See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/343471663

Controlling the thermoelectric power of silicon–germanium alloys in

different crystalline phases by applying high pressure

Article  in  CrystEngComm · August 2020

DOI: 10.1039/D0CE00672F

CITATIONS READS

7 677

4 authors:

Natalia Morozova Igor Korobeinikov

Institute of Metal Physics Institute of Metal Physics
36 PUBLICATIONS   400 CITATIONS    15 PUBLICATIONS   220 CITATIONS   

SEE PROFILE SEE PROFILE

N.V. Abrosimov Sergey V Ovsyannikov

Leibniz-Institut für Kristallzüchtung University of Bayreuth
488 PUBLICATIONS   6,011 CITATIONS    195 PUBLICATIONS   2,762 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Surface preparation and characterization for X-ray crystal optics for metrology and imaging. View project

Advanced Physical Research View project

All content following this page was uploaded by Sergey V Ovsyannikov on 22 September 2020.

The user has requested enhancement of the downloaded file.

 Volume 22
Number 33
7 September 2020
Pages 5403–5560

CrystEngComm
rsc.li/crystengcomm

ISSN 1466-8033

PAPER
Natalia V. Morozova et al.
Controlling the thermoelectric power of silicon–germanium
alloys in different crystalline phases by applying high pressure
CrystEngComm
PAPER

Controlling the thermoelectric power of silicon–

Cite this: CrystEngComm, 2020, 22,
germanium alloys in different crystalline phases by
5416 applying high pressure
Natalia V. Morozova, *a Igor V. Korobeinikov, a
Nikolay V. Abrosimovb and Sergey V. Ovsyannikov cd

Received 6th May 2020,
Accepted 6th July 2020
DOI: 10.1039/d0ce00672f
rsc.li/crystengcomm
Silicon, germanium and their alloys are classical semiconductors that play an important role in fundamental
sciences and are the basis for modern microelectronics, optoelectronics, energy conversion, and other
applications. The thermoelectric power (Seebeck coefficient) of p- and n-type materials in combination
with the electrical and thermal conductivities characterizes the efficiency of thermal-to-electric energy
conversion. In this work we experimentally show how one can effectively control the thermoelectric power
of silicon-germanium alloys using an applied high pressure. We measured the Seebeck coefficient and the
electrical resistance for several Si1−xGex crystals with different compositions under applied high pressure in
(i) their original semiconductor cubic-diamond structure, (ii) across a phase transition to a metal phase at
about 9–13 GPa, and (iii) across phase transformations to different metastable phases on pressure release.
These studies were carried out for several pressurization and decompression cycles. The Si–Ge samples
were examined by X-ray diffraction and Raman spectroscopy. After the high-pressure cycling the Si–Ge
samples transformed into two metastable phases, namely, a cubic bc8 phase (Si-III) with a p-type electrical
conductivity in the Si-dominant samples, and a tetragonal st12 phase (Ge-III) in the Ge-dominant alloys,
whose conductivity type depended on the Si content. The dramatic pressure-driven changes in the
thermoelectric power of Si–Ge crystals we found suggest that these semiconductors are promising for use
in various stress-controlled electronic junctions, such as switches, p–n diode elements, n–p–n (p–n–p)
transistors, and multi-layer heterostructures with alternating types of electrical conductivity.

1. Introduction temperature synthesis routes, a number of novel

Silicon, germanium and their alloys (Si–Ge) are prominent
semiconductors that play an important role in fundamental
sciences and have various industrial applications. Silicon–
germanium alloys are promising for their use in fields such
as bipolar technologies,1–3 photonic applications,4,5 and
lithium-ion batteries,6–9 and in energy conversion
technologies, in which, they serve as elements of either solar
cells or thermoelectric devices.10–21 Hence, these materials
are always the focus of further investigations. Using
different methods, for example, high-pressure high-
a
M. N. Miheev Institute of Metal Physics of Ural Branch of Russian Academy of
Sciences, 18 S. Kovalevskaya Str., Yekaterinburg 620137, Russia.
E-mail: morozova@imp.uran.ru
b
Leibniz-Institut für Kristallzüchtung (IKZ), Max-Born-Str. 2, Berlin, 12489,
Germany
c
Bayerisches Geoinstitut, Universität Bayreuth, Universitätsstrasse 30, D-95447,
Bayreuth, Germany. E-mail: sergey.ovsyannikov@uni-bayreuth.de
d
Institute for Solid State Chemistry of Ural Branch of Russian Academy of Sciences,
91 Pervomayskaya Str., Yekaterinburg 620219, Russia
polymorphs of Si and Ge can be fabricated, e.g., Si24
polymorph,22 Si10 polymorph,23,24 hexagonal phases of Ge
and SiGe alloys with direct band gaps,25 and many other
phases predicted to be stable.26–33
Because of low values of the thermal conductivity and
significant values of the Seebeck coefficient at high
temperatures bulk Si–Ge alloys are used in various
thermoelectric modules for energy harvesting.11–21 The
efficiency of such thermoelectric modules, figure of merit
(ZT), directly depends on the thermoelectric power (Seebeck
effect, S) as ZT = TS 2σ/κ, where T is the temperature, σ is the
electrical conductivity, and κ is the total thermal conductivity,
consisting of lattice and electron contributions. The
thermoelectric power, which shows a magnitude of
thermoelectric voltage that can be generated in a sample
under application of a temperature difference of 1 K, is very
sensitive to changes in crystal and electronic band structures
of this sample. Hence, a possibility to control the value and
sign of the thermoelectric power of materials in general, and
of Si–Ge alloys, in particular, would be highly important both
for thermoelectric technologies themselves and for

5416 | CrystEngComm, 2020, 22, 5416–5435 This journal is © The Royal Society of Chemistry 2020
CrystEngComm
fabrication of various controls and switches (e.g., p–n switch
of conductivity type) for novel nanoelectronic devices.
Like silicon and germanium, their alloys crystallize in a
cubic-diamond structure (Fig. 1(a) and (b)),34–36 whose lattice
parameter varies from 5.43 Å for silicon to 5.66 Å for
germanium with an insignificant deviation from Vegard's
law.34,37–39 Si1−xGex alloys (x > 0.85) have higher mobility
values than silicon,40–42 and their electrical conductivity
tends to increase with the Ge content.42 The fundamental
energy gap of Si1−xGex depends on its composition but in
different manners for Si- and Ge-dominant alloys (Fig. 1(c)).
As can be seen in Fig. 1(c) the energy gap in the Si-dominant
alloys moderately narrows with the Ge content; in contrast,
in the Ge-dominant alloys the band gap more progressively
widens with the Si content from 0.64 eV to about 0.85 eV for
the Si0.15Ge0.85 composition (Fig. 1).2,43–47
In Si–Ge alloys, which crystallize in the cubic-diamond-
type structure with the only unique crystallographic site for
atoms, the Si and Ge atoms can be randomly distributed over
a crystal volume.48,49 However, in spite of Si/Ge being
isovalent impurities for each other, because of the sizable
difference in their atomic radii (Fig. 1(a) and (b)) these alloys
may be characterized by different point defects depending on
their chemical composition and preparation method. For
minor Si/Ge substitutions one can expect a uniform chemical
composition over a sample, whereas the higher levels of Si/
Ge substitutions can lead to partial Si/Ge segregation and the
formation of regions that are richer either in Si or in Ge.50,51
In some work it was noted that the smaller Si atoms are more
Fig. 1 The cubic-diamond crystal structure of (a) germanium slightly
substituted with silicon, SixGe1−x and (b) silicon slightly substituted with
germanium, Si1−xGex. (c) Composition dependence of the fundamental
indirect energy gap of Si–Ge alloys replotted from the literature data
for relaxed solid solutions (open circles connected by a solid curve,
from ref. 43). The red arrows correspond to the compositions we
investigated in this work.
This journal is © The Royal Society of Chemistry 2020
Paper
prone to the formation of Si-rich clusters in the germanium
lattice thereby causing both local distortions of the crystal
structure and changes in the electron density
configuration.52,53 Meanwhile, the larger Ge atoms are prone
to entering the silicon lattice as separate atoms that leads to
the appearance of internal compressive strains.54–59 To
compensate these strains the Ge atoms interact with other
point defects, and often vacancies are formed near the Ge
atoms.60,61 One can surmise that an applied high pressure/
stress could modify the native defect structure of Si–Ge alloys
thereby changing their electronic and other properties.
Since semiconductor elements are the basis of modern
electronics, both novel materials and alternative methods,
which could effectively tune their optoelectronic properties,
are always in much demand.62 Variation in the temperature
can induce drastic changes in electronic transport properties
(e.g., p–n switching), for example, in Ag10Te4Br3,63 AgBiSe2,64
AgCuS,65 Ag10Te4Br2.6Cl0.4,66 and in LaxSr2−xTiFeO6
67
perovskites. However, this approach can only be used to a
limited extent in practical micro- or nanoelectronic devices.
Other methods like controlled doping of a surface layer,
implantation or irradiation and consequent annealing68 are
not always applicable too. Meanwhile, methods based on
strain engineering and tuneable applied stress, which are
capable of changing the properties in micro- or nanoscale
regions of semiconductors,69 seem more applicable to
different optoelectronic devices, e.g., in switches, diodes,
transistors, or memory elements. A number of academic
studies of semiconductors reported the observation of
remarkable pressure-induced structural or electronic
transitions that are concurrent with drastic changes in their
optoelectronic properties, including p–n inversions of the
dominant conductivity type.70–75 These findings corroborated
the high potential of this method.
In this work we investigated the effect of an applied
high pressure on the thermoelectric power of silicon–
germanium alloys with Si- and Ge-dominant compositions,
Si1−xGex (x = 1, 0.98, 0.93, 0.87, 0.026, and 0), in the
pressure range up to 17 GPa, that is, across a
semiconductor–metal phase transition to a metal β-Sn-type
phase at about 9–13 GPa.76–100 We found that the applied
pressure can dramatically change the value of the Seebeck
coefficient in the cubic-diamond structure of Si–Ge alloys,
and for some compositions it can even invert the sign of
the thermopower. High-pressure cycling across the
semiconductor–metal phase transition point76–100 allowed
stabilization of the metastable phases of Si1−xGex with
different crystal structures and different electronic
properties. The crystal structures of Si1−xGex alloys were
examined by X-ray diffraction and Raman spectroscopy. The
findings of our work suggest that an applied pressure can
directly affect the competition of different conductivity
mechanisms in Si–Ge alloys. These results are of interest
from both fundamental and applied perspectives. Based on
the results of our work we proposed several potential
innovative applications of Si–Ge alloys.
CrystEngComm, 2020, 22, 5416–5435 | 5417
Paper
2. Experimental details
2.1. Synthesis of the Si–Ge samples
Bulk crystals of Si0.974Ge0.026 were grown by the Czochralski
technique and characterized by conventional methods.101
These crystals had a p-type electrical conductivity and a low
hole concentration of about 5 × 1015 cm−3.102 Bulk crystals of
pure germanium with n- and p-type conductivities and low
carrier concentrations of about 1014 cm−3 were provided by
different suppliers. Large-grain polycrystalline Ge-dominant
alloys, Si0.02Ge0.98, Si0.07Ge0.93, and Si0.13Ge0.87 were
synthesized under high-pressure high-temperature conditions
in a multi-anvil press.103 The synthesis procedures were the
same as reported in previous studies.104–106 For the high-
pressure electronic transport measurements we selected
microscopic single-crystal grains of these Ge-dominant Si–Ge
alloys with diameters exceeding ∼150 μm. The compositions
of the samples were controlled by scanning electron
microscopy (SEM) using a LEO-1530 instrument. For the
exception of Si0.13Ge0.87, which exhibited minor fluctuations
in the composition over the volume, the other samples were
chemically uniform.
2.2. Characterization of the Si–Ge samples by Raman and
X-ray diffraction studies
Both the as-grown and recovered samples after the high-
pressure experiments were examined by Raman spectroscopy
and X-ray diffraction. For the Raman studies we utilized a
LabRam spectrometer and a He–Ne laser (λ = 632.8
nm).107,108 A spectral resolution of the setup amounted to
about 0.5 cm−1. The structural examinations were carried out
using high-brilliance Rigaku diffractometers with λ = 0.5594
Å (Ag Kα X-ray source) and 0.7108 Å (Mo Kα X-ray source). For
one sample, namely, Si0.974Ge0.026, we performed in situ
Raman spectroscopic experiments under applied high
pressure to 40 GPa. These Raman studies were accomplished
both for pressurization and decompression runs and allowed
us to document the formation of metastable polymorphs
upon pressure release. For this work we employed a diamond
anvil cell of a piston-cylinder-type (BX90)109 equipped with a
rhenium gasket. A hole in the rhenium gasket, in which the
samples were placed, was filled with a neon pressure-
transmitting medium using a BGI's gas loading apparatus.110
The neon medium provided a high-quality quasi-
hydrostaticity around the sample up to the maximum
pressure of 40 GPa.111 The pressure values were determined
by the shift of the ruby luminescence line.
2.3. Characterization of the Si–Ge samples by electronic
transport studies
Measurements of the thermoelectric power (Seebeck
coefficient) and electrical resistance under applied high
pressure were carried out in two different anvil-type high-
pressure cells. One cell was of a toroidal type; its anvils had a
working diameter of ∼1 mm and were characterized by
5418 | CrystEngComm, 2020, 22, 5416–5435
CrystEngComm
semispherical cavities in the centre. This cell allowed
measurements of bulk ‘3D’ samples with typical sizes of
about 150 × 150 × 150 μm3 under high pressure up to 9 GPa
(Fig. 2(a)).112 Another cell was of a modified Bridgman type,
and was equipped with sintered-diamond anvils having flat
working surfaces of 600 μm in diameter.113,114 In this cell we
could measure thin ‘2D’ samples with typical sizes of about
200 × 200 × 30 μm3 in the higher pressure range up to 20
GPa.112 The high-pressure cell with semispherical cavities in
the anvils provided a quasi-hydrostatic compression regime
for a sample.115,116 In another cell, which was equipped with
conventional flat anvils, the ratio of the sample thickness (30
μm) to the culet size of the anvils (600 μm) amounted to
about 0.05. This value is less than the threshold value of
0.055–0.057, which was found earlier to correspond to the
suppression of uniaxial pressure components in solid
media.117 In both cells a sample was loaded into a hole
drilled in the centre of a toroidal-shaped container made of
limestone mineral (predominantly CaCO3).114,118 This sample
container also served as a gasket and as a pressure-
transmitting medium. Limestone has a low yield strength
shear, and hence, it is a suitable material for pressure-
transmitting medium,119 which may be comparable with
NaCl powder.120 The main component of the limestone
(calcite) is known to undergo pressure-driven phase
Fig. 2 (a) A simplified scheme of the high-pressure cell with
semispherical cavities in the anvils that was used for the thermoelectric
measurements. 1 – Sample, 2 – sample container made of limestone, 3
– anvils, 4 – supporting plungers. The electrical probes show how the
thermoelectric voltage (ΔU) and the temperature difference (ΔT) were
measured. (b) Examples of the Seebeck coefficient determination from
linear slopes, as S = −ΔU/ΔT at fixed pressures for different Si–Ge
alloys. 1 – The metastable Ge-III-type phase of Si0.02Ge0.98 at about 0
GPa, 2 – Si0.974Ge0.026 at about 0 GPa after recovery from 2 GPa, 3 –
Si0.974Ge0.026 at about 10 GPa, 4 – Si0.13Ge0.87 at about 0 GPa, 5 –
Si0.07Ge0.93 at about 0 GPa.
This journal is © The Royal Society of Chemistry 2020
CrystEngComm
transitions at about 1.5–2 GPa, concurrent with notable
volumetric effects.121 This circumstance also contributed to
the improvement of quasi-hydrostaticity of the pressure
around a sample. Thus, both high-pressure cells equipped
with the limestone sample container could provide a quasi-
hydrostatic compression regime.
The high-pressure cells were loaded into an automated
mini-press setup, which smoothly generated a force applied
to a cell with assistance of electric motors, and automatically
recorded all relevant parameters.122 The measurements were
performed both for pressurization and decompression runs
for multiple pressure cycles. The values of the force applied
to a cell were automatically measured using a digital
dynamometer, and then, they were converted into pressure
values.112 Typical times of pressurization or decompression
cycles amounted to 15–20 minutes. Electrical resistance
values were measured by a quasi-four-probe method (two
bifurcated probes).72,123,124 For the thermoelectric power
measurements an upper anvil was electrically heated to
generate a temperature difference (ΔT) of several Kelvins
between the upper and lower sides of the sample (Fig. 2(a)
).125 This ΔT difference generated a thermoelectric voltage
(Fig. 2(b)), and it was measured using thermocouples
attached near the anvil tips (Fig. 2(a)).126
3. Results
The Raman spectra of the Si–Ge alloys are depicted in Fig. 3.
The main LO phonon mode of germanium in the Ge-
dominant samples only slightly softens with the Si content.
Fig. 3 Raman spectra of the Si–Ge alloys under ambient conditions.
The insets in (a and b) show the selected magnified parts of these
spectra. A photograph of the bulk Si0.974Ge0.026 single crystalline
sample is given in (b).
This journal is © The Royal Society of Chemistry 2020
Paper
For the maximal Si content of 13 at% the difference in the
wavenumbers with pure Ge amounted to only about 2 cm−1
(Fig. 3(a)). This observation was in line with previous Raman
studies on Si1−xGex.40,127–138 The other very weak peaks we
documented in the spectra of the Ge-dominant samples at
354, 385, and 403 cm−1 (Fig. 3(b)) are not observed in the
spectra of pure germanium, and hence, they could originate
from some Si–Ge-related vibrations. Previous Raman
examinations of Si–Ge alloys with intermediate compositions
also found a peak linked to Si–Ge vibrations about 400 cm−1
and noted its sensitivity to many factors, such as
composition, sample morphology and crystallinity.40,134–142
Compared to pure silicon, in the Si0.974Ge0.026 composition a
wavenumber of the strongest LO phonon softens a bit to 519
cm−1. Very weak and broad peaks in the spectra of
Si0.974Ge0.026 at 375 and 399 cm−1 (inset in Fig. 3(b)) have a
correspondence with the above weak peaks in the Ge-
dominant samples. The peaks at 301 and 430 cm−1 we
observed in Si0.974Ge0.026 were also reported for pure silicon,
and they were assigned in the literature to the transverse
acoustical phonon modes, 2TA(X) and 2TA(Σ),
respectively.79,137,139,143–147
We investigated the high-pressure behaviour of the
Seebeck coefficient of the Si–Ge alloys in two different high-
pressure cells. One cell could generate high pressures up to 9
GPa that corresponded to a stability region of the original
cubic-diamond phase (Si-I, Ge-I) (Fig. 4). The other cell could
generate high pressures somewhat above the semiconductor–
metal phase transition point about 9–13 GPa,76–96 and
allowed measurements of the Seebeck coefficient of both
metal phases with a β-Sn-type structure (Si-II, Ge-II) and the
metastable phases that appear upon pressure release
(Fig. 4).78,84,86,95,147–164 Below, we report the results of our
studies of the high-pressure behaviour of the thermoelectric
power and electrical resistance of the Ge-dominant Si–Ge
alloys (Fig. 5–8) and of Si0.974Ge0.026 (Fig. 9 and 10). We
supplement these results by high-pressure Raman
spectroscopic data for Si0.974Ge0.026 (Fig. 11 and 12) that
documented the phase transitions in pressurization and
decompression cycles.
3.1. Ge-Dominant Si–Ge alloys: high-pressure effect on the
thermoelectric power in the cubic-diamond phase
The pressure dependencies of the thermoelectric power of
the Ge-dominant Si–Ge samples for several pressure cycles
are shown in Fig. 5. Under normal conditions only pure Ge
was characterized by a negative Seebeck coefficient of −330
μV K−1 (Fig. 5(a)). This fact suggested a dominant n-type
electrical conductivity. The germanium substitution with Si
(Si0.02Ge0.98, Si0.07Ge0.93, and Si0.13Ge0.87 samples) led to the
stabilization of the p-type electrical conductivity under
normal conditions (Fig. 5(b and c)). This charge-carrier
inversion could result from the appearance of intrinsic point
defects in the cubic-diamond crystal structure of Ge.165,166 An
increase in the Si content led to a decrease in the Seebeck
CrystEngComm, 2020, 22, 5416–5435 | 5419
Paper CrystEngComm

