Effect of γ-irradiation on the heat capacity of an [NH2(CH3)2]2 · CuCl4 crystal in the temperature range 80–300 K

The heat capacity of [NH₂(CH₃)₂]₂ · CuCl₄ crystals prior to and after γ-irradiation with doses of 1, 5, 10, and 50 MR is measured by the calorimetric method in the temperature range 80–300 K. It is found that, as the temperature decreases, the temperature dependence C _p (T) exhibits two anomalies which correspond to phase transitions from the incommensurate to the ferroelectric phase at T _c =281 K and from the ferroelectric to the ferroelastic phase at T ₁=255 K. The nature of the anomalies is typical of a first-order phase transition. In addition, a smeared anomaly in the form of a small increase in the heat capacity of the ferroelectric phase is observed at T≈275 K. It is demonstrated that when the dose of γ-irradiation increases, the anomalies decrease in magnitude and the phase transition temperatures are displaced: T _c increases and T ₁ decreases.     

Phase transitions sequence in pyrochlore Cd2Nb2O7 studied by IR reflectivity

The infrared reflectivity of Cd₂Nb₂O₇ single crystal was studied in the temperature interval of 10-540 K, together with complementary dielectric measurements. A ferroelectric soft mode was revealed above the ferroelectric phase transition at T _c = 196 K coupled with a central-mode type dispersion in the near-millimetre range. This proves the mixed displacive and order-disorder nature of the transition. Below T _c many new modes were detected due to lowering of the symmetry, especially below the previously suggested incommensurate transition at 85 K. Discussion of the possible phase transitions based on symmetry considerations is presented with the conclusion that the ferroelectric transition is proper with the F_1u symmetry of the order parameter, whereas the intermediate ferroelastic transition is improper and triggered by the coupling with the ferroelectric order parameter. Received 17 July 2000     

Dielectric Properties of Nanoporous Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Films Filled with Ferroelectric SC(NH<Subscript>2</Subscript>)<Subscript>2</Subscript>

Temperature dependences of permittivity ε′ and third harmonic amplitude γ_3ω of nanocomposites obtained by embedding ferroelectric SC(NH₂)₂ in porous alumina films with pore sizes of 60 and 100 nm are studied. A substantial increase in the temperatures of ferroelectric phase transition T_c1 and T_c2 and that of phase transition T_i from incommensurate phase to paraphase are also observed. The temperatures of all phase transitions are found to rise as pore diameters shrink.     

Second harmonic generation in layered TunS2 in the vicinity of the low-temperature phase transitions

Second-harmonic generation in the ternary layered semiconductor TlInS₂ excited with the wavelength λ = 1.06 μm of YAG: Nd^{3 +} laser is investigated in the temperature range corresponding to the low-temperature phase transitions. It is shown that the intensity of the second-harmonic signal corresponding to the non-linear coefficients d_eff, d₂₁, d₂₂ reveals peculiarities close to the commensurate-incommensurate phase transitions. The temperature hysteresis of the second-harmonic signal in the low-temperature region (below and close to T_i2 = 206K) is explained assuming that an incomplete lock-in transition in TlInS₂ takes place at T_c1 =204K within the temperature range between a ferroelectric (T_c2 = 201K) and an incommensurate (T_i2 = 206 K) phases. It is shown that the monoclinic point group symmetry C₂ is preserved also at temperatures lower than the phase transition temperature Tc4 = 79K to a weak ferroelectric state.     

Anomalous states of the structure of (NH4)2SO4 crystals in the temperature range 4.2–300 K

Crystals of the (NH₄)₂SO₄ ammonium sulfate are studied using x-ray diffractometry. It is revealed that the temperature dependence of the lattice parameters exhibits an anomalous behavior, namely, a global hysteresis, and an anomalous increase in the lattice parameter a and the unit cell volume at temperatures below the ferroelectric phase transition point (T _c=223 K). The series of superstructure reflections observed corresponds to an incommensurate composite structure. Analysis of the temperature behavior of the mismatch parameters for the matrix (host) and superstructure (guest) lattices demonstrates that the (NH₄)₂SO₄ compound undergoes a number of phase transitions, including a transition to a three-dimensionally incommensurate composite phase and transitions to commensurate (along one of the crystallographic directions) composite phases.     

On the ferroelectric phase transition in polytypes of β-TlInS2 crystals

Permittivity measurements and x-ray diffraction study were performed for polytypes c and 2c of β-TlInS₂ crystals in the temperature range T = 160–250 K. Substantial differences are revealed in the temperature, sequence, and character of the structural phase transitions associated with the formation of incommensurate modulated structures and the occurrence of a ferroelectric state in these polytypes.     

