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ARTICLE

Hidden gapless states during thermal transformations of

preorganized zinc alkoxides to zinc oxide nanocrystals

Materials Horizons Accepted Manuscript

Received 00th January 20xx, Jakub Szlachetko,a,b Adam Kubas,b Anna Maria Cieślak,b Kamil Sokołowski,b Łukasz Mąkolski,c Joanna
Accepted 00th January 20xx Czapla-Masztafiak,a Jacinto Sá,a,d* Janusz Lewińskia,c*
DOI: 10.1039/x0xx00000x
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www.rsc.org/

Zinc oxide (ZnO) is one of the most versatile semiconductor Conceptual insights
material with multifarious potential applications. Easily accessible Among diverse strategies employed for the preparation of
alkylzinc alkoxides have been widely exploited as single-source semiconductor materials, single source precursor (SSP)
precursors of ZnO-based nanomaterials but their multi-step approach is widely regarded as one of the most promising for
decomposition pathways have not been understood in details. the preparation of bulk, thin-film, and nanocrystalline
Herein, the formation mechanism of ZnO nanocrystals via solid- materials. However, one of the key obstacles hampering
state thermal decomposition of a model pre-organised alkylzinc rational design of SSP precursors is the scarcity of mechanistic
alkoxide precursor, i.e. [tBuZn(μ3-OtBu)]4, is elucidated using in situ insights that are derived nowadays by state-of-the-art
valence-to-core X-ray emission (v2c-XES) and high energy combination of in situ spectroscopic measurements and
resolution off-resonant spectroscopy (HEROS) in conjunction with theoretical simulations. Herein, we track in situ formation of
theoretical calculations. Combination of in situ spectroscopic ZnO NCs via thermal decomposition of a preorganised alkylzinc
measurements and theoretical simulations indicate that the alkoxide using valence-to-core X-ray emission (v2c-XES) and
precursor structural evolution is initiated by homolytic cleavage of high energy resolution off-resonant spectroscopy (HEROS). The
the R-Zn bond which leads to the formation of a transient radical detailed in situ study on the decomposition process of the zinc
[•Zn(μ3-OR)][RZn(μ3-OR)]3 species, which is responsible for the alkoxide precursor, supported by computer simulations,
initial decomposition process. The ensuing multistep revealed that any nucleation and growth of a semiconducting
transformations involve the formation of intermediate radical zinc ZnO phase is preceded by cascade transformations involving the
oxo-alkoxide clusters with gapless electronic states. Hitherto, the formation of previously unreported intermediate radical zinc
formation of clusters of this type has not been considered neither oxo-alkoxide clusters with gapless electronic states. In this
as intermediate structures en-route to a semiconductor ZnO phase process homolytic cleavage of the R-Zn bond is responsible for
nor as potential species accounting for various defect states of ZnO the initial thermal decomposition process.
NCs, particularly the singly charged oxygen vacancy, Vo+.
nanomaterials and the research about their preparation1c,d,e,2
and utilisation3 have made an immense progress in the past
Introduction three decades. The development in the area has been
Design and preparation of well-defined nanomaterials in a accompanied by an advanced knowledge concerning various
controlled manner remains tremendous challenge and is aspects of semiconductor nanocrystals (NCs) formation, i.e.
acknowledged to be the biggest obstacle for exploitation of chemical reaction pathways of decomposition of NCs’
many nanoscale phenomena.1 This interest has triggered precursors as well as pre-nucleation, nucleation and growth
intense studies on the chemistry of semiconductor processes. However, in many cases the chemistry of intimate
steps of transformations from initial precursors to NCs is still not
well understood due to the high complexity of the reactions
a. Institute of Physical Chemistry Polish Academy of Sciences Kasprzaka 44/52, involved, and has remained a subject of constant debates.1c,e,3
01-224 Warsaw, Poland
b. Institute of Nuclear Physics Polish Academy of Sciences Radzikowskiego 152, Among diverse strategies employed for the preparation of
31-342 Kraków, Poland semiconductor NCs, the single source precursor (SSP) approach
c. Faculty of Chemistry Warsaw University of Technology Noakowskiego 3, 00-664

Warsaw, Poland
is widely regarded as one of the most effective method for
d. Physical Chemistry Division, Departament of Chemistry, Ångström Laboratory, fabrication of thin-film and nanocrystalline materials.4
Uppsala University, Lägerhyddsvägen 1, 75120 Uppsala, Sweden However, in most cases the SSPs are empirically designed and
† Footnotes relating to the title and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [details of any the transformation conditions are painstakingly optimised using
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x

