage of maximum positive or negative deviation on the wafer. **Density was calculated by weight gain of
the samples and their average thicknesses.
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All films were completely uniform and had a blue/violet, mirror-like appearance. The
deviation of the film thicknesses over the whole substrate area (5 x 5 cm2) was below ± 6 %
of the average film thickness. In principle, these results suggested ALD-conditions during the
film growth. Nonetheless, in an ideal case, saturation of the growth rate should occur with
higher pulse times of the precursor. In these experiments, no saturation of the growth rate was
observed (figure 87).
Figure 87. Dependence of the growth rate on the pulse time of the precursor. No saturation takes place.
The combined results suggested that thermal decomposition of the precursor occurs already at
200 °C. The average density of the films (5.1 ± 0.9 g/cm3) was lower than the density of bulk
NbN (8.4 g/cm3), but more dense than the films obtained in the case of TaN. XRD
measurements indicated the amorphous structure of the film and four point measurements
showed that the films were - as expected - insulating.
8.4 Conclusions for the ALD of tantalum and niobium nitride materials
The above mentioned experiments show the high complexity of ALD processes, even with
commercially available reactors. Additional parameters to MOCVD, e.g. pulse and purge
times, make it difficult to optimize the multi-dimensional system. Limits for the deposition
temperature, given by the less thermally stable metal organic compounds lead to amorphous
films. These films are chemically (i.e. high affinity towards post deposition oxidation) not
stable and do not have the electrical properties, required for an application as gate electrode
material or as a diffusion barrier. The use of thermally more stable precursors of this work,
145
e.g. tantalum guanidinato complexes may help to increase the deposition temperature of the
ALD process and yield more stable films. This, however, is not part of this work. In our
opinion it is difficult to obtain thin, conducting TaN or NbN films, without the use of
additional reactive compounds e.g. hydrogen or ammonia plasma.
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Chapter 9 Summary and Outlook
Chapter 9 Summary and outlook
During the course of the present study, new precursors were developed and tested for the
deposition of tantalum and niobium nitride thin films via Metal Organic Chemical Vapor
Deposition (MOCVD) and Atomic Layer Deposition (ALD). These films find their
application in the fabrication of microelectronic devices, namely as metal gate and diffusion
barrier materials. Both materials, TaN as well as NbN, feature high thermal stability, good
conductivity and excellent barrier properties, when deposited in the face centered cubic phase.
The challenge is to deposit carbon free and dense films that withstand post oxidation
processes and show good values for the work function of the material. The experimental work
and the results of this dissertation can be divided into two parts. The first part deals with the
chemical realization of new ligand concepts for MOCVD and ALD precursors. These
concepts comprise the increase of complexity of the metal organic complexes compared to
simple compounds, (mixed amido/imido complexes) having lower coordination numbers and
simple monodentate ligands. The influence on the chemical as well as thermal behavior has
been investigated. The second part consists of MOCVD and ALD experiments with newly
synthesized, as well as already known, but not fully tested precursors.
I. Synthesis and characterization of new precursors

All synthetic routes of new compounds were based on amido/imido complexes of tantalum
and niobium as starting compounds (S4-S9, figure 88). These four coordinated
tris(dialkylamido)-alkylimido-tantalum and niobium complexes were synthesized starting
from the metal chloride via a pyridine stabilized chloro/imido intermediate (S1-S3). The
synthetic routes were improved, in terms of yields and batch sizes (up to 40 g per batch). In
the following, these compounds were modified by transamination reactions with hydrazine
derivatives or the insertion of alkyl substituted carbodiimide derivatives. Thus, two new
classes of precursors were successfully synthesized: Mixed amido/imido/hydrazido
complexes of tantalum (A1-A3) as well as mixed amido/imido/guanidinato complexes of
tantalum and niobium (B1-B8; C1-C4). In the context of these experiments, some side
products of reactions were characterized and discussed e.g. hydrolyzed species or
decomposition products. The compounds were analyzed by means of 1H-NMR, 13C-NMR, EI-
Mass spectroscopy, CHN analysis, TG/DTA analysis and - when possible - by single crystal
X-ray diffractometry.
147
Figure 88. Reaction scheme depicting the syntheses of the complexes A1-A3 by transamination reactions (one
amido group is replaced by one hydrazido ligand) and of the guanidinato complexes B1-B8 and C1-C4 by
insertion reactions (two equivalents of carbodiimide insert into the metal nitrogen bond of the amido group).
The hydrazine containing compounds A1-A3 are all liquid at room temperature and by their
nature sufficiently volatile for application as precursors. Repeated quantitative distillation
without any sign of decomposition is possible. TG/DTA analysis showed that the
decomposition temperatures of A1, A2 and A3 are above 280 °C which is 90 °C higher than
the temperatures that lead to decomposition of the amido/imido compounds S4-S6. Along
with the higher thermal stability goes a significantly lower chemical reactivity, e.g. towards
hydrolysis. The crystal structure of A1 exhibits the η2-coordination of hydrazido ligand and
consequently a coordination number of five for tantalum in the solid state. Further exchange
of more than one amido group was not possible. The six coordinated guanidinato complexes
(B1-B8; C1-C4, figure 89) show a large window for the variation of ligand substituents (R1-
R4). However, not all carbodiimide derivatives could be inserted into the metal amido bonds
as a result of steric constraints. All guanidinato complexes are colorless solids that form
needle-like, agglomerated crystals from solution at reduced temperatures. Due to the chirality
of the molecules and the multiplicity of ligand types, the NMR spectra of these complexes
displayed high complexity. Crystal structures for eight of the twelve compounds could be
determined. The complexes are structurally very similar, with bond lengths and angles of the
solid state structures showing only minor variations. TG/DTA measurements and isothermal
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studies revealed the low volatility of the cy-cdi based complexes. This was rather unexpected,
considering the fact that the structural and chemical behaviors of these classes of compounds
are very similar. Thus, cy-cdi based complexes are in general not suitable for classical
MOCVD purposes due to a supposedly weak precursor transport. Still, application of the
compounds derived from cy-cdi in Liquid Injection MOCVD is feasible. The choice of
substituents of the amido or imido groups does not seem to have a significant impact on the
thermal behavior of the resulting complexes. Finally, thermal decomposition experiments of
B1-B3 clearly showed that highly complex pyrolysis reactions take place which nonetheless
lead to a clean decomposition of the selected precursors.
II. MOCVD and ALD experiments

MOCVD and ALD experiments were performed using different reactors. Preliminary, but
meaningful MOCVD experiments were conducted with a selfbuilt reactor for small substrates.
Precursors, showing promising properties were sent to our cooperation partner in Erlangen
(large-wafer instrument) or were tested with the industrial Aixtron 200 RF MOCVD or the
Aixtron 200 FE Liquid Injection MOCVD reactors, situated in our research group (table 24).
ALD experiments were performed in the commercially available ASM F 120 reactor.
MOCVD experiments applying mixed amido/imido compounds (S5, S6, S8) as single source
precursors led to the formation of conducting films that showed high contaminations of
carbon. On one hand, addition of ammonia reduced the amount of carbon drastically (most
probably due to transamination reactions), but on the other lowered the quality of the films by
means of lower density and deteriorated conductivity.
Experiments using the guanidinato complexes clearly showed that an increase of the
complexity of a precursor (higher coordination number, higher atomic percentage of carbon,
heterolepticety) for TaN-depositions does not necessarily conflict with the thin film quality
regarding carbon incorporation and the formation of cubic, conductive and carbon free
tantalum nitride. Interestingly, ammonia seems not to be a stringent requirement for the
formation of conductive cubic TaN and NbN using guanidinato containing complexes (B1-
B4, C1, C2) as precursors. A possible explanation is that the blocking of free coordination
sites at the metal center, due to the introduction of bidentate ligands inhibits carbon
incorporation caused by the formation of intermediate metal-carbon bonds during
decomposition. Thus, guanidinato complexes may have quite a potential for the MOCVD of
metal nitrides, although sufficient mass transport of the precursor to the reactor still remains a
challenge. LI-MOCVD experiments were performed with B2 to enhance the precursor
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transport into the reactor that indicated the formation of carbon free films. However, problems
occurred in terms of oxidation and the formation of amorphous TaNx, because the reactor was
originally designed for the deposition of oxide materials.
Table 24. Compounds that were used for MOCVD and ALD including a short summary of the results.
Formula Reactor type Chapter Qualitative results
S5 [Ta(NMeEt)3(N-t-Bu)] Selfbuilt MOCVD 6.2.1 Cubic TaN was deposited having high
reactor levels of impurities (O, C).
S6 [Ta(NEt2)3(N-t-Bu)] Aixtron 200 RF 6.2.2 Cubic, conductive TaN was deposited.
Low level of impurities (with ammonia
as reactive gas).
S6 [Ta(NEt2)3(N-t-Bu)] Large wafer 6.2.3 Heavily oxidized TaN was deposited.
reactor (Erlangen) Still, the films showed good electrical
properties.
S5 [Ta(NMeEt)3(N-t-Bu)] Large wafer 6.2.4 Heavily oxidized TaN was deposited.
reactor (Erlangen)
A3 [Ta(NEt2)2(tdmh)(N-t-Bu)] Selfbuilt MOCVD 6.3.1 Amorphous and insulating TaSixNy was
reactor deposited.
A2 [Ta(NMeEt)2(tdmh)(N-t-Bu)] Large wafer 6.3.2 Heavily oxidized TaSixNx was
reactor (Erlangen) deposited. The films were completely
insulating.
B2 [Ta(NMeEt){η2-(N-i- Selfbuilt MOCVD 6.4.1 Cubic TaN with almost no impurities
Pr)2C(NMeEt)}(N-t-Bu)] reactor was deposited without ammonia. (fair
electronic properties).
B2 [Ta(NMeEt){η2-(N-i- LI-MOCVD 6.4.2 Oxidized and insulating, but carbon
Pr)2C(NMeEt)}(N-t-Bu)] Aixtron (200 FE) free TaNx was deposited.
S8 [Nb(NMe2)3(N-t-Bu)] Selfbuilt MOCVD 7.1 Cubic NbN was deposited having high
reactor levels of impurities (O, C).
C1 [Nb(NMe2){η2-(N-i- Selfbuilt MOCVD 7.2 Cubic NbN with almost no impurities
Pr)2C(NMeEt)}(N-t-Bu)] reactor was deposited without ammonia.
S6 [Ta(NEt2)3(N-t-Bu)] ASM F 120 ALD 8.3.2 Amorphous and insulating films with
reactor low densities were deposited.
S9 [Nb(NEt2)3(N-t-Bu)] ASM F 120 ALD 8.3.2 Amorphous and insulating films with
reactor low densities were deposited.
MOCVD-experiments in the presence of ammonia using hydrazido containing precursors in a

selfbuilt reactor (A3) gave amorphous, insulating, but carbon free tantalum nitride films with
significant amounts of silicon, incorporated in the film. The presence of silicon in the films
concurrent to the absence of carbon is a very interesting finding due to the very high thermal
stability and excellent barrier properties of TaSixNy films according to the literature. The
intrinsic incorporation of Si into the layers is interesting as such and points to a special ligand
fragmentation of the hydrazido moiety of A2, which warrants further studies.
150
On the other hand, this property rules out the deposition of phase-pure crystalline cubic TaN
using A1-A3. Testing this class of precursors in a large scale reactor (Erlangen, A2) at least
showed that - in principle - this type of precursor is suitable for covering large wafers in terms
of precursor transport and reactor geometry. However, we failed to avoid undesired heavy
oxygen contamination with the reactor setup in Erlangen.
Within this work, the ASM F120 ALD reactor was installed in Bochum. Initial problems with
uniformity of the depositions were overcome by changing the reactor setup from a high
volume reactor to an almost zero-volume reactor. Experiments using S5, S6 and S9 as
precursors showed very moderate results. The films were less dense and completely
insulating. In addition even at a substrate temperature of 200 °C thermal CVD-like
decomposition contributed to the film growth. Thus no ideal ALD-behavior was observed for
TaN.
The oxidation of all films that can occur either during the deposition (e.g. by leakages or
impurities in the reactants) and/or after deposition represents a general problem when dealing
with oxophilic metal nitride films. Due to the absence of possibilities to measure the
composition of the films or their electrical properties contemporaneously to the fabrication of
the films, the source of oxygen could not be certainly identified. Figure 89 summarizes the
findings for the conductivities of all films, deposited within this work. For each experimental
row, the substrate temperature of the film having the lowest resistivity is displayed. Based on
these results amido/imido precursors still are the best alternative for fabricating diffusion
barriers or metal gate stacks. The fact that the resistivities of the samples prepared in Bochum
were not measured directly after deposition may lead to the impression that films, deposited in
Erlangen have better electrical properties (direct measurement after deposition). Regardless of
this issue, guanidinato complexes have a high potential due to their excellent ability to act as
single source precursors. No additional ammonia is required that would support the formation
of insulating N-rich Ta3N5. All results have to be taken with care, as it holds for all
publications regarding the MOCVD and ALD of thin nitride films. Many factors have an
effect on the electrical properties of a film: grade of crystallinity, grain boundaries, metal to
nitrogen ratio, and oxidation of the whole film or the surface of the film. These factors in turn
depend on the type of reactor (e.g. volume/design) and other parameters (e.g. flow rates,
pressure, precursor transport rate etc.). Therefore conclusions, drawn from these results, about
the suitability of a precursor have limited universal validity.
151
Figure 89. Diagram including the depositions experiments of this work. From each experimental row, the data set of the film with the lowest
resistivity is displayed. The green box marks the expectations of the industry that have to be met. Yellow boxes show experiments using the
precursors as SSP. Blue boxes indicate the use of ammonia during deposition. Grey boxes show ALD-experiments with additional ammonia.
152
Outlook
While the part of this work, dealing with the precursor synthesis was elucidated to a very
satisfying extent, further experiments are required to identify the decomposition pathways of
the precursors. So far the underlying mechanisms, e.g. the incorporation of silicon by using
hydrazido containing precursors have not been resolved. It is desirable to couple MOCVD
reactors or TG/DTA instruments with other analytical methods, e.g. EI-MS spectroscopy in
order to further analyze the decomposition products during the deposition of the films.
Furthermore detailed CVD studies for a use of the less volatile, but soluble guanidinato
complexes in liquid injection MOCVD can identify the potential of this precursor. However,
the reactor has to be designed for oxygen free depositions. Variation of the solvents (e.g.
usage of aliphatic instead of aromatic hydrocarbons) probably will have an effect on the
properties of the resulting films. ALD experiments, though less successful within this work,
can be performed at higher substrate temperatures using the guanidinato complexes. The
higher thermal stability of these complexes and the interesting decomposition behavior may
lead to ALD-like growth at higher temperatures. It is questionable, whether an increase of the
deposition temperature to about 250 °C is sufficient for the formation of dense and stable
electrically conductive metal nitride thin films.
153
Chapter 10 Experimental
In the beginning of this chapter the analytical techniques and the instruments that were used
for the characterization of new compounds (10.1) and thin films (10.2) are described. Chapter
10.3 comments the preparation of thin films via MOCVD and ALD, while the other parts
(10.4-10.9) address the preparation of the compounds and their analytical data (e.g. crystal
data).
10.1 Analytical characterization of the precursors
Proton- and carbon-NMR spectra were recorded of all synthesized compounds. The spectra
were integrated and further analyzed using the “Mestrec® Version 2.90” software suite. C6D6
and C7D8 were purchased from Deutero GmbH. Three different spectrometers were used for
the measurements of the 1H and 13C spectra.
Bruker Advance DPX 200 (1H: 200.1 Hz; 13C: 50.3 Hz, 25 °C)
Bruker Advance DPX 250 (1H: 250.1 Hz; 13C: 62.9 Hz, - 80 to 65 °C)
Bruker Advance DRX 400 (1H: 400.1 Hz; 13C: 100.6 Hz, 2-D Heteronuclear
Multiple-Quantum Correlation spectra at 25 °C)
CHN-analyses of all compounds were performed by Karin Bartholomäus of the analytical

service center of the faculty using a “CHNSO Vario EL” instrument (Elemental, Hanau).
Electronic Ionization (EI) mass spectra at ionization energies of 70 eV and 24 eV were

recorded by Jutta Schäfer using a “CHS-Mass spectrometer” by “Varian MAT” (Bremen).
Data were given as specific masses (m/z) based on the most abundant isotopes (11H, 12
6C,
14 28 93 181
7N, 14Si, 41Nb, 73Ta).
Thermal properties were analyzed by TG/DTA analysis using a “Seiko - TG/DTA6200/SII”

instrument. The samples were filled in an aluminum crucible (glovebox) with a punched lid.
Such an aluminum crucible was used as the reference in the measurements, too. In all
standard TG/DTA measurements, the heating rate was set to 5 °C per minute at a nitrogen
flow of 300 sccm. Starting temperature was 25 °C and the end temperature was between 550
and 600 °C, depending on the expected thermal stability of the compounds. For isothermal
154
studies (e.g. at 100 and 120 °C, 4 hours) the samples were heated to the target temperature at
a rate of 10 °C/min
Single crystal X-ray diffraction experiments were carried out at low temperatures (nitrogen
cooling) by Dr. Christian Gemel and Manuela Winter on an Oxford Xcalibur 2 CCD/PD
diffractometer with monochromated Mo-Kα radiation (0.71073Å). The structures were solved
by direct methods and refined anisotropically with SHELXL-97 program suite. The crystals
were selected using the perfluorated oil technique and mounted on a small glass wire enclosed
in the head of the goniometer. The parameters were refined against F2 and the R-values were
defined as
R1 = Σ(||F0|-|Fc||)/( Σ |F0|)0.5 and wR2 = [Σw(F02-Fc2)2/ Σw(F02)2]0.5
Details to the crystal structures are presented in tables 27 to 31. Besides a disorder of an atom
in the molecular structure of S8 (atom C4) and the incorporation of two equivalents of toluene
in the crystals structure of B7 (no interactions was observed between B7 and the toluene
molecules) no noticeable difficulties occurred.
10.2 Thin films analysis and instruments
In the following, the techniques for thin film analysis are explained, together with the
experimental parameters of the analyses.
X-ray diffraction (XRD) of thin (polycrystalline) films [181]

XRD was used in order to collect information about the crystalline structure of the films. The
data of this instrument give information about the crystallinity of the deposited film. Al-Kα
radiation emitted by an X-ray source interacts with the thin film deposited on the substrate.
The incident radiation is reflected at the crystalline lattice of the thin film and the underlying
Silicon (100). Constructive (intensifying) and destructive (attenuating) interference occurs
between different reflected beams, depending on the crystal lattice (distance d) and the
substrate / incident radiation angle. Reflexes can be observed as a function of the angle 2θ
(figure 90). The positive interference leading to the observed reflexes is described by Bragg’s
Law (eq. 4).
155
Figure 90. Scheme for the reflections of the incident X-ray beams at the planes within the crystals and equation
4 (d = dhkl).
An ideal poly-crystalline film with grain sizes between 500·nm and 5,000 nm would give
reflexes with very small half-widths and high intensities. Deviations from this case occur
because of several influences on the crystallinity of the thin film:
- Impurities (e.g. carbon) incorporated into the film.