Fig. 4 Selected crystal structures of silicon and germanium. (a) Under ambient conditions both silicon and germanium crystallize in the cubic-
diamond-type structure with the Fd3̄m space group, #227 (known as Si-I and Ge-I). (b) Under applied high pressure above 9–13 GPa this diamond-
type structure transforms into a metal β-Sn-type structure with the I41/amd space group, #141 (known as Si-II and Ge-II). (c) On decompression
the β-Sn-type structure of Ge usually transforms into a metastable st12 structure with the P43212 space group, #96 (known as Ge-III), which can
be quenched under ambient conditions. (d) On decompression the β-Sn-type structure of Si firstly transforms into a metastable r8 structure with
the R3̄ space group, #148 (known as Si-XII), and (e) then, on pressure release, transforms into a metastable bc8 structure with the Ia3̄ space group,
#206 (known as Si-III). Rarely, depending on stress conditions, after pressure release Ge can also adopt the same structure as Si-III (e) (known as
Ge-IV).

Fig. 5 Pressure dependencies of the thermoelectric power of the Ge-dominant Si–Ge alloys at 295 K under high-pressure cycling below the
semiconductor–metal phase transition point (about 10 GPa). (a) n-Type Ge. (b) Si0.02Ge0.98. (c) Si0.07Ge0.93. (d) Si0.13Ge0.87. The thin arrows indicate
the directions of pressure variation.

coefficient, from about +465 μV K−1 for x = 0.02 to about +200
μV K−1 for x = 0.13 (Fig. 5). At the initial compression of 1
GPa the sample of pure Ge irreversibly inverted the electrical
conductivity type, and on the successive pressure cycles it
behaved already as a p-type semiconductor (Fig. 5(a)). An n–p
inversion of the electrical conductivity type in pure Ge
samples was already documented in our previous work.73
This effect was attributed to a splitting of the ‘heavy’ and
‘light’ holes bands followed by a carrier transfer to the ‘light’
one, in which the holes are much more mobile.73 Thus, the
present results confirm these previous findings.
The entire pressure dependencies of the thermopower
plotted in Fig. 5 corresponded to the stability range of the
original cubic-diamond-type phase. All the samples
demonstrated the apparent kinks in the curves about 2–5
GPa for both pressurization and decompression cycles

5420 | CrystEngComm, 2020, 22, 5416–5435 This journal is © The Royal Society of Chemistry 2020
CrystEngComm
Fig. 6 Comparison of the pressure behaviour of the thermoelectric
power of the Ge-dominant Si–Ge alloys at 295 K from Fig. 5(a) for the
first pressurization cycle and (b) for the second pressurization and
decompression cycles. (a) Above 1 GPa all the samples demonstrate
rather similar dependencies of the Seebeck coefficients under
pressure. (b) All the curves exhibit a drop about 3–6 GPa marked by
the bulk arrow for Si0.02Ge0.98. The thin arrows indicate the directions
of pressure variation.
(Fig. 5). These features likely result from some reversible
reconstruction in their electronic band structures.
Remarkably, the samples with different Seebeck coefficients,
ranging from −330 μV K−1 to +465 μV K−1 at normal pressure,
demonstrated rather a similar pressure behaviour of the
thermopower above 1 GPa. For example, the thermopower
curves for n-type Ge and p-type Si0.07Ge0.93 almost coincided
above 1 GPa (Fig. 6(a)). These findings strongly suggested
that all the samples were characterized by an intrinsic
semiconductor conductivity, and the pressure behaviour of
their Seebeck coefficients was tightly linked to the Ge-like
band structures of these alloys.2,43–46 Thus, we can conclude
that the slightly compressed samples of pure and Si-
substituted germanium are always p-type conductors
irrespective of the conductivity type and crystallinity of the
original samples. A moderate compression above 5–6 GPa
strongly suppressed the thermoelectric power of these Ge-
dominant alloys (Fig. 6). Since the value of the indirect band
gap of germanium was found to widen insignificantly with
pressure,167–169 the suppression of the Seebeck coefficient
was likely caused by an enhancement of n-type contribution
that led to a nearly compensated electronic state (i.e., with
nearly equal partial conductivities of electrons and holes)
(Fig. 6). Starting from the second pressure cycle, the
pressure-driven changes in the thermopower curves of these
samples were reversible (Fig. 5). The bends in the
This journal is © The Royal Society of Chemistry 2020
Paper
thermopower curves about 2–5 GPa shifted a bit to higher
pressures with the cycle number likely because of a minor
deterioration of the samples (Fig. 5). After these high-
pressure-cycling experiments all the recovered samples were
characterized by nearly identical magnitudes of their Seebeck
coefficients of about +(170–200) μV K−1 (Fig. 5).
3.2. Ge-Dominant Si–Ge alloys: variation in the
thermoelectric power across the phase transitions under
pressure
The pressure dependencies of the thermoelectric power of
the p-type Ge-rich Si–Ge alloys measured across the phase
transition to the metal β-Sn structure (Ge-II) are shown in
Fig. 7. In the pressure range from 1 to 8 GPa these
thermopower curves for the first pressurization cycle were
quite similar to those measured in the toroidal high-pressure
cell are and shown in (Fig. 5(b–d)). On the first pressurization
cycle all the samples conserved the original p-type electrical
conductivity (Fig. 7). In the vicinity of the semiconductor–
metal phase transition about 9–13 GPa,76,77,83–92 the
thermopower curves exhibited a distinct turning point (insets
in Fig. 7(c) and (d)). Above the phase transition point in the
β-Sn-type structure the Seebeck coefficients of these samples
slightly increased with pressure.
Interestingly, on the first decompression cycle from the
metal β-Sn phase the thermopower curves for these samples
demonstrated very different dependencies. Thus, for pure
and slightly-substituted samples (Ge and Si0.02Ge0.98) we
observed an abrupt change in the Seebeck coefficients at 2–3
GPa to high negative values of about −(250–300) μV K−1
(Fig. 7(a) and (b)). This behaviour suggested the formation of
a phase with dominant n-type conductivity. The other two
samples, namely, Si0.07Ge0.93 and Si0.13Ge0.87, showed an
opposite tendency, and below 2 GPa their Seebeck
coefficients jumped to high positive values of about +(150 ÷
170) μV K−1 (Fig. 7(c) and (d)). On the re-pressurization cycles,
Ge and Si0.02Ge0.98 demonstrated a similar behaviour. Their
thermopower curves showed very smooth bends about 5 GPa
and an apparent phase transition to the metal β-Sn phase at
about 9 GPa, i.e., at nearly the same pressure as the
transition detected on the first cycle. Furthermore, this phase
transition was accompanied by a reversible n–p inversion
(Fig. 7(a) and (b)). In contrast, the Seebeck coefficient of the
Si0.07Ge0.93 sample showed a dependence on the cycle
number and demonstrated the alternating type of the
dominant electrical conductivity (Fig. 7(c)). In sample with
the highest Si content (Si0.13Ge0.87) the p-type conductivity
was conserved in the whole pressure range for all pressure
cycles. Note here that the above discussed pressure cycling
up to 8 GPa (Fig. 5), i.e., below the phase transition
point,76,77,83–92 did not result in such dramatic variations in
the Seebeck coefficients. Therefore, these changes should be
linked to the formation of the metastable phases on the
decompression pathway from the metal β-Sn
phase.84,85,92,150–156,162,163 Two metastable phases of
CrystEngComm, 2020, 22, 5416–5435 | 5421
Paper CrystEngComm

