Mössbauer investigations of the surface state of hexagonal ferrites Sr-M near the curie point

The temperature dependence of the parameters of the hyperfine interaction in the surface layers and in the bulk of macroscopic crystals of hexagonal ferrites of the type Sr-M (SrFe₁₂O₁₉) is investigated by the method of simultaneous gamma-, x-ray, and electron Mössbauer spectroscopy. It is shown experimentally that the transition of an ≈ 200 nm thick surface layer of macroscopic ferromagnets to the paramagnetic state occurs at a temperature 3° below the Curie point (T _c) for the bulk of the crystal. It was established that the transition temperatureT _c(L) of a thin layer localized at a depthL from the surface of the crystal increases away from the surface and reaches the valueT _c at the lower (away from the surface) boundary of the so-called “critical” surface layer. A nonuniform state in which the bulk region of the crystal is magnetically ordered while the surface region is disordered is observed nearT _N.     

Magnetic states of the surface and bulk of ferrites near a phase transition at the Curie temperature

Investigations of the magnetic state of a surface layer ~200 nm thick and of the bulk in macroscopic ferrite crystals of the type Ba-M (BaFe₁₂O₁₉) are performed in the phase transition region around the Curie temperature (T _c). The method of simultaneous gamma, x-ray, and electron Mössbauer spectroscopy, which made it possible to compare directly the phase states of the surface and bulk of the sample, is used for the measurements. It is observed experimentally that in BaFe₁₂O₁₉ the transition of a surface layer ~200 nm thick to the paramagnetic state occurs at temperatures below T _c. It is established that the transition temperature T _c(L) of a thin layer localized at depth L from the surface of the crystal increases with distance from the surface and reaches the value T _c at the lower boundary of the “critical” surface layer. Therefore, near T _c a nonuniform state in which the crystal is magnetically ordered in the bulk but disordered at the surface is observed. A phase diagram of the states of the surface and of the bulk of macroscopic magnets near the Curie (or Néel) point is proposed on the basis of all the experimental results obtained in the present work as well as previously published results.     

Critical behavior of the surface of FeBO3 single crystals

The behavior of the surface and near-surface layers of macroscopic FeBO₃ single crystals is studied over the temperature range from 291 K to Neél temperature (T _N ) using depth-selective conversion-electron Mössbauer spectroscopy. Three different phases or states, namely, an antiferromagnetically ordered phase (similar to the crystal bulk state), a surface phase, and a transition layer between them coexist near the Neél point in a surface layer ～500 nm thick. The critical parameters found for the bulk phase agree well with the theoretical critical index ν_th?0.63 predicted by the 3D Ising model. As the crystal surface is approached, the critical parameter β increases to 0.51(2) but remains smaller than the value of β=0.8 for the surface of a semi-infinite Heisenberg model. Therefore, the effective dimensionality of the system, being equal to 3 in the bulk, decreases at the crystal surface.     

Surface magnetism of Al-substituted Sr-M-type hexagonal ferrites

The surface and bulk magnetic structures of Sr-M-type single-crystal hexagonal ferrites (with the chemical formula SrFe_12?x Al_xO₁₉) have been directly compared by simultaneous gamma, x-ray, and electron Mössbauer spectroscopy. It was found, that when the magnetic lattice of Sr-M hexagonal ferrites is slightly diluted by diamagnetic Al ions, namely, for x=1.8 (SrFe_10.2Al_1.8O₁₉), a ～300-nm thick macroscopic anisotropic layer forms on the crystal surface, wherein iron-ion magnetic moments are oriented differently from those in the bulk of the sample. The reason for the onset of a noncollinear magnetic structure in the surface layer of SrFe_10.2Al_1.8O₁₉ crystals is the additional lowering of the exchange interaction energy caused by the presence of such a “defect” as the surface. Thus an anisotropic surface layer predicted theoretically by L. Néel in 1954 has been detected in ferromagnetic crystals.     

Simultaneous gamma, x-ray, and electron Mössbauer spectroscopy of the volume and surface magnetic structure of hexagonal M-ferrites

Direct comparative studies are made between the magnetic structures of a surface layer of thickness ～40 nm and the bulk magnetic structure of ferromagnetic single crystals of hexagonal M ferrites (BaFe₁₂O₁₉, SrFe₁₂O₁₉, PbFe₁₂O₁₉) with a magneto-plumbite structure. Measurements are made by simultaneous gamma, x-ray, and electron Mössbauer spectroscopy in order to investigate the properties of the surface layer and the bulk crystal simultaneously. Experimental data obtained with a depth resolution of ～ 10 nm show that the orientation of the magnetic moments of the iron ions (along the crystallographic c axis) does not change on approaching the surface from the crystal volume. Thus, to within an experimental error of ～ 10 nm, single crystals of the hexagonal ferrites BaFe₁₂O₁₉, SrFe₁₂O₁₉, and PbFe₁₂O₁₉ with a ferromagnetic structure do not have a “ transition” surface layer whose magnetic structure differs from that of the bulk crystal such as that which exists, with a depth of several hundred nm, in antiferromagnetic materials with weak ferromagnetism.     