- Non-stochiometric composition of the film.
- Mixtures of different crystalline phases that result in appearance of crystalline defects.
- Lattice defects in the crystalline film during growth.
- Grain boundaries in between poly-crystalline phases.
X-ray diffraction analysis was performed by Dr. Harish Parala on a Bruker D8 Advance
instrument with θ-2θ (Bragg-Brentano) geometry (figure 91). The X-ray source (Cu-Kα –
radiation; λ = 1.5418 Å, acceleration voltage: 40 kV, heating current 30-40 mA) and the
position sensitive detector are constrained to lie on a circle. A parabolic Göbel mirror is
mounted in the primary beam path (slit width: 0.2 mm) to separate parallel, pure Cu-Kα
radiation. Calibration in the flat sample mode was performed using standard quartz sample.
The 2θ-angle was varied for the measurements in a range of 20 to 65° with a step size of
0.0141 °/step (0.3 s per step for standard measurements and 4 s for long time measurements).
156
Figure 91. Scheme of a powder diffractometer in Bragg-Brentano geometry.
Secondary neutral mass spectroscopy (SNMS) [182]

SNMS analysis gives a depth profile of the composition of a film. For SNMS measurements,
the sample is bombarded with rare gas ions (in this case argon) at an energy range of 0.5 to 10
keV. Atoms are sputtered from the surface of the sample by this beam of argon ions. The flux
of sputtered particles consists of ions and neutral atoms. The neutral atoms are ionized by
electron bombardment when they enter the analyzer. SNMS gives more reliable results than
SIMS (Secondary ion mass spectroscopy). Due to matrix effects, the probability of sputtering
ionized particles from the sample heavily depends on the type of surface (0 - 10 % of all
sputtered particles). The percentage (yield) of neutral particles is therefore in the range of 90 -
99.999 %, which drastically reduces the influence of the sample composition/constitution on
the results. SNMS measurements show an accuracy of about ±1 atomic % with a detection
limit in the range of 0.1 - 1 atomic %, depending on the element. The calibration is straight
forward when the SNMS ion yields are available, as they are for most common species.
The samples were profiled using Sputtered neutral mass spectrometry (SNMS) on a VG
SIMSLABB IIIA instrument by Dr. Simon Romani (CSMA-MATS Company, Stokes-on-
Trent, England). The primary ion beam was argon at 10 keV, usually operated at high currents
(0.8 - 1.0 microampere) over large areas (from 0.5 to 4 mm raster size generally, depending
on total depth requirements). In situations where the yields were not already known from
empirical work (e.g. tantalum and niobium) an independent check using RBS was performed
to verify the yields of the metal. For certain species that require additional filtering (e.g. to
remove system background) reference materials were processed to provide on-the-day checks.
This was done for both oxygen and nitrogen.
157
Rutherford backscattering spectrometry (RBS) [183]

This measurement technique provides information about the composition of a film and the
concentration of atoms in the measured area of the film (atoms/cm2). For RBS measurements,
the samples are bombarded with helium ions that were accelerated at a bias voltage of several
megavolts. The high energetic helium ions penetrate the electron cloud of the atoms within
the sample and either pass the sample or are backscattered at the nuclei of the target atoms.
Depending on the weight of the target atom, the helium ions loose more or less energy at the
elastic hit. Thus, the backscattered ions can be assigned to the elements present in the sample.
The broadness of the peak is a result of the energy loss of the backscattered ions by
interaction with electrons in the sample. Depending on the depth of penetration, the energy of
the backscattered ion is lowered compared to the energy of ions, directly backscattered at the
surface of the sample. A theoretical curve is fitted to the measured diagram for determination
of the composition. Heavy elements can be detected with a relative high sensitivity due to the
high cross section of their nuclei. The existence of several light elements in the same sample
(e.g. carbon, nitrogen and oxygen) reduces the accuracy for the concentration (5 - 10 % error
of the determined absolute values).
RBS measurements within this work were performed by Dr. H. W. Becker in the Dynamitron
Tandem Laboratory located in the Ruhr-University Bochum. The acceleration bias was set to
2 MV at a detection angle of the backscattered ions relative to the incident beam of 40 °.
Scanning electron microscopy (SEM) and Electron dispersive X-ray analysis (EDX) [184]
SEM is a powerful analytical instrument for analyzing thin films deposited by CVD. It is
possible to acquire surface scans with resolutions of only a few nanometers. Scanning
electron microscopy uses electrons that are emitted by a heated tungsten filament. They are
focused as a beam and accelerated towards the sample. The incident beam of electrons
interacts with the sample and results in an emitting of different types of signals. There is an
emission of X-rays beams, Auger electrons, catholuminescense, backscattered electrons and
so called secondary electrons. The backscattered electrons can be collected and give
topographical information about the sample. The morphology of the surface (nanocrystalline,
amorphous etc.) and crystal sizes can be determined. Cross sections of samples are useful to
provide information about the behavior of the vertical growth and the growth rate during the
deposition. Samples with low conductivities (e.g. insulating and semiconducting materials)
have to be sputtered with gold or carbon in order to guarantee certain conductivity. Otherwise,
158
absorbed electrons cannot be removed and the sample will get charged (lowering of the
resolution). The EDX analyzer is added to the SEM instrument. Vacancies, left by the
emission of secondary electrons from the atoms in the film, are filled by electrons from higher
orbitals. The excess energy is emitted as X-rays that are specific for each element. Most of
the elements can be analyzed by this method. Problems occur when light elements with
similar molar masses have to be detected (in this case: oxygen, nitrogen and carbon).
SEM - samples were measured by Dr. Rolf Neusser on a 1530 Gemini Field Emission SEM
instrument by Leo (Zeiss), coupled with an INCA X-ray microanalysis system (EDX). These
instruments are situated in Bochum.
Spectroscopic ellipsometry [185]

Ellipsometry allows the determination of the film thickness and the refractive index of a
transparent, dielectric film. A laser beam of known polarization is reflected by the sample
which leads to a change in the polarization. The change depends on the thickness and
refractive index of the material. The fundamental equation of ellipsometry is given by
equation 5.
ρ = Rp/Rs = tan (Ψ)eiΔ (eq. 5)
Rp/Rs is the ratio of the amplitudes of the s and p components of the polarized light (s:
oscillation parallel to the sample surface; p: oscillation parallel to the plane of incidence),
tan(Ψ) is the amplitude ratio upon reflection and Δ is the phase shift. No calibration is
necessary as no absolute value is determined, but rather a ratio of two values. For
determination of the film thickness and refractive index, a model of stacked thin films is
compiled and fitted to the measured curve by an iterative procedure. Deviations between the
theoretical and experimental thickness are less than 1 nm.
Optical thickness measurements were performed by Martin Lemberger (Fraunhofer Institut

für Integrierte Schaltungen, Erlangen) using a Plasmos single-wavelength ellipsometer with
rotating analyzer at an angle of incidence of 70 ° and a He:Ne laser with a wavelength of
632.8 nm.
159
Atomic Force Microscopy [186]

AFM measurements were performed to collect information about the surface roughness of the
samples. The surface of the sample is scanned with a fine needle that is placed at the end of a
cantilever. The needle, normally fabricated from silicon carbide is moved up and downwards
by piezo electronic ceramics. Deflection of the cantilever is measured by the distraction of a
laser beam that is pointed onto the back of the cantilever.
The measurements in this work were performed by Dorothee Maier on a SPM (Scanning
Probe Microscope) Nanoscope IIIa AFM-instrument (Digital Instruments). The samples were
scanned in tapping mode (no continuous contact between the needle and the substrate). The
investigated area was 2x2 µm2.
X-ray photoelectron spectroscopy [187]

X-ray photoelectron spectroscopy measurements provide good information about the
composition of a characterized film. Al-Kα-radiation is emitted by an X-ray gun and focussed
on the sample surface. Core electrons of atoms in the uppermost few layers are removed from
the film. An attached electron detector registers the number of emitted electrons as a function
of their kinetic energy. Supposing that the well defined energy of the X-ray radiation (EX-ray)
is the sum of the kinetic energy of the electron (Ekin, electron) and the required energy to remove
the electron from a certain orbital, the ionization energy (IE) of the orbital can be calculated
as the difference of these two energies (IE = EX-ray – Ekin, electron). This energy is specific for a
certain element orbital and is slightly shifted depending on the coordination of the chemical
environment and binding state of the atom. Integration of the XPS-peaks (counts/s vs. binding
energy) and specific calibrations for each element provide reliable information about the
composition of the film. The estimated relative error of measurement is about ± 5 % of the
measured value, depending on the intensity of the analyzed peak. Reasons for this error are
the contribution of rests of gases in the vacuum to the intensity of the peaks (e.g. oxygen) and
problems with the internal calibration of the instrument.
Four Point Probe measurements after L. J. van der Pauw188

The van der Pauw method allows measurements of the specific resistivity of a flat sample of
arbitrary shape. Falsifications of the values by contact resistivities (surface/electrode) or
sample geometry can be excluded by this method. The sample is contacted by four probes (A,
B, C and D). A constant current is realized by two of the contacts (IAB) that results in a drop
160
of the potential between the other two contacts (VCD). This setup is alternated by exchanging
the contact electrodes. The resistivity of the film is given by:
ρ = [(π·t)/ln 2]·[0.5(RAB,CD + RBC,AD)]·f (eq. 6)
ρ = specific resistivity; f = correction factor, R = resistance; t = thickness of the sample.
The value for the specific resistivity has the dimension Ω·cm and can only be determined
when the thickness t of the film is known.
10.3 Details to MOCVD and ALD experiments
This chapter gives some information about special features with respect to the reactors that
were used in this work. A short description of each reactor was already given in 6.1. The large
wafer instrument in Erlangen and the Aixtron 200 FE reactor will not be discussed (all
experiments have been performed by Martin Lemberger (Erlangen) and Stephan Spöllmann
(Bochum)).
10.3.1 Wafer treatment
All samples were Si(100) wafers having a silicon dioxide layer of 20 nm. The SiO2-film was
thermally generated in an oxygen atmosphere and the thickness verified via ellipsometry
measurements. For the selfbuilt reactor, 150 mm wafers were cut to sizes of approximately
2.1 x 1.4 cm2. For the ALD-reactor, 150 mm wafers were cut to 5 x 5 cm2 sized samples.
Round 2-inch (5.08 cm) wafers were used for the Aixtron 200 FE reactor. The reactor in
Erlangen was loaded with up to two 150 mm wafers. Before loading the reactor, the wafers
were cleaned from dust particles in an argon stream. Further cleaning was not required,
supposing that the wafers were carefully treated during the cutting process.
10.3.2 Handling of the selfbuilt reactor
For preliminary experiments the selfbuilt horizontal coldwall reactor (figure 58)[176] was used.
After the sample was loaded into the reactor and the precursor-reservoir (bubbler) was
mounted to the setup, the whole system was evacuated by a turbo pump to a base pressure of
2.0 - 4.0·10-6 mbar. The nitrogen gas flow was set to the required flow rate whereby the
161
pressure in the reactor is regulated by a throttle valve. After all parts (substrate, heating tape,
airbath) had reached their temperature and are constant for at least 15 minutes, the deposition
was started by opening the teflon valves of the precursor reservoir. After the deposition, the
reactor was cooled down to room temperature before it was opened and the sample was
removed. Consumption of precursor was 50 - 200 mg per hour, depending on the type of
precursor and the conditions of evaporation. In order to determine the density of the films (or
the film thickness at given density), the weight gain of each sample was measured with an
accuracy of ± 0.00001 g. For example a 100 nm thick film of pure TaN (density 13.7 g/cm2)
on a 2.1 x 1.4 cm2 substrate showed a weight gain of 0.00044 g.
10.3.3 Handling of the ASM F-120 Reactor
After assembling of the reactor or a change of the reactor setup, leak tests were performed. A
mass spectrometer for helium was attached to the evacuated reactor and helium gas was
sprayed at all parts that are susceptible to leaks (valves and o-rings). The samples were
mounted in the quartz glass plates and the whole arrangement was inserted into the large glass
tube of the reactor. The reactor was then evacuated for at least half an hour at a nitrogen flow
of 400 sccm and afterwards flooded again with nitrogen. Precursor was filled into the
precursor boat in the glove box and covered with a piece of parafilm. The boat was inserted
into the reactor in a counter flow of nitrogen. Five temperature zones of the reactor (T1, T2,
T3, T4 and T5-T8) can be separately addressed by two thermocouples and one heating coil for
each zone. The precursor was by default placed in zone T2 while the reactor zone was T5-T8
(one zone). It was necessary to set T3 and T4 to temperatures above T2 to prevent
condensation of the precursor. Due to the massive character of the reactor quartz block of
setup II (weight: appr. 4 kg), a heating period of 3 hours was necessary until the target
temperature was reached.
10.4 General comments on synthesis and characterization
All manipulations of air- and moisture-sensitive compounds were performed on a

conventional vacuum/argon line using standard Schlenk techniques. Argon was purified over
CuI catalysts and dried over molecular sieve (4 Å). The Schlenk glassware (after Wilhelm
Schlenk, 1913 [189190]), used for the synthesis experiments was heated carefully under dynamic
vacuum prior to use. Preparations of samples for further analysis were carried out in argon
filled glove boxes. All solvents were purified by an MBraun solvent purification system (SPS)
and stored over activated molecular sieves (4Å). C6D6 and toluene-d8 were degassed and dried
162
over activated molecular sieves. Reagents were purchased from the following companies and
used without further purification:
Butyl-lithium (1.6 n solution in hexane, Merck)

