Germanium dioxide

Germanium dioxide, also called germanium oxide, germania, and salt of germanium, is an
inorganic compound with the chemical formula GeO₂. It is the main commercial source of
germanium. It also forms as a passivation layer on pure germanium in contact with atmospheric
oxygen.

Formula: GeO2

Molar mass: 104.61 g/mol

Melting point: 1,115 °C

Density: 4.25 g/cm³

Solubility: soluble in HF, insoluble in other acid. Soluble in strong alkaline conditions

Crystal structure: hexagonal

Flash point: Non-flammable

Reduced GeO2 Nanoparticles: Electronic Structure of a Nominal

GeOx Complex and Its Stability under H2 Annealing

A nominal GeOx (x≤ 2) compound contains mixtures of Ge, Ge suboxides, and GeO2, but the detailed

composition and crystallinity could vary from material to material. In this study, we synthesize GeOx
nanoparticles by chemical reduction of GeO2, and comparatively investigate the freshly prepared
sample and the sample exposed to ambient conditions. Although both compounds are nominally
GeOx, they exhibit different X-ray diffraction patterns. X-ray absorption fine structure (XAFS) is
utilized to analyse the detailed structure of GeOx. We find that the two initial GeOx compounds have

entirely different compositions: the fresh GeOx contains large amorphous Ge clusters connected by
GeOx, while after air exposure; the Ge clusters are replaced by a GeO2-GeOx composite. In addition,
the two GeOx products undergo different structural rearrangement under H2 annealing, producing
different intermediate phases before ultimately turning into metallic Ge. In the fresh GeOx, the
amorphous Ge remains stable, with the GeOx being gradually reduced to Ge, leading to a final
structure of crystalline Ge grains connected by GeOx. The air-exposed GeOx on the other hand,
undergoes a GeO2→GeOx→Ge transition, in which H2 induces the creation of oxygen vacancies at
intermediate stage. A complete removal of oxides occurs at high temperature.
Ge is one of the promising candidates for anode materials in Li-ion batteries1,2. It has a theoretical
capacity
as high as 1600mA h g−1
(upon formation of a Li4.4Ge alloy) and excellent Li+ diffusion rate at room
temperature1
. However, the drastic volume expansion in crystalline Ge that occurs after Li insertion
leads to capacity fading which limits its use in practical Li-ion devices3
. Researchers have been seeking
methods to enhance the stability of Ge anodes, such as minimizing the size of Ge4,5, surface
functionalization2,6,
morphology engineering7,8 and forming a composite structure by coating Ge with a layer of
carbon9,10. Recently, amorphous GeOx (x<2) structures have attracted great interest due to their
ability
to enhance the cycling life of Li-ion batteries11–14. Compared to crystalline Ge, oxidized Ge is lower
cost,
has better chemical stability, and improved cyclability. In fact, it has been reported that GeO2 is able
to
deliver a capacity up to 2152mA h g−1
if it reversibly stores 8.4 Li+ (reactions (1) and (2))14–16.

It has been proposed that presence of Ge0

in GeO2 has a unique role in that it can serve as a catalyst
to drive reaction (1) in the inverse direction, hence the formation of LiO2 is reversible.

effect of Ge has been demonstrated by Seng et al. using a GeO2/Ge/C nanocomposite as an anode
for
a Li battery test17. A nominal GeOx structure contains a mixture of Ge dioxides and sub-oxides, as
well
as elemental Ge. It is critical to understand the composition and the structure of GeOx to achieve
better
control of the crystallinity and grain size of the different constituents in terms of improving the
battery
performance.
Although there has been a large amount of work on synthesizing nanostructured GeOx with new
configurations12,14,18, less attention has been given to understanding the starting material itself
before
introducing it into a battery test. GeOx contains a mixture of Ge, GeOx, and GeO2, and in an
oxidizing
(or reducing) environment, these three components can transform from one species to another19–
21. In
fact, GeOx has been deliberately synthesized and served either as the precursor for making Ge
nanocrystals
and/or GeO2 nanostructures for the purpose of fabricating electronic and optical devices22–24.
Although there have been relatively large amount of early studies done on Ge nanocrystal
embedded
GeOx or SiOx thin films for the purpose of electronic devices fabrication, few reports are available on
the structure characterization of the free-standing Ge/GeOx/GeO2 nanocomposite in terms of
battery
applications. In particular, since amorphous Ge and GeOx are more promising for Li-ion anodes than
their crystalline counterparts, the standard crystal structure analysis tool X-ray diffraction (XRD) is
no longer capable of characterizing the crystal structure of GeOx. Transmission electron microscopy
(TEM) with high resolution can tell the crystallinity of individual nanoparticles. However, for
amorphous
structure, distinguishing different components (e.g. Ge and GeOx) almost entirely relies on the
contrast
of the image. In addition, the small sampling size of TEM lacks information on the averaged chemical

composition of the material.