Fig. 7 Pressure dependencies of the thermoelectric power of the Ge-dominant Si–Ge alloys at 295 K across the phase transition to the metal
β-Sn-type structure (Ge-II) about 10 GPa for selected pressure cycles for (a) p-type Ge, (b) Si0.02Ge0.98, (c) Si0.07Ge0.93, and (d) Si0.13Ge0.87. The thin
arrows indicate the directions of pressure variation. After the first decompression cycle, the metastable Ge-III-type phase was formed. Hence, the
second and following pressure cycles should correspond to the Ge-III → Ge-II phase transition. The bulk arrows indicate anomalies, which should
be linked to the phase transitions. The insets in (c) and (d) show the magnified parts of the thermopower curves, which demonstrate these
anomalies more distinctly.

germanium, which can be formed after different high-
pressure treatments, were reported in the literature. One of
them has a tetragonal st12 structure (Ge-III) (Fig. 4(c)) and is
often formed after slow decompression runs.84,85,163,164 The
other metastable phase adopts a cubic bc8 structure (Ge-IV)
and may be quenched to ambient conditions during very fast
decompression cycles (less than 1 second).154
To clarify the origin of the thermopower variations
observed on the decompression cycles (Fig. 7) we examined
the samples recovered under ambient conditions after these
experiments (Fig. 8(a)) by Raman spectroscopy and X-ray
diffraction (Fig. 8(c) and (b), (d)). Because of a notch filter
the Raman spectra below 200 cm−1 were cut, and we could
detect only three peaks at 226, 242 and 270 cm−1 in all the
samples (Fig. 8(c)). We noted that with the Si content the
wavenumbers of these phonons slightly shifted to higher
frequencies. In the literature these phonon modes were
assigned to the metastable tetragonal st12 structure (Ge-
III).73,155,156,170–176 A certain broadening in these spectra may
be attributed to a minor disorder in the crystal structure
owing to the pressure cycling over the phase transition
region.177 In the X-ray diffraction studies this conjecture has
been confirmed for all the Ge dominant samples
(Fig. 8(b) and (d)). Although, a quality of these structural data
was rather limited we could perform a full-profile analysis of
these patterns and confirmed that they all can be fit well by
the P43212 tetragonal space group (#96) of the Ge-III phase.
An example of these fits for pure Ge is given in Fig. 8(d). For
pure Ge we found the unit cell parameters and the atomic
coordinates to be as follows: a = 5.933(7) Å, c = 6.966(0) Å, V =
245.26(7) Å3, Z = 12, Ge1(0.0934, 0.0934, 0), and Ge2(0.1696,
0.3439, 0.2579) (Fig. 4(c)). These structural data were similar
to those reported previously in the literature.158
The significant values of the Seebeck coefficients of about
−(250–300) μV K−1 in the metastable tetragonal st12 phase
(Ge-III) of Ge and Ge-rich samples (Fig. 7) pointed out their
semiconducting character. A band gap value in this Ge-III
phase may be comparable with a gap of 0.67 eV in the cubic-
diamond structure of Ge.73 This finding agreed well with a
recent experimental determination of an indirect band gap of
0.59 eV in the pure Ge-III phase164 as well as with an earlier
predicted band-gap value of ∼0.7 eV.152 Our thermopower
data indicated that a native defect structure in the Ge-III
phase of pure and slightly substituted samples corresponds
to the n-type electrical conductivity (Fig. 7(a) and (b)). The
higher silicon content strongly shifted the conductivity in the
Ge-III phase to p-type (Fig. 7(c) and (d)). For Si0.13Ge0.87 this
led to the stabilization of the p-type conductivity in all the
phases. For the intermediate composition, Si0.07Ge0.93, the
thermopower fluctuations on the decompression cycles
pointed out a strong competition between the n- and p-type
partial conductivities (Fig. 7(c)). Under high pressure this
metastable Ge-III phase should also transform into the
thermodynamically stable metal β-Sn-type phase, but the
transition pressure remains a point of issue. On the one
hand, the transition pressure can correspond to the region of

5422 | CrystEngComm, 2020, 22, 5416–5435 This journal is © The Royal Society of Chemistry 2020
CrystEngComm Paper

Fig. 8 The metastable Ge-III-type phase in the Ge-dominant Si–Ge alloys and its characterization at 295 K. (a) Photograph in transmitted light of a
limestone sample container (it is labelled as 2 in Fig. 2(a)) with one of the Si–Ge samples recovered from the high-pressure experiments. (b)
Example of an azimuth X-ray diffraction image in the full range of 0–360° for the Si0.07Ge0.93 sample. This corresponds to the 1D diffraction pattern
of this sample shown below in (d). (c) Raman spectra of the samples recovered from the high-pressure-cycling experiments to about 17 GPa
(Fig. 7). The dashes indicate the wavenumbers reported for the Ge-III phase in ref. 156. (d) X-ray diffraction patterns for the same samples as in (c).
The Ge-III-type crystal structure of the samples was confirmed by Rietveld refinement. For pure Ge a simulated pattern (thick solid line) together
with the calculated reflection positions (dashes) for this structure is given. The asterisks in the pattern for the Si0.13Ge0.87 sample point out peaks
related to the remains of the limestone container. (e) Pressure dependencies of the electrical resistance for the Si–Ge samples across the Ge-III →
Ge-II phase transition (marked by the bulk arrow on the sample of Ge). (f) Pressure dependencies of the thermoelectric power of the Si–Ge
samples across the Ge-III → Ge-II phase transition, from Fig. 7. The bulk arrows indicate the direct and return phase transitions. The thin arrows in
(e) and (f) indicate the directions of pressure variation.

the thermodynamic stability of the β-Sn phase, i.e., it may
be the same as in the cubic-diamond-type Ge.76,77,83–92 But
on the other hand, since this metastable phase is already
strongly ‘pre-compressed’ by about 10–12%, compared to
the cubic-diamond one,84,85,148,174 less applied pressure is
needed to increase the density of the materials to a
critical level to cause this transition. Our results
demonstrated that the Ge-III → Ge-II phase transition
occurs rather abruptly and its transition pressure tends to
decrease with the Si content (Fig. 8(e) and (f)). These
findings hint that even the metal phase of the Si–Ge
alloys could be stabilized in thin strained films. Thus, our
work showed that the thermoelectric power of the Si–Ge
alloys may be dramatically changed by using an applied
high pressure. These thermopower changes are linked not
only to the structural phase transitions but to different
electronic states, which may be varied by using an applied
pressure.
3.3. Si-Dominant Si–Ge alloys: high-pressure effect on the
thermoelectric power in the cubic-diamond phase
The silicon-rich Si1−xGex crystal (Si0.974Ge0.026) had a p-type
electrical conductivity and showed a high value of the Seebeck
coefficient above 1 mV K−1 (Fig. 9(a)). We carried out the
measurements using high-pressure cells equipped with
pressed electrical probes, and for this reason we could not
measure the thermopower without applied pressure, i.e.,
under ambient conditions. We observed that application of
even a minor pressure of less than 1 GPa can spectacularly
change the electronic transport properties of this crystal
(Fig. 9). An electrical conductivity of Si0.974Ge0.026 was strongly
enhanced to 1 GPa by about three orders of magnitude (the
inset in Fig. 9(a)), and the dominant conductivity type was
changed from p- to n- (Fig. 9). Pure silicon did not exhibit
such effects on the electrical resistance178 and the
thermopower.179 We found that the pressure-driven drop in

This journal is © The Royal Society of Chemistry 2020 CrystEngComm, 2020, 22, 5416–5435 | 5423
Paper CrystEngComm

Fig. 9 Pressure dependencies of the thermoelectric power for two samples (#1 and #2) of Si0.974Ge0.026 below the semiconductor–metal phase
transition point at 295 K. The thin arrows indicate the directions of pressure variation. The inset in (a) shows a pressure dependence of the
electrical resistance for sample #1 for two pressurization cycles. The insets in (b) show the pressure and time dependencies of the thermopower
for sample #2 on relaxation release from a pre-compression run to 0.75 GPa. On this decompression a return n–p sign inversion of the Seebeck
coefficient occurs about 0.55 GPa.

Fig. 10 The formation of the metastable Si-III phase in Si0.974Ge0.026 and its characterization at 295 K. (a) Pressure dependencies of the
thermoelectric power of sample #3 of Si0.974Ge0.026 across the phase transition to the metal β-Sn-type phase (Si-II) about 11–13 GPa for three
pressure cycles. The thin arrows indicate the directions of pressure variation. After the first decompression run Si0.974Ge0.026 transformed into the
metastable Si-III-type phase. The inset in (a) depicts a pressure dependence of the electrical resistance of this sample across the Si-III → Si-II phase
transition. (b) Magnified pressure dependencies of the thermoelectric power from (a), which demonstrate smooth bends in the region of the phase
transition to the metal β-Sn phase about 11 GPa. The decompression cycles exhibit a dip about 4 GPa and a minimum at ∼0.6 GPa (better shown
in the inset), which could be related to the phase transitions to the metastable phases Si-XII and Si-III, respectively. The second and third
pressurization cycles show a feature about 2 GPa that could be linked to the Si-XII → Si-III phase transition. (c) Raman spectrum of the metastable
Si-III phase of Si0.974Ge0.026 collected from the sample recovered from the high pressure experiments to 17 GPa (a and b). The wavenumbers are
given near the peaks. Data from the literature for Si-III phase, based on the studies by OJ156 and HS,155 are shown by dashes. (d) X-ray diffraction
pattern of the metastable Si-III phase of Si0.974Ge0.026 collected from the sample recovered from the high-pressure cycling experiments to about
17 GPa (a and b). The Si-III-type crystal structure was confirmed by Rietveld refinement; a simulated pattern is shown by a solid line, and the
calculated reflection positions are shown by dashes. The inset in (d) shows a quarter of a 2D X-ray diffraction image of this sample.

the electrical resistance value is reversible and reproducible Meanwhile, the p–n inversion at 0.5–1 GPa may be reversible
for the successive pressure cycles (inset in Fig. 9(a)). only if the maximal applied pressure does not exceed

5424 | CrystEngComm, 2020, 22, 5416–5435 This journal is © The Royal Society of Chemistry 2020
CrystEngComm Paper