Diethylamine (>99 % purity, Merck)
Methylethylamine (>97 % purity, Fluka)
Pyridine (Normapur grade, VWR)
Chlorotrimethylsilane (98 % purity, Acros)
Lithiumdimethylamide (95 % purity , Aldrich)
Diisopropylcarbodiimide (99 % purity, careful: very toxic, Acros)
Dicyclohexylcarbodiimide (99 % purity, Aldrich)
Ditertbutylcarbodiimide (99 % purity, Fluka)
Bistrimethylsilylcarbodiimide (98 %, Fluka)
Carbodiimide (Cyanamide, 98 %, Aldrich)
1,1-Dimethylhydrazine (98 % purity, Aldrich)
Methyllithium (5 weight % in Et2O, Merck)
Niobium(V)chloride (99.999 % purity, H.C. Starck)
Tantalum(V)chloride (99.999 % purity, H.C. Starck)
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10.5 Synthesis of the starting compounds S1-S11
10.5.1 Synthesis of the chloro-containing intermediate compounds S1 - S3
[TaCl3(N-t-Bu)(py)2] (S1). Compound S1 was synthesized by adding H2N-t-Bu (78.0

ml, 54.3 g, 738.0 mmol) and SiMe3Cl (45 ml, 38.5 g, 359 mmol) to an orange suspension of
TaCl5 (60.0 g, 167.5 mmol) in toluene (250 ml, 0°C). After 1 hour, stirring at room
temperature, pyridine (90 ml) was added to the slightly yellow solution. (excess required in
order to keep all compound solved). The precipitated salts were removed by filtration and the
filtrate was dried in vacuo. The resulting yellow, sulphur-like solid was recrystallized from
hot toluene (appr. 120 ml). Yield: 68.4 g (134 mmol, 80% based on [TaCl5]). TaCl3C14H19N3
(516.63): calcd. C 32.55, H 3.71, N 8.31, found: C 32.41, H 3.98, N 8.91 %; δH (25 °C, 250
MHz, C6D6) 1.52 (s, 9 H, N-C(CH3)3), 6.28 (m, 2 H, m-C6H5N), 6.49 (m, 2 H, m-C6H5N),
6.83 (m, 1 H, p-C6H5N), 6.89 (m, 1H, p-C6H5N), 8.94 (m, 2 H, o-C6H5N), 9.15 (m, 2 H, o-
C6H5N). δC (25 °C, 62.5 MHz, C6D6) 31.9 (N-C(CH3)3), 66.4 (N-C(CH3)3), 124.0, 124.1 (m-
C6H5N), 138.1, 139.4 (p-C6H5N), 151.8, 153.0 (o-C6H5N).
[TaCl3(N-n-Pr)(py)2] (S2). The synthesis followed the synthetic route of S1. The
employed amounts of starting material were as follows: TaCl5 (20 g, 55.83 mmol), toluene
(150 ml), n-propylamine (20.2 ml, 14.52 g, 246 mmol), SiMe3Cl (15 ml, 118 mmol), pyridine
(25 ml, 24.5 g, 310 mmol). Compared to S1, the purified solid compound S2 had a green-
yellow color. Yield: 22.2 g (44.2 mmol, 79 % based on [TaCl5]). TaCl3C13H17N3 (502.60):
calcd. C 31.13, H 3.39, N 8.38, found: C 31.14, H 3.67, N 8.67 %; δH (25 °C, 250 MHz, C6D6)
1.17 (t, 3 H, N-CH2CH2CH3), 1.77 (d of q, 2 H, N-CH2CH2CH3), 5.03 (t, 2 H, N-
CH2CH2CH3), 6.23 (m, 2 H, m-C6H5N), 6.46 (m, 2 H, m-C6H5N), 6.59 (m, 1 H, p-C6H5N),
6.78 (m, 1 H, p-C6H5N), 8.75 (m, 2 H, o-C6H5N), 9.20 (m, 2 H, o-C6H5N). δC (25 °C, 62.5
MHz, C6D6) 12.7 (N-CH2CH2CH3), 26.8 (N-CH2CH2CH3), 63.4 (N-CH2CH2CH3), 123.9,
124.1 (m-C6H5N), 137.9, 139.0 (p-C6H5N), 152.0, 152.7 (o-C6H5N). EI-MS (70 eV): m/z 345
(M+- 2 py, 2 %), 79 (py+), 52 (C4H4+).
[NbCl3(N-t-Bu)(py)2] (S3). The compound was synthesized by adding H2N-t-Bu (68

ml, 47.6 g, 651 mmol) and SiMe3Cl (40 ml, 34.2 g, 315 mmol) to an orange suspension of
NbCl5 (40.0 g, 148.0 mmol) in toluene (400 ml, 0 °C). After a stirring period of 30 minutes,
pyridine (85 ml) was added to the slightly yellow solution. The precipitated salts were
164
removed by filtration and the filtrate was dried in vacuo. The resulting yellow-orange solid
was recrystallized from hot toluene (200 ml). Yield: 43.2 g (100.1 mmol, 68.1 % based on
[NbCl5]). NbCl3C14H19N3 (428.58): calcd. C 39.23, H 4.47, N 9.80, found C 39.53, H 4.64, N
10.61 %; δH (25 °C, 250 MHz, C6D6) 1.47 (s, 9 H, N-C(CH3)3), 6.25, 6.49 (m, 2 x 2 H, m-
C6H5N), 6.62, 6.79 (m, 2 x 1 H, p-C6H5N), 8.94 (m, 2 H, o-C6H5N), 9.15 (m, 2 H, o-C6H5N).
δC (25 °C, 62.5 MHz, C6D6) 29.5 (N-C(CH3)3), not present (N-C(CH3)3), 123.7 (m-C6H5N),
137.7, 138.9 (p-C6H5N), 151.6, 152.9 (o-C6H5N). EI-MS (70 eV): m/z 79 (py+, 100 %).
10.5.2 Synthesis of the mixed amido / imido complexes S4 - S8
[Ta(NMe2)3(N-t-Bu)] (S4). The complex was synthesized by adding a suspension of

LiNMe2 (3.98 g, 78.0 mmol) in toluene (50 ml) to a yellow suspension of S1 (25.2 mmol,
13.0 g) in toluene (50 ml, -78 °C). The mixture was warmed up to room temperature and
stirred for 24 hours. A white precipitation (LiCl) was formed and could be removed by
filtration from the yellow solution. The solid, low melting compound was short-way sublimed
at 80 °C in vacuum. Yield: 4.65 g (12.1 mmol, 48 % based on [TaCl3(NtBu)py2]). TaN4C10H27
(384.30): no CHN analysis was performed, but the proton NMR spectrum showed no signs of
impurities. δH (25 °C, 250 MHz, C6D6) 1.44 (s, 9 H, N-C(CH3)3), 3.19 (s, 18 H, N(CH3)2).
[Ta(NMeEt)3(N-t-Bu)] (S5) The compound was synthesized by adding LiNMeEt (254

mmol freshly prepared from HNMeEt (21.8 ml, 15.3 g, 254 mmol) and BuLi (254 mmol)),
suspended in a toluene/hexane solution, to [TaCl3(N-t-Bu)py2] (43.8 g, 84.6 mmol),
suspended in toluene (200 ml). The temperature was reduced to -78 °C at all time while the
yellow suspension turns greenish-brown during reaction. After 24 hours of stirring at room
temperature, lithium chloride was removed by filtration and the filtrate was concentrated.
Distillation at 85 °C gave a slightly yellow liquid. Yield: 30.66 g (71.9 mmol, 85 % based on
[TaCl3(N-t-Bu)py2]). TaN4C13H33 (426.38): calcd. C 36.62, H 7.80, N 13.14; found C 36.74,
H 7.95, N 13.35 %; δH (25 °C, 250 MHz, C6D6) 1.13 (t, 9 H, N-CH2-CH3), 1.44 (s, 9 H, N-
C(CH3)3), 3.19 (s, 9 H, N-CH3), 3.47 (q, 6 H, N-CH2-CH3). δC (25 °C, 62.5 MHz, C6D6) 16.4
(N-CH2-CH3), 34.6 (N-C(CH3)3), 41.9 (N-CH3), 52.6 (N-CH2-CH3), 66.4 (N-C(CH3)3).
[Ta(NEt2)3(N-t-Bu)] (S6). The compound was synthesized by adding 402 mmol

LiNEt2 (freshly prepared from HNEt2 (42.1 ml, 403 mmol) and BuLi (402 mmol, 1.6 m
solution in hexane)), suspended in a toluene/hexane solution, to [TaCl3(N-t-Bu)py2] (69.17 g,
134.0 mmol), suspended in toluene (100 ml). The temperature was kept at -78 °C while the
165
yellow suspension turned brown during reaction. After 24 hours of stirring at room
temperature, lithium chloride was removed by filtration and the filtrate was concentrated.
Distillation at 90 °C gave a slightly yellow liquid. Yield: 50.2 g (107.2 mmol, 80 % based on
[TaCl3(N-t-Bu)py2]). TaN4C16H39 (468.46): calcd. C 41.02, H 8.38, N 13.14; found C 40.97,
H 8.53, N 12.07 %; δH (25 °C, 250 MHz, C6D6) 1.15 (t, 18 H, N-CH2-CH3), 1.44 (s, 9 H, N-
C(CH3)3), 3.48 (q, 12 H, N-CH2-CH3). δC (25 °C, 62.5 MHz, C6D6) 17.3 (N-CH2-CH3),
34.4 (N-C(CH3)3), 47.6 (N-CH2-CH3), 66.3 (N-C(CH3)3).
[Ta(NEt2)3(N-n-Pr)] (S7). A suspension of lithium diethylamide (62 mmol) was

prepared in situ by addition of 40 ml of a 1.6 M BuLi-solution (hexane) to diethylamine (7.5
ml, 62 mmol) at -60 °C. After stirring the reaction mixture for 24 hours at room temperature,
the resulting suspension was added to a suspension of S4 (10 g, 20.8 mmol) in hexane at
-60 °C. The reaction mixture slowly turned yellow/orange and was filtered after stirring for
additional 24 hours. The yellow/orange filtrate was concentrated in order to obtain the dark
orange product S7. Yield: 8.38 g (18.4 mmol, 92 % based on S4). C15H37N4Ta (454.43):
calcd. C 39.65, H 8.20, N 12.33; found: C 39.87, H 7.80, N 12.49 %. All analyses (NMR,
MS) were in accordance with the previously published results.
[Nb(NMe2)3(N-t-Bu)] (S8). Three equivalents of LiNMe2 (5.54 g, 108.5 mmol,

suspension in 50 ml hexane) were added to a suspension of [NbCl3(N-t-Bu)(py)2] (15 g, 35
mmol) in hexane (100 ml) at -60 °C. The color of the mixture slowly turned from yellow to
green/brown. After a period of 24 hours at room temperature, the solvent was removed and
the dark-green liquid was distilled under reduced pressure (90 °C, 0.01 mbar). A crystalline,
green-orange solid (S8) was collected. m.p. 55 °C (uncorrected). Yield: 8.86 g (84 %, 29.3
mmol, based on [NbCl3(N-t-Bu)(py)2]). C10H27N4Nb (296.26) calcd.: C 40.54, H 9.18, N
18.91; found: C 40.49, H 9.41, N 19.49 %. δH (25 °C, 250 MHz, C6D6) 1.41 (9 H, s,
NC(CH3)3), 3.18 (18 H, s, N(CH3)2). δC (25°C, 62.5 MHz, C6D6) 33.4 (NC(CH3)3), 47.0
(N(CH3)2). EI-MS (70eV): m/z 296 (M+ , 73 %), 281 (M+ -Me, 100), 253 (M+ -NMe2, 10), 58
(t-Bu+, 10), 44 (NMe2+, 28).
166
10.5.3 Synthesis of N-Trimethylsilyl-N’,N’-dimethylhydrazine
Reaction 1
Methyllithium (268 mmol, 168.5 ml of a 1.59 M solution of MeLi in Et2O) was slowly added
to a solution of N,N-dimethylhydrazine (16.1 g, 268 mmol) in Et2O (30 ml, -78 °C). The
solution was allowed to warm up and was stirred for 1 hour at room temperature. After
cooling it down to -78 °C SiMe3Cl (34.15 ml, 268 mmol) was added. After removal of the
cooling bath, the clear solution turned cloudy; LiCl was formed. The suspension was filtered
and diethylether was removed in vacuum (water jet pump). Fractionated distillation gave pure
Htdmh in the temperature range of 93-102 °C. At higher temperatures, the twofold substituted
product, (SiMe3)2N-NMe2 was formed. Yield 12.5 g (95 mmol, 35 % based on H2NNMe2).
Reaction 2
Trimethylchlorosilane (72 g, 0.66 mol) was slowly added to a solution of N,N-
dimethylhydrazine (60.1 g, 1 mol) in diethylether (300 ml). The solution was refluxed for 5
hours, followed by filtration of the sideproduct N,N-dimethylhydrazoniumchloride. Removal
of diethylether and fractionated distillation gave 58 g (88 %) of Htdmh. No impurities were
found in proton-nmr spectra of Htdmh. C5H16N2Si (132.26). δH (25 °C, 250 MHz, C6D6) 0.13
(s, 9 H, Si(CH3)3) 2.12 (s, 6 H, N(CH3)2)
10.6 Synthesis involving hydrazines (A1-A5 and further reactions)
Compounds A1-A3 were easy accessible due to the uncomplicated transamination reaction
that takes place between the starting complexes and the free Htdmh. High yields can be
achieved and the free amines can be easily removed at reduced pressure at room temperature.
10.6.1 Synthesis of A1-A4
[Ta(NMe2)2(tdmh)(N-t-Bu)] (A1) Tert-butylimido-bis(dimethylamido)-(N-trimethylsilyl-

N’,N’-dimethylamido)tantalum was synthesized by adding Htdmh (5.78 g, 43.7 mmol) to
[Ta(NMe2)3(N-t-Bu)] (14.0 g, 36.4 mmol), dissolved in hexane (20 ml). The yellowish
solution was stirred for 48 hours at room temperature. After all volatiles were removed in
vacuo, the colorless, viscous liquid (A1) could be obtained by distillation at 135 °C, 0.01
mbar. Crystals, suitable for single crystal X-ray diffraction were obtained from a high
concentrated solution of A1 in hexane at -20 °C. Yield 13.1 g (27.8 mmol, 77 %, based on
167
[Ta(NMe2)3(N-t-Bu)]). C13H36N5SiTa (471.50): calcd. C 33.12, H 7.70, N 14.85; found C

33.15, H 7.49, N 15.20 %. δH (25 °C, 250 MHz, C6D6) 0.31 (s, 9 H, N-Si(CH3)3), 1.52 (s, 9 H,
N-C(CH3)3), 2.41 (s, 6 H, N-N(CH3)2), 3.40 (s, 12 H, Ta-N(CH3)2). δC (25 °C, 62.5 MHz,
C6D6) 3.8 (N-Si(CH3)3), 34.7 (N-C(CH3)3), 49.3 (N-N(CH3)2), 51.3 (Ta-N(CH3)2), 64.3 (N-
C(CH3)3). EI-MS (70 eV): m/z 471 (M+, 3 %), 456 (M+ - CH3, 8), 73 (SiMe3+, 12), 58 (H-t-
Bu+, 77), 44 (NMe2+, 100).
[Ta(NEtMe)2(tdmh)(N-t-Bu)] (A2). The preparation of A2 followed exactly the synthetic

route of A1. Instead of [Ta(NMe2)3(N-t-Bu)] as the metal containing starting compound,
[Ta(NMeEt)3(N-t-Bu)] (14.8 g, 34.0 mmol) was used in the synthesis. An amount of 14.8 g
(40.8 mmol) Htdmh was added. The colorless, viscous liquid (6) was obtained by distillation
at 140 °C, 0.01 mbar. Yield 14.1 g, 83 % (28.2 mmol) (based on [Ta(NMeEt)3(N-t-Bu)]),
C15H40N5SiTa (499.55): calcd. C 36.02, H 8.07, N 14.02; found C 36.00, H 7.65, N 14.33 %.
δH (25 °C, 250 MHz, C6D6) 0.32 (s, 9 H, N-Si(CH3)3), 1.23 (t, 12 H, N(CH3)-CH2-CH3), 1.49
(s, 9 H, N-C(CH3)3), 2.42 (s, 6 H, N-N(CH3)2), 3.15 (s, 6 H, Ta-N(CH3)-CH2-CH3), 3.68-3.86
(m, 4 H, N(CH3)-CH2-CH3). δC (25 °C, 62.5 MHz, C6D6) 3.8 (N-Si(CH3)3), 16.9 (N(CH3)-
CH2-CH3), 34.7 (N-C(CH3)3), 42.8 (N(CH3)-CH2-CH3), 51.3 (N-N(CH3)2), 57.1 (N(CH3)-
CH2-CH3), 64.3 (N-C(CH3)3). EI-MS (70 eV): m/z 499 (M+, 2 %), 484 (M+ - CH3, 5), 73
(SiMe3+, 12), 58 (H-t-Bu+, 76), 44 (NMe2+, 100).
[Ta(NEt2)2(tdmh)(N-t-Bu)] (A3). The preparation of A3 on the whole followed the synthetic

route employed for A1 and A2. Instead of [Ta(NMe2)3(N-t-Bu)] as the metal containing
starting compound, [Ta(NEt2)3(N-t-Bu)] (9.23 g, 19.7 mmol) was used in the synthesis. In this
reaction, a high excess of Htdmh (10.41 g, 78.7 mmol) was added. The mixture was refluxed
for 5 days. The unreacted ligand and the solvent were removed in vacuo. The colorless,
viscous liquid (5) was obtained by distillation at 143 °C, 0.01 mbar. Yield 9.2 g, 88 % (17.3
mmol) (based on [Ta(NEt2)3(N-t-Bu)]). C17H44N5SiTa (527.61) calcd.: C 38.70, H 8.41, N
13.27; found: C 38.50, H 8.27, N 13.65 %. δH (25 °C, 250 MHz, C6D6) 0.34 (s, 9 H, N-
Si(CH3)3), 1.12 (t, 12 H, N-CH2-CH3), 1.49 (s, 9 H, N-C(CH3)3), 2.43. δC (25 °C, 62.5 MHz,
C6D6) 3.8 (N-Si(CH3)3), 17.4 (N-CH2-CH3), 34.7 (N-C(CH3)3), 49.2 (N-CH2-CH3), 51.3 (N-
N(CH3)2), 64.3 (N-C(CH3)3). EI-MS (70 eV): m/z 527 (M+, 40 %), 512 (M+- CH3, 100 ), 441
(M+ -(N-t-Bu) - CH3, 38), 73 (SiMe3+, 23), 58 (H-t-Bu+, 60), 44 (NMe2+, 100).
168
[Li(tdmh)py]2 (A4) [Bis{(pyridine)(N-trimethyl-N’,N’-dimethylhydrazido)lithium}]

