Two Rare-Earth Molecular Ferroelectrics with High Curie Temperatures,Large Spontaneous Polarization,Switchable Second Harmonic Generation Effects,and Strong Photoluminescence

Smart multifunctional molecular ferroelectrics bearing high Curie temperatures and diverse excellent physical properties, such as second harmonic generation (SHG) responses, luminescence, and semiconductivity, among others, have significant applications but have seldom been documented. Herein, the rare-earth metals Nd and Pr are introduced into a simple molecular system (nBu₄N )₃[M(NO₃)_x(SCN)_y] (nBu₄N₌tetrabutyl ammonium, M=rare-earth metal, nBu=CH₃CH₂CH₂CH₂), and two new multifunctional molecular ferroelectrics are obtained: (nBu₄N )₃[Nd(NO₃)₄(SCN)₂] ( 1 ) and (nBu₄N )₃[Pr(NO₃)₄(SCN)₂] ( 2 ). Their distinct heat and dielectric anomaly dependence on temperature verifies that compounds 1 and 2 experience high-temperature para-ferroelectric phase transitions at 408 and 413 K, respectively. Strikingly, both molecular ferroelectrics possess large spontaneous polarization with P_s values of 9.05 and 8.50 μC cm⁻², respectively, and are further characterized by the appearance of multiple intersecting non-180° domains and polarization switching behavior. In particular, compounds 1 and 2 show good stability with only a small decrease in SHG intensity after switching cycles, suggesting that they have great potential for application in nonlinear optical (NLO) switches. Simultaneously, the rare-earth compounds 1 and 2 present bright yellow–red and bright green fluorescence, respectively, at room temperature.     

Ferroelectric Coordination Polymers Self‐Assembled from Mesogenic Zinc(II) Porphyrin and Dipolar Bridging Ligands

A new class of ferroelectric coordination‐based polymers has been developed by the self‐assembly of lipophilic zinc porphyrin ( ZnP ) and ditopic bridging ligands. The ligands contain dipolar benzothiadiazole or fluorobenzene units, which are axially coordinated to ZnP with the dipole moments oriented perpendicular to the coordination axes. The coordination‐based polymers show ferroelectric characteristics in the liquid crystalline state, as revealed by distinctive hysteresis in the polarization–electric field (P–E) loops and inversion current peaks in current–voltage (I–V) loops. The observed ferroelectric properties are explainable by flip–flop rotation of the dipolar axle ligands induced by the applied electric field, as demonstrated by the positive‐up–negative‐down (PUND) measurements. The present system provides a new operating principle in supramolecular ferroelectrics.     

Emergence of the sub‐THz central peak at phase transitions in artificial BaTiO3/(Ba,Sr)TiO3 superlattices

A prominent central peak in the sub‐THz frequency range was observed in the Raman spectra of BaTiO₃/(Ba,Sr)TiO₃ (BT/BST) superlattice grown on (001)MgO substrate. Both soft and central mode show an anomaly around 200 K and 280 K, which can be correlated with orthorhombic to monoclinic phase transition of BST and BT, respectively. The observed temperature dependence of the central mode enabled us to explain rather broad temperature dependence of the dielectric permittivity previously observed in BT/BST superlattices. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

A SIMPLIFIED MODEL FOR DOMAIN SWITCHING OF FERROELECTRIC CRYSTAL

I. INTRODUCTION Domain switching is the main source of nonlinear characteristics of ferroelectric materials. The trans-formation performance of domain is the basis for ferroelectric constitutive research. In many literatures[1??10], complete switching models were adopted, in which ferroelectric materials are considered tobe consist of several basic sorts of domains, which are independent of each other. Under the actionof su?ciently strong electric ?elds or mechanical stress, the orienta…     

Quasi-pyroelectricity in the TGS crystal

It has been shown that a side electrode perpendicular to the measurement ones can significantly enhance the transverse electric current in TGS. Such a current, measured in a zero external electric field, resembles the classic longitudinal one. However, the amplitude of the transverse current oscillation, observed while cooling and heating the sample, rises much more slowly with the time of the transverse electric field preliminary application. Such exposure to the transverse field is required prior to the measurements for the transverse current to be observed, in a similar way to a longitudinal field that is applied in order to achieve a single domain state before longitudinal pyroelectric current measurements. A huge difference in the time of reaction to the electric fields preliminarily applied in order to achieve the maximum amplitude of the current oscillations in both cases is the evidence that the transverse current cannot be considered to be originated just for geometrical reasons.     

