A nickel(II) guanidinate compound and its potential as CVD precursor for nickel related films

Article abstract of DOI:10.1016/j.poly.2018.09.043

In this study, a nickel(II) compound with guanidinate ligand of the general form [((Me)₂NC(ⁱPrN)₂)₂Ni] has been synthesized and isolated from the reaction of NiCl₂ with the corresponding lithium salt of guanidinate ligand [(Me)₂NC(ⁱPrN)₂Li] at 70 °C. Its structure was determined by ¹H NMR, elemental analysis, and single crystal X-ray diffraction. Thermogravimetric analysis (TGA) was employed to study the thermal properties (including thermal stability, volatility, vapor pressure and transport behavior) of compound. Furthermore, a deposition experiment was made to examine the compound's potential as CVD precursor, and a Ni metal film was successfully deposited. These preliminary results illustrate the potential of this compound to act as CVD precursor.

Full text of DOI:10.1016/j.poly.2018.09.043

Accepted Manuscript
A nickel(II) guanidinate compound and its potential as CVD precursor for nickel
related films
Yuxiang Zhang, Liyong Du, Xinfang Liu, Yuqiang Ding
PII:
S0277-5387(18)30595-3
https://doi.org/10.1016/j.poly.2018.09.043
POLY 13442
DOI:
Reference:
To appear in:
Polyhedron
Received Date:
Revised Date:
Accepted Date:
27 July 2018
10 September 2018
15 September 2018
Please cite this article as: Y. Zhang, L. Du, X. Liu, Y. Ding, A nickel(II) guanidinate compound and its potential as
CVD precursor for nickel related films, Polyhedron (2018), doi: https://doi.org/10.1016/j.poly.2018.09.043
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers
we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting proof before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

A nickel(II) guanidinate compound and its potential as CVD
precursor for nickel related films
a
a
b
a
Yuxiang Zhang , Liyong Du , Xinfang Liu , Yuqiang Ding *
aInternational Joint Research Center for Photoresponsive Molecules and Materials,
School of Chemical and Material Engineering, Jiangnan University, 1800 Lihu Road,
Wuxi 214122, P.R. China, Corresponding E-mail: yding@jiangnan.edu.cn
bHenan Key Laboratory of Function-Oriented Porous Materials, College of
Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471934,
P.R. China
Abstract: In this study, a nickel(II) compound with guanidinate ligand of the general
i
form [((Me)
2
NC( PrN)
2
)
2
Ni] has been synthesized and isolated from the reaction of
i
NiCl
2
with the corresponding lithium salt of guanidinate ligand [(Me)
2
NC( PrN)
2
Li] at
o
1
7
0 C. Its structure was determined by H NMR, elemental analysis, and single crystal
X-ray diffraction. Thermogravimetric analysis (TGA) was employed to study the
thermal properties (including thermal stability, volatility, vapor pressure and transport
behavior) of compound. Furthermore, a deposition experiment was made to examine
the compound’s potential as CVD precursor, and a Ni metal film was successfully
deposited. These preliminary results illustrate the potential of this compound to act as
CVD precursor.

Keywords: Synthesis; Nickel(II); Guanidinate; Thermal Properties; CVD Precursor
1
. Introduction
Guanidine is an important N-donor bidentate chelating type ligand, which presents
multiple formations by changing substituting group on the conjugated N–C–N
backbone [1]. Its chemical properties, including electronic and steric properties etc.,
can be easily adjusted to satisfy the various needs of different metal centres [1].
Corresponding metal compounds exhibit good catalytic properties and have shown
great potential in catalysis such as polymerization and oligomerization of olefins,
intramolecular hydroamination/cyclization, hydroamination, and hydrosilylation
[
2-7].
Moreover, in recent years, guanidine is also used as an important ligand for
precursors in chemical vapor deposition (CVD) or atomic layer deposition (ALD). To
date, various studies have been investigated the thermal properties of metal
guanidinates and their application in CVD or ALD. For instance, Coyle et al reported
synthesis of copper (I) guanidinates and their thermal chemistry in ALD process [8];
2
t
Chen et al prepared TaN film by CVD using [Ta(NMe
precursor [9]; Kim et al used [Ti(NMe (guan)] (guan=N,N’-diisopropyl-2-dimethyl-
amidoguanidinato) as precursor for CVD of N-doped TiO
reported ALD of HfO film employing [Hf(NMe (guan)
2
)
4
(η - BuNC(NMe )NEt)] as
2
)
2 3
2
film [10]; and Xu et al
2
2
)
2
2
] as precursor [11]. All
these studies made metal guanidinate compounds attract considerable scientific
interests. Relatively, the study involving chemistry of nickel guanidinate compound