Compound A4 was synthesized by adding n-butyl lithium (15.4 mmol, 9.68 ml of a 1.60
molar solution in hexane) to a cooled solution (-78 °C) of Htdmh (2.04 g, 15.4 mmol) and
pyridine (5.5 ml, 67.5 mmol) in 5 ml hexane. The solution turned red after warming up to
room temperature, was stirred for another 24 hours and then cooled down to -30 °C. The
compound crystallized in form of small, light brown crystals. m.p. 93 °C (uncorrected), yield
2.2 g, 64 % (based on Htdmh). C20H40N6Si2Li2 (434.60): calcd. C 55.27, H 9.28, N 19.34;
found: C 55.25, H 9.42, N 20.09 %. δH (25 °C, 250 MHz, C6D6) 0.36, 0.43 (s, 18 H, N-
Si(CH3)3), 2.67 (s, 12 H, N-N(CH3)2), 6.63 (d, 4 H, o-C5H5N), 6.91 (t, 1 H, p-C5H5N), 8.64 (t,
4 H, m-C5H5N). δC (25 °C, 62.5 MHz, C6D6) 5.7, 6.0 (N-Si(CH3)3), 53.8 (N-N(CH3)2), 133.0
(o-C5H5N), 136.6 (p-C5H5N), 149.9 (m-C5H5N). EI-MS (24 eV): m/z 284 (M+ -pyridine -
SiMe3, 8 %), 132 (Htdmh+, 26), 117 (Htdmh+ – Me, 17), 79 (pyridine+, 100), 73 (SiMe3+, 37),
52 (HNMe2Li+, 28).
10.6.2 Synthesis of A5
Dimethylhyrazine (1.28 g, 21.3 mmol) was directly added to TBTDET (S6, 1.0 g, 2.13
mmol). During addition, a clear, orange solution was formed. A sample was taken from the
solution for NMR-measurements. The sample (0.2 ml) was dried in vacuum and yielded an
orange powder. This powder was almost not soluble in C6D6, Et2O or CH2Cl2. The rest of the
solution (0.8 ml, S6 + Hdmh) was stored at -30 °C for 12 month. Slow diffusion of air into the
sealed Schlenk-flask led to the formation of crystalline A5. This synthesis could not be
reproduced.
10.6.3 Reactions with S6 (TBTDET) and dimethylhydrazine
Several reactions of S6 with Hdmh were carried out in an NMR tube. Various equivalents of
dimethylhydrazine were added to a solution of S6 in C6D6 (0.5 ml). When 3 or more
equivalents of Hdmh were added, decomposition and liberation of amines occurred too fast
for NMR-measurements. The following table (24) summarizes the experimental parameters.
Table 25. Reactions of S6 with Hdmh. The error in the masses was ± 3 mg.
S6 [Ta(NEt2)3(N-t-Bu)] Hdmh
60 mg (0.123 mmol) 7 mg (0.12 mmol)
60 mg (0.123 mmol) 15 mg (0.24 mmol)
60 mg (0.123 mmol) 22 mg (0.36 mmol)
60 mg (0.123 mmol) 29 mg (0.48 mmol)
169
10.6.4 Further reactions involving hydrazine derivatives
Li-tdmh was freshly prepared by addition of equimolar amounts of BuLi-solution to Htdmh,

dissolved in hexane (-78 °C). The addition of this solution to [TaCl3(N-t-Bu)py2] (S1) (in
toluene) was always carried out at -78 °C. The reaction parameters are listed in table 26. Both
products [Li(py)tdmh]2 (A4) and [Ta(tdmh)2Cl(N-t-Bu)] that were formed were volatile and very
soluble in toluene and hexane. Thus no complete separation was possible (15 % of A4
remained as impurities in [Ta(tdmh)2Cl(N-t-Bu)]). However, it was tried to replace the
remaining chloride at the tantalum complex by a reaction with LiNMe2 and LiNEt2, but no
reaction was observed, even after 4 days at 90 °C.
Table 26. Reactions of TaCl5 and [TaCl3(N-t-Bu)py2] with lithiated hydrazine derivatives.
Ta-reagent Hydrazine Comment
reagent
[TaCl3(N-t-Bu)py2] [Li-tdmh] White precipitate was formed; the overlaying solution was
(1.30 g; 2.52 mmol) (7.56 mmol) yellow orange. A4 ([Li(py)tdmh]2) crystallized from the
concentrated solution (2 ml) at -30 °C.
[TaCl3(N-t-Bu)py2] [Li-tdmh] Upsized batch of the previous reaction. In this case, the
(3.09 g; 6.0 mmol) (18 mmol) solution turned red during addition. The conversion to
([Ta(tdmh)2Cl(N-t-Bu)]) was not complete after 5 days at
room temperature.
[TaCl3(N-t-Bu)py2] [Li-tdmh] After five days at room temperature, the reaction was
(0.5 g; 0.96 mmol) (4.54mmol) complete and a mixture of A4 and ([Ta(tdmh)2Cl(N-t-Bu)])
was identified (orange solution over solid LiCl). It could not
be separated to a satisfying extend by fractionated
crystallization or sublimation.
[TaCl3(N-t-Bu)py2] [Li-tdmh] Upsized batch of the previous reaction. In this case, the
(2.0 g; 3.84 mmol) (19.36 mmol) solution turned brown/red during addition. Although larger
amounts were synthesized, complete separation was not
successful. (15% of impurities).
[TaCl5] [Li(py)tdmh]2 Although the reagents (dissolved in toluene) were cooled to
(0.36 g; 1 mmol) (2.5 mmol) -78 °C during addition, fast color change of the solution was
observed. A brown oil was obtained after removal of toluene
that consisted of a mixture of several SiMe3-containing
species (Proton-NMR).
[TaCl5] [Li-tdmh] Both reactions led to the formation of brown-red and green
(1.02 g; 2.85 mmol) (5.7 mmol) solutions. White solid precipitated (LiCl) during reaction.
After removal of the solvent (toluene) from the filtrated
[TaCl5] [Li-tdmh]
solutions brown oil was obtained. Again, NMR-
(0.41 g; 1.1 mmol) (5.9 mmol) spectroscopy indicated the presence of various species that
could not be separated.
170
10.7 Synthesis of the guanidinato-containing complexes of tantalum (B1-B8)
[Ta(NMe2){η2-(N-i-Pr)2C(NMe2)}2(N-t-Bu)] (B1) Two equivalents of diisopropylcarbo-

diimide (1.43 cm3, 1.15 g, 9.11 mmol) were added to a solution of [Ta(NMe2)3(N-t-Bu)] (1.75
g, 4.56 mmol) dissolved in hexane (20 ml). The temperature of the solution increased to about
45 °C during addition. After stirring the mixture for 24 hours, the solvent was partially
removed in vacuo and the solution was cooled to -30 °C. The product crystallized in form of
white, small crystallites from the colorless, clear solution. Filtration of the crystals and drying
in vacuo gave a white powder that could be sublimed at 130 °C/0.0001 mbar. m.p. 232 °C
(uncorrected), Yield: 2.61 g, 90% (based on [Ta(NMe2)3(N-t-Bu)]). C24H55N8Ta (636.65): C
45.27, H 8.71, N 17.60, found: C 45.22, H 9.00, N 17.83 %. δH (25 °C, 250 MHz, C6D6) 1.17,
1.18, 1.29, 1.31, 1.34, 1.37, 1.41, 1.61 (8 x d, 24 H, Ta{(N(CH(CH3)2))2C(NMe2)}), 1.55 (s, 9
H, Ta{NC(CH3)3}), 2.50, 2.55 (2 x s, 12 H, Ta{(N-i-Pr)2C(N(CH3)2)}), 3.55 (s, 3 H, Ta-
N(CH3)), 3.70, 3.82, 3.86, 4.04 (h, 4 x 1 H, Ta{(N(CH(CH3)2)2C(NMe2)}), 4.20 (s, 3 H, Ta-
N(CH3). δC (25 °C, 62.5 MHz, C6D6) 24.3, 24.6, 25.2, 25.7, 26.3, 26.3, 26.4, 27.1
(Ta{(N(CH(CH3)2)2C(NMe2)}), 35.1 (Ta{NC(CH3)3}), 40.1 (Ta{(N-i-Pr)2C(N(CH3)2)}),
46.0, 47.1, 47.4, 48.2 (Ta{(N(CH(CH3)2)2C(NMe2)}), 48.9, 59.0 (Ta{N(CH3)2}), 63.6
(Ta{NC(CH3)3}), 165.0, 169.3 (Ta{(N-i-Pr)2C(NMe2)}). EI-MS (70 eV): m/z 636 (M+ , 8 %),
593 (M+ -i-Pr, 17), 548 (M+ -i-Pr -HNMe2, 13), 467 (M+ -(N-i-Pr)2C(NMe2), 43), 424 (M+ -
(N-i-Pr)2C(NMe2) -i-Pr, 27), 171 (H(N-i-Pr)2C(NMe2) +, 4), 69 (C(N-i-Pr) +, 100), 43 (i-Pr+,
52).
[Ta(NMeEt){η2-(N-i-Pr)2C(NMeEt)}2(N-t-Bu)] (B2) The preparation of B2 followed the

synthetic route of B1. Instead of [Ta(NMe2)3(N-t-Bu)] as the metal containing starting
compound, [Ta(NMeEt)3(N-t-Bu)] (2.24 g, 5.25 mmol) was used in the synthesis.
Diisopropyl-carbodiimide (1.65 ml, 1.33 g, 10.51 mmol) was added. m.p. 217 °C
(uncorrected), Yield: 3.12 g, 87.4 % (based on [Ta(NMeEt)3(N-t-Bu)]). C27H61N8Ta (678.73):
C 47.78, H 9.06, N 16.51; found: C 47.90, H 9.26, N 16.8 %. Only the dominant isomeric
species is presented for 1H and 13C-NMR spectra. δH (25 °C, 250 MHz, C6D6) 0.91, 0.97 (2 x
t, 6 H, Ta{(N-i-Pr)2C(N(CH2CH3)Me)}), 1.07 (br, 3 H, Ta{(N(CH2CH3)Me)}), 1.15 (br, 3 H,
Ta{(N(CH(CH3)2)2-C(NEtMe)}), 1.26, 1.32, 1.34, 1.41, 1.44, 1.47, 1.63 (7 x t, 3 H,
Ta{(N(CH(CH3)2)2C(NEtMe)}), 1.55 (s, 9 H, Ta{N(C(CH3)3)}), 2.56 (s, 6 H, Ta{(N-i-
Pr)2C(NEt(CH3))}), 2.7-3.3 (m, 4 H, Ta{(N-i-Pr)2C(N(CH2CH3)Me)}), 3.1, 4.8 (br, 2 H,
Ta{N(CH2CH3)Me}), 3.77, 3.87, 3.90, 4.04 (4 x h, 4 H, Ta{(N(CH(CH3)2)2C(NEtMe)}), 4.24
171
(s, 3 H, Ta{NEt(CH3)}). δC (25 °C, 62.5 MHz, C6D6) 13.9 (Ta{(N-i-Pr)2C(N(CH2CH3)Me)}),

15.0 (Ta{(N(CH2CH3)Me)}), 24.4 (3x), 26.0, 26.3 (2x), 26.8, 28.3
(Ta{(N(CH(CH3)2))2C(NEtMe)}), 35.0 (Ta{N(C(CH3)3)}), 37.0 (Ta{(N-i-Pr)2C(NEt(CH3))}),
46.3, 47.4, 48.2 (2x) (Ta{(N(CH(CH3)2))2C(NEtMe)}), 47.1 (Ta{(N-i-
Pr)2C(N(CH2CH3)Me)}, 54.3 (Ta{N(CH2CH3)Me}), 54.6 (Ta{NEt(CH3)}), 63.8
(Ta{NC(CH3)3}), 166.1 (Ta{(N-i-Pr)2C(NMeEt)}). EI-MS (70 eV): m/z 678 (M+, 12 %), 621
(M -(t-Bu), 35), 495 (M+ -((N-i-Pr)2C(NEtMe)), 63), 452 (M+ -((N-i-Pr)2C(NEtMe)) -(i-Pr),
23).
[Ta(NEt2){η2-(N-i-Pr)2C(NEt2)}2(N-t-Bu)] (B3) The preparation of B3 followed the

synthetic route of B1. Instead of [Ta(NMe2)3(N-t-Bu)] as the metal containing starting
compound, [Ta(NEt2)3(N-t-Bu)] (1.83 g, 3.91 mmol) was used in the synthesis.
Diisopropylcarbodiimide (1.22 ml, 0.98 g, 7.82 mmol) was added. m.p. 210°C (uncorrected),
Yield 2.55 g, 91 % (based on [Ta(NEt2)3(N-t-Bu)]). C30H67N8Ta (720.81) calcd.: C 49.99, H
9.37, N 15.54. found: C 50.00, H 9.49, N 15.88 %. δH (25 °C, 250 MHz, C6D6) 0.89, 0.91,
1.03, 1.43 (4 x t,12 H, 2 x Ta{(N-i-Pr)2C(N(CH2CH3)2)}, 2 x Ta{N(CH2CH3)2}), 0.92-1.02
(br, 6 H, Ta{(N-i-Pr)2C(N(CH2CH3)2)}), 1.14, 1.26, 1.35, 1.37, 1.43, 1.49, 1.51, 1.66 (8 x d,
24 H, Ta{(N(CH(CH3)2))2C(NEt2)}), 1.55 (s, 9 H, Ta{NC(CH3)3}), 2.80-3.15 (m, 8 H,
Ta{(N-i-Pr)2C(N(CH2CH3)2)}), 3.44, 4.38, 4.63, 5.03 (4 x d of q, 4 H, Ta-N(CH2CH3)), 3.78,
3.88, 3.91, 4.04 (4 x h, 4 H, Ta{(N(CH(CH3)2))2C(NMe2)}) δC (25 °C, 62.5 MHz, C6D6) 13.4,
14.2, 15.4, 15.9 (2 x Ta{(N-i-Pr)2C(N(CH2CH3)2)}, 2 x Ta{N(CH2CH3)2}), 14.5, 15.2 (br,
Ta{(N-i-Pr)2C(N(CH2CH3)2)}), 24.1, 24.4, 24.8, 25.4, 26.0, 26.8, 27.1, 28.4
(Ta{(N(CH(CH3)2))2C(NEt2)}), 35.0 (Ta{NC(CH3)3}), 41.3, 42.5 (Ta{(N-i-
Pr)2C(N(CH2CH3)2)}), 43.2, 44.3 (br, Ta{(N-i-Pr)2C(N(CH2CH3)2)}), 46.5, 47.0, 48.1, 48.5
(Ta{(N(CH(CH3)2))2C(NEt2)}), 47.2, 58.1 (Ta{N(CH2CH3)2}), 64.0 (Ta{NC(CH3)3}), 166.1,
170.1 (Ta{(N-i-Pr)C(NEt2)}). EI-MS (70 eV): m/z 720 (M+, 10 %), 649 (M+ -(N-t-Bu), 100),
606 (M+ -(N-t-Bu) -(i-Pr), 37), 523 (M+ -((N-i-Pr)2C(NEt2)), 84), 480 (M +
-((N-i-
Pr)2C(NEt2))-(i-Pr), 27).
[Ta(NEt2){η2-(N-i-Pr)2C(NEt2)}2(N-n-Pr)] (B4) The synthesis of B4 followed in general the

