Full Paper

Received: 3 February 2010 Revised: 17 April 2010 Accepted: 19 April 2010 Published online in Wiley Online Library: 28 June 2010

(wileyonlinelibrary.com) DOI 10.1002/aoc.1672

Deposition of crystalline copper films

from tetranuclear copper (II) complexes
without application of reducing atmosphere
Muhammad Shahida , Muhammad Mazharb∗ , Mazhar Hamida ,
Paul O’ Brienc∗ , Mohammad A. Malikc and Madeleine Helliwellc
Crystalline copper films were deposited by aerosol-assisted chemical vapor deposition (AACVD) in the absence of hydrogen
from two newly synthesized complexes [Cu(deae)(TFA)]4 ·1.25THF (1) and [Cu4 (OAc)6 (bdmap)2 (H2 O)2 ]·4H2 O (2) [deae = N,
N-diethylaminoethanolate, TFA = trifloroacetate, OAc = acetate and bdmap = 1,3-bis(dimethylamino)-2-propanolato]. These
precursors were prepared in high yield using mixed ligands and crystallized in tetragonal and triclinic crystal systems with
space groups 141 /a and P − 1. Complexes 1 and 2 thermally decomposed at 290 and 250 ◦ C, respectively, to yield copper films
which were characterized by SEM/EDX for their morphology and composition and PXRD for their crystallinity and phase. These
films have smooth morphologies with particle sizes within the range of 0.3–0.6 µm and may find applications in fabrication of
ultralarge-scale integrated circuits. Copyright

c 2010 John Wiley & Sons, Ltd.
Supporting information may be found in the online version of this article.

Keywords: homometallic copper complexes; X-ray structure; AACVD; XRD; copper films

Introduction synthesized complexes are Cu(dmae)2 [15] and [Cu(dmae)Cl]4 ,[16]

which decompose to metallic copper in the absence of a reducing
Properties such as low electrical resistivity, high resistance to environment. The risk involved in the utilization of this type of
the electromigration[1] and resistance to formation of voids precursor is their lesser stability in the open atmosphere and the
induced by stress make copper superior to other metals in possibility of contamination with halogens in the film.
many applications. The most significant use of copper thin
In the present work, we report the deposition of crystalline
films is in the printing of ultralarge-scale integrated (ULSI)
copper thin films from the tetranuclear copper precursors [Cu
circuits[2] and multilevel coatings in device fabrication.[3] Such
(deae)(OAc)]4 ·1.25THF (1) and [Cu4 (OAc)6 (bdmap)2 (H2 O)2 ]·4H2 O
critical and low-dimensional features are accommodated by
(2), which were synthesized by a simple reaction of ligands,
the utilization of a chemical vapor deposition technique using
aminoalcohols and acetates in THF (tetrahydrofuran) and char-
stable precursors that have high volatility and low decomposition
acterized by various techniques, including X-ray crystallography.
temperature and that are readily available. Many homoleptic
Both complexes were used for the deposition of copper thin films
and heterolyptic complexes of copper with ligands including
by chemical vapor deposition without the use of an extraneous
alkoxides,[4] aminoalkoxides,[5] fluorinated[6] and unflorinated
reducing medium.
β-diketonates[7] and β-ketoiminates,[8] alkyl phosphines[9] and
alkyls have been tested. Films deposited from both fluorinated
and unfluorinated copper derivatives have been found to be
contaminated with carbon or fluorine impurities if decomposed
Experimental
in the absence of a reducing atmosphere of H2 , due to unwanted General Considerations
heat induced fragmentation.[10]
The commercially available precursor, (hfac)CuL, (where All reagents were purchased from Sigma-Aldrich and synthetic
L = trimethylvinylsilane[11] or 2-methyl-1-hexen-3-yne)[12,13] has work was carried out under an inert atmosphere of dry argon
been most successfully employed for the deposition of high-purity gas using Schlenk and glovebox techniques. Solvents were rigor-
Cu films without an external reducing agent. However, these com- ously dried on sodiumbenzophenoate. N,N-diethylaminoethanol
plexes are thermally unstable and need to be stored in a refrigerator
or preserved by the addition of a chemical stabilizer. Thermal sta-
∗ Correspondence to: Muhammad Mazhar, Department of chemistry, University
bility may be achieved by the addition of π -donor ligands, but
of Malaya, 50603 Kualalumpur, Malaysia. E-mail: mazhar42pk@yahoo.com
at the expense of vapor pressure. Another group of precursors
having fluorinated imino and amino alcoholate were reported to a Department of Chemistry, Quaid-I-Azam University, Islamabad 45320, Pakistan
have advantages of easy accessibility, higher volatility and better
thermal stability.[14] These precursors are capable of delivering b Department of chemistry, University of Malaya, 50603 Kualalumpur, Malaysia
copper metal in the presence of a low concentration of O2 in the c The School of Chemistry and School of Materials, The University of Manchester,
714