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trial and error approaches, and the predictive character is View Article Online
strongly limited. Metal alkoxides represent likely the most DOI: 10.1039/C8MH00106E
important class of SSP used in solution and solid-state synthetic
routes leading to metal oxide semiconductor NCs.5,6 In these
transformations, the formation of metal–oxygen–metal bridged
Scheme 1. Proposed first steps in thermal decomposition of alkylzinc alkoxides to
bonds represents the first step towards the build-up of the solid ZnO NCs: β hydrogen atom abstraction from an alkoxide group (gas-phase, path
1) and homolytic cleavage of a R-Zn bond (solid-state, path 2).
metal oxide structures, however the mechanisms for these oxo
bridges formation are manifold. In aqueous systems the water
resolution off-resonant spectroscopy (HEROS). Analysis of the
molecules usually donate the oxygen atom for oxide formation
experimental data along with theoretical calculations indicate
via complex hydrolysis and condensation processes.5,6 In turn,
that any nucleation and growth of a semiconducting ZnO phase
in nonhydrolytic sol-gel processes carried out in organic

Materials Horizons Accepted Manuscript

is preceded by cascade transformations involving the formation
solvents, the oxide formation is determined by the reactivity of
of intermediate radical zinc oxo-alkoxide clusters with gapless
metal-alkoxide subunits, and M-OH and M-O species are
electronic states, and homolytic cleavage of a R-Zn bond is
typically formed by classical non-radical organic reactions.6,7
responsible for the initial thermal decomposition processes
While reactions in gas phase and solution are usually easier to
(Scheme 1; path 2).
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track in situ, the solid-state processes are definitely more

challenging in terms of monitoring decomposition pathways
and structural evolutions from the precursor to the nucleation Results and discussion
and growth of NCs under reaction conditions.8 Undoubtedly, for
thermal decomposition of solid precursors mechanistic studies Thermolysis of the well-defined model heterocubane 114c,e,f
are much more tedious and the mechanisms are much less under inert argon atmosphere was tracked in situ using
known in comparison to solution based systems.6,9 From this advanced X-ray spectroscopy techniques.16 We applied v2c-XES
perspective, the scarcity of mechanistic insights derived from and HEROS (Figure 1A and 1B) techniques to reveal occupied
state-of-the-art combination of in situ spectroscopic and unoccupied electronic states around the Fermi level. The
measurements and theoretical simulations are one of the key potent combination of X-ray penetrating properties and X-ray
obstacles hampering rational design of SSPs. spectroscopy sensitivity enables element-specific
Zinc oxide (ZnO) has become the most widely studied metal
oxide material over the last decades as one of the most versatile
systems with multifarious potential applications.10 Easily
accessible alkylzinc alkoxides with a heterocubane architecture,
i.e. [RZn(μ3-OR’)]4-type compounds with the central Zn4O4 core,
have become natural candidates for the role of SSPs of
ZnO-based nanomaterials.10-14 While transformations of these
predesigned precursors to ZnO NCs under mild conditions in
organic solvents11 or thermal decomposition in gas phase,12 hot
surfactant solutions13 as well as the solid state7a,14 have been
extensively studied using various analytical techniques, their
multi-step decomposition pathways have not been understood
in details. Moreover, various defects are ubiquitous to ZnO NCs
but their nature and effect on physicochemical properties
essentially remain elusive and is subject of extensive and
continuous research.14a,15 Gas-phase experiments are
particularly attractive tools for the examination of intrinsic
reactivities of zinc alkoxides and, for example, β-hydrogen atom
abstraction from an alkoxide group by a zinc atom with the
formation of a zinc-hydride species was proposed as the first
step in gas-phase decomposition of heterocubane alkylzinc
alkoxides (Scheme 1, path 1).12 Similar mechanism was also
proposed for the solid state thermal decomposition of zinc,7a,14b
magnesium and aluminium alkoxides.7a However, to the best of
our knowledge, zinc-centred radical species and any other
intermediates with gapless electronic state have not been
considered en route from zinc alkoxides to ZnO NCs irrespective
Figure 1. (A) Representation of valence-to-core (v2c) (left) and off-resonant (right)
of state of matter. Here, we track in situ formation of ZnO NCs X-ray emission (HEROS) processes that allow probing of occupied and unoccupied
electronic states of scattering atom, (B) schematic representation of experimental
via solid-state thermolysis of an alkylzinc alkoxide set-up or high energy resolution dispersive-type spectroscopy using von Hamos
geometry.
[tBuZn(μ3-OtBu)]4 (1) using valence-to-core X-ray emission
(v2c-XES) and high energy

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Figure 3. Experimental and theoretical v2c-XES and HEROS spectra for the
predesigned cluster 1 along with the electronic density of states contributions to
valence and conduction states.