Aside from the crystal structure, understanding the chemical components in GeOx from the
electronic
structure perspective is also important. GeOx contains Ge in various oxidation states, from Ge0
up to Ge4+. The conventional characterization technique for studying the electronic structure of
GeO2/
Ge materials is photoelectron spectroscopy21. This technique requires the samples to have a clean
surface
and be in good electrical contact with the substrate. However, nanostructured GeOx for Li-ion
battery
applications are more often in the form of powder. The GeOx therefore have irregular surfaces,
which
makes removing surface impurities and ensuring good electrical contact very difficult. Consequently,
characterizing the electronic structure of these materials with photoelectron spectroscopy is very
challenging.
X-ray absorption spectroscopy, on the other hand, is an alternative tool for electronic structure
characterization that is flexible in terms of sample preparation. X-ray absorption fine structure
(XAFS)
probes the local environment of an element of interest in the material. The spectrum originates
from
the interference between incoming and outgoing electrons after single and/or multiple scattering. As
a
result, it is a local structure probe and doesn’t require the sample to be crystalline. By measuring the
Ge
K-edge XAFS, the chemical environment of Ge, such as its oxidation state (from the X-ray absorption
near-edge structure, XANES), the coordination number, and the bond distance between Ge and the
nearest neighbors (from the extended X-ray absorption fine structure, EXAFS) can be obtained14,25–
27.
GeOx nanostructures can be synthesized using various approaches, such as hydrothermal
methods13,
hydrolysis17, and by chemical reduction2,11. Herein we study the electronic structure of GeOx
nanoparticles
synthesized by simple chemical reduction. Such method produces GeOx which contains GeO2, Ge
sub-oxides, and most interestingly, Ge11. This serves as a good starting point to investigate the
electronic
structure of the GeOx, and the transitions between the three components under various conditions.
We
first compare the freshly prepared GeOx, and the one stored in ambient condition for 3 days. These
two
samples were then used as starting materials, and were annealed in H2 at various temperatures. The

change in the chemical environment of Ge under different annealing temperatures is studied.

Results and Discussion
The freshly prepared GeOx nanoparticles have an average size of 50nm. Figure 1a shows a
representative
transmission electron microscopy (TEM) image of these particles. X-ray diffraction (XRD)
measurement
reveals that the fresh GeOx and air-exposed GeOx have very different crystal structure (Fig. 1b–d).
The
fresh GeOx only contains two broad peaks, indicating its amorphous nature. The air-exposed GeOx,
on
the other hand, shows well-resolved features that resemble crystalline GeO2 with a quartz structure.

After annealing in H2 at 300 °C, the XRD patterns of both fresh GeOx and air-exposed GeOx are both
broadened to some extent, however, the features characteristic of GeO2 are still present in the
latter.
When the annealing temperature is increased to 500 °C, fresh GeOx crystallizes into an fcc structure,

with diffraction peaks matching cubic-phase metallic Ge. These features are further sharpened
under

annealing at 700 °C. As for air-exposed GeOx, the 500 °C annealing results in a mixed phase
containing
both GeO2 and Ge. From the intensity of the two peak series, the GeO2 is still the major component.
A
full conversion from GeO2 to Ge is observed at 700 °C annealing.
We analyse the crystalline grain size of our samples using the Scherrer equation (Eq. 3),

in which τ is the crystalline size, K is the shape factor, λ is the wavelength of the incident X-ray, β is
the
full width at half maximum. In this case, the values of β for 700 °C annealed fresh GeOx and air-
exposed

Figure 1. (a) TEM image of as-prepared fresh GeOx nanoparticles. (b–d) XRD patterns of GeOx
nanoparticles before and after annealing in comparison with standards. (b) fresh GeOx (sample
series 1); (c)
air-exposed GeOx (sample series 2); (d) standard XRD patterns of cubic Ge and quartz GeO2
33,34. Labels in
(b) and (c): (a) as-prepared samples; (b) samples annealed at 300 °C; (c) samples annealed at 500 °C;
(d) samples annealed at 700 °C. The intensity of 1-d is reduced in half to fit the panel.