and its application in CVD or ALD of nickel related films (such as nickel metal films,
nickel oxide films, and nickel silicide films etc.) is still a largely unexplored field
[
12].
Nickel related films have important application in many fields, such as information
storage [13-16], contact materials [17,18], and electrocatalyst [19] etc. With the
development of miniaturization of devices in the last two decades, more and more
researchers prepared nickel related films by CVD or ALD technology because of their
obvious advantages in film conformality and uniformity [20]. As known, precursor is
a key factor for accomplishment of CVD or ALD processes [20]. So far, numerous
precursors have been used for CVD or ALD of nickel related films including
compounds with carbonyl [21], amidinate [22-24], β-diketonate [25-27], diazadienyl
[
28-30], α-imino alkoxide [31], cycolpentadienly [32-35], and amido [36] ligands etc.
Despite these compounds have been successfully employed to deposit
nickel-containing film materials, it is necessary to develop new nickel compounds as
CVD or ALD precursors, because different structures of compounds greatly affect
their chemistry properties, and thus influencing the nature of the synthesized materials
and satisfying diverse requirements for industry [37]. And these strongly encouraged
us to investigate the chemistry involving nickel guanidinate compound and its utility
as CVD or ALD precursor for nickel related films.
The synthesis of cobalt(II) guanidinate compounds and their application in CVD
were studied in our previous report [38]. Based on this work, as a consecutive study,
herein we reported the synthesis and characterization of a solid nickel(II) guanidinate

i
compound [((Me)
2
NC( PrN)
2
) Ni]. Its thermal properties (including thermal stability,
2
volatility, vapor pressure and transport behavior) were examined by TGA. Besides, to
further evaluate whether the compound suits as a CVD precursor, an attempt was
performed to deposit relevant films using a hot-wall CVD reactor.
2
. Experimental procedure
2
.1. General synthesis
All manipulations were conducted using standard schlenk techniques. Diethyl ether,
hexane, and tetrahydrofuran were used freshly by distillation from sodium. LiNMe
2
was synthesized by means of the reference paper [39]. Other chemicals were obtained
from Aladdin and used as received. Melting point was measured by an X-4A melting
point apparatus. The C, H, N analysis was examined using a Vario EL III Elementar
microanalyzer. X-ray data was collected with a Bruker SMART APEX II CCD area
detector using monochromated Mo-Kα radiation (λ=0.71073 Å). NMR spectrum was
studied by a Bruker ACF-400 spectrometer.
[
LiNMe ]: To a 100 mL Schlenk flask charged with dimethylamine (2 M in THF
2
solution) (20.0 mL, 40.0 mmol) and hexane (30 mL), and then n-butyllithium (2.5 M
o
in hexane solution) (16.0 mL, 40.0 mmol) was added dropwise at -78 C. The
resultant suspension solution was stirred at ambient temperature for 4 h. Subsequently,
the mixture was filtered, and yellowish solids were obtained after washing by hexane
(
20 mL) three times.
i
[
((Me)
2
NC( PrN)
2
)
2
Ni] (1): To a 100 mL Schlenk flask charged with LiN(Me)
2