The influence of phase transitions in the Rb<Subscript>2</Subscript>CdI<Subscript>4</Subscript> ferroelastic on the exciton absorption spectrum

The parameters of the long-wavelength exciton band for Rb₂CdI₄ films are investigated in the temperature range 90–410 K. It is found that the Rb₂CdI₄ films undergo a sequence of phase transitions at temperatures T_c1=380 K (paraphase → incommensurate phase), T_c2=290 K (incommensurate phase → ferroelastic phase I), and T_c3 = 210 K (ferroelastic phase I → ferroelastic phase II). The parameters of the exciton band (such as the spectral position and the half-width) measured during heating and cooling of the Rb₂CdI₄ film differ significantly. This is especially true for the incommensurate phase. Upon heating of the incommensurate phase, the domain boundaries become frozen, whereas the cooling of this phase is accompanied by the generation of solitons and their pinning, which, in turn, results in a first-order phase transition at the temperature T_c2. It is revealed that the oscillator strength of the exciton band anomalously increases in the range of existence of commensurate phase I (T_c3<-T<-T_c2) due to ordering of the Rb₂CdI₄ crystal lattice.     

Ferroelectricity and phase transition from incommensurate phase into commensurate one in (NH4)2ZnCl4

Phase transition has been found in (NH₄)₂ZnCl₄ at T = 266 ± 0.5 K by NQR method. There is a ferroelectric phase below T_c with a space group P2₁cn and with the trebling of the elementary lattice parameter along the axis c. Above the phase transition temperature in the crystal (NH₄)₂ZnCl₄ an incommensurate phase is realized.     

Soft modes below the incommensurate transition in K2SeO4

A coordinated series of Raman and Brillouin scattering measurements were carried out in K₂SeO₄ with emphasis on temperatures near and below the incommensurate structural phase transition (T_i=129 K). Below the lock-in phase transition (T_c=99 K) Raman scattering from both the amplitude mode and the phase mode analog was observed. However, only the amplitude mode could be followed into the incommensurate phase. Details of the amplitude mode frequency and damping are reported for temperatures considerably closer to T_i than previously possible. Our results do not confirm the diverging linewidth extrapolated from earlier Raman work. We also report here the first Brillouin scattering results in K₂SeO₄. Although substancial interaction effects between the acoustic phonons and the soft amplitude mode are evident near T_i, the coupled mode lineshapes can be well described without the introduction of a relaxing self energy for the soft mode. Finally, limits on the characteristics of the phason are drawn from our failure to observe it directly in the incommensurate phase.     

Transferred hyperfine field of Rb2CoCl4 single crystals in the ferroelectric-incommensurate-normal phase by Rb NMR

The molecular susceptibility and paramagnetic shift of Rb₂CoCl₄ single crystals grown using the slow evaporation method were measured, and from these experimental results we obtained the transferred hyperfine interaction due to the transfer of spin density from Co²⁺ ions to Rb⁺ ions. The transferred hyperfine field was obtained for the ferroelectric, incommensurate, and normal phases. In the case of Rb(I), the transferred hyperfine interaction decreases with increasing temperature in the incommensurate phase, and increases with increasing temperature in the normal phase. The value of H_hf in the incommensurate and normal phases increases abruptly with increasing temperature in the case of Rb(II). These results indicate that the effects due to the transfer of spin density from Co²⁺ ions to the Rb(I) and Rb(II) ions are large above T_i. In particular, the effect due to the transfer of spin density to Rb(II) ions in the normal phase is very large; the variations with temperature of the transferred hyperfine interactions of the Rb(I) and Rb(II) nuclei are more or less continuous in T_c1 and T_i, and are not affected by the ferroelectric-incommensurate-normal phase transitions.     

Anomalous states of the crystal structure of (Rb0.1(NH4)0.9)2SO4 solid solutions in the temperature range 4.2–300 K

Crystals of (Rb_0.1(NH₄)_0.9)₂SO₄ solid solutions are studied using x-ray diffractometry. It is revealed that the temperature dependence of the lattice parameter a exhibits an anomalous behavior, namely, the “invar effect” at temperatures above the ferroelectric phase transition point T _c and an anomalous increase in the temperature range from T _c to the liquid-helium temperature. An anomalous increase in the lattice parameter a and an increase in the intensity of Bragg reflections with a decrease in the temperature are interpreted within the model of the coexistence of two sublattices hypothetically responsible for the ferroelectric phase transition. A series of superstructure reflections observed along the basis axes corresponds to a sublattice formed in the matrix of the host structure. Analysis of the ratio between the lattice parameters of these structures allows the inference that, in the temperature range 4.2–300 K, the structure of the crystal under investigation can be considered an incommensurate single-crystal composite.     

Effect of electron irradiation on the heat capacity of [NH2(CH3)2]2 · CuCl4 in the phase transition region

The specific heat of crystalline [NH₂(CH₃)₂]₂ · CuCl₄ in the ferroelectric phase, both nonirradiated and irradiated by electrons, was measured calorimetrically. The temperature region of existence of the ferroelectric phase was shown to broaden under electron irradiation. The existence of an incommensurate phase above the Curie point T _c1 in the crystal was confirmed. The phase-transition sequence observed in [NH₂(CH₃)₂]₂ · CuCl₄ is shown to be described by a phenomenological model for A ₂ BX ₄-type ferroelectrics with an organic cation.     

