Two iron-chalcogenide superconductors Li(x)[C5H5N](y)Fe(2-z)Se2 and Cs(x)Fe(2-z)Se2 in the as-prepared and annealed state have been investigated by means of the Moessbauer spectroscopy versus temperature. Multi-component spectra are obtained. One can
see a non-magnetic component due to iron located in the unperturbed Fe-Se sheets responsible for superconductivity. Remaining components are magnetically ordered even at room temperature. There is some magnetically ordered iron in Fe-Se sheets perturbed by presence of the iron vacancies. Additionally, one can see iron dispersed between sheets in the form of magnetically ordered high spin trivalent ions, some clusters of above ions, and in the case of pyridine intercalated compound in the form of alpha-Fe precipitates. Pyridine intercalated sample shows traces of superconductivity in the as-prepared state, while cesium intercalated sample in the as-prepared state does not show any superconductivity. Superconductors with transition temperatures being 40 K and 25 K, respectively, are obtained upon annealing. Annealing leads to removal/ordering of the iron vacancies within Fe-Se sheets, while clusters of alpha-Fe grow in the pyridine intercalated sample.
The compound BaFe2Se3 (Pnma) has been synthesized in the form of single crystals with the average composition Ba0.992Fe1.998Se3. The Moessbauer spectroscopy used for investigation of the valence states of Fe in this compound at temperature ranging fr
om 4.2 K till room temperature revealed the occurrence of mixed-valence state for iron. The spectrum is characterized by sharply defined electric quadrupole doublet above magnetic ordering at about 250 K. For the magnetically ordered state one sees four iron sites at least and each of them is described by separate axially symmetric electric field gradient tensor with the principal component making some angle with the hyperfine magnetic field. They form two groups occurring in equal abundances. It is likely that each group belongs to separate spin ladder with various tilts of the FeSe4 tetrahedral units along the ladder. Two impurity phases are found, i.e., superconducting FeSe and some other unidentified iron-bearing phase being magnetically disordered above 80 K. Powder form of BaFe2Se3 is unstable in contact with the air and decomposes slowly to this unidentified phase exhibiting almost the same quadrupole doublet as BaFe2Se3 above magnetic transition temperature.
The Fe(1+x)Sb compound has been synthesized close to stoichiometry with x = 0.023(8). The compound was investigated by 57Fe Mossbauer spectroscopy in the temperature range 4.2 - 300 K. The antiferromagnetic ordering temperature was found as 232 K i.e
. much higher than for the less stoichiometric material. Regular iron was found to occupy two different positions in proportion 2:1. They differ by the electric quadrupole coupling constants and both of them exhibit extremely anisotropic electric field gradient tensor (EFG) with the asymmetry parameter equal one. The negative component of both EFGs is aligned with the c-axis of the hexagonal unit cell, while the positive component is aligned with the <120> direction. Hence, a model describing deviation from the NiAs P63/mmc symmetry group within Fe-planes has been proposed. Spectra in the magnetically ordered state could be explained by introduction of the incommensurate spin spirals propagating through the iron atoms in the direction of the c-axis with a complex pattern of the hyperfine magnetic fields distributed within a-b plane. Hyperfine magnetic field pattern of spirals due to major regular iron is smoothed by the spin polarized itinerant electrons, while the minor regular iron exhibits hyperfine field pattern characteristic of the highly covalent bonds to the adjacent antimony atoms. The excess interstitial iron orders magnetically at the same temperature as the regular iron, and magnetic moments of these atoms are likely to form two-dimensional spin glass with moments lying in the a-b plane. The upturn of the hyperfine field for minor regular iron and interstitial iron is observed below 80 K. Magneto-elastic effects are smaller than for FeAs, however the recoilless fraction increases significantly upon transition to the magnetically ordered state.
A review of the magnetism in the parent compounds of the iron-based superconductors is given based on the transmission Moessbauer spectroscopy of 57Fe and 151Eu. It was found that the 3d magnetism is of the itinerant character with varying admixture
of the spin-polarized covalent bonds. For the 122 compounds a longitudinal spin density wave (SDW) develops. In the case of the EuFe2As2 a divalent europium orders antiferromagnetically at much lower temperature as compared to the onset of SDW. These two magnetic systems remain almost uncoupled one to another. For the non-stoichiometric Fe(1+x)Te parent of the 11 family one has a transversal SDW and magnetic order of the interstitial iron with relatively high and localized magnetic moments. These two systems are strongly coupled one to another. For the grand parent of the iron-based superconductors FeAs one observes two mutually orthogonal phase-related transversal SDW on the iron sites. There are two sets of such spin arrangements due to two crystallographic iron sites. The FeAs exhibits the highest covalency among compounds studied, but it has still a metallic character.
The optimally doped 122 iron-based superconductor Ba(0.6)K(0.4)Fe2As2 has been studied by 57Fe Moessbauer spectroscopy versus temperature ranging from 4.2 K till 300 K with particular attention paid to the superconducting transition around 38 K. The
spectra do not contain magnetic components and they exhibit quasi-continuous distribution of quadrupole split doublets. A distribution follows the electric field gradient (EFG) spatial modulation (wave) - EFGW. The EFGW is accompanied by some charge density wave (CDW) having about an order of magnitude lesser influence on the spectrum. The EFGW could be modeled as widely separated narrow sheets with the EFG increasing from small till maximum value almost linearly and subsequently dropping back to the original value in a similar fashion - across the sheet. One encounters very small and almost constant EFG between sheets. The EFGW shape and amplitude as well as the amplitude of CDW are strongly affected by a superconducting transition. All modulations are damped significantly at transition (38 K) and recover at a temperature being about 14 K lower. The maximum quadrupole splitting at 4.2 K amounts to about 2.1 mm/s, while the dispersion of CDW seen on the iron nuclei could be estimated far away from the superconducting gap opening and at low temperature as 0.5 el./a.u.^3. It drops to about 0.3 el./a.u.^3 just below transition to the superconducting state.