(
(
1.020 g, 20.0 mmol) and diethyl ether (25 mL), and then diisopropylcarbodiimide
o
2.524 g, 20.0 mmol) was added dropwise over 10 min at -78 C. The resultant
solution was stirred at ambient temperature for 12 h. Subsequently, the mixture was
added to a solution of nickel (II) chloride (1.296 g, 10.0 mmol) in 25 mL of
o
tetrahydrofuran and stirred overnight at 70 C. After all volatiles removed in vacuo,
the residue was extracted with hexanes (3 x 20 mL). The combined extracts were
filtered and concentrated, and violet crystals (3.234 g, 81% yield) were obtained after
o
o
1
o
cooling to -30 C for 3 days. Mp: 123.3-127.6 C. H NMR (C
s, 2H, CH), 2.327 (s, 6H, N(CH ), 1.562-1.574 (d, 12H, CH(CH
Ni: C, 54.15; H, 10.10; N, 21.05; Found: C, 54.03; H, 10.04; N, 21.16.
6
D
6
, 25 C, ppm): 3.502
(
3
)
2
)
3 2
). Anal. Calcd for
C
18
H
40
N
6
2
.2. Thermogravimetric analysis and CVD deposition
Thermogravimetric analysis was studied through a Netzsch STA 449C under an
inert atmosphere and argon was used as a carrier gas. A heating rate of 10 K/min was
used for the heating process. Plot of vapor pressure-temperature was obtained from
thermogravimetry based on the Langmuir and Antoine equation, and benzoic acid was
selected as a standard [40].
The deposition tests were carried out using a hot-wall CVD reactor and the films
o
were grown on Si(100) wafer with a 100 nm SiO
2
film at 250 C for 30 min. The
CVD apparatus has been described in the previous literature [41]. Compound 1 was
o
maintained at 130 C to produce sufficient vapor. The forming gas (N
2
/10%-H ) and
2
nitrogen were used as reactive and carrier gases, respectively. Other parameters of
deposition including forming gas (N /10%-H ) flow (100 mL/min), N flow (120
2
2
2

mL/min), and deposition pressure (5 torr).
2
.3. Characterization
The thickness and surface morphology of film was studied through scanning
electron microscopy (SEM) (Hitachi S-4800) and atomic force microscopy (AFM)
Bruker Multimode 8), respectively. The composition and crystalline phase of film
was analyzed through X-ray photoelectron spectroscopy (XPS) (Thermo ESCALAB
(
2
50Xi ) and X-ray diffraction (XRD) (Bruker D8), respectively.
. Results and Discussion
3
As displayed in Scheme 1, compound 1 was synthesized through a conventional
salt-elimination (LiCl) reaction by mixing the corresponding guanidinate lithium salt
(
originating from the reaction of diisopropylcarbodiimide with [LiN(Me)
2
]) and NiCl
2
o
in Et
2
O/THF (1:1, v/v) solvent at 70 C. Compound 1 was isolated as violet solid in a
o
8
1
1% yield and purified through crystallization at -30 C in n-hexane. It melts at
o
23.3-127.6 C and is sensitive to moisture and air.
Scheme 1. Synthesis of compound 1.
The selected N,N’-diisopropyl-2-dimethyl-amidoguanidinato ligand has been
widely used for preparation of other metal guanidinate compounds (including Ti and
Hf etc.) and corresponding compounds have been successfully applied in CVD or
ALD process [10,11]. It should be noted that the synthesis of nickel guanidinate

i
compound with other substituent group (such as ((SiMe
3
)
2
NC( PrN)
2
2
) Ni) was also
attempted, but no sufficient purity compound was obtained, and thus no further
research and discussion was made in this study.
1H NMR spectrum and elemental analysis were employed to analyze the structure
of compound 1. The result exactly matches with the structure presented in Scheme 1,
indicating that the purity and formation of compound is achieved as expected.
Meanwhile, to further study the structure information of compound 1, the
single-crystal x-ray diffraction was performed. The single-crystal x-ray diffraction
result of compound 1 (Fig. 1) demonstrates its monomer nature and the reliability of
the synthesis pathways. Selected bonds lengths and angles and corresponding
crystallographic datas for compound 1 are summarized in Tables 1 and 2, respectively.
As seen in Fig. 1, compound 1 adopts a mononuclear structure with distorted square
planar coordination geometry near Ni center atom which lies at a distance of 0.0061 Å
from the coordination plane. The Ni atom is surrounded by four N atoms and exists as
Ni-N bonds. The average Ni-N bonds lengths (1.933 Å) in compound 1 are similar to
those found in Ni(2,6-Me
2
C
6
H
3
NCHC(Me)NC
6
H
3
-2,6-Me
2
)
2
(1.921(1)-1.948(1) Å)
i
i
[
(
42], but are shorter than those of Ni(2,6- Pr
2
C
6
H
3
NCHC(Me)NC
6
H
3
-2,6- Pr
)
2 2
1.963(2)-1.999(2) Å) [42]. The lengths of C-N bonds (1.376(4) Å, 1.336(5) Å, and
t
1
.340(4) Å) compare well with those found in [Me
2
NC(N Bu)
2
Sn(NMe )] [43]. In
2
addition, the sum of angles about the {CN
3
} backbone approaching 360°, which
suggests a high degree delocalisation of π-electron [43]. Clearly, all above results
illustrate the rationality of the structure of compound 1.

