Nanoscale

REVIEW

Precision synthesis of colloidal inorganic nanocrystals

using metal and metalloid amides
Cite this: Nanoscale, 2013, 5, 8398

Maksym Yarema,ab Riccarda Caputoa and Maksym V. Kovalenko*ab

Received 25th April 2013
Accepted 9th June 2013
DOI: 10.1039/c3nr02076b
www.rsc.org/nanoscale
Rational selection of molecular precursors is the key consideration in the synthesis of inorganic nanocrystals
and nanoparticles. This review highlights the state-of-the-art and future potential of metal amides as
precursors in the solution-phase synthesis of monodisperse colloidal nanocrystals of metals and metal
alloys, as well as metal oxides and chalcogenides. We exclusively focus on homoleptic metal and
metalloid alkylamides M(NR2)n and silylamides M[N(SiMe3)2]n as predominant choice of element-
nitrogen bonded precursors, which are often advantageous to commonly used metal–oxygen and
metal–carbon bonded counterparts. In particular, these amides are highly reactive in oxidation,
reduction and metathesis reactions; they are oxygen-free, easy-to-make and/or commercially available.
A comprehensive literature review is complemented by our theoretical studies on the thermal stability
of metal silylamides using molecular dynamics simulations.

1 Introduction complex shapes,2–6 compositional gradients, multicomponent

The broad interest in colloidal inorganic nanocrystals (NCs)
emerged from their unique size-dependent physics and chem-
istry. Size quantization and surface effects allow size- and
shape-tuning of the fundamental optical, electronic, magnetic,
plasmonic and catalytic properties.1 Doubtlessly, chemical
methods opened access to a previously inaccessible variety of
nanomaterials characterized by their high monodispersity,1
a
Institute of Inorganic Chemistry, Department of Chemistry and Applied Biosciences,
ETH Zürich, CH-8093 Zürich, Switzerland. E-mail: mvkovalenko@ethz.ch
Laboratory for Thin Films and Photovoltaics, EMPA – Swiss Federal Laboratories for
b
architectures,4,6–9 and core–shell morphologies.10
Extensive literature from the last 10–20 years shows that the
selection of starting molecular precursors is oen the most
critical and difficult task when targeting a new synthesis of
highly uniform NCs.1 This is mainly because of the multiple
requirements imposed on the precursors. Fig. 1 illustrates the
major steps in the conversion of molecular precursors into
monodisperse NCs showing that typical molecular precursors
are required to be soluble in non-polar organic solvents, stable
at room temperature, sufficiently reactive at elevated tempera-
tures, not involved in undesired side reactions with the capping
ligands and solvents, and must yield target inorganic materials

Materials Science and Technology, CH-8600 Dübendorf, Switzerland in highly pure form. Not least important is the commercial

Maksym Yarema received his Riccarda Caputo received her

master degree in Chemistry from
Lviv National University
(Ukraine) in 2007. From 2008 to
2012, he worked towards his
doctorate degree at the Johannes
Kepler University Linz (Austria)
under supervision of Prof. Wolf-
gang Heiss. In 2012, he joined
the research group of Prof.
Maksym Kovalenko at ETH
Zürich and EMPA as a post-
doctoral fellow. His current
research revolves around synthetic approaches towards colloidal
nanocrystals with the aim of their further integration into photo-
voltaic devices as well as for lithium-ion batteries.
education in Chemistry (laurea
cum laude) and Materials
Science (PhD, 2005) at the
University “La Sapienza” in
Rome (Italy), aer a period of
training (Erasmus project) at the
University of Cambridge, UK,
Department of Chemistry.
Currently, she conducts post-
doctoral research at ETH Zürich
(Department of Chemistry,
Institute of Inorganic Chemistry)
on theoretical study of binary intermetallic phases, hetero-
graphites and compounds of interest in energy applications, in
particular, hydrogen storage and Li-ion batteries.

