Electrochemical and Solid-State Letters, 14 (12) E41-E43 (2011)

1099-0062/2011/14(12)/E41/3/$28.00 The Electrochemical Society

E41

One-Step Synthesis of a 12CaO 7Al2 O3 Electride via the Spark

Plasma Sintering (SPS) Method
Jun Ho Chung,a Jeong Ho Ryu,b, Jong Won Eun,a Bong Geun Choi,a and Kwang Bo Shima,z
a Division of Materials Science and Engineering, Hanyang University, Seongdong-Gu, Seoul 133-791, South Korea
b Department of Materials Science and Engineering, Chungju National University, Chungji-si, Chungbuk 380-702,

South Korea

Polycrystalline C12A7 electrides were successfully synthesized via spark plasma sintering (SPS) process. C2 2 ions, generated from
graphite by the spark plasma, presumably serve as a template for the formation of the C12A7 phase during the re-crystallization
process and are spontaneously released from the cage of C12A7 during the SPS process, remaining mobile electrons in the cage.
The polycrystalline C12A7 electride processed at 1100 C exhibits an electrical resistivity of 1.7 101  cm1 , an electron
concentration of 5.3 1019 /cm3 and optical absorptions of 0.4 eV and 2.7 eV at room temperature.
2011 The Electrochemical Society. [DOI: 10.1149/2.021112esl] All rights reserved.
Manuscript submitted July 29, 2011; revised manuscript received September 8, 2011. Published October 25, 2011.

Electrides are ionic materials in which an electron occupies a

crystallographic site, acting as an anion, the structural features of
which allow them to serve as a promising material for various applications, such as reducing agents, cold-cathode electron eld emitters
and refrigeration devices.14 However, most electrides are composed
of organic materials and are unstable at room temperature. These instabilities have restricted the practical applications of such material.5
In order to overcome these instabilities, inorganic electrides with good
stability at room temperature have been studied. Hosono et al. reported
the fabrication of a 12CaO 7Al2 O3 (C12A7) inorganic electride by replacing the extra oxygen ions in the framework with electrons.6
C12A7 is a constituent of alumina cement that has an unique
crystal structure, composed of 12 sub-nanometer-sized cages with an
inner free space diameter of 0.4 nm connected to a neighboring cage
through shared six-atom rings consisting of Ca-O-Al-O-Al-O.6 The
unit cell, called the framework, is composed of positively-charged
[Ca24 Al28 O64 ]4+ . To compensate for the positive charge of the framework, two O2 ions, free oxygen ions, are loosely bound in the cages
(C12A7:O2 ). These free oxygen ions can be substituted with monovalent ions, such as halogen ions (F , Cl ),7, 8 hydroxide ions (OH )9
or super radical hydrogen ions (H ),10 and converted to electride by
replacing free oxygen ions with electrons.6
The C12A7 electride has been fabricated via metal vapor
treatment6, 11 or a melt-solidication process.12, 13 However, the metal
vapor treatment requires a single crystal C12A7:O2 and long annealing time, and the melt-solidication process employs a complex
procedure for the decomposition of C12A7:O2 to C3A+CA and
recrystallization to C12A7 electride. In order to overcome these difculties, the SPS process is proposed for a simpler and faster fabrication
process of the C12A7 electride.
The SPS process is a fast sintering technique where the pulsed electric currents induce joule heating and spark plasma to pass through the
surfaces of the loaded powders, which rapidly increases the heating
rate and drastically reduces the reaction time.14, 15 During the SPS process, a carbon-rich atmosphere can be made by graphite die, the spark
plasma can activate the carbon ions, and the electric eld can promote
diffusion of the activated carbon ions into the samples. In addition,
rapid joule heating can maintain a homogeneous temperature.1618
In this work, we rstly demonstrate the SPS techniques as a simple and fast synthetic route for fabrication of C12A7 electrides. The
electrical and optical properties of the SPS processed C12A7 electride
was evaluated, and the electron replacement mechanism of the SPS
process was presented in detail.