carrier argon gas. Among other aminoalcohols, the most easily Oxford Road, Manchester M13 9PL, UK

Appl. Organometal. Chem. 2010, 24, 714–720 Copyright

c 2010 John Wiley & Sons, Ltd.
Deposition of crystalline copper films from tetranuclear copper (II) complexes
(deaeH) and 1,3-bis(dimethylamino)-2-propanol (bdmapH) were
dried by refluxing over K2 CO3 for 10 h and distilled immedi-
ately before use while Cu(TFA)2 was prepared by a literature
procedure.[17]
Elemental analyses were performed on a CHN analyzer LECO
model CHNS-932. Melting points were determined in a capillary
tube using an electrothermal melting point apparatus, model MP.D
Mitamura Riken Kogyo (Japan), and are reported as recorded. FT-
IR spectra were recorded as KBr pellets on a Bio-Rad Excaliber,
model FTS 300 MX spectrometer (USA), in the frequency range
4000–400 cm−1 . Controlled thermal analyses of the complexes
were investigated using a Seiko SSC/S200 thermal analyzer at
a heating rate of 10 ◦ C/min under N2 flow. Mass spectra were
recorded on a Micromass Platform II instrument. The phase and
crystallinity of deposited films were characterized by means of
a Bruker AXS D8 diffractometer using monochromatic Cu-Kα
(λ = 0.154184 nm) radiation on which a range of 2θ (from 35.00
to 90.00◦ ) was scanned, to cover the diffraction pattern of the
metallic Cu phase. Surface morphology of films was determined
by a FEG-SEM Philips XL30. Samples were carbon-coated before
observation and EDX-DX4 was used to determine the composition
of the films.
Synthesis of [Cu(deae)(TFA)]4 ·1.25THF (1)
A 0.28 g (2.4 mmol) aliquot of N,N-diethylaminoethanol (deaeH)
was added drop-wise from a syringe to a solution of 0.70 g
(2.4 mmol) Cu(TFA)2 in 15 ml of THF at room temperature. After
stirring for 2 h, the reaction mixture was evaporated to dry-
ness under vacuum and the solid was recrystallized from THF
to give 70% yield of blue cubic crystals after 7 days at room
temperature, m.p. 195 ◦ C. Anal. calcd For C37 H66 Cu4 F12 N4 O13.25 :
C, 35.24; H, 5.27; N, 4.44; F, 18.08. Found: C, 34.62; H, 5.45;
N, 4.59; F, 18.25%. FT-IR (KBr, cm−1 ): 2984m, 2881m, 1695s,
1423s, 1272 w, 1200s, 1181s, 1132s, 1067s, 1016m, 950s, 905m,
840m, 796s, 728s, 633m, 527m, 435 w. MALDI-MS (positive
mode) m/z: 818 [Cu2 (deae)4 (TFA)2 ]+ , 693 [M-(deae)(TFA)4 ]+ , 651
[Cu3 (deae)3 (TFA)]+ , 649 [Cu3 (deae)2 (TFA)2 ]+ , 542 [Cu3 (deae)3 ]+ ,
444 [M-Cu2 (deae)4 (TFA)2 ]+ , 401 [M/2–(deae)(TFA)]+ , 399
[M/2–(deae)2 ]+ , 297.5 [Cu(deae)2 ]+ . TGA: 83–213 ◦ C (2.98 wt%
loss), 213–290 ◦ C (residue 20.56%).
Synthesis of [Cu4 (OAc)6 (bdmap)2 (H2 O)2 ]·4H2 O (2)
A 0.50 g (2.75 mmol) aliquot of copper (II) acetate monohydrate
[Cu(OAc)2 ·H2 O] suspended in 20 ml of THF in 50 ml Schlenk
tube, fitted with magnetic stirrer and dry nitrogen line, was
added drop by drop from a syringe, 0.19 g (1.30 mmol) of
1,3-bis(dimethylamino)-2-propanol (bdmapH) and the mixture
was stirred for 2 h at room temperature. Excess of Cu(OAc)2 ·H2 O
was removed by cannula filtration. The filtrate was evaporated
to dryness under vacuum and the solid was redissolved in
5 ml of dichloromethane to give a 75% yield of blue crys-
tals after 10 days at room temperature. The resulting product
analyses closely matches for [Cu4 (OAc)6 (bdmap)2 (H2 O)2 ]·4H2 O,
as determined by X-ray crystallography, m.p. 90 ◦ C. Anal. calcd
For C26 H64 Cu4 N4 O20 : C, 31.01; H, 6.41; N, 5.56. Found: C, 30.71;
H, 6.57; N, 5.51%. FT-IR (KBr, cm−1 ): 3392br, 2961 w, 2881 w,
1654s, 1602s, 1402s, 1340s, 1290 w, 1249 w, 1203 w, 1114m,
1020m, 997m, 932 w, 905m, 680s, 616m, 542m, 483 w. APCI-
MS (positive scan) m/z: 998 [Cu4 (OAc)6 (bdmap)2 (O)6 ]+ , 857.8
[Cu4 (Oac)5 (bdmap)2 (H2 O)]+ , 815.1 [Cu4 (Oac)4 (bdmap)2 (H2 O)2 ]+ ,
Appl. Organometal. Chem. 2010, 24, 714–720 Copyright