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 Review
Fig. 1 (Top) An outline of the major processes involved in the solution phase
chemical synthesis of NCs: precursor-to-monomer conversion, homogeneous
nucleation and heterogeneous growth. (Bottom) Overview of typical metal
precursors and capping ligands used for NC synthesis (M stands for metal).
availability of the precursor or its well documented and simple
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preparation. The logic of colloidal synthesis also requires the
ability to independently tune the rate of the nucleation and
growth of NCs. In particular, fast nucleation rate followed by
slower growth from oversaturated solutions favour the forma-
tion of monodisperse NCs. To date, among the most commonly
used are M–O bonded precursors (e.g. carboxylates, alcoholates
or acetylacetonates),11–13 organometallic precursors (e.g.
carbonyl-, alkyl- or cyclopentadienyl-compounds),14–17 and M–Si
bonded compounds such as trimethylsilyl derivatives.18
Rapidly growing interest in element-nitrogen bonded
precursors, primarily metal and metalloid amides (from here
denoted as M–N compounds), motivated preparation of this
review. Herein we aim to acquaint the reader with most
common alkyl- and silylamides and to provide a comprehensive
discussion on their use in the synthesis of highly uniform
colloidal NCs of metals and their alloys, as well as metal chal-
cogenides, oxides and nitrides (Fig. 2). We also complement
this literature survey with our theoretical studies on the
bonding and thermal stability of M-silylamides using molecular
dynamics.
Maksym Kovalenko has been a
tenure-track Assistant Professor
of Inorganic Chemistry at ETH
Zürich since July 2011. His group
is also partially hosted by EMPA
(Swiss Federal Laboratories for
Materials Science and Tech-
nology) to support his highly
interdisciplinary research
program. He completed graduate
studies at Johannes Kepler
University Linz (Austria, 2004–
2007), followed by postdoctoral
training at the University of Chicago (USA, 2008–2011). His present
scientic focus is on the development of new synthesis methods for
inorganic nanomaterials, their surface chemistry engineering and
assembly into macroscopically large solids. His ultimate, practical
goal is to demonstrate novel design of inorganic materials for
rechargeable Li-ion batteries, photovoltaics and optoelectronics.
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Fig. 2 Roadmap for conversion of M-amide precursors into nanocrystalline
materials. [H] – reducing agent, [O], [S], [Se], [Te] – oxidation agents and chal-
cogen precursors, [N] – primary amine or ammonia.
2 Homoleptic alkyl- and silylamides of
metals and metalloids
Table 1 provides an overview of known homoleptic alkylamides
and silylamides of metals and metalloids. Bulky N(SiMe3)2-
ligand is highly suited for stabilizing low-coordination
complexes with valences of one to three. Smaller NMe2-ligand
can be accommodated in higher coordination number
compounds such as Sb(NMe2)5 and W(NMe2)6. The ready
availability of the inexpensive parent amines such as
HN(SiMe3)2 and their facile conversion into N-lithio-derivatives
are of great advantage.
Silylamides
The bis(trimethylsilyl)amide ligand, –N(SiMe3)2, has been
extensively used in coordination and organometallic chemistry
to stabilize undercoordinated metal centers.20,21 Since 1960s,
Burger and Wannagat reported the synthesis of a number of
ML3 (M ¼ Al, Ga, In, Cr and Fe),22,23 ML2 (M ¼ Be, Co, Ni, Zn, Cd
and Hg)23,24 and ML (M ¼ Li, Na and Cu)25 compounds. Later,
Bradley, Hursthouse, and others further extended the family of
isolable two-coordinate (Fe, Co, Mn, Mg, Ca, Sr, Ba)26–31 and
three-coordinate compounds (Sc, V, Cr, La, Ce, Pr, Nd, Sm, Eu,
Gd, Ho, Yb and Lu).20,28,32,33 Group 14 elements (Ge, Sn, Pb) form
relatively stable divalent complexes,34,35 again because of the
bulkiness of the silylamide ligand. Only a few examples of noble
metal or heavier coinage-metal derivatives have been reported,
such as the rst base-free gold amide {Au[m-N(SiMe3)2]4}.36
Silylamide complexes are typically synthesized by a metath-
esis reaction:
  in Et2 O=THF  
Li NðSiMe3 Þ2 þ MCln ƒƒƒƒƒƒƒƒƒƒƒ! M NðSiMe3 Þ2 n (1)
LiCl
or by transmetalation reactions in dimethoxyethane or THF
(for Sr, Mg, Ca, Ba):31
  in monoglyme=THF  
M þ Sn NðSiMe3 Þ2 2 ƒƒƒƒƒƒƒƒƒƒƒƒ! M NðSiMe3 Þ2 n (2)
Sn
Other methods involve reactions between alkyl-metals or
Grignard reagents as the metal source and amine (e.g.
HN(SiMe3)2) as a ligand source. Typically, silylamides are
monomeric (Fig. 3A)22,34,37 or associated to various extent
(Fig. 3B).27,36,38,39 Furthermore, metal and metalloid clusters are
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Table 1 Overview of known homoleptic silylamides and alkylamides of metals and metalloids, as found in the common scientific literature and in Cambridge
Crystallographic Data Centre.19 Marked in bold are compounds available from common chemical suppliers such as Sigma-Aldrich, Strem or Alfa Aesar
Valence of metal NR2-ligand, R ¼ Me, Et
1 Li, Na, K
2 Zn, Sn, Pb
3 Al, B, Ga, P, As, Sb, Mo, W, Bi, Ti, V, Cr
4 Hf, Ti, Zr, Si, Sn, Ge, V, Nb, Mo, Cr
5 Ta, Nb, W
6 W
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Fig. 3 Solid state crystal structures of (A) monomeric Bi[N(SiMe3)2]3, (B) dimeric Co2[N(SiMe3)2]4, and (C) Ge8[N(SiMe3)2]6 with a cluster-type Ge8 core, after ref. 37, 38
and 40. Representing colors: H, white; C, gray; N, blue; Si, yellow; Bi, violet; Co, light-blue; Ge, green.
well known, covered by protective silylamide ligand shells such
as Al77[N(SiMe3)2]202, Ga23[N(SiMe3)2]11, and Ge8[N(SiMe3)2]6
(Fig. 3C).40–42
Alkylamides
Homoleptic M(NR2)n complexes, where R is a methyl or ethyl
group, are known for all group IV–VI transition metals43 and for
many main group metals and metalloids (Table 1).20,44 They are
commonly synthesized in a fashion similar to silylamides:
reactions (1) and (2), though there are at least 11 methods for
their preparation. An excellent recent review of the metal amide
chemistry is provided by the book of Lappert and co-authors.20
3 Theoretical study of metal silylamides
It is well documented that silylamides are highly reactive
towards protic and unsaturated reagents due to the polar
character of the M–N single bond; they are sensitive to both
oxidative and reducing agents, and readily undergo various
metathesis reactions. This reactivity makes metal amides highly
suitable for NC syntheses discussed in the next section. Very
little, however, is known about the mechanism of thermal
decomposition of metal amides.
In the present work, we obtained an insight into the thermal
behaviour of metal silylamides by following the molecular
dynamics at different temperatures, from room temperature up
to 350  C (for details of the computational methodology see the
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N(SiMe3)2-ligand
Li, Na, K, Cu, Ag, Au
Zn, Sn, Ge, Be, Mn, Co, Fe, Ni, Cd, Hg, Pb, Se, Te,
Mg, Ca, Sr, Ba
La, Er, Nd, Eu, Yb, Ce, Gd, Pr, Ho, Lu, Sm, Tm, Y,
In, Dy, Bi, Sc, Ti, V, Cr, Al, Ga, Sb, Fe, U, Ne, Pu
Methods section). For simplicity, sterically hindered metal-
silylamides are considered to be monomeric and the possible
effect of the solvent is ignored.
As a rst step, the geometries of isolated molecules of metal
silylamides were optimized at DFT-D level of calculations to get
the equilibrium bond lengths and the total energies (Table 2).
As expected, the M–N bond lengths increase and binding
energies decrease with the atomic number of coordinated
metal, while the Si–N bond lengths remain in the range of 1.70–
1.77 Å. Along the period (e.g. In–N and Sn–N bonds), however,
the M–N binding energy increases. These two trends counter-
balance in In- and Bi-silylamides, in which very similar binding
energies are found. The bond lengths of isolated metal-silyla-
mides, presented in Table 2, are in good correspondence to
known experimental values.22,37,47 In particular, Al, Ga and In
atoms in respective silylamides are located at the centre of mass
of the triangle formed by nitrogen atoms, while Bi is located
0.895 Å above, forming a pyramid with a “three-nitrogen” base.
The Sn atom coordinates two silylamide groups, which at
equilibrium have the cis-conformation with the N–M–N angle of
100.63 . The conformation allows the maximum overlapping of
the p-orbitals of the two N atoms with the metal atom. In
addition, the cis-conformation brings the methyl groups at
equilibrium distances resulting from the two counterbalanced
contributions – repulsion and dipolar interactions.
It is commonly assumed, that the thermal stability of sily-
lamides is determined by the strength of metal–nitrogen
bonding, neglecting the possible contribution by other bonds,
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Table 2 Bond lengths (Å) and binding energies (kJ mol1) of the metal–nitrogen
and silicon–nitrogen bonds, calculated at DFT-D level of theory by using DMol3
code at T ¼ 0 K. For comparison, we report the same calculations for HN(SiMe3)2
(e.g. M ¼ H)