GeOx are 0.0055 rad (0.318⁰) and 0.0065 rad (0.370⁰), respectively. Taking K=0.89 (the typical value
of
the shape factor) and λ = 1.5406Å, we can obtain the averaged crystalline sizes for annealed fresh
GeOx
and air-exposed GeOx are 26nm and 22nm, respectively. The crystalline domain size of metallic Ge
by
annealing fresh GeOx is slightly larger than that of air-exposed GeOx.
Although after the final annealing, the two GeOx possess very similar XRD patterns, the initial and
intermediate phases are significantly different. Since XRD is only sensitive to structure of long-range
order (i.e. crystalline), we then turn to XAFS to further examine the local structure of GeOx
nanoparticles.
Figure 2 shows the Ge K-edge XANES for all GeOx samples, before and after annealing, in comparison
with commercial GeO2 powder. As a fully oxidized Ge standard, the XANES of GeO2 is dominated
by one sharp peak (marked by the dashed line in Fig. 2), which corresponds to the transition of an
electron
from the Ge 1s core level to an unoccupied 4p state. Compared to GeO2, both GeOx samples, with
or without heat treatment, have additional features at lower energy (marked by the dotted line in
Fig. 2),
indicating the presence of Ge with an oxidation states lower than that in GeO2. Recall from the XRD
pattern in Fig. 1 that the fresh GeOx is amorphous until annealed at a temperature above 500 °C.
From
XANES, we can see that there are both Ge- and GeO2-like structures in the fresh GeOx, and the lack
of
diffraction peaks in the XRD suggests that they are amorphous. Under annealing at 500 °C and 700
°C,
crystalline Ge appears (as confirmed by XRD, refer back to Fig.  1), although there is still amorphous
GeO2 present as evidenced by XANES. On the other hand, air-exposed GeOx is dominated by GeO2.
A
slight broadening at the lower energy side of the main peak is caused by the presence of Ge sub-
oxides
and Ge. A sudden transition occurs after annealing at 700 °C, in which almost all the GeO2
disappears,
and the spectrum is dominated by a low-valent species Ge (spectrum 2-d). The energy onset and the
spectral profile resembles the previously reported metallic Ge2,28. Unlike the fresh GeOx which has
a
mixture of metallic Ge and amorphous GeO2, air-exposed GeOx after 700 °C turns almost completely

to metallic Ge. We note that the XRD patterns for the fresh and air-exposed samples after annealing
at
700 °C are essentially the same, but the metallic Ge-related feature in the XANES is more intense for
the
air-exposed sample than the fresh sample, suggesting that in the air exposed sample, a larger
fraction
of the available Ge is converted to cubic Ge than in the fresh sample. This is further corroborated by
noting that the air-exposed sample lacks a clear GeO2-related feature in the XANES; suggesting that
so
much Ge has been converted to metallic Ge that a distinct GeO2 phase is unable to form. Recall that
the air-exposed sample annealed at 700 °C exhibits a smaller grain size for metallic Ge than the fresh

sample annealed at 700 °C. If any Ge oxide remaining in these samples after annealing at 700 °C
occupies
the space between the grains, if these grains are close-packed then the smaller grains in the air-
exposed
sample will lead to smaller domains of Ge oxide; possibly too small for a distinct GeO2 lattice to
form.
A closer examination of the oxidation states in Ge can be performed by examining the 1st derivative
of the XANES spectra. The plots are shown in Fig. 3, and the peak positions (the edge jump)
correspond
to the oxidation states of Ge in the samples. This method allows us to obtain the evolution of Ge
oxidation
states during annealing in detail. The lower energy dashed line marks the edge jump of Ge0
and
the higher energy line marks the one of Ge4+. Interestingly, the evolution of the edge jump positions
as
a function of annealing temperature is quite different between the two sets of GeOx.