The calculations revealed that the occupied (valence) states

consists mostly of the Zn 3d-orbitals along with the O and C 2p-
orbitals of the alkoxide ligand, while the unoccupied
(conduction) states consist of a mixture of several atomic
orbitals, with major g contributions from the Zn 4s, 4p, and the
3d-states overlapping with the O, C p-states (Figure 3). Analysis
of v2c-XES and HEROS spectra yields complete description of
reacting states.19 The determined valence and conduction band
positions are plotted in Figure 2B, together with band gap
values that are calculated from energy difference between
valence and conduction states. As Figure 2B displays, at
temperatures below 300 °C, the electronic structure of the
measured system shows significant splitting of valence and
conduction bands with approximate band gap value around 3.3
eV (region I). In the temperature range of 300-400 °C a sudden
convergence of valence and conduction electronic states is
observed that suggest the formation of a unique phase with a
gapless electronic state (region II). We note that the band-gap
narrowing to a value of 0.3 eV is induced by the shift of valence
states to higher energies by 2 eV that is simultaneously
accompanied with shift of conductions states downward by
about 1 eV. At temperatures above 400 °C, the valence and
conduction states split again to a band-gap value of about
Figure 2 (A) v2c and HEROS X-ray spectra recorded during thermal decomposition
1.2 eV (region III).20 This splitting is mostly induced by upward
of hetrocubane 1, (B) graph with determined valence and conduction band shift of conduction states, while valence states energy is being
positions (top) and band-gap values (bottom) during the thermal decomposition
with the three main phases marked corresponding to insulator, gapless and constant at position of around -1 eV. Respective v2c-XES and
semiconductor phases respectively.
HEROS spectra for the discussed temperature ranges I, II, and III
measurements of chemical systems transformations under are plotted together in Figure 4A. In Figure 4B, we zoom-in on a
working conditions.16 The experimental temperature- near-Fermi energy region for phase transitions from the
dependent v2c-XES and HEROS data of the thermal insulator-like to intermediate gapless states (top), and from the
decomposition of 1 are presented in Figure 2A. In Figure 3 the intermediate gapless states to semiconductor phase (bottom).
experimental and theoretical v2c-XES and HEROS spectra for Here, we should emphasize the effects of 1s core-hole and 3p
the precursor 1 are shown. Figure 4 depicts representative state lifetime broadening, experimental resolution and core-
spectra for temperature ranges I, II, and III that are marked in hole screening. As shown in Figure 3, the measured v2c-XES and
Figure 2A. The theoretical calculations were performed using
HEROS spectra exhibit valence- and conduction-edge smearing
FEFF program17 and Kramers-Heisenberg formalism18 and
that results from natural broadening of atomic states involved
showed good qualitative agreement with the experiments
in the scattering process.

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Figure 5. Molecular drawings of structures 1 (A), IB (B) and IIA (C, D) identified en
route to a bulk ZnO (hydrogens omitted for clarity) along with the most important
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bond lengths (in Å, black). For structure IIA that possess an open-shell character,
Löwdin spin populations are given in italic/magenta for key atoms in (C) while the
isosurface of the singly-occupied molecular orbital (SOMO) is given in panel (D).