Fig. 11 (a) Photographs of a central part of a high-pressure diamond anvil cell with the Si0.974Ge0.026 sample (marked by a bulk blue arrow) at
selected pressures on pressurization run. A ruby ball in the Centre was used for pressure determination. Above 16 GPa Si0.974Ge0.026 demonstrates
a metallic lustre consistent with the Si-I → Si-II phase transition.76–80,86–88,93–96,155–157 Raman spectra evolution for the Si0.974Ge0.026 crystal on (b)
pressurization and (c) decompression cycles indicated the semiconductor–metal phase transition between 13 and 16 GPa, and the transitions to
the metastable structures on pressure release. The asterisks mark the parasite peaks. The pressure values are given near the selected spectra. (b)
The inset shows the magnified parts of the Raman spectra in the metal phase. The spectra collected at 16 and 16.9 GPa correspond to the Si-II
phase, whereas the one at 18 GPa and above – to the Si-V phase, which has no Raman active modes.87 (c) The metastable phase Si-III was
quenched under ambient conditions. The wavenumbers in the spectrum of Si-III are given near the peaks. They were consistent with previous
studies.155,156

approximately 1 GPa. For instance, we compressed one
Si0.974Ge0.026 crystal to 0.75 GPa, and then slightly released the
force of the press. This led to relaxation changes in both the
pressure value in the high-pressure cell and the electronic
properties of the sample. Thus, for 40 minutes the pressure in
the cell gradually decreased to 0.45 GPa. This caused a return
n–p inversion about 0.55 GPa (insets in Fig. 9(b)). However, if
the applied pressure well exceeds 1 GPa (this approximately
corresponds to the negative extremum on the curves) the
original p-type conductivity can no longer be easily restored
upon decompression. The p–n inversion in Si0.974Ge0.026 is likely
linked to a modification of its native defect structure, and
hence, the return n–p inversion could be probably stimulated
by sample annealing. In one sample of Si0.974Ge0.026 cut from
the same crystal we observed even more spectacular effects
consisting of a triple p–n–p–n sign inversion upon compression
to 1.5 GPa (Fig. 9(a)). These anomalies were likely linked to
minor pressure gradients in the high-pressure cell that could
spontaneously appear in the solid pressure-transmitting
medium across the sample. A stronger compression of
Si0.974Ge0.026 crystals resulted in an electronic transition to a
compensated state that was characterized by nearly equivalent
partial conductivities of holes and electrons and close to zero
thermopower values (Fig. 9). This compensated state was rather
robust and preserved on pressure release. In this case, a
resulting value of the Seebeck coefficient was very small and
could be either positive or negative (Fig. 9). Generally, the effects
we found suggest that Si1−xGex crystals with a low Ge content
are highly promising for different piezoelectric and
optoelectronic technologies.
3.4. Si-Dominant Si–Ge alloys: variations in the
thermoelectric power across the phase transitions under
pressure
One sample of Si0.974Ge0.026 (#3) cut from the same bulk
single-crystalline ingot was subjected to pressure cycling up
to 17 GPa across the semiconductor–metal phase transition
(Fig. 10(a)). This sample #3 also exhibited a p–n inversion
after the start of the compression, but its thermopower
variations looked more smeared, compared to those observed
in samples #1 and #2 (Fig. 9). This difference can be
explained by the fact that the measurements of samples #1
and #2 were conducted in the toroidal high-pressure cell that
provided better quasi-hydrostaticity, compared to the higher-
pressure cell with flat anvils, which was utilized for the
measurements of sample #3. Similar to samples #1 and #2,
sample #3 also changed into a strongly compensated
electronic state above a few GPa (Fig. 10(a)). A gentle bend on
the thermopower curves for all pressurization cycles in the
vicinity of 11 GPa (Fig. 10(b)) can be attributed to the phase
transition to the metallic β-Sn phase (Si-
II).76–80,86–88,93–96,155–157 On the decompression cycles we
found a steeping dip on the curves about 4 GPa and a reverse
jump at 0.6 GPa (Fig. 10(b)). These features could be linked
to the formation of the metastable phases, namely, the
rhombohedral phase, r8 (Si-XII) and the body-centred cubic
phase, bc8 (Si-III) (Fig. 4), although, the higher transition
pressures for these phases were previously reported.88,158,159
Note here that the difference in the decompression pathways
for Si and Ge was explained in the literature by the fact that

This journal is © The Royal Society of Chemistry 2020 CrystEngComm, 2020, 22, 5416–5435 | 5425
Paper
Fig. 12 Pressure dependencies of the wavenumbers of the
Si0.974Ge0.026 crystal for pressurization and decompression cycles. (a)
The wavenumber of the main LO phonon exhibits a kink in its pressure
curve at 2 GPa. The inset shows the intensity variation of this LO
phonon peak under pressure. (b) The phonon at 430 cm−1, which is
shown in the inset and assigned to the 2TA(Σ) silicon mode, also
exhibits a kink at 2 GPa. It seems that this phonon peak probably splits
above 3 GPa. (c) Wavenumbers of the other phonon modes of Si-I, Si-
II, Si-III, and Si-XII phases. The inset illustrates the phase transition
between the metastable phases, Si-XII → Si-III on pressure release.
the kinetic barriers for the different phase transitions in Si
and Ge are not the same, and upon decompression from the
β-Sn phase each of these elements follows the kinetically
simplest pathway instead of a return transformation to the
more energetically-favourable cubic-diamond structure.162
To verify that sample #3 of Si0.974Ge0.026 recovered after
the pressure-cycling experiments up to 17 GPa
(Fig. 10(a) and (b)) indeed transformed into the metastable
Si-III-type phase we examined it by Raman spectroscopy and
X-ray diffraction (Fig. 10(c) and (d)). A Raman spectrum of
this sample looked nearly identical to those reported in the
literature for pure Si in the Si-III phase155–157,160,161,180–182
5426 | CrystEngComm, 2020, 22, 5416–5435
CrystEngComm
except the low-frequency region. In particular, we did not
observe a reported earlier peak at 182 cm−1 likely because of
a significant suppression of this region using a notch filter.
At the same time, we observed a new peak at 294 cm−1
(Fig. 10(c)), which was absent in the spectra of pure
Si.155–157,160,161,180–182 Note here that in the in-situ high-
pressure Raman spectroscopic studies of this sample that are
discussed below a similar peak was also observed (Fig. 11(c)).
The X-ray diffraction studies of this sample confirmed the
Ia3̄ space group (#206) and found the unit-cell parameters as
a = 6.623(4) Å, V = 290.56(3) Å3, and Z = 16 (Fig. 4(e)). These
results agreed well with the data of a recent high-quality
study on Si-III polymorphs.183
Thus, we can conclude that both the rhombohedral phase,
r8 (Si-XII), and the body-centred cubic phase, bc8 (Si-III), are
p-type conductors with a nearly semimetal conductivity
(Fig. 10(b)). A phase transition from these metastable phases
to the metallic β-Sn structure (Si-II) was not accompanied by
any dramatic changes in the transport properties, as seen
from the thermopower and the electrical resistance data
(inset in Fig. 10(a)). These findings are in line with the
thermopower data for pure Si.179 A previous study also
reported for the Si-III phase a p-type semimetal conductivity
with a hole concentration of 5 × 1020 cm−3.149 Following
investigations reported a semiconducting-like dependence of
the electrical resistivity at normal pressure for the Si-III
phase.183 More recent work discovered an ultra-narrow direct
band gap of 30 meV in this phase.184
3.5. Si-Dominant Si–Ge alloys: Raman spectroscopy under
high pressure
To examine the crystal structure stability of the Si–Ge
samples we carried out a Raman spectroscopic study on the
sample of Si0.974Ge0.026 (Fig. 11 and 12). We found that the
semiconductor–metal phase transition in Si0.974Ge0.026 occurs
between 13 and 16 GPa (Fig. 11(b)), i.e., at somewhat higher
pressures than in pure bulk Si.76–80,86–88,93–96,155–157 This
finding was in line with previous Raman studies of Ge-
substituted silicon.96 Tentatively, this increased transition
pressure can be explained by a minor lattice expansion due
to the incorporation of bigger Ge atoms (Fig. 1(b)).7,34,185–187
In visual examinations through a diamond window we
observed the appearance of a distinct metallic lustre in the
sample at a pressure of 16 GPa (Fig. 11(a)). In the metal
phase of Si0.974Ge0.026 we found a doublet at 385 and 405
cm−1 in a spectrum collected at 16 GPa and a single peak at
413 cm−1 in a spectrum collected at 16.9 GPa (inset in
Fig. 11(b)). At higher pressures up to 39 GPa no clear Raman
peaks were detected. These results generally agreed with
previous studies for Si.87 This work also reported the
appearance of a few phonon modes with similar
wavenumbers in the β-Sn-type phase of silicon (Si-II) and the
loss of the Raman spectra above 16 GPa.87
On a decompression cycle we observed the formation of
the metastable high-pressure phases (Fig. 11(c)). The Raman
This journal is © The Royal Society of Chemistry 2020
CrystEngComm
spectra of these phases were similar to those reported
previously,155–157,160,161,180–182 and should correspond to the
rhombohedral phase, r8 (Si-XII), and the body-centred cubic
phase, bc8 (Si-III), (Fig. 4(d) and (e)).78,159–161 The
discontinuities in the pressure evolution of some
wavenumbers of these spectra suggested a phase transition
between them about 3 GPa (the inset in Fig. 12(c)), in
agreement with previous studies for Si.155–159 A spectrum we
collected after the complete pressure release (Fig. 11(c)) was
nearly identical to the one we obtained in the sample
recovered from the electronic-transport studies up to 17 GPa
(Fig. 10(c)). This also agreed with the spectra of Si-III
polymorphs reported in the literature.155–157,160,161,180–182
These in situ Raman studies also detected a peak at 288 cm−1
(at normal pressure) and followed its pressure evolution on
the decompression cycle (Fig. 11(c)). Recall here that we
observed a similar peak at 294 cm−1 in the sample recovered
after the electronic-transport experiments up to 17 GPa
(Fig. 10(c)). Thus, the repeat observation of this peak at a bit
different wavenumber in another sample of Si0.974Ge0.026
suggested that this is an intrinsic feature, which could be a
local mode related to the presence of the Ge atoms in the Si-
III structure.
Pressure dependencies of the wavenumbers of
Si0.974Ge0.026 for pressurization and decompression cycles for
Si-I, Si-II, Si-XII, and Si-III phases are given in Fig. 12. The
main LO phonon of the cubic-diamond Si-I phase shifted to
higher frequencies with pressure (Fig. 12(a)). This behaviour
reflected a tightening of the chemical bond in Si-I upon
compression and generally agreed well with previous
studies.79,134,150,157,188 However, in contrast to previous
studies for pure Si we found a bend at 2 GPa in the
pressure dependence of this LO phonon in Si0.974Ge0.026
(Fig. 12(a)). This peculiarity had a correspondence with the
electronic transition to the compensated state we observed
in Si0.974Ge0.026 about 2 GPa (Fig. 9). Another peak at 430
cm−1, which was assigned to the 2TA(Σ) silicon mode,146
showed a similar behaviour with a kink at about 2 GPa
(Fig. 12(b)). Meanwhile, a peak at 300 cm−1, which was
assigned to the 2TA(X) silicon mode,146 demonstrated, in
contrast, a gradual softening with pressure (Fig. 12(c)).
Thus, our Raman studies of Si0.974Ge0.026 established a
correspondence between the changes in the electronic
transport properties (Fig. 9) on the one hand, and the
changes in the vibrational properties (Fig. 11 and 12), which
are linked to the local order, on the other hand.
4. Discussion
4.1. High-pressure effect on the thermopower of the Si–Ge
alloys
The thermoelectric power of intrinsic semiconductors with
two-band electrical conductivity depends directly on the band
gap value (Eg) and competition between partial conductivities
of electrons (σn) and holes (σp) as follows:189
This journal is © The Royal Society of Chemistry 2020
Paper
     
k σ n − σ p Eg 5 σn 5 σp 3 m*p
S¼ − × þ rn þ − rp þ − ln ;
jej σ n þ σ p 2kT 2 σn þ σp 2 σ n þ σ p 4 m*n
(1)
where e is the electron charge, k is Boltzmann's constant, T is
 