Fig. 1. ORTEP diagram of compound 1 showing 30% probability ellipsoids.
Table 1 Selected bonds lengths [Å] and angles [deg] for compound
1
.
Ni(1)-N(2) 1.933(3) N(2)-Ni(1)-N(3)
Ni(1)-N(3) 1.932(3) N(4)-Ni(1)-N(5)
69.26(11)
69.03(12)
Ni(1)-N(4) 1.936(3) N(2)-Ni(1)-N(5) 174.90(11)
Ni(1)-N(5) 1.931(3) N(3)-Ni(1)-N(5) 110.56(12)
C(3)-N(1) 1.376(4) N(2)-Ni(1)-N(4) 111.62(12)
C(3)-N(2) 1.336(4) N(3)-Ni(1)-N(4) 175.01(12)
C(3)-N(3) 1.340(4) C(3)-N(2)-Ni(1)
N(1)-C(1) 1.449(4) C(3)-N(3)-Ni(1)
N(1)-C(2) 1.447(4)
90.2(2)
90.1(2)

Table 2 Crystallographic datas for compound 1.
Formula
Mw
C
18
H
40NiN
6
a/Å
b/Å
c/Å
20.5448(6)
15.9804(4)
27.7038(7)
90
399.27
150
Temperature (K)
Crystal system
Space group
o
Orthorhombic
P b c a
α/
o
β/
90
o
Wavelength Mo Kα (Å)
0.71073
γ/
90
-
3
3
D
x
/g cm
1.166
V/Å
Z
9095.6(4)
16
o
2
θ range/
2.184-26.397
Absorption
coefficient,mm
R, wR2 (I > 2σ(I))
0.0542, 0.1353
0.0898, 0.1617
0.865
-
1
R, wR2 (all data)
CCDC number
1826546
To verify that the compound 1 is a suitable precursor for CVD of nickel-based films,
its thermal behavior was analyzed through TGA. Fig. 2 shows the evaporation of
o
compound 1 starts at 125 C and occurs in a single step with residual mass (12.3%).
The evaluation of volatility of compound 1 is based on the T50 which is the
temperature that 50% mass of the compound has volatilized, and the relatively low T50
value (176 °C) suggests its good volatility. Nevertheless, the residual mass (12.3%) is
a relative high value, demonstrating that a percentage of decomposition may exists in
the evaporation process. It can be seen that a trailing exists in the TG curves of
o
compound 1 at approximately 200 C, implying that thermal decomposition starts at
this temperature. Indeed, relative low thermal stability of precursor may be benefit for

accomplishment of a CVD process to some extent, because thermal decomposition of
precursor is the key step in CVD processes and thus greatly influences the film
deposit [20]. And it should be mentioned that this is based on a premise--the precursor
must possesses sufficient volatility and thermal stability for delivery to CVD reactor
without decomposition.
Fig. 2. Thermogravimetric analyses of compound 1.
Vapor pressure data is important in deposition process control, and is necessary to
evaluate the transport behavior of compound. Based on the plot of vapor pressure and
temperature, a suitable evaporation temperature would be easy to select to ensure that
the precursor flow is maintained at an appropriate level. As seen in Fig. 3, it is found
that compound 1 can provide sufficient vapor pressure at a relative low temperature
o
(
130 C). Combination of the above mentioned experiment results of TG show that
compound 1 can delivered from evaporation zone to deposition reactor without
decomposition by maintaining at a suitable evaporation temperature, which
demonstrates the feasibility of compound 1 as a CVD precursor.