M d (M–N) Eb (M–N) d (Si–N) Eb (Si–N)

Li 1.813 355.96 1.698, 1.708 557.78

Al 1.831 397.49 1.772, 1.775 516.10
1.832 1.763, 1.761
1.837 1.764, 1.761
Ga 1.898 317.59 1.761, 1.759 518.28
1.890 1.771, 1.772
1.902 1.762, 1.761
In 2.157 273.49 1.745, 1.746 538.27
2.157
2.157
Sn 2.156 341.63 1.756, 1.754 501.46
2.146 1.756. 1.755
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Bia 2.277 275.11 1.763, 1.768 418.62

2.275 1.768, 1.764
2.275
H 1.021 578.73 1.751, 1.750 513.56
a
The GGA PBE functional is used and the dispersion corrections are
accounted for by using the damping function as the Grimme scheme
for all except for bismuth tris[bis(trimethylsilyl)]amide, in which the
Grimme method is not parameterized for the element Bi.45,46

such as Si–C or C–H. Our molecular dynamics simulations

showed that, in agreement with experiment, all studied metal
silylamides are stable at room temperature, at which only
vibrations and rotations of methyl groups along the axis passing
through the C–Si bond are active, but for temperatures above
180  C the C–H bonds may undergo cleavage. Higher temper-
ature weakens the metal–nitrogen bonds and the subsequent
decomposition pathways may signicantly differ for different
metal atoms (Fig. 4 and 5). For comparison, the molecular
dynamics up to 350  C for HN(SiMe3)2 conrmed the thermal
stability of all bonds, in obvious agreement with the strong N–H
bond. In Li-silylamide, the C–H bond cleavage of one methyl
group started at 250  C. At T ¼ 327  C the H atom of the cle
C–H bond moved to form a LiH moiety, while the remaining
–CH2 group formed a three-centre conformation with the
nearest N and Si atoms, as shown in Fig. 4A. Closely relevant
Fig. 5 Two snapshots of the molecular dynamics of Ga-silylamide at T ¼ 300  C.
(A) The first two deprotonating processes occurred on the same methyl group, of
which the remaining –CH group is bound to nitrogen. (B) The first two depro-
tonating processes involved two methyl groups, which then bound to form a new
C–C bond. Representing colours: H, white; C, gray; N, blue; Si, yellow; Ga, light-
brown.
experimental observations were reported by Withnall and co-
workers for LiNMe2,48 where the formation of imide CH2 ¼ NMe
and LiH was explained via a four-centre transition state in
which one hydrogen atom moves from the methyl group to the
lithium atom.
The Group 13 (Al, Ga, In) metal-silylamides also exhibited a
sequential C–H bond cleavage with increasing the temperature,

Fig. 4 The snapshots of molecular dynamics simulations of metal-silylamides. (A) Li-silylamide shows formation of a three-centre transition (N–Si–C) state and Li–H
bonding at T ¼ 327  C. (B) Sn-silylamide shows a four-centre (Sn–N–Si–C) intermediate at T ¼ 277  C. (C) Bi-silylamide shows the cleavage of Bi–N bond already at T ¼
180  C. Representing colours: H, white; C, gray; N, blue; Si, yellow; Li, brown; Sn, dark-green; Bi, purple.

