Article

pubs.acs.org/crystal

Pressure Effects on the Size of Type‑I and Type-II Si-Clathrates

Synthesized by Spark Plasma Sintering
S. Stefanoski, M. C. Blosser, and G. S. Nolas*
Department of Physics, University of South Florida, Tampa, Florida 33620, United States
*
S Supporting Information

ABSTRACT: The crystallinity of clathrate-I Na8Si46 and clathrate-II Na24Si136

was investigated as a function of applied pressure and temperature employing
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spark plasma sintering. Na8Si46 and Na24Si136 with full Na and Si occupancies
were obtained at 450 and 600 °C, respectively. Microcrystalline powders were
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obtained at 60 MPa, and single crystals were obtained at 100 MPa. The size of
the crystals increased with pressure for the clathrate-II Na24Si136, while a
threshold value in pressure separated microcrystalline and single-crystal
clathrate-I Na8Si46.

1. INTRODUCTION products were investigated as a function of the applied pressure

In spark plasma sintering (SPS), a pulsed dc current is sourced
through a specimen enclosed in a punch and die assembly
placed between two electrodes. The two electrodes, which
source current through the specimen and die assembly, also act
for application of uniaxial pressure. The application of electrical
current in SPS influences the generation and mobility of point
defects.1 The fast heating rates and more uniform heating, as
compared with other consolidation techniques, generally result
in faster densification, and have typically been employed for the
densification of refractory materials.2−4 These characteristics
make SPS a state-of-the-art consolidation technique.2−4 In
addition to consolidation, SPS was employed for the synthesis
of various materials ranging from ceramics to metals, polymers,
and semiconductors.5−7
The SPS approach allows for mass transport of ions to take
place within a precursor while under pressure. It can, therefore,
be used for clathrate formation and crystal growth. Recently,
SPS was used for the synthesis of single-crystal clathrate-II
Na24Si136.8 Intermetallic clathrates represent open-framework
materials in which guest atomic species are enclosed within the
host framework.9,10 The interest in group 14 clathrates stems
from the unique properties that have been reported in these
materials,9,11−19 making them promising for a range of
applications, including thermoelectric,9,14,15 magnetocalor-
ic,16,17,20 optoelectronic,12,21 and superconductivity.19 Single
crystals of clathrate-II Na24Si136 were synthesized via SPS at 600
°C under uniaxial pressure of 100 MPa for 3 h.8 At 550 °C,
approximately 10% of clathrate-I Na8Si46 was observed as an
impurity, whereas reactions performed at 700 °C yielded a
similar fraction of α-Si.8 The synthesis procedure reported here
allows for the selective synthesis of single-crystal Na8Si46 and
Na24Si136 using SPS. Size and crystallinity of the clathrate
and temperature.
2. EXPERIMENTAL SECTION
The Na4Si4 precursor was synthesized by direct reaction of elemental
Na (Alfa Aesar, 99.98%) and Si powder (Alfa Aesar, 99%). A Na/Si
atomic ratio of 1.1:1 was placed inside a tungsten crucible that was
inside a sealed stainless steel canister and reacted at 650 °C for 36 h.
The resulting product was a dark gray crystalline material and was used
as the precursor in the SPS process.
The SPS investigations were carried out using the Thermal
Technology, Inc. 10-3 system. Na4Si4 precursor was loaded in a
graphite die with uniaxial pressures of 60, 80, and 100 MPa applied
using graphite punches. The maximum pressure applied with graphite
die and punches was 100 MPa. Tantalum foil was used to prevent
direct reaction between the precursor and the graphite die and
punches, as well as to provide a tight fit of the die assembly. Pulsed dc
current, with a pulse-on time of 36 ms and a pulse-off time of 2 ms,
was sourced through the precursor and die from the bottom electrode
(anode) to the top electrode (cathode) while under uniaxial pressure
in a vacuum of 10−3 Torr for 3 h after flushing the chamber three times
with high-purity N2. The product of the reaction was separated from
any unreacted Na4Si4 by washing with ethanol and distilled water.
Single-crystal XRD data of Na8Si46 and Na24Si136 crystals were
obtained at 293 K on a STOE diffractometer using a graphite
monochromator and a Mo Kα fine-focus sealed tube with a
wavelength of 0.71073 Å. Structural refinements were performed
using SHELXL-97 (Tables S1−S5 in the Supporting Information).
Powder X-ray diffraction (XRD) patterns were collected with a
Bruker D8 Focus diffractometer in Bragg−Brentano geometry using
Cu Kα,β radiation and a graphite monochromator. NIST Si 640c
internal standard was used for determination of lattice parameters.
Received: September 14, 2012
Revised: November 16, 2012
Published: November 20, 2012

