Physica B xxx (xxxx) xxx–xxx

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Physica B
journal homepage: www.elsevier.com/locate/physb

Pressure induced superconductivity in very lightly doped

LaFeAsO0.975F0.025
⁎ ⁎
K. Miyoshia, , K. Otsukaa, A. Shiotaa, Y. Shimojoa, G. Motoyamaa, K. Fujiwaraa, H. Kitagawaa, ,
⁎
S. Nishigorib,
a
Department of Materials Science, Shimane University, Matsue 690-8504, Japan
b
Department of Materials Analysis, ICSR, Shimane University, Matsue 690-8504, Japan

A R T I C L E I N F O A BS T RAC T

Keywords: We have investigated whether or not superconductivity is induced by the application of pressure in very lightly
Superconductivity F-doped LaFeAsO1−x Fx , which shows spin density wave (SDW) state at ambient pressure, through the
Iron-pnictides measurements of DC magnetization and electrical resistivity under pressure using pulse current sintered
LaFeAsO (PCS) high density polycrystalline specimens. It has been confirmed that the specimens with x = 0.025 shows
High pressure
superconductivity with Tcdia ∼ 15 K under pressure above ∼ 1.3 GPa. The pressure induced superconductivity
can be explained by the lattice compression along c-axis, which enhances the electron doping from LaO layers to
FeAs layers.

1. Introduction
A great deal of effort has been made to understand the paring
mechanism in iron-pnictide superconductors and explore high Tc
superconductivity in the related compounds. Indeed, iron-pnictide
superconductor is known to comprise a wide variety of materials,
e.g., RFeAsO1−x Fx (R = lanthanoid) [1,2], Ba1−x KxFe 2 As2 [3,4], LiFeAs
(Tc = 18 K ) [5,6], FeSe (Tc = 8 K ) [7], and K 0.8Fe 2 Se 2 (Tc = 32 K) [8]
with Tc ranging from 8 K to 55 K, where the superconductivity is
developed in iron-pnictide (Fe-Pn) layers consisting of edge-sharing
FePn 4 tetrahedron. Among these, LaFeAsO1−x Fx (Tc = 26 K) is the first
iron-arsenide compound to be found to exhibit superconductivity [1].
In this system, superconductivity is induced by electron doping into
FeAs layers, which is realized by substituting O by F in LaO layers. In
non-doped LaFeAsO, a structural phase transition from tetragonal to
orthorhombic structure occurs at To = 160 K [9], which is followed by a
magnetic phase transition into spin density wave (SDW) state at
TSDW = 140 K [9,10]. These transitions are known to be suppressed
with the appearance of superconductivity by F doping [11].
In iron-pnictide compounds, superconductivity can be also induced
by the application of pressure, not only by carrier doping, as seen in
AFe 2 As2 (A = Ba [12,13], Sr [12,14–16] and so on), where spin-
density-wave (SDW) state with orthorhombic structure disappears and
superconductivity with tetragonal structure appears under pressure.
Also, recent measurements under pressure on FeSe have revealed the
interesting temperature-pressure (T − P ) phase diagram, in which Tc
increases in three steps under pressure with the appearance of nematic
or SDW phase [17,18]. Pressure induced superconductivity in non-
doped LaFeAsO has been previously investigated by some groups but
the critical pressure Pc above which superconductivity is induced varies
depending on the report [19,20], probably due to the difference of
oxygen deficiency in the samples. The relation between superconduc-
tivity and SDW or nematic phase in the T − P phase diagram remains
unclear and will be an interesting subject to be solved to throw further
light on the paring mechanism of the superconductivity in iron-
pnictide compounds.
In the present work, we have synthesized very lightly doped pulse
current sintered (PCS) polycrystalline specimens of LaFeAsO1−x Fx with
x = 0.025 and performed the measurements of dc magnetization and
electrical resistivity under pressure. We report whether or not super-
conductivity is induced by the application of pressure in the specimens.
It is expected that the very lightly doping lowers Pc and enables us to
establish the T − P phase diagram by the measurements under
relatively low pressure in the future study.
2. Experimental
Powder samples of LaFeAsO1−x Fx (0 ≤ x ≤ 0.04 ) were synthesized by
a solid state reaction technique [21] heating the heating pelletized
mixtures of LaAs, Fe, Fe2O3 and FeF2 powders at 1200 °C for 12 h in a
Ta container, which is put into an evacuated silica tube. LaAs was
prepared by reacting La and As powders in an evacuated silica tube at

⁎
Corresponding authors.
E-mail address: miyoshi@riko.shimane-u.ac.jp (K. Miyoshi).

http://dx.doi.org/10.1016/j.physb.2017.09.080
Received 29 June 2017; Received in revised form 30 August 2017; Accepted 18 September 2017
0921-4526/ © 2017 Elsevier B.V. All rights reserved.