Observation of mechanical fracture and corresponding domain structure changes of polycrystalline PbTiO3 nanotubes

PbTiO₃ (PTO) nanotubes (NTs) were synthesized at various temperatures by gas phase reaction between PbO gas and anatase TiO₂ NTs and characterized by piezoresponse force microscopy (PFM). PTO ferroelectric phase was synthesized at as low as 400 °C as evidenced by PFM domain images and piezoresponse hysteresis loop measurement. Furthermore, the PTO NTs fabricated at above 500 °C underwent mechanical fracture through development of nanocracks due to grain growth, leading to ferroelectric domains with larger size and lower aspect ratio. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Nanoscale retention‐loss dynamics of polycrystalline PbTiO3 nanotubes

We observed the nanoscale retention dynamics of polycrystalline PbTiO₃ nanotubes using piezoresponse force microscopy. We found that the retention loss of the nanodot domains on the nanotubes showed the stretched exponential relaxation behaviors with stretched exponential factor n being less than 1 (0.523 and 0.692), which are similar to the thin films. In addition, the nanodot domains showed a diverse relaxation time constant τ due to different remnant polarization of each dot domains. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A Molecular Thermochromic Ferroelectric

Molecular ferroelectrics have attracted considerable interests because of their easy and environmentally friendly processing, low acoustical impedance and mechanical flexibility. Herein, a molecular thermochromic ferroelectric, N,N′‐dimethyl‐1,4‐diazoniabicyclo[2.2.2]octonium tetrachlorocuprate(II) ([DMe‐DABCO]CuCl₄) is reported, which shows both excellent ferroelectricity and intriguing thermochromism. [DMe‐DABCO]CuCl₄ undergoes a ferroelectric phase transition from Pca2₁ to Pbcm at a significantly high Curie temperature of 413 K, accompanied by a color change from yellow to red that is due to the remarkable deformation of [CuCl₄]^2? tetrahedron, where the ferroelectric and paraelectric phases correspond to yellow and red, respectively. Combined with multiple bistable physical properties, [DMe‐DABCO]CuCl₄ would be a promising candidate for next‐generation smart devices, and should inspire further exploration of multifunctional molecular ferroelectrics.     

High‐Tc Enantiomeric Ferroelectrics Based on Homochiral Dabco‐derivatives (Dabco=1,4‐Diazabicyclo[2.2.2]octane)

1,4‐Diazabicyclo[2.2.2]octane (dabco) and its derivatives have been extensively utilized as building units of excellent molecular ferroelectrics for decades. However, the homochiral dabco‐based ferroelectric remains a blank. Herein, by adding a methyl (Me) group accompanied by the introduction of homochirality to the [H₂dabco]²⁺ in the non‐ferroelectric [H₂dabco][TFSA]₂ (TFSA=bis(trifluoromethylsulfonyl)ammonium), we successfully designed enantiomeric ferroelectrics [R and S‐2‐Me‐H₂dabco][TFSA]₂. The two enantiomers show two sequential phase transitions with transition temperature (T_c) as high as 405.8 K and 415.8 K, which is outstanding in both dabco‐based ferroelectrics and homochiral ferroelectrics. To our knowledge, [R and S‐2‐Me‐H₂dabco][TFSA]₂ are the first examples of dabco‐based homochiral ferroelectrics. This finding opens an avenue to construct dabco‐based homochiral ferroelectrics and will inspire the exploration of more eminent enantiomeric molecular ferroelectrics.