c 2010 John Wiley & Sons, Ltd.
736.6 [Cu3 (Oac)4 (bdmap)2 (H2 O)]+ , 601.6 [Cu3 (Oac)2 (bdmap)2 ]+ ,
475.4 [Cu2 (Oac)(bdmap)2 ]+ , 416.6 [Cu2 (bdmap)2 ]+ , 354.4
[Cu(bdmap)2 ]+ , 329.4 [Cu2 (Oac)(bdmap)]+ , 271.1 [Cu2 (bdmap)]+ ,
208.5 [Cu(bdmap)]+ . TGA: 70–116 ◦ C (2.16 wt% loss), 116–205 ◦ C
(11.54 wt% loss), 205–350 ◦ C (residue wt 25.98%).
X-ray Crystallography
Single crystal X-ray data measurements were made using graphite
monochromated Mo-Kα radiation on a Bruker APEX diffractometer.
The structures were solved by direct methods[18] and refined
by full-matrix least squares on F2 .[19] All non-hydrogen atoms
were refined with anisotropic atomic displacement parameters.
Hydrogen atoms bonded to C were placed in calculated positions,
assigned isotropic thermal parameters and allowed to ride on their
parent carbon atoms. Those bonded to the water O atoms in 2 were
found by difference Fourier methods and refined isotropically.
Table 1 summarizes the crystal data and refinement details for
both the complexes.
Thin Film Deposition
Copper thin films were grown on bare glass substrates in a hot-
walled reactor containing a quartz (1.5 cm diameter) tube, by
gas phase reactions of the precursors in an argon environment
using a self-designed aerosol-assisted chemical vapor deposition
(AACVD) assembly described elsewhere.[20] In a typical experiment,
0.1 g of precursor dissolved in 15 ml THF in a two-neck round-
bottomed flask was connected via rubber tubing to a quartz
reactor into which 2.5 × 1 cm substrate slides were placed inside a
carbolite tube furnace and a flow of argon gas was regulated
using a Platon flow gage on the other neck. The flask was
mounted on piezoelectric modulator of an ultrasonic humidifier
for atomization of the precursor solution to tiny droplets of aerosol
that were ultimately transferred by the carrier gas into the reactor
chamber. Glass substrates were treated with concentrated nitric
acid, followed by several washings with deionized water and then
oven dried at 100 ◦ C before deposition. Deposition was carried
out at 290 ◦ C for complex (1) and 250 ◦ C for (2) at a constant argon
flow rate of 130 ml/min on glass substrates for 1 h.
Results and Discussion
Synthesis and Characterization
Cu(TFA)2 reacts with with N,N-(diethylamino)ethanol (deaeH) in
a 1 : 1 molar ratio to give complex 1 and Cu(OAc)2 ·H2 O reacts
with 1,3-bis(dimethylamino)-2-propanol (bdmapH) in a 2 : 1 molar
ratio to give complex 2, in THF at room temperature as shown in
Scheme 1.
In the FT-IR spectrum of 1, the most characteristic bands are
those attributable to the TFA ligands that appear at 1695 cm−1
for νasy (CO2 ) and 1423 cm−1 for νsy (CO2 ) indicating the presence
of bridging TFA ligands. The absorption frequencies due to the
µ-deae (νC−H ) are prominent in the range 2800–3000 cm−1 , while
the absorption band close to 530 cm−1 for Cu–O is in accordance
to the literature.[21,22] The spectrum of 1 was also characterized
by three strong C–F and C–O absorption bands in range the
1120–1210 cm−1 , corresponding to the TFA ligands. The FT-IR
spectrum of 2 showed the presence of a broad band at 3392 cm−1
which was due to absorption by the O–H group of the water
715
molecules, but no peak in the range 3300–3400 cm−1 was present
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 M. Shahid et al.