same procedure as for B1 using [Ta(NEt2)3(N-n-Pr)] (1.83 g, 4.03 mmol) and di-iso-
propylcarbodiimide (1.01 g, 8.06 mmol). m.p. 195 °C (uncorrected). Yield: 2.39 g (3.38
mmol, 84 % based on [Ta(NEt2)3(N-n-Pr)]). C29H65N8Ta (706.84): calcd. C 49.28, H 9.27, N
15.85; found: C 49.28, H 9.17, N 16.10 %. δH (25 °C, 250 MHz, C6D6) 0.89 (t, 1J = 6.9 Hz, 3
172
H, Ta(NCH2CH2CH3)), 0.91, 2 x 0.96, 1.06, 1.07, 1.47 (6 x t, 1J = 6.7, 2 x 7.0, 7.4, 6.8, 7.0
Hz, 6 x 3 H, 4 x Ta{(N-i-Pr)2C(N(CH2CH3)2)} and 2 x TaN(CH2CH3)2), 1.16, 1.23, 1.35,
1.38, 2 x 1.40, 1.47, 1.58 (8 x d, 1J = 6.4, 6.4, 6.5, 6.0, 2 x 6.0, 6.4, 6.5 Hz, 24 H,
Ta{(N(CH(CH3)2))2C(NEt2)}), 1.72 (sextet, 1J = 7.3 Hz, 2 H, Ta (NCH2CH2CH3)), 2.80-3.15
(m, 8 H, Ta{(N-i-Pr)2C(N(CH2CH3)2)}), 3.41, 4.25, 4.59, 4.73 (4 H, 1J = 6.3, 6.0, 6.0, 5.9 Hz,
4 x d of q, TaN(CH2CH3)), 3.76, 3.87, 3.94, 4.10 (4 x septet, 1J = 6.5, 6.4, 6.4, 6.5 Hz, 4 H,
1
Ta{(N(CH(CH3)2))2C(NEt2)}), 4.31, 4.37 (2 x d of t, J = 6.8, 6.7 Hz, 2 H,
Ta(NCH2CH2CH3)). δC (25 °C, 62.5 MHz, C6D6) 12.40 (Ta(NCH2CH2CH3)), 13.6, 14.0, 14.8,
15.7, 17.0 (Ta{(N-i-Pr)2C(N(CH2CH3)2)} and TaN(CH2CH3)) 23.5, 24.5, 25.0, 25.2, 25.9,
26.1, 26.5, 28.0 (Ta{(N(CH(CH3)2))2C(NEt2)}), 28.5 (Ta(NCH2CH2CH3)), 41.4, 42.3, 43.7
(br) (Ta{(N-i-Pr)2C(N(CH2CH3)2)}), 46.8, 56.7 (TaN(CH2CH3), 47.2, 47.5, 48.4, 48.8
(Ta{(N(CH(CH3)2))2C(NEt2)}), 61.9 (Ta(NCH2CH2CH3)), 166.5, 170.3 (Ta{(N(i-
Pr)2C(NEt2)}). EI-MS (70 eV): m/z 706 (M+, 12 %), 635 (M+-NEt2, 79), 509 (M+ -
guanidinate-ligand, 100), 466 (M+ - guanidinate-ligand, - i-Pr, 29), 407 (calcd. 409) ((M+ -
guanidinate-ligand, - i-Pr, -N-Pr (i or n), 10), 198 (guanidinate-ligand+, 4), 141 (N(i-
Pr)2C(NH)+, 15), 126 ( i-Pr-N=C=N-i-Pr+, 5), 69 (i-Pr-N-C+, 34), 58 (HN-Pr+, 10), 43 (i-Pr,
10).
[Ta(NMe2){η2-(N-cy)2C(NMe2)}2(N-t-Bu)] (B5) Diicyclohexylcarbodiimide (1.52 g, 7.83

mmol) in hexane (20 ml) was added to a solution of [Ta(NMe2)3(N-t-Bu)] (1.55 g, 4.03
mmol) dissolved in hexane (40 ml). The temperature of the solution increased to about 45 °C
during addition, no color change was observed. After stirring the mixture for 24 hours, the
solvent was removed in vacuo. Small, white crystallites, suitable for X-ray analysis were
obtained by recrystallization the crude product from toluene. m.p. 210 °C (uncorrected).
Yield: 2.73 g (3.43 mmol, 85 % based on [Ta(NMe2)3(N-t-Bu)]). C36H71N8Ta (796.96): calcd.
C 45.27, H 8.71, N 17.60; found: C 45.22, H 9.00, N 17.83 %. δH (25 °C, 250 MHz, C6D6)
1.30-2.10 (m, cyclohexyl), 1.58 (s, 9 H, Ta{NC(CH3)3}), 2.58, 2.62 (2 x s, 2 x 6 H, Ta{(N-
cy)2C(N(CH3)2)}), 3.2-3.7 (m, 4 H, cyclohexyl, N-C-H) 3.59 (s, 3 H, Ta-N(CH3)2), 4.20 (s, 3
H, Ta-N(CH3)2). δC (25 °C, 62.5 MHz, C6D6) 26.2, 26.5, 26.6 (2x), 26.7 (3x), 27.1 (2x), 27.2,
27.4(2x) (cyclohexyl, 3,4-position), 35.2 (Ta{NC(CH3)3}), 34.3, 34.5, 35.2, 36.3, 36.6, 37.0,
37.1, 37.5 (cyclohexyl, 2-position), 40.3 (Ta{(N-cy)2C(N(CH3)2)}), 49.1, 59.3
(Ta{N(CH3)2}), 55.1, 56.0, 57.3, 57.5 (cyclohexyl, N-C), 63.6 (Ta{NC(CH3)3}), 164.8, 169.3
(Ta{(N-cy)2C(NMe2)}). EI-MS (70 eV): m/z 796 (M+ , 0.5 %), 590 (M+ –cy-cdi, 15), 206 (cy-
173
cdi+, 25), 124 (cy-N=C=N-H+, 45), 83 (cy+, 80), 55 (C4H7+, 100), 43 (C3H7+, 70), 41 (C3H5+,
75).
[Ta(NEtMe){ η2-(N-cy)2C(NEtMe)}2(N-t-Bu)] (B6) The synthesis of B6 followed the same

procedure as for B5 using [Ta(NEtMe)3(N-t-Bu)] (1.72 g, 4.03 mmol) and
dicyclohexylcarbodiimide (1.52 g, 7.83 mmol). m.p. 218 °C (uncorrected). Yield: 2.77 g (3.30
mmol, 82 % based on [Ta(NEtMe)3(N-t-Bu)]). C39H77N8Ta (839.03): calcd. C 53.98, H 9.25,
N 13.36; found: C 53.62, H 9.34, N 13.48 %. δH (25 °C, 250 MHz, C6D6) 0.9-1.1 (3 x q, 3 x 3
H, 2x Ta{(N-cy)2C(N(CH2CH3)Me)} and Ta{N(CH2CH3)Me}), 1.10-2.10 (m, cyclohexyl),
1.57 (s, 9 H, Ta{NC(CH3)3}), 2.62, 2.63, 2.64 (no assignment possible, most probably Ta{(N-
cy)2C(N(CH3)Et)}), 2.9-3.7 (m, cyclohexyl, N-C-H, Ta{(N-cy)2C(N(CH2CH3)Me)} and
Ta{N(CH2CH3)Me}), 4.25 (s, 3 H, Ta{NEt(CH3)}), δC (25°C, 62.5 MHz, C6D6) 14.0 (Ta{(N-
cy)2C(N(CH2CH3)Me)}), 15.2 (Ta{(N(CH2CH3)Me)}), 35.4 (Ta{N(C(CH3)3)}), 54.5, 54.6
(Ta{N(CH2CH3)Me} and Ta{NEt(CH3)}), 63.8 (Ta{NC(CH3)3}), 166.1 (Ta{(N-
cy)2C(NMeEt)}) Peaks that cannot be clearly assigned: 26.0, 26.7, 27.1, 27.3 27.5, 24.4, 35.1,
36.6., 37.0, 56.5, 57.4. EI-MS (70eV): EI-MS (70 eV): m/z 576 (M+ – guanidinate-ligand
3 %), 265 (guanidinate-ligand+, 10), 206 (cy-cdi+, 10), 163 (cy-cdi+ – C3H7, 37), 124 (cy-
N=C=N-H+, 35), 83 (cy+, 67), 55 (C4H7+, 97), 43 (C3H7+, 100), 41 (C3H5+, 97).
[Ta(NEt2){η2-(N-cy)2C(NEt2)}2(N-t-Bu)] (B7). The synthesis of B7 followed the same

procedure as for B5 using [Ta(NEt2)3(N-t-Bu)] (1.89 g, 4.03 mmol) and
mmol, 87 % based on [Ta(NEt2)3(N-t-Bu)]). C42H83N8Ta (881.11): calcd. C 57.25, H 9.49, N
12.72; found: C 57.41, H 10.18, N 11.96 %. δH (25°C, 250 MHz, C6D6) 0.9-1.1 (m, 12 H, 4 of
6 CH3 groups of Ta{(N-cy)2C(N(CH2CH3)2)}and Ta{N(CH2CH3)2}), 1.40, 1.46 (m, 2 of 6
CH3 groups of Ta{(N-cy)2C(N(CH2CH3)2)} and Ta{N(CH2CH3)2}), 1.20-2.20 (m,
cyclohexyl), 1.58 (s, 9 H, Ta{NC(CH3)3}), 2.9-3.2 (m, 8 H, Ta{(N-i-Pr)2C(N(CH2CH3)2)}),
3.30-3.70 (m, 4 H, cyclohexyl, N-C-H, and 1H, Ta-N(CH2CH3)), 4.44, 4.66, 5.00 (3 x d of q,
1
J = 6.5, 6.2, 6.3 Hz, 3 x 1 H, Ta-N(CH2CH3)). δC (25 °C, 62.5 MHz, C6D6) 13.5, 14.3, 15.7,
15.9 (Ta{(N-cy)2C(N(CH2CH3)2)} and TaN(CH2CH3)) 26.0, 26.5, 26.6 (2x), 26.7, 26.8 (2x),
26.9, 27.2, 27.3, 27.5, 27.6 (cyclohexyl, 3,4-position), 34.0, 34.5, 34.6, 35.9, 36.4, 37.1, 37.6,
38.7 (cyclohexyl, 2-position), 35.2 ((Ta{NC(CH3)3}), 41.5, 43.0, 43.1 (br), 44.6 (br) (Ta{(N-
cy)2C(N(CH2CH3)2)}), 47.5, 58.1 (TaN(CH2CH3), 55.6, 56.2, 57.5, 58.8 (cyclohexyl, N-C),
64.1 (Ta{NC(CH3)3}), 166.2, 170.2 (Ta{(N-cy)2C(NEt2)}). EI-MS (70 eV): m/z 810 (M+ -
174
NEt2, 3 %), 604 (calc. 605) (M+-cy-cdi, 3), 206 (cy-cdi+, 27), 163 (cy-cdi+ – C3H7, 48), 124
(cy-N=C=N-H+, 44), 83 (cy+, 81), 55 (C4H7+, 100), 43 (C3H7+, 70), 41 (C3H5+, 71).
[Ta(NEt2){η2-(N-cy)2C(NEt2)}2(N-n-Pr)] (B8). The synthesis of B8 followed the same

procedure as for B5 using [Ta(NEt2)3(N-n-Pr)] (1.83 g, 4.03 mmol) and
mmol, 65 % based on [Ta(NEt2)3(N-n-Pr)]). C41H81N8Ta (866.61): calcd. C 56.80, H 9.41, N
12.92; found: C 56.13, H 10.04, N 13.20 %. Small amounts of unreacted cy-cdi probably
caused the deviation of the value for the carbon content. δH (25 °C, 250 MHz, C6D6) 0.97,
0.98, 2 x 1.02, 1.08, 1.09 (6 x t, coupling constants cannot not been determined properly, 18
H, Ta(NCH2CH2CH3), 3 x Ta{(N-cy)2C(N(CH2CH3)2)} and 2 x Ta(N(CH2CH3)2)), 1.49 (t, 1J
= 7.1 Hz, 3 H, Ta{(N-cy)2C(N(CH2CH3)2)}), 1.73 (m, Ta (NCH2CH2CH3)), 1.2-2.3 (m,
cyclohexyl), 2.90-3.20 (m, 8 H, Ta{(N-cy)2C(N(CH2CH3)2)}), 3.30-3.80 (m, 5 H, 4 x
cyclohexyl (N-C-H) and 1 x Ta(N(CH2CH3)2)), 4.25-4.50 (m, 3 H, 2 x Ta(NCH2CH2CH3) + 1
x Ta(N(CH2CH3)2)), 4.62, 4.76 (2 x sextet, 1J = 5.8, 6.0 Hz, 2 H, Ta(N(CH2CH3)2)). δC (25°C,
62.5 MHz, C6D6) 12.56 (Ta(NCH2CH2CH3)), 13.6, 13.9, 14.90 (br), 15.9, 16.8 (Ta{(N-
cy)2C(N(CH2CH3)2 and TaN(CH2CH3)), 26.5, 2 x 26.6, 26.7, 26.8, 26.9, 2 x 27.0, 2 x 27.1,
27.5, 27.6, 28.5 (12 x cyclohexyl (3,4-position), 1 x (Ta(NCH2CH2CH3)), 33.5, 34.8, 35.7,
35.8, 36.6, 2 x 36.7 (cyclohexyl, 2-position), 39.1, 41.5, 42.5, 44.0 (br) (Ta{(N-
cy)2C(N(CH2CH3)2)}), 47.5 (1 x TaN(CH2CH3)2), 55.7 55.9, 56.2, 56.9, 58.0, 58.3 (1 x
TaN(CH2CH3)2, 4 x cyclohexyl (N-C)), 62.0 (Ta(NCH2CH2CH3)), 166.6, 170.3
(Ta{(N(cy)2C(NEt2)}). Small amounts of free cy-cdi were found in the 13C-NMR spectrum of
this compound. EI-MS (70eV): m/z 795 (calc. 794) (M+-NEt2, 0.5%), 589 (calc. 588) (M+ -
guanidinate, 0.5), 206 (cy-N=C=N-cy+, 20), 82 (cy+, 61), 56 (100), 55 (C4H7+), 43 (C3H7+,
60), 41 (C3H5+, 67).
10.8 Synthesis of the guanidinato-containing complexes of niobium (C1-C4)
[Nb(NMe2){(N-i-Pr)2C(NMe2)}2(N-t-Bu)] (C1). Two equivalents of diisopropylcarbo-

diimide (4.4 ml, 3.6 g, 28.25 mmol) were added to a solution of [Nb(NMe2)3(N-t-Bu)] (4.0 g,
13.5 mmol) dissolved in hexane (20 ml). The temperature of the solution increased to about
45 °C during addition. After stirring the mixture for 24 hours, the solvent was completely
removed in vacuo. The white, crude product was recrystallized from hot toluene. It
crystallized in form of white, small crystallites from the colorless, clear solution. Filtration of
175
the crystals and drying in vacuo gave a white powder that can be sublimed at 130 °C/0.001
mbar. m.p. 211 °C (uncorrected), Yield 6.38 g (86 %, based on [Nb(NMe2)3(N-t-Bu)]), calcd.
C24H55N8Nb (548.66): calcd. C 52.36, H 11.79, N 20.44; found: C 52.43, H 11.08, N 20.43 %.
δH (25 °C, 250 MHz, C6D6) 1.19, 1.22, 1.28, 1.29, 1.35, 1.36, 1.38, 1.56 (8 x d, 24 H,
Nb{(N(CH(CH3)2))2C(NMe2)}), 1.51 (s, 9 H, Nb{NC(CH3)3}), 2.53, 2.58 (2 x s,12 H,
Nb{(N-i-Pr)2C(N(CH3)2)}), 3.50 (s, 3 H, Nb-N(CH3)), 3.68, 3.70, 3.76, 3.88 (h, 4 x 1 H,
Nb{(N(CH(CH3)2)2C(NMe2)}), 4.05 (s, 3 H, Nb-N(CH3). δC (25 °C, 62.5 MHz, C6D6) 24.5,
24.8, 25.4, 25.9, 26.3, 2 x 26.5, 27.0 (Nb{(N(CH(CH3)2)2C(NMe2)}), 33.5 (Nb{NC(CH3)3}),
40.2 (Nb{(N-i-Pr)2C(N(CH3)2)}), 46.3, 47.3, 47.7, 48.4 (Nb{(N(CH(CH3)2)2C(NMe2)}), 49.6,
59.7 (broad, Nb{N(CH3)2}), 165.9, 169.5 (Nb{(N-i-Pr)2C(NMe2)}). EI-MS (70eV): m/z 548
(M+, 1 %), 503 (M – HNMe2, 17), 378 (M+ - (N-i-Pr)2C(NMe2), 100), 170 ((N-i-
Pr)2C(NMe2)+, 5), 111 (30), 43 (i-Pr+, 18).
[Nb(NEt2){(N-i-Pr)2C(NEt2)}2(N-t-Bu)] (C2). The preparation of C2 followed the synthetic

route of C1. Instead of [Nb(NMe2)3(N-t-Bu)] as the metal containing starting compound,
[Nb(NEt2)3(N-t-Bu)] (1.55 g, 4.18 mmol) was used in the synthesis. 1.28 ml (1.05 g, 8.72
mmol) diisopropylcarbodiimide was added. m.p. 184 °C (uncorrected), yield 2.1 g (79 %,
based on [Nb(NEt2)3(N-t-Bu)]). C30H67N8Nb (632.82): calcd. C 56.94, H 10.67, N 17.81;
found: C 56.65, H 10.80, N 17.81 %. δH (25 °C, 250 MHz, C6D6) 0.90, 0.94, 1.04, 1.40 (4 x t,
12 H, 2 x Nb{(N-i-Pr)2C(N(CH2CH3)2)}, 2 x Nb{N(CH2CH3)2}), 0.90-1.05 (br, 6 H, Nb{(N-
i-Pr)2C(N(CH2CH3)2)}), 1.17, 1.28, 2 x 1.36, 1.43, 1.44, 1.46, 1.64 (8 x d, 24 H,
Nb{(N(CH(CH3)2))2C(NEt2)}), 1.51 (s, 9 H, Nb{NC(CH3)3}), 2.80-3.20 (m, 8 H, Nb{(N-i-
Pr)2C(N(CH2CH3)2)}), 3.29, 4.22, 4.83, 4.96 (4 x d of q, 4 H, Nb-N(CH2CH3)), 3.60-3.90 (m,
4 H, Nb{(N(CH(CH3)2))2C(NMe2)}) δC (25 °C, 62.5 MHz, C6D6) 13.6, 14.4, 15.2, 15.5 (2 x
Nb{(N-i-Pr)2C(N(CH2CH3)2)}, 2 x Nb{N(CH2CH3)2}), 24.4, 24.5, 24.9, 25.7, 26.2, 26.9,
27.0, 28.3 (Nb{(N(CH(CH3)2))2C(NEt2)}), 33.5 (Nb{NC(CH3)3}), 41.5, 42.7 (Nb{(N-i-
Pr)2C(N(CH2CH3)2)}), 46.8, 47.1, 48.2, 48.7 (Nb{(N(CH(CH3)2))2C(NEt2)}), 48.3, 59.2 (br,
Nb{N(CH2CH3)2}), 166.8, 170.1 (Nb{(N-i-Pr)C(NEt2)}). EI-MS (70 eV): m/z 561 (calcd.
560) (M+ -NEt2, 6 %), 434 (M+ - guanidinate, 6), 127 (126) (i-Pr-cdi+, 6), 59 (58) (HN-i-Pr+,
100), 44 (43) (i-Pr+, 57).
[Nb(NMe2){(N-cy)2C(NMe2)}2(N-t-Bu)] (C3). Two equivalents of diicyclohexyl-