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which for In-silylamide and Ga-silylamide was required to be as
high as 300  C and 250  C, respectively to initiate. In particular,
the molecular dynamics at 250  C of Ga-silylamide showed that
the C–H bond cleavage can induce a reorientation of the
remaining –CH2 group and the formation of an intermediate
four-centre conguration (Ga–N–Si–C). With the further
temperature rise to 300  C, the subsequent C–H bond cleavage
can follow two different pathways with similar probability,
depending on whether the same –CH3 group or an adjacent
methyl group is involved. When the C–H bond cleavage involved
the same methyl group, the remaining –CH group moved to
bind to nitrogen forming a strong C–N bond, 1.493 Å long, as
shown in Fig. 5A. Instead, the C–H bond cleavage on an
adjacent methyl group favoured the C–C bond leading to –CH2–
CH2–, as shown in Fig. 5B. In our molecular dynamics calcula-
tions the former path (Fig. 5A) gives lower total energy.
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Interestingly, in the presence of one molecule of tri-n-octyl-
phosphine (TOP), the molecular dynamics of Ga-silylamide at
250  C preferentially showed the second path of decomposition
(Fig. 5B).
Of the Group 14 metal-silylamides, the Sn(II) compound
exhibited interesting dynamics. At T ¼ 180  C, only vibrations
and rotations are activated. For higher temperatures, the rst
C–H bond cleavage on one branch of the ligands initiates a
rearrangement and subsequent C–H bond cleavage leading at
equilibrium at 277  C to the formation of new bonds, Sn–H and
Si–H, while the two initial methyl groups, which lost the
hydrogen atoms, rearrange to form a –(C–CH2) group bound to
Si and Sn atoms in a four-centre intermediate state, as shown in
Fig. 4B. The bond lengths of the new Sn–H and Si–H bonds,
aer further geometry optimization of the thermally equili-
brated structure, are 1.736 Å and 1.498 Å, respectively, compa-
rable with the corresponding values reported in the literature.
The four-centre (Sn–N–Si–C) state remains stable up to 327  C,
at which the Sn–N bond cleaves.
Of the Group 15 metal-silylamides, the studied Bi-silylamide
exhibited an activation of the rotations and vibrations of the
methyl group up to at least 180  C, but differently from the other
silylamides considered in the present work, a further increase of
the temperature enlarged and cleaved the Bi–N bond, without
forming any multi-centred transition states.
In order to compare thermal stabilities of metal amides with
typical M–O bonded precursors such as metal carboxylates, we
run molecular dynamics for Sn(II) hexanoate as a case study and
compare that with Sn-silylamides. In particular, we found
similar values of bond lengths (T ¼ 0 K) for Sn–O and Sn–N
bonds, 2.270 Å and 2.151 Å respectively, but clearly different
dynamic behavior. In contrast to Sn-silylamide, which decom-
poses at T > 180  C, the Sn-carboxylate showed no signs of
decomposition up to 300  C, but only activated stretching and
bending modes of the C–H bonds. The Sn–O bond lengths are
slightly enlarged but not broken. This computational result
conrms the multiple experimental evidence, usually showing
higher reactivity of M–N precursors in respect to M–O bonded
elemental sources.49 As will be shown in the next section,
facile but controlled thermal decomposition or chemical
reduction of metal and metalloid amides at temperatures below
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300  C serves as a basis for the synthesis of metallic and metal
alloy NCs.
4 Examples of colloidal inorganic
nanocrystals derived from silyl- and
alkylamide precursors
Metallic nanocrystals and nanoparticles
Since 1990s, M–N compounds have proven their utility in thin
lm deposition by atomic layer deposition (ALD) and by
chemical vapour deposition (CVD) of metals, oxides, and
nitrides; oen providing lower levels of carbonization as
compared to that by M–C compounds.50–57 Since the advent of
colloidal synthesis in non-aqueous non-polar solvents, M–N
precursors turned out to be highly suited for a low-tempera-
ture (RT-250  C) synthesis of monodisperse NCs of various
transition metals and main group elements. For this purpose,
the absence of oxygen atoms in the precursor is also highly
benecial, while the mild reaction temperatures allow
controlling the NC size of low-melting metals (In, Sn, Bi, Pb).
These efforts were pioneered by Chaudret et al.71,75,97 and then
extended by others to semiconductor compounds such as
SnTe NCs.49 As of March 2013, Fig. 2 and Table 3 contain all
known examples of uniform colloidal NCs derived from M–N
precursors, although this list may not be exhaustive. All
synthetic protocols can be subdivided in 2 categories: where
the M–N precursor is pre-synthesized ex situ (majority of
examples) and where the M–N precursor is formed in situ
during the one-pot synthesis of NCs.
It should be noted that long-chain alkylamines such as
oleylamine (OLA) and hexadecylamine (HDA) are amongst
most commonly used coordinating solvents and capping
ligands in NC synthesis, owing to their ability to coordinate/
solubilize metal salts and to passivate the metal atoms on the
NC surface. For instance, highly monodisperse PbS, CdS,
Cu2xS(Se), ZnS are usually grown in the neat OLA.104–106 More
comprehensively, the role of OLA in the synthesis of nano-
materials has been recently reviewed by Liz-Marzan and
Mourdikoudis.107 It is commonly assumed that alkylamine
binds as a neutral molecule (L-type ligation, e.g. amino-
complexes), unless X-type ligation is promoted by the depro-
tonation of the parent amine (e.g. amides, this study). It is
therefore important to emphasize that this review deals with
ex situ synthesized amides or with the cases where strong
evidence for the in situ formation of amido-complexes was
demonstrated.
Fig. 6 illustrates compositional diversity, narrow size distri-
butions (down to several %) and shape-uniformity that can be
reproducibly achieved without any post-synthetic size- and
shape-sorting. Such qualities make these NCs ideal building
blocks for articial solids, also known as NC superlattices
(Fig. 7), which are spontaneously formed upon the evaporation
of the solvent from the stable colloidal dispersion of NCs or by a
diffusion-controlled precipitation approach.
Moderately stable precursors such as Sn(NMe2)2 and Bi-
[N(SiMe3)2]3 can be readily thermally decomposed directly into
corresponding metallic NCs at 100–150  C.61,63,64,97 Furthermore,
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Table 3 List of colloidal nanocrystals synthesized from metal and metalloid alkyl and silylamidesa

NC material Size range, nm M–N precursor(s) Reaction type T C Surfactant(s) Ref.

Ag2S 3.1–3.6 [Ag[m-N(SiMe3)2]]4[in situ] MR 70 ph + am 58

Ag2Se 2.0–3.4 [Ag[m-N(SiMe3)2]]4[in situ] MR 70 ph + am 58
Ag2Te 3.2 [Ag[m-N(SiMe3)2]]4[in situ] MR 70 ph + am 58
AlN 20 Al[N(SiMe3)2]3[in situ] TD 350 am 59
BaS 30 Ba[N(SiMe3)2]2(C4H8O)2 MR RT-200 — 60
Bi 3–115 Bi[N(SiMe3)2]3 TD 100–180 am, poly 61–63
Bi 4–29 Bi[N(SiMe3)2]3[in situ] TD 200 poly 64
CdSe 1.8 Cd[N(SiMe3)2]2[in situ] MR 140 am + ph 58
CdTe 3.1 Cd[N(SiMe3)2]2[in situ] MR 120 am + ph 58
Co 3–20 Co[N(SiMe3)2]2 [H] RT poly, am 65 and 66
Co rods 5  40–5  100 Co[N(SiMe3)2]2 TD, [H] 150 am + ac 67
CoFe2O4 3 Fe[N(SiMe3)2]2 and H2O, [O] RT am 68
Co[N(SiMe3)2]2
Cu 1.8–7.8 [CuNHR]n[in situ] TD, [H] 100 am 69 and 70
Cu 6.9–8.9 Cu2[(NHiPr)2(CHCH3)]2 TD, [H] 80–110 am 70
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Fe 1.5–27 Fe[N(SiMe3)2]2 TD 150 am (+ac) 71–74