Table 1. Crystal data and refinement parameters for the complexes [Cu(deae)(TFA)]4 ·1.25THF (1) and [Cu4 (OAc)6 (bdmap)2 (H2 O)2 ]·4H2 O (2)

Empirical formula C37 H66 Cu4 F12 N4 O13.25 C26 H64 Cu4 N4 O20

Formula weight 1261.10 1006.97

Temperature 100 (2)K 100(2)K
Wavelength 0.71073 Å 0.71073 Å
Crystal system Tetragonal Triclinic
Space group I4(1)/a P−1
Unit cell dimensions a = 16.892(3) Å a = 9.1202(7) Å
b = 16.892(3) Å b = 10.5896(8) Å
c = 17.777(6) Å c = 11.4716(8) Å
α = β = γ = 90◦ α = 102.2150(1)◦
β = 101.6470(1)◦
γ = 100.7180(1)◦
Volume 5073(2) Å 3 1029(13) Å 3
Z 4 1
Density (calculated) 1.651 mg/m3 1.624 mg/m3
Absorption coefficient 1.760 mm−1 2.116 mm−1
F(000) 2584 524
Crystal size(mm) 0.40 × 0.35 × 0.20 0.50 × 0.50 × 0.30
θ range for data collection 1.66 to 26.32◦ 1.88 to 26.37◦
Index ranges −21 ≤ h ≤ 15, −8 ≤ h ≤ 11,
−17 ≤ k ≤ 18, −13 ≤ k ≤ 12,
−16 ≤ l ≤ 21 −14 ≤ l ≤ 11
Reflections collected 7894 5976
Independent reflections 2573 [R(int) = 0.0270] 4098 [R(int) = 0.0137]
Maximum and minimum transmission 0.7198 and 0.5396 0.5694 and 0.4177
Refinement method Full-matrix least-squares on F 2 Full-matrix least-squares on F 2
Goodness-of-fit on F 2 1.299 1.048
Final R indices [I > 2σ (I)] R1 = 0.0332, wR2 = 0.0766 R1 = 0.0258, wR2 = 0.0706
R indices (all data) R1 = 0.0449, wR2 = 0.0799 R1 = 0.0279, wR2 = 0.0719
Largest difference peak and hole 0.432 and −0.237 e × Å −3 0.424 and −0.383 e × Å −3

CuCl2 2NaO
CH 3 OCC
2LiO H3 ·3H
2O

4Cu(OCH3)2 4Cu(OOCCH3)2·H2O

4CF3COOH 2bdmapH
4deaeH THF
THF room temp
room temp

[Cu(deae)(TFA)]4·1.25THF (1) [Cu4(OAc)6(bdmap)2(H2O)2] ·4H2O (2)

+ 4CH3OH + 2CH3COOH

Scheme 1. Synthetic scheme for complexes 1 and 2.