Fig. 3. Vapor pressure–temperature curves of compound 1.
After the aforementioned studies, compound 1 was performed in a hot-wall CVD
reactor to provide a straightforward result for its potential as CVD precursor. The film
o
was grown on SiO
2
/Si (100) substrate at 250 C for 30 min. The thickness of film was
measured by cross sectional SEM (Fig. 4) and a film with thickness of about 133 nm
o
was deposited. The deposition experiment below 250 C was also attempted, but
nearly no film deposited. The surface morphology of the as-deposited film is
presented in Fig. 5. The AFM image shows that the film is continuous and has a
surface roughness with root-mean-square roughness (RMS) value of 8.18 nm.
o
Fig. 4. Cross sectional SEM image of film deposited at 250 C.

o
Fig. 5. AFM image of film deposited at 250 C.
XPS was employed to study the composition and bonding states of the as-grown
+
films after Ar sputtering for 30s to exclude the surface contamination prior to
measurement. The survey spectra (Fig. 6) demonstrates that the film is mainly
composed of Ni (92.2%), together with a small amount of C (6.3%) and negligible N
(
0.8) and O (0.7%) content. Fig. 7a shows high-resolution Ni 2p3/2 XPS spectra of the
film, and it is found that the Ni 2p3/2 spectra constitutes two components, which are
located at 852.7 eV and 853.5 eV, respectively. Among the two peaks, the peak at
8
52.7 eV and 853.5 eV should be attributed to metallic Ni and Ni–C, respectively [44].
Fig. 7b shows that C 1s spectrum can be separated into two peaks, each of which can
be ascribed to C-Ni at 283.5 eV and C-C at 284.5 eV, respectively [44,45]. The C
contamination is probably caused by the producing of byproduct in deposition process
[
46]. All these results suggest the deposited film is a Ni metal material.

o
Fig. 6. XPS survey spectra of film deposited at 250 C.
o
Fig. 7. (a) Ni 2p3/2 XPS spectra of film deposited at 250 C and (b) C 1s XPS spectra
o
of film deposited at 250 C.
XRD was performed to further investigate the composition and crystalline phase of
film deposited at 250 °C. As presented in Fig. 8, two strong diffraction peaks at 2θ =
o
o
4
4.6 and 52 are associated with Ni(111) and Ni(200) orientation, respectively.
Meanwhile, two weak diffraction peaks correspond to Ni C(110) and Ni C(006)
3
3
o
o
orientation are observed at 2θ = 39.1 and 42 respectively [44,47,48], which
demonstrates the existent small amount of Ni-C. Undoubtedly, the result of XRD is
consistent with XPS, and all these results illustrate that compound 1 is suitable for

CVD precursor.
o
Fig. 8. XRD spectra of film deposited at 250 C.
4
. Conclusion
i
In conclusion, a nickel(II) guanidinate compound [((Me)
2
NC( PrN)
2
2
) Ni] was
obtained from the reaction of NiCl with the corresponding lithium salt of guanidinate
2
i
o
ligand [(Me)
2
NC( PrN)
2
Li] at 70 C with high yields. The structure and thermal
1
behavior of compound was examined by H NMR, single crystal X-ray diffraction,
elemental analysis, and TGA, respectively. The potential of compound as CVD
precursor was evaluated through a hot-wall CVD reactor, and a Ni metal film was
successfully prepared. All these results demonstrate that this compound is capable of
CVD precursor.
Appendix A. Supplementary Material
CCDC 1826546 contains the supplementary crystallographic data for 1. These data
can be obtained free of charge via http:// www.ccdc.cam.ac.uk/conts/retrieving.html,

or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.
Notes
The authors declare no competing financial interest.
Acknowledgments
We gratefully acknowledge financial support of this work by the National Natural
Science Foundation of China-Henan joint fund (No. U1604143) and the Fundamental
Research Funds for the Central Universities (JUSRP51627B).
References
[
1] F.T. Edelmann, in: A.F. Hill, M.J. Fink (Eds.), Advances in the Coordination
Chemistry of Amidinate and Guanidinate Ligands, Elsevier Inc., San Diego, 2008, pp.
83-352.
1
[
[
[
[
2] E. Smolensky, M.S. Eisen, Dalton Trans. (2007) 5623-5650.
3] S. Ge, A. Meetsma, B. Hessen, Organometallics 27 (2008) 3131-3135.
4] S. Collins, Coord. Chem. Rev. 255 (2011) 118-138.
5] C. Alonso-Moreno, A. Antinolo, F. Carrillo-Hermosilla, A. Otero, Chem. Soc. Rev.
4
3 (2014) 3406-3425.
[
[
6] W. Zhang, L.R. Sita, J. Am. Chem. Soc. 130 (2008) 442-443.
7] F.T. Edelmann, Chem. Soc. Rev. 41 (2012) 7657-7672.