Fe58Co42 15, 20 Co(N(SiMe3)2)2 TD, [H] 150 am + ac 75 and 76
FeNi 2.8, 3.8 Fe[N(SiMe3)2]2 TD 150 am + ac 77
Fe1yO 5 Fe[N(SiMe3)2]2 H2O RT am 78
Fe2O3 3 Fe[N(SiMe3)2]2 H2O, [O] RT am 68
Fe80Rh20 2.1 Fe[N(SiMe3)2]2 TD, [H] 110 am 79
GaN 3 [Ga(NH)3/2]n TD 360 am 80
GaN 2.4 [Ga(NMe2)3]2 TD 360 am 81
GaN 10 Ga[N(SiMe3)2]3[in situ] TD 240 am 82
GaN (hollow) 20 shell Ga[N(SiMe3)2]3[in situ] TD 380 am 83
GaN rods 20 Ga[N(SiMe3)2]3 TD 250 ph this work
Ge 3–7 Ge[N(SiMe3)2]2 TD 300 am 84 and 85
GeTe 4.3–30.7 Ge[N(SiMe3)2]2 MR 220–250 am, ph 86 and 87
HfO2 3.7 Hf[NMe2]4 H2O 270 ac + am 88
In 8.6–18.6 In[N(SiMe3)2]3 [H] 155 am 89
InSb 3.4–7 Sb[N(SiMe3)2]3 [H] 240–260 am + ph 90
InSb 6–12 In[N(SiMe3)2]3 and TD 180–300 am + ph 91
Sb[NMe2]3
In1xSnx 8.6–18.6 In[N(SiMe3)2]3 and [H] 155 am 89
Sn[N(SiMe3)2]2
In3Sn wires >100 nm Sn(NMe2)2 UVD RT am 92
LaS1.5x 100 La[N(SiMe3)2]3 MR 40–80 — 93
Pb 4.4–20 Pb[N(SiMe3)2]2[in situ] TD 220 ph + ac + am 94
PbSe 3.5–13.8 Pb[N(SiMe3)2]2[in situ] MR 120–160 am 95
PbTe 1.9 Pb[N(SiMe3)2]2[in situ] MR 120 am 95
Pd 5–20 [Pd(NH2R)4](acac)2[in situ] TD 150 am 96
Sn 20 Sn(NMe2)2 TD 140 poly 63 and 97
Sn 15 Sn(NMe2)2 UVD RT am 98
Sn 8–20 Sn-oleylamide[in situ] [H] 130–210 am 99
SnS 7–10 Sn[N(SiMe3)2]2 MR 170 ph + ac + am 100
SnSe 4–10 Sn[N(SiMe3)2]2 MR 65–175 am 101
SnTe 4.5–15 Sn[N(SiMe3)2]2 MR 150 am 49
ZnO 15 Zn[N(SiMe3)2]2 H2O RT — 102
ZnO 3.3–7.3 [Zn(NiBu2)2]2 H2O RT-120 am + ac 103
a
Reaction type: [H] – reducing; H2O – hydrolysis; MR – metathesis reaction; [O] – oxidation; TD – thermal decomposition; UVD – UV-assisted
decomposition. Surfactant type: ac – carboxylic acid; am – long-chain amine; ph – tri-n-octylphosphine; poly – polymer. Other acronyms: acac –
acetylacetonate; iBu – isobutyl; Me – methyl; iPr – isopropyl, R – long hydrocarbon chain; RT – room temperature.

room-temperature photochemical lability of Sn(NMe2)2 can also
provide convenient means for the formation of Sn-based
nanomaterials upon UV-illumination.92,98,108 Buhro et al. repor-
ted the synthesis of 3–100 nm Bi NCs109,110 from the Bi-
[N(SiMe3)2]3 precursor and long-chain polymeric stabilizer in
1,3-diisopropylbenzene at 200  C. The synthesis was tailored to
provide the best nanocatalyst for growing semiconductor
nanowires of II–VI (CdTe, CdSe, ZnTe) and III–V (InP, InAs,
GaAs) compounds,108 but the use of long-chain polymers as
stabilizers hampers the utility of Bi NCs for other purposes. The
necessity for polymer can be avoided if a long-chain amine such
as OLA or HDA is used as a coordinating solvent. For instance,
highly monodisperse 11–22 nm Bi NCs (Fig. 6A) were grown in
HDA according to:62

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Fig. 6 TEM and high-resolution TEM images of various metallic nanocrystals, prepared from metal-amides: (A and B) Bi,62 (C and D) Sn,99 (E and F) Fe,72 (G and H)
Co,66,67 (I) Pb,94 (J) In,89 and (K) In1xSnx.89 Inset in K: compositional modulation of In–Sn alloyed NCs. Reprinted with permission from (A and B) ref. 62 Copyright 2010
American Chemical Society; (C and D) from ref. 99 Copyright 2013 American Chemical Society; (E and F) from ref. 72 Copyright 2008 American Chemical Society; (H)
from ref. 66 Copyright 2012 American Chemical Society; (I) from ref. 94 Copyright 2010 American Chemical Society; (J and K) from ref. 89 Copyright 2012 American
Chemical Society. (G) Reprinted from ref. 67, Copyright 2007, with permission from Elsevier.