in the case of complex 1, due to the absence of any O–H
or water molecules in the structure. The absorption frequency
of monodentate carboxylate appeared at 1654 cm−1 , while the
absorption bands at 1602 cm−1 for νasy (CO2 ) and 1402 cm−1 for
νsy (CO2 ) indicated the presence of bridging acetate ligands.[23]
In the MALDI-MS (positive mode) of complex 1, the molecular ion
peak did not appear due to the breakdown of the complex under
MS conditions but instead gave various fragments of different m/z
ratios. The heaviest fragment observed was [Cu2 (deae)4 (TFA)2 ]+
at m/z (818), with the base peak at m/z (444) corresponding
to [M–Cu2 (deae)4 (TFA)2 ]+ . The mass spectrum (positive scan)
716
since it broke down under MS conditions to give various
fragments. In the case of 2, the base peak was at m/z (736.6)
[Cu3 (Oac)4 (bdmap)2 (H2 O)]+ , with the largest fragment observed
being [Cu4 (OAc)6 (bdmap)2 (O)6 ]+ , m/z (998). This indicates the low
stability of both the complexes under MS conditions but devoid
of any molecular association.
Crystal Structural Analyses of 1 and 2
A plot of the labeled molecular structure of 1 is shown in Fig. 1(a);
the crystal data with structure refinement parameters are given in

of complex 2 again did not show any molecular ion peak, Table 1, while selected metrical data are listed in Table 2. The single

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c 2010 John Wiley & Sons, Ltd. Appl. Organometal. Chem. 2010, 24, 714–720
Deposition of crystalline copper films from tetranuclear copper (II) complexes
(a)
Figure 1. (a) A plot of the labeled molecular structure of [Cu(deae)(TFA)]4 ·1.25THF (1). The disordered THF molecules and hydrogen atoms are not shown
for clarity. (b) Diagram showing the core structure of 1.
crystal X-ray structure shows that the complex is tetranuclear, with
the asymmetric unit consisting of one-quarter of the molecule. The
four copper atoms, related by −4 symmetry, are interconnected
by four chelating-bridging deae and four briding trifluoroacetate
groups, and have a distorted octahedral geometry. The core unit
of complex 1 is a distorted cube (Fig. 1b) which consists of four
copper and four oxygen atoms (from the deae ligands) which are
present on alternate positions. Cu(1) has a six-coordinated CuO5 N
coordination sphere comprising one O,N-chelating deae, two
O-bridging deae and two bridging trifluoroacetate groups. Each
µ3 -oxygen of the chelating-bridging deae ligands bridges three Cu
atoms in the core unit, as found in [Cu(dmae)Cl]4 .[15] The equatorial
Cu-O distances are in range 1.934(2)–1.961(2) Å, and the equatorial
Cu–N distance is 2.076(2) Å, which is comparable with the reported
range.[19] The axial Cu–O(2)#2 (symmetry equivalent #2 −y + 1/4,
x + 1/4, −z + 9/4) and Cu–O(3)#3 (symmetry equivalent #3 −x,
−y + 1/2, z) distances are much longer at 2.558(2) and 2.711(2) Å,
respectively, due to Jahn–Teller distortion.[24] The angles about
the Cu atoms are also distorted from regular octahedral, with
O(3)#1–Cu(1)–O(3)#3 (symmetry equivalent #1 y − 1/4, −x + 1/4,
−z + 9/4) being reduced to 70.01(6)◦ (less than the ideal 90◦ )
and N(1)–Cu(1)–O(3)#3 being enlarged from the ideal 90◦ to
111.48(6)◦ . Also an axial–axial O(2)#2–Cu(1)–O(3)#3 bond angle
[144.86(5)◦ ] deviates from 180◦ , while the deae O–Cu–O ‘bite’
angle [86.38(7)◦ ] is less than 90◦ . All the four TFAs coordinate to
the Cu atoms in a µ-bridging fashion and each TFA coordinates to
two different Cu atoms.
Figure 2 shows the solid-state molecular structure for 2 and
the crystallographic data with refinement parameters are listed
in Table 1, while the selected geometric parameters are given in
Table 3. The acetate ligands coordinate in several coordination
modes, i.e. behaving as chelating to Cu(2), bidentate, bridging
between Cu(1) and Cu(2), and bridging monodentate, with the
oxygen O(4) bridging between Cu(1) and its inversion related
counterpart, Cu(1)#4 (symmetry equivalent #4 −x, −y, −z). The
bdmap ligands act as tridentate and bridge the two copper
centers, Cu(1) and Cu(2). The structure of 2 can be viewed as
two Cu2 (bdmap)(OAc)2 (H2 O) monomers linked together through
the µ2 -oxygen of the two monodentate acetate ligands. In each
monomeric unit, the two copper atoms are bridged by an oxygen
atom of the bdmap ligand and a bridging acetate group.
Appl. Organometal. Chem. 2010, 24, 714–720 Copyright