Electrochemical Society Active Member.

z

E-mail: kbshim@hanyang.ac.kr

Experimental
The starting C12A7 powder was prepared using a conventional
citrate-gel method. Synthesized C12A7 powders (1 g) were loaded
into a cylindrical graphite die with a diameter of 15 mm and heated
R
using the SPS (Dr. Sinter model
, SPS-2080, Japan) process within a
temperature range of 900 to 1100 C, with a heating rate of 100 C/min
and an uni-axial pressure of 40 MPa in vacuum (106 Torr). The
samples were held for 10 min at each temperature. The direct current
was 1500 A with a pulsed duration of 12 ms and a pulse interval of
2 ms. After SPS process, the samples are grinded and polished for
removed carbon lms on the surface using SiC abrasive paper. The
thickness samples were about 2 mm.
Phase analysis was performed using an X-ray diffractometer
(Rigaku D/MAX2C, Japan, Cu- ( = 1.5046 )). Optical absorption
spectra were measured by UV-Vis spectroscopy (UV 3600, Shimadzu,
Japan) in a range of 0.4 - 4.0 eV, and Raman spectra were measured
(NRS-3000, laser ( = 532nm)) in a range of 4002000 cm1 at
room temperature. The electron concentration and electrical resistivity
were measured using four-probe type Hall measurement (RESISTEST
8300, DongYang Tech, Japan).
Results and Discussion
Photographs of the C12A7 samples at different processing temperatures are presented in Figure 1. The colors of the samples changed
depending on the temperature; white at 900 C, gray at 1000 C and
dark green color at 1100 C. This change was suggested to be induced
by the optical absorption level (2.7 eV) generated by the electrons that
replaced the free oxygen ions.20
Figure 2 shows optical absorption results of the C12A7 samples
depending on the processing temperature. The sample processed at
900 C showed no specic absorption peak; however, the samples
processed at 1000 C and 1100 C showed absorption peaks near the
0.4 and 2.7 eV regions, indicating electron trapping in the C12A7

Figure 1. Photograph of C12A7 specimens via SPS at different processing

temperatures.

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E42

Electrochemical and Solid-State Letters, 14 (12) E41-E43 (2011)

2.7 eV

0.4 eV

Absorption(Kubelaka-Munk)

5
4
3

1100oC

1000oC
900oC

1
0
4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.5

0.0

Phothon Energy(eV)
Figure 2. UV-Vis spectra of the C12A7 specimens processed via SPS at
different processing temperatures.

13

10

10

3.2 x 1011 cm

5.3 x 1019 /cm3

3.2 x 1017 /cm3

10

10

10

2.6 x 102 cm

10

10

21

10

17

10

13

10

10

-3

10

Electron concentration(cm )

Electric Resistivity( cm)

cage structure.20 The energy level of the 2.7 eV peak reects the color
change from white to dark green, as shown in Figure 1. The optical
absorption levels of 0.4 eV and 2.7 eV can be caused by an inter-cage
transition (0.4 eV) and intra-cage transition (2.7 eV), respectively.2022
Figure 3 shows the electric resistivities and electron concentrations of the C12A7 samples at different processing temperatures.
The electric resistivity of the C12A7 sample processed at 900 C was
3.2 1011  cm, indicating a perfect insulator. The electric resistivities of the samples processed at 1000 C and 1100 C dramatically
decreased to 2.6 102 and 1.7 101  cm1 , respectively. While
the electron concentrations of the samples processed at 900 C were
6.1 108 /cm3 , those of the C12A7 samples processed at 1000 C and
1100 C were 3.2 1017 and 5.3 1019 /cm3 , respectively. The results
of the sample processed at 1100 C were comparable with previous
results19 and conrmed that the SPS process can successfully convert
C12A7 to C12A7 electrides.
Figure 4a represents the XRD results of the C12A7 samples depending on the processing temperature. Compared with the powder
sample, the SPS processed sample at 900 C showed mixed phases
composed of 3CaO Al2 O3 (C3A) and CaO Al2 O3 (CA) with the
C12A7 phase. Increasing processing temperature to 1000 C decreased
the peak intensities of the C3A+CA phases, which are completely disappeared at 1100 C, indicating that the C12A7 phase decomposed to

6.1 x 108 /cm3

1.7 x 10-1 cm

-2

900

1000

1100
o

Sintering Temp( C)

Figure 3. Electric resistivity and electron concentration of the C12A7 specimens at room temperature (300 K).

Figure 4. (a) X-ray diffraction patterns and (b) raman spectroscopy of the
C12A7 specimens produced via SPS at different processing temperatures.