the temperature, rn(rp) and m*n m*p are the scattering
parameters and the effective masses of density of states of
electrons (holes), respectively.
It was established that the fundamental indirect band gap
of silicon moderately narrows with pressure,80,168,190 whereas
the fundamental gaps of Ge and Ge-dominant alloys, SixGe1−x
(x < 0.2), in contrast, insignificantly increase with pressure
in their cubic-diamond phases.168,169,191 The direct band gaps
of all the Si–Ge semiconductors were found to widen with
pressure.192–196 Thus, the dramatic pressure-driven changes
in the thermopower of the Si–Ge samples we observed (Fig. 5,
6, and 9) could not be explained by these pressure
dependencies of the band gaps. Hence, in accordance with
eqn (1), they should be linked to some intricate changes in
the electronic band structure parameters, which led to
variations in the ratio of the partial conductivities of
electrons and holes (σn/σp). Under normal conditions the
Seebeck coefficient of the Ge-dominant alloys was found to
decrease with the Si content (Fig. 5), whereas the
fundamental band gap should widen with the Si content
(Fig. 1(c)), thereby suggesting the opposite trend for the
thermopower (eqn (1)). Rough estimations for these Ge-
dominant alloys by using eqn (1) with the band-gap values
estimated from Fig. 1(c), k/|e| ≈ 86.4 μV K−1, and 2kT ≈ 50
meV (at 300 K), gave the partial conductivities ratios as σn/σp
= 0.56 for Si0.02Ge0.98 with S ≈ +330 μV K−1, σn/σp = 0.65 for
Si0.07Ge0.93 with S ≈ +272 μV K−1, and σn/σp = 0.77 for
Si0.13Ge0.87 with S ≈ +182.7 μV K−1 (Fig. 7). In the case of pure
germanium the n–p inversion under compression (Fig. 5(a))
was attributed to splitting of overlapping bands of “light”
and “heavy” holes on the top of the valence band followed by
a carrier transfer to the ‘light’ one, in which the holes are
much more mobile.73
Since the atomic radii of Si and Ge are notably different
(110 vs. 125 pm) (Fig. 1(a) and (b)), fabrication of their ideal
solid solutions seems to be not an easy task.197–200 In real Si–
Ge materials, even in single crystals, a distribution of Si and
Ge atoms may not be truly uniform, and a slight tendency to
Si/Ge segregation can occur. For example, synchrotron
topographic studies of bulk Si–Ge crystals with a low Ge
content (1.4–2.6 at%) observed weak but numerous Ge
striations and showed that high-temperature annealing can
make these crystals more uniform.37,199 Minor negative
deviations of the lattice parameter a of the Si–Ge alloys with
cubic-diamond structures from the linear Vegard's law were
noted both in epitaxial films201 and in single crystals.37 These
findings together with others suggest the presence of local
strains in Si–Ge materials, which are linked to variations in
both bond lengths and bond angles between Si(Ge) atoms.202
These strains can affect the properties of the Si–Ge alloys.
CrystEngComm, 2020, 22, 5416–5435 | 5427
Paper
For example, as found in Raman spectroscopic studies, the
phonon modes of the Si–Ge alloys with nominally the same
chemical compositions can have different wavenumbers
because of the contribution of these spontaneous local
strains.203,204
Thus, for the Si–Ge alloys with intrinsic semiconductor
conductivity and low values of carrier concentrations, the
pressure-driven changes in their electronic transport
properties should depend not only on variations in their
electronic band structures but also on modifications in their
native defect structures. For example, the abrupt pressure-
induced p–n inversion in the conductivity type of the
Si0.974Ge0.026 crystals (Fig. 9) should be linked to the applied-
pressure effect on the defect complexes. Germanium atoms
are larger than the silicon ones (Fig. 1(a) and (b)), and they
could be effective traps for vacancies.102,205–208 The enthalpy
of electron ionization in such Ge-vacancy-related complexes
in Si rich Si1–xGex crystals was established to increase strongly
with the increase in the average Si–Si distance in the cubic-
diamond crystal structure.102,205 From this result it follows
that under applied pressure that leads to contraction in the
average Si–Si distance, the enthalpy of electron ionization is
expected to reduce progressively, and hence, n-type partial
conductivity can be enhanced. The pressure dependencies of
the Seebeck coefficient of the Si0.974Ge0.026 crystals up to
about 1 GPa (Fig. 9) were in line with this conjecture. In
addition, the thermopower curves demonstrated that above
some threshold pressure of about 1 GPa this p–n switching
becomes irreversible, which can be interpreted as an
irreversible modification of the defect structure under the
applied pressure. The thermopower data also disclosed the
existence of the second threshold pressure of about 2–4 GPa,
which corresponded to a gradual and irreversible transition of
Si0.974Ge0.026 crystals to the strongly compensated electronic
state (i.e., with σn ≈ σp) (Fig. 9). Likely, this transition was
caused by another irreversible modification of the defect
structure, for example, by filling the vacancies and
subsequent annihilation of their-related complexes. Note that
because of the very low semiconductor-like concentrations of
these defects their detailed characterization by other methods
like transmission electron microscopy is hardly possible.
The stabilization of the p-type conductivity in the Ge-
dominant Si–Ge samples (Fig. 5) may also be linked to the
occurrence of intrinsic point defects.165,166 It was found that
the formation of significant number of holes is inevitable for
the SiGe layer with high Ge concentration, even if dopants
are carefully excluded.165 For a set of Si1–xGex (0.19 < x <
0.77) films grown by molecular beam epitaxy it was
demonstrated that the p-type conductivity is associated with
acceptor-like states that result from intrinsic point
defects.165,166 GeSi/Si heterostructure research found that the
main source of holes in SiGe layers is clusters of intrinsic
point defects, which are formed due to interaction of
dislocations, but not individual dislocations.209 Likely, the
applied high pressure can also modify the defect structure of
the Ge-dominant Si–Ge samples and somehow affect these
5428 | CrystEngComm, 2020, 22, 5416–5435
CrystEngComm
acceptor-like levels. However, as seen from their
thermopower data for the cubic-diamond phase (Fig. 5 and
6), these acceptor-like levels were very robust, and the
samples conserved the p-type conductivity despite the
apparent irreversible changes in their electronic properties
resulting from the defect structure modification. As also seen
from these thermopower data (Fig. 5 and 6), the irreversible
changes occurred only on the first pressure cycle, and from
the second cycle the pressure-induced variations were
reversible. The irreversible changes in the electronic
properties of the samples after their quenching from high
pressure to ambient conditions could be, to some extent,
linked to residual strains.
4.2. Potential innovative applications of the Si–Ge alloys
The highly spectacular pressure-driven variations in the
Seebeck coefficients in the Si–Ge alloys we revealed in this
work (Fig. 5–10) hint that these and associated effects can
have industrial potential. In practical applications, the
applied-pressure effect can be simulated by various methods,
which are easier to implement. They include, for example,
thin epitaxial films deposited on appropriate substrates, in
which high internal strains corresponding to pressures of up
to 20 GPa can be created,210,211 and nanoindentation with a
hard tip, which can generate high stresses in microscopic
areas at the sample surface.212,213 Stress-controlled switches
are already utilized in a number of technological processes
and electronic devices. For example, on the basis of the
nanoindentation technique a new concept of data recording
was offered and a novel memory device was developed by
IBM company.214,215 It was demonstrated on a sample of
silicon that by using the nanoindentation method one can
“write” electrically-conductive areas (metastable Si-III phase)
on the surface of semiconducting silicon,212 as well as can
stabilize another metastable phase, r8 (Si-XII).216 These
metastable phases can persist under ambient conditions as
long as they are not annealed.217,218 Note here that such ‘pre-
compressed’ metastable phases can be prepared also either
by high-pressure torsion,219,220 or by other techniques even
not using high pressure, e.g., by colloidal synthesis.221
Apparently, the pressure-induced changes in the Seebeck
coefficient of the Si–Ge alloys are of potential interest for
thermoelectric applications of these materials.10–21 However,
it is more interesting that the effects we discovered suggest
that these inexpensive and environment-friendly materials
have potential for the use in nanoelectronic devices as
‘smart’ elements whose optoelectronic properties can be
controlled or switched by applied stress. In Fig. 13 we
present several simple stress-related applications of the Si–
Ge alloys, which can be surmised from the thermopower
data. High stresses on the surface of these alloys can be
generated, for example, by electronically-controlled hard tips
(Fig. 13(a)). This technique can be used to ‘write’ zones or
electrical circuits with different types of electrical
conductivities on the surfaces of the Si–Ge alloys. These
This journal is © The Royal Society of Chemistry 2020
CrystEngComm Paper

Fig. 13 Potential innovative applications of Si–Ge alloys. (a) Schematic side view of hard tip for surface indentation. (b) Top view of hypothetical
the Si–Ge substrate, in which, the electrical conductivity types may be inverted by an appropriate applied stress, as displayed in detail in (c)–(e).
This example illustrates “writing” the zones or circuits of different electrical conductivities. (c–e) Depth profiles of zones whose electrical
conductivity was modified by applied stress. (c) An applied stress above 3 GPa can irreversibly turn the conductivity of n-type Ge to p-type
(Fig. 5(a)), thereby creating a p–n junction. An applied stress higher than 14 GPa can fabricate the metastable st12 polymorph (Ge-III) after stress
release (Fig. 7(a) and (b)). This will form also an underlying p-type layer of Ge-I because of the stress distribution under the hard tip, thereby
creating a n–p–n layered structure. (d) In p-type Ge slightly substituted with Si (p-SixGe1−x) one can form similar layers of the metastable st12
polymorph (Ge-III) by an applied stress above 14 GPa, but the electrical conductivity in these layers can have both n- and p-types, depending on
the Si content (Fig. 7). (e) Applied stresses of 1–2 GPa can switch the conductivity of p-type Si slightly substituted with Ge (p-Si1−xGex) to n-type;
for stresses less than 1 GPa this p–n inversion is reversible, but for stresses above 1.5 GPa it becomes irreversible (Fig. 9(b)). Applied stresses of 2–4
GPa can change p-Si1−xGex into a strongly compensated state with nearly equal partial conductivities of holes and electrons (shown as n ≈ p)
(Fig. 9(a)). Higher applied stresses exceeding 14 GPa allow the formation of the metastable Si-III polymorph with p-type conductivity after stress
release (Fig. 10). This treatment will also result in the formation of two intermediate layers with the compensated (p ≈ n) and n-type conductivity
between the p-Si-III layer and p-Si1−xGex substrate.

‘written’ zones look rather simple from the top (Fig. 13(b)),
but, in fact, because of the stress distribution under the
applied hard tip the depth profiles of these zones may be
intricate. For example, we found that pure Ge with n-type
intrinsic electrical conductivity irreversibly changes into a
p-type semiconductor under applied pressure above 3 GPa
(Fig. 5(a) and 13(c)). Higher stresses somewhat above the
semiconductor–metal phase transition point76,77,83–92 can
stabilize the metastable st12 phase (Ge-III) with the n-type
conductivity after stress release (Fig. 7(a) and 13(c)). This
treatment should also lead to the formation of an
intermediate p-type layer with the original cubic-diamond
structure because of the stress distribution in the sample
(Fig. 13(c)). In germanium crystals with a moderate Si
content the p-type conductivity became dominant in the
original phase, and for the Si content somewhat exceeding
7 at.% the p-type conductivity was conserved in the
metastable st12 phase too (Ge-III) (Fig. 7(d)). For the lower
Si content this metastable phase had an n-type conductivity
as in pure Ge (Fig. 7(b) and (c) and 13(d)).
The thermopower data for the p-type Si1−xGex crystals with
a low Ge content disclosed more options for the electrical
conductivity variation depending on the applied stress value
(Fig. 9 and 10). For example, a minor applied stress of about
1–2 GPa inverted the conductivity to n-type, whereas higher
applied stresses irreversibly changed Si0.974Ge0.026 into the
strongly compensated state (i.e., with nearly equal p- and
n-type partial conductivities) (Fig. 9(a) and 13(e)). Much
higher applied stresses above the semiconductor–metal
phase transition point76–80,86–88,93–96,155–157 resulted in the
formation of the metastable bc8 phase (Si-III) with a p-type
conductivity after stress release (Fig. 10(b)). However, two
intermediate layers, one with the compensated and the other
with the n-type conductivity, should be formed here also
because of the stress distribution (Fig. 9 and 13(e)). The
above cases are only the simplest options on how to
implement the high-pressure effects in Si1−xGex alloys
revealed in our work. In real applications, this approach may
be extended to fabricate much more intricate cascades of
diodes, transistors, and entire integrated circuits.