carbodiimide (1.50 g, 7.1 mmol), dissolved in hexane (20 ml) were added to a solution of
[Nb(NMe2)3(N-t-Bu)] (1.00 g, 3.37 mmol) dissolved in hexane (20 ml). After stirring the
176
mixture for 24 hours, the solvent was removed in vacuo to yield a yellow, microcristalline
powder. m.p. 210 °C (uncorrected), Yield 1.96 g (2.76 mmol, 82 % (based on [Nb(NMe2)3(N-
t-Bu)]). C36H71N8Nb (708.11): C 60.99, H 10.10, N 15.80. found: C 59.63, H 9.93, N
15.97 %. Small amounts of unreacted cy-cdi probably caused the deviation of the value for
the carbon content. δH (25 °C, 250 MHz, C6D6) 1.30-2.10 (m, cyclohexyl), 1.54 (s, 9 H,
Nb{NC(CH3)3}), 2.61, 2.64 (2 x s,12 H, Nb{(N-cy)2C(N(CH3)2)}), 3.1-3.5 (m, 4 H,
cyclohexyl, N-C-H) 3.54 (s, 3 H, Nb-N(CH3)2), 4.06 (s, 3 H, Nb-N(CH3)2). δC (25 °C, 62.5
MHz, C6D6) 26.3, 26.6, 2 x 26.7, 3 x 26.8, 27.1, 2 x 27.2, 2 x 27.4 (cyclohexyl, 3- and 4-
position), 33.7 (Nb{NC(CH3)3}), 34.6, 34.7, 35.3, 36.7, 37.0, 37.2, 37.3, 37.6 (cyclohexyl, 2-
position), 40.4 (Nb{(N-cy)2C(N(CH3)2)}), 49.8, 59.9 (broad, Nb{N(CH3)2}), 55.4, 56.2, 57.6,
57.7 (cyclohexyl, N-C), 165.6, 169.5 (Nb{(N-cy)2C(NMe2)}). EI-MS (70 eV) m/z: 665 (M+ -
NMe2 2 %), 458 (M+ - guanidinate, 8), 206 ( cy-cdi, 38), 163 (cy-cdi+ -C3H7 ,59) 124 (cy-cdi+
-cy, 33), 83 (cy+ 65), 55 (C4H7+ 100), 43 (C3H7+, 72), 41 (C3H5+, 62).
[Nb(NEt2){(N-cy)2C(NEt2)}2(N-t-Bu)] (C4). The synthesis of C4 followed exactly the same

procedure as for C3. Instead of [Nb(NMe2)3(N-t-Bu)] as the metal containing starting
compound, [Nb(NEt2)3(N-t-Bu)] (1.55 g, 4.18 mmol) was used in the synthesis. 1.55 g (7.98
mmol) dicyclohexylcarbodiimide was added. m.p. 197 °C (uncorrected), Yield 72 % (3.02
mmol, 2.4g) based on [Nb(NEt2)3(N-t-Bu)]). C42H83N8Nb (792.27): C 63.61, H 10.55, N
14.13; found: C 63.44, H 10.87, N 14.43 %. δH (25 °C, 250 MHz, C6D6) 0.9-1.1 (m, 12 H, 4 of
6 CH3 groups of Nb{(N-cy)2C(N(CH2CH3)2)} and Nb{N(CH2CH3)2}), 1.20-2.20 (m,
cyclohexyl and the remaining two triplets of Nb{(N-cy)2C(N(CH2CH3)2)}), 1.55 (s, 9 H,
Nb{NC(CH3)3}), 2.9-3.2 (m, 8 H, Nb{(N-i-Pr)2C(N(CH2CH3)2)}), 3.2-3.50 (m, 4 H,
cyclohexyl, N-C-H, and 1H, Nb-N(CH2CH3)), 4.27, 4.88, 4.91 (3 x d of q, 3 H, Nb-
N(CH2CH3)). δC (25 °C, 62.5 MHz, C6D6) 13.6, 14.4, 15.4, 15.6 (Nb{(N-
cy)2C(N(CH2CH3)2)} and NbN(CH2CH3)) 26.1, 2 x 26.6, 26.7, 26.8, 3 x 26.9, 27.2, 27.3,
27.4, 27.6 (cyclohexyl, 3- and 4-position), 33.7 ((Nb{NC(CH3)3}), 34.3, 34.7, 34.8, 36.2,
36.6, 37.2, 37.7, 38.8 (cyclohexyl, 2-position), 41.7, 43.2 (Nb{(N-cy)2C(N(CH2CH3)2)}),
48.6, 59.2 (NbN(CH2CH3), 55.9, 56.3, 57.6, 58.9 (cyclohexyl, N-C), 166.8, 170.2 (Nb{(N-
cy)2C(NEt2)}). EI-MS (70 eV): m/z 514 (M+ - guanidinate, 11 %), 279 (calcd. 278)
(guanidinate+, 10), 206 (cy-cdi+, 32), 163 (cy-cdi+ – C3H7, 52), 124 (cy-N=C=N-H+, 45), 83
(cy+, 83), 55 (C4H7+, 100), 43 (C3H7+, 85), 41 (C3H5+, 75).
177
10.9 Crystallographic data
In this section, the crystallographic data of the following compounds are presented (see
below). For the data that was already published, the CCDC - number is given. The labeling of
the structures that can be found in the CCDC database (Cambridge Crystallographic Data
Centre) do not necessarily match the labeling in this work.
S3’ not yet registered

S8 not yet registered
A1 CCDC: 282096
A4 CCDC: 282097
A5 not yet registered
B1 CCDC: 266742
B2 CCDC: 611058
B3 CCDC: 611059
B4 CCDC: 611062
B5 CCDC: 611060
B7 CCDC: 611061
C1 not yet registered
C2 not yet registered
178
10.9.1 Crystallographic data of S3’ and S8
Table 27. Crystallographic data of S3’ and S8.

S3’ S8
Empirical formula C42Cl3H54N6Nb2O C10H27N4Nb
Formula mass 986.53 296.27
T [K] 111(2) 111(2)
Crystal system monoclinic trigonal
Space group P21/c R(-3)
a [Ǻ] 16.547(6) 11.208(19)
b [Ǻ] 15.358(15) 11.208(19)
c [Ǻ] 21.044(18) 21.16(2)
α [°] 90 90
β [°] 120.13(5) 90
γ [°] 90 120
3
V [Ǻ ] 4625(6) 2302(6)
Z 4 6
-3
Density (calcd.) [g cm ] 1.417 1.282
-1
μ(Mo-Kα) [mm ] 0.764 0.766
Tmax./Tmin. 0.957/0.899 0.930/0.853
F(000) 2023 936
Crystal size [mm] 0.09 x 0.06 x 0.02 0.12 x 0.08 x 0.05
θ range [°] 2.95 – 25.08 3.64 – 25.99
Completeness to θ [%] 99.5 99.6
-19≤h≤15 -13≤h≤13
Index ranges -18≤k≤17 -13≤k≤13
-25≤l≤24 -26≤l≤25
Reflections collected 37047 10657
Independent reflections 8186 1006
Data/restraints/parameters 8186/7/491 1006/0/60
2
Goodness-of-fit on F 1.193 1.124
R indices [I > 2σ(I)] R1 0.0898 0.0338
wR2 0.1699 0.0749
R indices (all data) R1 0.1264 0.0420
wR2 0.1884 0.0786
-3
Largest diff. peak/hole [e Ǻ ] 3.895/-1.063 0.634/-0.851
179
10.9.2 Crystallographic data of A1, A4 and A5
Table 28. Crystallographic data of A1, A4 and A5.

A1 A4 A5
Empirical formula C13H36N4SiTa C10H20LiN3Si C14H44N14O1Ta2
Formula mass 636.71 217.32 786.53
T [K] 105(2) 203(2) 108(2)
Crystal system monoclinic monoclinic triclinic
Space group P21/c P21/c P-1
a [Ǻ] 9.3189(7) 9.063(7) 11.4714(9)
b [Ǻ] 33.5381(18) 19.277(8) 11.9075(7)
c [Ǻ] 13.6538(4) 8.008(3) 12.5753(9)
α [°] 90 90 86.575(5)
β [°] 102.595(6) 105.113(10) 65.631(7)
γ [°] 90 90 66.801(6)
3
V [Ǻ ] 4164.6(5) 1364.0(10) 1427.28(17)
Z 8 4 2
-3
Density (calcd.) [g cm ] 1.504 1.058 1.83017
-1
μ(Mo-Kα) [mm ] 5.366 0.146 7.692
F(000) 1888 472 760
Crystal size [mm] 0.20 x 0.15 x 0.08 0.4 x 0.35 x 0.25 not determined
θ range [°] 3.03 – 27.56 2.33 - 25.07 3.48 – 27.50
Completeness to θ [%] 94.9 99.4 98.2
-11≤h≤11 -10≤h≤10 -14≤h≤14
Index ranges -43≤k≤43 -11≤k≤22 -15≤k≤15
-17≤l≤17 -9≤l≤9 -16≤l≤16
Reflections collected 32885 7796 26558
Independent reflections 9121 2408 6490
Data/restraints/parameters 9121/0/385 2408/0/155 6490/18/269
2
Goodness-of-fit on F 1.104 1.019 1.154
R indices [I > 2σ(I)] R1 0.0667 0.0511 0.0478
wR2 0.1155 0.1135 0.1177
R indices (all data) R1 0.0860 0.0988 0.0613
wR2 0.1213 0.1315 0.1238
-3
Largest diff. peak/hole [e Ǻ ] 3.819/-2.136 0.235/-0.320 6.637/-2.825
180
10.9.3 Crystallographic data of B1-B5 and B7
Table 29. Crystallographic data of B1-B3.

B1 B2 B3
Empirical formula C24H55N8Ta C27H61N8Ta C30H67N8Ta
Formula mass 636.71.79 678.79 720.87
T [K] 105(2) 108(2) 105(2)
Crystal system orthorhombic orthorhombic orthorhombic
Space group Pbca Pbca Pbca
a [Ǻ] 9.5129(11) 10.7124(7) 11.4691(11)
b [Ǻ] 18.099(2) 18.2835(10) 18.1889(18)
c [Ǻ] 34.801(4) 34.0026(18) 34.854(3)
α [°] 90 90 90
β [°] 90 90 90
γ [°] 90 90 90
3
V [Ǻ ] 5991.8(12) 6659.8(7) 7270.8(12)
Z 8 8 8
-3
Density (calcd.) [g cm ] 1.412 1.354 1.317
-1
μ(Mo-Kα) [mm ] 3.694 3.328 3.053
Tmax./Tmin. 0.603/0.497 0.967/0.787 0.643/0.589
F(000) 2624 2816 3008
Crystal size [mm] 0.13 x 0.09 x 0.02 0.21 x 0.06 x 0.01 0.16 x 0.10 x 0.07
θ range [°] 3.16 - 25.31 2.99 - 25.00 2.92 – 25.00
-11≤h≤11 -12≤h≤12 -13≤h≤13
Index ranges -21≤k≤21 -21≤k≤19 -21≤k≤21
-41≤l≤41 -40≤l≤40 -39≤l≤40
2
R indices [I > 2σ(I)] R1 0.0455 0.0869 0.0707
wR2 0.0707 0.1086 0.1447
wR2 0.0759 0.1138 0.1663
-3
Largest diff. peak/hole [e Ǻ ] 3.142/-1.103 2.699/-1.589 4.998/-1.103
181
Table 30. Crystallographic data of B4, B5 and B7.

B4 (CVD99) B5 (CVD101) B7 (CVD76)
Empirical formula C29H65N8Ta C36H71N8Ta C42H83N8Ta
Formula mass 706.84 796.96 881.11
T [K] 111(2) 113(2) 108(2)
Crystal system monoclinic triclinic monoclinic
Space group P2(1)/n P-1 P2(1)/c
a [Ǻ] 11.0993(12) 10.1139(9) 14.4945(9)
b [Ǻ] 19-395(4) 16.8089(14) 17.4746(8)
c [Ǻ] 15.960(2) 23.796(2) 21.6152(14)
α [°] 90 80.815(7) 90
β [°] 91.702(9) 88.860(7) 98.182(5)
γ [°] 90 78.771(7) 90
V [Ǻ3] 3434.2(9) 3916.8(6) 5045.2(5)
Z 4 4 4
Density (calcd.) [g cm-3] 1.367 1.351 1.160
μ(Mo-Kα) [mm-1] 3.230 2.841 2.211
Tmax./Tmin. 0.529/0.298 0.833/0.465 0.733/0.556
F(000) 1472 1664 1856
Crystal size [mm] 0.25 x 0.17 x 0.11 0.18 x 0.08 x 0.03 0.16 x 0.11 x 0.07
θ range [°] 2.76 – 25.00 2.60 – 25.00 3.01 – 27.56
-13≤h≤13 -12≤h≤12 -17≤h≤15
Index ranges -23≤k≤23 -19≤k≤19 -22≤k≤19
-18≤l≤18 -28≤l≤27 -28≤l≤28
2
R indices [I > 2σ(I)] R1 0.0406 0.0662 0.0562
wR2 0.0977 0.0960 0.1119
wR2 0.1000 0.1016 0.1221
Largest diff. peak/hole [e Ǻ-3] 2.954/-1.558 1.771/-0.725 3.882/-1.493
182
Figure 92. Molecular structures of B1 and B2 in the solid state.
183
184
185
10.9.4 Crystallographic data of C1 and C2
Table 31. Crystallographic data of C1 and C2.