c 2010 John Wiley & Sons, Ltd.
(b)
Table 2. Selected metrical data for complex (1)
Bond distances (Å)
Cu(1)–O(3) 1.934(2) Cu(1)–N(1) 2.076(2)
Cu(1)–O(3)#1 1.947(2) Cu(1)–O(2)#2 2.558(2)
Cu(1)–O(1) 1.961(2) Cu(1)A–O(3)#3 2.711(2)
Bond angles (deg)
O(3)–Cu(1)–O(3)#1 89.98(8) O(3) #1–Cu(1)–N(1) 175.37(7)
O(3)–Cu(1)–O(1) 170.96(7) O(2)#2–Cu(1)–O(3)#3 144.86(5)
O(3) #1–Cu(1)–O(1) 92.59(7) O(3) #1–Cu(1)–O(3) #3 70.01(6)
O(3)–Cu(1)–N(1) 86.38(7) O(3) #3–Cu(1)–N(1) 111.48(6)
Symmetry transformations used to generate equivalent atoms: #1,
y − 1/4, −x + 1/4, −z + 9/4; #2, −y + 1/4, x + 1/4, −z + 9/4; #3, −x,
−y + 1/2, z.
The Cu(1) center has coordination number 5 with a distorted
square pyramidal geometry consisting of two bridging oxygen
[O(4), O(4)#4] atoms of the monodentate acetate groups, one
oxygen atom [O(3)] of the bridging acetate and the oxygen and
nitrogen atoms [O(1), N(2)] of the bridging bdmap ligand. A
distorted square pyramidal geometry is evident from the apical
substituent group, i.e. the doubly bridged O(4) of the monodentate
acetate ligand, being displaced towards O(4)#4 and away from
O(1), resulting in the angle O(4)–Cu(1)–O(1) being enlarged from
the ideal 90–109.12(5)◦ and O(4)–Cu(1)–O(4)#4 being reduced to
74.92(5)◦ . In addition, the copper-oxygen bond distance of Cu(1) to
the apical oxygen atom O(4) is much longer [2.400(1) Å] than all the
other Cu–O bond lengths around Cu(1), which are comparable to
the sum of the ionic radii, 1.92 Å. The distorted square pyramidal
geometry of Cu(1) in the complex 2 is also in accordance with
similar compounds of copper(II) reported in the literature.[25,26]
The relatively unusual monodentate acetate[25] is stabilized by
hydrogen bonding interactions (see below). The geometry around
Cu(2) can be described as distorted octahedral comprising five
oxygen and one nitrogen atoms. The octahedral environment is
generated by atoms O(6) and O(7) from the acetate ligand in
a chelating mode, O(2) of bridging acetate, two donor atoms
O(1), N(1) of the bdmap group and O(8) of the water, as auxiliary
ligand. The geometry of Cu(2) is distorted octahedral due to the
717
displacement of one apical atom O(7) towards O(6) and away from
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 M. Shahid et al.

Figure 2. An ORTEP plot of the molecular structure of [Cu4 (OAc)6 (bdmap)2 (H2 O)2 ]·4H2 O (2). Water molecules are omitted for clarity.

Table 3. Selected metrical data for complex (2) Table 4. Hydrogen-bond geometry (Å, deg) of 2

D–H· · ·A d(D–H) d(H· · ·A d(D· · ·A) < (D–HA)