Please cite this article as: Miyoshi, K., Physica B (2017), http://dx.doi.org/10.1016/j.physb.2017.09.080
K. Miyoshi et al. Physica B xxx (xxxx) xxx–xxx

Fig. 1. The Rietveld refinement pattern and difference plots of the powder X-ray
diffraction data for pulse current sintered (PCS) specimens of LaFeAsO1−x Fx (x = 0.025)
at room temperature. The rows of ticks indicate the Bragg-peak positions for the main
phase.

250–1000 °C , as described in the literature [22]. These operations were

carried out in an Ar atmosphere. High density polycrystalline samples
of LaFeAsO1−x Fx were prepared by a pulse current sintering (PCS)
technique, which is known commercially as spark plasma sintering,
allows ceramics and metal powders to be sintered at low temperature
for short time. The details are shown in the literature [23]. The
sintering condition for LaFeAsO1−x Fx powders were at 40 MPa and
1150 °C for 10 min, resulting more than 95% of theoretical density.
Fig. 1 shows a powder X-ray diffraction for LaFeAsO1−x Fx with x =
0.025 after the PCS process. The diffraction data are analyzed by
Rietveld refinement, yielding lattice parameters of a = 4.0269(0) Å and
c = 8.7185(6) Å. Measurements of DC magnetization under pressure
were performed by a miniature diamond anvil cell (DAC) combined
with a sample rod of a commercial SQUID magnetometer. Details of
the DAC are given in elsewhere [24]. A small piece of polycrystalline
specimen was loaded into the gasket hole together with a small piece of
high-purity lead (Pb) to determine the pressure from the Tc shift of Pb.
The measurements have been successfully applied to study other
superconductors under pressure [17,25–27]. Measurements of elec-
trical resistivity were carried out by a four probe technique under
pressure using piston cylinder type cell. As pressure transmitting
media, we used Daphne oil 7373.
3. Results and discussion
In this paper, we show the experimental results for LaFeAsO1−x Fx
PCS specimens with x = 0.025 and report the pressure induced
superconductivity. It should be noted that our specimens with x
≥0.05 were found to be superconducting at ambient pressure but those
with 0.015 ≤ x ≤ 0.035 were confirmed to show a pressure induced
superconductivity above the critical pressure Pc . We also found that Pc
tends to increase for smaller x but it decreases after PCS process
probably due to the increase of oxygen deficiencies or the additional F-
doping realized by heating some remaining unreacted FeF2 in the
process.
We show zero-field-cooled magnetization (M) versus temperature
(T) data for LaFeAsO1−x Fx PCS specimen with x = 0.025 under various
pressure (P) up to ∼ 5 GPa in Figs. 2(a) and (b). In the figure, it is
found that the M-T curves at P = 1.07 and 1.18 GPa does not show any
signature of the emergence of diamagnetic magnetization but that at P
= 1.37 GPa clearly exhibits a diamagnetic response below Tcdia ∼ 14 K,
indicating that superconductivity is induced by the application of
pressure above Pc ∼ 1.3 GPa. With increasing pressure, Tcdia shows no
remarkable change and an almost constant value of ∼15 K up to P
∼5 GPa. The amplitude of diamagnetic magnetization is also found to
be almost unchanged up to P ∼5 GPa. Although we cannot estimate the
magnetization amplitude per unit sample mass in the present study,
the amplitude is thought to be fairly smaller than that for bulk
superconductivity, comparing with the amplitude of diamagnetic
Fig. 2. Temperature dependence of zero-field-cooled DC magnetization for pulse current
sintered specimens of LaFeAsO1−x Fx (x = 0.025) measured in a magnetic field of 20 Oe
under various pressures below 2.86 GPa (a) and above 3.31 GPa (b). The measurements
have been done by using Daphne oil 7373 as a pressure transmitting medium (PTM). The
data are intentionally shifted along the longitudinal axis for clarity.
response observed for optimum doped LaFeAsO1−x Fx measured by
using the same miniature DAC in our previous work [25]. Similar
results were reproduced in the measurements using different pieces of
the sample, indicating good sample homogeneity.
In order to confirm the pressure induced superconductivity ob-
served in the PCS specimens with x = 0.025, we have performed the
electrical resistivity ( ρ) measurements under pressure. The results are
shown in Fig. 3. In the figure, the ρ − T curve at ambient pressure
shows a metallic behavior but exhibits a rapid reduction below
TSDW ∼ 120 K, corresponding to the appearance of the spin density
wave state, similar to that observed in non-doped LaFeAsO at
TSDW ∼ 145 K [19]. It has been reported that TSDW for LaFeAsO1−x Fx
decreases with increasing x, showing TSDW ∼ 120 K for x = 0.04 [11],
which is consistent with that for the PCS specimen with x = 0.025. The
ρ − T curve at P = 0.56 GPa shows a similar behavior to that at
ambient pressure but shows a drop below ∼8 K, as seen in the inset of
Fig. 3. Although TSDW appears to be almost unchanged with increasing
pressure, the temperature at which the ρ − T curve shows a marked
drop (≡Tconset ) increases with increasing pressure, and ρ − T curve at P
= 2.3 GPa shows zero resistivity, indicating the superconducting
transition.
In Fig. 4, Tcdia and Tconset are plotted as a function of pressure,
Fig. 3. Temperature dependence of electrical resistivity ( ρ ) under various pressure up to
2.3 GPa for pulse current sintered specimens of LaFeAsO1−x Fx (x = 0.025). The inset
shows an enlarged view of the ρ − T curves at low temperatures.