C1 C2
Empirical formula C24H55N8Nb C30H67N8Nb
Formula mass 548.67 632.83
T [K] 108(2) 108(2)
Crystal system monoclinic orthorhombic
Space group P21/c Pbca
a [Ǻ] 19.7356(8) 11.4815(9)
b [Ǻ] 18.2221(4) 18.2528(18)
c [Ǻ] 18.3713(8) 34.814(3)
α [°] 90 90
β [°] 113.094(4) 90
γ [°] 90 90
3
V [Ǻ ] 6077.3(4) 7295.9(11)
Z 8 8
-3
Density (calcd.) [g cm ] 1.199 1.152
-1
μ(Mo-Kα) [mm ] 0.421 0.359
Tmax./Tmin. 0.943/0.913 0.976/0.931
F(000) 2368 2752
Crystal size [mm] 0.14 x 0.10 x 0.06 0.14 x 0.08 x 0.02
θ range [°] 2.66 – 27.50 3.08 – 25.00
Completeness to θ [%] 99.7 99.8
-24≤h≤25 -13≤h≤13
Index ranges -19≤k≤23 -21≤k≤21
-23≤l≤23 -39≤l≤41
Reflections collected 61092 56871
Independent reflections 13962 6417
Rint 0.0512 0.1846
Data/restraints/parameters 13962/0/629 6417/0/352
2
Goodness-of-fit on F 1.034 1.211
R indices [I > 2σ(I)] R1 0.0375 0.0964
wR2 0.0814 0.01305
R indices (all data) R1 0.0604 0.1845
wR2 0.0915 0.1584
-3
Largest diff. peak/hole [e Ǻ ] 1.966/-0.487 0.634/-0.851
186
Appendix
Appendix
A Content lists of figures and tables

A-1 List of figures
A-2 List of tables
B Own publications and contributions to conferences

B-1 Publications
B-2 Oral presentations
B-3 Poster presentations
B-4 Additional publications (not based on results from this PhD thesis)
C Curriculum vitae
D References
187
Appendix
A Content lists of figures and tables
A-1 List of figures
Figure 1. Trends in the number of new patents for NbN and TaN materials. Left: Number
of new patents per year; Right: Number of patents accumulated. ........................ 2
Figure 2. Structures of a) the cubic δ-TaN and b) the hexagonal δ-TaN (view from the
top). ....................................................................................................................... 5
Figure 3. Reported niobium nitride phases, arranged by increasing nitrogen content from
left to right............................................................................................................. 6
Figure 4. Changes in the MOSFET-structure. Replacement of aluminium by copper and
the introduction of a TaN-diffusion barrier. Furthermore, replacement of
polycrystalline Si by TaN as gate electrode material. ........................................... 9
Figure 5. Reactive sputtering of TaN. Nitrogen (blue) is incorporated into the TaN-film
(blue-yellow). ...................................................................................................... 12
Figure 6. a) Scheme of the reactions involved in a CVD process; b) Arrhenius plot of the
growth rate as function of the inverse substrate temperature (1/T). Three regimes
can be identified. 1: growth, controlled by surface reactions; 2: growth,
controlled by diffusion; 3: depletion of the precursor in the diffusion zone above
the substrate......................................................................................................... 14
Figure 7. Idealized ALD process showing one cycle of deposition. In reality, less than one
monolayer is formed and normally undesired thermal decomposition of the
precursor occurs. ................................................................................................. 17
Figure 8. Thermal decomposition of PDEAT during distillation. ...................................... 21
Figure 10. MO-Precursors that have been tested for the MOCVD of NbNx thin films....... 29
Figure 11. Proposed reactions for the ALD of TaNx using a) TaCl5 and ammonia or b)
ammonia and gaseous zinc.................................................................................. 30
Figure 12. Synthetic routes for S1-S3, which are the intermediate compounds for the
synthesis of S4-S9. .............................................................................................. 34
Figure 13. Synthetic route for S4-S9. The second step of the two-step synthesis is shown. 35
Figure 14. Molecular structure of S8 in the solid state. The C3-rotation axis goes along the
C(3)-N(2)-Nb(1) axis. ......................................................................................... 37
Figure 15. Molecular structure of S3 and S3’ in the solid state. The structure of S3 has
already been reported. The carbon atoms of the pyridine ligands of S3’ are
omitted for reasons of clarity. ............................................................................. 38
Figure 16. Left: Weight loss of compounds S5, S7 and S9 in µg per 5 seconds as a function
of temperature (heating rate: 5 °C/min). The sudden increase in weight loss
marks the beginning of thermal decomposition. In the case of S4, S6 and S8, this
step cannot be observed (right side).................................................................... 40
Figure 17. Complete TG/DTA analysis of the two congeners S4 (a) and S8 (b). Comparison
of the TG-curves of the pairs S4 / S8 (c) and S6 / S9 (d).................................... 41
Figure 18. The two ways for the synthesis of Htdmh. I: Involvement of MeLi is required
(W. L. Gladfelter); II: Straightforward synthesis via liberation of HCl and
consequent formation of a hydrazonium salt as an insoluble byproduct. ........... 42
188
Appendix
Figure 19. Ligands used for the synthesis of precursors mentioned either in this work or in
closely related publications. ................................................................................ 45
Figure 20. Reaction equations for the formation of A1-A3 by ligand exchange reactions
between S1-S3 and Htdmh.................................................................................. 47
Figure 21. 1H-NMR spectra of A1 and A2 (25°C, C6D6, 250 MHz). .................................. 49
Figure 22. Molecular structure of A1 in the solid state. Hydrogen atoms are omitted for
reasons of clarity. ................................................................................................ 50
Figure 23. TG/DTA spectra of A1-A3, recorded at a heat rate of 5 °C/min and 300 sccm
nitrogen flow. TG spectrum of A1-A3 and TBTDET for comparison (bottom
right). ................................................................................................................... 51
Figure 24. Reaction pathway of the decomposition reaction of TBTDET, induced by
Hdmh................................................................................................................... 52
Figure 25. Decomposition reaction of TBTDET with Hdmh. Ratio of TBTDET (left), the
intermediate compound (middle) and HNEt2 (right) to C6D6 (=1) as a function of
reaction time. The ratios were determined by comparing the integrals of the C6D6
peaks with the triplets of the NEt2-groups of the three compounds.................... 53
Figure 26. Proton NMR-spectra of the reaction of TBTDET and one equivalent of Hdmh
after 20 min, 70 min, 700 min and 30 hours. The peaks for TBTDET, the
intermediate compound, free Hdmh and HNEt2 are marked............................... 53
Figure 27. Molecular structure of A5 in the solid state (atoms are labeled)......................... 55
Figure 28. Bond distances and bond angles of A5 in the solid state (deviations are omitted
for reasons of clarity). ......................................................................................... 55
Figure 29. ChemDraw-scheme of A5, including the bond orders of the Ta-O and Ta-N
bonds. .................................................................................................................. 56
Figure 30. Molecular structure of A4 in the solid state. Hydrogen atoms are omitted for
reasons of clarity. ................................................................................................ 59
Figure 31. Ionic and neutral representatives of guanidines. A large variety of derivatives is
known (R = H, Me, i-Pr, cyclohexyl, t-Bu, phenyl). In this work, the
monoanionic guanidinate ligand was used.......................................................... 61
Figure 32. The two resonance forms of a monoanionic guanidinate ligand......................... 61
Figure 33. Synthetic route for guanidinate complexes by salt metathesis reactions. ........... 63
Figure 34. Mechanism for the insertion of a carbodiimide derivative into a metal amido-
bond (R1, R2, R3 = alkyl-groups)......................................................................... 63
Figure 35. Reactions of carbodiimides with S4-S7 (S1: R1, R2 = Me, R4 = t-Bu; S2: R1 =
Me, R2 = Et, R4 = t-Bu; S3: R1, R2 = Et, R4 = t-Bu; S4: R1, R2 = Et, R4 = n-Pr).66
Figure 36. The two carbodiimides of type a feature an α-hydrogen, thus enabling the
nitrogen to coordinate to the Ta-center. In the structure type b (t-Bu-, SiMe3-cdi)
steric hindrance, evoked by the methyl groups at the substituents of the
carbodiimide cannot be avoided by rotation of the substituent........................... 67
Figure 37. The two chiral forms of the mixed amido/imido/guanidinato complexes. The
specific bonds that show a hindered rotation are marked with arrows. .............. 69
Figure 38. a) Full 1H-NMR-spectrum of compound B1 and b) an enlarged section of the
spectrum. The doublets of the i-Pr-groups are numbered from 1-8. ................... 70
Figure 39. NMR spectra of B1 at low and high temperatures in different solvents. ............ 70
189
Appendix
Figure 40. 1H-NMR spectrum of B2.................................................................................... 71

Figure 41. Proton NMR spectrum of B3. Left side: full spectrum including the assignments
of the α-hydrogen atoms. Right side: enlarged section of the spectrum, showing
all doublets (D) and triplets (T) of the CH3-groups. Two triplets are not
resolved... ............................................................................................................ 71
Figure 42. Proton NMR spectra for B4 and B8 (RT, C6D6). The α-hydrogen atoms are
assigned by the colored dots and squares............................................................ 72
Figure 43. 2D-HMQC spectrum of B3. The proton-NMR data are allocated at the x-axis,
while the carbon-NMR data are allocated at the y-axis of the spectrum. ........... 73
Figure 44. NMR spectrum of the mono-inserted product of the reaction between S5 and one
i-Pr-carbodiimide. Addtionally, small amounts of B2 (twofold inserted product)
and S5 can be also observed. The peaks for the protons of the CH2-group (Ta-
N(Me)CH2CH3) cannot be clearly assigned. ..................................................... 73
Figure 45. Reaction of the amido/imido complexes S4-S6 (R1, R2 = Me/Et) with one
equivalent of i-Pr-cdi. Attempts to crystallize the mono-inserted product lead to
the formation of the solid di-substituted complexes. .......................................... 74
Figure 46. Crystals of B1 in five-fold magnification. The different colors of particular
crystals are generated by polarized light that is refracted at the boundaries within
the crystals. These boundaries clearly show that the crystals are not single
crystalline, but agglomerates of conjoined smaller crystals................................ 75
Figure 47. Comparison of the structural features of the guanidinato ligand in complex X1
and B1. While X1 is clearly present in form of structure type A, the structure of
the ligand in complex B1 is in between the two mesomeric forms A and B. The
out of plane distortion angles of the C-NMe2 moiety are given (150° and 177°)
as well as the twisting angles of the amido moiety versus the endocyclic Ta-N-C-
N group (Newman projection). ........................................................................... 77
Figure 48. Ortep/Povray plots of the structures of B1 and B2. The planes, spanned by Ta(1),
N(6), N(5) and C(16) are displayed in both molecules. Substituents, e.g. i-Pr-
groups are removed for reasons of clarity........................................................... 80
Figure 49. Molecular structure of B1 in the solid state. ....................................................... 81
Figure 50. Clarification of the coordination sphere of the six nitrogen atoms around the
tantalum center. Left: Ortep/Povray plot of a cutout of B1. Right: The
geometrical figure corresponds to a distorted octahedron. The labeling of the
nitrogen atoms is consistent for all compounds B1-B8....................................... 81
Figure 51. Synthesis of the complexes C1-C4. The assignment of R1-R3 can be found in
table 11. ............................................................................................................... 83
Figure 52. Ortep/Povray plot of the molecular structure of C1 in the solid state. The N(6)-
Nb(1)-N(5)-C(16) plane is colored in yellow. The distortion of the endocyclic
planes (green) and the planes, spanned by the exocyclic amido groups (red) are
indicated. ............................................................................................................. 85
Figure 53. TG/DTA spectra of B4 and B8. The stars indicate the endothermic peaks for a
phase change. In addition, the melting point and the onset of decomposition of
B4 and B8 are assigned. ...................................................................................... 88
Figure 54. TG-DTA spectrum of B1 as a function of time. The heating rate was 5 °C per
minute. The absence of the endothermic peak during the second period of
190
Appendix
heating can be clearly observed. No weight loss was observed, i.e. the loss of
solvent can be excluded....................................................................................... 89
Figure 55. Isothermal studies of the compounds B1-B6. Compounds, synthesized by
insertion of iso-propyl carbodiimide (B1-B4) are significantly more volatile
(higher mass loss), than the cyclohexyl-substituted complexes (B5 and B6)..... 90
Figure 56. Device for testing the decomposition behavior of B1-B3. The bubbler as well as
the glas joints were heated by heating tapes, while a quartz glas tube was heated
to 600 °C in a tube shaped oven. The length of the tube was 40 cm in order to
ensure complete decomposition of the precursor................................................ 91
1
Figure 57. H-NMR of the decomposition products of B3 at 600 °C, ingested by C6D6.
Free diethylamine as well as i-Pr-cdi can be observed. The peaks, marked with a
star can probably be assigned to decomposition products, still containing diethyl
and iso-propyl groups.......................................................................................... 92
Figure 58. Scheme of the selfbuilt horizontal cold wall reactor (substrate size: 1.4 x 2.0
cm2). .................................................................................................................... 95
Figure 59. Scheme of the horizontal cold wall reactor in Erlangen. The reactor is
constructed for two 150 mm wafers.................................................................... 97
Figure 60. Scheme of the Aixtron 200 RF reactor................................................................ 97
Figure 61. Left: Picture of the Aixtron 200 RF MOCVD reactor. The reactor part in
operation is shown in the right picture. ............................................................... 98
Figure 62. Glass bubblers for a) the Aixtron 200 RF reactor and b) the reactor in Erlangen
(large wafer instrument). In order to ensure a minimum filling height, glass
pearls can be added to the precursor to reduce the required amount of
precursor.... .................................................................................................... 99
Figure 63. XRD-spectra of films deposited by means of MOCVD using S5 at different
evaporation temperatures and a substrate temperature of 600 °C..................... 101
Figure 64. a) Cross sectional and b) top view on a section of the sample S5-2. The
columnar growth of the crystallites can clearly be seen.................................... 102
Figure 65. SEM-recordings of the particles on the samples S5-2 and S5-3. Pictures a, b and
d show the top of a particle from the top, while c shows a partially dissected
particle. One can clearly see the cone-shaped form of the particle (the arrows
indicate the growth directions).......................................................................... 103
Figure 66. SNMS spectrum of a deposition in the Aixtron 200 RF reactor using S6 and NH3
as precursor and reactive gas, respectively (Tsubstr = 600 °C). The film consists of
app. 70-80 nm, deposited during the experiment time and appr. 160 nm
deposited during the warm up phase in which condensed precursor in the lines
caused the growth.............................................................................................. 105
Figure 67. SEM - picture of a) a cross section and b) an on-top view of sample S6-3’’. The
other, thinner samples show no good resolution. .............................................. 108
Figure 68. XRD spectra of films deposited at various temperatures using S6 ([Ta(NEt2)3(N-
t-Bu)]) in the Aixtron 200 RF reactor. The peaks are slightly broadened at lower
substrate temperatures and the peak positions deviate from the peaks expected
for bulk TaN. ..................................................................................................... 109
Figure 69. XRD spectra of films deposited at various NH3-flow rates (Tsubstrate = 650 °C;
Precursor: S6; Aixtron 200 RF reactor). Crystallinity of the films does not differ
191
Appendix
significantly at different amounts of ammonia that are added during deposition.