Bond distances (Å)
Cu(1)–O(4)#4 1.959(1) Cu(2)–O(6) 1.958(1) O(8)–H(1O)· · ·O(6)#5 0.78(3) 1.97(3) 2.744(2) 173(3)
Cu(1)–O(3) 1.972(1) Cu(2)–O(2) 1.981(1) O(8)–H(2O)· · ·O(2s) 0.75(3) 2.06(3) 2.813(2) 174(3)
Cu(1)–N(2) 2.062(2) Cu(2)–N(1) 2.058(2) O(1s)–H(1s)· · ·O(2)#6 0.82(3) 2.17(3) 2.981(2) 168(3)
Cu(1)–O(4) 2.400(1) Cu(2)–O(8) 2.279(2) O(1s)–H(2s)· · ·O(7) 0.86(3) 1.97(3) 2.831(2) 171(3)
Cu(2)–O(1) 1.929(1) Cu(2)–O(7) 2.725(1) O(2s)–H(3s)· · ·O(5)#4 0.74(4) 2.16(4) 2.877(2) 165(4)
Bond angles (deg) O(2s)–H(4s)· · ·O(5)#7 0.80(4) 2.02(4) 2.815(2) 174(4)
O(1)–Cu(1)–N(2) 83.35(6) O(1)–Cu(2)–O(8) 93.23(6) Symmetry transformations used to generate equivalent atoms: #4, −x,
O(3)–Cu(1)–N(2) 170.81(6) O(6)–Cu(2)–O(8) 102.62(6) −y, −z; #5, x + 1, −y + 1, −z + 1; #6, −x + 1, −y, −z + 1; #7, x, y + 1, z.
O(1)–Cu(1)–O(4) 109.12(5) O(2)–Cu(2)–O(8) 86.52(6)
O(4)#4–Cu(1)–O(4) 74.92(5) N(1)–Cu(2)–O(8) 93.78(7)
N(2)–Cu(1)–O(4) 97.67(6) O(2)–Cu(2)–O(8 152.90(6)
O(1)–Cu(2)–O(6) 163.95(6) O(7)–Cu(2)–O(6) 53.43(5)
O(1)–Cu(2)–N(1) 85.39(6) O(1)–Cu(2)–O(7) 111.62(6)

Symmetry transformations used to generate equivalent atoms: #4, −x,

−y, −z.

O(1), resulting in an O(7)–Cu(2)–O(6) angle of 53.43(5)◦ (less than

90◦ ) and an O(1)–Cu(2)–O(7) angle of 111.63(5)◦ (greater than
90◦ ). Also the unequal copper–oxygen bond distances of Cu(2)
to the axial oxygen atoms O(8), O(7), i.e. 2.279(2) and 2.725(2) Å,
respectively, are much longer than the equatorial Cu–O bond
distances around Cu(2) that range from 1.929(1) to 1.981(1) Å (i.e.
close in value to the sum of the ionic radii, 1.92 Å), again indicative
of Jahn–Teller distortion. Figure 3. Thermogravimetric plot showing loss in weight with rise in
In crystal structure, the molecules are stabilized by intermolec- temperature for (a) complex 1 and (b) complex 2.
ular O–H· · ·O hydrogen bonds (Table 4). Each hydrogen atom of
one of the water molecules of hydration, O(2S), forms hydrogen
bonds with the uncoordinated carbonyl oxygen atoms, O(5) of gas (130 ml/min) at a heating rate of 10 ◦ C/min (Fig. 3). The
the monodentate acetate, linking two different molecules. Also thermograms show a smooth thermal decomposition with more
the coordinated water molecule O(8) forms hydrogen bonds with than one stage of weight loss, to produce copper metal. The TGA
the chelating acetate group, via O(6) and the water molecule of curve of 1 (Fig. 3a) shows two weight loss steps in the temperature
hydration, O(2S), whilst O1S links two molecules of the complex range 83–290 ◦ C with the maximum mass loss (76.46%) between
via hydrogen bonds to the chelating acetate atom, O(7), and the 213 and 290 ◦ C. The decomposition completes at about 290 ◦ C
bidentate bridging acetate group, via O(2). to leave a residue of 20.56% of the initial mass, which is in good
agreement with 20.15%, calculated for complete conversion of 1
to metallic copper. The TG curve of 2 shows three stages of weight
Thermogravimetric Studies
loss (Fig. 3b). The first two small steps are completed between 70
The thermal decomposition behavior of complexes 1 and 2 was and 205 ◦ C with the weight losses of 2.16 and 11.54%, respectively.
examined by thermogravimetric analysis (TGA), in the temperature The third and major one starts at 205 ◦ C and is completed at 250 ◦ C,
718

range 25–400 ◦ C under an inert atmosphere of flowing argon resulting in a residue amounting to 25.98% of the initial weight.