combined with the carbonyl compound of a different metal, as

in the preparation of Co0.4Fe0.6 NCs from Co[N(SiMe3)2]2 and
Fe(CO)5.75,76
Nucleation as well as growth kinetics of metallic NCs can
Similar preparation of Ge NCs proceeds via thermolysis of
also be conveniently tuned by adding organic-soluble reducing
Ge-[N(SiMe3)2]2 upon its injection into an oleylamine–octade-
agents such as lithium triethylborohydride, Li[Et3BH] (also
cene mixture at 300  C.84 Fe[N(SiMe3)2]2 has been widely used
known as a “super-hydride”) and diisobutylaluminium hydride
for growing Fe and Fe-based alloy nanoparticles.71–74,77,79 7 nm
(DIBAH, (i-Bu2AlH)2). In–Sn NCs with tunable Sn content up to
Fe nanocubes (Fig. 7A) were obtained by slow thermally assisted
10 at% can be synthesized at 155  C from the mixture of In-
reduction of Fe[N(SiMe3)2]2 by H2 at 150  C in the presence of
[N(SiMe3)2]3 and Sn[N(SiMe3)2]2 upon addition of Li[Et3BH]:89
long chain acids and amines.71,72 More recently, the same
authors reported the synthesis of Fe NCs without the use of
dihydrogen.74 HDA was suggested to act not only as a capping
agent, but also as a sufficiently powerful reducing agent. A
plausible mechanism, in our opinion, may involve trans-
amination reaction leading to less stable Fe-hexadecylamide, As an example of DIBAH-based preparation, monodisperse
which readily decomposes via a-hydrogen elimination leading Co NCs were synthesized from Co[N(SiMe3)2]2 in toluene at
to Fe and imine (as observed by the authors experimentally). temperatures as low as 50  C.65 Earlier studies in lanthanide-
Analogous preparations were reported for Co,66,67 as well as for silylamide chemistry showed that reduction with DIBAH
metal alloys such as Fe0.5Ni0.5 and Fe0.8Rh0.2 NCs.77,79 In the case involves formation of intermediate Al–N bonds, leading to
of alloys, the silylamide precursor of one metal is oen transient metal–hydride species. These species would quickly