109
Figure 70. a) SNMS-spectrum of sample S6-8 (50 sccm NH3, Tsubstr = 650 °C) and b) the
change in film composition as a function of the ammonia flow rate. ............... 111
Figure 71. Growth rate vs. reactor pressure in experiments using A3 at substrate
temperature of 600 °C. The growth rate was determined by the weight gain of
the samples and a density, considered to be 13.7 g/cm3................................... 116
Figure 72. a) Surface AFM (rms = 1.6 nm) and b) SEM-cross section of a film, deposited at
700 °C using A3 and additional ammonia. ....................................................... 117
Figure 73. RBS-measurements of samples, deposited without (a, 600 °C) and with (b,
700 °C) additional ammonia. ............................................................................ 117
Figure 74. XRD spectra of depositions using B2. Very high crystallinity is observed at
800 °C. Below 650 °C no peaks can be observed. ............................................ 122
Figure 75. Cross sectional SEM-analysis (a,b) and SNMS analysis (c) of a film deposited at
750 °C using B2 as precursor. The high uniformity of the film is displayed in the
SEM recordings................................................................................................. 124
Figure 76. SNMS analysis of a film, deposited using B2 as precursor on the Aixtron 200 FE
reactor at 600 °C. It can be assumed that a mixture of Ta3N5 and Ta2O5 was
formed. .............................................................................................................. 126
Figure 77. Energy diagram for an MOS-capacitor structure. The unit consists of p-doped
silicon (with constant work-function, ФS and band gap), the insulation oxide and
the metal gate material (here: TaN) that can have miscellaneous work functions
(ФM).................................................................................................................. 128
Figure 78. a) XRD of films deposited at 600-700 °C using S8. The reflexes are slightly
shifted in comparison to the theoretical positions for cubic NbN. This can be
caused by the presence of cubic niobium carbide. b) / c) SEM pictures (600 °C,
precursor: S8). No particle formation could be observed. ................................ 131
Figure 79. SNMS-analysis of a film using S8 ([Nb(NMe2)3(N-t-Bu)]), deposited at 700 °C.
The oxygen concentrations at a sputter depth of 100 and 2750 nm are displayed.
132
Figure 80. SNMS-analyses of niobium nitride films, deposited using C1 at a) 500 °C and b)
600 °C, respectively. The oxygen concentrations at directly below the surface
and close to the silicon substrate are marked. ................................................... 135
Figure 81. Picture of the ASM F 120 ALD reactor in Bochum. ........................................ 136
Figure 82. Scheme of the ASM F 120 reactor. a) The whole tube-system; only three of the
six glass tubes are displayed. b) Enlarged scheme of one of the tubes with the
inner and outer tube and the precursor boat. c) switching mechanism of the
valves................................................................................................................. 137
Figure 83. Schemes of the two reactor types for the ASM F 120 reactor (left: setup I, right:
setup II). ............................................................................................................ 138
Figure 84. One film, having one of the highest uniformities is shown as an image (left,
Pulse(precursor) = 1.2 s; 2000 cycles, 300 sccm N2). The blue sides of the wafer
correspond to a film thickness of appr. 80 nm. On the right side, the 3-
dimensional thickness profile of the film is displayed...................................... 141
192
Appendix
Figure 85. Dependence of the uniformity of the films on the variation of certain parameters
(precursor S5). The standard deviation and its percentage of the average
thickness of the film are listed. A variation of the ammonia flow rate (not
displayed) also did not lead to higher uniformity. ............................................ 142
Figure 86. 3-dimensional plot of the film thicknesses of a) TaN-3 and b) TaN-2. Film
thickness was determined at the white and black spots. ................................... 144
Figure 87. Dependence of the growth rate on the pulse time of the precursor. No saturation
takes place. ........................................................................................................ 145
Figure 88. Reaction scheme depicting the syntheses of the complexes A1-A3 by
transamination reactions (one amido group is replaced by one hydrazido ligand)
and of the guanidinato complexes B1-B8 and C1-C4 by insertion reactions (two
equivalents of carbodiimide are inserted into the metal nitrogen bond of the
amido group). .................................................................................................... 148
Figure 90. Scheme for the reflections of the incident X-ray beams at the planes within the
crystals and equation 4 (d = dhkl). .................................................................... 156
Figure 91. Scheme of a powder diffractometer in Bragg-Brentano geometry. .................. 157
Figure 92. Molecular structures of B1 and B2 in the solid state. ....................................... 183
193
Appendix
A-2 List of tables
Table 1. Phases of tantalum nitride and their structure types. The phases, that have been
deposited via chemically based gasphase methods (not necessary the quoted
references) are highlighted. ...................................................................................... 4
Table 2. Experiments for the ALD of TaN thin films using metal halides. .......................... 30
Table 3. Experiments for the ALD of TaN thin films using metal organic compounds. ...... 32
Table 4. Experiments for the ALD of TaN thin films using metal organic compounds. ...... 33
Table 5. Yields of the reactions for the formation of S4-S9 from our experiments, compared
to the experiments from previous works. [120-124] ................................................... 36
Table 6. Thermal parameters of the compounds S4-S9 (n.d. = not determined; n.v. not
clearly visible) ........................................................................................................ 39
Table 7. Selected bond lengths and angles of the crystal structure of A1. ........................... 50
Table 8. Overview of the synthesized guanidinato complexes of tantalum. ........................ 67
Table 9. Selected data for the crystal structures of B1-B5 and B7....................................... 75
Table 10. Selected bond length and bond angles of B1-B5 and B7. ...................................... 82
Table 11. Overview of the synthesized guanidinato complexes of niobium........................... 83
Table 12. Selected bond length and bond angles of C1 and C2.............................................. 86
Table 13. Thermal parameters of the compounds B1-B8 and C1-C4 (n.v. = not clearly
visible). The results for the melting point as well as the onset of decomposition
have to be taken with care (large errors are possible). ........................................... 87
Table 14. Compounds that were used for MOCVD experiments including a short summary of
the results................................................................................................................ 93
Table 15. Parameters and results of the depositions using S5 as precursor. Film thickness is
determined via SEM-measurements or weight gain of the films (in combination
with the density of fcc-TaN (13.7 g/cm3)) ........................................................... 100
Table 16. Parameters of the depositions using S6 as precursor in the Aixtron 200 RF reactor.
Repeated experiments are marked with an apostrophe. The experiments S6-3 and
S6-3’ are listed twice due to their relevance for both experimental rows (bold
entries, substrate temperature (first row) and NH3-flow (second row))............... 107
Table 17. Results of the depositions using S6 as precursor in the Aixtron 200 RF reactor. The
results for the thicknesses are afflicted with large errors of appr. ± 10 nm.
Therefore thicknesses were defined, based on the trend that was concluded from
the less precise results of weight gain-, SEM- and SNMS measurements........... 107
Table 18. Results for the depositions of other groups using TBTDET (S6, [Ta(NEt2)3(N-t-
Bu)]), TAIMATA ([Ta(NEt2)3(NCMe2Et]) or ([Ta(N(Me)(t-Bu))3(N-t-Bu)]).... 112
Table 19. Composition of the films, deposited using B2 as precursor in two different reactor
setups.................................................................................................................... 126
Table 20. Results and parameters of the depositions using C1 as precursor in the self-built
reactor (n.d. = not determined). Results for one film using B2 as precursor are
listed for comparison of the compositions. .......................................................... 133
194
Appendix
Table 21. Results and parameters of the depositions using trimethylaluminum (TMA) and
water (T(substrate) = 300 °C), primary flow = 700 sccm N2, secondary flow = 100
sccm N2 on Si(100) substrates.............................................................................. 142
Table 22. Results and parameters of the depositions using S6 and ammonia, primary flow =
700 sccm N2, secondary flow = 100 sccm N2 on Si(100) substrates (20 nm SiO2);
T(precursor) = 55 °C.1500 cycles. ....................................................................... 143
Table 23. Parameters and results of the depositions using S9 and ammonia, primary flow =
700 sccm N2, secondary flow = 100 sccm N2 on Si(100) substrates (20 nm SiO2);
T(precursor) = 60 °C. Purge times: 3 s (after precursor pulse) and 10 s (after
ammonia pulse). Thickness measurements were performed by ellipsometry...... 144
Table 24. Compounds that were used for MOCVD and ALD including a short summary of
the results.............................................................................................................. 150
Table 25. Reactions of S6 with Hdmh. The error in the masses is ± 3 mg. .......................... 169
Table 26. Reactions of TaCl5 and [TaCl3(N-t-Bu)py2] with lithiated hydrazine derivatives.170
Table 27. Crystallographic data of S3’ and S8...................................................................... 179
Table 28. Crystallographic data of A1, A4 and A5. ............................................................. 180
Table 29. Crystallographic data of B1-B3............................................................................. 181
Table 30. Crystallographic data of B4, B5 and B7. .............................................................. 182
Table 31. Crystallographic data of C1 and C2. ..................................................................... 186
195
Appendix
B Own publications and contributions to conferences
B-1 Publications
[I] A. Baunemann, M. Lemberger, A. J. Bauer, H. Parala, R. A. Fischer, Chem. Vap.

Deposition 2006, DOI: 10.1002/CVDE.200606514. “MOCVD of TaN using the all
nitrogen coordinated precursors: [Ta(NEtMe)3(N-t-Bu)], [Ta(NEtMe)(N-t-Bu){C(N-i-
Pr)2(NEtMe)}2] and [Ta(NMeEt)2(N-t-Bu){Me2N-N(SiMe3)}].”
[II] A. Baunemann, M. Winter, K. Csapek, C. Gemel, R. A. Fischer, Eur. J. Inorg. Chem.

2006, DOI: 10.1002/ejic.200600653. “Mixed Amido/Imido/Guanidinato complexes of
tantalum: Effects of ligand substitution on thermal properties.”
[III] A. Baunemann, Y. Kim, M. Winter, R. A. Fischer, Dalton Trans. 2006, 121. “Mixed
hydrazido amido/imido complexes of tantalum, hafnium and zirconium: potential
precursors for metal nitride MOCVD.”
[IV] A. Baunemann, D. Rische, A. Milanov, Y. Kim, M. Winter, C. Gemel, R. A.

Fischer, Dalton Trans. 2005, 3051. “Tantalum complexes with all nitrogen
coordination sphere: mixed amido-, imido-, guanidinato complexes of tantalum and
their thermal behaviour.”
[V] A. Baunemann, K. Csapek, M. Winter, C. Gemel, R. A. Fischer, in progress.

“Transferring a concept: Mixed amido/imido/guanidinato complexes of Nb as
precursors for the MOCVD of niobium nitride.”
[VI] M. Lemberger, A. Baunemann, A. J. Bauer, Proceedings WODIM - Workshop on

Dielectrics on Microelectronics 2006, Santa Tecla, Italy 2006, submitted. “Chemical
Vapor Deposition of Tantalum Nitride Films for Metal Gate Application using
TBTDET and Novel Single-Source MOCVD Precursors.”
B-2 Oral presentations
[I] “Guanidinato complexes of tantalum and niobium: Effects of ligand substitution on

thermal properties.” by A. Baunemann, D. Rische, A. Milanov, R. A. Fischer, 231st
ACS National Meeting, Atlanta, GA, 26.-30. March 2006.
[II] “From Molecules to Materials - Precursor Chemistry for the ALD and MOCVD of
Tantalum Nitride.” by A. Baunemann, Anorganisch Analytisches Kolloquium, January
2006.
B-3 Poster presentations
[I] A. Baunemann, R. A. Fischer, J. Niinistö, M. Puttkonen, L. Niinistö, ALD 2004

conference, Helsinki, Finland, 2004. “Atomic Layer Deposition of Tantalum Nitride
Applying a Mixed Amino/Imino Tantalum Precursor.”
196
Appendix
[II] A. Baunemann, Y. Kim, R. A. Fischer, Materials Discussion 7, London, England,

2004. “Mixed imido/hydrazido tantalum complexes as potential precursors for the
deposition of TaN thin films via MOCVD.”
[III] A. Baunemann, D. Rische, Y. Kim, H. Parala, A. Bauer, M. Lemberger, R. A. Fischer,

EUROCVD 15, Bochum, 2006. “Chemistry of mixed ligand all nitrogen coordinated
Ta, Hf and W precursors for metal nitride MOCVD.”
B-4 Additional publications (not based on results from this PhD thesis)
[I] A. Baunemann, M. Hellwig, A. Varade, R. K. Bhakta, M. Winter, S. A. Shivashankar,

R. A. Fischer, A. Devi, Dalton Trans. 2006, 3485-3490.
[II] A. Baunemann, R. Thomas, R. Becker, M. Winter, R. A. Fischer, P. Ehrhart, R.

Waser, A. Devi, Chem. Commun. 2004, 1610.
[III] Y. Kim, A. Baunemann, H. Parala, A. Devi, R. A. Fischer, Chem. Vap. Dep. 2005, 11,
294-297.
[IV] D. Rische, A. Baunemann, M. Winter, R. A. Fischer, Inorg. Chem. 2006, 45, 269-277.
[V] A. P. Milanov, R. K. Bhakta, A. Baunemann, M. Winter, A. Devi, Inorg. Chem.

submitted.
[VI] R. Thomas, E. Rije, P. Ehrhart, R. Bhakta, A. Baunemann, A. Milanov, U. Patil, A.

Devi, R. Waser, J. Electrochem. Soc. submitted.
197
Appendix
C Curriculum vitae
Persönliche Angaben
Staatsangehörigkeit: deutsch
Geburtsdatum: 23. Juni 1978
Geburtsort: Düsseldorf
Familienstand: ledig
Ausbildung/Zivildienst
10/2003 bis 12/2006 Promotion in anorganischer Chemie an der Ruhr-Universität Bochum
Thema: „MOCVD und ALD von Tantal- und Niobiumnitrid:
Precursorchemische Untersuchungen”
02/2005 Nebenfachprüfung in dem Fach „Finanzierung und Investition“ an der

Fakultät für Wirtschaftswissenschaften der Ruhr-Universität Bochum
10/1998 bis 05/2003 Studium der Chemie an der Ruhr-Universität Bochum

Vordiplom (09/2000)
Diplom (05/2003)
11/2002 bis 05/2003 Diplomarbeit in anorganischer Chemie am Lehrstuhl für Anorganische

Chemie II der Ruhr-Universität Bochum (verfasst in englischer Sprache)
Thema: „Synthesis and the precursor-chemical characterization of organo-
metal precursors for gate-oxide materials”
02/2002 bis 06/2002 Auslandssemester an der University of California at Los Angeles, Department
of Chemical Engineering
08/1997 bis 09/1998 Zivildienst bei der „Freizeitgemeinschaft e.V. Behinderte und
Nichtbehinderte“ in Hilden; Betreuung von behinderten Grundschülern
08/1988 bis 06/1997 Besuch des Dietrich-Bonhoeffer Gymnasiums in Hilden
Stipendien und Preise

Promotionsstipendium des Fonds der Chemischen Industrie (04/2004 -
05/2006)
Stipendiat der Studienstiftung des deutschen Volkes (03/2001 - 06/2003)
E-fellows Internetstipendium (seit 05/2001)
Studienabschlussstipendium der Ruth und Gert Massenberg Stiftung
Wilke Preis für hervorragende Studienleistungen durch die Ruhr-Universität
Bochum
198
Appendix
Zusatzqualifikationen
09/2003 bis 06/2005 Zertifikat „Wirtschaft für Nichtökonomen", ausgestellt von der Ruhr-
Universität Bochum und der Industrie- und Handelskammer NRW
Grundvorlesungen in BWL und VWL
Seminare zu den Themen Recht, Marketing und
Personalmanagement
10/2005 bis 02/2006 Teilnahme an der Vorlesung „Business to Business Marketing” von Prof. Dr.
Mario Rese (Wirtschaftswissenschaften, Veranstaltung im Hauptstudium)
Praktika/Berufserfahrung
04/2005 bis 06/2005 Praktikum bei der Bayer AG, Leverkusen im Bereich Business Consulting
06/2003 bis 08/2003 Praktikum bei der Firma Celanese AG, Kronberg im Bereich Strategic
Planning
09/2002 bis 12/2006 Assistent für Erstsemester-Studierende
10/2001 bis 09/2002 Studentische Hilfskraft am Lehrstuhl für Anorganische Chemie II, Ruhr-
Universität Bochum (Erstellung von Praktikumsversuchen)
10/2001 bis 03/2002 Leitung eines Orientierungstutoriums für Studienanfänger
Sprachen
Englisch (fließend)
Außeruniversitäre
Aktivitäten/Sonstiges
01/2000 bis 10/2006 Aktives Mitglied im Jungchemikerforum Bochum
(Sprecher ab 07/2000)
05/2000 bis 05/2003 Mitglied im Fachschaftsrat und in Gremien der Fakultät Chemie
(Fakultätsrat, Prüfungsausschuss)
199
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208
Appendix
Ich erkläre hiermit, dass ich die vorliegende Dissertation selbst verfasst und mich dabei keiner
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erkläre hiermit des Weiteren, dass ich an keiner anderen Stelle ein Prüfungsverfahren
beantragt bzw. die Dissertation in dieser oder anderer Form bereits anderweitig als
Prüfungsarbeit verwendet oder einer anderen Fakultät als Dissertation vorgelegt habe.
Bochum, den
Arne Baunemann
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Precursor Chemistry of Ta and NB Nitride For MOCVD and ALD Applications

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Precursor Chemistry of Ta and NB Nitride For MOCVD and ALD Applications

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Precursor Chemistry of Tantalum and Niobium Nitride

for MOCVD and ALD Applications

(Ayn Rand in “Atlas Shrugged”, 1957)

Chapter 1 Introduction and motivation 1

Chapter 2 State of the art in research and motivation 19

Chapter 3 Starting compounds and their synthesis 34

Chapter 4 Hydrazido based precursors of tantalum 44

Chapter 5 Guanidinato based precursors of tantalum and niobium 60

5.4 Synthesis of amido / imido / guanidinato compounds of niobium C1-C4 83

Chapter 6 MOCVD of tantalum nitride 93

Chapter 7 MOCVD of niobium nitride 130

Chapter 8 ALD of metal (oxo) nitride materials 136

Chapter 9 Summary and outlook 147

Chapter 10 Experimental 154

10.3.2 Handling of the selfbuilt reactor 161

AFM Atomic Force Microscopy

Chapter 1 Introduction and motivation

1.1 Motivation and goals

1.2 Phases of group(V) nitrides and their properties

1.3 Applications of tantalum and niobium nitrides

Application of TaN as liner material for diffusion barriers in Si/MN/Cu device

Application of NbN in the formation of Josephson Junctions

Application of Ta3N5 as a photoelectrode material or gate dielectric

1.4 Techniques for deposition of thin films via gasphase

1.4.1 Physical Vapor Deposition (PVD)

As an alternative to reactive sputtering, polycrystalline TaN-targets (no nitrogen required) can

1.4.2 Metal Organic Chemical Vapor Deposition (MOCVD)

[f] So called line-of-sight-growth

certain temperature, growth rate decreases, caused by a hydrodynamic depletion of precursor

1.4.2.1 Properties of a “good” precursor

Transport of the precursor to the substrate without decomposition

Clean decomposition of the precursor at the desired temperature regime

Formation of the right phase in the right degree of crystallinity

Simple and up-scalable synthesis, low toxicity

Chemical and long-term thermal stability

1.4.3 Atomic Layer Deposition (ALD)

 Homogeneous and heterogeneous parasitic thermal decomposition occurs (CVD-

Chapter 2 State of the art in research and motivation

2.1 Previously reported MOCVD experiments for group(V) nitrides

some drawbacks in terms of damaging the underlying substrates. In addition, approximately

2.1.1 MOCVD of tantalum nitride

The precursor PDEAT (Pentakisdiethylamidotantalum) is a topic on its own. This compound

Figure 8. Thermal decomposition of PDEAT during distillation.

Mixed amido/imido compounds

Halide-containing metal organic precursors

Other precursors, not tested for CVD

2.1.2 Conclusions of past reports about the MOCVD of tantalum nitride

Crystalline vs. amorphous films (high vs. low substrate temperatures)

Ambiguous impact of ammonia

Oxidation of the films

Use of plasma assisted MOCVD

2.1.3 MOCVD of niobium nitride

2.2 Previously reported ALD experiments for group(V) nitrides

2.2.1 ALD of tantalum nitride

ALD using TaCl5 and TaBr5 as precursors

ALD using metal organic precursors (TBTDET and TAIMATA)

2.2.2 ALD of niobium nitride

Chapter 3 Starting compounds and their synthesis

3.1 Synthesis of mixed amido / imido compounds of tantalum and niobium

3.1.2 Thermal properties of the compounds S4-S9

Although thermal decomposition of the compounds already occured at temperatures below

3.2 Ligand synthesis

3.2.1 Synthesis of N-trimethylsilyl-N’,N’-bisdimethylhydrazine (Htdmh)

Chapter 4 Hydrazido based precursors of tantalum

4.2 Synthesis of amido / imido / hydrazido complexes A1-A3 by

Homogeneous and heterogeneous parasitic thermal decomposition occurs (CVD-

Will it be possible to deposit conducting TaN thin films?