C3A+CA phases at 900 C and re-crystallized at 1100 C during the

SPS process. Raman spectra of the SPS processed samples are shown
in Figure 4b. At 900 C, the CaC2 band at 1870 cm1 , which is attributed to C3A+CA phases, was formed through the decomposition
of the C12A7 phase. The CaC2 band was still present at 1000 C;
however, its intensity decreased compared to that at 900 C due to a
decrease in the amount of C2 2 ions and the gradual re-crystallization
from C3A+CA phases to the C12A7 phase. This CaC2 band disappeared at 1100 C because the decomposed C3A+CA phases were
completely re-crystallized to C12A7 phase. These results conrmed
that the SPS processed specimen at 1100 C was successfully converted to the C12A7 electride.
Figures 5a5d schematically show the fabrication procedures of
the C12A7 electride during the SPS process. In the SPS system, the
graphite die lled with C12A7 powders was placed between the lower
and upper electrodes, as shown in Figure 5a. An external DC pulsed
discharge power source provided the electric current which generated
the electric eld.1618 Through charging and discharging processes by
the electric current, a high temperature spark plasma was momentarily generated between the surfaces of the C12A7 particles23, 24 and
then activated carbon ions like C2 2 from the graphite. Therefore,
C12A7 particles have locally high temperature regions about several
thousand C, which can be decomposed from C12A7 to C3A+CA, as

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Electrochemical and Solid-State Letters, 14 (12) E41-E43 (2011)

E43

Figure 5. Schematics of a one-step fabrication route for C12A7 electride using the PECS process. (a) The C12A7:O2 powders were placed between two graphite
rams in a cylindrical graphite die, (b) decomposition from C12A7 phase to C3A+CA phases due to spark plasma-induced electric current, (c) diffusion of carbon
ions (C2 2 ) into decomposed C3A+CA phases and re-crystallization from C3A+CA to C12A7:C2 2 by C2 2 ions and (d) transition from C12A7:C2 2 to
C12A7:e and emission of carbon ions as 2C or 2CO into the atmosphere.

shown in Figure 5b. The decomposed C3A+CA phases were combined with C2 2 ions diffused into samples by the electric eld and
re-crystallized to the C12A7 phase by C2 2 ions, as shown in Figures
5c5d according to the following reaction,
C3A + CA + C2 2 C12A7 : C2 2

[1]

As shown in Figures 4a, processed below 1000 C, the decomposed C3A+CA phases were not perfectly re-crystallized to C12A7
because of insufcient temperatures for re-crystallization. However,
above 1100 C, only a single C12A7 phase existed, indicating that the
decomposed C3A+CA phases were perfectly re-crystallized to the
C12A7 phase, as shown Figure 5d. During the SPS process, C2 2 ions
are diffused into the C3A+CA phases by the electric eld, and then
the decomposed C3A+CA phases can be re-crystallized to the C12A7
phase by C2 2 ions. Therefore, the C2 2 ions instead of O2 ions serve
as a template for compensating positive charges of [Ca24 Al28 O64 ]4+
because the ionic radius of the C2 2 ion (1.2 ) is similar to that
of O2 (1.4 ).19 The C2 2 ions trapped in the cages of the C12A7
were only stable in the initial stage of re-crystallization and were then
released from the cages during the re-crystallization procedure. In this
process, the electrons were generated in cages of the C12A7 via the
following reactions,
C2 2 (graphite) C2 2 (cage) 2C (solid) + 2e (cage)

[2]

and/or
C2 2 (cage) + 2O2 2 (cage) 2CO (atmosphere) + 6e (cage)
[3]
Through above process, C2 2 ions generate electrons to the cages
and release 2C or 2CO into the atmosphere.19
Conclusions
Polycrystalline C12A7 electride was successfully fabricated via
the SPS process. The optical absorption bands at 0.4 eV and 2.7 eV and
electric properties such as electric resistivity and electron concentration conrmed that C12A7:O2 was successfully converted to C12A7
electride. The C12A7 electride synthesized via the one-step SPS process is attributable to the carbon-related anion, C2 2 , generated by
spark plasma induced by the charging-discharging process. The C2 2
ion serves as the template anion, instead of the O2 anions, to stabilize the C12A7 phase and then is removed from the cage, remaining
electrons in the cages of C12A7 during the re-crystallization process.

The resultant polycrystalline C12A7 electride showed an electrical

resistivity and electron concentration of 1.7 101  cm1 and
5.3 1019 /cm3 , respectively. Therefore, we concluded that the SPS
process is an effective and simple technique for the fabrication of a
C12A7 electride.
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