Influence of polytypism on structural phase transformations in TlGaSe2 crystals

The polytypism is found to have a significant influence on the structural transformation of the crystal lattice of the TlGaSe₂ ferroelectric with variations in temperature. In the 2C-polytype, unlike the C-polytype, a first-order structural phase transition, which leads to a change in the translational symmetry along the C axis, is not observed in the temperature range T = 90–300 K and a second-order phase transition due to the formation of an incommensurate phase occurs at a higher temperature.     

Properties of the secondary order parameter in Rb2ZnCl4

The dielectric constants and the spontaneous polarization of Rb₂ZnCl₄-crystals have been investigated in order to characterize the nature of the transitions at 303, 195 and 74.5 K. The dielectric anomalies around 303 K hint at a critical exponent β = 0.36 ± 0.03 in the incommensurate phase. Close to 195 K the commensurate state can be induced by electric fields in agreement with an appropriate Clausius-Clapeyron relation. The polarization measurements further show that Rb₂ZnCl₄ has a (second) ferroelectric transformation at 74.5 K.     

Time relaxation of dielectric constant in the commensurate phase of TlGaSe2

The results of measurements of the time dependences of the dielectric constant of TlGaSe₂ in the commensurate ferroelectric phase are presented. From the result of the observation of the decay of ε at different stabilized temperatures below the commensurate phase transition temperature after cooling from the incommensurate phase, the presence of two different characteristic relaxation time constants with the same temperature behaviour has been revealed. This peculiarity is considered as a result of a coexistence of two polar sublattices in the temperature range below 110 K. According to these results, the previously reported dielectric anomaly at about 103 K is considered as a final lock-in phase transition accompanied by the forming of the antiferroelectric state in TlGaSe₂.     

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.     

Dynamic shift of the phase-transition temperature in (Sn1−x In(2/3)x)2P2S6 crystals with incommensurate phase

The dielectric properties of ferroelectric (Sn_1?x In_(2/3)x )₂P₂S₆ crystals were studied in the region of incommensurate phase transitions occurring upon fast cooling and heating (0.2–11 K/min). The dynamic phase-transition shift observed in these materials was examined.     

Magnetic inversion symmetry breaking and ferroelectricity in TbMnO3

TbMnO3 is an orthorhombic insulator where incommensurate spin order for temperature T(N)<41 K is accompanied by ferroelectric order for T<28 K. To understand this, we establish the magnetic structure above and below the ferroelectric transition using neutron diffraction. In the paraelectric phase, the spin structure is incommensurate and longitudinally modulated. In the ferroelectric phase, however, there is a transverse incommensurate spiral. We show that the spiral breaks spatial inversion symmetry and can account for magnetoelectricity in TbMnO3.     

Structure and orientational ordering of nitrogen molecules physisorbed on graphite

The structure and orientational ordering of nitrogen molecules physisorbed on graphite have been studied by low-energy diffraction (LEED). A two-sublattice in-plane herringbone structure with glide lines along two perpendicular directions is inferred from LEED patterns at T < 30 K from the monolayer where the molecular centers have the commensurate $\text{(}\text{3}\text{×}\text{3}\text{)}$ 30° structure. The orientational order-disorder transition of this commensurate phase was examined by superlattice spot intensity and angular profile measurements for 20 < T < 38 K. A rapid drop in superlattice intensity is observed near 27 K. The persistence of some intensity to 38 K. is suggestive of residual short-range orientational ordering and perhaps finite size or heterogeneity effects. For increasing coverage at T = 15 K, there is first a transition to a previously unobserved uniaxial incommensurate phase and then a transition to an apparently triangular incommensurate phase. The orientational superlattice spots are clearly present in the uniaxial phase, but are much weaker in the triangular incommensurate phase. At 31 < T < 35 K, an apparently triangular incommensurate phase with no detectable orientational superlattice spots is observed. The lattice constant versus equilibrium vapor pressure curve has been determined in the latter case assuming a continuous transition. The lattice constants of the incommensurate phases are used to place limits on the extent of possible phase-coexistence regions between the commensurate, uniaxial incommensurate, and triangular incommensurate phases. The LEED patterns from the bilayer at T = 15 K indicate a double-period superlattice structure of the triangular incommensurate phase which does not have the glide line symmetries of the commensurate monolayer. Some effects of heterogeneity on these phase transitions are discussed. A phase diagram for 10 < T < 40 K is proposed.     

Pyroelectric properties of a ferroelectric single crystal [NH2(CH3)2]3Sb2Cl9 (DMACA)

The pyroelectric properties of DMACA single crystals have been measured in the range 135–293 K, revealing the existence of ferroelectric second order phase transition at T_c = 243 K. The saturation value of spontaneous polarization P_s along a-axis amounts to 6.8 × 10⁻³ Cm⁻² at about 203 K. Critical exponent β = 0.5 has been found in the region 0.5–10 K away from T_c.