[
8] J.P. Coyle, W.H. Monillas, G.P.A. Yap, S.T. Barry, Inorg. Chem. 47 (2008)
83-689.
9] T. Chen, C. Xu, T.H. Baum, G.T. Stauf, J.F. Roeder, A.G. Dipasquale, A.L.
Rheingold, Chem. Mater. 22 (2010) 27-35.
10] S.J. Kim, K. Xu, H. Parala, R. Beranek, M. Bledowski, K. Sliozberg, H.-W.
6
[
[
Becker, D. Rogalla, D. Barreca, C. Maccato, C. Sada, W. Schuhmann, R.A. Fischer, A.
Devi, Chem. Vap. Deposition 19 (2013) 45-52.
[
11] K. Xu, A.P. Milanov, H. Parala, C. Wenger, C. Baristiran-Kaynak, K. Lakribssi, T.
Toader, C. Bock, D. Rogalla, H.-W. Becker, U. Kunze, A. Devi, Chem. Vap.
Deposition 18 (2012) 27-35.
[
12] F.A. Stokes, L. Kloo, P.J. Harford, A.J. Peel, R.J. Less, A.E.H. Wheatley, D.S.
Wright, Aust. J. Chem. 67 (2014) 1081-1087.
13] M.-B. Martin, B. Dlubak, R.S. Weatherup, H. Yang, C. Deranlot, K.
[
Bouzehouane, F. Petroff, A. Anane, S. Hofmann, J. Robertson, A. Fert, P. Seneor, ACS
Nano 8 (2014) 7890-7895.
[
14] S. Seo, M.J. Lee, D.H. Seo, E.J. Jeoung, D.-S. Suh, Y.S. Joung, I.K. Yoo, I.R.
Hwang, S.H. Kim, I.S. Byun, J.-S. Kim, J.S. Choi, B.H. Park, Appl. Phys. Lett. 85
(
[
2004) 5655-5657.
15] S. Seo, M.J. Lee, D.C. Kim, S.E. Ahn, B.-H. Park, Y.S. Kim, I.K. Yoo, I.S. Byun,
I.R. Hwang, S.H. Kim, J.-S. Kim, J.S. Choi, J.H. Lee, S.H. Jeon, S.H. Hong, B.H.
Park, Appl. Phys. Lett. 87 (2005) 263507.
[
16] Y.-H. You, B.-S. So, J.-H. Hwang, W. Cho, S.S. Lee, T.-M. Chung, C.G. Kim,

K.-S. An, Appl. Phys. Lett. 89 (2006) 222105.
17] D. Ma, D.Z. Chi, M.E. Loomans, W.D. Wang, A.S.W. Wong, S.J. Chua, Acta
Mater. 54 (2006) 4905-4911.
18] D.Z. Chi, D. Mangelinck, A.S. Zuruzi, A.S.W. Wong, S.K. Lahiri, J. Electron.
Mater. 30 (2001) 1483-1488.
[
[
[
[
19] X. Fan, Z. Peng, R. Ye, H. Zhou, X. Guo, ACS Nano 9 (2015) 7407-7418.
20] M.A. Malik, P. O’Brien, in: A.C. Jones, M.L. Hitchman (Eds.), Basic Chemistry
of CVD and ALD Precursors, Royal Society of Chemistry, London, 2009, pp.
07-271.
2
[
[
21] F. Fau-Canillac, F. Maury, Surf. Coat. Technol. 64 (1994) 21-27.
22] Z. Li, R.G. Gordon, V. Pallem, H. Li, D.V. Shenai, Chem. Mater. 22 (2010)
3
060-3066.
[
[
[
23] B.S. Lim, A. Rahtu, R.G. Gordon, Nat. Mater. 2 (2003) 749-754.
24] K. Li, J. Feng, J. Kwak, J. Yang, R.G. Gordon, J. Appl. Phys. 121 (2017) 175301.
25] M.Z. Sialvi, R.J. Mortimer, G.D. Wilcox, A.M. Teridi, T.S. Varley, K.G. Upul
Wijayantha, C.A. Kirk, ACS Appl. Mater. Interfaces 5 (2013) 5675-5682.
26] P. Moravec, J. Smolík, H. Keskinen, J.M. Mäkelä, S. Bakardjieva, V.V.
Levdansky, Mater. Sci. Appl. 2 (2011) 258-264.
27] M. Utriainen, M. Kröger-Laukkanen, L.-S. Johansson, L. Niinistö, Appl. Surf.
Sci. 157 (2000) 151-158.
[
[
[
(
28] T.J. Knisley, M.J. Saly, M.J. Heeg, J.L. Roberts, C.H. Winter, Organometallics 30
2011) 5010-5017.

