Slajd 1 - Mössbauer Spectroscopy Division

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Superconducting FeSe studied by Mössbauer spectroscopy
and magnetic measurements
A. Błachowski 1, K. Ruebenbauer 1, J. Żukrowski 2, J. Przewoźnik 2,
K. Wojciechowski 3, Z.M. Stadnik 4
1
2 Solid
Mössbauer Spectroscopy Division, Institute of Physics,
Pedagogical University, Cracow, Poland
State Physics Department, Faculty of Physics and Applied Computer Science,
AGH University of Science and Technology, Cracow, Poland
3 Department
of Inorganic Chemistry, Faculty of Material Science and Ceramics,
AGH University of Science and Technology, Cracow, Poland
4 Department
of Physics, University of Ottawa, Ottawa, Canada
Fe-Se phase diagram
The following phases form close to the FeSe stoichiometry:
1) tetragonal P4/nmm structure similar to PbO, called α-FeSe (or β-FeSe)
2) hexagonal P63/mmc structure similar to NiAs, called β-FeSe (or δ-FeSe)
3) hexagonal phase Fe7Se8 with two different kinds of order, i.e., 3c (α-Fe7Se8) or 4c (β-Fe7Se8)
A tetragonal P4/nmm phase transforms into Cmma
orthorhombic phase at about 90 K,
and this phase is superconducting with Tc ≈ 8 K.
Crystal structure of α-FeSe
Superconductivity has been discovered for compound with excess iron
FeSe0.88
[F.C. Hsu et al., Proc. Natl. Acad. Sci. U.S.A. 105, 14262 (2008)].
Aim of this contribution is to answer two questions concerned with
tetragonal/orthorhombic FeSe:
1) what kind of defects makes excess iron:
interstitial iron Fe1+xSe
or
selenium vacancies FeSe1-x ?
2) is there electron spin density on iron ?
Fe1.05Se (FeSe0.95)
A synthesis was carried at 750°C for 6 days in evacuated silica tube.
Subsequently the sample was slowly cooled with furnace to room temperature.
Resulting ingot was powdered and annealed at 420°C for 2 days in evacuated silica
tube and subsequently quenched in ice water.
Experimental
1) Powder X-ray diffraction pattern was obtained at room temperature by using
Siemens D5000 diffractometer.
2) Magnetic susceptibility was measured by means of the vibrating sample
magnetometer (VSM) of the Quantum Design PPMS-9 system.
3) Mössbauer spectra were collected at room temperature (RT), 80 K, 4.2 K and in
the external magnetic field up to 9 T oriented along the γ-ray beam axis and at
temperatures from the region of superconducting state.
S = 0.46 mm/s
Δ = 0.26 mm/s
S = 0.55 mm/s
Δ = 0.28 mm/s
Magnetic susceptibility measured upon cooling and subsequent warming in field of 5 Oe
- point A corresponds to the spin rotation in hexagonal phase
- region B shows transformation between tetragonal and orthorhombic structures
- point C shows transition to the superconducting state
tetragonal
T (K)
A (%)
S (mm/s) Δ (mm/s)  (mm/s)
RT
91(1)
0.457(1)
0.261(1)
9(1)
0.225(2)
0.418(3)
91
0.564(1)
0.274(1)
9
0.581(4)
0.46(1)
91
0.562(1)
0.283(1)
9
0.586(6)
0.44(1)
80 K
4.2 K
orthorhombic
orthorhombic
and
superconducting
0.147(1)
0.202(2)
0.212(2)
A - relative contributions obtained from RT spectrum
and kept constant in remaining fits
S - total spectral shift versus RT α-Fe
Δ - quadrupole splitting
 - absorber linewidth common for all lines
Change in isomer shift (electron density on Fe nucleus)
for minor doublet (corrected for SOD)
S80 - SRT = +0.25 mm/s
↓ α  0.29 a.u. mm s
ρ80 - ρRT = –0.86 electron a.u.-3
3
1
Mössbauer spectra obtained in external magnetic field aligned with γ-ray beam
Hyperfine magnetic fields on both Fe sites are equal to applied external magnetic field.
Principal component of the electric field gradient (EFG) on Fe nucleus
was found as negative on regular Fe sites,
and seems to be positive for intercalated Fe atoms.
Conclusions
1. Dominant defects for excess iron are formed as intercalated iron
on the octahedral sites between iron selenium layers.
The electron density between iron selenium layers lowers upon
transition to the orthorhombic phase making system more 2-dimensional.
2. There is no net electron spin density in the unit cell. Hence,
there is no magnetic moment on Fe nuclei in the superconducting FeSe.
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