Influence of surface on the effective magnetic fields in α-Fe2O3 and FeBO3

First measurements of the effective magnetic fields as a function of the depth at which the iron ions are in the surface layer of α-Fe₂O₃ and FeBO₃ single crystals are reported. The method used is the depth-selective conversion-electron Mössbauer spectroscopy. An analysis of experimental spectra revealed that the magnetic properties of the crystal surface vary smoothly from the bulk to surface characteristics within a layer ～100 nm thick. The layers lying below ～100 nm from the surface are similar in properties to the bulk of the crystal, and their spectra consist of narrow lines. The spectral linewidths increase smoothly as one approaches the crystal surface. The spectra obtained from a ～10-nm thick surface layer consist of broad lines indicating a broad distribution of effective magnetic fields. Calculations show that the field distribution width in this layer is δ=2.1(3) T, for an average value H _eff=32.2(4) T. It has been experimentally established that, at room temperature (291 K), the effective magnetic fields smoothly decrease as one approaches the crystal surface. The effective fields in a 2.4(9)-nm surface layer of α-Fe₂O₃ crystals are lower by 0.7(2)% than the fields at the ion nuclei in the bulk of the sample. In the case of FeBO₃, the effective fields decrease by 1.2(3)% in a surface layer 4.9(9) nm thick.     

Investigations of the magnetic structure of the surface and volume of aluminum-substituted Sr-M type hexaferrites

The magnetic structure of the surface layer of single crystals of hexagonal ferrites of the type Sr-M (SrFe₁₂O₁₉) in which some iron ions are replaced by diamagnetic Al ions is investigated, in direct comparison with the magnetic structure in the bulk of the sample, by the method of simultaneous gamma, x-ray, and electron Mössbauer spectroscopy. It is found that under conditions of diamagnetic dilution of the magnetic lattice of hexagonal ferrites of the type Sr-M by Al ions, a layer ~200 nm thick in which the orientation of the magnetic moments is not collinear with the direction of the moments in the bulk of the sample is observed on the surface of SrFe_10.2Al_1.8O₁₉ crystals. Thus a “transitional” surface layer has been observed on macroscopic ferromagnetic crystals.     

Mössbauer studies of the surface and bulk magnetic structure of scandium-substituted Ba-M-type hexaferrites

A direct comparison of the magnetic structures of a surface layer and of the bulk of Ba-M-type hexagonal ferrites with iron ions partially replaced by Sc diamagnetic ions (BaFe_12?x Sc_xO₁₉) has been made by simultaneous Mössbauer spectroscopy with detection of gamma rays, characteristic x-ray emission, and electrons. It has been found that, if the magnetic lattice of a Ba-M-type hexagonal ferrite is weakly diluted by Sc diamagnetic ions, a ～300-nm thick macroscopic layer forms on the surface of a BaFe_11.4Sc_0.6O₁₉ crystal, in which the iron-ion magnetic moments are noncollinear with the moments in the bulk. The noncollinear magnetic structure forms in the near-surface layer of BaFe_12?x Sc_xO₁₉ crystals because the exchange interaction energy is additionally reduced by the presence of such a “defect” as the surface. This is the first observation in ferromagnetic crystals of an anisotropic surface layer whose magnetic properties, as predicted by Néel, differ from those of the bulk.     

Mössbauer studies of the surface and bulk properties of substituted iron-garnet films in the vicinity of the Curie point

The magnetic properties of the surface layer and bulk of iron-garnet films of composition Y_2.6Sm_0.4Fe_3.7Ga_1.3O₁₂, grown by liquid-phase epitaxy on substrates of a gadolinium-gallium garnet single crystal, are investigated. The method of simultaneous gamma-ray, x-ray, and electron Mössbauer spectroscopy is used for the investigations. It is found that the temperature T _c(L) of the transition to the paramagnetic state of a thin layer localized at a depth L below the surface within ～300 nm decreases smoothly with decreasing distance from the surface. The causes of the difference between the temperature of the transition to the paramagnetic state in the surface layer and that bulk of the film are: 1) variation of the degree of substitution of gallium for iron in the surface layer; 2) weakening of exchange interactions at the surface of the sample.     