© 2012 American Chemical Society 195 dx.doi.org/10.1021/cg3013443 | Cryst. Growth Des. 2013, 13, 195−197
Crystal Growth & Design Article

Scanning electron micrographs (SEM) were collected using a JEOL
JSM-6390LV, and energy-dispersive X-ray spectroscopic (EDS) data
were collected using an Oxford INCA X-Sight 7582M.
3. RESULTS AND DISCUSSION
Specimens with the clathrate-I and clathrate-II crystal structures
were synthesized by SPS processing of Na4Si4 at the respective
temperatures of 450 and 600 °C, and uniaxial pressures of 60,
80, and 100 MPa for 3 h. As described in ref 8, Na transport
occurs during SPS, thereby resulting in a redox reaction. The
temperature ramp rates were 100 °C/min for the clathrate-I
phase, and 25 °C/min up to 450 °C and then 10 °C/min up to
600 °C for the clathrate-II phase. Selective synthesis was
achieved by choosing the appropriate temperature, 450 °C for
the clathrate-I phase and 600 °C for the clathrate-II phase
(Figure 1; Figure S1 in the Supporting Information). No
other.22−27 Also, impurities of α-Si have been typically observed
in NaxSi136 using this technique.22−27 It is also known that an
insulating oxide layer can readily form on the grains of
microcrystalline specimens28 and presents difficulties in
densification and interpretation of the measured data.29,30
Less than 5 wt % α-Si and no clathrate impurities were
observed in the clathrate-II Na24Si136 microcrystalline specimen
using this SPS approach (Figure S1, Supporting Information).
Only single-crystal Na24Si136 are free of α-Si and other
impurities and allow for intrinsic physical properties measure-
ments.31 It is, therefore, of interest to investigate the size and
crystallinity of single-crystal clathrates employing SPS.
Details of the SPS synthesis parameters, including temper-
ature, T, pressure, P, and average size, L, of the resulting
products, are given in Table 1. The grain size of the powders
was calculated using the Debye−Scherrer equation.32,33 The
average size of the single crystals was obtained from SEM
analyses.

Table 1. Processing Conditions for SPS Synthesis from the

Precursor Na4Si4
T (°C) P (MPa) phase crystallinity L (μm)
450 60 clathrate-I microcrystalline 10
80 clathrate-I microcrystalline 10
100 clathrate-I single crystal 150
550 60 clathrate-I + II microcrystalline 10
80 clathrate-I + II microcrystalline + single 10/150
crystal
100 clathrate-I + II microcrystalline + single 10/150
crystal
600 60 clathrate-II microcrystalline 15
Figure 1. X-ray diffraction patterns of powdered Na8Si46 and Na24Si136,
80 clathrate-II single crystal 50
collected from crushed single crystals, Na4Si4, and Si demonstrating
100 clathrate-II single crystal 250
the selective synthesis of single-crystal clathrates at 100 MPa.
650 100 silicon nanocrystalline 0.065