This journal is © The Royal Society of Chemistry 2020 CrystEngComm, 2020, 22, 5416–5435 | 5429
Paper
Conclusions
We synthesized several Si- and Ge-dominant Si–Ge crystals
(Si0.974Ge0.026, Si0.02Ge0.98, Si0.07Ge0.93, Si0.13Ge0.87, and Ge)
and investigated the applied high-pressure effect on their
thermoelectric and electrical properties in the pressure range
up to 17 GPa at room temperature under multiple pressure
cycling. In addition, the crystal structure of the samples was
examined by Raman spectroscopy and X-ray diffraction. We
found that the thermoelectric power value of these Si–Ge
samples in their original cubic-diamond-type phases can be
crucially changed by the applied pressure. In some cases even
the sign inversion of the Seebeck coefficient occurred under
the applied pressure. Across the phase transitions on
pressurization and decompression cycles the thermoelectric
power of the Si–Ge crystals was significantly varied too. We
found that after high-pressure cycling the Si-dominant
samples transformed into a cubic bc8 phase (Si-III) with a
p-type electrical conductivity, whereas the Ge-dominant alloys
changed into a tetragonal st12 phase (Ge-III) whose
conductivity type depended on the Si content. Thus, our work
demonstrated how one can control the thermopower of Si–Ge
alloys. The unusual pressure behaviour of the Seebeck
coefficient of Si–Ge crystals we disclosed points out that they
may be promising for diverse industrial applications, in
which the optoelectronic properties of elements are
controlled or switched by tuning the applied stress.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This research was carried out within the state assignment of
the Ministry of Science and Higher Education of the Russian
Federation (theme “Electron” No. AAAA-A18-118020190098-5).
The authors thank Dr. A. V. Kurnosov (BGI) for gas loading of
the high-pressure cell, and Prof. L. Dubrovinsky (BGI) for
providing the high-pressure cell for the Raman spectroscopic
experiments. S. V. O. acknowledges funding from the
Deutsche Forschungsgemeinschaft (DFG, German Research
Foundation) - Grant No. OV-110/3-1.
Notes and references
1 T. Wood, M. Naffouti, J. Berthelot, T. David, J.-B. Claude, L.
Métayer, A. Delobbe, L. Favre, A. Ronda, I. Berbezier, N.
Bonod and M. Abbarchi, ACS Photonics, 2017, 4, 873–883.
2 S. Sant, S. Lodha, U. Ganguly, S. Mahapatra, F. O. Heinz, L.
Smith, V. Moroz and S. Ganguly, J. Appl. Phys., 2013, 113,
033708.
3 S. Pouch, M. Amato, M. Bertocchi, S. Ossicini, N. Chevalier,
T. Mélin, J.-M. Hartmann, O. Renault, V. Delaye, D. Mariolle
and Ł. Borowik, J. Phys. Chem. C, 2015, 119, 26776–26782.
4 H. I. T. Hauge, S. Conesa-Boj, M. A. Verheijen, S. Koelling
and E. P. A. M. Bakkers, Nano Lett., 2017, 17, 85–90.
5430 | CrystEngComm, 2020, 22, 5416–5435
CrystEngComm
5 D. M. Zhigunov, A. B. Evlyukhin, A. S. Shalin, U. Zywietz
and B. N. Chichkov, ACS Photonics, 2018, 5, 977–983.
6 P. R. Abel, A. M. Chockla, Y.-M. Lin, V. C. Holmberg, J. T.
Harris, B. A. Korgel, A. Heller and C. B. Mullins, ACS Nano,
2013, 7, 2249–2257.
7 D. Duveau, B. Fraisse, F. Cunin and L. Monconduit, Chem.
Mater., 2015, 27, 3226–3233.
8 Y. Yang, S. Liu, X. Bian, J. Feng, Y. An and C. Yuan, ACS
Nano, 2018, 12, 2900–2908.
9 H. Kim, Y. Son, C. Park, M.-J. Lee, M. Hong, J. Kim, M.
Lee, J. Cho and H. C. Choi, Nano Lett., 2015, 15,
4135–4142.
10 J. P. Dismukes, L. Ekstrom, E. F. Steigmeier, I. Kudman and
D. S. Beers, J. Appl. Phys., 1964, 35, 2899–2907.
11 O. Yamashita and N. Sadatomi, J. Appl. Phys., 2000, 88,
245–251.
12 G. Joshi, H. Lee, Y. Lan, X. Wang, G. Zhu, D. Wang, R. W.
Gould, D. C. Cuff, M. Y. Tang, M. S. Dresselhaus, G. Chen
and Z. Ren, Nano Lett., 2008, 8, 4670–4674.
13 X. W. Wang, H. Lee, Y. C. Lan, G. H. Zhu, G. Joshi, D. Z.
Wang, J. Yang, A. J. Muto, M. Y. Tang, J. Klatsky, S. Song,
M. S. Dresselhaus, G. Chen and Z. F. Ren, Appl. Phys. Lett.,
2008, 93, 193121.
14 C. Bera, M. Soulier, C. Navone, G. Roux, J. Simon, S. Volz
and N. Mingo, J. Appl. Phys., 2010, 108, 124306.
15 B. Yu, M. Zebarjadi, H. Wang, K. Lukas, H. Wang, D. Wang,
C. Opeil, M. Dresselhaus, G. Chen and Z. Ren, Nano Lett.,
2012, 12, 2077–2082.
16 E. K. Lee, L. Yin, Y. Lee, J. W. Lee, S. J. Lee, J. Lee, S. N.
Cha, D. Whang, G. S. Hwang, K. Hippalgaonkar, A.
Majumdar, C. Yu, B. L. Choi, J. M. Kim and K. Kim, Nano
Lett., 2012, 12, 2918–2923.
17 E. M. J. Hedegaard, S. Johnsen, L. Bjerg, K. A. Borup and
B. B. Iversen, Chem. Mater., 2014, 26, 4992–4997.
18 Y. Lee, A. J. Pak and G. S. Hwang, Phys. Chem. Chem. Phys.,
2016, 18, 19544–19548.
19 R. Murugasami, P. Vivekanandhan, S. Kumaran, R. Suresh
Kumar and T. John Tharakan, Scr. Mater., 2018, 143, 35–39.
20 K. Delime-Codrin, M. Omprakash, S. Ghodke, R. Sobota, M.
Adachi, M. Kiyama, T. Matsuura, Y. Yamamoto, M. Matsunami
and T. Takeuchi, Appl. Phys. Express, 2019, 12, 045507.
21 S. Ahmad, A. Singh, R. Basu, S. Vitta, K. P. Muthe, S. C.
Gadkari and S. K. Gupta, J. Electron. Mater., 2019, 48,
649–655.
22 D. Y. Kim, S. Stefanoski, O. O. Kurakevych and T. A. Strobel,
Nat. Mater., 2015, 14, 169–173.
23 L. Rapp, B. Haberl, C. J. Pickard, J. E. Bradby, E. G. Gamaly,
J. S. Williams and A. V. Rode, Nat. Commun., 2015, 6, 7555.
24 K. Luo, Z. Zhao, M. Ma, S. Zhang, X. Yuan, G. Gao, X.-F.
Zhou, J. He, D. Yu, Z. Liu, B. Xu and Y. Tian, Chem. Mater.,
2016, 28, 6441–6445.
25 E. M. T. Fadaly, A. Dijkstra, J. R. Suckert, D. Ziss, M. A. J. van
Tilburg, C. Mao, Y. Ren, V. T. van Lange, K. Korzun, S.
Kölling, M. A. Verheijen, D. Busse, C. Rödl, J. Furthmüller, F.
Bechstedt, J. Stangl, J. J. Finley, S. Botti, J. E. M. Haverkort
and E. P. A. M. Bakkers, Nature, 2020, 580, 205–209.
This journal is © The Royal Society of Chemistry 2020
CrystEngComm
26 Y. Guo, Q. Wang, Y. Kawazoe and P. Jena, Sci. Rep., 2015, 5,
14342.
27 Q. Fan, C. Chai, Q. Wei and Y. Yang, Phys. Chem. Chem.
Phys., 2016, 18, 12905–12913.
28 M. Hu, Z. Wang, Y. Xu, J. Liang, J. Li and X. Zhu, Phys.
Chem. Chem. Phys., 2018, 20, 26091–26097.
29 B. Haberl, T. A. Strobel and J. E. Bradby, Appl. Phys. Rev.,
2016, 3, 040808.
30 M. Amsler, S. Botti, M. A. L. Marques, T. J. Lenosky and S.
Goedecker, Phys. Rev. B: Condens. Matter Mater. Phys.,
2015, 92, 014101.
31 B. E. Smith, X. Zhou, P. B. Roder, E. H. Abramson and P. J.
Pauzauskie, J. Appl. Phys., 2016, 119, 185902.
32 Z. Ma, X. Liu, X. Yu, C. Shi and F. Yan, Materials, 2017, 10,
599.
33 Q. Fan, H. Wang, W. Zhang, M. Wei, Y. Song, W. Zhang and
S. Yun, Curr. Appl. Phys., 2019, 19, 1325–1333.
34 J. P. Dismukes, L. Ekstrom and R. J. Paff, J. Phys. Chem.,
1964, 68, 3021–3027.
35 G. Queisser, W. A. Grosshans and W. B. Holzapfel, EPL,
1987, 3, 1109–1112.
36 A. Werner, J. A. Sanjurjo and M. Cardona, Solid State
Commun., 1982, 44, 155–158.
37 A. Misiuk, N. V. Abrosimov, P. Romanowski, J. Bak-Misiuk,
A. Wnuk, B. Surma, W. Wierzchowski, K. Wieteska, W.
Graeff and M. Prujszczyk, Mater. Sci. Eng., B, 2008, 154–155,
137–140.
38 R. W. Olesinski and G. J. Abbaschian, Bull. Alloy Phase
Diagrams, 1984, 5, 283–285.
39 M. H. F. Sluiter and Y. Kawazoe, Mater. Trans., 2001, 42,
2201–2205.
40 T. Maeda, H. Hattori, W. H. Chang, Y. Arai and K.
Kinoshita, Appl. Phys. Lett., 2015, 107, 152104.
41 S. R. Mehrotra, A. Paul and G. Klimeck, Appl. Phys. Lett.,
2011, 98, 173503.
42 A. Levitas, Phys. Rev., 1955, 99, 1810–1814.
43 R. Braunstein, A. R. Moore and F. Herman, Phys. Rev.,
1958, 109, 695–710.
44 E. R. Johnson and S. M. Christian, Phys. Rev., 1954, 95,
560–561.
45 A. Levitas, C. C. Wang and B. H. Alexander, Phys. Rev.,
1954, 95, 846–846.
46 J. Weber and M. I. Alonso, Phys. Rev. B: Condens. Matter
Mater. Phys., 1989, 40, 5683–5693.
47 F. Herman, Phys. Rev., 1954, 95, 847–848.
48 T. Honda, M. Suezawa and K. Sumino, Jpn. J. Appl. Phys.,
1996, 35, 5980–5985.
49 X. Guo, Z. Tian, T. Gao, Q. Xie, Y. Liang, Y. Mo and Y.
Wanjun, Phys. Chem. Chem. Phys., 2017, 19, 4695–4700.
50 V. Saltas, A. Chroneos and F. Vallianatos, Sci. Rep., 2017, 7,
1374.
51 S.-R. G. Christopoulos, N. Kuganathan and A. Chroneos,
Sci. Rep., 2019, 9, 10849.
52 V. G. Deibuk, S. I. Shakhovtsova, V. A. Shenderovski and
V. M. Tsmots, Semicond. Phys., Quantum Electron.
Optoelectron., 2002, 5, 5–8.
This journal is © The Royal Society of Chemistry 2020
Paper
53 J. Schilz and V. N. Romanenko, J. Mater. Sci.: Mater.
Electron., 1995, 6, 265–279.
54 D. Yang, Phys. Status Solidi A, 2005, 202, 931–938.
55 D. R. Yang and J. Chen, Defect Diffus. Forum, 2005, 242–244,
169–184.
56 D. Yang, X. Yu, X. Ma, J. Xu, L. Li and D. Que, J. Cryst.
Growth, 2002, 243, 371–374.
57 A. Misiuk, D. Yang, B. Surma, C. A. Londos, J. Bak-Misiuk
and A. Andrianakis, Mater. Sci. Semicond. Process., 2006, 9,
82–87.
58 W. Jung, A. Misiuk and D. Yang, Nucl. Instrum. Methods
Phys. Res., 2006, 253, 214–216.
59 S.-L. Sihto, J. Slotte, J. Lento, K. Saarinen, E. V. Monakhov,
A. Y. Kuznetsov and B. G. Svensson, Phys. Rev. B: Condens.
Matter Mater. Phys., 2003, 68, 115307.
60 A. Chroneos, H. Bracht, C. Jiang, B. P. Uberuaga and R. W.
Grimes, Phys. Rev. B: Condens. Matter Mater. Phys., 2008, 78,
195201.
61 P. Venezuela, G. M. Dalpian, A. J. R. da Silva and A. Fazzio,
Phys. Rev. B: Condens. Matter Mater. Phys., 2002, 65, 193306.
62 S. N. Guin and K. Biswas, Phys. Chem. Chem. Phys.,
2015, 17, 10316–10325.
63 T. Nilges, S. Lange, M. Bawohl, J. M. Deckwart, M. Janssen,
H.-D. Wiemhöfer, R. Decourt, B. Chevalier, J. Vannahme, H.
Eckert and R. Weihrich, Nat. Mater., 2009, 8, 101–108.
64 C. Xiao, X. Qin, J. Zhang, R. An, J. Xu, K. Li, B. Cao, J. Yang,