cleavage in intermediate of type IB is favoured over the same

process in 1 by 10.0 kcal/mol, and leads to a dicubane IIA
(ΔHIB→IIA = 65.9 kcal/mol), which can be drawn as two resonance
Figure 4. (A) v2c-XES and HEROS spectra for three temperature regions: I – up to electronic structures, highlighted in Scheme 2. The order of Zn-
300 degrees (black), II – from 300 to 400 °C (red) and III – above 400 °C (blue), and
schematic structures for the initial and the final phases are shown on the right. Zn bond in IIA is less than one as the O-Zn-Zn unit has a three-
Note that the final stage III relates to the formation of wurtzite ZnO NCs as
confirmed by powder X-ray diffraction.6d (B) Zoom-in on around Fermi level centre-three electron-bonding event. According to our
energies and transitions from I→II (top) and II→III (bottom). The directions of the
spectral changes are marked by arrows and compared to theoretical calculations calculations (vide infra), the proposed resonance hybrid has a
for v2c and HEROS spectra shown on right.
low excitation energy thus, it is the best candidate for the
In case of Zn atom, the 1s and 3p lifetime broadenings are 1.6 gapless region II, cf. Scheme 2 and Figure 2. Intermediates of
eV and 2.1 eV, respectively. The experimental spectra are type IIA experience further transformations by the homolytic
further broadened by convolution of Lorentz-like atomic cleavage of the Zn-Zn bonds, accompanied with loss of the alkyl
lifetimes with experimental resolution of 1.5 eV given by substituents, triggers the formation of (ZnO)n clusters, followed
Gaussian function of the spectrometer response. Due to this, by structural rearrangement to the more thermodynamically
the v2c-XES and HEROS spectra exhibit broadening of states favoured the wurtzite phase. Interestingly, upon clustering of
visible in Figure 3. two putative (ZnO)4 cubanes IIIA a drum-like (ZnO)8 structure IIIB
To the best of our knowledge, this is the first time an is favoured.25
intermediate featuring a gapless electronic state has been Intermediate clusters in the proposed mechanism can be
observed en-route from pre-organized zinc alkoxides to nano- grouped according to the first excitation energies (ΔEexc). In all
sized ZnO particles. Below we propose a mechanism, which cases, such excitations are of highest occupied–lowest
accounts for all experimental changes in the thermal unoccupied molecular orbital character (HOMO-LUMO
decomposition of 1 and investigate this mechanism using transitions). These can be considered as the first approximation
density functional theory.21 The proposed novel mechanism of to a direct band-gap of a solid state probed approximately also
stepwise transformations of the pre-organised zinc alkoxide 1 in the X-ray experiments (comparison with a simpler method
to ZnO NCs is depicted in Scheme 2 and key optimised that considers only HOMO-LUMO gap can be found in the
molecular structures are presented in Figure 5. The reaction is Supplementary Information). The ΔEexc calculated with
initiated by a homolytic Zn-C bond cleavage in 1 and leads to the B3LYP/ROCIS method for all intermediates depicted in
formation of a transient radical [•Zn(μ3-OR)][RZn(μ3-OR)]3 (IA) Scheme 2 are provided in Table S1. Molecule 1 along with the
species with one zinc-centred radical at the corner;22 the intermediate geometries IA and IB are typical insulators with an
alternative homolytic O-C cleavage is 24.2 kcal/mol higher in expected band-gap of more than 3 eV. This links these states
energy. The resulting radicals IA can dimerise though a Zn-Zn- with experimentally defined region I in Figure 2 where for
bond formation to form a dicubane IB23 and the enthalpy temperatures up to 300°C the average band gap was found to
associated with this process is strongly negative (ΔHIA→IB = -59.7 be about 3.3 eV. The open-shell state IIA has a very low ΔEexc of
kcal/mol). We note that the formation of Zn-Zn bonds is not 0.14 eV. Thus, it can be associated with increasing approximate
unprecedented in organometallic chemistry but molecular band-gap obtained from the X-ray experiments upon thermal
compounds featuring a zinc-zinc bond between monovalent decomposition of 1.14e Such low excitation energy derives from
zinc centres are not common. 23 The following C-O bond a delocalised nature of unpaired electron in IIA. Löwdin
population analysis (Figure 5D) reveals the

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oxygen atoms it is expected that the low-energy excitations will

develop a low-energy band observed as a gapless phase II.
Above 400°C, the experimental average band-gap is 1.2 eV with

Materials Horizons Accepted Manuscript

a tendency to widen in higher temperatures. In this region III
wurzite phase ZnO nanoclusters forms via a series of structural
rearrangements. Although with the current set-up we cannot
exactly track this final process, we can obtain ΔEexc of growing
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zinc oxide clusters in vacuum. The calculated excitation energies