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Fig. 7 Spontaneously formed, long-range ordered superlattices of (A) cubic Fe,63
(B) spherical CoFe,64 and (C and D) In89 NCs. Inset (A) electron diffraction of (A);
inset (B) SEM picture of the superlattice surface (scale bar is 50 nm). From ref. 63
reprinted with permission from AAAS. Reprinted with permission from Macmillan
Publishers Ltd: Nat. Mater., ref. 64, copyright 2005. Reprinted with permission
from ref. 89 Copyright 2012 American Chemical Society.
decompose generating metal atoms for NC nucleation and
HN(SiMe3)2.111 Such [N(SiMe3)2] / [H] transformation may be
ideally suited for the formation of metallic NCs.
Particularly attractive can be one-pot synthesis in which the
actual metal–nitrogen bonded precursor is formed in situ. This
can be attained via a simple metathesis reaction between
inexpensive metal chlorides and a source of ligand (e.g. LiNR2,
LiN(SiMe3)2 and HN(SiMe3)2). In situ precursor formation may
eliminate the need for the elaborate synthesis, isolation and
handling of air and moisture-sensitive amide precursors.
Buhro and Wang showed that Bi[N(SiMe3)2]3 formed ex situ or
in situ from BiCl3 and NaN(SiMe3)2 yielded identical results in
the synthesis of Bi NCs.64 Very recently, Kravchyk et al.
demonstrated in situ formed Sn-oleylamide as an actual
intermediate in the synthesis of monodisperse Sn NCs (Fig. 6C
and D).99 The synthesis was traced by 119Sn NMR spectroscopy,
revealing that Li-oleylamide initially reacts with Sn(II) chloride,
forming the Sn-oleylamide precursor. The latter is then con-
verted into Sn NCs at 130–210  C upon injection of DIBAH or
Li-[Et3BH]:
Strong experimental evidence for the in situ formation of
metal-silylamide precursors can also be found in several other
recent reports. Guyot-Sionnest and Zolotavin94 demonstrated
highly monodisperse Pb NCs by reacting Pb stearate with Sn-
or Li-silylamide at elevated temperatures, suggesting the
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formation of Pb-silylamides as an intermediate. Using proton
NMR-spectroscopy, Wolf et al. elucidated the mechanism of Pd
NC formation from the mixture of Pd(II) acetylacetonate and
hexadecylamine, and concluded that the reaction proceeds via
formation of Pd–hexadecylamido complexes as intermediates.96
Chaudret and co-workers proposed the formation of transient
Cu–amide precursors by metalation of octylamine or dodecyl-
amine with mesitylcopper(I), followed by the formation of Cu
NCs under a dihydrogen atmosphere.69,70
Nanocrystals of metal oxides
Central to the formation of metal oxide is the formation of
M–O–M bonds, followed by the further progression of the
condensation and restructurization leading to a metal oxide
lattice. Transition metal alkylamides and silylamides have
either dn or d0 conguration and all are highly oxygen
sensitive. In the reactions of dn complexes, the oxidation of
the metal center is oen a key step, and may proceed without
alteration of coordinating ligands. The oxidation of d0 metal
complexes mainly concerns the M–N bond and serves as a
basis for the use of Ti, Zr, Hf, Nb, Ta alkylamides in CVD
growth of corresponding oxides. The fast, room-temperature
reactions with oxygen were shown to form isolable oxo- and
aminoxo-moieties, containing desired M–O–M units.112 An
alternative commonly used approach to metal oxides is based
on the reactions with water and alcohols, for instance, in ALD
growth.113 Thus far, such reactions had been only seldom
used in the NC synthesis.68,78,88,102,103 3–15 nm ZnO NCs
(Fig. 8A–C) can be synthesized either by slow reaction of Zn-
[N(SiMe3)2]2 with water,102 or from Zn(NiBu2)2 reacted
with humid air.103 Similarly, wüstite (Fe1yO, y # 0.08) NCs
can be derived from Fe[N(SiMe3)2]2 that slowly reacts with
water in non-polar solvents at room-temperature under
argon.78 The same reaction in air leads to a maghemite phase
(g-Fe2O3):68
Fig. 8 Low-resolution TEM image (A), size-dependent XRD patterns (B), and
high-resolution TEM image (C) of ZnO nanocrystals.103 HR-TEM images of (D)
Fe2O3 and (E) CoFe2O4 nanoparticles.68 Reprinted with permission from ref. 103
Copyright 2009 American Chemical Society. Reproduced from ref. 68 with
permission from The Royal Society of Chemistry.
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Similarly, CoFe2O4 NCs were obtained by hydrolytic decom-
position of Fe and Co silylamides,68 while 5 nm HfO2–Au core–
shell NCs were grown by hydrolysis of Hf(NMe2)4 followed by
coating with an Au shell.88
Metal chalcogenide nanocrystals
Monodisperse SnTe NCs49 may serve as a good illustration of
low-temperature growth of metal chalcogenide NCs. 4.5–15
SnTe NCs nm (Fig. 9) were synthesized by reacting Sn-
[N(SiMe3)2]2 and TOPTe in oleylamine at 90–150  C:
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Any less reactive tin(II) precursor, such as tin(II) oleate,
acetate or chloride, yielded polydisperse, sub-micron precipi-
tates of SnTe.49 Similar to Sn[N(SiMe3)2]2-based preparation of
SnTe NCs, Baumgardner et al. synthesized 4–9 nm SnSe NCs
from Sn[N(SiMe3)2]2 and TOPSe,101 while Hickey et al. obtained
SnS NCs using thioacetamide as a sulphur source.100 Analogous
Ge-precursor Ge[N(SiMe3)2]2 can be converted into GeTe NCs,
with the size tunable in the range of 4.3–30.7 nm.86,87
Gaseous H2S can also serve as a convenient sulfur precursor,
for instance, in the preparation of BaS60 and La2S3 (ref. 93) NCs
from La[N(SiMe3)2]3 and Ba[N(SiMe3)2]2(THF)2, respectively.
Remarkably, Sn[N(SiMe3)2]2 has been found to promote the
formation of monodisperse PbSe, and also PbTe NCs.95 The
Fig. 9 High quality tin(II) chalcogenide nanoparticles prepared from Sn-
[N(SiMe3)2]2.49,100,101 Reprinted with permission from ref. 49. Copyright 2007
American Chemical Society. Reprinted with permission from ref. 100. Copyright
2008 American Chemical Society. Reprinted with permission from ref. 101.
Copyright 2010 American Chemical Society.
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reaction between PbCl2 and TOPSe in oleylamine at 140–160  C
leads to PbSe NCs (Fig. 10) only if Sn[N(SiMe3)2]2 is introduced
into the precursor solution.95 The size of obtained PbSe can be
adjusted in the 5.5–14 nm range by the amount of added Sn-
[N(SiMe3)2]2. Very narrow size-distributions are comparable if
not superior to those obtained in the direct synthesis from
TOPSe and lead oleate.114 More specically, the smaller the
amount of Sn[N(SiMe3)2]2 the larger the NC size. This is in
agreement with the nucleation controlled formation of NCs, in
which the higher the nucleation rate the smaller the resulting
nanoparticles. The effect of Sn[N(SiMe3)2]2 was attributed to the
fast formation of transient SnSe species, which undergo
conversion into PbSe. However, the same reaction kinetics and
dependence of the nucleation rate on the concentration of Sn-
[N(SiMe3)2]2 can also be ascribed to the formation of transient
Pb-silylamide. This mechanism is further supported by the
follow-up work of Heiss and co-workers, where small and
uniform Ag2S, Ag2Se, Ag2Te, CdSe and CdTe NCs were synthe-
sized from the metal salt and trioctyphosphine chalcogenide in
the presence of LiN(SiMe3)2 instead of Sn[N(SiMe3)2]2.58
Nanocrystals of III–V semiconductors
Homoleptic M–N precursors are already extensively used for
the growth of metal nitride lms by CVD or ALD
methods,52,53,57,115–117 or nitride nanocrystalline powders.118 In
analogy with H2O-based synthesis of metal oxides, these growth
processes are based on transamination reactions with gaseous
Fig. 10 Highly monodisperse PbSe nanocrystals: (A) SEM images, (B and C) high-
resolution TEM and (D and E) size-dependent absorption and emission spectra.
Reproduced from ref. 95 Copyright 2008, with permission from John Wiley &
Sons, Inc.
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NH3 or primary alkylamines. An alternative approach can make
use of the thermal decomposition of metal-amide precursors, if
the M–N chemical bond is sufficiently strong and, therefore, is