wileyonlinelibrary.com/journal/aoc Copyright

c 2010 John Wiley & Sons, Ltd. Appl. Organometal. Chem. 2010, 24, 714–720
Deposition of crystalline copper films from tetranuclear copper (II) complexes
Figure 4. XRD patterns of Cu films obtained from (a) precursor 1 and (b) 2
at 290 and 250 ◦ C, respectively.
The residual weight (25.98%) is slightly greater but close to the
expected value of 25.24% for metallic copper. The TG analyses
of both precursors performed under similar conditions indicate
that the complex 2 is a better precursor for the deposition of
copper metal thin films, due its low decomposition temperature
as compared with 1. Thus, the new robust precursor 2 is suitable
for producing Cu metal films at the relatively low temperature of
250 ◦ C. The residual mass in both the cases indicates the complete
removal of any carbonaceous matter either from the organic
groups or solvent molecules, resulting in impurity-free copper
metal.
Thin Films Studies
The above TGA data results aid in defining the AACVD reactor
temperature which was adjusted at 290 ◦ C for 1 and 250 ◦ C
for 2. Thin films were deposited by following the procedure
as described in the Experimental section. The films deposited from
both the complexes exhibited excellent adhesion properties to
the substrate as verified by the ‘Scotch tape test’ and are stable
towards air and moisture. A diffractogram of the films (Fig. 4)
obtained from the title complexes shows the formation of the
cubic Cu-phase which matches very well with the ICDD standard
data 03-065-9026.[27] The peaks observed in the XRD spectra
were indexed to their respective Miller indices. In both the cases,
the identified Cu phase is highly crystalline and this observation
suggests that the decomposition of complexes 1 and 2 proceeds
according to the following equation:
[Cu(deae)(TFA)]4·1.25THF (1) AACVD
4Cu + Volatiles
250-290°C
[Cu4(OAc)6(bdmap)2(H2O)2]·4H2O (2)
The surface of the deposited films was characterized by
SEM. The electron micrographic images (Fig. 5) showed that the
metallic copper thin films have a compact continuous nature and
smooth morphology. The spherical particles are homogenously
dispersed with well-defined clear grain boundaries. The thickness
of the film and crystallite size can be controlled by the time of
deposition and the concentration of the precursor solution.[28]
The film deposition parameters, i.e. conc. (0.1 g/15 ml of THF),
constant argon flow rate of 130 ml/min and deposition time
(60 min) support the growth of crystallites in the size range
Appl. Organometal. Chem. 2010, 24, 714–720 Copyright

c 2010 John Wiley & Sons, Ltd.
(a) (b)
Figure 5. SEM micrographs of thin films deposited on glass substrates
(a) for complex 1 and (b) for 2 using argon as carrier gas.
0.3–0.6 µm for complex 1 and 0.3–0.5 µm for 2 as calculated
from the scanning electron micrograph. The SEM image of films
obtained from 2 also shows the conversion of spherical particles
to copper-rods, which is not seen in the case of complex 1. The
energy dispersive X-ray (EDX) analyses (Fig. 6) show the presence
of Cu metal only on the films, eliminating the possibility of
the inclusion of any impurity either from the precursor or the
solvent.
Conclusions
The mixed ligand copper precursors [Cu(deae)(TFA)]4 ·1.25THF]
(1) and [Cu4 (OAc)6 (bdmap)2 (H2 O)2 ]·4H2 O (2) were prepared by
simple methods and characterized by their elemental analyses,
FT-IR, MS, TGA and single crystal X-ray determinations. These
complexes when subjected to thermal decomposition under
an inert atmosphere of argon give a stable copper residue
at relatively low temperature. The precursors are potentially
useful for the fabrication of pure copper thin films in an
atmosphere of nitrogen rather than the hazardous reducing
H2 atmosphere. The deposited thin films have uniform surface
morphology having well-defined grain boundaries with particles
of 0.3–0.6 µm for complex 1 and 0.3–0.5 µm for 2, under the
applied AACVD conditions. These precursors can be utilized for
large-scale printing of copper-based integrated circuits in electrical
devices.
Acknowledgments
M.S., M.H. and M.M. would like to thank the Higher Education
Commission, Islamabad, Pakistan for financial support through the
Indigenous 5000 and open merit 200 Ph.D. Scholarship Scheme
and Pakistan Science Foundation through project PSF/RES/C-
QU/CHEM(408).
Supporting Information
CCDC No. 763071 and 661774 contains the supplemen-
tary crystallographic data for compounds 1 and 2, respec-
tively. These data can be obtained free of charge via
http://www.ccdc.cam.ac.uk/conts/retrieving.html or from Cam-
bridge crystallographic Data Centre, 12 Union Road, Cam-
bridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or email: de-
posit@ccdc.cam.ac.uk. Supporting information can also be found
719
in the online version of this article.
wileyonlinelibrary.com/journal/aoc

Figure 6. EDX spectrum of films deposited on bare glass from precursor (1).
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