B. Ye and Y. Xie, J. Am. Chem. Soc., 2012, 134, 18460–18466.
65 S. N. Guin, J. Pan, A. Bhowmik, D. Sanyal, U. V. Waghmare
and K. Biswas, J. Am. Chem. Soc., 2014, 136, 12712–12720.
66 O. Osters, M. Bawohl, J.-L. Bobet, B. Chevalier, R. Decourt
and T. Nilges, Solid State Sci., 2011, 13, 944–947.
67 P. Roy and T. Maiti, J. Phys. D: Appl. Phys., 2018, 51, 065104.
68 A. E. Karkin, V. I. Voronin, N. V. Morozova, S. V.
Ovsyannikov, K. Takarabe, Y. Mori, S. Nakamura and V. V.
Shchennikov, J. Phys. Chem. C, 2016, 120, 9692–9701.
69 N. V. Morozova, I. V. Korobeinikov and S. V. Ovsyannikov,
J. Appl. Phys., 2019, 125, 220901.
70 V. V. Shchennikov, N. P. Gavaleshko and F. M. Frasunyak,
Phys. Solid State, 1995, 37, 1943–1944.
71 S. V. Ovsyannikov, I. V. Korobeinikov, N. V. Morozova, A.
Misiuk, N. V. Abrosimov and V. V. Shchennikov, Appl. Phys.
Lett., 2012, 101, 062107.
72 S. V. Ovsyannikov, A. E. Karkin, N. V. Morozova, V. V.
Shchennikov, E. Bykova, A. M. Abakumov, A. A. Tsirlin,
K. V. Glazyrin and L. Dubrovinsky, Adv. Mater., 2014, 26,
8185–8191.
73 I. V. Korobeinikov, N. V. Morozova, V. V. Shchennikov and
S. V. Ovsyannikov, Sci. Rep., 2017, 7, 44220.
74 N. V. Morozova, I. V. Korobeinikov, K. V. Kurochka, A. N.
Titov and S. V. Ovsyannikov, J. Phys. Chem. C, 2018, 122,
14362–14372.
75 T. Wen, Y. Wang, N. Li, Q. Zhang, Y. Zhao, W. Yang, Y. Zhao
and H.-K. Mao, J. Am. Chem. Soc., 2019, 141, 505–510.
76 S. Minomura and H. G. Drickamer, J. Phys. Chem. Solids,
1962, 23, 451–456.
77 J. C. Jamieson, Science, 1963, 139, 762–764.
CrystEngComm, 2020, 22, 5416–5435 | 5431
Paper
78 R. H. Wentorf and J. S. Kasper, Science, 1963, 139, 338–339.
79 B. A. Weinstein and G. J. Piermarini, Phys. Rev. B: Solid
State, 1975, 12, 1172–1186.
80 B. Welber, C. K. Kim, M. Cardona and S. Rodriguez, Solid
State Commun., 1975, 17, 1021–1024.
81 D. Olego and M. Cardona, Phys. Rev. B: Condens. Matter
Mater. Phys., 1982, 25, 1151–1160.
82 T. Soma, H. Iwanami and H. Matsuo, Solid State Commun.,
1982, 42, 469–471.
83 M. Baublitz and A. L. Ruoff, J. Appl. Phys., 1982, 53,
5669–5671.
84 S. B. Qadri, E. F. Skelton and A. W. Webb, J. Appl. Phys.,
1983, 54, 3609–3611.
85 C. S. Menoni, J. Z. Hu and I. L. Spain, Phys. Rev. B: Condens.
Matter Mater. Phys., 1986, 34, 362–368.
86 H. Olijnyk, S. K. Sikka and W. B. Holzapfel, Phys. Lett. A,
1984, 103, 137–140.
87 H. Olijnyk, Phys. Rev. Lett., 1992, 68, 2232–2234.
88 A. Mujica, A. Rubio, A. Muñoz and R. J. Needs, Rev. Mod.
Phys., 2003, 75, 863–912.
89 A. Di Cicco, A. C. Frasini, M. Minicucci, E. Principi, J.-P. Itiè
and P. Munsch, Phys. Status Solidi B, 2003, 240, 19–28.
90 A. Di Cicco, E. Principi, M. Minicucci, S. De Panfilis, A.
Filipponi, F. Decremps, F. Datchi, J.-P. Itié, P. Munsch and
A. Polian, High Pressure Res., 2004, 24, 93–99.
91 E. Principi, A. Di Cicco, F. Decremps, A. Polian, S. De
Panfilis and A. Filipponi, Phys. Rev. B: Condens. Matter
Mater. Phys., 2004, 69, 201201.
92 F. Coppari, J. C. Chervin, A. Congeduti, M. Lazzeri, A.
Polian, E. Principi and A. Di Cicco, Phys. Rev. B: Condens.
Matter Mater. Phys., 2009, 80, 115213.
93 J. Z. Hu, L. D. Merkle, C. S. Menoni and I. L. Spain, Phys.
Rev. B: Condens. Matter Mater. Phys., 1986, 34, 4679–4684.
94 G. A. Voronin, C. Pantea, T. W. Zerda, L. Wang and Y. Zhao,
Phys. Rev. B: Condens. Matter Mater. Phys., 2003, 68, 020102.
95 H. Katzke, U. Bismayer and P. Tolédano, Phys. Rev. B:
Condens. Matter Mater. Phys., 2006, 73, 134105.
96 J. J. Guo, D. Pan, X. Q. Yan, T. Fujita and M. W. Chen, Appl.
Phys. Lett., 2010, 96, 251910.
97 S. Anzellini, M. T. Wharmby, F. Miozzi, A. Kleppe, D.
Daisenberger and H. Wilhelm, Sci. Rep., 2019, 9, 15537.
98 F. Coppari, A. Polian, N. Menguy, A. Trapananti, A.
Congeduti, M. Newville, V. B. Prakapenka, Y. Choi, E.
Principi and A. Di Cicco, Phys. Rev. B: Condens. Matter
Mater. Phys., 2012, 85, 045201.
99 F. Coppari, A. Di Cicco, A. Congeduti, J. C. Chervin, F.
Baudelet and A. Polian, High Pressure Res., 2009, 29,
103–107.
100 F. Coppari, A. Di Cicco, E. Principi, A. Trapananti, N. Pinto,
A. Polian, S. Chagnot and A. Congeduti, High Pressure Res.,
2010, 30, 28–34.
101 N. V. Abrosimov, S. N. Rossolenko, W. Thieme, A.
Gerhardt and W. Schröder, J. Cryst. Growth, 1997, 174,
182–186.
102 V. P. Markevich, A. R. Peaker, L. I. Murin and N. V.
Abrosimov, Appl. Phys. Lett., 2003, 82, 2652–2654.
5432 | CrystEngComm, 2020, 22, 5416–5435
CrystEngComm
103 D. J. Frost, B. T. Poe, R. G. Trønnes, C. Liebske, A. Duba
and D. C. Rubie, Phys. Earth Planet. Inter., 2004, 143–144,
507–514.
104 S. V. Ovsyannikov, H. Gou, A. E. Karkin, V. V. Shchennikov,
R. Wirth, V. Dmitriev, Y. Nakajima, N. Dubrovinskaia and
L. S. Dubrovinsky, Chem. Mater., 2014, 26, 5274–5281.
105 S. V. Ovsyannikov, M. Bykov, E. Bykova, D. P. Kozlenko,
A. A. Tsirlin, A. E. Karkin, V. V. Shchennikov, S. E.
Kichanov, H. Gou, A. M. Abakumov, R. Egoavil, J. Verbeeck,
C. McCammon, V. Dyadkin, D. Chernyshov, S. van Smaalen
and L. S. Dubrovinsky, Nat. Chem., 2016, 8, 501–508.
106 S. V. Ovsyannikov, M. Bykov, E. Bykova, K. Glazyrin, R. S.
Manna, A. A. Tsirlin, V. Cerantola, I. Kupenko, A. V.
Kurnosov, I. Kantor, A. S. Pakhomova, I. Chuvashova, A. I.
Chumakov, R. Rüffer, C. McCammon and L. S.
Dubrovinsky, Nat. Commun., 2018, 9, 4142.
107 S. V. Ovsyannikov, E. Bykova, A. Pakhomova, D. P.
Kozlenko, M. Bykov, S. E. Kichanov, N. V. Morozova, I. V.
Korobeinikov, F. Wilhelm, A. Rogalev, A. A. Tsirlin, A. V.
Kurnosov, Y. G. Zainulin, N. I. Kadyrova, A. P. Tyutyunnik
and L. Dubrovinsky, Inorg. Chem., 2017, 56, 6251–6263.
108 N. V. Morozova, S. V. Ovsyannikov, I. V. Korobeinikov, A. E.
Karkin, K. Takarabe, Y. Mori, S. Nakamura and V. V.
Shchennikov, J. Appl. Phys., 2014, 115, 213705.
109 I. Kantor, V. Prakapenka, A. Kantor, P. Dera, A. Kurnosov, S.
Sinogeikin, N. Dubrovinskaia and L. Dubrovinsky, Rev. Sci.
Instrum., 2012, 83, 125102.
110 A. Kurnosov, I. Kantor, T. Boffa-Ballaran, S. Lindhardt, L.
Dubrovinsky, A. Kuznetsov and B. H. Zehnder, Rev. Sci.
Instrum., 2008, 79, 045110.
111 S. Klotz, J.-C. Chervin, P. Munsch and G. Le Marchand,
J. Phys. D: Appl. Phys., 2009, 42, 075413.
112 V. V. Shchennikov, S. V. Ovsyannikov and A. Y. Manakov,
J. Phys. Chem. Solids, 2010, 71, 1168–1174.
113 V. V. Shchennikov, S. V. Ovsyannikov and A. V. Bazhenov,
J. Phys. Chem. Solids, 2008, 69, 2315–2324.
114 V. V. Shchennikov, N. V. Morozova and S. V. Ovsyannikov,
J. Appl. Phys., 2012, 111, 112624.
115 F. P. Bundy, Phys. Rep., 1988, 167, 133–176.
116 L. G. Khvostantsev, V. N. Slesarev and V. V. Brazhkin, High
Pressure Res., 2004, 24, 371–383.
117 A. K. Bandyopadhyay, S. Chatterjee, E. S. R. Gopal and S. V.
Subramanyam, Rev. Sci. Instrum., 1981, 52, 1232–1235.
118 I. V. Korobeinikov, N. V. Morozova, L. N. Lukyanova, O. A.
Usov, V. A. KulbachinskII, V. V. Shchennikov and S. V.
Ovsyannikov, J. Phys. D: Appl. Phys., 2018, 51, 025501.
119 M. I. Eremets, High Pressure Experimental Methods, Oxford
University Press, Oxford–New York–Toronto, 1996.
120 A. Celeste, F. Borondics and F. Capitani, High Pressure Res.,
2019, 39, 608–618.
121 T. Pippinger, R. Miletich, M. Merlini, P. Lotti, P.
Schouwink, T. Yagi, W. A. Crichton and M. Hanfland, Phys.
Chem. Miner., 2015, 42, 29–43.
122 V. V. Shchennikov, S. V. Ovsyannikov, A. Y. Derevskov and
V. V. Shchennikov, J. Phys. Chem. Solids, 2006, 67,
2203–2209.
This journal is © The Royal Society of Chemistry 2020
CrystEngComm
123 S. V. Ovsyannikov, X. Wu, G. Garbarino, M. Núñez-
Regueiro, V. V. Shchennikov, J. A. Khmeleva, A. E. Karkin,
N. Dubrovinskaia and L. Dubrovinsky, Phys. Rev. B:
Condens. Matter Mater. Phys., 2013, 88, 184106.
124 S. V. Ovsyannikov, N. V. Morozova, I. V. Korobeinikov, L. N.
Lukyanova, A. Y. Manakov, A. Y. Likhacheva, A. I. Ancharov,
A. P. Vokhmyanin, I. F. Berger, O. A. Usov, V. A. Kutasov,
V. A. KulbachinskII, T. Okada and V. V. Shchennikov, Appl.
Phys. Lett., 2015, 106, 143901.
125 S. V. Ovsyannikov, N. V. Morozova, I. V. Korobeinikov, V.
Haborets, R. Yevych, Y. VysochanskII and V. V.
Shchennikov, Dalton Trans., 2017, 46, 4245–4258.
126 N. V. Morozova, V. V. Shchennikov and S. V. Ovsyannikov,
J. Appl. Phys., 2015, 118, 225901.
127 D. W. Feldman, M. Ashkin and J. H. Parker, Phys. Rev. Lett.,
1966, 17, 1209–1212.
128 W. J. Brya, Solid State Commun., 1973, 12, 253–257.
129 J. S. Lannin, Phys. Rev. B: Solid State, 1977, 16, 1510–1518.
130 H. D. Fuchs, C. H. Grein, M. I. Alonso and M. Cardona,
Phys. Rev. B: Condens. Matter Mater. Phys., 1991, 44,
13120–13123.
131 Z. Sui, H. H. Burke and I. P. Herman, Phys. Rev. B: Condens.
Matter Mater. Phys., 1993, 48, 2162–2168.
132 F. Pezzoli, L. Martinelli, E. Grilli, M. Guzzi, S. Sanguinetti,
M. Bollani, H. D. Chrastina, G. Isella, H. von Känel, E.
Wintersberger, J. Stangl and G. Bauer, Mater. Sci. Eng., B,
2005, 124–125, 127–131.
133 D. Rouchon, M. Mermoux, F. Bertin and J. M. Hartmann,
J. Cryst. Growth, 2014, 392, 66–73.
134 T. Ishidate, S. Katagiri, K. Inoue, M. Shibuya, K. Tsuji and
S. Minomura, J. Phys. Soc. Jpn., 1984, 53, 2584–2591.
135 C. H. Grein and M. Cardona, Phys. Rev. B: Condens. Matter
Mater. Phys., 1992, 45, 8328–8333.
136 M. Franz, K. F. Dombrowski, H. Rücker, B. Dietrich, K.
Pressel, A. Barz, U. Kerat, P. Dold and K. W. Benz, Phys. Rev.
B: Condens. Matter Mater. Phys., 1999, 59, 10614–10621.
137 S. Rath, M. L. Hsieh, P. Etchegoin and R. A. Stradling,
Semicond. Sci. Technol., 2003, 18, 566–575.
138 O. Pagès, J. Souhabi, V. J. B. Torres, A. V. Postnikov and
K. C. Rustagi, Phys. Rev. B: Condens. Matter Mater. Phys.,
2012, 86, 045201.