2
K. Miyoshi et al.
Fig. 4. Pressure dependence of Tcdia and Tconset for the pulse current sintered (PCS)
specimens of LaFeAsO1−x Fx (x = 0.025). Tcdia and Tconset are defined as the temperature
below which the diamagnetic response and the resistive drop is observed, respectively.
indicating the appearance of superconducting phase under pressure
above ∼ 1 GPa. The pressure induced superconductivity can be
explained by the lattice compression along c-axis, which enhances
the electron doping from LaO layers to FeAs layers. Superconductivity
induced by lattice compression along c-axis is a characteristic of non-
doped or very lightly doped system, since Tc has been found to be
enhanced by the lattice extension along a- or c-axises in optimal doped
RFeAsO systems both from experimental and theoretical studies
[25,28]. It is noted that Tconset is observed at lower pressure compared
with Tcdia , suggesting that electrical resistivity is more sensitive for
detecting the formation of local superconducting current network. For
non-doped LaFeAsO, it has been reported in the previous work that
superconductivity is induced under pressure above P ∼ 1.5 GPa and
Tconset determined from the resistive drop in the ρ − T measurements
increases from ∼ 10–20 K with increasing pressure but remains a
nearly constant (∼ 20 K) for 5 ≤ P ≤ 15 GPa [19]. There seems to be
some similarities between these behaviors and the results of the
present work, since Tconset increases with increasing pressure below
2 GPa but Tcdia is nearly constant, as seen in Fig. 4. Electrical resistivity
measurements under high pressure above 2 GPa is desired to clarify
the pressure evolution of superconductivity and also of TSDW .
4. Summary
In the present work, we have performed the measurements of DC
magnetization and electrical resistivity under pressure for very lightly
doped LaFeAsO1−x Fx (x = 0.025) using high density PCS specimens to
confirm whether pressure induced superconductivity is realized or not.
It has been found that superconductivity is induced under pressure and
is observed above ∼1.3 GPa (∼0.5 GPa) with Tcdia ∼ 15 K (Tconset ∼ 8 K),
although the transition at TSDW remains almost unaffected by the
application of pressure of 2.3 GPa. To establish the T − P phase
diagram of LaFeAsO1−x Fx will be an interesting subject of the future
study. For the purpose, it is essential to investigate the pressure
variation of the transition at TSDW under higher pressure.
Physica B xxx (xxxx) xxx–xxx
Acknowledgment
This work is supported by the technical staff at Department of
Materials Analysis, ICSR, Shimane University. The authors thank H.
Katsube, Y. Kida, and S. Tsuchiya for experimental help.
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