change in the precursor was observed at temperatures below

400 °C. At 550 °C, a mixture of both phases was observed. SPS
processing at 650 °C yields the α-Si phase. The highest yield of
single crystals was achieved at 450 and 600 °C for the clathrate-
I and clathrate-II phases, respectively, at 100 MPa. This
approach allowed for the selective synthesis of single-crystal
(Figure 1) and microcrystalline (Figure S1, Supporting
Information) Na8Si46 and Na24Si136 as a function of the applied
pressure. At 60 MPa, high-purity microcrystalline products
were observed. When the pressure was increased from 60 to 80
MPa, clathrate-II single crystals started to form but clathrate-I
single crystals formed at 100 MPa.
Compositions with stoichiometries of Na8Si46 and Na24Si136
were obtained from refinement of the single-crystal XRD data
(Tables S1−S5, Supporting Information). Compositions with
stoichiometries of Na8Si46 and Na24Si136 were obtained from
the refinement of powder XRD data collected on microcrystal-
line clathrate-I and clathrate-II specimens, respectively (Tables
S6−S8, Supporting Information). EDS analyses of these single
crystal stoichiometries, Na7(1)Si46 and Na23(1)Si136, corroborate
the single-crystal XRD results. The crystal structure for the
microcrystalline specimens of both phases was obtained from
Rietveld refinement (Figures S2 and S3, Supporting Informa-
tion).
Microcrystalline Na8Si46 and Na24−xSi136 (0 < x < 24)
clathrates have traditionally been synthesized by thermal
decomposition of the Na4Si4 precursor under dynamic vacuum
with one clathrate phase present as an impurity in the
196
The average size of the clathrate-I phase does not change as
the pressure is increased from 60 to 80 MPa (Table 1), in
contrast to the clathrate-II phase. The average crystal size for
the clathrate-II phase at 80 MPa is smaller than that at 100
MPa, suggesting that the crystal size increases with increasing
pressure. In the case of the clathrate-I phase, 100 MPa seems to
be the optimum pressure for graphite tooling at which single-
crystal growth takes place. SPS processing at 60 and 80 MPa
resulted in only microcrystalline products, whereas at 100 MPa,
only single crystals were observed at the appropriate temper-
atures. The average size of the single-crystal products, 150 and
250 μm for the clathrate-I and clathrate-II phases, respectively,
(Table 1) is comparable to that obtained from other single-
crystal synthesis methods.34 At 550 °C and 100 MPa, a mixture
of powders and single crystals of both clathrate phases was
observed (Table 1). The relative clathrate fraction in the
synthesis product as a function of reaction time was also
investigated. When the precursor was reacted at 600 °C for 30
min, the clathrate-I phase was estimated to be approximately
60%, whereas the clathrate-II phase was approximately 40%,
from powder XRD analyses (Figure S4, Supporting Informa-
tion). As the reaction time increased at the same temperature,
the intensity of the clathrate-I reflections in the XRD spectra
decreased. For a reaction time of 3 h, only the clathrate-II phase
was observed.
The average size of Si obtained by SPS processing of the
Na4Si4 precursor at 650 °C is 65 nm (Table 1). Si nanoparticles
dx.doi.org/10.1021/cg3013443 | Cryst. Growth Des. 2013, 13, 195−197
Crystal Growth & Design
of 3 nm can been synthesized by a microwave assisted
technique35 and are of interest for the green chemistry as they
are considered to be nontoxic, biocompatible, and biodegrad-
able.35,36 The high heating rates and localized heating in the
SPS, considered two of the most important factors for the
synthesis of Si nanoparticles,35 may reveal SPS to be a
promising method for the synthesis of Si nanoparticles. Further
investigations are necessary in order to determine the full
potential of SPS in this direction.
4. CONCLUSION
Selective synthesis of single-crystal and microcrystalline
clathrate-I Na8Si46 and clathrate-II Na24Si136 was achieved via
SPS. The size of the product increased with pressure in the case
of clathrate-II Na24Si136, in contrast with the clathrate-I Na8Si46.
Microcrystalline specimens were obtained at 60 MPa and
single-crystal specimens at 100 MPa, at temperatures of 450
and 600 °C for the clathrate-I and clathrate-II phases,
respectively. This approach may also have promise for the
preparation of nanocrystalline Si, as Si nanoparticles with an
average size of 65 nm were synthesized by SPS.
■
ASSOCIATED CONTENT
*
S Supporting Information
Figures showing XRD patterns and Reitveld refinement data,
tables containing XRD and Rietveld refinement data, and
crystallographic data in CIF format.This material is available
free of charge via the Internet at http://pubs.acs.org.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: gnolas@usf.edu.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We acknowledge support by the U.S. Department of Energy,
Basic Energy Sciences, Division of Materials Science and
Engineering, under Award No. DE-FG02-04ER46145 for
single-crystal synthesis, structural analyses, and measured and
simulated pXRD, SEM, and EDS measurements and analyses.
We also acknowledge C. D. Malliakas and M. G. Kanatzidis for
collecting the single-crystal XRD data.
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