139 K. Gao, S. Prucnal, A. Mücklich, W. Skorupa and S. Zhou,
Acta Phys. Pol., A, 2013, 123, 858–861.
140 M. I. Alonso and K. Winer, Phys. Rev. B: Condens. Matter
Mater. Phys., 1989, 39, 10056–10062.
141 A. Picco, E. Bonera, E. Grilli, M. Guzzi, M. Giarola, G.
Mariotto, D. Chrastina and G. Isella, Phys. Rev. B: Condens.
Matter Mater. Phys., 2010, 82, 115317.
142 J. S. Reparaz, A. Bernardi, A. R. Goñi, M. I. Alonso and M.
Garriga, Appl. Phys. Lett., 2008, 92, 081909.
143 J. B. Renucci, R. N. Tyte and M. Cardona, Phys. Rev. B: Solid
State, 1975, 11, 3885–3895.
144 X. S. Zhao, Y. R. Ge, J. Schroeder and P. D. Persans, Appl.
Phys. Lett., 1994, 65, 2033–2035.
145 P. Mishra and K. P. Jain, Phys. Rev. B: Condens. Matter
Mater. Phys., 2001, 64, 073304.
This journal is © The Royal Society of Chemistry 2020
Paper
146 O. Moutanabbir, S. Miyamoto, E. E. Haller and K. M. Itoh,
Phys. Rev. Lett., 2010, 105, 026101.
147 B. C. Johnson, B. Haberl, J. E. Bradby, J. C. McCallum and
J. S. Williams, Phys. Rev. B: Condens. Matter Mater. Phys.,
2011, 83, 235205.
148 F. P. Bundy and J. S. Kasper, Science, 1963, 139, 340–341.
149 J. M. Besson, E. H. Mokhtari, J. Gonzalez and G. Weill,
Phys. Rev. Lett., 1987, 59, 473–476.
150 T. P. Mernagh and L.-G. Liu, J. Phys. Chem. Solids, 1991, 52,
507–512.
151 M. Oh-ishi, S. Akiyama, K. Uchida, S. Nozaki and H.
Morisaki, Phys. Status Solidi B, 2001, 223, 391–395.
152 A. Mujica and R. J. Needs, Phys. Rev. B: Condens. Matter
Mater. Phys., 1993, 48, 17010–17017.
153 A. Mujica, S. Radescu, A. Munoz and R. J. Needs, Phys.
Status Solidi B, 2001, 223, 379–384.
154 R. J. Nelmes, M. I. McMahon, N. G. Wright, D. R. Allan and
J. S. Loveday, Phys. Rev. B: Condens. Matter Mater. Phys.,
1993, 48, 9883–9886.
155 M. Hanfland and K. Syassen, High Pressure Res., 1990, 3,
242–244.
156 H. Olijnyk and A. P. Jephcoat, Phys. Status Solidi B,
1999, 211, 413–420.
157 L. Q. Huston, A. Lugstein, J. S. Williams and J. E. Bradby,
Appl. Phys. Lett., 2018, 113, 123103.
158 J. Crain, G. J. Ackland, J. R. Maclean, R. O. Piltz, P. D.
Hatton and G. S. Pawley, Phys. Rev. B: Condens. Matter
Mater. Phys., 1994, 50, 13043–13046.
159 R. O. Piltz, J. R. Maclean, S. J. Clark, G. J. Ackland, P. D.
Hatton and J. Crain, Phys. Rev. B: Condens. Matter Mater.
Phys., 1995, 52, 4072–4085.
160 O. O. Kurakevych, Y. Le Godec, W. A. Crichton, J. Guignard,
T. A. Strobel, H. Zhang, H. Liu, C. Coelho Diogo, A. Polian,
N. Menguy, S. J. Juhl and C. Gervais, Inorg. Chem., 2016, 55,
8943–8950.
161 Z. Zeng, Q. Zeng, W. L. Mao and S. Qu, J. Appl. Phys.,
2014, 115, 103514.
162 J.-T. Wang, C. Chen, H. Mizuseki and Y. Kawazoe, Phys. Rev.
Lett., 2013, 110, 165503.
163 B. Haberl, M. Guthrie, B. D. Malone, J. S. Smith, S. V.
Sinogeikin, M. L. Cohen, J. S. Williams, G. Shen and J. E.
Bradby, Phys. Rev. B: Condens. Matter Mater. Phys., 2014, 89,
144111.
164 Z. Zhao, H. Zhang, D. Y. Kim, W. Hu, E. S. Bullock and T. A.
Strobel, Nat. Commun., 2017, 8, 13909.
165 M. Satoh, K. Arimoto, K. Nakagawa, S. Koh, K. Sawano, Y.
Shiraki, N. Usami and K. Nakajima, Jpn. J. Appl. Phys.,
2008, 47, 4630–4633.
166 M. Satoh, K. Arimoto, J. Yamanaka, K. Nakagawa, K.
Sawano and Y. Shiraki, Jpn. J. Appl. Phys., 2012, 51,
105801.
167 W. Paul and D. M. Warschauer, J. Phys. Chem. Solids,
1958, 5, 89–101.
168 W. Paul, J. Phys. Chem. Solids, 1959, 8, 196–204.
169 K. Tanaka, Phys. Rev. B: Condens. Matter Mater. Phys.,
1991, 43, 4302–4307.
CrystEngComm, 2020, 22, 5416–5435 | 5433
Paper
170 R. J. Kobliska, S. A. Solin, M. Selders, R. K. Chang, R.
Alben, M. F. Thorpe and D. Weaire, Phys. Rev. Lett.,
1972, 29, 725–728.
171 S. Nozaki, S. Sato, S. Rath, H. Ono and H. Morisaki, Bull.
Mater. Sci., 1999, 22, 377–381.
172 S. Rath, S. Sato, H. Ono, S. Nozaki and H. Morisaki, Mater.
Chem. Phys., 1998, 54, 244–246.
173 A. Kailer, K. G. Nickel and Y. G. Gogotsi, J. Raman
Spectrosc., 1999, 30, 939–946.
174 B. D. Malone and M. L. Cohen, Phys. Rev. B: Condens.
Matter Mater. Phys., 2012, 86, 054101.
175 L. Q. Huston, B. C. Johnson, B. Haberl, S. Wong, J. S.
Williams and J. E. Bradby, J. Appl. Phys., 2017, 122, 175108.
176 Y. Ikoma, K. Kumano, K. Edalati, K. Saito, Q. Guo and Z.
Horita, Philos. Mag. Lett., 2017, 97, 27–34.
177 D. J. Oliver, J. E. Bradby, J. S. Williams, M. V. Swain and P.
Munroe, J. Appl. Phys., 2007, 101, 043524.
178 G. Andersson, B. Sundqvist and G. Bäckström, J. Appl.
Phys., 1989, 65, 3943–3950.
179 S. V. Ovsyannikov, V. V. Shchennikov, A. Misiuk and V. V.
Shchennikov, Solid State Commun., 2004, 132, 545–549.
180 G. Weill, J. L. Mansot, G. Sagon, C. Carlone and J. M.
Besson, Semicond. Sci. Technol., 1989, 4, 280–282.
181 A. Kailer, Y. G. Gogotsi and K. G. Nickel, J. Appl. Phys.,
1997, 81, 3057–3063.
182 M. M. Khayyat, G. K. Banini, D. G. Hasko and M. M.
Chaudhri, J. Phys. D: Appl. Phys., 2003, 36, 1300–1307.
183 A. Wosylus, H. Rosner, W. Schnelle and U. Schwarz, Z.
Anorg. Allg. Chem., 2009, 635, 700–703.
184 H. Zhang, H. Liu, K. Wei, O. O. Kurakevych, Y. Le Godec, Z.
Liu, J. Martin, M. Guerrette, G. S. Nolas and T. A. Strobel,
Phys. Rev. Lett., 2017, 118, 146601.
185 H. Aharoni, Vacuum, 1978, 28, 571–578.
186 M. F. A. Alias, N. Rammo and M. Makadsi, Renewable
Energy, 2001, 24, 347–351.
187 C. Xu, C. L. Senaratne, R. J. Culbertson, J. Kouvetakis and J.
Menéndez, J. Appl. Phys., 2017, 122, 125702.
188 N. N. Ovsyuk and S. G. Lyapin, Appl. Phys. Lett., 2020, 116,
062103.
189 K. Seeger, Semiconductor Physics, Springer, New York, 1973.
190 W. Paul and D. M. Warschauer, J. Phys. Chem. Solids,
1958, 5, 102–106.
191 W. Paul and D. M. Warschauer, J. Phys. Chem. Solids,
1958, 6, 6–15.
192 M. Cardona and W. Paul, J. Phys. Chem. Solids, 1960, 17,
138–142.
193 B. Welber, M. Cardona, Y.-F. Tsay and B. Bendow, Phys. Rev.
B: Solid State, 1977, 15, 875–879.
194 A. R. Goni, K. Syassen and M. Cardona, Phys. Rev. B:
Condens. Matter Mater. Phys., 1989, 39, 12921–12924.
195 G. G. N. Angilella, N. H. March, I. A. Howard and R. Pucci,
J. Phys.: Conf. Ser., 2008, 121, 032006.
196 C. V. de Alvarez and M. L. Cohen, Solid State Commun.,
1974, 14, 317–320.
197 R. H. Deitch, S. H. Jones and T. G. Digges, J. Electron.
Mater., 2000, 29, 1074–1078.
5434 | CrystEngComm, 2020, 22, 5416–5435
CrystEngComm
198 M. Arivanandhan, Y. Saito, T. Koyama, Y. Momose, H.
Ikeda, A. Tanaka, T. Tatsuoka, D. K. Aswal, Y. Inatomi and
Y. Hayakawa, J. Cryst. Growth, 2011, 318, 324–327.
199 N. V. Abrosimov, A. Lüdge, H. Riemann and W. Schröder,
J. Cryst. Growth, 2002, 237-239, 356–360.
200 A. I. Veinger, A. G. Zabrodski, T. V. Tisnek, S. I.
Goloshchapov and N. V. Abrosimov, Semiconductors,
2007, 41, 666–672.
201 E. Kasper, A. Schuh, G. Bauer, B. Holländer and H. Kibbel,
J. Cryst. Growth, 1995, 157, 68–72.
202 I. Yonenaga and M. Sakurai, Phys. Rev. B: Condens. Matter
Mater. Phys., 2001, 64, 113206.
203 F. Pezzoli, E. Bonera, E. Grilli, M. Guzzi, S.
Sanguinetti, D. Chrastina, G. Isella, H. von Känel, E.
Wintersberger, J. Stangl and G. Bauer, J. Appl. Phys.,
2008, 103, 093521.
204 M. R. Islam, M. Yamada, N. V. Abrosimov, M. Kiyama
and M. Tatsumi, Eur. Phys. J.: Appl. Phys., 2004, 27,
325–328.
205 V. P. Markevich, A. R. Peaker, J. Coutinho, R. Jones, V. J. B.
Torres, S. Öberg, P. R. Briddon, L. I. Murin, L. Dobaczewski
and N. V. Abrosimov, Phys. Rev. B: Condens. Matter Mater.
Phys., 2004, 69, 125218.
206 A. R. Peaker, V. P. Markevich, F. D. Auret, L. Dobaczewski
and N. Abrosimov, J. Phys.: Condens. Matter, 2005, 17,
S2293–S2302.
207 A. R. Peaker, V. P. Markevich, B. Hamilton, I. D. Hawkins,
J. Slotte, K. Kuitunen, F. Tuomisto, A. Satta, E. Simoen
and N. V. Abrosimov, Thin Solid Films, 2008, 517,
152–154.
208 J. Chen, T. Wu, X. Ma, L. Wang and D. Yang, J. Appl. Phys.,
2008, 103, 123519.
209 P. N. Grillot, S. A. Ringel, J. Michel and E. A. Fitzgerald,
J. Appl. Phys., 1996, 80, 2823–2832.
210 M. Baleva and E. Mateeva, Phys. Rev. B: Condens. Matter
Mater. Phys., 1994, 50, 8893–8896.
211 A. Kadir, T. Ganguli, R. Kumar, M. R. Gokhale, A. P. Shah,
S. Ghosh, B. M. Arora and A. Bhattacharya, Appl. Phys. Lett.,
2007, 91, 111913.
212 S. Ruffell, K. Sears, J. E. Bradby and J. S. Williams, Appl.
Phys. Lett., 2011, 98, 052105.
213 S. Wong, B. Haberl, J. S. Williams and J. E. Bradby, Appl.
Phys. Lett., 2015, 106, 252103.
214 P. Vettiger, G. Cross, M. Despont, U. Drechsler, U. Durig, B.
Gotsmann, W. Haberle, M. A. Lantz, H. E. Rothuizen, R.
Stutz and G. K. Binnig, IEEE Trans. Nanotechnol., 2002, 1,
39–55.
215 M. I. Lutwyche, M. Despont, U. Drechsler, U. Dürig, W.
Häberle, H. Rothuizen, R. Stutz, R. Widmer, G. K.
Binnig and P. Vettiger, Appl. Phys. Lett., 2000, 77,
3299–3301.
216 S. Wong, B. Haberl, B. C. Johnson, A. Mujica, M. Guthrie,
J. C. McCallum, J. S. Williams and J. E. Bradby, Phys. Rev.
Lett., 2019, 122, 105701.
217 S. Mannepalli and K. S. R. N. Mangalampalli, J. Appl. Phys.,
2019, 125, 225105.
This journal is © The Royal Society of Chemistry 2020
CrystEngComm
218 S. Wong, B. C. Johnson, B. Haberl, A. Mujica, J. C.
McCallum, J. S. Williams and J. E. Bradby, J. Appl. Phys.,
2019, 126, 105901.
219 Y. Ikoma, B. Chon, T. Yamasaki, K. Takahashi, K. Saito, Q.
Guo and Z. Horita, Appl. Phys. Lett., 2018, 113, 101904.
This journal is © The Royal Society of Chemistry 2020
View publication stats
Paper
220 B. Chon, Y. Ikoma, M. Kohno, J. Shiomi, M. R.
McCartney, D. J. Smith and Z. Horita, Scr. Mater.,
2018, 157, 120–123.
221 S. Ganguly, N. Kazem, D. Carter and S. M. Kauzlarich,
J. Am. Chem. Soc., 2014, 136, 1296–1299.
CrystEngComm, 2020, 22, 5416–5435 | 5435