Magnetic state of a system of barium hexaferrite nanocrystals in the vicinity of the curie temperature

In order to study the magnetic state of a system of nanocrystals of highly anisotropic hexagonal barium ferrite in the vicinity of the Curie temperature, a macrocrystal surface layer comparable in thickness to the particles of the system is chosen as a model. As revealed by simultaneous application of gamma-, x-ray, and electron Mössbauer spectroscopy, the transition of a ～200-nm-thick surface layer to the paramagnetic state starts 55 K and is complete 3 K below the Curie temperature of the bulk of the crystal. This temperature range overlaps the range where the particles transfer from the magnetically stable to the superparamagnetic state. The data obtained made it possible to refine the high-temperature part of the H-T diagram for particles with a close-to-critical volume. The regions of the diagram where mixed magnetic states originating simultaneously from the size and surface factors coexist are identified.     

Surface and volume phase states of Fe<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ga<Subscript>x</Subscript>BO<Subscript>3</Subscript> crystals in the vicinity of the Néel point

The behavior of the magnetic system of a surface layer of macroscopic Fe_1?xGa_xBO₃ crystal (x=0, 0.3) in the vicinity of the Néel temperature T_N was studied. The studies were made by a method involving simultaneous gamma, x-ray, and electron Mössbauer spectroscopy that made it possible to obtain information simultaneously from surface layers and from the bulk of a macroscopic crystal. It was found that the temperature T_N(L) at which a thin layer at a depth L from the surface switches to a disordered state is lower than T_N for the bulk and is lower the closer this layer is to the surface. In the vicinity of T_N, a nonuniform state is observed in which the bulk of the crystal is magnetically ordered and the surface layer is disordered. The transition temperature T_N(L) decreases from T_N to its surface value within a surface layer of a “critical” thickness.     

Piezoelectric effect in the LaBGeO<Subscript>5</Subscript> ferroelectric crystal

Room-temperature piezoelectric moduli of a new high-temperature ferroelectric crystal, LaBGeO₅ (LBGO), are for the first time determined experimentally. It is shown that the piezoactivity of this crystal is close to that of quartz. Comparative analysis of temperature dependences of spontaneous polarization and spontaneous deformation was carried out, and the piezomoduli were measured at room temperature. Based on these data, it was shown that this crystal, which undergoes the change of symmetry 32 → 3 during the phase transition (T _c = 533°C), is not a multiferroelectric. Its “transient” piezomoduli should not undergo noticeable anomalies at the Curie point, and the dependence d _3i ～ (T _c ? T)^?1/2, which is common for uniaxial ferroelectrics, is expected for morphic piezomoduli associated with polarization along axis 3.     

Thermal expansion of single crystal Tb-50% Ho in the vicinity of the Curie temperature

Measurement of c-axis strain made during the cooling of single crystal Tb-50% Ho indicate a Curie temperature of 73.7 ± 0.1 K, approximately 8 K lower than previous observations. On raising the temperature T_c increases, depending on previous thermal history. The abrupt change in c-axis parameter at T_c is ～ 54% smaller than the corresponding change in dysprosium.     

Electret states and the phase transition in a surface layer of the TlGaSe2 ferroelectric semiconductor

The electret polarization is investigated in the TlGaSe₂ ferroelectric semiconductor. It is proved for the first time that stable internal electric fields associated with residual electret polarization are induced in crystals of the TlGaSe₂ ferroelectric semiconductor at temperatures T < 200 K. It is experimentally established that the peak of the pyroelectric current measured in the vicinity of the phase transition to the ferroelectric polar phase depends substantially on the temperature at which the external electric field is switched off when the TlGaSe₂ ferroelectric crystal under investigation is preliminarily cooled from room temperature. The results obtained are discussed in the framework of a model according to which internal electret fields are induced by charges localized at different levels in the bulk and on the surface of the TlGaSe₂ ferroelectric crystal. These fields drastically change at temperatures in a narrow range near 135 K. The inference is made that a phase transition occurs in the surface layer of the TlGaSe₂ crystal at a temperature close to ～135 K.     

The superconducting transition temperature of bulk samples of the niobium-germanium A15-phase after implantation of Ge,Si, O and Ar ions

Bulk material of Nb₃ (Ge_0.8Nb_0.2) with A15 structure and a superconducting transition temperature T_c of 6.5 K has been implanted with Ge, Si, Ar and O ions and subsequently annealed at high temperatures. After annealing between 700 and 750°C the Ge implanted samples showed a strong increase in T_c up to 16.2 K. With Si ions only a T_c of 13 K was obtained, with Ar and O ions T_c remained below 9 K. From X-ray measurements carried out on high T_c Ge implanted samples it could be concluded that the implanted surface layer grows up to a high degree epitaxially on the single crystallites of the bulk material. The lattice constant $\text{a}$₀ of the implanted film was reduced by 0.02 Å with respect to the bulk material. This reduction in $\text{a}$₀ is stronger than expected from the transition temperature of the implanted surface layer.     