increase from 2.60 eV to 3.25 eV when going from a bare [ZnO]4
cubane cluster to a larger [ZnO]8 drum-like form. This compares
favourably with the observed experimental band gap of about
Figure 6. HRTEM images of ZnO NCs posing a final product of the thermal
decomposition of 1 obtained during the v2c-XES and HEROS experiments: (A) FFT 3.3 eV as well as with growth process leading to ZnO NCs of
analysis on selected area indicating diffraction fringes related to the (100) plane
of wurzite ZnO (0.28 nm) and (B) size distribution analysis. wurtzite phase. This is consistent with the reported v2c-XES and
HEROS experiments and HRTEM images of the resulting ZnO
unpaired electron distribution between two bridging Zn atoms NCs (Figure 6). Moreover, the proposed formation of zinc- and
(spin populations of 0.3 each) and under-coordinated oxygen oxygen-centred radical species is in line with, and might account
atom (spin population of 0.2). This picture is consistent with the for, the observed various defect states (particularly the singly
composition of the singly-occupied molecular orbital (SOMO) charged oxygen vacancy, Vo+, and EPR activity of ZnO NCs
shown in Figure 5D where the SOMO is essentially a linear derived from thermal decomposition of alkylzinc alkoxides14a,b,
combination of σZn-Zn bonding orbital and oxygen 2p atomic (notably, ZnO NCs derived from a wet self-supporting
orbital. The low-energy excitation is thus due to excitations of organometallic procedure are EPR silent in standard
electrons occupying σZn-C bonds into the SOMO. In the bulk, condition26).
where more Zn-Zn bonds are present in close vicinity to oxo-

Scheme 2. Representation of the proposed [tBuZn(µ3-OtBu)] solid state thermal decomposition steps and the intermediate structures evolutions; the species are
assigned to the experimentally derived regions I-III that correspond to certain band-gap ranges (see Figure 2).

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2015/18/E/ST3/00444 (J. Szlachetko) and

2015/17/D/ST4/00112 (A. Kubas) as well as the Foundation for
Conclusions Polish Science TEAM Program co-financed by the European

Materials Horizons Accepted Manuscript

In summary, we demonstrate great potential of advanced X-ray Union under the European Regional Development Found
spectroscopy techniques, i.e. v2c-XES and HEROS which, in TEAM/2016-2/14 (J. Lewiński, A. Kubas) and the program START
conjunction with theoretical calculations, allowed elucidation of (A. M. Cieślak). Access to high performance computing
the intimate steps of solid-state thermal transformations of the resources was provided by the Interdisciplinary Centre for
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model heterocubane alkylzinc alkoxide to ZnO nanoclusters. Mathematical and Computational Modelling under grant no.
The reported mechanistic insights into the thermolysis of the G64-9. We also thank Dr M. K. Leszczyński for his assistance with
organometallic SSP indicates the formation of previously TEM measurements and data analysis.
unreported open-shell radical zinc oxo-alkoxide clusters with
gapless electronic states as the key steps en route to
semiconductor ZnO NCs. The proposed intermediate zinc- and
Notes and references
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from the thermal decomposition of alkylzinc alkoxides.14 In a and T. Hyeon, Acc. Chem. Res., 2008, 41, 1696; d) Z. Zhuang,
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Conflicts of interest 8 In the solid state processes involving SSPs, the organic
There are no conflicts to declare. residues are usually removed through the formation of
volatile organics species under thermal conditions which can
be further analysed by various analytical techniques.
9 A. Tiwari and B. Raj, in Reactions and mechanisms in thermal
Acknowledgements analysis of advanced materials; Hoboken, New Jersey: John
Wiley & Sons, 2015.
The authors acknowledge for the access to the SuperXAS 10 H. Morkoç and U. Özgür in Zinc Oxide: Fundamentals,
beamline at the Swiss Light Source. We also acknowledge the Materials and Device Technology; Willey-VCH: Weinheim,
National Science Centre for partial support under grants no. 2009.

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10.1039/C8MH00106E
A. De Toni, T. Goes and S. Polarz, J. Am. Chem. Soc., 2008, determined from v2c-XES and HEROS to a high precision.
130, 16601; c) C. L. Pueyo, S. Siroky, S. Landsmann, M. W. E. 21 R. O. Jones, Rev. Mod. Phys., 2015, 87, 897 and references
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Materials Horizons Accepted Manuscript

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19 The positions of valence bands were obtained from fit of
Gaussian function to first spectral derivative. The obtained
inflection points on high-energy side of v2c-XES gave the
inflection point on low energy side of HEROS spectra.
20 We note, that unlike optical band-gap measurements, the X-
ray spectroscopy measurements do not allow determining
the absolute band-gap values, but permit to observe changes
as relative energies. This effect is due to the screening of a
deep lying 1s core-hole state that affects measured energy
positions of valence/conduction states. Within the
femtosecond time scale of scattering process, the core-hole
acts onto the electronic states of the atom and as
consequence leads to the shift of the electronic states
energies. For this reason, the band-gap values as extracted
from v2c-XES and HEROS measurements will differ in
absolute values to the gap values as measured with optical
probes. Nonetheless, we would like to stress, that beside the

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