retained during the thermal decomposition. To this end, several
reports dealt with GaN NCs. Micic et al. reported the synthesis
of sub-5 nm GaN NCs (Fig. 11A) using polymeric gallium imide
[Ga(NH)3/2]n as a precursor,80 in which the lack of any organic
substituents helps in obtaining a carbon- and oxygen-free
product. This precursor is rst prepared by treating dimeric
Ga(III) dimethylamide, Ga2(NMe2)6, with ammonia and then
thermally decomposed in trioctylamine (TOA) at 360  C for 24
hours. Van Patten and co-workers developed the synthesis of 2.4
nm GaN NCs through the direct thermolysis of Ga2(NMe2)6 in
the reuxing mixture of TOA and HDA for 60 hours.81 Because of
the presence of HDA in the system, authors suggested that the
transamination process was involved to drive the formation of
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GaN NCs. Rao and co-workers reported the synthesis of 4–12 nm
GaN NCs, grown by the solvothermal reaction between Ga(III)
cupferron and HN(SiMe3)2 at 240  C in toluene,82 and extended
this method to colloidal AlN NCs.59 In line with previous
examples, Kuo et al. attempted synthesis of GaN via in situ
formed Ga-silylamide by heating GaCl3 and LiN(SiMe3)2 in TOA
at 380  C.83 Instead, Ga–GaN core–shell morphology formed
aer 24 h of reaction and has been ascribed to the formation of
the Ga droplets at the early stages of reaction, followed by their
partial conversion into GaN. Pure GaN phase can be obtained by
post-synthetic dissolution of Ga-core in aqua regia (Fig. 11B).83
Another long-lasting challenge in the chemistry of colloidal
III–V NCs is the synthesis of InSb quantum dots. During the
preparation of this Article, two reports appeared describing the
rst steps towards this material. Liu et al. reported the synthesis
of 3.3–6.5 nm colloidal InSb NCs with zinc-blende crystal
structure via the reaction between InCl3 and Sb[N(SiMe3)2]3 in
OLA in the presence of lithium triethylborohydride, Li[Et3BH].90
Li[Et3BH] is added in a quantity twice as large as needed to
completely reduce precursors to In0 and Sb0. Yarema and
Kovalenko proposed an alternative synthesis of 6–12 nm InSb
NCs using the reaction between In[N(SiMe3)2]3 and Sb(NMe2)3
in TOA or TOP without the use of an additional reducing
agent:91
Fig. 11 (A) Small GaN nanocrystals synthesized from Ga polyimide85 and (B)
hollow GaN nanoparticles.88 Reprinted with permission from ref. 85 Copyright
1999, American Institute of Physics. Reprinted with permission from ref. 88
Copyright 2009 American Chemical Society.
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The latter approach also allows obtaining zinc-blende and
wurtzite polymorphs of InSb by controlling the In-to-Sb
precursor molar ratio. Furthermore, the rod-like InSb NCs
formed when pre-synthesized In NCs were introduced into the
reaction mixture as catalysts in order to induce the solution–
liquid–solid growth of InSb nanorods.91
5 Conclusions and outlook
This review has reviewed the progress in the NC synthesis
enabled by metal amides as precursors and outlined the future
potential of these compounds. Dozens of examples illustrate
versatility of these precursors for the low-temperature forma-
tion of NCs of various metals, metal chalcogenides, oxides and
pnictides. The key benets are the high reactivity of element–
nitrogen bonds, absence of oxygen atoms in the reaction
medium, easy thermal decomposition, and facile reduction of
metal centres as well as various oxidation and metathesis
pathways.
As the questions of reactivity and thermal stability are oen
closely related, we carried out computer simulations of the
thermal decomposition of several homoleptic silylamides. At
least qualitatively, molecular dynamic simulations are in
agreement with experimental observations such as facile
thermal decomposition of Bi-silylamide, high thermal stability
of Li-silylamide and moderate thermal stability of Sn and In
amides at temperatures below 300  C. These simulations also
illustrate that in contrast to general wisdom, the decomposition
of amides is not primarily determined by the metal–nitrogen
bonding energy, but is also facilitated by the activation and
cleavage of the C–H bonds. Calculations also suggest that
thermal decomposition may be also be favoured in proton-rich
environments, such as primary long-chain amines as solvents.
As a suggestion for a future work in this research area, we
propose that besides silylamides and alkylamides, many other
element-nitrogen bonded precursors may be considered as
promising candidates for preparing high-quality colloidal
nanoparticles. A very recent report of the Chaudret group can
serve as an example,70 where Cu nanoparticles were prepared
from a Cu amidinate precursor. Metal amidinates and also
guanidinates have been introduced to CVD methods almost a
decade ago.119 To date, these complexes have already
proven their utility for depositing metals, oxides, and
nitride lms.51,120,121 Other promising precursors may include
bis(dimethylsilyl)amides (e.g. Hf[N(SiHMe2)2]4), other “less-
symmetric” and mixed alkyl-silylamides,122,123 also aryla-
mides,124 pyrrolyl-125 and piperidyl-derivatives,126 etc.
6 Methods
Computational methodology
Metal amides were considered as isolated molecular systems.
The total energies were calculated at DFT level by using DMol3
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(ref. 127 and 128) and CASTEP129 codes, as implemented in
Materials Studio 6.0. For the DFT exchange-correlation poten-
tial, we used gradient-corrected functional of PBE type (GGA-
PBE). Non-covalent forces, in particular van der Waals (vdW)
interactions, were accounted for in both codes by introducing
damped atom-pairwise dispersion corrections of the form
C6R6 in the DFT formalism, in particular the Grimme
scheme.45,46 In DMol3, Effective Core Potentials (ECP) and
Double Numerical plus d-function (DNP) basis set were used for
all atoms. In CASTEP, the Norm-Conserving Pseudo-Potentials
(NC-PP) in the reciprocal space representation were employed.
For the carbon, nitrogen and silicon atoms the core region
contained the two electrons of the 1s orbital. For the metal
atoms, the d-orbitals were considered to be in the valence shell
only for gallium and bismuth, for which the 3d and 5d states
were explicitly included into the valence shell. The equilibrium
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structures were obtained aer geometry minimization with
convergence thresholds for energy change, maximum force,
maximum displacement and maximum step size between
optimization cycles set to 0.001 mHa per atom, 0.001 Ha Å1,
0.002 Å, and 0.1 Å in dmol, and 0.01 meV per atom, 0.001 eV
Å1, 0.001 Å in CASTEP, respectively, for the convergence
tolerance of the energy, maximum force and maximum
displacement of atoms. The binding energies (Eb) of the metal–
nitrogen and silicon–nitrogen bonds were calculated by using
DMol3 as energy differences Eb ¼ Eisol  Eeq of the molecular
system, with the corresponding bonds broken (Eisol) and the
molecular system at equilibrium (Eeq). An insight into the
thermal stability of the metal silylamides was achieved by
following the molecular dynamics at different temperatures
from room temperature to 350  C. Each molecular system was
treated as a canonical ensemble (NVT) in both cases, in DMol3
as an isolated molecule and in CASTEP as an isolated molecule
in a large box (25 Å edge). The Nose'-Hoover thermostat and a
time step of 2.0 fs were used in both molecular dynamics
simulations, keeping the same functionals and cut-off energy
settings as in the geometry optimizations for the electronic
calculations at each step.
Acknowledgements
This work was supported by Marie Curie Co-fund in the frame of
Empa Postdocs Programme, by Swiss SNF (project number
200021_140245) and by ERC (Starting Grant “NANOSOLID”,
contract number 306733). Computing resources are provided by
the ETH Zurich, Brutus linux cluster and Computer facilities at
the Institute of Inorganic Chemistry.
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