[
29] J. Park, H. Jeon, H. Kim, W. Jang, C. Kang, J. Yuh, H. Jeon, Jpn. J. Appl. Phys.
4 (2015) 025501.
30] M.M. Kerrigan, J.P. Klesko, K.J. Blakeney, C.H. Winter, ACS Appl. Mater.
Interfaces 10 (2018) 14200-14208.
5
[
[
(
[
[
[
(
[
31] L.C. Kalutarage, P.D. Martin, M.J. Heeg, C.H. Winter, J. Am. Chem. Soc. 135
2013) 12588-12591.
32] J.-K. Kang, S.-W. Rhee, J. Mater. Res. 15 (2000) 1828-1833.
33] J.-K. Kang, S.-W. Rhee, Thin Solid Films 391 (2001) 57-61.
34] L. Brissonneau, R. Sahnoun, C. Mijoule, C. Vahlas, J. Electrochem. Soc. 147
2000) 1443-1448.
35] J. Chae, H.-S. Park, S.-w. Kang, Electrochem. Solid-State Lett. 5 (2002)
C64-C66.
[
(
[
[
[
36] A.N. Cloud, L.M. Davis, G.S. Girolami, J.R. Abelson, J. Vac. Sci. Technol., A 32
2014) 020606.
37] L. Du, S. Yu, X. Liu, Y. Ding, New J. Chem. 42 (2018) 4553-4558.
38] Y. Zhang, L. Du, X. Liu, Y. Ding, New J. Chem. 42 (2018) 9110-9115.
39] M. Rusek, T. Komossa, G. Bendt, S. Schulz, J. Cryst. Growth 470 (2017)
1
28-134.
[
(
[
[
40] S.F. Wright, D. Dollimore, J.G. Dunn, K. Alexander, Thermochim. Acta 421
2004) 25-30.
41] L. Du, W. Chu, H. Miao, C. Xu, Y. Ding, RSC Adv. 5 (2015) 71637-71643.
42] N. Muresan, T. Weyhermuller, K. Wieghardt, Dalton Trans. (2007) 4390-4398.

[
43] I.Y. Ahmet, M.S. Hill, P.R. Raithby, A.L. Johnson, Dalton Trans. 47 (2018)
031-5048.
44] Y. -P. Wang, Z.-J. Ding, Q.-X. Liu, W.-J. Liu, S.-J. Ding, D.W. Zhang, J. Mater.
Chem. C 4 (2016) 11059-11066.
45] M. Hasegawa, K. Sugawara, R. Suto, S. Sambonsuge, Y. Teraoka, A. Yoshigoe, S.
Filimonov, H. Fukidome, M. Suemitsu, Nanoscale Res. Lett. 10 (2015) 421.
46] L. Brissonneau, D. de Caro, D. Boursier, R. Madar, C. Vahlas, Chem. Vap.
Deposition 5 (1999) 143-149.
47] Y. Goto, K. Taniguchi, T. Omata, S. Otsuka-Yao-Matsuo, N. Ohashi, S. Ueda, H.
Yoshikawa, Y. Yamashita, H. Oohashi, K. Kobayashi, Chem. Mater. 20 (2008)
156-4160.
48] S.I. Dorovskikh, A.V. Alexeyev, N.V. Kuratieva, T.V. Basova, V.G. Kiselev, L.A.
Sheludyakova, Y.V. Shubin, N.B. Morozova, I.K. Igumenov, J. Organomet. Chem.
41-742 (2013) 122-130.
5
[
[
[
[
4
[
7

i
A nickel(II) guanidinate compound [((Me)
2
NC( PrN)
2
2
) Ni] has been synthesized and
1
characterized by H NMR, elemental analysis and X-ray diffraction. Its thermal
properties, including volatility, stability, and transport behavior, were studied by
thermogravimetric analysis (TGA). Moreover, deposition test was conducted in a
hot-wall CVD reactor to verify its potential as a CVD precursor.