Specific features of the central peak in the Raman spectra of a lithium niobate crystal

The low-frequency Raman scattering (RS) spectra of a LiNbO₃ ferroelectric crystal are studied in the temperature range 300–1423 K. The central peak characterizing the relaxation susceptibility of the crystal lattice is observed over the entire temperature range studied, including at temperatures much lower than the Curie temperature (T _c = 1470 K). Far from T _c, the characteristics of the central peak are shown to be unlike those expected in the framework of the standard approaches. (i) The central-peak width γ_R increases as the temperature increases to T ～ 1300 K, and the critical slowing down (γ_R ∝ T _c ? T) occurs only above this temperature. (ii) A central peak arises in the RS geometry where the scattering by “nonferroelectric” E phonons is allowed. The experimental results are interpreted with allowance for relaxation dynamics in local regions of the crystal lattice.     

Spin-reorientation phase transition on the surface and in the bulk of α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> single crystals

Direct comparison of the properties of a thin surface layer and the bulk of macroscopic hematite (α-Fe₂O₃) crystals was used to study the magnetic structure of the surface layer and the bulk and the processes attendant on spin-reorientation phase transition (SRT). The investigation tool was simultaneous γ-ray, X-ray, and electronic Mössbauer spectroscopy, which enabled us to study the bulk and surface properties of macroscopic samples simultaneously and to compare them directly. Direct evidence of the existence of a surface “transition layer” on hematite crystals is obtained. The existence of this layer was suggested and described by Krinchik and Zubov [JETP 69, 707 (1975)]. The study in the SRT region showed that (1) the Morin SRT in the crystal bulk occurs in a jump (as a first-order phase transition), whereas in the surface layer of about 200 nm thick, some smoothness appears in the mechanism of magnetic-moment reorientation; (2) SRT in the surface layer, as in the bulk, involves an intermediate state in which low-and high-temperature phases coexist; and (3) SRT in the surface layer occurs at a temperature several degrees higher than in the bulk. Our experimental evidence on the SRT mechanism in the surface layer correlates with the inferences from phenomenological theory developed by Kaganov [JETP 79, 1544 (1980)].     

Temperature dependent energy-dispersive X-ray diffraction and magnetic study of Fe/Al interface

In situ temperature dependent energy-dispersive structural and magnetic study of electron beam evaporated Fe/Al multilayer sample (MLS) has been investigated. The structural studies show the formation of an intermixed FeAl transition layer of a few nanometers thick at the interface during deposition, which on annealing at 300 °C transforms to B2FeAl intermetallic phase. Magnetization decreases with increase in temperature and drops to minimum above 300 °C due to increase in anti-ferromagnetic interlayer coupling and formation of nonmagnetic FeAl phase at the interface. The Curie temperature (T_c) is found to be 288 °C and is much less than that of bulk bcc Fe.     

Kinetic effects in an La0.8Ba0.2MnO3 single crystal

Results are presented of a complex study of the magnetic and resistive properties, the Hall effect, the thermal emf, and the longitudinal Nernst-Ettingshausen effect of an La_0.8Ba_0.2MnO₃ single crystal at temperatures between 77 and 400 K. A maximum was observed near the Curie temperature T _c on the temperature dependences of the resistivity, the thermal emf, and the normal Hall coefficient. It was established that the Hall mobility remains constant near T _c. It is shown that these anomalies in the kinetic properties are attributable to a change in the position of the mobility edge relative to the Fermi level. A semiphenomenological theory is put forward to quantitatively describe the temperature and magnetic-field dependences of the resistivity and thermal emf of lanthanum manganites near the phase-transition temperature.     

Magnetostriction and thermal expansion anomalies near the Curie point of the compound La0.7Sr0.3MnO3 with the perovskite structure

It is found that the bulk part ω of the magnetostriction near the Curie temperature T _c in a La_0.7Sr_0.3MnO₃ single crystal with the perovskite structure is negative and that the temperature dependence of |ω| has a maximum near T _c . The quantity |ω| at the maximum increases rapidly with increasing magnetic field. The thermal expansion coefficient near T c increases with temperature much faster than linearly. The paramagnetic Curie temperature determined from the Curie-Weiss law, which the paramagnetic susceptibility of this crystal satifies, was found to be lower than T _c . These anomalies and also the near-T _c metal-insulator transition which is characteristic for this material are explained by the existence of a magnetically two-phase state consisting of a conducting ferromagnetic matrix containing antiferromagnetic insulating microregions occupying not more than 5% of the sample volume. Pis’ma Zh. éksp. Teor. Fiz. 65, No. 6, 449–453 (25 March 1997)